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CN1134657A - Herbicidal AZA bisphosphonic acid compositions - Google Patents

Herbicidal AZA bisphosphonic acid compositions Download PDF

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Publication number
CN1134657A
CN1134657A CN94194096A CN94194096A CN1134657A CN 1134657 A CN1134657 A CN 1134657A CN 94194096 A CN94194096 A CN 94194096A CN 94194096 A CN94194096 A CN 94194096A CN 1134657 A CN1134657 A CN 1134657A
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alkyl
hydrogen
halogen
ethyl
independent separately
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K·J·菲什
F·X·伍拉德
J·M·格得斯
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Syngenta Ltd
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Zeneca Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • C07F9/405—Esters of poly(thio)phosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/5532—Seven-(or more) membered rings
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    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/568—Four-membered rings
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    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/60—Quinoline or hydrogenated quinoline ring systems
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/65031—Five-membered rings having the nitrogen atoms in the positions 1 and 2
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings

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  • Life Sciences & Earth Sciences (AREA)
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  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Herbicidal compositions comprising: (A) a compound of formula (I), wherein R<1> is hydrogen, hydroxy, C1-C4 alkoxy, halogen, C1-C4 alkyl, C1-C4 haloalkyl, hydroxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy or N(R<6>) (R<7>), wherein R<6> and R<7> are each independently hydrogen or C1-C3 alkyl; R<2> and R<3> are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; or substituted hydrocarbyl-S(O)m-; or R<2> and R<3> together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio or N(R<8>) (R<9>) wherein R<8> and R<9> are each independently hydrogen or C1-C12 alkyl; and R<4> and R<5> are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or are of the formula N (R<10>) (R<11>) wherein R<10> and R<11> are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R<4> and R<5> together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl.

Description

The AZA bisphosphonic acid compositions that is used for weeding
On the one hand, the present invention relates to the AZA bisphosphonic acid compositions of weeding, said composition comprises: (A) a kind of AZA bisphosphonic acid, wherein the carbon atom that links to each other of nitrogen-atoms and two phosphonate groups is connected and (B) a kind of their carrier that suits by single carbon atom.On the other hand, the present invention relates to the method for controlling plant growth, this method comprises this azepine-double phosphinic acid compounds from effective weeding amount to the place of wishing the controlling plant growth that use.Also have an aspect, the present invention relates to some new azepine-double phosphinic acid compounds.
Lay special stress on is not badly in need of the necessity of effective weed killer herbicide.Because the competitive leaf that suppresses crops of weeds, the production of fruit and seed is so control weeds and the edible wild herbs do not expected have great economic worth.Be running to weeds and lower harvest and the quality of crops.The weeds of non-planting area can cause fire, causes the drift of the husky or snow of not expecting, and/or causes the stimulation to irritated patient.So, the weed growth that suppresses not expect just seems highly beneficial and schemes.
In addition, extremely wish when weed killer herbicide uses plant is shown the effect of expectation behind bud, and almost significantly not active when before bud, using.This class weed killer herbicide for example can be controlled the weeds that existed in the farmland, and does not injure the crop that does not also germinate.
Correspondingly, one of target of the present invention is, effectively new Herbicidal combinations is provided, and the new method of weeding is provided, and some new herbicides compounds are provided.Further object of the present invention is, new composition is provided, and new herbicidal methods and new herbicides compounds do not show control action before the tangible bud so that reach control effect behind the fabulous bud.
Although reported some two phosphonic acids and AZA bisphosphonic acid herbicides compounds in the document, these herbicides compounds do not have the carbon atom that links to each other with two phosphonate groups and are connected to structure on the amino nitrogen atom by single carbon atom.
Like this, phosphonate group only is connected on the single carbon atom in the weeding double phosphinic acid compounds of open 54-147925 (Nissan Chemical) invention of Japan Patent.The general formula of this compounds or their salt is:
Figure A9419409600131
X and the Y hydrogen of respectively doing for oneself wherein, halogen, alkyl or cycloalkyl.
At United States Patent (USP) 4.447,256 (Suzuki etc.); BP 1.508,772 (Der-lin); The open 54-37829 (Nissoan Chemical) of Japan Patent; The open 54-144383 (Nissan Chemical) of Japan Patent; " herbicidal performance of aminophosphonic acid microorganism " literary composition of Japan Patent open (Nissan chemical) and Dr.y.Okamoto (sees Lst In-ternational Congress on Phosphorus Compounols, Rabat, Octobor 17-21,1977, PP.649-652), the carbon atom that is connected with two phosphonate groups in the weeding azepine-double phosphinic acid compounds of middle report is to be directly connected on the amino nitrogen-atoms.
Invented the herbicides compounds of some following general formulas and their alkali metal salt among the open 55-98193 of Japan Patent, wherein R is a hydrogen, low alkyl group or
Figure A9419409600132
Halogen; X is-CH 2-, S or O; Y is hydrogen, low alkyl group or halogen.
Though once reporting some in the document is the azepine-double phosphinic acid compounds that is connected with nitrogen-atoms by single carbon atom with the carbon atom that two phosphonate groups link to each other, and does not point out that these specific compounds have activity of weeding.Like this, United States Patent (USP) 3,962, the compound of 318 inventions are as the flame retarding agent; The compound of German patent DE 2754821 inventions is as the chelating agent in the water treatment; United States Patent (USP) 5,133,972 and 4,990,503, European patent discloses 96,931 European patents disclose 96,933, and European patent discloses 186405, European patent discloses 274,138, European patent discloses 522,576 and Deutsche Bundespatent bulletin DE3, all specific compounds of invention all are as medicinal in 804,686.
On the one hand, the present invention relates to Herbicidal combinations, said composition comprises:
(A) compound and the agricultural salt thereof of general formula (I), wherein
Figure A9419409600141
R 1Be nitrogen, hydroxyl, C 1-C 4Alkoxyl, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, hydroxyl-C 1-C 4-alkyl, hydroxyl-C 1-C 4-alkoxyl or N (R 6) (R 7), R in the base 6And R 7Independent separately is hydrogen or C 1-C 3Alkyl;
R 2And R 3Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Alkyl-S (O) m-or substituted hydrocarbon radical-S (O) m-; Or
R 2And R 3The common 3-6 unit carbocyclic ring that forms, this carbocyclic ring be arbitrarily by halogen, hydroxyl, C 1-C 6Alkyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, or N (R 8) (R 9) replacement, wherein R 8And R 9Independent separately is nitrogen or C 1-C 12Alkyl;
R 4And R 5Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Sulfenyl; Replace sulfenyl; Pyridine radicals; Substituted pyridinyl; Or be general formula N (R 10) (R 11) base, R wherein 10And R 11From independence is hydrogen, alkyl or substituted hydrocarbon radical; Or
R 4And R 5Form aziridine, piperazine, morpholine, thiomorpholine with the nitrogen that is connected jointly; the thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethylene imine, piperidines; tetrahydropyridine, pyridine imidazoles, pyrroles; triazole, tetrahydropyrimidine, glyoxalidine; pyrrolin, azetidine, perhydrogenate indoles; the perhydrogenate quinoline, rings such as perhydrogenate isoquinolin or pyrrolidines, any one ring wherein can be optionally by C 1-C 12Alkyl, halogen, C 6-C 10Aryl, halogen or C 1-C 6The C that alkyl replaces 6-C 10Aryl, C 7-C 16Aralkyl, halogen or C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, phenoxy group, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 2-C 10Thiazolinyl or cyano group replace; Or
R 2And R 4Common nitrogen that is connected with them and carbon atom form aziridine, piperazine, morpholine, thiomorpholine; the thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethylene imine, piperidines; tetrahydropyridine, pyrazoles, imidazoles, pyrroles; triazole, tetrahydropyrimidine, glyoxalidine; pyrrolin, azetidine, perhydrogenate indoles; the perhydrogenate quinoline, rings such as perhydrogenate isoquinolin or pyrrolidines, any one ring wherein can be optionally by C 1-C 12Alkyl, halogen, C 6-C 10Aryl, halogen or C 1-C 6The C that alkyl replaces 6-C 10Aryl, C 7-C 16Aralkyl, halogen or C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10-alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, phenoxy group, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 1-C 10Thiazolinyl or cyano group replace;
And m is zero, 1 or 2;
With
(B) and agrochemistry acceptable carrier.
On the other hand, the present invention relates to the method for controlling plant growth, this method is included in expectation and controls the compound that the above-mentioned general formula (I) of herbicidally effective amount is used in the place of weeds.
Also have an aspect, the present invention relates to some noval chemical compounds in above-mentioned general formula (I) range of structures.
