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CN118344271A - Alkoxy substituted benzoyl oxo cyclohexene sulfide compound, preparation method and application thereof - Google Patents

Alkoxy substituted benzoyl oxo cyclohexene sulfide compound, preparation method and application thereof Download PDF

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Publication number
CN118344271A
CN118344271A CN202410062649.XA CN202410062649A CN118344271A CN 118344271 A CN118344271 A CN 118344271A CN 202410062649 A CN202410062649 A CN 202410062649A CN 118344271 A CN118344271 A CN 118344271A
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CN
China
Prior art keywords
alkyl
cycloalkyl
haloalkyl
methyl
compound
Prior art date
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CN202410062649.XA
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Chinese (zh)
Inventor
王现全
秦博
陈恩昌
张天柱
邹亚波
郭志江
胡玲
沈盛丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liaoning Xianda Agricultural Science Co ltd
Shenyang Wanling Biotechnology Co ltd
Original Assignee
Liaoning Xianda Agricultural Science Co ltd
Shenyang Wanling Biotechnology Co ltd
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Publication of CN118344271A publication Critical patent/CN118344271A/en
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    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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Abstract

The invention discloses an application of tetra-substituted cyclohexene sulfide compound and agriculturally acceptable salt thereof as herbicide, wherein the compound is shown as a general formula (I):

Description

Alkoxy substituted benzoyl oxo cyclohexene sulfide compound, preparation method and application thereof
The application claims the priority of the prior application with the patent application number 202310058371.4, named as a tetra-substituted phencyclized hexenyl sulfide compound and application thereof, which are submitted to the China national intellectual property office by the applicant in 2023 1-16. The entirety of this prior application is incorporated by reference into this disclosure.
Technical Field
The present disclosure belongs to the field of herbicides, and in particular relates to alkoxy substituted benzoyl oxy cyclohexene sulfide compounds, and a preparation method and application thereof.
Background
Due to succession and transition of weed populations and generation and rapid development of drug resistance to chemical pesticides, people continuously strengthen awareness of ecological environment protection, awareness of chemical pesticide pollution and pesticide influence on non-target organisms and importance of homing problems in pesticide ecological environments are continuously improved. With the gradual decrease of the cultivated land area, the continuous increase of population and the increase of the demand for grains, people are forced to rapidly develop agricultural production technology, improve and perfect cultivation system, and new compounds and compositions with herbicidal activity and good safety to crops are required to be continuously developed.
US5525580a reports that certain thio compounds have herbicidal activity, for example, wherein compound No. 95 of tables 3-7 has been developed as commercial herbicides (mesotrione):
WO2003066607a reports that certain thio compounds have herbicidal activity, for example, compounds 2329 and 2335 (KC 1 and KC 2) have better weed control at a dose of 0.25 kg/ha when pre-emergence treatments are applied:
there is still a need to develop new compounds which have herbicidal activity and are safe for crops.
Disclosure of Invention
To ameliorate the above problems, the present disclosure provides a compound of formula I, a stereoisomer or a agropharmaceutically acceptable salt thereof;
wherein:
X 1 is selected from hydrogen, cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, Y 1-S(O)m -;
X 2 is selected from hydrogen, cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 halocycloalkyl, Y 1-O-、Y1-S(O)m -;
X 3 is selected from cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, Y 1O-、Y1OC1-C6 alkyl, Y 1OC1-C6 alkyloxy, Y 1Y2-NH-、Y1Y2-N-C1-C6 alkyl, Y 1-S(O)m-、Y1-S(O)m-C1-C3 alkyl, Y 1-S(O)m-C1-C6 alkyloxy 、-C(O)Y1、-C(O)OY1、-OC(O)OY1、-N(Y1)C(O)OY2、-C(O)N(Y1)(Y2)、-N(Y1)C(O)N(Y1)(Y2)、-OC(O)N(Y1)(Y2)、-C(O)N(Y1)OY2、-N(Y1)S(O)2Y2、-N(Y1)C(O)Y2、-OS(O)2Y1、-CH＝NOY1、-C1-C6 alkylene-ch= NOY 1、-C1-C6 alkylene-O-n=cy 1Y2、C6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl;
Each Y 1、Y2 is the same or different and is independently selected from C 1-C6 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents selected from nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C6 cycloalkyl, C 3-C6 cycloalkyloxy, C 2-C6 alkenyl, C 2-C6 alkynyl, phenyl or halophenyl;
R 1、R2, which are identical or different, are independently of one another selected from hydrogen, C 1-C6 alkyl, C 3-C6 cycloalkyl, C 3-C6 alkenyl, C 3-C6 alkynyl;
Q is selected from hydrogen, cyano, C 1-C10 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl, C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 1-C6 alkyl, c 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, 3-14 membered heterocyclyl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3S(O)mC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) R 3、-C(O)OR3、C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-CH＝NOR3、-C1-C6 alkylene-ch=nor 3、-C1-C6 alkylene-O-n=cr 3R4、-P(＝S)(OR3)2;
Wherein X 3, Q are independently of each other optionally substituted with 1, 2, 3, 4 or 5 substituents selected from Y 3;
Each Y 3 is identical or different and is selected, independently of one another, from halogen, hydroxy, cyano, nitro, carboxyl, oxo (=O), C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 2-C6 haloalkenyl, C 2-C6 haloalkynyl, C 6-C14 aryl, C 6-C14 haloaryl, C 6-C14 arylC 1-C6 alkyl, C 6-C14 aryloxy, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, C 1-C6 alkylamino-, C 1-C6 alkyl C (O) -, C 1-C6 alkyl S (O) m-、-C(O)OC1-C6 alkyl, -C (O) NR 3R4、(R3O)R4 N-or R 3R4 N-;
Each R 3、R4 is the same or different and is independently selected from hydrogen, C 1-C6 alkyl
M is selected from 0, 1 or 2;
n is selected from 0, 1 or 2.
According to a preferred embodiment of the present disclosure, the above substituents may independently have the following definitions:
X 1 is selected from hydrogen, cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, Y 1-S(O)m -;
X 2 is selected from hydrogen, cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 halocycloalkyl, Y 1-O-、Y1-S(O)m -;
x 3 is selected from Y 1OC1-C6 alkyl;
Y 1 is selected from C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents selected from nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C6 cycloalkyl, C 3-C6 cycloalkyloxy, C 2-C6 alkenyl, C 2-C6 alkynyl, phenyl or halophenyl, 5 to 7 membered alicyclic ring containing 1 to 4 heteroatoms, 5 to 7 membered alicyclic C 1-C6 alkyl containing 1 to 4 heteroatoms or 5 to 7 membered heteroaromatic C 1-C6 alkyl containing 1 to 4 heteroatoms;
R 1、R2, which are identical or different, are independently of one another selected from hydrogen, C 1-C6 alkyl, C 3-C6 cycloalkyl, C 2-C6 alkenyl, C 2-C6 alkynyl;
Q is selected from hydrogen, cyano, C 1-C10 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl, C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 1-C6 alkyl, c 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, 3-14 membered heterocyclyl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3S(O)mC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) R 3、-C(O)OR3、C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-CH＝NOR3、-C1-C6 alkylene-ch=nor 3、-C1-C6 alkylene-O-n=cr 3R4、-P(＝S)(OR3)2;
Wherein X 3, Q are independently of each other optionally substituted with 1, 2, 3, 4 or 5 substituents selected from Y 3;
Each Y 3 is identical or different and is selected, independently of one another, from halogen, hydroxy, cyano, nitro, carboxyl, oxo (=O), C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 2-C6 haloalkenyl, C 2-C6 haloalkynyl, C 6-C14 aryl, C 6-C14 haloaryl, C 6-C14 arylC 1-C6 alkyl, C 6-C14 aryloxy, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, C 1-C6 alkylamino-, C 1-C6 alkyl C (O) -, C 1-C6 alkyl S (O) m-、-C(O)OC1-C6 alkyl, -C (O) NR 3R4、(R3O)R4 N-or R 3R4 N-;
Each R 3、R4 is the same or different and is independently selected from hydrogen, C 1-C6 alkyl
M is selected from 0, 1 or 2;
n is selected from 0, 1 or 2.
According to embodiments of the present disclosure, the above substituents may independently have the following definitions:
X 1 is selected from halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, Y 1-S(O)m -;
X 2 is selected from C 1-C6 haloalkyl, Y 1-S(O)m -;
x 3 is selected from Y 1OC1-C6 alkyl;
y 1 is selected from the group consisting of C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, and 5-7 membered alicyclic C 1-C6 alkyl containing 1-4 heteroatoms;
R 1、R2, identical or different, are independently of one another selected from hydrogen, C 1-C6 alkyl;
q is selected from the group consisting of C 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 5-14 membered heteroarylC 1-C6 alkyl, -C 1-C6 alkylene C (O) OR 3;
Wherein X 3, Q are independently of each other optionally substituted with 1, 2, 3, 4 or 5 substituents selected from Y 3;
Each Y 3, which is the same or different, is independently selected from halogen, hydroxy, cyano, nitro, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 6-C14 arylC 1-C6 alkyl, 3-10 membered heterocyclyl, C 1-C6 alkyl C (O) -, or R 3R4 N-;
Each R 3、R4 is the same or different and is independently selected from hydrogen, C 1-C6 alkyl
M is selected from 0, 1 or 2;
n is selected from 0, 1 or 2.
According to embodiments of the present disclosure, Q may be selected from hydrogen, cyano, C 1-C10 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl, C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 1-C6 alkyl, c 6-C14 aryl, 5-14 heteroaryl, 3-14 heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 3-14 heteroarylC 1-C6 alkyl, 3-14 membered heterocyclyl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3S(O)mC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) R 3、-C(O)OR3、-C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、-C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-CH＝NOR3、-C1-C6 alkylene-ch=nor 3、-C1-C6 alkylene-O-n=cr 3R4、-P(＝S)(OR3)2;
According to embodiments of the present disclosure, Q may be selected from hydrogen, cyano, C 1-C10 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 aryl C 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) OR 3、-C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、-C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-P(＝S)(OR3)2;
According to embodiments of the present disclosure, Q may be selected fromY 5、Y6、Y7、Y8, which are identical or different, are independently selected from H, C 1-C8 alkyl, C 1-C8 alkyloxy; or Y 5 and Y 6 form with their respective attached N the following groups unsubstituted or optionally substituted with one, two or more Y q1: 3-14 membered heterocycle or 5-14 membered heteroaryl ring; or Y 7 and Y 8 form with their respective attached N the following groups unsubstituted or optionally substituted with one, two or more Y q2: 3-14 membered heterocycle or 5-14 membered heteroaryl ring; y q1 and Y q2 are identical or different and are selected independently of one another from H, halogen, C 1-C8 alkyl, C 1-C8 alkyloxy;
According to embodiments of the present disclosure, Q may be selected from the following groups, unsubstituted or optionally substituted with Q Y 3: c 6-C14 aryl (e.g. phenyl, naphthyl or anthracyl, e.g. ) A 5-membered heterocyclic group (e.g) 6 Membered heterocyclic group5-14 Membered heteroaryl (e.g., benzoheteroaryl, such as For example heteroaryl-heteroaryl groups, e.g) ; Q is selected from 0, 1, 2, 3, 4 or 5.
According to embodiments of the present disclosure, Q may be selected from the following groups that are unsubstituted or optionally substituted with one, two or more Y 3: c 1-6 alkyl, cyclohexenyl, furyl, thienyl, thiazolinyl, oxazolinyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, pyrimidinyl, pyridyl, triazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzopyrazinyl, phenyl, naphthyl, anthracenyl, purinyl;
according to embodiments of the present disclosure, Q may be selected from methyl, ethyl, propyl, isopropyl, cyano,
According to embodiments of the present disclosure, X 1 may be selected from hydrogen, nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 alkyl;
According to embodiments of the present disclosure, X 1 may be selected from hydrogen, nitro, halogen, C 1-C4 alkylsulfonyl, C 1-C4 alkyl;
according to embodiments of the present disclosure, X 1 may be selected from halogen, methyl, nitro, methylsulfonyl;
According to embodiments of the present disclosure, X 1 may be selected from F, cl, br, methyl, trifluoromethyl or methylsulfonyl;
According to embodiments of the present disclosure, X 2 may be selected from hydrogen, nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 alkyl, C 1-C6 haloalkyl;
According to embodiments of the present disclosure, X 2 may be selected from hydrogen, nitro, halogen, C 1-C4 alkylsulfonyl, C 1-C4 alkylsulfinyl, C 1-C4 haloalkyl;
According to embodiments of the present disclosure, X 2 may be selected from halogen, C 1-C4 alkylsulfonyl, C 1-C4 haloalkyl;
According to embodiments of the present disclosure, X 2 may be selected from CF 3、-SO2CH3.
According to embodiments of the present disclosure, when X 1 is Cl, X 2 is-SO 2CH3 or CF 3; when X 1 is CH 3, X 2 is-SO 2CH3.
According to embodiments of the present disclosure, X 3 may be selected from-CH 2OY1.
According to embodiments of the present disclosure, Y 1 may be selected from C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy C 1-C3 alkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C3 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, 5-7 membered heterocyclyl-C 1-C6 alkyl containing 1-2 oxygen atoms.
According to embodiments of the present disclosure, Y 1 may be selected from C 1-C3 alkyl, C 1-C3 haloalkyl, C 1-C3 alkoxy C 1-C3 alkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C3 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, 5-7 membered heterocyclyl-C 1-C3 alkyl containing 1-2 oxygen atoms.
According to embodiments of the present disclosure, Y 1 may be selected from methyl,
According to embodiments of the present disclosure, Y 3 may be selected from halogen, hydroxy, cyano, nitro, carboxy, oxo (=o), C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 2-C6 haloalkenyl, C 2-C6 haloalkynyl, C 6-C14 aryl, C 6-C14 haloaryl, C 6-C14 arylC 1-C6 alkyl, c 6-C14 aryloxy, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, 5-10 membered heteroaryl C 1-C6 alkyl, 3-10 membered heterocyclyl C 1-C6 alkyl, C 1-C6 alkylamino-, C 1-C6 alkyl C (O) -, C 1-C6 alkyl S (O) m-、-C(O)OC1-C6 alkyl, -C (O) NR 3R4、(R3O)R4 N-, or R 3R4 N-.
According to an embodiment of the disclosure, Y 3 is selected from F, cl, br, NO 2、OH、CN、CF3、C(O)OH、NH2, oxo (=o), thio (=s), methyl, ethyl, vinyl, ethynyl, methoxy, ethoxy, methylthio, furyl, phenyl, chlorophenyl, methylsulfonyl, isopropoxy, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, methoxyamino, ethoxyamino, C (=o) OCH 3, piperidinyl, morpholinyl,
According to an embodiment of the disclosure, Y 3 is selected from F, cl, br, NO 2、OH、CN、CF3, methyl, ethyl, methoxy, ethoxy, methylamino, dimethylamino, ethylamino, isopropylamino, piperidinyl, morpholinyl, benzyl, acetyl.
According to an embodiment of the disclosure, R 1 and R 2 are the same or different and are independently selected from hydrogen, C 1-C6 alkyl;
According to an embodiment of the disclosure, R 1 and R 2 are the same or different and are independently selected from hydrogen, methyl;
according to an embodiment of the present disclosure, R 1 and R 2 are simultaneously H.
According to an embodiment of the present disclosure, R 1 and R 2 are both methyl.
According to an embodiment of the disclosure, X 1 is selected from Cl;
X 2 is selected from methylsulfonyl;
X 3 is selected from-CH 2OY1;
Y 1 is selected from methyl, 2-trifluoroethyl, 2-difluoroethyl, 2-tetrahydrofuranylmethyl, 2-tetrahydropyranylmethyl;
R 1、R2 are each selected from hydrogen;
q is selected from the substituents shown below:
Or selected from the benzene ring, naphthalene ring as shown below:
or a 5-membered heterocyclic group selected from the following:
Or a 6 membered heterocyclic group selected from the following:
or a benzoheterocyclyl group selected from the following:
or a heterocyclo-heterocyclyl selected from the following:
The above Q groups may be substituted with Q Y 3: F. cl, br, hydroxy, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, benzyl, acetyl, piperidine, morpholine, methylamino, ethylamino, isopropylamino or dimethylamino; q is selected from 0, 1,2, 3, 4 or 5;
n is selected from 0, 1 or 2.
