CN105541581B - A kind of stereospecific synthesis of tetra-substituted olefin compounds and method thereof - Google Patents
A kind of stereospecific synthesis of tetra-substituted olefin compounds and method thereof Download PDFInfo
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- toluene
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- -1 olefin compounds Chemical class 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract 5
- 230000015572 biosynthetic process Effects 0.000 title abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title abstract description 30
- 230000000707 stereoselective effect Effects 0.000 title abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 159
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 58
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 53
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 2
- 238000003818 flash chromatography Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 100
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 69
- 239000000243 solution Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 26
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 25
- 238000005160 1H NMR spectroscopy Methods 0.000 description 25
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 25
- 239000003208 petroleum Substances 0.000 description 25
- 239000000758 substrate Substances 0.000 description 23
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 8
- QMYPTKKUYUWNII-UHFFFAOYSA-N 2-chlorohept-2-enal Chemical compound ClC(C=O)=CCCCC QMYPTKKUYUWNII-UHFFFAOYSA-N 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- IBZDVYYTEPRIGF-NXVVXOECSA-N (2Z)-2-(1-phenylbutan-2-ylidene)hexanal Chemical class C(CCC)/C(/C=O)=C(\CC)/CC1=CC=CC=C1 IBZDVYYTEPRIGF-NXVVXOECSA-N 0.000 description 3
- OSNBYKPHJVWFPL-MSUUIHNZSA-N (2Z)-2-[1-(4-methylphenyl)butan-2-ylidene]hexanal Chemical class CCCC/C(=C(\CC)/CC1=CC=C(C=C1)C)/C=O OSNBYKPHJVWFPL-MSUUIHNZSA-N 0.000 description 3
- YNBMLYPOIDOVIL-FOCLMDBBSA-N (E)-3-(cyclohexylmethyl)-4-methyl-2-propylpent-2-enal Chemical class CCC/C(=C(/CC1CCCCC1)\C(C)C)/C=O YNBMLYPOIDOVIL-FOCLMDBBSA-N 0.000 description 3
- XGNQWFVDKLNVOA-UHFFFAOYSA-N 2-benzylpent-2-enal Chemical class CCC=C(C=O)CC1=CC=CC=C1 XGNQWFVDKLNVOA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CPEGDAMKSMZUSB-UHFFFAOYSA-N C(C1=CC=CC=C1)C(C=O)=C=CC Chemical compound C(C1=CC=CC=C1)C(C=O)=C=CC CPEGDAMKSMZUSB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- AUCOQXJDRCYQCE-UHFFFAOYSA-N hepta-1,4-dien-3-one Chemical compound CCC=CC(=O)C=C AUCOQXJDRCYQCE-UHFFFAOYSA-N 0.000 description 3
- XDFUNZJKZIEFPV-UHFFFAOYSA-N 1-(2,3,8,8-tetramethyl-1,3,4,4a,5,6,7,8a-octahydronaphthalen-2-yl)ethanol Chemical compound C1C(C)C(C(O)C)(C)CC2C1CCCC2(C)C XDFUNZJKZIEFPV-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- MKRVHLWAVKJBFN-UHFFFAOYSA-N diphenylzinc Chemical compound C=1C=CC=CC=1[Zn]C1=CC=CC=C1 MKRVHLWAVKJBFN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- OWQUYBAASOSGNO-CDNKMLFNSA-N 2-[[(Z)-N-(2-hydroxy-5-sulfoanilino)-C-phenylcarbonimidoyl]diazenyl]benzoic acid Chemical compound C1=CC=C(C=C1)/C(=N/NC2=C(C=CC(=C2)S(=O)(=O)O)O)/N=NC3=CC=CC=C3C(=O)O OWQUYBAASOSGNO-CDNKMLFNSA-N 0.000 description 1
- NYZVECNZMHKDGQ-UHFFFAOYSA-N C(C1=CC=CC=C1)C(C=O)=C=CCCC Chemical compound C(C1=CC=CC=C1)C(C=O)=C=CCCC NYZVECNZMHKDGQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000265 myristoleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical compound [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
- 229940043798 zincon Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种立体专一性合成四取代烯烃类化合物及其新方法，通过2,3‑联烯醛与有机锌试剂的共轭加成反应，再进一步用酸淬灭，高区域选择性和高立体选择性地合成四取代烯烃类化合物。本发明方法操作简单，原料和试剂易得，反应具有高区域选择性，高立体选择性，官能团兼容性较好，产物易分离纯化，可直接得到立体结构单一的四取代烯烃类化合物。The invention discloses a stereospecific synthesis of tetra-substituted olefin compounds and a novel method thereof. Through the conjugate addition reaction of 2,3-alkenal and an organozinc reagent, and further quenching with acid, high regioselectivity is achieved. Synthesis of tetra-substituted alkenes in a stable and highly stereoselective manner. The method of the invention is simple to operate, the raw materials and reagents are readily available, the reaction has high regioselectivity, high stereoselectivity, good functional group compatibility, easy separation and purification of the product, and can directly obtain a tetra-substituted olefin compound with a single stereostructure.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of four substituted olefine class chemical combination of Stereospecific synthesis
Object and its method.
Background technique
The single compound of stereochemical structure has a wide range of applications in life science, medicine and chemistry.Its neutral body knot
The single alkene of structure is indispensable a kind of compound.It is well known that the isomers of various configuration may have different lifes
Manage activity (Harper, M.J.K.；Walpole,A.L.Nature 1966,212,87).Existing compound stereoscopic structure it is single four
The method of substituted olefine has limitation mostly, generally all obtains the mixture of stereoisomer, and cannot get four single substitutions
Alkene (Flynn, A.B.；Ogilvie,W.W.Chem.Rev.2007,107,4698-4745；Mori,
M.Eur.J.Org.Chem.2007,4981-4993；Shindo,M.；Matsumoto,K.Top.Curr.Chem.2012,327,
1-32.；Paek,S.-M.Molecules 2012,17,3348-3358).Therefore develop a kind of to go out from raw material simple and easy to get
Hair, synthesizing to stereocpecificity four substituted olefines is the important breakthrough to existing synthetic method.
