CN108250153B - Preparation method of trans-disubstituted olefin - Google Patents

Preparation method of trans-disubstituted olefin Download PDF

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CN108250153B
CN108250153B CN201810144381.9A CN201810144381A CN108250153B CN 108250153 B CN108250153 B CN 108250153B CN 201810144381 A CN201810144381 A CN 201810144381A CN 108250153 B CN108250153 B CN 108250153B
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张春艳
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Qingdao University of Science and Technology
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Abstract

The invention discloses a preparation method of trans-disubstituted alkene, belonging to the technical field of organic chemical synthesis. The method adopts simple alcohol and methyl nitrogen heterocyclic ring as initial raw materials, and obtains the trans-disubstituted alkene compound through a transition metal catalytic olefination reaction. The reaction raw materials, the catalyst and the additive are cheap and easy to obtain, the synthesis process is simple, and the synthesis cost is greatly reduced; the reaction condition is mild, the yield is high, and the industrialization is easy to realize; the reaction raw materials and the catalyst are clean and nontoxic, and the environmental pollution is small. The trans-disubstituted alkene compound and the derivative thereof are used as important fine chemicals and widely applied to the industries of medicines, pesticides, spices, photoelectricity and the like.

Description

Preparation method of trans-disubstituted olefin
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and relates to a preparation method of trans-disubstituted alkene.
Background
Olefin is an important fine chemical, and has wide application in the industries of pesticides, medicines, spices and the like. The alkene group is a common pharmacophore, widely exists in various natural products and synthetic drugs with physiological activities, and is also a fragment constituting various functional materials. For example, the trans disubstituted alkene, montelukast, is useful for the prevention and long-term treatment of asthma in adults over 15 years of age, including the prevention of daytime and nighttime asthmatic symptoms, the treatment of aspirin-sensitive asthmatics, and the prevention of exercise-induced bronchoconstriction. Due to the specific use of these compounds, a number of synthetic methods have been developed in recent years.
There are a number of conventional methods for synthesizing trans-disubstituted olefins: (1) many human name reactions (Witting, Horner-Wadsworth-Emmons, Peterson interference, Julia interference, etc.); (2) catalyzing Heck reaction; (3) carrying out Suzuki coupling reaction; (4) olefin metathesis. Although these methods have high yield, most of the above methods require an equivalent amount of a phosphine reagent, a metal reagent or use of an aldehyde and an equivalent amount of an initiator and various additives, and the practical application is extremely limited.
Figure BDA0001578415730000011
All the previous reactions are based on the participation of equivalent metal reagents or phosphine ylide reagents, so that a large amount of metal waste and organic phosphine compounds are inevitably generated, the reaction economy is not high, and meanwhile, the environment is greatly stressed, and the requirements of green sustainable development are not met. Due to the utilization of various additives, the development of reaction substrates is severely limited, the compatibility of the functional groups of the reaction substrates is poor, and the economic applicability is not high.
Therefore, the method directly utilizes alcohol without aldehyde to directly carry out an olefination reaction with a methyl heterocyclic compound, the by-products are only water and hydrogen, and the method has important theoretical significance and wide application prospect in preparing the trans-disubstituted olefin derivative with wide substrate applicability range and high atom economy and meets the requirement of green chemistry.
Disclosure of Invention
The invention aims to provide a simple and efficient preparation method of trans-disubstituted olefin.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for preparing the trans-disubstituted olefin uses primary alcohol and methyl nitrogen-containing heterocycle as raw materials, and carries out an olefination reaction under the catalysis of a transition metal catalyst to obtain a compound with a trans-disubstituted olefin structure, and the compound is reacted for 23 to 48 hours under nitrogen; after the reaction is finished, pumping out the solvent, and carrying out column chromatography to obtain the trans-disubstituted alkene compound;
the general reaction formula is as follows:
Figure BDA0001578415730000021