According to embodiments of the present disclosure, each group in the compounds of formula I may optionally be further substituted with one or more substituents which may include, but are not limited to: hydrogen, oxo (=o), halogen, cyano, nitro, hydroxy, mercapto, carboxyl, amino, arylamino, aminoalkyl, alkyl, alkyloxy, alkylthio, alkenyl, alkynyl, hydroxyalkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl 、-C(＝O)R、-ORa、-C(＝O)ORa、-OC(＝O)Ra、-SO2Ra、-NRbRc、-CONRbRc、-SO2NRbRc、-C(NRbRc)＝NRd, or = NR d: wherein R, R a、Rb、Rc and R d are each independently selected from: hydrogen, cyano, amino, alkyl, alkylamino, arylamino, alkylthio, alkyloxy, aryloxy, hydroxy, mercapto, alkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, alkylsulfonyl, aminosulfonyl, hydroxyalkyl, aminoalkyl, alkanoyl or aminoacyl. Wherein each alkylamino, arylamino, alkyloxy, aryloxy, hydroxy, mercapto, alkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, alkylsulfonyl, sulfamoyl, hydroxyalkyl, aminoalkyl, alkanoyl, aminoacyl, and alkylthio in the substituents have the meanings described in the disclosure, and each may optionally be further monosubstituted by a substituent described in the disclosure or the same or different polysubstituted.
According to embodiments of the present disclosure, the compound represented by formula I may be selected from compounds 1 to 270 in example table 1.
The present disclosure also provides a process for the preparation of a compound of formula I, a stereoisomer or a pharmaceutically acceptable salt thereof, the process comprising the steps of:
Wherein X 1、X2、X3、R1、R2, Q, n have the above-described definition independently of each other.
According to embodiments of the present disclosure, a compound of formula II is reacted with a compound of formula III to provide a compound of formula I.
According to an embodiment of the present disclosure, the preparation method further comprises resolving to obtain a stereoisomer thereof after obtaining the compound shown in formula I, or reacting with an acid or a base to prepare an agropharmaceutically acceptable salt thereof.
According to an embodiment of the present disclosure, the reaction may be performed in the presence of a solvent, which may be selected from at least one of dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide, dimethylsulfoxide, or the like.
According to embodiments of the present disclosure, the reaction may be performed under the action of a base, which may be selected from an organic base such as triethylamine, N-dimethylaniline, pyridine, or the like, or an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, or the like.
According to embodiments of the present disclosure, the temperature of the reaction may be from-10 ℃ to 150 ℃, such as from 20 ℃ to 120 ℃.
According to embodiments of the present disclosure, the reaction time may be 0.5 to 48 hours, for example 1 to 24 hours.
According to embodiments of the present disclosure, compounds of formula III are commercially available or may be prepared by one skilled in the art selecting appropriate starting materials, for example, with reference to: asian Journal of Chemistry (2015), 27 (1), 287-291.
According to an embodiment of the present disclosure, a method for preparing a compound of formula II comprises the steps of:
Wherein X 1、X2、X3、R1、R2, independently of one another, have the above-described definition.
According to embodiments of the present disclosure, the compound of formula IV is reacted with a halogenating reagent to yield the compound of formula II.
According to an embodiment of the present disclosure, the halogenating agent may be a chlorinating agent, for example, at least one selected from oxalyl chloride, sulfoxide chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, or the like. Suitable solvents are selected from at least one of dichloromethane, 1, 2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid, dioxane or liquid halogenating agents, etc.
According to embodiments of the present disclosure, the temperature of the reaction may be from-10 ℃ to 150 ℃, such as from 20 ℃ to 120 ℃.
According to embodiments of the present disclosure, the reaction time may be 0.5 to 48 hours, for example 1 to 24 hours.
The present disclosure also provides the use of a compound of formula I, a stereoisomer thereof, or an agropharmaceutically acceptable salt thereof, in weeding, for example as a herbicide.
The present disclosure also provides a herbicidal composition comprising at least one of a compound of formula I, a stereoisomer thereof, or an agropharmaceutically acceptable salt thereof.
According to an embodiment of the present disclosure, the herbicidal composition comprises 1 to 99% by weight of the active ingredient, preferably 1 to 99% by weight of the total weight of all active ingredients.
According to embodiments of the present disclosure, the active ingredient may comprise at least one selected from the group consisting of the compound of formula I, a stereoisomer thereof, or an agropharmaceutically acceptable salt thereof.
The compounds of the present disclosure may be used alone or in combination with other known pesticides, fungicides, plant growth regulators or fertilizers, and the like.
Or alternatively, the herbicidal composition may further comprise other agropharmaceutically acceptable active ingredients which may be those known in the art, for example selected from the compounds described in WEED RESEARCH, 441-445 (1986), THE PESTICIDE Manual, 15 th edition; and are agriculturally active ingredients, for example, useful as inhibitors of the following enzymes: acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II and/or protoporphyrinogen oxidase.
Alternatively, the other agropharmaceutically acceptable active ingredient may be selected from herbicides or plant growth regulators known in the literature, for example all application forms of the compounds described below as examples, for example free compounds, acid addition salts, base addition salts, esters, solvates such as hydrates, isomers such as stereoisomers, optical isomers and the like.
Herbicides, for example, selected from at least one of the following: acetochlor (acetochlor), acifluorfen (acifluorfen), acifluorfen sodium salt (alloxydim-sodium), benalafen (aclonifen), alachlor (alachlor), alachlor (allidochlor), gramox (alloxydim, alloxydim-sodium), ametryn (ametryn), amicarbazone (amicarbazone), mefenacet (amidochlor), Amidosulfuron (amidosulfuron), 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylic acid, ciprofloxacin acid (aminocyclopyrachlor), ciprofloxacin potassium salt, benpropenone, quinclorac (Benquitrione), mequintocet-mexyl (Pyraquinate), ciprofloxacin methyl (aminocyclopyrachlor-methyl), aminopyralid (aminopyralid), mefenamic acid (amitrole), Ammonium sulfamate (ammoniumsulfamate), anilofos (anilofos), sulfentrazone (asulam), atrazine, carfentrazone-ethyl (azafenidin), primisulfuron (azimsulfuron), fluobutamid (beflubutamid), benazolin (benazolin), benazolin ethyl, flumetsulam (benfluralin), furoxanide (benfurate), bensulfuron (bensulfuron), bensulfuron methyl, triazophos (bensulide), bentazone (bentazone), bicyclomethyl (benzobicyclon), pyripyroxsulam (benzofenap), fluroxypyr (bicyclopyron), carboxin (bifenox), bialaphos (bilanafos), bialaphos sodium, bispyribac-sodium (bispyribac), bispyribac-sodium, clomazone (bixlozone), triclopyr (bromacil), brombutamide (bromobutide), bromfenoxime (bromofenoxim), Bromoxynil (bromoxynil), butyl bromoxynil, potassium bromoxynil, heptyl bromoxynil, octyl bromoxynil, oxycodone (busoxinone), butachlor (butachlor), butachlor (butafenacil), imazalil (butamifos), butachlor (butenachlor), butralin (butralin), butoxycyclic ketone (butroxydim), ding Caodi (butylate), carfentrazone (cafenstrole), bisoxamate (carbetamide), Carfentrazone-ethyl (carfentrazone), carfentrazone-ethyl (carfentrazone-ethyl), dicamba (chloramben), tribromone (chlorbromuron), 1- { 2-chloro-3- [ (3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl) carbonyl ] -6- (trifluoromethyl) phenyl } piperidin-2-one, 4- { 2-chloro-3- [ (3, 5-dimethyl-1H-pyrazol-1-yl) methyl ] -4- (methylsulfonyl) benzoyl } -1, 3-dimethyl-1H-pyrazol-5-yl-1, 3-dimethyl-1H-pyrazole-4-carboxylate, Valicarb (chlorfenac), valicarb sodium salt, oat ester (chlorfenprop), chlormethodane (chlorflurenol), chlormethodane methyl ester, chloroxamine (chloridazon), chlorimuron-ethyl (chlorimuron, chlorimuron-ethyl), 2- [ 2-chloro-4- (methylsulfonyl) -3- (morpholin-4-ylmethyl) benzoyl ] -3-hydroxycyclohex-2-en-1-one, 4- { 2-chloro-4- (methylsulfonyl) -3- [ (2, 2-trifluoroethoxy) methyl ] benzoyl } -1-ethyl-1H-pyrazol-5-yl-1, 3-dimethyl-1H-pyrazole-4-carboxylic acid ester, Chlorophthalimide (chlorophthalim), chlortoluron (chlorotoluron), dimethyl chlorophthalide (chlorthal-dimethyl), 3- [ 5-chloro-4- (trifluoromethyl) pyridin-2-yl ] -4-hydroxy-1-methylimidazolidin-2-one, chlorsulfuron (chlorsulfuron), indolone (cinidon), indoxyl (cinidon-methyl), cyclohepta-methyl ether (cinmethylin), cinosulfuron (cinosulfuron), chloracyl phosphine (clacyfos), Clethodim (clethodim), clodinafop-propargyl (clodinafop), clodinafop-propargyl (clodinafop-propargyl), clomazone (clomazone), clomazone (clomeprop), clopyralid (clomazone), clomazone (cloransulam), clomazone (cloransulam-methyl), bensulfuron (cumyluron), cyanamide (cyanamide), cyanamide, benazolin (cycloate), benazolin-ethyl, and benazolin-ethyl, cyclopyranil, cyclopyrimorate, cyclosulfamuron (cyclosulfamuron), thioxanthone (cycloxydim), cyhalofop-butyl (cyhalofop, cyhalofop-butyl), cyprodinil, 2, 4-D-butoxyethyl, 2, 4-D-butyl, 2, 4-D-dimethylammonium salt, 2, 4-D-alkanolamine, 2, 4-D-ethyl, 2, 4-D-2-ethylhexyl, 2, 4-D-isobutyl, 2, 4-D-isooctyl, 2, 4-D-isopropylammonium salt, 2, 4-D-potassium salt, 2, 4-D-triisopropanolamine, 2, 4-D-triethanolamine, 2, 4-DB-butyl, 2, 4-DB-dimethyl ammonium salt, 2, 4-DB-isooctyl, 2, 4-DB-potassium salt, 2, 4-DB-sodium salt, chlorazuron (daimuron (dymron)), coumarone (dalapon), dazomet (dazomet), n-decanol, betalain (desmedipham), desulfonyl-pyrazolote (detosyl-pyrazolate (DTP)), dicamba (dicamba), chlorazuron (dicamba), Difenoxanil (dichlobenil), 2, 4-D propionic acid (dichlorprop-P), sethoxydim (diclofop, diclofop-methyl), sethoxydim (diclofop-P-methyl), dichlorsulfamide (diclosulam), difenoconazole (difenzoquat), diflufenican (diflufenican), diflufuron (diflufenzopyr), diflufuron sodium, oxazouron (dimefuron), Perambulator (DIMEPIPERATE), dimethenamid (dimethachlor), isowurtzite (DIMETHAMETRYN), dimethenamid (DIMETHENAMID), dimethenamid (DIMETHENAMID-P), 3- (2, 6-dimethylphenyl) -6- [ (2-hydroxy-6-oxocyclohex-1-en-1-yl) carbonyl ] -1-methylquinazoline-2, 4 (1H, 3H) -dione, 1, 3-dimethyl-4- [2- (methylsulfonyl) -4- (trifluoromethyl) benzoyl ] -1H-pyrazol-5-yl-1, 3-dimethyl-1H-pyrazole-4-carboxylate, dimetrasulfuron, dichlormid (dinitramine), terfenacet (dinoterb), bispyribac-sodium (diphenamid), diquat (diquat), dibromodiquat (diquat-dibromid), dithiopyr (dithiopyr), diuron (diuron), DMPA, DNOC, endo-rope (endothal), EPTC, penoxsulam (esprocarb), ethaboxam (ethalfluralin), amicarbazone (ethametsulfuron, triamcinolone, ethametsulfuron-methyl), buprofezin (ethiozin), ethofumesan (ethofumesate), fluorolactofen (ethoxyfen, ethoxyfen-ethyl), ethoxypyr sulfuron (ethoxysulfuron), acetochlor (etobenzanid), ethyl- [ (3- { 2-chloro-4-fluoro-5- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) -3, 6-dihydropyrimidin-1 (2H) -yl ] phenoxy } pyridin-2-yl) oxy ] acetate, F-9960, F-5231, N- { 2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -5-oxo-4, 5-dihydro-1H-tetrazol-1-yl ] phenyl } ethanesulfonamide, F-7967, 3- [ 7-chloro-5-fluoro-2- (trifluoromethyl) -1H-benzimidazol-4-yl ] -1-methyl-6- (trifluoromethyl) pyrimidine-2, 4 (1H, 3H) -dione, fenoxaprop-P-ethyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxaprop-P-ethyl (fenoxasulfone), fenquinotrione, metamifop (fentrazamide), wheat straw fluoride (flamprop), high-efficiency wheat straw fluoroisopropyl (flamprop-M-isopropyl), high-efficiency wheat straw fluoromethyl (flamprop-M-methyl), flazasulfuron (flazasulfuron), florasulam (florasulam), haloxyfop-butyl (fluazifop), Haloxyfop (fluazifop-P), haloxyfop-butyl (fluazifop-butyl), haloxyfop-butyl (fluazifop-P-butyl), flucarbazone-sodium (flucarbazone), flucarbazone sodium salt, fluazifop-sodium (flucetosulfuron), haloxyfop-methyl (fluchloralin), flufenacet (flufenacet), fluazifop-butyl (flufenpyr), fluidazin ester (flufenpyr-ethyl), flumetsulam (flumetsulam), Fluoroenoxac acid (flumiclorac), flumetofen (flumiclorac-pentyl), flumioxazin (flumioxazin), fluometuron (fluometuron), imazalil (flurenol), fluorenol butyl (flurenol-butyl), fluorenol dimethyl ammonium salt, fluorenol methyl ester, fluoroglycofen-ethyl (fluoroglycofen), fluoroglycofen-ethyl, fluopropionic acid (flupropanate), fluflazasulfuron (flupyrsulfuron, flupyrsulfuron-methyl-sodium), fluazinone (fluridone), fludioxonil (flurochloridone), fluroxypyr (fluroxypyr), fluroxypyr-meptyl (fluroxypyr-meptyl), furbenone (flurtamone), oxaziclomefone (fluthiacet), methyl oxazinate, fomesafen (fomesafen), fomesafen sodium salt, formylsulfuron (foramsulfuron), penoxsulam (fosamine), glufosinate (glufosinate), Ammonium glyphosate, sodium salt of refined ammonium glyphosate, ammonium salt of refined ammonium glyphosate, sodium salt of refined ammonium glyphosate, glyphosate (glyphosate), ammonium glyphosate, isopropyl ammonium glyphosate, diammonium glyphosate, dimethyl ammonium glyphosate, potassium glyphosate, sodium glyphosate, trimethyl sulfonium glyphosate, H-9201, O- (2, 4-dimethyl-6-nitrophenyl) O-ethyl isopropyl thiophosphamide ester, clopyralid (halauxifen), clopyralid (halauxifen-methyl), flunidesulfonamide (halosafe), halosulfuron (halosulfuron), haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl (haloxyfop-ethoxyethyl), haloxyfop-ethoxyethyl (haloxyfop-P-ethoxyethyl), haloxyfop-methyl (haloxyfop-methyl), haloxyfop-methyl (haloxyfop-P-methyl), hexazinone (hexazinone), HW-02, i.e., 1- (dimethoxyphosphoryl) ethyl- (2, 4-dichlorophenoxy) acetate, 4-hydroxy-1-methoxy-5-methyl-3- [4- (trifluoromethyl) pyridin-2-yl ] imidazolidin-2-one, 4-hydroxy-1-methyl-3- [4- (trifluoromethyl) pyridin-2-yl ] imidazolidin-2-one, (5-hydroxy-1-methyl-1H-pyrazol-4-yl) (3, 4-trimethyl-1, 1-dioxo-2, 3-dihydro-1-benzothien-5-yl) methanone, 6- [ (2-hydroxy-6-oxocyclohex-1-en-1-yl) carbonyl ] -1, 5-dimethyl-3- (2-methylphenyl) quinazolin-2, 4 (1H, 3H) -dione, Imazamethabenznz, imazethapyr (imazamox), imazethapyr ammonium salt, imazapic (imazapic) niacin, imazapic (imazapyr), imazapic isopropyl ammonium salt, imazapic (imazaquin), imazapic (imazethapyr), imazethapyr (imazethapyr-immonium), halosulfuron-methyl (imazosulfuron), indenone (indanon), Iodosulfuron (iodosulfuron), iodosulfuron sodium salt (iodosulfuron-methyl-sodium), ioxynil (ioxynil), xin Xiandian benzonitrile (ioxynil-octanoate), ioxynil potassium salt, ioxynil sodium salt, triazoxamide (ipfencarbazone), isoproturon (isoproturon), isoxaron (isouron), isoxaflutole (isoxaben), isoxaflutole (isoxaflutole), terfenacet (karbutilate), KUH-043, 3- ({ [5- (difluoromethyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl ] methyl } sulfonyl) -5, 5-dimethyl-4, 5-dihydro-1, 2-oxazole, ketal cyclosulfamuron (ketospiradox), lactofen (lactofen), cycloxaprine (lenacil), linuron (linuron), MCPA-butoxyethyl, MCPA-dimethyl ammonium salt, MCPA-2-ethylhexyl ester, MCPA-isopropyl ammonium salt, MCPA-potassium salt, MCPA-sodium salt, MCPB, MCPB-methyl ester, MCPB-ethyl ester, MCPB-sodium salt, 2-methyl-4-chloropropionic acid (mecoprop), sodium 2-methyl-4-chloropropionate (mecoprop-sodium), butoxyethyl 2-methyl-4-chloropropionate, 2-methyl-4-chloropropionate (mecoprop-P), butoxyethyl 2-methyl-4-chloropropionate, dimethyl ammonium salt of 2-methyl-4-chloropropionate, 2-ethylhexyl 2-methyl-4-chloropropionate, potassium 2-methyl-4-chloropropionate, mefenacet (mefenacet), fluorosulfonamide (mefluidide), Mesosulfuron (mesosulfuron-methyl), mesotrione (mesotrione), mefone (methabenzthiazuron), methabenzthiazuron (metam), oxaziclomefone (metafop), oxaziclomefone (metamitron), metazachlor (metazachlor), metazosulfuron (metazosulfuron), metsulfuron, mesosulfuron (methiopyrsulfuron), Isoxazoline (methiazolin), 2- ({ 2- [ (2-methoxyethoxy) methyl ] -6- (trifluoromethyl) pyridin-3-yl } carbonyl) cyclohexane-1, 3-dione, methyl isothiocyanate, 1-methyl-4- [ (3, 4-trimethyl-1, 1-dioxo-2, 3-dihydro-1-benzothien-5-yl) carbonyl ] -1H-pyrazole-5-ylpropane-1-sulfonate, bromovalley (metobromuron), metolachlor (metolachlor), cumyl (S-metolachlor), mefenamide (I), Sulfentrazone (metosulam), methosulfuron (metoxuron), metribuzin (metribuzin), mesosulfuron (metsulfuron, metsulfuron-methyl), molinate (molinat), chlorsulfuron (monolinuron), monosulfuron (monosulfuron), monosulfuron ester (monosulfuron-ester), MT-5950, N- (3-chloro-4-isopropylphenyl) -2-methylpentanamide, NGGC-011, dichlormid (napropamide), NC-310, namely [5- (benzyloxy) -1-methyl-1H-pyrazol-4-yl ] (2, 4-dichlorophenyl) methanone, bensulfuron (neburon), nicosulfuron (nicosulfuron), lupulone (pelargonic acid), fluben (norflurazon), oleic acid (fatty acid), prosulfocarb (orbencarb), azosulfuron (orthosulfamuron), sulfenamide (oryzalin), oxadiargyl (oxadiargyl), oxadiazon (oxadiazon), epoxy sulfosulfuron (oxasulfuron), Oxazinone (oxaziclomefon), oxyfluorfen (oxyfluorfen), paraquat (paraquat), paraquat dichloride (paraquatdichloride), kecao (pebulate), pendimethalin (PENDIMETHALIN), penoxsulam (penoxsulam), pentachlorophenol (pentachlorphenol), cyclopentaoxadiazon (pentoxazone), clethodim (pethoxamid), mineral oil, betanin (PHENMEDIPHAM), Picloram (picloram), fluopicolide (picolinafen), pinoxaden (pinoxaden), piprad (piperophos), pretilachlor (pretilachlor), primisulfuron (primisulfuron, primisulfuron-methyl), trifluralin (prodiamine), fenpropion (profoxydim), chlorphenamine (prometon), prometryn (prometryn), pretilachlor (propachlor), Propanil (propanil), oxaziclomefone (propaquizafop), chlorphenamine (propazine), propyzamide (propham), isopropamide (propisochlor), prosulfuron (propoxycarbazone, propoxycarbazone-sodium), propyrisulfuron (propyrisulfuron), propyzamide (propyzamide), prosulfuron (prosulfocarb), prosulfuron (prosulfuron), Bispyribac-sodium (pyraclonil), pyraclonil (pyraflufen, pyraflufen-methyl), sulfonyloxaziclomefone (pyraclostrobin), pyrazolote (pyrazolynate (pyrazolate)), pyrazosulfuron-ethyl (pyrazosulfuron, pyrazosulfuron-methyl), benoxadiazon (pyrazoxyfen), pyriproxyfen (pyribambenz), isoproturon (pyribambenz-isopropyl), Propyl ester grass ether (pyribambenz-propyl), pyribenzoxim (pyribenzoxim), barnyard grass pill (pyributicarb), dazomet (pyridafol), pyridate (pyridate), pyriftalid (pyriftalid), pyriminobac-methyl ether (pyriminobac), methyl pyriminobac-methyl ether (pyriminobac-methyl), pyrithiofide (pyrimisulfan), pyriminobac-methyl (pyrithiobac, pyrithiobac-sodium), Metazachlor (pyroxasulfone), sulfentrazone-ethyl (pyroxsulam), quinclorac (quinclorac), cloquintocet-mexyl (quinmerac), methoquinone (quinoclamine), quizalofop (quizalofop), quizalofop-ethyl (quizalofop-ethyl), quizalofop-P-ethyl (quizalofop-P), quizalofop-ethyl (quizalofop-P-ethyl), quizalofop-P-furfuryl (quizalofop-P-tefuryl), quizalofop-ethyl, QYM-201, QYR-301, rimsulfuron (rimsulfuron), saflufenacil (saflufenacil), sethoxydim (sethoxydim), cyclouron (siduron), simazine (simazine), simetryn (simetryn), SL-261, sulcotrione (sulcotrion), sulfentrazone (sulfentrazone), azosulfuron (sulfometuron), mesosulfuron (sulfometuron-methyl), sulfosulfuron (sulfosulfuron), SYN-523, SYP-249, 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5- [ 2-chloro-4- (trifluoromethyl) phenoxy ] -2-nitrobenzoate, SYP-300, 1- [ 7-fluoro-3-oxo-4- (prop-2-yn-1-yl) -3, 4-dihydro-2H-1, 4-benzoxazin-6-yl ] -3-propyl-2-thioimidazolidine-4, 5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, buthiuron (tebuthiuron), furosemide (tefuryltrione), Cyclosulfamone (tembotrione), pyrone (tepraloxydim), terbutadine (terbacil), terbutaline (terbucarb), terbutaline (terbumeton), terbutaline (terbutryn), tebuflomoxaprop (tetflupyrolimet), thenocimine (thenylchlor), thiazopyr acid (thiazopyr), thifensulfuron methyl (thiencarbazone, thiencarbazone-methyl), thifensulfuron methyl (thifensulfuron), thifensulfuron-methyl), graminium (thiobencarb), fluoxastrobin (tiafenacil), tolpyralate, topramezone (topramezone), tricresyl (tralkoxydim), triamcinolone acetochlor (triafamone), dicamba (tri-allate), cinosulfuron (triasulfuron), tribenuron-methyl (tribenuron, tribenuron-methyl), triclopyr (triclopyr), Oxford (trietazine), trifloxysulfuron (trifloxysulfuron), trifloxysulfuron sodium (trifloxysulfuron-sodium), trifloxysulfuron (trifludimoxazin), trifluralin (trifluralin), trifloxysulfuron (triflusulfuron), flusulfamuron Long Jiazhi (triflusulfuron-methyl), trifloxysulfuron (tritosulfuron), urea sulfate, dichlormid (vernolate), trifloxysulfuron, ZJ-0862 is 3, 4-dichloro-N- {2- [ (4, 6-dimethoxypyrimidin-2-yl) oxy ] benzyl } aniline.
Plant growth regulators, for example, at least one selected from the group consisting of: activated ester (acibenzolar), benzothiadiazole (acibenzolar-S-methyl), 5-aminolevulinic acid, pyrimidinol (ancymidol), 6-benzylaminopurine, brassinolide (Brassinolid), catechin (catechine), chlormequat (chlormequat chloride), mevalonic acid (cloprop), cyclopropamic acid (cyclanilide), 3- (cyclopropyl-1-enyl) propionic acid, butyryl hydrazine (daminozide), dazomet, N-decanol, furoic acid (dikegulac), sodium furoate (dikegulac-sodium), polyacid (endothal), dipotassium, disodium, single (N, N-dimethylalkyl ammonium) polyacid, ethephon (ethephon), flumetramine (flumetralin), bezoatin, butyl alcohol, azoxystrol (flurprimidol), flupirurea (forchlorfenuron), gibberellic acid (gibberellic acid), anti-fall amine (inabenfide), indole-3-acetic acid (IAA), 4-indol-3-yl butyric acid, vinyl (isoprothiolane), allyl (8), thiazole (728), maleic acid (721-methyl), fuzoic acid, 1-naphtaline (paclobutrazol), naphthalene-2-methyl acetate, naphthalene-2-methyl acetate, naphthalene-1-methyl-ethyl acetate (8232-methyl), naphthalene-2-methyl acetate (8232-methyl) and the mixtures thereof, N- (2-phenylethyl) -beta-aminopropionic acid, N-phenylphthalic acid (N-PHENYLPHTHALAMIC ACID), propiolic acid (prohexadione), calcium propionine, jasmone (prohydrojasmone), salicylic acid, strigolactone (strigolactone), tetrachloronitrobenzene (tecnazene), thidiazuron (thidiazuron), triacontanol (triacontanol), trinexapac-ethyl (trinexapac, trinexapac-ethyl), tsitodef, uniconazole (uniconazole), and mevalonazole (uniconazole-P).
According to embodiments of the present disclosure, the herbicidal composition further comprises an agropharmaceutically acceptable carrier. Preferably, the agropharmaceutically acceptable carrier may be selected from at least one of inert materials, surfactants, solvents and other additives, for example.
According to embodiments of the present disclosure, the herbicidal composition may be present in a suitable form, for example it may be formulated as at least one of the following formulations: wettable Powders (WP), water-soluble concentrates, emulsifiable Concentrates (EC), aqueous Solutions (SL), emulsions (EW), for example oil-in-water or water-in-oil emulsions, sprayable solutions or sprayable emulsions, suspension Concentrates (SC), oil-or water-based dispersions, suspension emulsions, powders (DP), seed dressing materials, granules for soil application or for sowing, water-dispersed granules (WG), ULV formulations, microcapsules or waxes.
Such formulations are known in the art, for example:
Wettable powders (sprayable powders) are products which are uniformly dispersible in water and which, in addition to the active ingredient, contain ionic or nonionic surfactants (wetting agents, dispersants) such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols or fatty amines, alkyl sulfonates or alkylbenzene sulfonates, sodium lignin sulfonate, sodium 2,2 '-dinaphthyl methane-6, 6' -disulfonate, sodium dibutylnaphthalene sulfonate or sodium oleoyl methyl taurate, and diluents or inert materials.
The emulsifiable concentrate is prepared by the following method: the active ingredient is dissolved in an organic solvent (e.g., butanol, cyclohexanone, dimethylformamide, xylene, or higher boiling aromatic or hydrocarbon compounds) and one or more ionic or nonionic surfactants (emulsifiers) are added. Examples of emulsifiers that can be used are: calcium salts of alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; or nonionic emulsifiers, for example fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
The powder is obtained by: the active ingredient is ground together with finely divided solid materials (e.g. talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth).
Suspension Concentrates (SC) may be water-based or oil-based. They can be prepared by: wet milling, for example, with a commercially available bead mill; and, if appropriate, surfactants (as already mentioned in the case of other formulation types, for example, above) are also added.
Emulsions, such as oil-in-water Emulsions (EW), can be prepared by: the aqueous organic solvents and, if appropriate, further surfactants (which have been mentioned, for example, in the case of the other formulation types above) are used by means of stirrers, colloid mills and/or static mixers.
The granule can be prepared by the following modes: the active ingredient is sprayed onto the absorbent particulate inert material or the active ingredient concentrate is applied to the surface of a carrier (e.g., sand, kaolinite, or particulate inert material) with the aid of a binder (e.g., polyvinyl alcohol, sodium polyacrylate, or mineral oil). Suitable active ingredients can also be granulated in a manner customary for preparing fertilizer granules, if desired as a mixture with a fertilizer. Typically, water-dispersible granules are prepared by conventional methods such as spray drying, fluid bed granulation, pan granulation, mixing with a high speed mixer and extrusion without the need for solid inert materials.
Typically, the formulations comprise from 1 to 99% by weight of the active ingredient, depending on the type of formulation. For example, the concentration of the active ingredient in the wettable powder is, for example, about 10 to 95% by weight, with the remainder being composed of conventional formulation ingredients. In the case of emulsifiable concentrates, the concentration of the active ingredient can reach, for example, from 5 to 80% by weight. In some cases, the formulations in powder form comprise 5-20% by weight of the active ingredient, and the sprayable solution comprises about 0.2-25% by weight of the active ingredient. In the case of granules, such as dispersible granules, the content of active ingredient depends in part on whether the active ingredient is present in liquid or solid form, and what granulation aids and fillers are used. Typically, in the case of water-dispersible granules, the content amounts to 10-90% by weight.
Further, the above herbicidal composition or formulation may contain conventional adhesives, wetting agents, dispersants, emulsifiers, preservatives, antifreezes, solvents, fillers, colorants, carriers, defoamers, evaporation inhibitors, pH regulators or viscosity regulators, if appropriate.
The herbicidal compositions or formulations of the present disclosure may further comprise the following ingredients: for example, a surfactant, preferably a wetting agent selected from fatty alcohol polyglycol ethers. The fatty alcohol polyglycol ether preferably contains 10 to 18 carbon atoms in the fatty alcohol group and 2 to 20 ethylene oxide units in the polyglycol ether group. The fatty alcohol polyglycol ether may be nonionic or ionic, for example in the form of fatty alcohol polyglycol ether sulfate (for example as alkali metal salts (for example sodium or potassium salts) or ammonium salts, and also as alkaline earth metal salts such as magnesium salts), for example sodium C 12/C14 -fatty alcohol polyglycol ether sulfate. Nonionic fatty alcohol polyglycol ethers are, for example, (C 10-C18) -, preferably (C 10-C14) -fatty alcohol polyglycol ethers (e.g. isotridecyl alcohol polyglycol ether) containing 2 to 20, preferably 3 to 15, ethylene oxide units.
In addition, it is known that fatty alcohol polyglycol ethers such as nonionic or ionic fatty alcohol polyglycol ethers (e.g., fatty alcohol polyglycol ether sulfate) are also suitable as penetrants and synergists for many other herbicides.
The herbicidal compositions or formulations of the present disclosure may further comprise a vegetable oil. By vegetable oil is meant an oil from an oil plant species, for example at least one selected from the group consisting of soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, safflower oil, castor oil and transesterification products thereof, such as alkyl esters.
