CN105541581B - A kind of four substituted olefine class compounds and methods of Stereospecific synthesis - Google Patents

A kind of four substituted olefine class compounds and methods of Stereospecific synthesis Download PDF

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CN105541581B
CN105541581B CN201510966985.8A CN201510966985A CN105541581B CN 105541581 B CN105541581 B CN 105541581B CN 201510966985 A CN201510966985 A CN 201510966985A CN 105541581 B CN105541581 B CN 105541581B
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toluene
cdcl
propyl
nmr
olefine
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CN105541581A (en
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麻生明
戴健鑫
傅春玲
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Zhejiang University ZJU
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    • 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
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    • C07B2200/09—Geometrical isomers

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Abstract

The invention discloses a kind of four substituted olefine class compound of Stereospecific synthesis and its new methods, pass through 2,3- joins the conjugate addition reaction of olefine aldehydr and organic zinc reagent, is further quenched with acid, synthesizes four substituted olefine class compounds to high regioselectivity and highly-solid selectively.The method of the present invention is easy to operate, and raw materials and reagents are easy to get, and reaction has high regioselectivity, and highly-solid selectively, functional group compatibility is preferable, the easily separated purifying of product, can directly obtain four single substituted olefine class compounds of stereochemical structure.

Description

A kind of four substituted olefine class compounds and methods of Stereospecific synthesis
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.

Claims (6)

1. synthesizing to a kind of stereocpecificity the method for four substituted olefine class compounds, which is characterized in that 2,3- join olefine aldehydrs and have The generation conjugate addition reaction of the high regioselectivity of machine zincon, is further quenched with acid, obtains four substituted olefine class compounds, Reaction equation is as follows:
In the reaction equation (a),
R is ethyl or butyl or isopropyl or phenyl；R1For methyl or ethyl or propyl or butyl or allyl or benzyl；R2For Methyl or heptyl or nonyl or decyl or cyclohexyl or benzyl or 3- chloropropyl or 8- nonenyl or phenyl or p-methylphenyl.
2. preparation method according to claim 1, which is characterized in that specific preparation process is as follows:
2,3- connection olefine aldehydr and toluene are sequentially added into dry reaction flask under nitrogen protection, organic zinc is added dropwise at a temperature of first Reagent is stirred to react at the first temperature, and carboxylic acid is then added dropwise at the first temperature, is gone up to after being stirred to react at room temperature, according to Secondary dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium chloride solution are washed, and water phase is merged, and water phase is extracted with ether, are merged organic Phase, concentration, rapid column chromatography obtain four substituted olefine class compounds.
3. preparation method according to claim 1, which is characterized in that the carboxylic acid includes acetic acid or propionic acid.
4. preparation method according to claim 2 or 3, which is characterized in that first temperature is -30 DEG C to 30 DEG C.
5. the preparation method according to claim 4, which is characterized in that 2, the 3- connection olefine aldehydr and the organic zinc reagent Molar ratio is 1.0:1.8~3.0.
6. preparation method according to claim 2 or 3, which is characterized in that 2, the 3- connection olefine aldehydr and the organic zinc try The molar ratio of agent is 1.0:1.8~3.0.
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CN103030536A (en) * 2012-11-23 2013-04-10 浙江大学 High-selectivity synthesis method of alpha,beta-unsaturated iodoketenes and olefine aldehydes

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* Cited by examiner, † Cited by third party
Title
Action des dialkylcuprates de lithium sur les aldéhydes α,β-éthyléniques;Chuit, C. et al;《Tetrahedron》;1980;第36卷(第16期);2305-2310
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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