Summary of the invention
The present invention joins the conjugate addition reaction of olefine aldehydr and organic zinc reagent by 2,3-, is further quenched with acid, high area
Synthesize four substituted olefine class compounds to field selectivity and highly-solid selectively.The method of the present invention is easy to operate, raw materials and reagents
It is easy to get, reaction has high regioselectivity, and highly-solid selectively, functional group compatibility is preferable, the easily separated purifying of product, can be direct
Obtain four single substituted olefine class compounds of stereochemical structure.
The present invention is achieved through the following technical solutions:
Four single substituted olefine class compounds of a kind of stereochemical structure, the structure such as formula of the four substituted olefines class compound
(I) shown in:
In formula (I),
R is alkyl or aryl；R1For alkyl or allyl or benzyl；R2For aryl or benzyl or alkyl or have functional group
Alkyl.
As a further improvement, R of the present invention is level-one or secondary alkyl；R1For the alkyl of C1~C4；R2For C1
The alkyl of~C10.
As a further improvement, R of the present invention is ethyl or butyl or isopropyl or phenyl；R1For methyl or second
Base or propyl or butyl or allyl or benzyl；R2For methyl or heptyl or nonyl or decyl or cyclohexyl or benzyl or 3- chlorine third
Base or 8- nonenyl or phenyl or p-methylphenyl.
A kind of method that four substituted olefine class compounds are synthesized the invention also discloses stereocpecificity, described 2,3-
The generation conjugate addition reaction for joining olefine aldehydr and the high regioselectivity of organic zinc reagent, is further quenched with acid, obtains the four of formula (1)
Substituted olefine class compound, reaction equation are as follows:
In reaction equation (a),
R is alkyl or aryl；R1For alkyl or allyl or benzyl；R2For aryl or benzyl or alkyl or have functional group
Alkyl.
As a further improvement, of the present invention, specific preparation process is as follows:
2,3- connection olefine aldehydr and toluene are sequentially added into dry reaction flask under nitrogen protection, being added dropwise at a temperature of first has
Machine zincon, is stirred to react at the first temperature, is then added dropwise carboxylic acid at the first temperature, gos up to being stirred to react at room temperature
Afterwards, dilute hydrochloric acid, saturated sodium bicarbonate solution are successively used, saturated sodium chloride solution is washed, and water phase is merged, and water phase is extracted with ether, is closed
And organic phase, concentration, rapid column chromatography obtain single (1) the four substituted olefine class of formula of stereochemical structure described in claim 1
Close object.
As a further improvement, carboxylic acid of the present invention includes acetic acid or propionic acid.
As a further improvement, the first temperature of the present invention is -30 DEG C to 30 DEG C.
As a further improvement, the molar ratio of 2,3- connection olefine aldehydr of the present invention and the organic zinc reagent is 1.0:
1.8~3.0.
Beneficial effects of the present invention are as follows:
The method of four substituted olefine class compounds is synthesized the invention discloses a kind of stereocpecificity.Present invention preparation side
Method overcomes the drawbacks of conventional method, including following advantages: mild condition, and functional group compatibility is good, and reaction has high three-dimensional selection
Property and high regioselectivity, product are easily separated, directly obtain four single substituted olefine class compounds of stereochemical structure.
Specific embodiment
In conjunction with following specific embodiments and reaction equation, the present invention is described in further detail, and the present invention protects not office
It is limited to following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and
Advantage is all included in the present invention, and using appended claims as protection scope.Implement process of the invention, item
Part, reagent, experimental method etc. are among the general principles and common general knowledge in the art in addition to what is specifically mentioned below, this
There are no special restrictions to content for invention.Following embodiment helps to understand the present invention, but does not limit the scope of the present invention.
Note: the equiv. in following embodiment reaction equation indicates equivalent；Mmol expression mM；Et2Zn indicates diethyl
Zinc；n-Bu2Zn indicates dibutyl zinc；i-Pr2Zn indicates diisopropyl zinc；Ph2Zn indicates diethyl zinc；Toluene indicates first
Benzene；AcOH indicates acetic acid.
The synthesis of embodiment 1 (Z) -2,3- diethyl -2- fulure (001)
A dry Shi Lanke reaction flask is taken, substitutes gas three times under nitrogen.Under nitrogen protection, in reaction flask successively
14 carbon of 2- ethyl -2,3-, two olefine aldehydr (0.2358g, 1.0mmol) and toluene (20mL) is added, uses injection under -10 DEG C of stirrings
It is added dropwise diethyl zinc solution (1.2mL, 2.0M in toluene, 2.4mmol), is dripped off in 4 minutes.Reaction stirs 1 at -10 DEG C
Hour, acetic acid (2mL) then is added dropwise with injection under -10 DEG C of stirrings, is dripped off in 2 minutes, goes back up to room temperature later.20 minutes
Afterwards, ethyl acetate (20mL) is added, successively uses dilute hydrochloric acid (20mL), saturated sodium bicarbonate solution (20mL), saturated sodium-chloride is molten
Liquid (20mL) is washed, and water phase is merged, and water phase is extracted with ether (20mL × 2), merges organic phase, and anhydrous sodium sulfate dries, filters, and is revolved
Rapid column chromatography separation (petroleum ether (30-60 DEG C)/ethyl acetate=100:1) after solvent is gone to obtain (Z) -2,3- diethyl -2-
Fulure (0.2339g, 88%): liquid；1HNMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.53 (t, J=
8.0Hz,2H,CH2),2.36-2.19(m,4H,CH2×2),1.54-1.42(m,2H,CH2),1.41-1.18(m,16H,CH2×
8), 1.10 (t, J=7.7Hz, 3H, CH3), 0.94 (t, J=7.5Hz, 3H, CH3), 0.88 (t, J=6.6Hz, 3H, CH3)；13C
NMR(75MHz,CDCl3)δ191.1,163.8,137.7,31.7,30.7,30.0,29.54,29.45,29.4,29.25,
29.18,27.3,22.5,18.2,13.9,12.7；IR(neat)ν(cm-1)2961,2925,2872,2854,2752,1668,
1620,1463,1397,1376,1337,1287,1253,1155,1059；MS (70ev, EI) m/z (%) 266 (M+,31.47),
237(100)；HRMS calcd for C18H34O[M+]:266.2610,found:266.2613.