The present disclosure also provides a method of removing unwanted plants comprising applying a compound of formula I, a stereoisomer thereof or an agropharmaceutically acceptable salt thereof, or the herbicidal composition, in an herbicidally active amount to unwanted plants, plant seeds and/or their growing environment.
The present disclosure also relates to a method of controlling unwanted plants comprising applying a compound of formula I, a stereoisomer thereof or an agropharmaceutically acceptable salt thereof or the herbicidal composition to unwanted plants, plant seeds and/or their growing environment.
The present disclosure also provides a method of controlling unwanted plants comprising applying a herbicidally effective amount of the herbicidal compositions of the present disclosure to unwanted plants, plant seeds, and/or their growing environment.
According to embodiments of the present disclosure, the term "grass" or "unwanted plant" means a plant other than a crop, for example a plant that is harmful or detrimental to the growth of the crop, such as a weed.
According to embodiments of the present disclosure, the term "growing environment" includes, but is not limited to, the locus of growth of an unwanted plant or plant seed or the surface of a growing medium thereof.
According to embodiments of the present disclosure, a preferred "herbicidally effective amount" may be from 1 gram to 1000 grams per hectare, with an effective dosage of from 10 grams to 500 grams per hectare being preferred. In some embodiments, one or more of the other herbicides described above can be added to the herbicidal compositions of the present disclosure, thereby producing additional advantages and effects.
According to embodiments of the present disclosure, the term "control" or "removal" means that the growth of unwanted plants is reduced by more than 10% as compared to untreated unwanted plants. Preferably, the growth of unwanted plants is significantly reduced (60-79%); more preferably, the growth of unwanted plants is largely or completely inhibited (80-100%); in particular, the growth of unwanted plants is almost completely or completely inhibited (90-100%).
According to embodiments of the present disclosure, the compound, stereoisomer thereof, or agropharmaceutically acceptable salt thereof, or the herbicidal composition may be applied in divided applications over time. Or alternatively, the compound, stereoisomer or agropharmaceutically acceptable salt thereof, or the herbicidal composition is applied pre-emergence followed by post-emergence application, or early post-emergence application followed by mid-or late post-emergence application.
According to embodiments of the present disclosure, the "grass" or "unwanted plant" includes, but is not limited to, one or more weed species selected from the group consisting of: agastache species (Ageratum spp.), mao Man bean species (Calopogonium spp.), lotus seed species (ALTERNANTHERA spp.), fenghua species (Boreiria spp.), duck grass species (Commelina spp.), eupatorium species (Chromolaena spp.), mimosa species (mimosa spp.), The species of genus Trifolium (Tridax spp.), species of genus Mesona (Brachiaria spp.), species of genus Mesona (Platosporaspp.), species of genus crabgrass (DIGITARIA spp.), species of genus Cymosa (SYNEDRELLA spp.), species of genus Panicum (Panicumspp.), species of genus Cyperus (Cyperus spp.), species of genus Imperata (Imperata spp.), species of bermudagrass (Cynodonspp), species of genus pennisetum (Pennisetum spp.), The plant species of the genus Myzus (Mariscus spp.), euphorbia species (Euphorbia spp.), euphorbia species (Talinum spp.), pteris species (Pteridium spp.), molasses species (Melinis spp.), sida spp, portulaca species (Portulaca spp.), impatientis species (Rottboellia spp.), sorghum species (Sorgum spp.), solanum species (Ipomea spp.), and, The species of the genus Leptopetalum (Dactyloctenium spp.), the species of the genus Symphytum (Spigelia spp.), the species of the genus Boerhavia (Boerhaavia spp.), the species of the genus Boerhavia (Aspilia spp.), the species of the genus Aneilima spp, the species of the genus Leptopetalum (HYPARRHENIA spp.), the species of the genus Manchurian grass (Andropogonanspp), the species of the genus paspalum (Paspalum spp.), the species of the genus red grass (Rhynchelytrum spp.), the species of the genus Orthosiphon (Eleusine spp.), the species of the genus Orthosiphon (Eleusine spp.), The species of Setaria (Setaria spp.), species of Boea (Triumfetta spp.), species of pseudoverbena (STACHYTARPHETA spp.), species of Desmodium (Desmodium spp.), species of Gomphrenaspp (Gomphrenaspp.), species of Acacia (Tephrosia spp.), species of Barbate (Acanthospermum spp.), species of Combretaceae (Hyptis spp.), species of Tribulus (Cenchrus spp.), species of Tribulus terrestris, Vanilla species (Urena spp.), vernonia species (Vernonia spp.), buddleia species (Cleome spp.), paederia species (Crotalaria spp.), centipeda species (Kyllinga spp.), jute species (Corchorus spp.), sweet potato species (Ipomoea spp.), calplia species (Mitracarpus spp.), geum species (MELANTHERA spp.), pelargonium species (Centrosema spp.), pachyrhizus species (P), An Emilia spp, a Croton spp, a Phyllanthus spp, a Passiflora Passiflora spp, a carpet seed Axonopus spp, a Oldenlandiaspp, a SCHWENCKIA spp, an acalypha spp Acalypha spp, a Coleus spp Solenostemona spp, a feather cockscomb Celosia spp, a seed, The species of the genus cerulosa (Indigofera spp.), the species of the genus rhodomyrtus (heteotisspp.), the species of the genus malus (Acmella spp.), the species of the genus acacia (Leucaena spp.), the species of the genus flaveria (boerhaviaspp.), the species of the genus toyophyllum (Spermacoce spp.), the species of the genus sphaera (Oplismenus spp.) and the species of the genus fangofera (Fimbristylis spp.).
Preferably, the weed species is selected from one or more of the following: herba Agastaches, mao Man bean, lotus, fenghua, duck grass, herba Lycopi, mimosa, trigonella, mesona, panicum, cyperus, imperata, cynanchum, euphorbia, fern species, molasses species, sida species, purslane species, coltsfoot species, sorghum species, yam species, densefruit species, zygium species, desmodium species, kusnezoff species, acacia species, acanthopanax species, hanxiang species, tribulus species, vanilla species, vernonia species and buddleia species.
As an example, the weeds are selected from one or more of the following: herba Cirsii Japonici (Ageratum conyzoides), mao Mandou (Calopogoniummucunoides), herba Nelumbinis (ALTERNANTHERA SESSILIS), boreiria ocymoides, herba Momordicae Charantiae (Commelinaerecta), herba Lycopi (Chromolaena odorata), herba Mimosae Brazil (Mimosa invisa), herba Polygoni Capitati (Commelina benghalensis), Trifolium praecox (Tridax procumbens), brachiaria delfexa, mesona africana (Platostoma africanum), crabgrass (DIGITARIA ADSCENDENS), crabgrass (Digitariahorizontalis), golden waist arrow (SYNEDRELLA NODIFLORA), semen Panici Miliacei (Panicum maximum), rhizoma Cyperi (Cyperus rotunda), cyperus esculentus (Cyperus esculentus), Rhizoma Imperatae (IMPERATA CYLINDRICA), radix Berberidis Amurensis (Cynodon dactylon), herba Euphorbiae Fischerianae (Pennisetum polystachion), herba Itali albi (Pennisetumpurpureum), herba Euphorbiae Fischerianae (Pennisetum violaceum), mariscus alternifolius, scarlet caterpiller fungus (Euphorbia heterophylla), herba Euphorbiae Humifusae (Euphorbia hirta), Radix Ginseng (Talinum triangulare), herba Fimbristylis Dichotomae (Pteridium aquilinum), herba Saururi (Melinis ninutiflora), herba Rhodomyrti (Sida acuta), herba Melastomatis Dodecandri (Sida rhombifolia), herba Equiseti Arvinsis (Commelina diffusa), herba Portulacae (Portulaca oleraceae), rhizoma Imperatae (Rottboellia exaltata), rhizoma Imperatae (Rottboellia cochinchinensis), herba Pogostemonis, Sorghum halepense (Sorghum halepense), sorghum halepense She Shu (Ipomea triloba), rhizoma aristolochiae (Dactylocteniumaegyptium), brachiara lata, columniform flower cluster (SPIGELIA ANTHEMIA), upright yellow caret (Boerhaaviaerecta), hemostatic grass (ASPILIA AFRICANA), aneilima beniniense, bracteatum (Hyparrheniainvolucrate), and plant tissue, Herba Verniciae Cannabifoliae (Andropogon gayanus), herba Erodii seu Geranii (Paspalum conjugatum), sagittaria circular (Paspalum orbiculatum), herba Salicorniae Cabernet (Rhynchelytrum repens), herba Gryllus chinensis (Eleusineindica), herba Setariae herba Scutellariae Barbatae (Seria barbeta), herba Setariae viridis (SETARIA MEGAPHYLLA), triumfetta cordifolia, radix Cynomorii (STACHYTARPHETA CAYENNENSIS), herba Setariae viridis, Desmodium scorpion (Desmodium scorpiurus), amaranthus lonicera (Gomphrena celosioides), tephrosia bracteolata, acanthopanax (Acanthospermum hispidum), hanxiang (Hyptis suaveolens), tribulus terrestris (Cenchrusbiflorus), persica (Urena lobata), vernonia mongolica (Vernonia ambigua), vernonia aurea (Cleomeviscosa), Semen Cuscutae (Cuscuta australis), corchorus olitorius (Corchorus olitorius), fructus Saussureae Involueratae (Mitracarpus villosus), MELANTHERA SCANDENS, semen Vignae Cylindricae (Centrosema pubescens), herba Caesalpiniae cristae (Emilia coccinea), fructus crotonis (Croton hirtus), herba Senecionis Cannabis (Phyllanthus amarus), corchorus olitorius (Corchorus trilocularis), herba Corchondri Veronici (semen Lini), longzhu (Passiflora foetida), sweet potato with bud (Ipomoeainvolucrate), carpet grass (Axonopus compressus), umbelliferae (Oldenlandia corymbosa), ACALYPHA CILIATA, american schlieren (SCHWENCKIA AMERICANA), purple boot grass (Solenostemonmonostachyus), feather cockscomb (Celosia trigyna), Mao Mulan (Indigofera hirsute), caulis et folium Clerodendri Bungei (Heterotis rotundifolia), herba Lespedezae Cuneatae (Acmella brachyglossa), herba Acaciae Lespedezae Cuneatae (Leucaenaleucocephala), herba Polygoni Ciliinerve (Boerhavia diffusa), luo Lefeng flower (Spermacoce ocymoides), herba Lophatheri (Oplismenus burmannii), herba Solani Nigri (Fimbristylis littoralis), herba Veronici, Crushed nutgrass galingale rhizome (Cyperusiris) and upright centipede (KYLLINGA ERECTA).
More preferably, the unwanted plant may be selected from at least one of broadleaf weeds (such as amaranth, carp intestines, ash, abutilon, descurainia sophia, salpings, chenopodium album, polygonum syringae, alisma orientale, tulip), grassy weeds (such as barnyard grass, green bristlegrass, moleplant seed, crabgrass, brome, festival wheat, ryegrass, wild oat), sedge (such as garrulous sedge, heterocypa, iris).
It should be apparent that various changes and modifications can be made within the scope of the present disclosure as defined in the claims.
Advantageous effects
The tetra-substituted cyclohexene sulfide compound disclosed by the invention has excellent herbicidal activity, selectivity and/or improved crop safety, and has good commercial application prospect. In addition, the preparation method of the compound is simple and convenient, and is suitable for industrial production.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents and publications referred to in this disclosure are incorporated by reference in their entirety into this disclosure.
The following definitions as used herein should be applied unless otherwise indicated. For the purposes of this disclosure, chemical elements are consistent with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, general principles of organic chemistry may be found in "Organic Chemistry", thomas Sorrell, university Science Books, sausalato 1999, and "March's Advanced Organic Chemistry"by Michael B.Smith and Jerry March,John Wiley&Sons,New York:2007, the entire contents of which are incorporated herein by reference.
The term "optional" or "optionally" means that the subsequently described event or circumstance may but need not occur. That is, the description includes cases in which the event or situation occurs as well as cases in which it does not occur. For example, "optionally substituted with 1, 2,3, or 4 …" includes the case where the group is substituted with 1, or 2, or 3, or 4 substituents as described, as well as the case where the group is not substituted with the substituents described. Further, when the group is substituted with 1 or more of the substituents, the substituents are independent of each other, that is, the 1 or more substituents may be different from each other or the same.
As described in the present disclosure, the compounds of the present disclosure may be optionally substituted with one or more substituents, such as the compounds of the formula above, or as in the specific examples, subclasses, and classes of compounds encompassed by the present disclosure. In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a specific substituent. An optional substituent group may be substituted at each substitutable position of the group unless otherwise indicated. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. Wherein the "one or more substituents" means one or more substituents, and the number of specific substituents is determined by the number of positions where the substituted group may be substituted. The substituents may include, but are not limited to, hydrogen, oxo (=o), halogen, cyano, nitro, hydroxy, mercapto, carboxyl, amino, arylamino, aminoalkyl, alkyl, alkyloxy, alkylthio, alkenyl, alkynyl, hydroxyalkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl 、-C(＝O)R、-ORa、-C(＝O)ORa、-OC(＝O)Ra、-SO2Ra、-NRbRc、-CONRbRc、-SO2NRbRc、-C(NRbRc)＝NRd, or = NR d: wherein R, R a、Rb、Rc and R d are each independently hydrogen, cyano, amino, alkyl, alkylamino, arylamino, alkylthio, alkyloxy, aryloxy, hydroxy, mercapto, alkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, alkylsulfonyl, aminosulfonyl, hydroxyalkyl, aminoalkyl, alkanoyl or aminoacyl. Wherein each alkylamino, arylamino, alkyloxy, aryloxy, hydroxy, mercapto, alkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, alkylsulfonyl, sulfamoyl, hydroxyalkyl, aminoalkyl, alkanoyl, aminoacyl, and alkylthio in the substituents have the meanings described in the disclosure, and each may be further monosubstituted by a substituent described in the disclosure, or the same or different polysubstituted.
In addition, unless explicitly indicated otherwise, the description used in this disclosure of the manner in which "each … is independently" and "… is independently" and "… is independently" are to be understood in a broad sense as meaning that the particular choices expressed between the same symbols in different groups do not affect each other, or that the particular choices expressed between the same symbols in the same groups do not affect each other.
The numerical ranges recited in the specification and claims are equivalent to at least each specific integer number recited therein unless otherwise stated. For example, a numerical range of "1-20" corresponds to each integer number of the numerical range of "1-10", i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer number of the numerical range of "11-20", i.e., 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. As another example, a numerical range of "1-10" corresponds to each integer number recited in the numerical range of "1-10," i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. Furthermore, when certain numerical ranges are not defined as "integers," it is understood that two endpoints of the range, each integer within the range, and each fraction within the range are recited. For example, "1-99%" should be interpreted to describe not only each integer of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%,.
As used herein, "a plurality of" or "a plurality of" means 2 or more, for example, an integer number of 2 or more, for example, 2,3, 4, 5, 6, 7, 8, 9, or 10 or more.
The terms "at least one" or "at least one" as described herein mean "one or more" or "one or more".
As used herein, "more" or "more" in "one, two or more", "one, two or more" means an integer greater than 2, such as greater than or equal to 3, such as 3,4, 5, 6, 7, 8, 9 or 10, etc.
In various parts of the present specification, substituents of compounds of the disclosure are disclosed in terms of the group species or scope. It is specifically pointed out that the present disclosure includes each individual subcombination of the individual members of these group categories and ranges. For example, the term "C 1-6 alkyl" refers specifically to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl. "C 1-4 alkyl" refers to the independently disclosed methyl, ethyl, C 3 alkyl (i.e., propyl, including n-propyl and isopropyl), C 4 alkyl (i.e., butyl, including n-butyl, isobutyl, sec-butyl, and tert-butyl).