Herbicidal combinations of the present invention comprises the double phosphinic acid compounds and the agricultural salt thereof of general formula (I):
Figure A9419409600161
Wherein
R 1Be hydrogen, hydroxyl, C 1-C 4Alkoxyl, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, hydroxyl-C 1-C 4-alkyl, hydroxyl-C 1-C 4Alkoxyl or N (R 6) (R 7), R wherein 6And R 7Independent separately is hydrogen or C 1-C 3Alkyl;
R 2And R 3Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Alkyl-S (O) m-, substituted hydrocarbon radical-S (O) m-; Or
R 2And R 3The common 3-6 unit carbocyclic ring that forms, this carbocyclic ring be arbitrarily by halogen, hydroxyl, C 1-C 6Alkyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group or N (R 8) (R 9) replace a R wherein 8And R 9Independent separately is hydrogen or C 1-C 12Alkyl;
R 4And R 5Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Sulfenyl; Replace sulfenyl; Pyridine radicals; Substituted pyridinyl; Or be general formula N (R 10) (R 11) base, R wherein 10And R 11Independent separately is hydrogen, alkyl or substituted hydrocarbon radical;
Or R 4And R 5Form aziridine, piperazine, morpholine, thiomorpholine with the nitrogen that links to each other jointly; the thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethylene imine, piperidines; tetrahydropyridine, pyrazoles, imidazoles, pyrroles; triazole, tetrahydropyrimidine, glyoxalidine; pyrrolin, azetidine, perhydrogenate indoles; the perhydrogenate quinoline, rings such as perhydrogenate isoquinolin or pyrrolidines, wherein any ring all can be arbitrarily by C 1-C 12Alkyl, halogen, C 6-C 10Aryl, halogen or C 1-C 6Alkyl is substituted by C 6-C 10Aryl, C 7-C 16Aralkyl, halogen or C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, phenoxy group, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 1-C 10Thiazolinyl or cyano group replace; And
M is zero, and 1 or 2 preferential selections are:
R 1Be hydrogen, hydroxyl, halogen or C 1-C 4Alkyl;
R 2And R 3Independent separately is hydrogen; C 1-C 12Alkyl; C 2-C 12Thiazolinyl; C 2-C 12Alkynyl; Halo-C 1-C 12Alkyl; Halo-C 2-C 12Thiazolinyl; Halo-C 2-C 12Alkynyl; C 6-C 14Aralkyl; C 1-C 12Alkoxyl; Or C 1-C 12Alkylthio group;
R 4And R 5Independent separately is C 1-C 6Alkyl; C 2-C 6Thiazolinyl; C 2-C 6Alkynyl; Halo-C 1-C 6Alkyl; Halo-C 2-C 6Thiazolinyl; Halo-C 2-C 6-alkynyl; Pyridine radicals; Substituted pyridinyl; Phenyl; Substituted-phenyl; C 7-C 4Aralkyl; Or replacement C 7-C 14Aralkyl; Or
R 4And R 5The common nitrogen formation tetrahydropyrimidine that is connected with them, tetrahydropyridine, imidazoles etc. encircle or-(CH 2) n-N-ring, wherein n is 2-6, these rings show arbitrarily by halogen, hydroxyl, C 1-C 6Alkoxyl, nitro, C 1-C 6Alkyl, C 7-C 16Aralkyl or C 1-C 6Alkylthio group replaces.Selection more preferably is:
R 1Be hydrogen or hydroxyl;
R 2And R 3Independent separately is hydrogen or C 1-C 6Alkyl;
R 4And R 5Independent separately is hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, benzyl, C 1-C 6The benzyl that alkyl or halogen replace, or
R 1And R 5The common nitrogen that they connect forms pyrrolidines or piperidine ring, and any ring in them all can be arbitrarily by fluorine, hydroxyl, C 1-C 6Alkoxyl or C 1-C 6Alkyl replaces.
The particularly preferred compound that uses in Herbicidal combinations of the present invention and the method comprises: 2-(R-alpha-methyl benzyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(2-methyl-propyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(1-(4-methyl isophthalic acid, 3-imidazole radicals)) ethyl-1, the two phosphonic acids of 1-; 2-(1-pyrrolidinyl) ethyl-1, the two phosphonic acids of 1-; 2-(1-piperidyl) ethyl-1, two phosphonic acids 2-(third amino) ethyls-1 of 1-, the two phosphonic acids of 1-; 2-(N, N-Methylethyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(normal-butyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(propyl group amino) ethyl-1, the two phosphonic acids of 1-; 2-(1-(1,2,3, the 6-tetrahydropyridine)) ethyl-1, the two phosphonic acids of 1-; And 2-(N, N-dipropyl amino) ethyl-1, the two phosphonic acids of 1-.
On the other hand, the present invention relates to the new azepine-double phosphinic acid compounds of some types.
New azepine-double phosphinic acid compounds of one type in the scope of the invention comprises those compounds and the agricultural salt thereof of general formula I I structure: Wherein
R 12And R 13Independent separately is hydrogen, C 1-C 6The straight or branched alkyl, hydroxyl, C 2-C 6Thiazolinyl, C 1-C 6Alkoxyl or C 1-C 6Alkoxy-C 1-C 6Alkyl; Specific compound in such scope comprises: 2-(N, N-di-n-butyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(N, N-diethylamino) ethyl-1, the two phosphonic acids of 1-; 2-(N, N-di amino) ethyl-1, the two phosphonic acids of 1-; 2-(third amino) ethyl-1, the 1-di 2 ethylhexyl phosphonic acid; 2-(isopropylamino) ethyl-1, the two phosphonic acids of 1-; 2-(third amino) ethyl-1, the two phosphonic acids tetrabutylammonium salts of 1-; 2-(third amino) ethyl-1, the two phosphonic acids three fourth ammonium salts of 1-; 2-(uncle's fourth amino) ethyl-1, the two phosphonic acids of 1-; 2-(n-butyl amine base) ethyl-1, the two phosphonic acids of 1-; 2-(just oneself is amino) ethyl-1, the two phosphonic acids tetrabutylammonium salts of 1-; 2-(fourth-3-alkenyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(positive ethylamino) ethyl-1, the two phosphonic acids of 1-; 2-(isobutyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(ethylamino) ethyl-1, the two phosphonic acids of 1-; 2-(third-2-alkenyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(methoxyl group amino) ethyl-1, the two phosphonic acids of 1-; 2-(N-methoxyl group, N-methyl base amino) ethyl-1, the two phosphonic acids of 1-; 2-(N-hydroxyl, N-methylamino) ethyl-1, the two phosphonic acids of 1-; And 2-(2-ethoxyethyl amino) ethyl-1, the two phosphonic acids of 1-.
New azepine-two phosphonic acids in the scope of the invention also comprise those compounds and the agricultural salt thereof of general formula III:
Figure A9419409600201
Wherein q is 0-10; J is 0-3; R 14And R 15Independent separately is hydrogen or C 1-C 6Alkyl; Ar is a phenyl, pyridine radicals, pyrimidine radicals, pyrazinyl, naphthyl, pyrazolyl, imidazole radicals, triazolyl, thiazolyl, furyl, thienyl, pyrrole radicals, azoles base or piperazine di azoly; R 16Be halogen, C 1-C 10Alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, halo-C 1-C 10-alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphinyl, phenoxy group, substituent phenoxy, C 1-C 10Thiazolinyl or cyano group; And R 17, R 18And R 19Independent separately is hydrogen, C 1-C 10Alkyl, C 1-C 10Substituted alkyl, C 7-C 10Aralkyl, or C 2-C 10Thiazolinyl
When q is 2 or bigger when several, each R 14And R 15Self can independently be hydrogen or C all 1-C 3Alkyl.Similarly, when j is 2 or bigger when several, each R 16Can be identical or different.
Specific compound in the type comprises:
2-(alpha-methyl benzyl amino) ethyl-1, the two phosphonic acids of 1-;
2-(2-methyl-benzyl amino) ethyl-1, the two phosphonic acids of 1-;
2-(3-methyl-benzyl amino) ethyl-1, the two phosphonic acids of 1-;
2-(2-phenylethyl amino) ethyl-1, the two phosphonic acids of 1-;
2-(benzylamino) ethyl-1, the two phosphonic acids of 1-;
2-(S-alpha-methyl benzyl amino) ethyl-1, the two phosphonic acids of 1-; With
2-(R-alpha-methyl benzyl amino) ethyl-1, the two phosphonic acids of 1-.
2-(R-alpha-methyl benzyl amino) ethyl-1, the tetrabutylammonium salt of the two phosphonic acids of 1-.
Other newtype compound in the scope of the invention is the compound of general formula (IV): Wherein A is C 1-C 6The alkylidene radical (alkylenidene) of 3-6 the carbon atom that alkyl replaces, and they can be agricultural salt.Specific compound in such scope comprises:
2-(1-pyrrolidinyl) ethyl-1, the two phosphonic acids of 1-;
2-(2.5-dimethyl-1-pyrrolidinyl)) ethyl-1, the two phosphonic acids of 1-;
2-(1-pyrrolidinyl) ethyl-1, the two phosphonic acids tetramethyl ammonium salts of 1-;
2-(1-pyrrolidinyl) ethyl-1, the two phosphonic acids three fourth ammonium salts of 1-;
2-(1-pyrrolidinyl) ethyl-1, the two phosphonic acids trimethyl sulfonium salts of 1-;
2-(1-hexamethyleneimino) ethyl-1, the two phosphonic acids of 1-;
2-(4-methyl isophthalic acid-piperidyl) ethyl-1, the two phosphonic acids of 1-;
2-(2-methyl isophthalic acid-piperidyl) ethyl-1, the two phosphonic acids of 1-; With
2-(3-methyl isophthalic acid-piperidyl) ethyl-1, the two phosphonic acids of 1-.
Another kind of noval chemical compound in the scope of the invention is compound or its agricultural salt of general formula (V): R wherein 20Be hydrogen or hydroxyl; B is C 2-C 4Alkylidene connects base, and this connects base arbitrarily by C 1-C 6Alkyl replaces.
Specific compound in such scope comprises:
The two phosphonic acids of 1-(2-piperidyl)-1-methylol-1.1-;
The two phosphonic acids of 1-(2-pyrrolidinyl)-1-methylol-1.1-; And
The two phosphonic acids three fourth ammonium salts of 1-(2-pyrrolidinyl)-1-methylol-1.1-.
Another kind of compound in the scope of the invention is the compound of general formula VI and their agricultural salt:
Figure A9419409600231
R wherein 21And R 22Independent separately is C 1-C 6Alkyl, or a formation C 1-C 6The C that alkyl arbitrarily replaces 3-C 5Alkylidene.
Descriptive compound in the scope of the invention comprises:
2-amino-1-hydroxy-2-methyl propyl group-1.1-diphosphonate hydrochlorate; With
The two phosphonic acids of 1-(1-amino cyclopentyl)-1-methylol-1.1-.
Also having a class noval chemical compound in the scope of the invention is compound and its agricultural salt of general formula (VII); Wherein t is 2,3 or 4; R 23And R 24Independent separately is hydrogen, C 1-C 10Alkyl, halogen, nitro, C 1-C 9Alkoxyl, C 1-C 10Aralkyl, cyano group, trifluoromethyl or represent a unsaturated unit; R 25Be hydrogen, C 1-C 6Alkyl, C 7-C 10Aralkyl, halogen, nitro, trifluoromethyl or cyano group.Each R 23And R 24List the different members of gene above self can being.
Descriptive compound in the scope of the invention comprises:
2-(1-(2-methyl isophthalic acid, 4,5,6-tetrahydrochysene-1,3-pyrimidine radicals)) ethyl-1, the two phosphonic acids of 1-; And
2-(1-(4-methyl isophthalic acid, 3-imidazole radicals)) ethyl-1, the two phosphonic acids of 1-.
The general formula that provides above plans to comprise the dynamic isomer of the structure of drawing here, and the trim that comprises the compound that physically can distinguish, for example these compounds can come from the difference arrangement of molecule in lattice, a part that perhaps comes from molecule is obstructed with respect to rotating freely of another part, or come from geometrical isomerismization, or come from the molecule or intermolecular hydrogen bonding, or come from other approach.