The synthesis of embodiment 2 (Z) -2,3- diethyl -2- tridecylene aldehyde (002)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- ethyl -2,3- oleatridecadiene aldehyde
(0.2221g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -2,3- diethyl -2- tridecylene aldehyde (0.2273g, 90%) (petroleum ether (30-60 DEG C)/ethyl acetate
=100:1): liquid；1HNMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.53 (t, J=7.8Hz, 2H, CH2),
2.34-2.20(m,4H,CH2×2),1.57-1.42(m,2H,CH2),1.41-1.19(m,14H,CH2× 7), 1.10 (t, J=
7.5Hz,3H,CH3), 0.94 (t, J=7.7Hz, 3H, CH3), 0.88 (t, J=6.8Hz, 3H, CH3)；13C NMR(75MHz,
CDCl3)δ191.2,163.9,137.7,31.7,30.7,30.0,29.6,29.41,29.39,29.3,29.2,27.3,22.5,
18.2,13.9,12.7；IR(neat)ν(cm-1)2961,2926,2855,2752,1669,1618,1464,1376,1336,
1287,1251,1155,1060；MS (70ev, EI) m/z (%) 252 (M+,30.82),223(100)；HRMS calcd for
C17H32O[M+]:252.2453,found:252.2448.
The synthesis of embodiment 3 (Z) -2- methyl -3- ethyl -2- tridecylene aldehyde (003)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- methyl -2,3- oleatridecadiene aldehyde
(0.2076g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -2- methyl -3- ethyl -2- tridecylene aldehyde (0.2181g, 92%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.09 (s, 1H, CHO), 2.55 (t, J=7.8Hz, 2H,
CH2), 2.28 (q, J=7.5Hz, 2H, CH2),1.75(s,3H,CH3),1.58-1.41(m,2H,CH2),1.40-1.17(m,
14H,CH2× 7), 1.08 (t, J=7.7Hz, 3H, CH3), 0.88 (t, J=6.8Hz, 3H, CH3)；13C NMR(75MHz,
CDCl3)δ191.4,164.5,131.6,31.8,30.5,30.4,29.6,29.5,29.4,29.3,29.2,28.1,22.6,
14.0,11.9,10.1；IR(neat)ν(cm-1)2957,2925,2855,2752,1671,1623,1467,1396,1377,
1325,1282,1156,1029；MS (70ev, EI) m/z (%) 238 (M+,27.08),43(100)；HRMS calcd for
C16H30O[M+]:238.2297,found:238.2297.
The synthesis of embodiment 4 (Z) -3- ethyl -2- propyl -2- undecylenic aldehyde (004)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -2,3- undecadienal
(0.2078g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -3- ethyl -2- propyl -2- undecylenic aldehyde (0.2090g, 88%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.53 (t, J=7.8Hz, 2H,
CH2),2.35-2.15(m,4H,CH2×2),1.60-1.42(m,2H,CH2),1.41-1.18(m,12H,CH2×6),1.09
(t, J=7.5Hz, 3H, CH3),0.96-0.82(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ191.6,164.5,
136.3,31.7,30.9,30.0,29.6,29.3,29.1,27.5,27.0,22.7,22.5,14.1,14.0,12.7；IR
(neat)ν(cm-1)2959,2927,2869,2857,2753,1670,1617,1464,1394,1377,1346,1154,1090,
1066；MS (70ev, EI) m/z (%) 238 (M+,45.52),41(100)；HRMS calcd for C16H30O[M+]:
238.2297,found:238.2300.
The synthesis of embodiment 5 (Z) -3- ethyl -2- propyl -2- tridecylene aldehyde (005)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -2,3- oleatridecadiene aldehyde
(0.2359g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -3- ethyl -2- propyl -2- tridecylene aldehyde (0.2314g, 87%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.53 (t, J=7.8Hz, 2H,
CH2),2.35-2.15(m,4H,CH2×2),1.57-1.41(m,2H,CH2),1.40-1.19(m,16H,CH2×8),1.09
(t, J=7.7Hz, 3H, CH3),0.95-0.81(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ191.5,164.4,
136.3,31.8,30.9,30.0,29.6,29.5,29.4,29.3,29.2,27.5,27.0,22.7,22.6,14.1,14.0,
12.7；IR(neat)ν(cm-1)2959,2926,2855,2753,1669,1617,1464,1397,1377,1348,1153,
1067；MS (70ev, EI) m/z (%) 266 (M+,35.18),43(100)；HRMS calcd for C18H34O[M+]:
266.2610,found:266.2614.