The term "alkyl" as used in this disclosure means a saturated straight or branched monovalent hydrocarbon group. When "alkyl" is described without the number of carbon atoms, it is meant that the alkyl has any number of carbon atoms. When describing "alkyl" the number of carbon atoms is used, meaning that the alkyl has the number of carbon atoms described. For example, an alkyl group may be a C 1-C20 alkyl group, which represents a saturated, straight or branched, monovalent hydrocarbon group containing 1 to 20 carbon atoms, wherein the alkyl group may be optionally substituted with one or more substituents described in this disclosure. Unless otherwise specified, alkyl groups contain 1 to 20 carbon atoms. In some embodiments, the alkyl group contains 1 to 12 carbon atoms, such as "C 1-C12 alkyl"; in other embodiments, the alkyl group is an alkyl group containing 1-6 (1, 2,3, 4,5, or 6) carbon atoms, i.e., "C 1-C6 alkyl"; in still other embodiments, the alkyl group is an alkyl group containing 1-4 (1, 2,3, or 4) carbon atoms, i.e., "C 1-C4 alkyl"; in other embodiments, the alkyl group contains 1 to 3 carbon atoms, i.e., "C 1-C4 alkyl".
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH 3), ethyl (Et, -CH 2CH3), n-propyl (n-Pr, -CH 2CH2CH3), isopropyl (i-Pr, -CH (CH 3)2), N-butyl (n-Bu, -CH 2CH2CH2CH3), isobutyl (i-Bu, -CH 2CH(CH3)2), sec-butyl (s-Bu, -CH (CH 3)CH2CH3), tert-butyl (t-Bu, -C (CH 3)3), N-pentyl (-CH 2CH2CH2CH2CH3), 2-pentyl (-CH (CH 3)CH2CH2CH3), 3-pentyl (-CH (CH 2CH3)2), 2-methyl-2-butyl (-C (CH 3)2CH2CH3)), 3-methyl-2-butyl (-CH (CH 3)CH(CH3)2), 3-methyl-1-butyl (-CH 2CH2CH(CH3)2), 2-methyl-1-butyl (-CH 2CH(CH3)CH2CH3), n-hexyl (-CH 2CH2CH2CH2CH2CH3), 2-hexyl (-CH (CH 3) CH 2CH2CH2CH3), 3-hexyl (-CH (CH 2CH3)(CH2CH2CH3), 2-methyl-2-pentyl (-C (CH 3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH (CH 3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH (CH 3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C (CH 3)(CH2CH3)2), 2-methyl-3-pentyl (-CH (CH 2CH3)CH(CH3)2), 2, 3-dimethyl-2-butyl (-C (CH 3)2CH(CH3)2)), 3, 3-dimethyl-2-butyl (-CH (CH 3)C(CH3)3), n-heptyl, n-octyl, and the like).
The term "alkenyl" denotes a straight or branched monovalent hydrocarbon radical having at least one carbon-carbon sp 2 double bond. When "alkenyl" is described without the number of carbon atoms, it is meant that the alkenyl group has any number of carbon atoms selected from 2 or more. When describing an "alkenyl group" using the number of carbon atoms, it is meant that the alkenyl group has the number of carbon atoms described. For example, the alkenyl group is a "C 2-C12 alkenyl group" which represents a straight or branched monovalent hydrocarbon group containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp 2 double bond. Wherein the alkenyl group may be optionally substituted with one or more substituents described in this disclosure, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In some embodiments alkyl groups, the alkenyl group contains 2 to 8 (2, 3, 4, 5, 6,7, or 8) carbon atoms; in other embodiments, the alkenyl group comprises 2 to 6 (2, 3, 4, 5, or 6) carbon atoms; in still other embodiments, the alkenyl group comprises 2 to 4 (2, 3, or 4) carbon atoms, or comprises 3 to 6 (3, 4, 5, or 6) carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-ch=ch 2), allyl (-CH 2CH＝CH2), allyl (-ch=ch 3), and the like.
The term "alkynyl" denotes a straight or branched monovalent hydrocarbon radical having at least one carbon-carbon sp triple bond. When "alkynyl" is described without the number of carbon atoms, it is meant that the alkynyl has any number of carbon atoms selected from 2 or more. When describing "alkynyl" the number of carbon atoms is used, it is intended that the alkynyl group has the number of carbon atoms described. For example, the alkynyl group is a "C 2-C12 alkynyl" group, which represents a straight or branched monovalent hydrocarbon group containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond. Wherein the alkynyl group may be optionally substituted with one or more substituents described in this disclosure. In some embodiments, an alkynyl group contains 2-8 (2, 3,4, 5, 6, 7, or 8) carbon atoms; in other embodiments, alkynyl groups contain 2 to 6 (2, 3,4, 5, or 6) carbon atoms; in still other embodiments, alkynyl groups contain 2 to 4 (2, 3, or 4) carbon atoms, or 3 to 6 (3, 4,5, or 6) carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, and the like.
The term "cycloalkyl" refers to a monovalent or multivalent, non-aromatic, saturated monocyclic, bicyclic, or tricyclic ring system. When "cycloalkyl" is described without the number of carbon atoms, it is meant that the cycloalkyl has any number of carbon atoms selected from 3 or more. When describing "cycloalkyl" the number of carbon atoms is used, meaning that the cycloalkyl has the number of carbon atoms described. For example, the "cycloalkyl" is "C 3-C12 cycloalkyl" which refers to a monovalent or polyvalent, non-aromatic, saturated monocyclic, bicyclic, or tricyclic ring system containing 3 to 12 ring carbon atoms. In some embodiments, cycloalkyl comprises 3 to 10 (3, 4,5, 6, 7, 8, 9, or 10) ring carbon atoms; in other embodiments, cycloalkyl groups contain 3 to 8 (3, 4,5, 6, 7, or 8) ring carbon atoms; in still other embodiments, cycloalkyl groups contain 3-6 (3, 4,5, or 6) ring carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The cycloalkyl group may be optionally substituted with one or more substituents described in this disclosure.
The term "cycloalkenyl" refers to a partially unsaturated, non-aromatic, monocyclic, bicyclic, or tricyclic ring system. When "cycloalkenyl" is described without the number of carbon atoms, it is meant that the cycloalkenyl has any number of carbon atoms selected from 3 or more. When describing "cycloalkenyl" the number of carbon atoms is used, meaning that the cycloalkenyl has the indicated number of carbon atoms. For example, the "cycloalkenyl" is a "cycloalkenyl" group containing 3-12 ring carbon atoms. In some embodiments, cycloalkenyl contains 3-10 (3, 4, 5, 6, 7, 8, 9, or 10) ring carbon atoms; in other embodiments, cycloalkenyl groups contain 3-8 (3, 4, 5, 6, 7, or 8) ring carbon atoms; in still other embodiments, cycloalkenyl groups contain 3-6 (3, 4, 5, or 6) ring carbon atoms. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. The cycloalkenyl group may be optionally substituted with one or more substituents described in this disclosure.
The term "C 6-14 aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring ("C 6-14 aryl") having a monovalent aromatic or partially aromatic nature of 6,7,8, 9, 10, 11, 12, 13 or 14 carbon atoms, in particular a ring having 6 carbon atoms ("C 6 aryl"), such as phenyl; Or biphenyl, or a ring having 9 carbon atoms ("C 9 aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl"), Such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl"), such as anthracyl. When the C 6-20 aryl group is substituted, it may be mono-substituted or poly-substituted. The substitution site is not limited, and may be, for example, ortho, para or meta substitution. The aryl group includes a ring system formed by fusing an aromatic ring and an aromatic ring or an aromatic ring and a non-aromatic carbon ring. Examples of aryl groups may include phenyl, naphthyl, anthracenyl, 1,2,3, 4-tetrahydronaphthyl, 2, 3-dihydro-1H-indenyl, bicyclo [4,2,0] oct-1 (6), 2, 4-trialkenyl. The aryl group may be substituted or unsubstituted, wherein the substituents include, but are not limited to, fluoro, chloro, bromo, oxo (=o), cyano, nitro, carboxyl, hydroxyl, amino, aminomethyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methylsulfonyl, aminosulfonyl, acetyl, methoxy, phenoxy, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, imidazolyl, imidazolinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furanyl, pyrrolyl, phenyl, Pyridyl, pyrimidinyl, -C (=nh) NH 2, trifluoromethyl, or the like.
The term "3-14 membered heterocyclyl" refers to a saturated or unsaturated, non-aromatic ring or ring system, e.g., which is a 3-, 4-, 5-, 6-, or 7-membered monocyclic, 7-, 8-, 9-, 10-, 11-, or 12-membered bicyclic (e.g., fused, bridged, spiro) or 10-, 11-, 12-, 13-, or 14-membered tricyclic ring system, and contains at least one, e.g., 1,2,3, 4,5, or more heteroatoms selected from O, S and N, wherein N and S may also optionally be oxidized to various oxidation states to form the nitrogen oxides, -S (O) -or-S (O) 2 -state. Unless otherwise indicated, the heterocyclyl group may be a carbon or nitrogen group, and the-CH 2 -group may optionally be replaced by-C (=o) -. The sulfur atom of the ring may optionally be oxidized to an S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxide. In some embodiments, the heterocyclyl is a heterocyclyl consisting of 5 to 12 atoms; in other embodiments, the heterocyclyl is a heterocyclyl consisting of 5 to 8 atoms; in still other embodiments, the heterocyclyl is a heterocyclyl consisting of 5 to 7 atoms; in some embodiments, the heterocyclyl is a 5-6 atom constituent heterocyclyl. The heterocyclyl may also be a bicyclic heterocyclyl; in some embodiments, the heterocyclyl is a bicyclic heterocyclyl consisting of 7-12 atoms; in other embodiments, the heterocyclyl is a bicyclic heterocyclyl consisting of 7 to 10 atoms; in still other embodiments, the heterocyclyl is a bicyclic heterocyclyl consisting of 8-10 atoms.
Examples of heterocyclyl groups include, but are not limited to: oxiranyl, azetidinyl, oxetanyl, pyrrolidinyl, pyrazolidinyl, dihydrothienyl, 1, 3-dioxacyclopentyl, 1, 3-dioxacyclohexyl, 1, 4-dioxacyclohexyl, dithiocyclopentyl, tetrahydropyranyl, tetrahydrothiopyranyl, piperidinyl, 1, 2-dihydropyridinyl, morpholinyl, thiomorpholinyl, hexahydropyrimidinyl, 1, 6-dihydropyrimidinyl, 1, 2-dihydropyrazinyl, 1, 3-oxazinyl, piperazinyl, oxazolidinyl, dioxanyl, dithianyl, thiaoxaalkyl, homopiperazinyl, homopiperidinyl, oxacycloheptyl, thiepinyl, 2-oxa-5-azabicyclo [2.2.1] hept-5-yl. Examples of the substitution of the-CH 2 -group in the heterocyclic group by-C (=o) -include, but are not limited to, 2-oxopyrrolidin-1-yl, oxo-1, 3-thiazolidine, 2-oxooxazolidin-3-yl, 2-oxopiperidin-1-yl, 3-oxomorpholinyl, 2-oxopiperazin-1-yl, 3, 5-dioxopiperidinyl, 2-oxotetrahydropyrimidin-1 (2H) -yl and 2-oxodihydropyrimidin-1 (2H) -yl. Examples of sulfur atoms in the heterocyclic group that are oxidized include, but are not limited to, sulfolane, 1-dioxothiomorpholinyl, and 1, 1-dioxo-1, 2-thiomorpholinyl. The heterocyclyl group may be substituted or unsubstituted, wherein the substituents include, but are not limited to, fluoro, chloro, bromo, oxo (=o), cyano, nitro, carboxyl, hydroxyl, amino, aminomethyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methylsulfonyl, aminosulfonyl, acetyl, methoxy, phenoxy, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, imidazolyl, imidazolinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrolyl, phenyl, pyridyl, pyrimidinyl, -C (=nh) NH 2, or trifluoromethyl, and the like.
In some embodiments, heterocyclyl is a heterocyclyl consisting of 5-6 atoms, meaning a saturated or partially unsaturated monocyclic ring containing 5 or 6 ring atoms, at least one of which is selected from nitrogen, sulfur and oxygen atoms. Examples of heterocyclic groups consisting of 5 to 6 atoms include, but are not limited to: pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, oxazolyl, piperidinyl, 1, 2-dihydropyridinyl, morpholinyl, thiomorpholinyl, hexahydropyrimidinyl, 1, 6-dihydropyrimidinyl, 1, 2-dihydropyrazinyl, 1, 3-oxazinyl, piperazinyl, 1,2,3, 6-tetrahydropyridinyl, 1,2,3, 4-tetrahydropyrimidinyl, 2, 5-dihydro-1H-pyrrolyl, and the like. the-CH 2 -group in the heterocyclic group consisting of 5 to 6 atoms may be replaced by-C (=O) -or the sulfur atom therein may be oxidized to S-oxide. And, the 5-6 atom constituent heterocyclyl group may be optionally substituted with one or more substituents described in this disclosure.
When the heterocyclic group is connected with other groups to form the compound disclosed in the invention, the carbon atom on the heterocyclic group can be connected with other groups, or the heteroatom on the heterocyclic ring can be connected with other groups.
The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic (e.g., fused, bridged, spiro) or tricyclic ring systems: having 5 to 14 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, wherein at least one ring (or the ring as a whole) is aromatic. Wherein one or more attachment points in the heteroaryl group are attached to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group includes a ring system formed by fusing a heteroaromatic ring to an aromatic ring, a heteroaromatic ring to a heteroaromatic ring, or a heteroaromatic ring to a non-aromatic carbocyclic or heterocyclic ring. In some embodiments, a heteroaryl group of 5-10 atoms composition comprises 1,2, 3, or 4 heteroatoms independently selected from oxygen, sulfur, and nitrogen. In some embodiments, heteroaryl is a heteroaryl consisting of 7-12 atoms, comprising 1,2, 3, or 4 heteroatoms independently selected from O, S and N; heteroaryl groups of 7 to 12 atoms may be monocyclic or bicyclic containing two rings. In other embodiments, heteroaryl is a heteroaryl consisting of 7 to 10 atoms, comprising 1,2, 3, or 4 heteroatoms independently selected from oxygen, sulfur, and nitrogen; heteroaryl groups of 7 to 10 atoms may be monocyclic or bicyclic containing two rings. The heteroaryl group may be substituted or unsubstituted, wherein the substituents include, but are not limited to, fluoro, chloro, bromo, oxo (=o), cyano, nitro, carboxyl, hydroxyl, amino, aminomethyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methylsulfonyl, aminosulfonyl, acetyl, methoxy, phenoxy, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, imidazolyl, imidazolinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrolyl, phenyl, pyridyl, pyrimidinyl, guanidino (-NHC (=nh) NH 2)、-N＝C＝S、-C(＝NH)NH2 or trifluoromethyl, and the like.
Examples of heteroaryl groups include, but are not limited to, furyl, imidazolyl such as 1H-imidazol-1-yl, isoxazolyl, oxazolyl (e.g., 2-oxazolyl) pyrrolyl, 1,3, 4-oxadiazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), thiazolyl (e.g., 2-thiazolyl), 2-thienyl, 3-thienyl, pyrazolyl (e.g., 4-pyrazolyl, 1H-pyrazol-1-yl), pyrazinyl, 1,3, 5-triazinyl, triazolyl, tetrazolyl, and the like; the following bicyclic rings are also included, but are in no way limited to: benzopyrrolyl, 6, 7-dihydrothiophen [3,2-c ] pyrrol-5 (4H) -yl, 1, 3-dioxoisoindolin-2-yl, pyrimidoimidazol, benzimidazolyl, benzofuranyl, dihydrobenzofuranyl, benzothiophenyl, indolyl (e.g., 1H-indol-1-yl), isoindolin-2-yl, benzo [ d ] thiazol-2-yl, indazolyl (e.g., 1H-indazol-1-yl, etc.), quinolinyl (e.g., 2-quinolinyl, 3-quinolinyl, 4-quinolinyl), isoquinolinyl (e.g., 1-isoquinolinyl, 3-isoquinolinyl, or 4-isoquinolinyl), 5,6,7, 8-tetrahydroquinolinyl, 3, 4-dihydro-2H-pyrano [3,2-b ] pyridinyl, 2, 3-dihydro- [1,4] dioxino [2,3-b ] pyridinyl, 2, 3-dihydrobenzo [ b ] [1,4] dioxino [1, 6, 7-dihydro-quinolin-1-yl, etc.), 2-pyrrolyl, 3-dihydro [2,3-b ] quinolinyl, 3-dihydro [2, 3-oxo ] pyrrolyl, etc.