The compound of this class general formula can exist with enantiomter.The present invention now comprises single enantiomter, comprises the mixture of all proportions of two enantiomters again.
As used herein, the substituting group on it self perhaps represented in term " alkyl ", or large-substituent (for example at alkoxyl, alkyl-S (O) m-benzene) Ding Yi a part comprises C 1-C 16Alkyl.So the term alkyl comprises for example straight chain and the C that props up chain isomerism 1-C 16Alkyl (for example methyl, ethyl, propyl group, isopropyl, second hexyl, hexyl); C 3-C 16Cycloalkyl (for example cyclopropyl, cyclobutyl and cyclohexyl); C 2-C 16Thiazolinyl is pi-allyl and cyclobutenyl for example); C 2-C 16Alkynyl (for example propinyl); Phenyl; The benzene alkyl; Alkyl phenyl; The thiazolinyl phenyl; Alkynyl phenyl; Alkyl benzyl; The thiazolinyl benzyl; The alkynyl benzyl; Naphthyl and similar gene.
When using " alkyl " when " replacement " this term and go up (or similarly term on), only otherwise be specifically noted, just have a mind to comprise alkyl defined above, this alkyl contains one or more substituting groups, and these substituting groups are selected from halogen (being fluorine, chlorine, bromine and iodine); C 1-C 10Alkoxyl; C 1-10Alkyl-S (O) m-; Cyano group, nitro; Hydroxyl; And their salt, acid amides and ester; C 2-C 10Chain acyl; One or more C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkyl-S (O) m-, nitro, fluorine, chlorine, bromine, cyano group, or the random phenyl that replaces of trifluoromethyl.In the superincumbent definition, m is zero, 1 or 2.
Furtherly, when alkyl was substituted aryl (for example phenyl, benzyl or naphthyl), substituting group can comprise the substituting group that one or more front final stages are listed, and also can comprise nitro.Those substituting groups of describing in detail in the top substituted aryl had a mind to comprise in term " substituted pyridinyl ".
In addition, only otherwise specify, straight chained alkyl, branched alkyl and cycloalkyl just had a mind to comprise in term " alkyl ".Term defined above " halogen " comprises fluorine, chlorine, bromine and iodine.In many halogeno-groups, halogen can be identical, also can be different.
Find that compound of the present invention has activity of weeding, have value, can be used for removing the weeds of wide range, comprise broad-leaved and standing grain herbaceous weed as post-emergence herbicide.
So the invention still further relates to the method for the unwanted edible wild herbs of control, this method comprises to be used the compound of the present invention of effective weeding amount described herein and a kind of being suitable on the excrescence of this class weeds in the place that this class weeds of expectation control grows with shared inert diluent of weed killer herbicide or one in carrier.
Term used herein " weed killer herbicide " or " weed killer herbicide " are inhibitory control or the modifications that illustrates the plant growing of not expecting.Inhibitory control and modify comprise growing naturally all depart from, for example integral body is killed, the retardance growth, disleave, dehydration is regulated, retardance is grown, and tillers, and stimulates withered and short and smallization of leaf.Term " herbicidally effective amount " be used for illustrating when with compound administration of the present invention to the plant of not expecting from one's body or any amount that reaches this class control or modify when being administered to the place of this class plant growing.Seeds germinated had a mind to comprise in term " plant ", and the unearthed seed and the vegetation of shaping comprise root and acrial part two parts.
Term " agricultural salt " just is easy to determine by the common technology of document, and comprises alkali metal salt, ammonium salt, phosphonium salt, sulfonium salt, their organic microbial and similar compounds.
Generally just can make wherein R by two phosphonic acids tetraethyl esters of ethenylidene and the amine reaction that suits 1Compound of the present invention for hydrogen.This class reaction, for example at acetonitrile, ether, toluene, oxolane and is similarly reacted in the solvent typically carrying out in suitable atent solvent between about 0 ℃ and 100 ℃.Remove ester group with desalination trimethyl silane or aqueous hydrochloric acid solution then.
The two phosphonic acids tetraethyl esters of ethenylidene can be according to C, and the method for Degenhardt etc. (see J, Qrg.Chem., Vol 51, PP 3488-3490 (1986)) preparation.The amine that uses or can buy from the market, can be according to the preparation of the known method of document, for example by Gabriel synthetic from corresponding bromating agent preparation (be Vogel, " A Textbook of Practi-cal Qrganic Chemistry ", 3d Ed., PP 569).
When preparation wherein contains the amines of sensitivity genes, can at first use the compound of bromination trimethyl silane one class to make ester group carry out ester exchange reaction.This class group then can the hydrolysis deprotection.
In addition, prepare wherein R 1When being not the compound of hydrogen, can use phosphorus trichloride according to the document known method, phosphoric acid or diphosphorus trioxide make suitable carboxylic acid, and acid amides or nitrile transform.
Composition of the present invention is made up of the compound and the suitable carrier of top general formula (I), and this class carrier is known in the literature.Compound of the present invention is useful weed killer herbicide, and can use according to distinct methods known in the document and variable concentrations.Compound of the present invention can be used to control the weed growth of not expecting by the place of using expectation control weed growth behind the bud.In fact, compound of the present invention uses with the prescription that contains various excipients such as carrier, and these excipients or carrier are known or are used to excipient or the carrier strengthening disperseing in industry.The selection of the prescription of any compound and use pattern all can influence its activity, thereby can do corresponding selection.Like this, but compound of the present invention can fill a prescription wet powder, fills a prescription into emulsible concentrate, fills a prescription into pulvis or dust agent, but fills a prescription flowable, fills a prescription into solution, suspending agent or emulsifier, or fill a prescription and become to draw to release agent, for example microencapsulation.Calculate by weight, these prescriptions can contain few to 0.5% active component to as many as 95% or more content.The optimum amount of any given compound depends on the attribute of controlled plant.Ratio and consumption are generally about 0.01 pound to 10 pounds/acre, preferably about 0.02 pound to 4 pounds/acre.
The form of wettable powder be in water or other liquid-carrier in the fine particle that disperses easily.The active component that this particle contains remains in the solid matrix.Typical solid matrix comprises bleaching earth, kaolin, silica and other easy wetting organic or inorganic solid.Wettable powder normally contains about 5% to about 95% active component and a small amount of wetting agent, dispersant or emulsifier.
But emulsifying concentrated solution is a homogeneous liquid composition, can be scattered in the water or in other liquid, and can all be made up of active component and liquid or solid emulsifier, perhaps can also contain liquid-carrier, meta-xylene for example, heavy oil, different Fo Er cave and other non-volatile organic solvent.These concentrates are distributed in the water or in other liquid, normally are to be sprayed onto on the processed ground as spray during use.The content range of active component is about 0.5% to about 95% of a concentrate.
Dust agent is an active component and the free-pouring mixture of the solid that grinds very carefully, for example with talcum powder, and clay, flour and other free flowing mixture as the organic and inoganic solids of dispersant and carrier.
Microencapsulation is wrapped in the drops or the solution of the active material in the inertia porous shell typically, and the porous shell allows that the material of parcel is discharged in the environment with the speed of controlling.The diameter that is bundled into the drops of capsule typically is 1 to 50 micron.The material of parcel typically constitutes the about 50% to 95% of capsules weight, removes the active ingredient beyond the region of objective existence, can also comprise solvent.Shell or film material comprise natural rubber and synthetic rubber, cellulose substances, SB, polyacrylonitrile, polypropylene ester, polyester, polyamide, polyureas, polyureas alkane, starch xanthate.
Other useful prescription as weed killer herbicide comprises the simple solution that active component and solvent constitute, and active component can dissolve under the concentration of expectation in this solvent fully, and solvent comprises for example water, acetone, alkylated naphthalene, meta-xylene and other organic solvent.Wherein the compression spraying agent that disperses with very little particle shape of active component can by evaporation low boiling dispersion solvent carrier for example freon obtain, this compression spraying agent also can be used.
Many these prescriptions comprise humectant, dispersant or emulsifier.Example has alkyl and alkaryl carbonic ester and sulfuric ester and their salt; Poly-chain alcohol; Polyethoxy acetate; Ester and fatty amine.During normal the use, these reagent account for 0.1% to 15% of formulation weight.
Above-mentioned each prescription can be made the packing that contains weed killer herbicide and other formula components (thinner, emulsifier, surfactant etc.).Prescription can also be by the preparation of case bulk method, and each component obtains respectively in this method, is carrying the merging of training place then.
Compound of the present invention also can be used for and other weed killer herbicide and/or defoliant, dehydrating agent, and growth inhibitor and similar composition share.Other material of this class can account for about 5% to 95% of active component in the prescription.These combinations usually provide the effect of high-caliber control weeds, and the unavailable result of single prescription of each weed killer herbicide usually is provided.