The synthesis of embodiment 6 (Z) -3- ethyl -2- propyl -2- fulure (006)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 14 carbon of 2- propyl -2,3-, two olefine aldehydr
(0.2501g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.2mL, 2.0M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -3- ethyl -2- propyl -2- fulure (0.2521g, 90%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.53 (t, J=7.8Hz, 2H,
CH2),2.35-2.15(m,4H,CH2×2),1.57-1.41(m,2H,CH2),1.40-1.20(m,18H,CH2×9),1.09
(t, J=7.5Hz, 3H, CH3),0.96-0.82(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ191.5,164.4,
136.3,31.8,30.9,30.0,29.6,29.5,29.4,29.3,29.2,27.5,27.0,22.7,22.6,14.1,14.0,
12.7；IR(neat)ν(cm-1)2959,2926,2869,2854,2753,1670,1618,1465,1397,1377,1349,
1326,1230,1154,1067；MS (70ev, EI) m/z (%) 280 (M+,62.68),237(100)；HRMS calcd for
C19H36O[M+]:280.2766,found:280.2764.
The synthesis of embodiment 7 (Z) -2- propyl -3- (cyclohexyl methyl) -2- pentenals (007)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -4- cyclohexyl -2,3- fourth two
Olefine aldehydr (0.1921g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol)
(Z) -2- propyl -3- (cyclohexyl methyl) -2- pentenals (0.1911g, 86%) (petroleum ether (30-60 is obtained with acetic acid (2mL)
DEG C)/ethyl acetate=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.05 (s, 1H, CHO), 2.45 (d, J=
7.2Hz,2H,CH2),2.34-2.17(m,4H,CH2×2),1.81-1.59(m,5H,CH and CH2×2),1.55-1.13
(m,6H,CH2× 3), 1.08 (t, J=7.5Hz, 3H, CH3),1.03-0.85(m,5H,CH2and CH3)；13C NMR(75MHz,
CDCl3)δ191.4,162.6,137.6,38.2,36.9,33.2,27.5,27.1,26.1,22.7,14.1,12.6；IR
(neat)ν(cm-1)2960,2926,2853,2755,1668,1615,1449,1397,1376,1349,1324,1293,1269,
1154,1093,1068,1038；MS (70ev, EI) m/z (%) 222 (M+,23.11),55(100)；HRMS calcd for
C15H26O[M+]:222.1984,found:222.1986.
The synthesis of embodiment 8 (Z) -3- ethyl -2- propyl -5- phenyl -2- pentenals (008)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl 5- phenyl -2,3- pentadiene
Aldehyde (0.1997g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and
Acetic acid (2mL) obtain (Z) -3- ethyl -2- propyl -5- phenyl -2- pentenals (0.2068g, 90%) (petroleum ether (30-60 DEG C)/
Ethyl acetate=50:1): liquid；1H NMR(300MHz,CDCl3)δ9.86(s,1H,CHO),7.31-7.23(m,2H,ArH),
7.22-7.08(m,3H,ArH),2.88-2.73(m,4H,CH2× 2), 2.28 (q, J=7.7Hz, 2H, CH2),2.23-2.14
(m,2H,CH2),1.38-1.23(m,2H,CH2), 1.10 (t, J=7.5Hz, 3H, CH3), 0.90 (t, J=7.4Hz, 3H,
CH3)；13C NMR(75MHz,CDCl3)δ191.1,162.0,140.3,136.9,128.4,128.3,126.2,36.5,31.8,
27.3,27.1,22.6,14.2,12.6；IR(neat)ν(cm-1)3085,3062,3027,2962,2933,2872,2756,
1667,1615,1496,1464,1454,1397,1377,1347,1323,1292,1152,1075；MS(70ev,EI)m/z
(%) 230 (M+,1.05),91(100)；HRMS calcd for C16H22O[M+]:230.1671,found:230.1673.
The synthesis of the chloro- 2- heptenal (009) of embodiment 9 (Z) -3- ethyl -2- propyl -7-
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: chloro- 2, the 3- heptadienal of 2- propyl -7-
(0.1870g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -3- ethyl -2- propyl -7- chloro- 2- heptenal (0.1890g, 87%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=20:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 3.57 (t, J=6.3Hz, 2H, CH2),
2.58 (t, J=8.0Hz, 2H, CH2),2.37-2.16(m,4H,CH2×2),1.90-1.77(m,2H,CH2),1.74-1.60
(m,2H,CH2),1.40-1.24(m,2H,CH2), 1.11 (t, J=7.5Hz, 3H, CH3), 0.91 (t, J=7.4Hz, 3H,
CH3)；13C NMR(75MHz,CDCl3)δ191.3,163.2,136.8,44.4,32.2,29.1,27.8,27.4,27.1,
22.7,14.2,12.7；IR(neat)ν(cm-1)2961,2932,2871,2756,1667,1616,1462,1456,1399,
1377,1348,1301,1225,1154,1067；MS (70ev, EI) m/z (%) 218 (M+(37Cl),17.40),216(M+
(35Cl),48.51),55(100)；HRMS calcd forC12H21O35Cl[M+]:216.1281,found:216.1279.
The synthesis of embodiment 10 (Z) -3- ethyl -2- propyl -2,12- oleatridecadiene aldehyde (010)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -2,3,12- tridecatriene
Aldehyde (0.2338g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.2mL, 2.0M in toluene, 2.4mmol) and
Acetic acid (2mL) obtains (Z) -3- ethyl -2- propyl -2,12- oleatridecadiene aldehyde (0.2374g, 90%) (petroleum ether (30-60
DEG C)/ethyl acetate=100:1): liquid；1H NMR(300MHz,CDCl3)δ10.07(s,1H,CHO),5.90-5.72(m,1H,
=CH), 5.05-4.88 (m, 2H ,=CH2), 2.53 (t, J=7.8Hz, 2H, CH2),2.36-2.15(m,4H,CH2×2),
2.04 (q, 2H, J=7.0Hz, CH2),1.57-1.20(m,14H,CH2× 7), 1.09 (t, J=7.7Hz, 3H, CH3),0.90
(t, J=7.4Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ191.5,164.4,139.0,136.3,114.1,33.7,
30.9,30.0,29.6,29.2,28.9,28.8,27.5,27.0,22.7,14.1,12.7；IR(neat)ν(cm-1)3076,
2962,2928,2856,2754,1735,1669,1641,1617,1464,1376,1291,1229,1153；MS(70ev,EI)
264 (M of m/z (%)+,20.23),55(100)；HRMS calcd for C18H32O[M+]:264.2453,found:
264.2451.