When the heteroaryl is linked to other groups to form the disclosed compounds, the carbon atom on the heteroaryl may be linked to other groups, or the heteroatom on the heteroaryl ring may be linked to other groups.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g. positional isomers thereof. Thus, for some illustrative non-limiting examples, forms that may include substitution at 1,2, or more of its 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-positions, etc. (if present) or bonding to other groups include pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thienyl or thienylene include thiophen-2-yl, thienylene-2-yl, thiophen-3-yl and thienylene-3-yl; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, and pyrazol-5-yl.
The term "oxo" refers to the substitution of a carbon atom, nitrogen atom or sulfur atom in a substituent with an oxo group (=o) formed after oxidation.
The term "alkyloxy" means that the alkyl group is attached to the remainder of the molecule through an oxygen atom, i.e., "alkyloxy," wherein the alkyl group has the meaning as described in the present disclosure. In some embodiments, the alkyloxy group contains 1 to 6 carbon atoms; in other embodiments, the alkyloxy group contains 1 to 4 carbon atoms; in still other embodiments, the alkyloxy group contains 1 to 3 carbon atoms. The alkyloxy group may be optionally substituted with one or more substituents described in this disclosure. Examples of alkyl oxy groups include, but are not limited to, methoxy (MeO, -OCH 3), ethoxy (EtO, -OCH 2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH 2CH2CH3), and the like.
The term "alkylamino" means an amino group substituted with one or two alkyl groups, where the alkyl groups have the meaning as described in the present disclosure. Examples include, but are not limited to, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-diethylamino, and the like.
The term "cycloalkylamino" means that the amino group is substituted with one or two cycloalkyl groups, where the cycloalkyl groups have the meanings as described in the present disclosure. Examples include, but are not limited to, N-cyclopropylamino, and the like.
The term "alkylcarbonyl" means an alkyl group attached to the remainder of the molecule through a carbonyl (-C (=o) -) group, wherein the alkyl group has the meaning described in this disclosure. Examples include, but are not limited to, CH 3 -C (=o) -, and the like.
The term "cycloalkylcarbonyl" means that the cycloalkyl group is attached to the remainder of the molecule through a carbonyl (-C (=o) -) group, wherein the cycloalkyl group has the meaning described in the present disclosure. Examples of such include, but are not limited to,Etc.
The term "alkylaminocarbonyl" means that an alkylamino group is attached to the remainder of the molecule through a carbonyl (-C (=o) -) group, wherein the alkylamino group has the meaning described in this disclosure. Examples include, but are not limited to, N-dimethylamino-C (=o) -, and the like.
The term "cycloalkylaminocarbonyl" means that the cycloalkylamino group is attached to the remainder of the molecule through a carbonyl group (-C (=o) -) where the cycloalkylamino group has the meaning described in the present disclosure. Examples of such include, but are not limited to,Etc.
The term "cycloalkylalkyl" means that the cycloalkyl group is attached to the remainder of the molecule through an alkyl group, wherein the cycloalkyl group and alkyl group have the meanings set forth in the present disclosure. Examples of such include, but are not limited to,Etc.
The term "arylalkyl" means that the aryl group is attached to the remainder of the molecule through an alkyl group, wherein the aryl group and the alkyl group have the meanings set forth in the present disclosure. Examples of such include, but are not limited to,Etc.
The term "aryloxy" means that an aryl group is attached to the remainder of the molecule through an oxygen atom, wherein the aryl group has the meaning described in the present disclosure.
The term "alkyloxy-alkyl" means that the alkyloxy group is attached to the remainder of the molecule through an alkyl group, wherein the alkyloxy group and alkyl group have the meanings described in the present disclosure. Examples include, but are not limited to, -CH 2OCH3, and the like.
The term "cycloalkenyl-alkyl" means that the cycloalkenyl group is attached to the remainder of the molecule through an alkyl group, i.e., the alkyl group is substituted with one or more cycloalkenyl groups, where the alkyl and cycloalkenyl groups have the meanings as described in the present disclosure.
The term "haloalkyl" means an alkyl group substituted with one or more halo groups. Examples include, but are not limited to, -CF 3, etc.
The term "haloalkyloxy" means an alkyl oxy group substituted with one or more halogen groups, examples of which include, but are not limited to, -OCF 3, and the like.
The term "haloaryl" means an aryl group substituted with one or more halo groups, examples of which include, but are not limited to,Etc.
The term "haloalkyloxy-alkyl" means that the alkyloxy-alkyl group is substituted with one or more halogen groups, examples of which include, but are not limited to, CF 3OCH2 -, and the like.
The term "haloalkenyl" means that the alkenyl group is substituted with one or more halogen groups.
The term "haloalkynyl" means that the alkynyl group is substituted with one or more halo groups.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The "acceptable salts" of the present disclosure include acid-and base-addition salts, suitable bases being alkali and alkaline earth metal hydroxides, carbonates, bicarbonates, especially sodium, potassium, magnesium, and calcium salts, and ammonium, primary, secondary, and tertiary amines having a (C 1-C4) -alkyl group, mono-, di-, and trialkanolamines of (C 1-C4) -alkanols, choline, and choline chloride.
The salt may be a salt added with an inorganic acid, which may be hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid, or a salt added with an organic acid, which may be formic acid, carbonic acid, and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or monounsaturated or diunsaturated C 6-C20 fatty acid, alkylsulfate monoester, alkylsulfonic acid (sulfonic acid having a linear or branched alkyl group of 1 to 20 carbon atoms), arylsulfonic acid or arylsulfonic acid (aromatic groups having a linear or branched alkyl group of 1 to 20 carbon atoms such as phenyl and naphthyl), alkylphosphonic acid (aromatic groups having a linear or branched alkyl group of 1 to 20 carbon atoms such as phenyl and naphthyl), arylphosphonic acid or aryldiphosphonic acid (aromatic groups having one or two phosphonic groups such as phenyl and naphthyl), wherein the alkyl and aryl groups may bear other substituents such as p-toluenesulfonic acid, salicylic acid, p-aminobenzoic acid, 2-acetylbenzoic acid, and the like.
Depending on their molecular structure, the compounds of the present disclosure may be chiral, and thus various enantiomeric forms may exist. These compounds may thus be present in racemic or optically active form. The compounds of the present disclosure encompass isomers or mixtures, racemates thereof, wherein each chiral carbon is in the R or S configuration. The compounds of the present disclosure or intermediates thereof may be isolated as enantiomer compounds by chemical or physical methods well known to those skilled in the art, or used in this form for synthesis. In the case of racemic amines, diastereomers are prepared from the mixture by reaction with an optically active resolving agent. Examples of suitable resolving agents are optically active acids, such as tartaric acid, diacetyltartaric acid, dibenzoyltartaric acid, mandelic acid, malic acid, lactic acid, suitable N-protected amino acids (e.g.N-benzoylproline or N-benzenesulfonylproline) or various optically active camphorsulfonic acids in R and S form. The chromatographic resolution can also advantageously be carried out with the aid of optically active resolving agents, such as dinitrobenzoylphenylglycine, cellulose triacetate or other carbohydrate derivatives or chiral derivatized methacrylate polymers, immobilized on silica. Suitable eluents for this purpose are aqueous or alcoholic solvent mixtures, for example hexane/isopropanol/acetonitrile.
The corresponding stable isomer may be isolated according to known methods, for example by extraction, filtration or column chromatography.
Detailed Description
The technical scheme of the present disclosure will be described in further detail below with reference to specific embodiments. It should be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the present disclosure. All techniques implemented based on the foregoing disclosure are intended to be within the scope of the disclosure.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1 synthesis of key intermediate M:
(1) Synthesis of 2-chloro-4-methylsulfonyl-3- (2, 2-trifluoroethoxy) methylbenzoyl chloride
To the reaction flask was added 2-chloro-4-methylsulfonyl-3- (2, 2-trifluoroethoxy) methylbenzoic acid (15 g, 43.3 mmol) and 1, 2-dichloroethane (100 mL), and thionyl chloride (15.4 g, 129.8 mmol) was slowly added, and then 0.5mL of DMF was added, and the mixture was refluxed for 3 hours, and the solvent was distilled off under reduced pressure to give 16 g of yellow solid, which was directly taken into the next step.
(2) Synthesis of 3-oxocyclohex-1-en-1-yl 2-chloro-4-methylsulfonyl-3- (2, 2-trifluoroethoxy) methylbenzoate
To the reaction flask were added 1, 3-cyclohexanedione (5.4 g, 48.2 mmol), methylene chloride (100 ml), triethylamine (8.87 g, 87.6 mmol) and a methylene chloride solution (50 ml) of step 2-chloro-4-methylsulfonyl-3- (2, 2-trifluoroethoxy) methylbenzoyl chloride. Stirring at room temperature for 1 hour, evaporating the solvent under reduced pressure, adding ethyl acetate (1000 ml) to the residue, extracting with water (500 ml) in a liquid-separated manner, washing the organic phase with saturated brine (500 ml) in turn, drying over anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, separating the residue by column chromatography to obtain 18.3 g of yellow solid, yield: 94.7%.
(3) Synthesis of 2- (2-chloro-4-methylsulfonyl) -3- (2, 2-trifluoroethoxy) methylbenzoyl) cyclohexane-1, 3-dione
3-Oxocyclohexane-1-en-1-yl 2-chloro-4-methylsulfonyl-3- (2, 2-trifluoroethoxy) methylbenzoate (18 g, 40.8 mmol), 1, 2-dichloroethane (50 ml), triethylamine (8.3 g, 81.7 mmol) and acetone cyanohydrin (1 ml) were added to the reaction flask, the mixture was allowed to react at 60℃for 6 hours, cooled to room temperature, water (100 ml) was added to the reaction mixture, the layers were separated by shaking sufficiently, the aqueous phase was adjusted to a pH of between 2 and 3 with 20% hydrochloric acid, the aqueous phase was extracted twice with ethyl acetate (100 ml), the organic phase was washed with saturated brine (50 ml) successively, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 15.4 g of pale yellow solid, yield: 85.6%.
(4) Synthesis of 3-chloro-2- (2-chloro-4-methylsulfonyl) -3- (2, 2-trifluoroethoxy) methylbenzoyl) cyclohex-2-en-1-one
To the reaction flask was added 2- (2-chloro-4-methylsulfonyl) -3- (2, 2-trifluoroethoxy) methylbenzoyl) cyclohexane-1, 3-dione (1 g, 2.3 mmol), 1, 2-dichloroethane (15 ml) and DMF (1 drop), oxalyl chloride (0.34 g, 2.7 mmol) was slowly added and the mixture stirred at 70℃for 1 hour and the solvent was distilled off under reduced pressure to give the key intermediate M as a yellow oil 1.1 g which was used directly in the next step.
Example 2 synthesis of compound 84:
To the reaction flask was added 2-mercapto-4-methylpyrimidine (0.45 g, 3.6 mmol), water (6 ml), naOH (0.14 g, 3.59 mmol) and then tris (2-carboxyethyl) phosphine (0.03 g, 0.12 mmol) with stirring at 0 ℃ and a solution of intermediate I (1.1 g, 2.4 mmol) in acetonitrile (10 ml) was added dropwise. Stirring was carried out at room temperature for 1 hour. Ethyl acetate (80 ml) was added to the reaction solution, water (80 ml) was extracted by liquid-separation, and the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give 0.84 g of compound 84, purity 97.5%, yield: 62.5%. LC-MS [ m+h ] +＝547.1、[M+Na]+ = 569.1.
Example 3 synthesis of compound 97:
Into the reaction flask was added cyclohexanediol (0.40 g, 3.6 mmol), water (6 ml), naOH (0.14 g, 3.6 mmol) and then tris (2-carboxyethyl) phosphine (0.03 g, 0.12 mmol) with stirring at 0 ℃ and a solution of intermediate I (1.1 g, 2.4 mmol) in acetonitrile (10 ml) was added dropwise. Stirring was carried out at room temperature for 1 hour. Ethyl acetate (80 ml) was added to the reaction solution, water (80 ml) was extracted by liquid separation, and the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give 0.95 g of compound 97, purity 96.9%, yield: 72.2%. LC-MS [ m+h ] +＝533.1、[M+Na]+ = 555.1.
Example 4 synthesis of compound 121:
To the reaction flask was added 2-mercapto-4-methylpyrimidine (0.91 g, 7.19 mmol), water (6 ml), naOH (0.14 g, 3.59 mmol) and then tris (2-carboxyethyl) phosphine (0.03 g, 0.12 mmol) with stirring at 0 ℃ and acetonitrile solution (10 ml) of intermediate I (1.1 g, 2.4 mmol) was added dropwise. Stirring was carried out at room temperature for 1 hour. Ethyl acetate (80 ml) was added to the reaction solution, water (80 ml) was extracted by liquid-separation, and the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give 0.58 g of compound 287, purity 96.4%, yield: 44.3%. LC-MS [ m+h ] +＝549.1、[M+Na]+ = 571.1.
Example 5 synthesis of compound 255:
To a reaction flask was added compound 84 (0.3 g, 0.55 mmol) prepared in example 2, dichloromethane (6 ml) and m-chloroperoxybenzoic acid (0.094 g, 0.55 mmol). Stirred at room temperature for 2 hours. Ethyl acetate (20 ml) was added to the reaction solution, water (20 ml) was extracted by liquid separation, the organic phase was washed with saturated brine (20 ml) in this order, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to obtain 0.24 g of compound 255 with a purity of 95.1%, yield: 73.9%. LC-MS [ m+h ] +＝563.0、[M+Na]+ = 585.0.
Example 6 synthesis of compound 259:
to a reaction flask was added compound 84 (0.3 g, 0.55 mmol) prepared in example 2, dichloromethane (6 ml) and m-chloroperoxybenzoic acid (0.24 g, 1.37 mmol). Stirred at room temperature for 3 hours. Ethyl acetate (20 ml) was added to the reaction solution, water (20 ml) was extracted by liquid separation, and the organic phase was washed with saturated brine (20 ml) in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give 0.22g of compound 259, purity 97.6%, yield: 67.6%. LC-MS [ m+h ] +＝579.1、[M+Na]+ =603.1.
With reference to the above process, other compounds of formula I can be obtained by substituting different materials as starting materials, see table 1 for specific compounds of formula I:
TABLE 1 Structure and physical Properties of part of the Compound of general formula I (X 3 is-CH 2OY1)
1 H NMR data for some compounds were as follows:
compounds of formula (I) 81(600MHz,DMSO)：8.00(d,1H),7.56(d,1H),5.21(s,2H),4.24(q,2H),3.64(s,3H),3.34(s,3H),3.27(t,2H),3.06(t,2H),2.76(t,2H),2.36(t,2H),2.01(t,2H).
Compounds of formula (I) 82(600MHz,DMSO)：7.99(d,1H),7.67-7.66(m,1H),7.53(d,1H),6.46(dd,1H),6.43(d,1H),5.20(s,2H),4.49(s,2H),4.24(q,2H),3.34(s,3H),3.31(s,3H),3.15(t,2H),2.37(t,2H),2.01(t,2H).
Compounds of formula (I) 85(600MHz,CDCl3)：8.01(d,1H),7.43(d,1H),7.33-7.28(m,4H),5.31(s,2H),4.16(s,2H),4.04-3.97(m,2H),3.20(s,3H),2.95(t,2H),2.42(t,2H),2.08(t,2H).
Compounds of formula (I) 87(600MHz,DMSO)：8.01(d,1H),7.55(d,1H),7.35-7.23(m,5H),5.22(s,2H),4.26(q,2H),3.38-3.35(m,5H),3.06(t,2H),2.96(t,2H),2.36(t,2H),1.99(t,2H).
Compounds of formula (I) 88(600MHz,CDCl3)：8.13(d,1H),7.51(d,1H),7.42(d,1H),6.39(d,1H),5.35(s,2H),4.01(q,2H),3.22(s,3H),2.60(t,2H),2.43(t,2H),2.39(d,3H),2.00(t,2H).
Compounds of formula (I) 91(600MHz,CDCl3)：8.10(d,1H),7.62(s,1H),7.56(s,1H),7.47(d,1H),7.38(m,3H),7.27(dd,2H),5.34(d,4H),3.99(m,2H),3.20(s,3H),2.54(t,2H),2.39(t,2H),1.95(m,2H).