Other weed killer herbicide that can use with compounds of the present invention, defoliant, dehydrating agent, the example of plant growth inhibitor has: A. benzo-2,1,3-thia diazine-4-ketone-2,2-dioxide, for example ben-tagone; B. hormone weed killer herbicide, particularly phenoxyalkanoic acids, for example methyl chlorophenoxyacetic acid, methyl chlorophenoxyacetic acid-sulphur ethyl ester, dichlorprop, 2,4,5-trichlorophenoxyacetic acid, MCPB, 2,4 dichlorophenoxyacetic acid, 2,4-DB, Mecoprop, trichlopyr, fluroxypyr, clopy-ralid and their derivative (for example salt, ester and acid amides); C.1,3-dimethyl pyrazole Zole derivatives, Pyragoxyfen for example, pyrazolate and benzofe-nap; D. dinitrophenol dinitrophenolate and derivative thereof (for example acetic acid esters dinitro-o-cresol for example, Dinoterb, dinoseb and its ester, dinoseb acetic acid esters); E. dinitraniline weedicide, dinitramine for example, trifluralin, ethalfluralin, pendimethalin; And orgzalin; F. aryl carbamide weedicide, diuron for example, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and methabenzthiazuron; G. phenyl amino formyloxy carbanilate, for example phenmedipham and desmedipham; H.2-phenyl pyrazoline pyridazin-3-one, for example chloridazon and norflurazon; I. uracil weed killer herbicide, lenacil for example, bromacil and terbacil; J. triazine herbicides, atruzine for example, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn; The K.phosphorothioate weed killer herbicide, piperophos for example, bensulide, and butami-fos; L. thiocarbamate herbicide, cycloute for example, vernolate, molinate, thiobencarb, butylate *, EPTC *, triallate, diallate, ethyl espro carb, tiocarbazil, pyridate, and dimepiperate; M.1,2,4-triazine-5-herbicides, for example metamitron, and metribuzin; N. benzoic acid herbicides, for example 2,3,6-TBA, dicamb, and chloramben; O. anilid weed killer herbicide, pretilachlor for example, butachlor, corresponding alachlor, corresponding propachlor compound, propanil, metazarchlor, metoachlor, ace-tochlor, and timethachlor; P. dihalo-benzonitrile weed killer herbicide, dichlobenil for example, bromoxynil and ioxynil; Q. halogenated alkane acid herbicide, dalapon for example, trichloroacetic acid and salt thereof; R. diphenyl ether weed killer herbicide, lactofen for example, fluroglycofen or their salt or ester, nifrofen, bifenox, acifluorfen, and their salt and ester, oxyfluorfen, and fomesafen; Chlornitrofen and chlomethoxyfen; S. phenoxy group phenoxypropionic acid ester weed killer herbicide, for example diclofop and ester class, its methyl esters for example, fluazifop and its ester class, haloxyfop and its ester class, quizalofop and its ester class and fenoxaprop and its ester class, for example ethyl ester; T. cyclohexanedione herbicide, for example alloxydim and its salt, sethoxydim, cy-cloxydim, sulcotrione, tralkoxy dim and clethodim; U. sulphonyl urine weed killer herbicide, chlorosulfuron for example, sulfometuron, metsulfuron and its ester class; Benzsulfuron and its ester class, for example its methyl esters; DPX-M6313, the ester class of chlorimuron and it, its ethyl ester for example, pirimisulfuron and its ester class, its methyl esters for example, DPX-LS300 and pyrazosulfuron; V. imidazolidimedione weed killer herbicide, imazaquin for example, imazamethabenz, imazapyr and its isopropyl ammonium salt, imazethapyr; W. aryl-acyl aniline weed killer herbicide, for example flamprop and its ester class, benzoylprop-ethyl, diflufenican; X. amino acid weed killer herbicide, for example glyphosate and gluyfosinate and their salt and ester class, sulphosate, and bilanafos; Y. organoarsenic herbicide, for example MSMA; Z. remove Oxamide derivatives, napropamide for example, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam.AA. miscellany weed killer herbicide comprise ethofumesate, cinmethylin, the salt of difenzoquat and they, Methylsulfate salt for example, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, (with 3: 1 ratios) flurochloridone, quinchlorac and mefanacet; The example of BB. useful contact herbicide comprises the bipyridylium weed killer herbicide, those compounds that for example wherein active entity is paraquit and diquat.
* these compounds are advocated and safener, for example with 2, and the 2-dichloro.
N, N-two-2-propylene acetamide (dichlormid) share.
These prescriptions can be applied to the region of expectation with conventional method control.For example dust composition and fluid composition can be used the electric power duster, and suspension rod and manual sprayer and spraying duster spray.Prescription also can use as dust or spray from aircraft, or uses by the rope bar.
Be the example of representative formula below.5% dust agent: 5 parts of reactive compounds
95 parts of talcum powder 2% dust agents: 2 parts of reactive compounds
The silicic acid of 1 part of high degree of dispersion
97 parts of talcum powder
These dust agents are to grind to form the granularity of hope again after will component mixing and make.
Wettable powder: 70% 70 parts of reactive compounds
5 parts of dibutyl sodium naphthasulfonates
3 portions of naphthalene sulfonic acids/benzene sulfonic acid/formaldehyde concentrates (3: 2: 1)
10 parts of kaolin
12 parts of champague chalk 40%:40 part reactive compounds
5 parts of wooden sodium sulfonates
1 part of nekal
54 parts of silicic acid 25%:25 part reactive compounds
4.5 part wooden calcium sulfonate
1.9 part champagne chalk/hydroxyethylcellulose (1: 1)
1.5 part nekal
19.5 part silicic acid
19.5 part champagne chalk
28.1 part kaolin 25%:25 part reactive compound
2.5 part iso-octyl phenoxy group-polyvinyl ethanol
1.7 part champagne chalk/hydroxyethylcellulose (1: 1)
8.3 part sodium aluminium silicate
16.5 part diatomite
46 parts of kaolin 10%:10 part reactive compounds
The mixture of 3 parts of saturated fatty alcohol sulfuric ester sodium salts
5 portions of naphthalene sulfonic acids/formaldehyde concentrates
82 parts of kaolin
Be in suitable blender reactive compound to be mixed immediately with auxiliary material when preparing these wettable powder, the mixture of generation grinds in flour mill or cylinder machine.Emulsible concentrate: 25%:25 part reactive compound
2.5 part peroxidating vegetable oil
10 parts of alkyl aryl sulfonate/fatty alcohol polyglycol ether mixtures
5 parts of dimethyl formamides
57.5 part dimethylbenzene
The amount that constitutes this composition of herbicidally effective amount depends on processed seed or the character of plant.The ratio of the active component of using is every acre about 0.01 to about 25 pounds, and preferably every acre about 0.10 to 10 pound, actual amount depends on the result of total cost and expectation.Can recognize expressly that from document the dosage that the composition that shows low activity of weeding will reach the control of same degree and needs is higher than more active compound.
Embodiment
The following examples are intended to that the invention will be further described, the intention that does not limit the scope of the invention by any way.
Embodiment 1 preparation 2-(1-(1-(1,2, the 4-triazole)) ethyl-1, the two phosphonic acids (compound 3) of 1-.1g1,2, the 4-triazole is dissolved in the 40ml oxolane under-78 ℃ and nitrogen protection.Drip the 974mg n-BuLi then, the white suspension that obtains stirred 5 minutes in-78 ℃.After being warming up to room temperature, mixture stirred 45 minutes, and then was chilled to-78 ℃.In 20 minutes time, drip the two phosphonic acids tetraethyl esters of 4.78g ethenylidene inward.After adding, mixture is warming up to 0 ℃ then in-78 ℃ of stirrings 15 minutes, and continues to stir 1 hour.Reactant mixture 10ml water cessation reaction, the pressure reducing and steaming oxolane, thick product that obtains and 35ml wet chemical merge.The mixture that obtains (3 * 100ml) dichloromethane extractions.The combined benzene extract, anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent obtains mobile grease.Use silica gel chromatography,, obtain 1.3g2-(1-(1,2, the 4-triazole)) ethyl-1,1-di 2 ethylhexyl phosphonic acid tetraethyl ester with 10% ethanol/methylene wash-out.This product and 500mol% bromo trimethyl silane were in 45 ℃ of hydrolysis 4 hours, and volatile materials is removed in decompression then, generates compound 3.Residual grease refluxed in water 30 minutes, was chilled to room temperature then, removed under the high vacuum and anhydrated, and was separated to compound 3 quantitatively.
Embodiment 2 preparation 1-hydroxyl-(2-amino-2-methyl) propyl group-1, the two phosphonic acids (compound 8) of 1-
Flask is equipped with condenser pipe at the bottom of the 250ml three neck figure, mechanical agitation, and oil bath and thermometer add the 2.37g2-aminoisobutyric acid, 85ml chlorobenzene and 3.2g phosphoric acid in bottle.Mixture adds hot reflux and is chilled to 50 ℃ after 1 hour.Add the 9.62g phosphorus trichloride then, mixture under agitation adds hot reflux 5 hours again.The end mixture was chilled to room temperature in 5 hours, and inclining carefully chlorobenzene.Add new chlorobenzene of 85ml and 80ml6N hydrochloric acid inward, mixture under agitation adds hot reflux.After 6 hours, yellow suspension is chilled to room temperature, with Dai Kalite diatomite filtration under diminished pressure, removes volatile components under the high vacuum, obtains colourless syrup.Grinding with ethanol under steam heated, obtain 3.09g compound 8, is white solid after the vacuum filtration.
Embodiment 3 preparation 1-hydroxyl-1-(2-pyrrolidinyl)-1, the two phosphonic acids (compound 9) of 1-
The 200ml three-neck flask is equipped with mechanical agitation and has the reflux condenser of nitrogen conduit, adds the 4g proline inward, 5.7g phosphoric acid and 25ml dioxane.80 ℃ drip the 9.6g phosphorus trichloride down, and mixture stirred 2 hours in 80 ℃.After reactant mixture is chilled to room temperature, add 150ml water, the mixture active carbon filtration that obtains.Filtrate decompression concentrates, and residual limpid grease is put into that (60 ℃) spend the night in the vacuum drying oven.Residue grinds with ethanol then, the white solid filtration under diminished pressure that obtains.Solid is 60 ℃ of dryings in vacuum drying oven, obtain 5.9g compound 9.
Embodiment 4 preparation 2-(fourth-3-alkenyl amino) ethyls-1, the two phosphonic acids (compound 29) of 1-
At room temperature the solution with the amino fourth of 1.08g1--3-alkene and 5ml methyl alcohol is added in the two phosphonic acids tetraethyl esters of 3.8g ethenylidene.After mixture stirs and spends the night, add the amino fourth of 0.12g1--3-alkene again, stirred again 4 hours.With the reactant mixture concentrating under reduced pressure, get 4.56g2-(fourth-3-alkenyl amino) ethyl-1 then, the two phosphonic acids tetraethyl esters of 1-.4.4g this product and 5ml acetonitrile and 7.2ml bromo trimethyl silane merge.After the stirring at room 48 hours, vlil 4 hours, concentrating under reduced pressure then.Four (trimethyl silicane) esters that generate and 25ml water reflux and were hydrolyzed in 30 minutes.Volatile materials is removed in freeze drying, obtains 3.2g compound 29, and is colourless for hard, hygroscopicity bubble gum sample thing.
Embodiment 5 preparation 2-(3-methyl isophthalic acid-piperidyl) ethyls-1, the two phosphonic acids (compound 37) of 1-.