The synthesis of embodiment 11 (Z) -2- propyl -3- (4- methylbenzyl) -2- pentenals (011)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -4- (4- aminomethyl phenyl) -2,
3- butadiene aldehyde (0.1999g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.2mL, 2.0M in toluene,
2.4mmol) and acetic acid (2mL) obtains (Z) -2- propyl -3- (4- methylbenzyl) -2- pentenals (0.1956g, 85%) (petroleum
Ether (30-60 DEG C)/ethyl acetate=100:1): liquid；1HNMR(300MHz,CDCl3)δ10.18(s,1H,CHO),7.11(d,J
=7.8Hz, 2H, ArH), 7.04 (d, J=8.1Hz, 2H, ArH), 3.90 (s, 2H, CH2),2.38-2.17(m,7H,CH3and
CH2×2),1.48-1.31(m,2H,CH2), 1.06 (t, J=7.5Hz, 3H, CH3), 0.94 (t, J=7.4Hz, 3H, CH3)；13C
NMR(75MHz,CDCl3)δ192.0,161.1,137.9,136.2,135.4,129.3,128.3,34.6,27.4,27.0,
22.8,20.9,14.3,12.7；IR(neat)ν(cm-1)3048,3021,2962,2932,2871,2755,1668,1619,
1513,1463,1399,1377,1346,1326,1294,1150,1117,1108,1067,1045；MS(70ev,EI)m/z
(%) 230 (M+,19.69),187(100)；HRMS calcd for C16H22O[M+]:230.1671,found:230.1666.
The synthesis of embodiment 12 (Z) -2- butyl -3- benzyl -2- pentenals (012)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- butyl -4- phenyl -2,3- butadiene
Aldehyde (0.2003g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and
Acetic acid (2mL) obtains (Z) -2- butyl -3- benzyl -2- pentenals (0.2063g, 90%) (petroleum ether (30-60 DEG C)/acetic acid second
Ester=100:1): liquid；1H NMR(300MHz,CDCl3)δ10.17(s,1H,CHO),7.35-7.10(m,5H,ArH),3.92
(s,2H,CH2), 2.33 (t, J=7.5Hz, 2H, CH2), 2.22 (q, J=7.6Hz, 2H, CH2),1.45-1.28(m,4H,CH2
× 2), 1.05 (t, J=7.5Hz, 3H, CH3), 0.92 (t, J=6.9Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ
191.5,160.2,138.3,138.1,128.5,128.3,126.4,34.8,31.6,26.9,25.0,22.8,13.8,12.5；
IR(neat)ν(cm-1)3062,3027,2959,2932,2872,2756,1668,1617,1601,1495,1453,1399,
1377,1277,1151,1072,1028；MS (70ev, EI) m/z (%) 230 (M+,17.38),145(100)；HRMS calcd
for C16H22O[M+]:230.1671,found:230.1670.
The synthesis of embodiment 13 (Z) -2- butyl -3- (4- methylbenzyl) -2- pentenals (013)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- butyl -4- (4- aminomethyl phenyl) -2,
3- butadiene aldehyde (0.2141g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.2mL, 2.0M in toluene,
2.4mmol) and acetic acid (2mL) obtains (Z) -2- butyl -3- (4- methylbenzyl) -2- pentenals (0.2098g, 86%) (petroleum
Ether (30-60 DEG C)/ethyl acetate=100:1): liquid；1H NMR(300MHz,CDCl3)δ10.18(s,1H,CHO),7.10(d,
J=8.1Hz, 2H, ArH), 7.03 (d, J=7.8Hz, 2H, ArH), 3.89 (s, 2H, CH2),2.37-2.27(m,5H,CH3and
CH2), 2.22 (q, J=7.6Hz, 2H, CH2),1.44-1.27(m,4H,CH2× 2), 1.06 (t, J=7.7Hz, 3H, CH3),
0.92 (t, J=6.8Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ191.8,160.8,138.1,136.1,135.3,
129.3,128.3,34.5,31.7,26.9,25.1,23.0,20.8,13.9,12.6；IR(neat)ν(cm-1)3048,3021,
2958,2931,2872,2757,1667,1620,1513,1460,1398,1377,1335,1278,1185,1151,1118,
1105,1072,1043,1021；MS (70ev, EI) m/z (%) 244 (M+,16.09),187(100)；HRMS calcd for
C17H24O[M+]:244.1827,found:244.1829.
The synthesis of embodiment 14 (Z) -2- allyl -3- ethyl -2- tridecylene aldehyde (014)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- allyl -2,3- oleatridecadiene
Aldehyde (0.2343g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and
Acetic acid (2mL) obtain (Z) -2- allyl -3- ethyl -2- tridecylene aldehyde (0.2324g, 88%) (petroleum ether (30-60 DEG C)/
Ethyl acetate=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.09 (s, 1H, CHO), 5.85-5.68 (m, 1H ,=
), CH 4.99-4.87 (m, 2H ,=CH2),3.02(dd,J1=5.7Hz, J2=0.9Hz, 2H, CH2), 2.58 (t, J=8.0Hz,
2H,CH2), 2.29 (q, J=7.4Hz, 2H, CH2),1.60-1.45(m,2H,CH2),1.43-1.18(m,14H,CH2×7),
1.09 (t, J=7.7Hz, 3H, CH3), 0.88 (t, J=6.2Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ190.6,
165.8,135.8,133.4,114.3,31.7,30.7,30.2,29.6,29.40,29.36,29.2,29.1,28.8,27.6,
22.5,13.9,12.3；IR(neat)ν(cm-1)3079,2957,2925,2855,2752,1671,1638,1619,1467,
1396,1378,1328,1153,1068；MS (70ev, EI) m/z (%) 264 (M+,6.56),123(100)；HRMS calcd
for C18H32O[M+]:264.2453,found:264.2452.