Compounds of formula (I) 92(600MHz,CDCl3)：8.13(d,1H),7.49(d,1H),7.20(d,1H),5.34(d,2H),4.01(q,2H),3.22(s,3H),2.68(t,2H),2.56(d,3H),2.45(t,2H),2.01(t,2H).
Compounds of formula (I) 101(600MHz,CDCl3)：8.14(d,1H),7.71(d,1H),7.59(d,1H),7.55(d,1H),7.48(t,1H),7.38(t,1H),5.35(s,2H),4.02(q,2H),3.23(s,3H),2.49(t,2H),2.44(t,2H),2.04(t,2H).
Compounds of formula (I) 114(600MHz,CDCl3)：8.62(d,1H),8.09(d,1H),7.73(dd,1H),7.58(d,1H),7.52(d,1H),5.32(s,2H),3.99(q,2H),3.20(s,3H),2.66(t,2H),2.44(t,2H),1.99(t,2H).
Compounds of formula (I) 117(600MHz,CDCl3)：8.78(s,1H),8.06(d,2H),7.61(s,1H),7.45(s,1H),5.32(s,2H),4.00(s,2H),3.19(s,3H),2.69(s,2H),2.50(s,2H),2.07(s,2H).
Compounds of formula (I) 118(600MHz,CDCl3)：8.70(d,1H),8.10(d,1H),7.93(d,1H),7.67(d,1H),5.32(s,2H),4.01(q,2H),3.19(s,3H),2.80(t,2H),2.57(dd,2H),2.15(p,2H).
Compounds of formula (I) 122(600MHz,CDCl3)：8.06(d,1H),7.67(d,1H),6.91(s,1H),5.33(s,2H),4.01(q,2H),3.20(s,3H),2.96(t,2H),2.54(t,2H),2.46(s,6H),2.13(t,2H).
Compounds of formula (I) 123(600MHz,CDCl3)：8.08(d,1H),7.71(d,1H),5.89(s,1H),5.32(s,2H),4.01(q,2H),3.93(s,6H),3.19(s,3H),3.08(t,2H),2.56(t,2H),2.17(t,2H).
Compounds of formula (I) 136(600MHz,DMSO)：8.07(d,1H),7.91(d,1H),7.86(d,1H),7.75(d,1H),7.57(d,1H),7.52(d,1H),5.24(s,2H),4.28(q,2H),3.38(s,3H),2.78(t,2H),2.47(t,2H),1.98(t,2H).
Compounds of formula (I) 138(600MHz,CDCl3)：8.16(d,1H),7.80(d,1H),7.55(dd,2H),7.44(dd,1H),5.34(s,2H),4.02(q,2H),3.23(s,3H),2.83(t,2H),2.53(t,2H),2.08(t,2H).
Compounds of formula (I) 141(600MHz,DMSO)：8.24(d,1H),8.17(d,1H),8.06(d,1H),7.74(d,1H),7.66(t,1H),7.61(t,1H),5.23(s,2H),4.25(q,2H),3.37(s,3H),2.78(t,2H),2.44(t,2H),1.94(t,2H).
Compounds of formula (I) 142(600MHz,CDCl3)：8.12(d,1H),7.81(d,1H),7.59(d,1H),7.52(d,1H),7.44(d,1H),5.33(s,2H),4.00(q,2H),3.20(s,3H),2.86(t,2H),2.48(t,2H),2.06–2.02(m,2H).
Compounds of formula (I) 143(600MHz,CDCl3)：8.13(d,1H),7.70(d,1H),7.50(dd,2H),7.31–7.24(m,1H),5.33(s,2H),4.01(d,2H),3.21(s,3H),2.85(t,2H),2.48(t,2H),2.03(t,2H).
Compounds of formula (I) 146(600MHz,CDCl3)：8.70(t,2H),8.28(d,2H),7.47(d,1H),7.05(d,1H),6.92(d,1H),6.80(dd,1H),6.66(dd,1H),6.54(d,1H),5.31(dd,2H),5.00(dd,2H),3.88(dd,4H),3.77(s,3H),3.63(s,3H),3.20(d,6H),2.79–2.76(m,4H),2.58–2.45(m,4H),2.17–2.11(m,2H),2.07–2.00(m,2H).
Compounds of formula (I) 147(600MHz,CDCl3)：8.70(dd,2H),8.28(d,2H),7.46(d,1H),7.03(s,1H),6.91(d,1H),6.79(dd,1H),6.65(dd,1H),6.53(d,1H),5.31(dd,2H),5.00(dd,2H),3.99–3.95(m,2H),3.95–3.85(m,5H),3.75–3.70(m,1H),3.20(d,6H),2.77(d,4H),2.46–2.56(m,4H),2.15–2.02(m,4H),1.39–1.31(m,6H).
Compounds of formula (I) 150(600MHz,CDCl3)：8.73(s,1H),8.28(dd,1H),7.44(s,1H),7.33(s,1H),6.94(s,1H),6.85(d,1H),6.79(s,1H),5.34(s,1H),4.98(s,1H),3.84(s,2H),3.19(s,3H),2.71(s,2H),2.51(s,2H),2.35(s,2H),2.28(s,1H),2.13(s,1H),2.03(s,1H).
Compounds of formula (I) 161(600MHz,CDCl3)：8.08(d,1H),7.43(d,1H),5.17(s,2H),4.06(qd,1H),3.81-3.79(m,1H),3.74-3.69(m,4H),3.62-3.58(m,2H),3.29(s,3H),3.23(t,2H),2.96(t,2H),2.70(t,2H),2.45(t,2H),2.13(t,2H),1.97-1.90(m,1H),1.89-1.81(m,2H),1.61-1.58(m,1H).
Compounds of formula (I) 177(600MHz,CDCl3)：8.12(d,1H),7.56(d,2H),7.54–7.44(m,4H),5.20(s,2H),4.10–4.06(m,1H),3.82(q,1H),3.73(q,1H),3.64–3.60(m,2H),3.32(s,3H),2.47(t,2H),2.40(t,2H),1.96–1.92(m,3H),1.90–1.86(m,2H),1.62–1.58(m,1H).
Compounds of formula (I) 182(600MHz,CDCl3)：8.11(d,1H),7.59(d,2H),7.49(d,1H),7.42(m,2H),5.18(s,2H),4.09–4.05(m,1H),3.83–3.79(m,1H),3.75-3.71(m,1H),3.65–3.56(m,2H),3.30(s,3H),2.47–2.38(m,4H),1.96–1.92(m,3H),1.91–1.81(m,2H),1.60–1.56(m,1H).
Compounds of formula (I) 183(600MHz,CDCl3)：8.11(dd,1H),7.57-7.54(m,2H),7.49(dd,1H),7.18–7.14(m,2H),5.18(d,2H),4.09–4.05(m,1H),3.85–3.78(m,1H),3.75–3.71(m,1H),3.66–3.57(m,2H),3.30(d,3H),2.45–2.40(m,3H),2.42–2.37(m,1H),1.96–1.92(m,3H),1.91–1.81(m,1H),1.61–1.58(m,1H),1.25(m,1H).
Compounds of formula (I) 184(600MHz,CDCl3)：8.10(d,1H),7.46(dd,3H),6.96(d,2H),5.18(s,2H),4.08–4.05(m,1H),3.85(s,3H),3.84–3.77(m,1H),3.75–3.70(m,1H),3.61(m,2H),3.30(s,3H),2.44(t,2H),2.38(t,2H),1.98–1.86(m,2H),1.89–1.80(m,2H),1.60–1.56(m,1H),0.89–0.80(m,1H).
Compounds of formula (I) 189(600MHz,CDCl3)：8.14(d,1H),7.75(t,1H),7.61–7.48(m,3H),5.19(s,2H),4.11-4.06(m,1H),3.85–3.79(m,1H),3.78-3.70(m,1H),3.66-3.60(m,2H),3.31(s,3H),2.50–2.42(m,3H),2.08–1.81(m,5H),1.59-1.50(m,2H).
Compounds of formula (I) 194(600MHz,CDCl3)：8.64(d,1H),8.11(d,1H),7.74(dd,1H),7.58(d,1H),7.52(d,1H),5.19(s,2H),4.11-4.07(m,1H),3.83–3.80(m,1H),3.73(dd,1H),3.64–3.57(m,2H),3.31(s,4H),2.67(t,2H),2.46(dd,2H),2.01(d,1H),1.96–1.91(m,1H),1.89–1.83(m,2H),1.62–1.56(m,2H).
Compounds of formula (I) 195(600MHz,CDCl3)：8.89(d,1H),8.11(dd,1H),7.96(dd,1H),7.69(d,1H),7.58(dd,1H),5.19(s,2H),4.06-4.10(m,1H),3.69-3.88(m,2H),3.60-3.62(m,2H),3.30(d,J＝2.0Hz,3H),2.77(t,J＝6.0Hz,2H),2.51(t,J＝6.6Hz,2H),2.02-2.07(m,2H),1.78-2.01(m,3H),1.51-1.69(m,1H).
Compounds of formula (I) 200(600MHz,CDCl3)：8.16(d,1H),7.54(d,1H),5.18(d,2H),4.10-4.05(m,1H),3.87–3.69(m,2H),3.65-3.59(m,2H),3.32(s,3H),2.55–2.39(m,4H),2.07-2.04(m,2H),1.98–1.80(m,3H),1.66–1.49(m,1H).
Compounds of formula (I) 221(600MHz,CDCl3)：8.14(t,2H),7.94(d,1H),7.59(t,1H),7.52(dd,2H),5.19(s,2H),4.20–4.04(m,1H),3.82-3.74(m,2H),3.67-3.61(m,2H),3.32(s,3H),2.82(t,2H),2.48(t,2H),2.10–1.82(m,6H),
1.64-1.58(m,1H).
Compounds of formula (I) 225(600MHz,CDCl3)：8.66(d,1H),8.27(dd,1H),7.59(d,1H),7.17(t,1H),7.07–6.96(m,2H),5.12(dd,1H),4.86(dd,1H),4.06–3.92(m,1H),3.73-3.60(m,2H),3.56–3.38(m,2H),3.28(d,3H),2.80-2.75(m,2H),2.60–2.42(m,2H),2.21–2.00(m,2H),1.90-1.75(m,3H),1.45-1.38(m,1H).
Compounds of formula (I) 226(600MHz,CDCl3)：8.63(dd,1H),8.26(dd,1H),7.05(s,1H),6.69–6.40(m,2H),5.15-5.08(m,1H),4.88-4.80(m,1H),4.02-3.91(m,1H),3.85–3.59(m,5H),3.56–3.37(m,2H),3.28(t,3H),2.76(s,2H),2.61–2.42(m,2H),2.08(d,2H),1.93–1.75(m,3H),1.45-1.36(m,1H).
Compounds of formula (I) 231(600MHz,CDCl3)：8.68–8.56(m,1H),8.30-8.24(m,1H),7.56–7.44(m,1H),7.18–7.05(m,1H),6.99–6.89(m,1H),6.71(d,1H),5.15-5.08(m,1H),5.02–4.79(m,1H),4.02-3.5(m,1H),3.79–3.60(m,2H),3.50–3.38(m,2H),3.28(dd,3H),2.79-2.72(m,2H),2.63–2.40(m,2H),2.13-2.02(m,2H),1.89-1.78(m,3H),1.43-1.38(m,1H).
Biological measurement example
Test example 1 after the raw material acetone or DMF is dissolved, 1%Tween 80 is used for standing tap water according to the test requirement to prepare the liquid to be tested with the required concentration. The following tests were performed. The results were observed after all treatments for 20 d.
The efficacy observation was carried out visually, expressed as 0 to 100%, with "0" representing no control and "100%" representing complete kill, as follows:
0-the same as the control, drug resistance and prevention effect of less than 10%;
1-growth is slightly influenced, slightly inhibited, has poor activity and has a control effect of 10% to less than 30%;
2-growth has influence, slight whitening, poor activity and prevention effect of 30 to less than 50 percent;
3-growth has influence, whitening is remarkable, activity is moderate, and prevention effect is 50% to less than 70%;
4-is sensitive, the whitening is obvious, the activity is good, and the prevention effect is 70% to less than 90%;
5-extremely sensitive, completely whitened, basically dead, and 90-100% of prevention effect;
post-emergence test experiment:
Sowing broadleaf weeds (amaranth, ash, abutilon) and grassy weeds (barnyard grass, green bristlegrass and crabgrass) seeds into paper cups with 7cm diameter and containing nutrient soil, covering 1cm after sowing, compacting, watering, culturing in a greenhouse according to a conventional method, and carrying out post-seedling stem leaf spray treatment after 2-3 leaf periods of weeds. The treated plants and controls were observed after 20d in the greenhouse.
TABLE 2 post-emergence compound Activity test results
The test results show that the compound of the embodiment shown in the general formula I has high prevention effect on various weeds. Among the compounds tested, some of the compounds of the example of formula I had better control effects on barnyard grass, green bristlegrass, crabgrass, amaranth, gray or abutilon at an application dose of 150g a.i./hm 2 than the control compounds KC1, KC2 and bicyclosultone.
According to the test method, part of the compounds of the examples of the general formula I and the control compounds are selected for carrying out parallel tests on the herbicidal activity and the crop safety, and the results are shown in Table 3.
TABLE 3 post-emergence compound Activity test results
As can be seen from table 3, the above-described example compounds of the general formula I are significantly superior to the control compounds KC1, KC2 and mesotrione in herbicidal activity and safety.
And the compound disclosed by the invention has good selectivity to grass lawns such as goosegrass, bermuda grass, broom corn millet, bluegrass, ryegrass and the like, and can prevent and remove a plurality of key grass weeds and broadleaf weeds. Tests on wheat, soybean, cotton, rape, potato, sorghum, vegetables etc. under different modes of administration also showed excellent selectivity and have excellent commercial value.
The embodiments of the technical solutions of the present disclosure have been described above by way of example. It should be understood that the protection scope of the present disclosure is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principles of the present disclosure should be included in the scope of the claims of the present disclosure.

Claims (10)

1. A compound of formula I, a stereoisomer or a pharmaceutically acceptable salt thereof;
wherein:
X 1 is selected from hydrogen, cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, Y 1-S(O)m -;
X 2 is selected from hydrogen, cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 halocycloalkyl, Y 1-O-、Y1-S(O)m -;
X 3 is selected from cyano, nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, Y 1O-、Y1OC1-C6 alkyl, Y 1OC1-C6 alkyloxy, Y 1Y2-NH-、Y1Y2-N-C1-C6 alkyl, Y 1-S(O)m-、Y1-S(O)m-C1-C3 alkyl, Y 1-S(O)m-C1-C6 alkyloxy 、-C(O)Y1、-C(O)OY1、-OC(O)OY1、-N(Y1)C(O)OY2、-C(O)N(Y1)(Y2)、-N(Y1)C(O)N(Y1)(Y2)、-OC(O)N(Y1)(Y2)、-C(O)N(Y1)OY2、-N(Y1)S(O)2Y2、-N(Y1)C(O)Y2、-OS(O)2Y1、-CH＝NOY1、-C1-C6 alkylene-ch= NOY 1、-C1-C6 alkylene-O-n=cy 1Y2、C6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl;
Each Y 1、Y2 is the same or different and is independently selected from C 1-C6 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents selected from nitro, halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C6 cycloalkyl, C 3-C6 cycloalkyloxy, C 2-C6 alkenyl, C 2-C6 alkynyl, phenyl or halophenyl;
R 1、R2, which are identical or different, are independently of one another selected from hydrogen, C 1-C6 alkyl, C 3-C6 cycloalkyl, C 3-C6 alkenyl, C 3-C6 alkynyl;
Q is selected from hydrogen, cyano, C 1-C10 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl, C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 1-C6 alkyl, c 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, 3-14 membered heterocyclyl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3S(O)mC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) R 3、-C(O)OR3、C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-CH＝NOR3、-C1-C6 alkylene-ch=nor 3、-C1-C6 alkylene-O-n=cr 3R4、-P(＝S)(OR3)2;
Wherein X 3, Q are independently of each other optionally substituted with 1, 2, 3, 4 or 5 substituents selected from Y 3;
Each Y 3 is identical or different and is selected, independently of one another, from halogen, hydroxy, cyano, nitro, carboxyl, oxo (=O), C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 2-C6 haloalkenyl, C 2-C6 haloalkynyl, C 6-C14 aryl, C 6-C14 haloaryl, C 6-C14 arylC 1-C6 alkyl, C 6-C14 aryloxy, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, C 1-C6 alkylamino-, C 1-C6 alkyl C (O) -, C 1-C6 alkyl S (O) m-、-C(O)OC1-C6 alkyl, -C (O) NR 3R4、(R3O)R4 N-or R 3R4 N-;
each R 3、R4, which are the same or different, are independently selected from hydrogen, C 1-C6 alkyl;
m is selected from 0, 1 or 2;
n is selected from 0, 1 or 2.