Drips of solution with 1ml 3-methyl piperidine and 5ml methyl alcohol under the room temperature is added in the two phosphonic acids tetraethyl esters of 2.43g ethenylidene.Reaction is stirred and is spent the night, and the mixture concentrating under reduced pressure gets 3.4g 2-(3-methyl isophthalic acid-piperidyl) ethyl-1, the two phosphonic acids tetraethyl esters of 1-.3.37g this product is dissolved in the 5ml acetonitrile, adds 5ml bromo trimethyl silane then.The mixture that obtains refluxes and spends the night, and is chilled to room temperature, concentrating under reduced pressure then.Add 25ml water in residual grease, mixture stirred 3 hours.Under high vacuum, remove and anhydrate and other volatile materials, obtain 2.84g compound 37, for hard, moisture absorption, colourless bubble gum shape thing.
Embodiment 6 preparation 2-(4-methyl-benzyl amino) ethyls-1, the two phosphonic acids (compound 67) of 1-.
In the 100ml kieldahl flask, add 3.5g ethenylidene bis phosphoric acid tetraethyl ester, 20ml acetonitrile and 1.5g4-methylbenzylamine.The mixture that obtains magnetic stirrer stirred overnight at room temperature.The pressure reducing and steaming solvent gets the two phosphonic acids tetraethyl esters of 4.66g 2-(4-methyl-benzyl amino) ethyl-1.1-then.3.87g this product is put in the 100ml kieldahl flask that electromagnetic agitation is housed and refluxed 4 hours with the 25ml concentrated hydrochloric acid.Remove volatile materials under the high vacuum, get 3.21g compound 67, be colourless hygroscopicity vitreum.
Embodiment 7 adopts and top similar operation, makes the following compound of listing in the Table I:
Table I
Compound numbering R1     R 2     R 3    R 4     R 5 1.          H       H       H       H  2.          H       H       H       H   3.          H       H       H       -N＝CH-N＝CH- 4.          H       H       H       -CH 2-CH 2-CH 2-CH 2-compound numbering R1     R 2     R 3     R 4         R 5 5.         H       H       H       -CH 2CH 2-CH 2-CH 2-tetramethyl-ammonium Yan 6. H H H-CH2-CH 2-CH 2-CH 2-CH 2- 7.         -OH     H       H       -CH＝N-CH＝CH- 8.         -OH     -CH 3   -CH 3H H hydrochloride 9.Compound numbering R1       R 2      R 3     R 4      R 5 10.                                    
Figure A9419409600391
San butyl amine salt 11. H H H-CH2-CH 2-CH 2-CH 2-San butyl amine salt 12. H H H H-nC3H 7 13.                H          H        H       -CH 2-CH 2-CH 2-CH 2-San methyl sulfosalt 14. H H H H 15.                H          H        H       H         -iC 3H nCompound numbering R1      R 2     R 3     R 4     R 5 16.       H        H       H        H      -tC 4H 9 17.                      
Figure A9419409600401
18.       H        H       H       -CH 3   -CH 3 19.                       Compound numbering R1    R 2    R 3    R 4    R 5 20.     H      H      H      21.     H      H      H     
Figure A9419409600412
22.     H      H      H       H     -iC 4H 9 23.     H      H      H       -C 2H 5 -C 2H 5 24.     H      H      H       H     -nC 3H 7San butyl amine salt 25. H H H H-nC3H 7Si butyl amine salt 26.-NH2  H      H       H     -CH 3 27.     H      H      H       H     -nC 4H 9Compound numbering R1    R 2   R 3    R 4       R 5 28.     H      H      H      H        -OCH 3 29.     H      H      H      H        -CH 2CH 2CH＝CH 2 30.     H      H      H      H        -nC 6H 13 31.     H      H      H              
Figure A9419409600421
32.     H      H      H      H        -CH 2CH＝CH 2 33.     H      H      H      -nC 3H 7 -nC 3H 7 34.     H      H      H      -CH 3    -OCH 3 35.     H      H      H      -CH 3-OH compound numbering R1      R 2     R 3     R 4     R 5 36.     H        H        H       H       -C 2H 5 37.     H        H        H        38.     H        H        H       H       
Figure A9419409600432
39.     -OH      H        H       H       -CH 3 40.     H        H        H       -nC 4H 9-nC 4H 9 41.     H        H        H       H       -nC 6H 13TBuA Yan 42. H H H HCompound numbering R1     R 2     R 3     R 4     R 5 43.     H       H       H       H         44.     H       H       H       H         45.     H       H       H       H         46.     H       H       H       H         47.     H       H       H       H         Compound numbering R1    R 2    R 3    R 4        R 5 48.      H      H       H      -CH 2-CH 2-CH 2-CH 2-CH 2-CH 2- 49.      H      H       H     
Figure A9419409600451
50.      H      H       H       H 
Figure A9419409600452
5l.      H      H       H      -CH 3  -nC 3H 7 52.      H      H       H      -CH 3  -iC 3H 7 53.      H      H       H      Compound numbering R1    R 2     R 3     R 4           R 5 54.     H      H       H       H              
Figure A9419409600461
55.     H      H       H       56.     H      H       H       H             
Figure A9419409600463
57.     H      H       H      -CH 2-CH＝CH 2  -CH 2-CH＝CH 2 58.     H      H       H       H              
Figure A9419409600464
59.     H      H       H      -CH 2-CH 2-O-CH 2-CH 2-compound numbering R1     R 2     R 3     R 4      R 5 60.     H       H        H      -C 2H 5  -nC 3H 7 61.     H       H        H      H        -CIF 2-CF 3 62.     H       H        H      -C 2H 5  -CH 2-CH＝CH 2 63.     H       H        H      -CH 3    -CH 2-CH＝CH 2 64.     H       H        H      H       
Figure A9419409600471
65.     H       H        H      -CH 2-CH 2-CH 2-CH 2-CH 2- 66.     H       H        H      Compound numbering R1    R 2   R 3    R 4        R 5 67.       H      H      H      H      
Figure A9419409600481
68.       H      H      H      H      
Figure A9419409600482
69.       H      H      H      H       70.       H      H      H      H      
Figure A9419409600484
71.       H      H      H      H      
Figure A9419409600485
Compound numbering R1   R 2  R 3   R 4   R 5 72.     H     H     H     -CH 2-CH＝CH-CH 2-CH 2- 73.     H     H     H     H     74.     H     H     H    
Figure A9419409600492
75.     H     H     H     H    
Figure A9419409600493
76.     H     H     H     H    
Figure A9419409600494
Compound numbering-R1    R 2   R 3    R 4     R 5 77.      H      H      H      H      
Figure A9419409600501
78.      H      H      H      H      
Figure A9419409600502
79.      H      H      H      H      
Figure A9419409600503
80.      H      H      H      H       Compound numbering-R1     R 2   R 3     R 4       R 5 81.       H       H       H       H       
Figure A9419409600511
82.       H       H       H       H      -CH 2-CH＝CH-CH 3 83.       H       H       H       H      84.       H       H       H       H      -CH 2-CH 2CH 2Cl 85.       H       H       H       86.       H       H       H      -nC 3H 7
Figure A9419409600514
Compound numbering R1    R 2    R 3   R 4         R 5 87.     H      H      H      -nC 3H 7   -nC 4H 9 88.     H      H      H     
Figure A9419409600521
89.     H      H      H      -nC 3H 7    90.     H      H      H      H            91.     H      H      H      H         
Figure A9419409600524
92.     H      H      H      H         
Figure A9419409600525
Compound numbering R1    R 2    R 3   R 4        R 5 93.     H      H      H      94.     H      H      H      -nC 3H 7 
Figure A9419409600532
95.     H      H      H     
Figure A9419409600533
96.     H      H      H      -nC 3H 7  -nC 6H 13 97.     H      H      H      
Figure A9419409600534
98.     H      H      H      Compound numbering R1    R 2   R 3   R 4     R 5 99.     H      H      H    H     
Figure A9419409600541
100.    H      H      H    -nC 3H 7 101.    H      H      H   
Figure A9419409600543
102.    H      H      H    -CH 2-CH 2-CH 2- 103.    H      H      H    -nC 3H 7 -nC 5H 11 104.    H      H      H      H    
Figure A9419409600544
Compound numbering R1    R 2   R 3    R 4    R 5 105.    H      H      H      H     106.    H      H      H      H    
Figure A9419409600552
107.    H      H      H      H     108.    H      H      H      H     Compound numbering R1    R 2   R 3    R 4       R 5 109.    H      H      H      H      
Figure A9419409600561
110.    H      H      H   
Figure A9419409600562
111.    H      H      H    -CH＝N-CH＝CH- 112.    H      H      H    -nC 3H 7  -nC 10H 21 113.    H      H      H   
Figure A9419409600563
Compound numbering R1    R 2   R 3    R 4    R 5 114.    H      H      H            
Figure A9419409600571
115.    H      H      H            
Figure A9419409600572
116.    H      H      H            
Figure A9419409600573
117.    H      H      H            
Figure A9419409600574
118.    H      H      H             Compound numbering R1    R 2   R 3    R 4    R 5 119.    H      H      H      H    
Figure A9419409600581
120.    H      H      H     
Figure A9419409600582
121.    H      H      H      H     122.    H      H      H      H     123.    H      H      H      H    
Figure A9419409600585
Compound numbering R1    R 2  R 3    R 4    R 5 124.    H      H      H      H     
Figure A9419409600591
125.    H      H      H      -CH 3 -C 2H 5 126.    H      H      H      H     
Figure A9419409600592
127.    H      H      H     
Figure A9419409600593
128.    H      H      H      Compound numbering R1   R 2   R 3     R 4    R 5 129.    H      H      H     
Figure A9419409600601
130.    H      H      H      131.    H      H      H      -C＝N-CH 2-CH 2-CH 2-Shuan NHyYan 132. H H H H-CH2-CH(OH)-CH 3Hydrochloride 133. H H H H-CH2-CH(OH)-CH 3San methyl sulfosalt 134. H H H H-CH2-CH(OH)-CH 3Tetrabutylammonium salt compound numbering R1    R 2   R 3    R 4    R 5 135.    H      H      H      H    
Figure A9419409600611
Hydrochloride 136. H H H H
Figure A9419409600612
137.    H      H      H      H    
Figure A9419409600613
Hydrochloride 138. H H H H
Figure A9419409600614
Tetrabutylammonium salt 139. H H H HSan methyl sulfosalt
The weeding screening test
The compound of listing in the previous table has been measured activity of weeding in the ratio and the whole bag of tricks of various uses.Provide the result of some mensuration below.The result who obtains in the weeding screening is subjected to the influence of series of factors, and these factors comprise: amount of sunlight, soil types, the PH of soil, temperature, humidity, the degree of depth of plantation, the vegetative period of plant, the ratio of use, and many other factorses.In all assay methods, all use the minimum active component that can change.Used the equipment and the state of the art of document that screening process is consistent with credible.