The synthesis of -2 benzyl -2- pentenals (015) of embodiment 153- ethyl
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- benzyl -2,3- pentadienal
(0.1718g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtain -2 benzyl -2- pentenals (0.1777g, 88%) of 3- ethyl (petroleum ether (30-60 DEG C)/ethyl acetate=50:
1): liquid；1H NMR(300MHz,CDCl3)δ10.18(s,1H,CHO),7.27-7.18(m,2H,ArH),7.17-7.07(m,
3H,ArH),3.65(s,2H,CH2), 2.64 (q, J=7.6Hz, 2H, CH2), 2.31 (q, J=7.5Hz, 2H, CH2),1.19(t,
J=7.7Hz, 3H, CH3), 0.99 (t, J=7.5Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ191.2,167.8,
140.2,134.3,128.2,127.9,125.6,30.1,27.7,23.3,15.3,12.1；IR(neat)ν(cm-1)3084,
3061,3027,2972,2935,2875,2755,1667,1617,1494,1453,1378,1328,1281,1246,1153,
1074,1042,1030；MS (70ev, EI) m/z (%) 202 (M+,59.88),91(100)；HRMS calcd for C14H18O[M+]:202.1358,found:202.1360.
The synthesis of embodiment 16 (Z) -2- propyl -3- butyl -2- undecylenic aldehyde (016)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -2,3- undecadienal
(0.2079g, 1.0mmol), toluene (20mL), dibutyl zinc solution (2.4mL, 1.0M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -2- propyl -3- butyl -2- undecylenic aldehyde (0.2387g, 90%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.52 (t, J=7.8Hz, 2H,
CH2),2.33-2.14(m,4H,CH2×2),1.57-1.17(m,18H,CH2×9),1.00-0.83(m,9H,CH3×3)；13C
NMR(75MHz,CDCl3)δ191.6,163.5,136.6,34.5,31.8,31.0,30.6,29.7,29.3,29.1,27.2,
23.1,22.7,22.6,14.2,14.0,13.9；IR(neat)ν(cm-1)2958,2927,2858,2753,1668,1616,
1465,1397,1378,1348,1154,1083；MS (70ev, EI) m/z (%) 266 (M+,37.72),126(100)；HRMS
calcd for C18H34O[M+]:266.2610,found:266.2611.
The synthesis of embodiment 17 (Z) -2- propyl -3- butyl -2- fulure (017)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 14 carbon of 2- propyl -2,3-, two olefine aldehydr
(0.2502g, 1.0mmol), toluene (20mL), dibutyl zinc solution (2.4mL, 1.0M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -2- propyl -3- butyl -2- fulure (0.2710g, 88%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=200:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 2.53 (t, J=8.0Hz, 2H,
CH2),2.31-2.15(m,4H,CH2×2),1.57-1.21(m,24H,CH2×12),1.00-0.83(m,9H,CH3×3)；13C
NMR(75MHz,CDCl3)δ191.5,163.4,136.6,34.5,31.8,31.0,30.57,30.55,29.6,29.52,
29.45,29.32,29.26,27.2,23.1,22.7,22.6,14.2,14.0,13.8；IR(neat)ν(cm-1)2958,2926,
2855,2752,1670,1615,1464,1397,1378,1348,1311,1271,1229,1152,1081；MS(70ev,EI)
308 (M of m/z (%)+,25.06),43(100)；HRMS calcd for C21H40O[M+]:308.3079,found:
308.3080.
The synthesis of embodiment 18 (Z) -2- propyl -3- phenethyl -2- heptenal (018)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -5- phenyl -2,3- pentadiene
Aldehyde (0.1998g, 1.0mmol), toluene (20mL), dibutyl zinc solution (2.4mL, 1.0M in toluene, 2.4mmol) and
Acetic acid (2mL) obtains (Z) -2- propyl -3- phenethyl -2- heptenal (0.2296g, 89%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=50:1): liquid；1H NMR(300MHz,CDCl3)δ9.87(s,1H,CHO),7.31-7.23(m,2H,ArH),7.23-
7.09(m,3H,ArH),2.88-2.73(m,4H,CH2×2),2.31-2.13(m,4H,CH2×2),1.54-1.21(m,6H,
CH2×3),1.10-0.85(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ191.1,160.9,140.4,137.3,
128.4,128.3,126.3,36.6,34.2,32.3,30.5,27.3,23.0,22.6,14.2,13.8；IR(neat)ν(cm-1)
3085,3063,3027,2959,2931,2871,2756,1668,1614,1496,1464,1454,1397,1379,1379,
1347,1150,1097,1075,1031；MS (70ev, EI) m/z (%) 258 (M+,4.46),91(100)；HRMS calcd
for C18H26O[M+]:258.1984,found:258.1985.