2. The compound, stereoisomer or agropharmaceutically acceptable salt thereof according to claim 1,
X 1 is selected from halogen, C 1-C6 alkyl, C 1-C6 haloalkyl, Y 1-S(O)m -;
X 2 is selected from C 1-C6 haloalkyl, Y 1-S(O)m -;
x 3 is selected from Y 1OC1-C6 alkyl;
y 1 is selected from the group consisting of C 1-C6 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, and 5-7 membered alicyclic C 1-C6 alkyl containing 1-4 heteroatoms;
R 1、R2, identical or different, are independently of one another selected from hydrogen, C 1-C6 alkyl;
q is selected from the group consisting of C 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 5-14 membered heteroarylC 1-C6 alkyl, -C 1-C6 alkylene C (O) OR 3;
Wherein X 3, Q are independently of each other optionally substituted with 1, 2, 3, 4 or 5 substituents selected from Y 3;
Each Y 3, which is the same or different, is independently selected from halogen, hydroxy, cyano, nitro, C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 6-C14 arylC 1-C6 alkyl, 3-10 membered heterocyclyl, C 1-C6 alkyl C (O) -, or R 3R4 N-;
Each R 3、R4 is the same or different and is independently selected from hydrogen, C 1-C6 alkyl
M is selected from 0, 1 or 2;
n is selected from 0, 1 or 2;
Preferably, Q is selected from the group consisting of hydrogen, cyano, C 1-C10 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl, C 1-C6 alkyl, C 3-C6 halocycloalkyl, C 1-C6 alkyl, c 6-C14 aryl, 5-14 heteroaryl, 3-14 heterocyclyl, C 6-C14 arylC 1-C6 alkyl, 3-14 heteroarylC 1-C6 alkyl, 3-14 membered heterocyclyl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3S(O)mC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) R 3、-C(O)OR3、-C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、-C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-CH＝NOR3、-C1-C6 alkylene-ch=nor 3、-C1-C6 alkylene-O-n=cr 3R4、-P(＝S)(OR3)2;
Preferably, Q may be selected from hydrogen, cyano, C 1-C10 alkyl, C 3-C6 alkenyl, C 3-C6 alkynyl, C 1-C6 haloalkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C6 alkyl, C 3-C6 halocycloalkyl C 1-C6 alkyl, C 6-C14 aryl, 5-14 membered heteroaryl, 3-14 membered heterocyclyl, C 6-C14 aryl C 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, 5-14 membered heteroaryl C 1-C6 alkyl, R 3R4N-、R3OC1-C6 alkyl, R 3-NH-C1-C6 alkyl, -C (O) OR 3、-C(S)OR3、-C1-C6 alkylene C (O) OR 3、-C1-C6 alkylene Si(OR3)3、-C(O)NR3R4、-C(S)NR3R4、-C(O)N(R3)OR4、-C(＝NH)NR3、-P(＝S)(OR3)2;
Preferably, Q may be selected from the following groups which are unsubstituted or optionally substituted with Q Y 3: c 6-C14 aryl (e.g. phenyl, naphthyl or anthracyl, e.g. ) A 5-membered heterocyclic group (e.g ) 6 Membered heterocyclic group 5-14 Membered heteroaryl (e.g., benzoheteroaryl, such asFor example heteroaryl-heteroaryl groups, e.g) ; Q is selected from 0, 1, 2, 3, 4 or 5;
Preferably, Q may be selected from Y 5、Y6、Y7、Y8, which are identical or different, are independently selected from H, C 1-C8 alkyl, C 1-C8 alkyloxy; or Y 5 and Y 6 form with their respective attached N the following groups unsubstituted or optionally substituted with one, two or more Y q1: 3-14 membered heterocycle or 5-14 membered heteroaryl ring; or Y 7 and Y 8 form with their respective attached N the following groups unsubstituted or optionally substituted with one, two or more Y q2: 3-14 membered heterocycle or 5-14 membered heteroaryl ring; y q1 and Y q2 are identical or different and are selected independently of one another from H, halogen, C 1-C8 alkyl, C 1-C8 alkyloxy;
Preferably, Q may be selected from the following groups which are unsubstituted or optionally substituted with one, two or more Y 3: c 1-6 alkyl, cyclohexenyl, furyl, thienyl, thiazolinyl, oxazolinyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, pyrimidinyl, pyridyl, triazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzopyrazinyl, phenyl, naphthyl, anthracenyl, purinyl;
preferably, Q is selected from methyl, ethyl, propyl, isopropyl, cyano,
3. A compound, stereoisomer or agropharmaceutically acceptable salt thereof according to claim 1 or 2, wherein X 1 can be selected from hydrogen, nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 alkyl;
Preferably, X 1 may be selected from hydrogen, nitro, halogen, C 1-C4 alkylsulfonyl, C 1-C4 alkyl;
Preferably, X 1 may be selected from halogen, methyl, nitro, methylsulfonyl;
Preferably, X 1 may be selected from F, cl, br, methyl, trifluoromethyl or methylsulfonyl;
Preferably, X 2 may be selected from hydrogen, nitro, halogen, C 1-C6 alkylsulfonyl, C 1-C6 alkyl, C 1-C6 haloalkyl;
Preferably, X 2 may be selected from hydrogen, nitro, halogen, C 1-C4 alkylsulfonyl, C 1-C4 alkylsulfinyl, C 1-C4 haloalkyl;
Preferably, X 2 may be selected from halogen, C 1-C4 alkylsulfonyl, C 1-C4 haloalkyl;
preferably, X 2 may be selected from CF 3、-SO2CH3.
Preferably, when X 1 is Cl, X 2 is-SO 2CH3 or CF 3; when X 1 is CH 3, X 2 is-SO 2CH3.
4. A compound according to any one of claims 1 to 3, a stereoisomer or a agropharmaceutically acceptable salt thereof, wherein X 3 may be selected from-CH 2OY1;
Preferably, Y 1 can be selected from C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 alkoxy C 1-C3 alkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C3 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, 5-7 membered heterocyclyl-C 1-C6 alkyl containing 1-2 oxygen atoms;
Preferably, Y 1 can be selected from C 1-C3 alkyl, C 1-C3 haloalkyl, C 1-C3 alkoxy C 1-C3 alkyl, C 3-C6 cycloalkyl, C 3-C6 cycloalkyl C 1-C3 alkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, 5-7 membered heterocyclyl-C 1-C3 alkyl containing 1-2 oxygen atoms;
Preferably, Y 1 is selected from methyl,
5. A compound according to any one of claims 1 to 4, a stereoisomer or a agropharmaceutically acceptable salt thereof, wherein Y 3 is selected from halogen, hydroxy, cyano, nitro, carboxy, oxo (=o), C 1-C6 alkyl, C 1-C6 haloalkyl, C 1-C6 Alkyloxy, C 1-C6 haloalkyloxy, C 3-C8 cycloalkyl, C 2-C6 alkenyl, C 2-C6 alkynyl, C 2-C6 haloalkenyl, C 2-C6 haloalkynyl, C 6-C14 aryl, C 6-C14 haloaryl, C 6-C14 arylC 1-C6 alkyl, c 6-C14 aryloxy, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, 5-10 membered heteroaryl C 1-C6 alkyl, 3-10 membered heterocyclyl C 1-C6 alkyl, C 1-C6 alkylamino-, C 1-C6 alkyl C (O) -, C 1-C6 alkyl S (O) m-、-C(O)OC1-C6 alkyl, -C (O) NR 3R4、(R3O)R4 N-, or R 3R4 N-;
preferably, Y 3 is selected from F, cl, br, NO 2、OH、CN、CF3、C(O)OH、NH2, oxo (=o), thio (=s), methyl, ethyl, vinyl, ethynyl, methoxy, ethoxy, methylthio, furyl, phenyl, chlorophenyl, methylsulfonyl, isopropoxy, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, methoxyamino, ethoxyamino, C (=o) OCH 3, piperidinyl, morpholinyl,
Preferably, Y 3 is selected from F, cl, br, NO 2、OH、CN、CF3, methyl, ethyl, methoxy, ethoxy, methylamino, dimethylamino, ethylamino, isopropylamino, piperidinyl, morpholinyl, benzyl, acetyl;
Preferably, R 1 and R 2 are the same or different and are independently selected from hydrogen, C 1-C6 alkyl;
preferably, R 1 and R 2 are the same or different and are selected from hydrogen, methyl;
Preferably, R 1 and R 2 are both H;
Preferably, R 1 and R 2 are both methyl;
Preferably, X 1 is selected from Cl;
X 2 is selected from methylsulfonyl;
X 3 is selected from-CH 2OY1;
Y 1 is selected from methyl, 2-trifluoroethyl, 2-difluoroethyl, 2-tetrahydrofuranylmethyl, 2-tetrahydropyranylmethyl;
R 1、R2 are each selected from hydrogen;
q is selected from the substituents shown below:
Or selected from the benzene ring, naphthalene ring as shown below:
or a 5-membered heterocyclic group selected from the following:
Or a 6 membered heterocyclic group selected from the following:
or a benzoheterocyclyl group selected from the following:
or a heterocyclo-heterocyclyl selected from the following:
The above Q groups may be substituted with Q Y 3: F. cl, br, hydroxy, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, benzyl, acetyl, piperidine, morpholine, methylamino, ethylamino, isopropylamino or dimethylamino; q is selected from 0, 1,2, 3, 4 or 5;
n is selected from 0, 1 or 2.
6. The compound, stereoisomer or agropharmaceutically acceptable salt thereof according to any one of claims 1 to 5, wherein the compound of formula I can be selected from compounds 1 to 270 of example table 1.
7. A process for the preparation of a compound of formula I, a stereoisomer or a pharmaceutically acceptable salt thereof as claimed in any one of claims 1 to 6, wherein the process comprises the steps of:
wherein X 1、X2、X3、R1、R2, Q, n have the definition as defined in any one of claims 1 to 6 independently of each other;
Preferably, the compound of formula II reacts with the compound of formula III to obtain the compound of formula I;
For example, the preparation method further comprises the steps of resolving to obtain stereoisomers of the compounds shown in the formula I after the compounds shown in the formula I are obtained, or reacting the stereoisomers with acid or alkali to prepare pharmaceutically acceptable salts of the compounds;
preferably, the process for the preparation of the compound of formula II comprises the steps of:
Wherein X 1、X2、X3、R1、R2 independently of one another have the definition as defined in any one of claims 1 to 6;
preferably, the compound of formula IV is reacted with an acyl halogenating reagent to provide the compound of formula II.
8. Use of a compound of formula I as defined in any one of claims 1 to 6, a stereoisomer thereof or a pharmaceutically acceptable salt thereof for herbicidal use, for example as herbicide.
9. A herbicidal composition comprising at least one of a compound of formula I as defined in any one of claims 1 to 6, a stereoisomer thereof or an agropharmaceutically acceptable salt thereof;
Preferably, the herbicidal composition comprises 1 to 99 weight percent of active ingredients, preferably 1 to 99 weight percent of all active ingredients;
Preferably, the herbicidal composition may further comprise other agropharmaceutically acceptable active ingredients; for example, the other agropharmaceutically acceptable active ingredient may be selected from herbicides or plant growth regulators known in the literature;
For example, the herbicidal composition may be selected from at least one of the following formulations: wettable Powders (WP), water-soluble concentrates, emulsifiable Concentrates (EC), aqueous Solutions (SL), emulsions (EW), for example oil-in-water or water-in-oil emulsions, sprayable solutions or sprayable emulsions, suspension Concentrates (SC), oil-or water-based dispersions, suspension emulsions, powders (DP), seed dressing materials, granules for soil application or for sowing, water-dispersed granules (WG), ULV formulations, microcapsules or waxes;
preferably, the grass may be at least one selected from broadleaf weeds (such as amaranth, carp intestines, herba Chenopodii, abutilon, descurainia sophia, veronica, quinoa, polygonum caryophyllum, alisma orientale, and tulip), grassy weeds (such as barnyard grass, green bristlegrass, moleplant seed, crabgrass, brome, festival wheat, ryegrass, and wild oat), and sedge (such as garrulous cyperus, heterotypic cyperus, and iris).
10. A method for removing unwanted vegetation which comprises applying a compound of the formula I as claimed in any one of claims 1 to 6, its stereoisomers or their agrochemically acceptable salts or the herbicidal composition in herbicidally active amounts to unwanted vegetation, to plant seeds and/or to their environment of growth.
CN202410062649.XA 2023-01-16 2024-01-16 Alkoxy substituted benzoyl oxo cyclohexene sulfide compound, preparation method and application thereof Pending CN118344271A (en)

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Publication number Priority date Publication date Assignee Title
US4762551A (en) * 1986-06-09 1988-08-09 Stauffer Chemical Company Certain 3-(substituted thio)-2-benzoyl-cyclohex-2-enones
US5152826A (en) * 1991-10-16 1992-10-06 Imperial Chemical Industries Plc Certain substituted bis(2-benzoyl-3-oxo-cyclohexenyl) thioglycols
DE4241999A1 (en) * 1992-12-12 1994-06-16 Hoechst Ag Benzoylcyclohexenones, process for their preparation and their use as herbicides and plant growth regulators
US5525580A (en) * 1993-03-18 1996-06-11 Sds Biotech K.K. Substituted benzoyl cyclic enone, process for preparation, and herbicide
AR027575A1 (en) * 2000-03-06 2003-04-02 Bayer Ag SUBSTITUTED BENZOILCICLOHEXENONAS
JP2001335573A (en) * 2000-05-25 2001-12-04 Ishihara Sangyo Kaisha Ltd Cyclohexenone delivative, method for producing the same and herbicide containing the same
JP2002080460A (en) * 2000-07-06 2002-03-19 Nippon Bayer Agrochem Co Ltd Herbicidal tetrazole derivative
DE10043074A1 (en) * 2000-09-01 2002-03-14 Aventis Cropscience Gmbh Herbicidally active benzoylcyclohexanediones
CA2456241A1 (en) * 2001-08-08 2003-02-20 Basf Aktiengesellschaft Benzoylcyclohexenone derivatives
DE10144529A1 (en) * 2001-09-11 2003-03-27 Bayer Cropscience Gmbh New aminocarbonylalkyl-substituted 3-benzoyl-cyclohexane-1,3-dione derivatives, useful as broad-spectrum herbicides for selective pre- or post-emergence weed control, especially in wheat, maize or rice
JP2003238540A (en) * 2002-02-08 2003-08-27 Bayer Ag Tetrazole derivative and herbicide
DE10215723A1 (en) * 2002-04-10 2003-10-30 Bayer Cropscience Gmbh 3-keto or 3-oxime ether substituted benzoylcyclohexanediones
WO2011012247A1 (en) * 2009-07-29 2011-02-03 Bayer Cropscience Ag 2-(3-alkylthiobenzoyl)cyclohexanediones and their use as herbicides
WO2011101321A1 (en) * 2010-02-19 2011-08-25 Bayer Cropscience Ag 3-aminocarbonyl-substituted benzoylcyclohexanediones and their use as herbicides
CN107353238B (en) * 2017-08-17 2019-09-03 青岛清原化合物有限公司 Substituted benzoylcyclohexan cyclohexadione compounds or its tautomer, salt, preparation method, Herbicidal combinations and application
CN114591230A (en) * 2022-03-07 2022-06-07 沈阳万菱生物技术有限公司 Cyclohexenone compound, application thereof and pesticide herbicide

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