Weeding test before the bud
Handle the previous day several different weeds seed plant only contain micro-content organism sun-drenched fertile soil on the ground.Show the breeding situation among each row, a kind is gone with 1, and every row is crossed over the width (19.5 * 9.5 * 6cm) of aluminium sheet.The weeds of plantation is green fox-brush (green foxtail) (" Setvi "), wild oat (oat) (" Avefa ") barnyardgrass (Echinochloacrusgalli) (" Echcg ").The broad-leaved weeds of using is charlock (wild mustard also claims sinapsis alba) (" Sinar "), deer leaf grass (fiber crops) (" Abuth ") and morning glory (Ipomoea SPP.) (" I-poss ").Yellow nut sand-grass (Cyperus esculentus) (" Cypes ") and nutlets have also been planted in addition.The degree of depth of sowing is 1.0 to 1.5cm, and planting density is every row 3 to 25 strains, and this depends on the kind of plant.
Take by weighing 18.8mg and 74.7mg testing compound, in the 60ml wide-mouth bottle, be dissolved in 14ml and contain the 0.5%v/v polysorbas20 (polyoxyethylene sorbitol acid anhydride glylorin emulsifier) is in the deionized water of surfactant, prepares 1 and 4 kilogram/hectare solution respectively.If need dissolved compound, solubilizer again, inexcessive 2ml (15% sprayed volume).
Soil surface sprays in the linearity spraying workbench of a sealing, and workbench is equipped with nozzle, and nozzle exceeds soil line 30.5cm (12 inches).Proofread and correct the spraying workbench, make to discharge 748 liters/hectare (80% adds human relations/are), application percentage is 4.0kg/ hectare or 1kg/ hectare (Table II of face as follows).After the processing, aluminium sheet is put in the greenhouse, and thoroughly waters with shower nozzle.The environmental system in greenhouse provides natural daylight and artificial (using the halo metalized lamp) light to plant, makes to keep illumination in 14 hours every day.Daytime and evening temperature are protected respectively at 29 ℃ and 21 ℃.
Estimated and the controlled degree of record weeds in 17～21 days after the processing, and compared, obtain the percentage control rate of weeds with the growth of the weeds of identical kind same age on the undressed control board.Because all factors comprise: suppress to sprout, retardance is grown, deformity, and the plant injury of decolouring and other type is so the percentage control rate is the total injury to plant.The proportion of control is 0% to 100%, and wherein 0% expression does not have the control effect to plant growing, equals untreated control group, and 100% expression is killed fully.Dash is illustrated on the level of application and does not finish test.
Herbicidal evaluation behind the bud
According to the methodology of describing in the test before the bud, use identical kind, preparation soil and sowing.Plate is put into the greenhouse behind the bud under equivalent environment that the bud header board is described and condition, thoroughly waters with shower nozzle then.Plant growing 10 to 12 days (or reaching suitable vegetative period) before the medication.Medication behind long 3 to 4 leaves of weeds, broadleaved herb medication behind long 1 to 2 leaf.Yellow nut sand-grass is long to the medication afterwards of 7cm height.Identical spray solution with preparation in the test before the bud is being sprayed medicine from leaf 30.5cm eminence (12 English) to plant.Application percentage is 4.0kg/ hectare or 1.0kg/ hectare (Table III of face as follows).The plant of handling and then put back to the greenhouse, water every day, not wet leaves.Estimated the degree of weeds control in 17～21 days after the medication, record percentage control rate, and with identical kind, unprocessed, the weeds of same age compare.The percentage control range (0-100%) of estimating the bud pre-treatment also is used for the evaluation that bud is handled.
Table II
Pre-Ya Qian Shi Yan-Testina, (4.0kg/ha) compound numbering, wild oat, ECHCG, green bristlegrass, Shang Ma, Qian Niu flower, sinapsis alba, sand-grass, 1., 0, 0, 0, 0, 0, 0, 0, 2., 0, 0, 0, 0, 0, 0, 0, 3., 0, 0, 0, 0, 0, 0, 0, 4., 0, 0, 25, 0, 0, 0, 0, 5., 0, 0, 0, 0, 0, 0, 0, 6., 0, 0, 0, 0, 0, 0, 0, 7., 0, 0, 0, 0, 0, 0, 0, 8., 0, 0, 0, 0, 0, 0, 0, 9., 0, 0, 0, 0, 0, 0, 010., 0, 0, 0, 10, 0, 30, 011.*, 0, 0, 0, 0, 0, 0, 012.*, 0, 0, 0, 0, 0, 0, 013.*, 0, 0, 0, 0, 0, 0, 014., 0, 0, 0, 0, 0, 0, 015., 0, 0, 0, 0, 0, 0, 016., 0, 0, 0, 0, 0, 0, 017., 0, 0, 0, 0, 0, 0, 018., 0, 0, 0, 0, 0, 0, 019., 0, 0, 0, 0, 0, 0, 020., 0, 0, 0, 0, 0, 0, 0 compound numbering, wild oat, ECHCG, green bristlegrass, Shang Ma, Qian Niu flower, sinapsis alba, sand-grass 21., 0, 0, 0, 0, 0, 0, 022., 0, 0, 0, 0, 0, 0, 023.*, 0, 0, 0, 0, 0, 0, 024.*, 0, 0, 0, 0, 0, 0, 025.*, 0, 0, 0, 0, 0, 0, 026., 0, 0, 0, 0, 0, 0, 027.*, 0, 0, 0, 0, 0, 0, 028.*, 0, 0, 0, 0, 0, 0, 029.*, 0, 0, 0, 0, 0, 0, 030.*, 0, 0,--, 0, 0, 0, 031.*, 0, 0, 0, 0, 0, 0, 032.*, 0, 0, 0, 0, 0, 0, 033.*, 0, 0, 0, 0, 0, 0, 034.*, 0, 0, 0, 0, 0, 0, 035.*, 0, 0, 0, 0, 0, 0, 036.*, 0, 0, 0, 0, 0, 0, 037.*, 0, 0, 0, 0, 0, 0, 038.*, 0, 0, 0, 0, 0, 0, 039., 0, 0, 0, 0, 0, 0, 040.*, 0, 0, 0, 0, 0, 0, 041.*, 0, 0, 0, 0, 0, 0, 042.*, 0, 0, 0, 0, 0, 0, 043.*, 0, 0, 0, 0, 0, 0, 0 compound numbering, wild oat, ECHCG, green bristlegrass, Shang Ma, Qian Niu flower, sinapsis alba, sand-grass
44.*????????0????????0??????????0????????0????????0????????0???????0
45.*????????0????????0??????????0????????0????????0????????0???????0
46.*????????0????????0??????????0????????0????????0????????0???????0
47.*????????0????????0??????????0????????0????????0????????0???????0
48.*????????0????????0??????????0????????0????????0????????0???????0
49.*????????0????????0??????????0????????0????????0????????0???????0
50.*????????0????????0??????????0????????0????????0????????0???????0
51.*????????0????????0??????????0????????0????????0????????0???????0
52.*????????0????????0??????????0????????0????????0????????0???????0
53.*????????0????????0??????????0????????0????????0????????0???????0
54.*????????0????????0??????????0???????15???????25????????5???????0
55.*????????0????????0??????????0????????0????????0????????0???????0
56.*????????0????????0??????????0????????0????????0????????0???????0
57.*????????0????????0??????????0????????0????????0????????0???????0
58.*????????0????????0??????????0????????0????????0????????0???????0
59.*????????0????????0??????????0????????0????????0????????0???????0
60.*????????0????????0??????????0????????0????????0????????0???????0
61.*????????0????????0??????????0????????0????????0????????0???????0
62.*????????0????????0??????????0????????0????????0????????0???????0
63.*????????0????????0??????????0????????0????????0????????0???????0
64.* 0000000 compound number wild oat ECHCG green foxtail merchants fiber crops morning glory sinapsis alba sand-grass
65.*????????0?????????0????????0????????0????????0?????????0???????0
66.*????????0?????????0????????0????????0????????0?????????0???????0
67.*????????0?????????0????????0????????0????????0?????????0???????0
68.*????????0?????????0????????0????????0????????0?????????0???????0
69.*????????0?????????0????????0????????0????????0?????????0???????0
70.*????????0?????????0????????0????????0????????0?????????0???????0
71.*????????0?????????0????????0????????0????????0?????????0???????0
72.*????????0?????????0????????0????????0????????0?????????0???????0
73.*????????0?????????0????????0????????0????????0?????????0???????0
74.*????????0?????????0????????0????????0????????0?????????0???????0
75.*????????0?????????0????????0????????0????????0?????????0???????0
76.*????????0?????????0????????0????????0????????0?????????0???????0
77.*????????0?????????0????????0????????0????????0?????????0???????0
78.*????????0?????????0????????0????????0????????0?????????0???????0
79.*????????0?????????0????????0????????0????????0?????????0???????0
80.*????????0?????????0????????0????????0????????0?????????0???????0
81.*????????0?????????0????????0????????0????????0?????????0???????0
82.*????????0?????????0????????0????????0????????0?????????0???????0
83.*????????0?????????0????????0????????0????????0?????????0???????0
84.*????????0?????????0????????0????????0????????0?????????0???????0
85.*????????0?????????0????????0????????0????????0?????????0???????0
86.*????????0?????????0????????0????????0????????0?????????0???????0
87.*????????0?????????0????????0????????0????????0?????????0???????0