The synthesis of the chloro- 2- heptenal (019) of embodiment 19 (Z) -2- propyl -3- butyl -7-
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: chloro- 2, the 3- heptadienal of 2- propyl -7-
(0.1865g, 1.0mmol), toluene (20mL), dibutyl zinc solution (2.4mL, 1.0M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -2- propyl -3- butyl -7- chloro- 2- heptenal (0.2107g, 86%) (petroleum ether (30-60 DEG C)/acetic acid
Ethyl ester=30:1): liquid；1H NMR(300MHz,CDCl3) δ 10.07 (s, 1H, CHO), 3.56 (t, J=6.3Hz, 2H, CH2),
2.58 (t, J=8.0Hz, 2H, CH2),2.32-2.14(m,4H,CH2×2),1.90-1.76(m,2H,CH2),1.74-1.59
(m,2H,CH2),1.52-1.23(m,6H,CH2×3),1.00-0.85(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ
191.2,162.0,137.0,44.4,34.3,32.1,30.5,29.6,27.8,27.2,23.0,22.6,14.1,13.8；IR
(neat)ν(cm-1)2959,2929,2871,2756,1667,1616,1464,1399,1378,1347,1311,1269,1228,
1153,1080；MS (70ev, EI) m/z (%) 246 (M+(37Cl),8.05),244(M+(35Cl),24.25),55(100)；HRMS
calcd for C14H25O35Cl[M+]:244.1594,found:244.1597.
The synthesis of embodiment 20 (Z) -3- butyl -2- allyl -2- tridecylene aldehyde (020)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- allyl -2,3- oleatridecadiene
Aldehyde (0.2341g, 1.0mmol), toluene (20mL), dibutyl zinc solution (2.4mL, 1.0M in toluene, 2.4mmol) and
Acetic acid (2mL) obtain (Z) -3- butyl -2- allyl -2- tridecylene aldehyde (0.2598g, 89%) (petroleum ether (30-60 DEG C)/
Ethyl acetate=100:1): liquid；1H NMR(300MHz,CDCl3) δ 10.08 (s, 1H, CHO), 5.84-5.68 (m, 1H ,=
), CH 4.99-4.87 (m, 2H ,=CH2),3.02(dt,J1=5.9Hz, J2=1.6Hz, 2H, CH2), 2.57 (t, J=8.0Hz,
2H,CH2), 2.25 (t, J=7.8Hz, 2H, CH2),1.60-1.15(m,20H,CH2×10),0.99-0.81(m,6H,CH3×
2)；13C NMR(75MHz,CDCl3)δ190.8,165.0,135.9,133.8,114.4,34.6,31.8,30.9,30.8,
30.3,29.7,29.5,29.4,29.3,29.2,29.0,23.1,22.6,14.0,13.8；IR(neat)ν(cm-1)3079,
2957,2926,2856,2752,1669,1638,1617,1466,1379,1330,1153,1098；MS(70ev,EI)m/z
(%) 292 (M+,8.02),41(100)；HRMS calcdfor C20H36O[M+]:292.2766,found:292.2769.
The synthesis of embodiment 21 (E) -4- methyl-2-propyl -3- (cyclohexyl methyl) -2- pentenals (021)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- propyl -3- cyclohexyl -2,3- fourth two
Olefine aldehydr (0.1922g, 1.0mmol), toluene (20mL), diisopropyl base zinc solution (2.4mL, 1.0M in toluene,
2.4mmol) and acetic acid (2mL) obtain (E) -4- methyl-2-propyl -3- (cyclohexyl methyl) -2- pentenals (0.1980g,
84%) (petroleum ether (30-60 DEG C)/ethyl acetate=100:1): liquid；1H NMR(300MHz,CDCl3)δ10.05(s,1H,
), CHO 3.04 (heptet, J=7.0Hz, 1H, CH), 2.41 (d, J=7.2Hz, 2H, CH2),2.32-2.22(m,2H,CH2),
1.78-1.59(m,5H,CH and CH2×2),1.51-1.04(m,12H,CH2×3and CH3×2),1.01-0.84(m,
5H,CH3and CH2)；13C NMR(75MHz,CDCl3)δ192.6,165.0,137.5,39.6,33.6,33.5,32.6,27.2,
26.4,26.2,23.0,21.0,14.2；IR(neat)ν(cm-1)2961,2927,2872,2852,2759,1667,1601,
1462,1449,1397,1384,1364,1349,1313,1267,1183,1148,1087,1035；MS(70ev,EI)m/z
(%) 236 (M+,15.61),193(100)；HRMS calcd for C16H28O[M+]:236.2140,found:236.2138.
The synthesis of embodiment 22 (Z) -3- ethyl -2- benzyl -2- heptenal (022)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- benzyl -2,3- heptadienal
(0.2001g, 1.0mmol), toluene (20mL), diethyl zinc solution (1.6mL, 1.5M in toluene, 2.4mmol) and second
Sour (2mL) obtains (Z) -3- ethyl -2- benzyl -2- heptenal (0.2015g, 88%) (petroleum ether (30-60 DEG C)/ethyl acetate
=50:1): liquid；1HNMR(300MHz,CDCl3)δ10.18(s,1H,CHO),7.28-7.04(m,5H,ArH),3.65(s,
2H,CH2), 2.60 (t, J=7.8Hz, 2H, CH2), 2.30 (q, J=7.7Hz, 2H, CH2),1.60-1.30(m,4H,CH2×
2),1.04-0.87(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ191.1,166.4,140.2,134.8,128.2,
127.8,125.6,33.0,30.2,29.9,28.0,22.8,13.7,12.1；IR(neat)ν(cm-1)3062,3027,2961,
2932,2873,2750,1668,1615,1495,1453,1378,1282,1152,1074,1030；MS(70ev,EI)m/z
(%) 230 (M+,43.53),91(100)；HRMS calcd for C16H22O[M+]:230.1671,found:230.1671.