88.*, 0, 0, 0, 0, 0, 0, 0 compound numbering, wild oat, ECHCG, green bristlegrass, Shang Ma, Qian Niu flower, sinapsis alba, sand-grass, 89.*, 0, 0, 0, 0, 0, 0, 0, 90.*, 0, 0, 0, 0, 0, 0, 0, 91.*, 0, 0, 0, 0, 0, 0, 0, 92.*, 0, 0, 0, 0, 0, 0, 0, 93.*, 0, 0, 0, 0, 0, 0, 0, 94.*, 0, 0, 0, 0, 0, 0, 0, 95.*, 0, 0, 0, 0, 0, 0, 0, 96.*, 0, 0, 0, 0, 0, 0, 0, 97.*, 0, 0, 0, 0, 0, 0, 0, 98.*, 0, 0, 0, 0, 0, 0, 0, 99.*, 0, 0, 0, 0, 0, 0, 0, 100.*, 0, 0, 0, 0, 0, 0, 0, 101.*, 0, 0, 0, 0, 0, 0, 0, 102.*, 0, 0, 0, 0, 0, 0, 0, 103.*, 0, 0, 0, 0, 0, 0, 0, 104.*, 0, 0, 0, 0, 0, 0, 0, 105.*, 0, 0, 0, 0, 0, 0, 0, 106.*, 0, 0, 0, 0, 0, 0, 0, 107.*, 0, 0, 0, 0, 0, 0, 0, 108.*, 0, 0, 0, 0, 0, 0, 0, 109.*, 0, 0, 0, 0, 0, 0, 0, 110.*, 0, 0, 0, 0, 0, 0, 0, 111.*, 0, 0, 0, 0, 0, 0, 0, 112.*, 0, 0, 0, 0, 0, 0, 0 compound numbering, wild oat, ECHCG, green bristlegrass, Shang Ma, Qian Niu flower, sinapsis alba, sand-grass, 113.*, 0, 0, 0, 0, 0, 0, 0, 114.*, 0, 0, 0, 0, 0, 0, 0, 115.*, 0, 0, 0, 0, 0, 0, 0, 116.*, 0, 0, 0, 0, 0, 0, 0, 131.*, 0, 0, 0, 0, 0, 0, test Xia 0* Zai 1.0kg/ hectare
Table III
Postemergence test (4.0kg / ha) Compound No. wild oats ECHCG foxtail Shangma petunia white mustard sand grass 1.0 0 0 0 - 0. 2. 59595256090203. 105,300,560 0 4.100 100,100,100,100,100 50 5.100 100,100,100,100,100 80 6.100 100 10,070,100,100,207. 601,001,007,570,100 11 8. 00,000,009. 0 0 600090510. 101,070,510,801,511. * 100 959,580,701,002,512. * 100 100,100,709,510,030 13 * 60 901,002,020,100,514. 98989860 601001015. 50 606,015,701,002,516. 8,550,605,601,001,517. 00100010018. 55500585019. 6,030,100,303,010,015 20. 100,858,550,901,005 Compound No. wild oats ECHCG foxtail Shangma petunia white mustard sand D.21. 30505003095022. 1,009,898,989,010,070 23. * 404,080,151,095,524 * 1,001,001,007,010,010,025 25. * 100 100 100,601,001,002,026. 50,501,010,027 * 7,090,952,010,851,528. * 000,000,029. * 80 1,009,010,101,002,030. * 75506001050031 * 9,070,802,010,103,032. * 100 989,830,701,005,033. * 100 100,981,006,010,010 34. * 510400050035 * 506010010036 * 4060500010137 * 50305001030538 * 015205540039. 000000040 * 98988505301041 * 95609500982542. * 100 100,100,989,010,085 43. * 8080602010405 Compound No. wild oats ECHCG Setaria Shangma Morning Glory White mustard sand D.44. * 8,090,907,551,007,545. * 80855015560546 * 805,040,510,151,547 * 605305550 10 48. * 60,606,001,585,049 * 909,095,530,100,550. 000,000,051 * 1,009,510,075,851,002,552. * 1,001,009,550,651,001,053 * 5050525054 * 959,595,606,010,015 55. * 98155003025056. 000000057 * 959,510,010,159,810 58. * 40709025520559 * 95254059515060. * 100 100,100,709,010,010 61 * 2005000062 * 8,590,801,010,951,063. * 100 959,585,851,006,064. * 100 959,510,901,002,065 * 1,001,001,007,010,010,020 Compound No. wild oats ECHCG foxtail Shangma petunia white mustard sand D.66. * 10098983060 100 567 * 956,075,510,202,068 * 9,570,301,010,101,069. * 30203005201570 * 103,020,010,101,071 * 901001006010 906 072 * 1,001,001,009,010,010,050 73 * 5015205051074 * 0010005075 * 1,009,895,609,510,050 76. * 605015510 101 077 * 5015105515578 * 60105055579 * 75301510105580 * 907,025,515,251,081 * 50608555 85582 * 9,810,098,101,510,030 83. * 1,001,009,850,351,003,084. * 100 989,815,251,005,085 * 15402001090086 * 10098987015 100 587. * 100 100,100,752,010,020 88. * 9,810,098,703,090,589. * 001,005,100 Compound No. wild oats ECHCG foxtail Shangma petunia white mustard sand grass 90 * 75 8,010,060,101,003,091. * 100 100,100,959,810,060 92. * 100 100,100,809,010,015 93. * 1,009,810,098,901,001,094. * 0101010510095 * 40 40801015151096 * 859,095,302,090,597 * 10303010520098 * 1,009,895,505,098,599. * 100 98957010010015 100 * 100 1,009,070,309,010,101. * 100 60704020300102 * 50907010251005 103. * 100 859,515,308,510,104 * 0510205100105 * 75 7060105205106 * 506,015,551,510,107 * 505,050,051,510,108 * 6,030,305,103,010,109. * 30502055150110 * 85 909,830,151,005,111. * 100 981,007,510,010,030 112. * 101,510,510,200,113 * 051,005,100 Compound No. Shangma wild oats ECHCG foxtail grass sand petunia white mustard 114 * 01050550115 * 10,098,987,020,985 116. * 1,007,040,510,200,131. * 95 1,001,001,001,001,005 * at 1.0kg / ha measured at the data show that the compound of the present claim postemergence preemergence weed plants an effective, safe....

Claims (22)

1. Herbicidal combinations, said composition comprise compound and its agricultural salt of (A) general formula (I) Wherein
R 1Be hydrogen, hydroxyl, C 1-C 4Alkoxyl, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, hydroxyl-C 1-C 4-alkyl, hydroxyl-C 1-C 4-alkoxyl or N (R 6) (R 7), R wherein 6And R 7Independent separately is hydrogen or C 1-C 3Alkyl;
R 2And R 3Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Alkyl-S-(O) m-or substituted hydrocarbon radical-S-(O) m-; Or
R 2And R 3One forms 3-6 unit carbocyclic ring, and this carbocyclic ring is arbitrarily by halogen, hydroxyl, C 1-C 6Alkyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group or N (R 8) (R 9) replacement, wherein R 8And R 9Independent separately is hydrogen or C 1-C 12Alkyl;
R 4And R 5Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Alkyl-S-(O) m-; Replace hydrocarbon-S-(O) m-; Pyridine radicals; Substituted pyridinyl; Or general formula N (R 10) (R 11) base, R wherein 10And R 11Independent separately is hydrogen, alkyl or substituted hydrocarbon radical; Or
R 4And R 5The nitrogen-atoms that is connected with them forms aziridine piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl; the thiomorpholine sulfonyl, hexamethylene imine, piperidines, tetrahydropyridine; pyrazoles, imidazoles, pyrroles, triazole; tetrahydropyrimidine, glyoxalidine, pyrrolin; azetidine, perhydrogenate indoles, perhydrogenate quinoline; perhydrogenate isoquinolin, or ring such as pyrrolidines, wherein any ring all can be arbitrarily by C 1-C 12Alkyl, halogen, C 6-C 10Aryl is by halogen or C 1-C 6The C that alkyl replaces 1-C 10Aryl, C 7-C 16Aralkyl is by halogen or C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10-alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, phenoxy group, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 2-C 10Thiazolinyl or cyano group,
R 2And R 4Common nitrogen that is connected with them and carbon atom form aziridine, piperazine, morpholine, thiomorpholine; the thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethylene imine, piperidines; tetrahydropyridine, pyrazoles, imidazoles, pyrroles; triazole, the pyridine of tetrahydrochysene miaow, glyoxalidine, pyrrolin; azetidine, perhydrogenate indoles, perhydrogenate quinoline; perhydrogenate isoquinolin, or ring such as pyrrolidines, wherein any ring can be arbitrarily by C 1-C 12Alkyl, halogen, C 6-C 10Aryl is by halogen or C 1-C 6The C that alkyl replaces 6-C 10Aryl, C 7-C 16Aralkyl, by halogen or-C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, phenoxy group, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 1-C 10Thiazolinyl or cyano group replace;
M is zero, 1 or 2;
(B) their carrier of acceptable on the agrochemistry.
2. the composition of claim 1, wherein R 1Be hydrogen or hydroxyl.
3. the composition of claim 2, wherein R 3And R 4Independent separately is hydrogen or C 1-C 6Alkyl.
4. the composition of claim 3, wherein R 4And R 5Independent separately is hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, benzyl or by C 1-C 6The benzyl that alkyl or halogen replace.
5. the composition of claim 3, wherein R 4And R 5Form pyrrolidines or pyridine ring with the nitrogen-atoms that is connected jointly, this encircles arbitrarily by fluorine, hydroxyl, C 1-C 6Alkoxyl or C 1-C 6Alkyl replaces.
6. the composition of claim 1, wherein R 1Hydrogen, hydroxyl, halogen or C 1-C 4Alkyl; R 2And R 3Independent separately is C 1-C 12Alkyl; C 2-C 12Thiazolinyl; C 2-C 12Alkynyl; Halo-C 1-C 12Alkyl; Halo-C 2-C 12Thiazolinyl; Halo-C 2-C 12Alkynyl; C 6-C 14Aralkyl; C 1-C 12Alkoxyl; Or C 1-C 12Alkylthio group; R 4And R 5Independent separately is hydrogen; C 1-C 6Alkyl; C 2-C 6Thiazolinyl; C 2-C 6Alkynyl; Halo-C 1-C 6Alkyl; Halo-C 2-C 6Thiazolinyl; Halo-C 2-C 6Alkynyl; Pyridine radicals; Substituted pyridinyl; Phenyl; Substituted-phenyl; C 7-C 14Aralkyl; Or replacement C 7-C 14Aralkyl; Or R 4And R 5The nitrogen-atoms that is connected with them forms tetrahydropyrimidine jointly, tetrahydropyridine or imidazole ring, or form (CH 2) n-N-ring, wherein n is 3-6, these encircle arbitrarily by halogen, hydroxyl, C 1-C 6Alkoxyl, nitro, C 1-C 6Alkyl, C 7-C 16Aralkyl or C 1-C 6Alkylthio group replaces.