The synthesis of embodiment 23 (E) -3- ethyl -2- benzyl -2- heptenal (023)
By method described in embodiment 1, the difference is that substrate used and reagent are as follows: 2- benzyl -2,3- pentadienal
(0.1721g, 1.0mmol), toluene (20mL), dibutyl zinc solution (2.4mL, 1.0M in toluene, 2.4mmol) and second
Sour (2mL) obtains (E) -3- ethyl -2- benzyl -2- heptenal (0.1954g, 85%) (petroleum ether (30-60 DEG C)/ethyl acetate
=100:1): liquid；1H NMR(300MHz,CDCl3)δ10.18(s,1H,CHO),7.28-7.04(m,5H,ArH),3.65(s,
2H,CH2), 2.60 (t, J=7.8Hz, 2H, CH2), 2.30 (q, J=7.7Hz, 2H, CH2),1.60-1.30(m,4H,CH2×
2),1.04-0.87(m,6H,CH3×2)；13C NMR(75MHz,CDCl3)δ191.1,166.4,140.2,134.8,128.2,
127.8,125.6,33.0,30.2,29.9,28.0,22.8,13.7,12.1；IR(neat)ν(cm-1)3062,3027,2961,
2932,2873,2750,1668,1615,1495,1453,1378,1282,1152,1074,1030；MS(70ev,EI)m/z
(%) 230 (M+,43.53),91(100)；HRMS calcd for C16H22O[M+]:230.1671,found:230.1671.
The synthesis of the chloro- 2- heptenal (024) of embodiment 24 (E) -2- propyl -3- phenyl -7-
A dry Shi Lanke reaction flask is taken, substitutes gas three times under nitrogen.Under nitrogen protection, in reaction flask successively
Chloro- 2, the 3- heptadienal (0.1869,1.0mmol) of 2- propyl -7- and toluene (20mL) is added, uses injection under -30 DEG C of stirrings
The toluene suspension (20mL) of diphenyl zinc (0.5391g, 2.4mmol, 98%) is added dropwise, is dripped off in 4 minutes.Reaction is at -30 DEG C
Then stirring 11 hours is added dropwise acetic acid (2mL) with injection under -30 DEG C of stirrings, drips off in 2 minutes, go back up to room temperature later.30
It after minute, is added ethyl acetate (20mL), successively uses dilute hydrochloric acid (20mL), saturated sodium bicarbonate solution (20mL) is saturated chlorination
Sodium solution (20mL) is washed, and water phase is merged, and water phase is extracted with ether (20mL × 2), merges organic phase, anhydrous sodium sulfate is dry, mistake
Filter, rotation go rapid column chromatography separation (petroleum ether (30-60 DEG C)/ethyl acetate=30:1) after solvent to obtain (E) -2- propyl -3-
The chloro- 2- heptenal of phenyl -7- (0.1982g, 75%): liquid；1H NMR(300MHz,CDCl3)δ10.27(s,1H,CHO),
7.46-7.29 (m, 3H, ArH), 7.17-7.09 (m, 2H, ArH), 3.48 (t, J=6.5Hz, 2H, CH2), 2.89 (t, J=
7.7Hz,2H,CH2),2.09-1.98(m,2H,CH2),1.85-1.71(m,2H,CH2),1.64-1.49(m,2H,CH2),
1.33-1.17(m,2H,CH2), 0.71 (t, J=7.4Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ191.6,159.5,
141.1,138.3,128.3,127.6,126.9,44.3,32.04,31.95,29.0,26.1,22.5,14.1；IR(neat)ν
(cm-1)3078,3058,3019,2960,2931,2869,2752,1668,1611,1596,1490,1463,1442,1394,
1346,1319,1274,1199,1106,1074,1026；MS (70ev, EI) m/z (%) 266 (M+(37Cl),20.77),264(M+(35Cl),62.47),173(100)；HRMS calcd for C16H21O35Cl[M+]:264.1281,found:264.1277.
The synthesis of embodiment 25 (E) -2- butyl -3- phenyl -4- (4- aminomethyl phenyl) -2- crotonaldehyde (025)
By method described in embodiment 24, the difference is that substrate used and reagent are as follows: 2- benzyl -2,3- pentadienal
(0.2138g, 1.0mmol), toluene (20mL), the toluene suspension (20mL) of diphenyl zinc (0.5387g, 2.4mmol, 98%)
(E) -2- butyl -3- phenyl -4- (4- aminomethyl phenyl) -2- crotonaldehyde (0.2334g, 80%) (petroleum ether is obtained with acetic acid (2mL)
(30-60 DEG C)/ethyl acetate=50:1): liquid；1H NMR(300MHz,CDCl3)δ10.41(s,1H,CHO),7.32-7.18
(m,3H,ArH),7.06-6.87(m,6H,ArH),4.13(s,2H,CH2),2.26(s,3H,CH3), 2.13 (t, J=7.8Hz,
2H,CH2),1.33-1.06(m,4H,CH2× 2), 0.72 (t, J=7.2Hz, 3H, CH3)；13C NMR(75MHz,CDCl3)δ
192.1,157.5,141.1,138.9,136.0,134.3,129.1,128.5,128.0,127.5,127.1,38.1,31.5,
26.7,22.6,20.9,13.6；IR(neat)ν(cm-1)3078,3051,3021,3000,2957,2928,2860,2825,
2751,1674,1667,1614,1596,1575,1513,1489,1455,1442,1394,1379,1334,1308,1186,
1108,1075,1023；MS (70ev, EI) m/z (%) 293 (M++1,5.98),292(M+,27.01),235(100)；HRMS
calcd for C21H24O[M+]:292.1827,found:292.1825.
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| Dana, Gilbert et al.Déshydration des diols-1,2α,β-éthyléniques IV:1 rôle de la stéréomutation des carbocations allyliques α-hydroxylés sur l’orientation des réactions observées.《Canadian Journal of Chemistry》.1980,第58卷(第14期), |
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