7. the composition of claim 6, wherein R 1Be hydrogen or hydroxyl; R 2And R 3Independent separately is hydrogen or C 1-C 6Alkyl; R 4And R 5Independent separately is hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, benzyl, C 1-C 6The benzyl that alkyl or halogen replace; Or R 4And R 5Form pyrrolidines or piperidine ring with the nitrogen-atoms that is connected jointly, these encircle arbitrarily by fluorine, hydroxyl, C 1-C 6Alkoxyl or C 1-C 6Alkyl replaces.
8. the composition of claim 1, wherein component (A) comprises 2-(1-pyrrolidinyl) ethyl-1, the two phosphonic acids of 1-; 2-(1-piperidyl) ethyl-1, the two phosphonic acids of 1-; 2-(third amino) ethyl-1, the two phosphonic acids of 1-; 2-(N-methyl-N-ethylamino) ethyl-1, the two phosphonic acids of 1-; 2-(Aden's amino) ethyl-1, the two phosphonic acids of 1-; 2-(2-acrylic amino) ethyl-1, the two phosphonic acids of 1-; 2-(R-alpha-methyl benzyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(2-methyl-propyl amino) ethyl-1, the two phosphonic acids of 1-; 2-(1-(4-methyl isophthalic acid, 3-imidazole radicals)) ethyl-1, the two phosphonic acids of 1-; Or 2-(1-(1,2,3,6-tetrahydro pyridyl)) ethyl-1, the two phosphonic acids of 1-;
9. the method for controlling plant growth, this method comprise the position of the compound of the general formula of herbicidally effective amount (I) or its agricultural salt being used this class plant: Wherein
R 1Be hydrogen, hydroxyl, C 1-C 4Alkoxyl, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, hydroxyl C 1-C 4Alkyl, hydroxyl-C 1-C 4Alkoxyl or N (R 6) (R 7), R wherein 6And R 7Independent separately is hydrogen or C 1-C 3Alkyl;
R 2And R 3Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Alkyl-S-(O) m-; Or substituted hydrocarbon radical-S-(O) m-;
R 2And R 3The common 3-6 unit carbocyclic ring that forms, this encircles arbitrarily by halogen, hydroxyl, C 1-C 6Alkyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group or N (R 8) (R 9) replace a R wherein 8And R 9Independent separately is hydrogen or C 1-C 12Alkyl;
R 4And R 5Independent separately is hydrogen; Alkyl; Substituted hydrocarbon radical; Oxyl; Replace oxyl; Sulfenyl; Replace sulfenyl; Pyridine radicals; Or general formula N (R 10) (R 11) base, R wherein 10And R 11Independent separately is hydrogen, alkyl or substituted hydrocarbon radical; Or
R 4And R 5Form aziridine, piperazine, morpholine, thiomorpholine with the nitrogen-atoms that is connected jointly; the thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimino, piperidines; tetrahydropyridine, pyrazoles, imidazoles, pyrroles; triazole, the pyridine of tetrahydrochysene miaow, glyoxalidine, pyrrolin; azetidine, perhydrogenate indoles, perhydrogenate quinoline; perhydrogenate isoquinolin, or ring such as pyrrolidines, wherein arbitrary ring all can be arbitrarily by C 1-C 12Alkyl, halogen, C 6-C 10Aryl is by halogen or C 1-C 6The C that alkyl replaces 6-C 10Aryl, C 7-C 16Aralkyl is by halogen or C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, benzene nitrogen base, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 2-C 10Thiazolinyl or cyano group replace;
R 2And R 4Common nitrogen that is connected with them and carbon atom form aziridine, piperazine, morpholine, thiomorpholine; the thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimino, piperidines; tetrahydropyridine, pyrazoles, imidazoles, pyrroles; triazole, tetrahydropyrimidine, glyoxalidine, pyrrolin; azetidine, perhydrogenate indoles, perhydrogenate quinoline; perhydrogenate isoquinolin, or ring such as pyrrolidines, wherein arbitrary ring all can be arbitrarily by C 1-C 12Alkyl, halogen, C 6-C 10Aryl, halogen or C 1-C 6The C that alkyl replaces 6-C 10Aryl, C 7-C 16Aralkyl, halogen or C 1-C 6The C that alkyl replaces 7-C 16Aralkyl, nitro, halo-C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphonyl, phenoxy group, halogen or C 1-C 6The phenoxy group that alkyl replaces, C 2-C 10Thiazolinyl or cyano group replace; Or
M is zero, 1 or 2
10. the method for claim 9, wherein R 1Be hydrogen or hydroxyl.
11. the method for claim 10, wherein R 2And R 3Independent separately is hydrogen or C 1-C 6Alkyl.
12. the method for claim 11, wherein R 4And R 5Independent separately is hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, benzyl or C 1-C 6The benzyl that alkyl or halogen replace.
13. the method for claim 11, wherein R 4And R 5Form pyrrolidines or piperidine ring with the nitrogen-atoms that is connected jointly.
14. the method for claim 9, wherein R 1Be hydrogen, hydroxyl, halogen or C 1-C 4Alkyl; R 2And R 3Independent separately is C 1-C 12Alkyl; C 2-C 12Thiazolinyl; C 2-C 12Alkynyl; Halo-C 2-C 12Alkyl; Halo-C 2-C 12Thiazolinyl; Halo-C 2-C 12Alkynyl; C 6-C 14Aralkyl; C 1-C 12Alkoxyl; Or C 1-C 12Alkylthio group;
R 4And R 5Independent separately is hydrogen; C 1-C 6Alkyl; C 2-C 6Thiazolinyl; C 2-C 6Alkynyl; Halo-C 1-C 6Alkyl; Halo-C 2-C 6Thiazolinyl; Halo-C 2-C 6Alkynyl; Pyridine radicals; Substituted pyridinyl; Phenyl; Or substituted-phenyl; C 7-C 14Aralkyl; C 7-C 14Substituted aralkyl; Or
R 4And R 5The common nitrogen-atoms that is connected with them forms tetrahydropyrimidine; Tetrahydropyridine; Or imidazole ring; Or-(CH 2) n-N-ring, wherein, n is 3-6; They are arbitrarily by halogen, hydroxyl, C 1-C 6Alkoxyl, nitro, C 1-C 6Alkyl, C 7-C 16Aralkyl or C 1-C 6Alkylthio group replaces.
15. the method for claim 14/, wherein
R 1Be hydrogen or hydroxyl;
R 2And R 3Independent separately is hydrogen or C 1-C 6Alkyl;
R 4And R 5Independent separately is hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, benzyl, C 1-C 6The benzyl that alkyl or halogen replace; Or
R 4And R 5The common nitrogen-atoms that is connected with them forms pyrrolidines or piperidine ring, and these encircle arbitrarily by fluorine, hydroxyl, C 1-C 6Alkoxyl or C 1-C 6Alkyl replaces.
16. the method for claim 9, wherein said compound is: 2-(1-pyrrolidinyl) ethyl-1,1-bis phosphoric acid; 2-(1-piperidyl) ethyl-1, the 1-bis phosphoric acid; 2-(third amino) ethyl-1, the 1-bis phosphoric acid; 2-(N, N-Methylethyl amino) ethyl-1, the 1-bis phosphoric acid; 2-(n-butyl amine base) ethyl-1, the 1-bis phosphoric acid; 2-(2-acrylic amino) ethyl-1, the 1-bis phosphoric acid; 2-(R-alpha-methyl benzyl amino) ethyl-1, the 1-bis phosphoric acid; 2-(2-methyl-propyl amino) ethyl-1, the 1-bis phosphoric acid; 2-(1-(4-methyl isophthalic acid, 3-imidazole radicals)) ethyl-1, the 1-bis phosphoric acid; Or 2-(1-(1,2,3, the 6-tetrahydro pyridyl)) ethyl-1, the 1-bis phosphoric acid.
17. have compound or its agricultural salt of general formula I I structure: Wherein
R 12And R 13Independent separately is hydrogen, C 1-C 6The straight or branched alkyl, hydroxyl, C 2-C 6Thiazolinyl, C 1-C 6Alkoxyl or C 1-C 6Alkoxy-C 1-C 6Alkyl.
The compound of 18 general formula III or its agricultural salt:
Figure A9419409600092
Wherein q is 0-10; J is 0-3; R 14And R 15Independently hydrogen or C separately 1-C 6Alkyl; Ar is a phenyl, pyridine, pyrimidine, pyrrole pyridazine, naphthalene, pyrazoles, imidazoles, triazole, piperazine azoles, furans, thiophene, pyrroles, oxazole or thiadiazoles; R 16Be halogen, C 1-C 10Alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, halo-C 1-C 10Alkyl, C 1-C 10Alkoxyl, C 1-C 10Alkylthio group, C 1-C 10Alkyl sulphinyl, phenoxy group, substituent phenoxy, C 2-C 10Thiazolinyl or cyano group; R 17, R 18And R 19Independent separately is hydrogen, C 1-C 10Alkyl, C 1-C 10Substituted alkyl, C 7-C 10Aralkyl or C 2-C 10Thiazolinyl.
19. general formula (compound of IV or its agricultural salt:
Figure A9419409600101
Wherein A is C 3-C 6Alkylidene radical, this base is arbitrarily by C 1-C 6Alkyl replaces.
20. the compound of general formula (V) or its agricultural salt:
Figure A9419409600102
R wherein 20Be hydrogen or hydroxyl; B is C 2-C 4Alkylidene connects base, and this base is arbitrarily by C 1-C 6Alkyl replaces.
21. the compound of general formula (VI) or its agricultural salt: R wherein 21And R 22Independent separately is C 1-C 6Alkyl or constitute C jointly 3-C 5Alkylidene radical, this alkylidene radical is arbitrarily by C 1-C 6Alkyl replaces.
22. the compound of general formula (VII): Wherein t is 2,3 or 4; R 23And R 24Independent separately is hydrogen, C 1-C 10Alkyl, halogen, nitro, C 1-C 9Alkoxyl, C 1-C 10Aralkyl, cyano group, trifluoromethyl or be-unsaturated unit; R 25Be hydrogen, C 1-C 6Alkyl, C 7-C 10Aralkyl, halogen, nitro, trifluoromethyl or cyano group.
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