the structural formula of the methyl nitrogen-containing heterocyclic ring is as follows:
Figure BDA0001578415730000022
wherein:
x, Y, Z is an independent carbon atom or nitrogen atom, R1Each group is independently selected from hydrogen, halogen or methoxy.
The alcohol derivative has the structure:
Figure BDA0001578415730000023
wherein:
R2the radicals being selected from C1～C10Aliphatic radical of (e.g. ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4～C10An aromatic group (e.g., furyl derivative, pyridyl derivative, thienyl derivative, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl).
Or the like, or, alternatively,
Figure BDA0001578415730000024
the structural formula of the methyl nitrogen-containing heterocyclic ring is as follows:
Figure BDA0001578415730000025
wherein:
x 'and Y' are independent carbon atoms or nitrogen atoms, R3Each group is independently selected from hydrogen, halogen or methoxy;
the alcohol derivative has the structure:
Figure BDA0001578415730000026
wherein:
R4the radicals being selected from C1～C10Aliphatic radical of (e.g. ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4～C10An aromatic group (e.g., furyl derivative, pyridyl derivative, thienyl derivative, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl).
Or the like, or, alternatively,
Figure BDA0001578415730000031
the structural formula of the methyl nitrogen-containing heterocyclic ring is as follows:
Figure BDA0001578415730000032
the condensed amine aldehyde derivative has the structure as follows:
Figure BDA0001578415730000033
wherein:
R5the radicals being selected from C1～C10Aliphatic radical of (e.g. ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4～C10An aromatic group (e.g., furyl derivative, pyridyl derivative, thienyl derivative, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl).
The base is potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium hydride, sodium hydride, lithium hydride, potassium carbonate or sodium carbonate; potassium hydroxide, sodium hydroxide or potassium hydride is preferred.
The catalyst is manganese pentacarbonyl bromide (Mn (CO)2Br) or manganese decacarbonyl (Mn)2(CO)10) The dosage of the catalyst is 0.5 to 10 percent of the molar weight of the aminal derivative.
The ligand is (E) -1- (2-pyridyl) -N- (2-picolyl) azomethine
[ (E) -1- (pyridin-2-yl) -N- (pyridin-2-ylmethy l) methanimine ], (E) -1- (2-pyridyl) -N- (2-picolyl) ethylenimine [ (E) -1- (pyridin-2-yl) -N- (pyridin-2-ylmethy l) ethane-1-imine ], (E) -2- ((2- (2-pyridyl) hydrazono) methyl) pyridine [ (E) -2- ((2- (pyridine-2-yl) hydrazono) methyl) pyridine ] or [ (E) -2- (2- (1- (2-pyridyl) ethylidene) hydrazono) pyridine ] [ (E) -2- (2- (1- (pyridine-2-yl) ethylidene) hydrazono) pyridine ].
The organic solvent is one or two of benzene, nitromethane, toluene, benzotrifluoride, xylene, mesitylene, 1, 4-dioxane, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, diethyl ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol and tert-amyl alcohol. The mixed solvent of tert-amyl alcohol and toluene is preferred.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages that the alcohol and the methyl nitrogen-containing heterocycle react under the catalysis of the industrially cheap and easily available metal catalyst, the trans-disubstituted alkene compound can be efficiently prepared by one step through the alkenylation method, the reaction raw materials and the catalyst are cheap and easily available, the synthesis process is simple, and the synthesis cost is greatly reduced;
2. the invention can efficiently synthesize the trans-disubstituted alkene by one step, which is to obtain the trans-disubstituted alkene compound by the first time of utilizing alcohol through the alkene reaction.
3. The method has the advantages of mild reaction conditions, simple operation, high yield, wide substrate applicability range and easy industrialization.
4. The reaction raw material (alcohol) and the catalyst (manganese) are clean, nontoxic, cheap and have little pollution to the environment.
5. The reaction process is clean and meets the requirement of green chemistry.
6. The reaction has high conversion efficiency, can realize gram-scale amplification experiments, and is easy to realize industrialization.
Detailed Description
The present invention is further described below.
Example 1
Preparation of trans-disubstituted alkene derivatives 3a
The synthetic route is as follows:
Figure BDA0001578415730000041
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylpyrazine 1a (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 a. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.65(s,1H),8.55(s,1H),8.41(d,J＝2.3Hz,1H),7.76(d,J＝16.1Hz,1H),7.61(d,J＝8.1Hz,2H),7.43–7.32(m,3H),7.17(d,J＝16.1Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝124.0,127.3,128.9,129.0,135.2,136.0,142.8,143.8,144.4,151.3ppm.CAS Registry Number:35782-36-6.
Example 2
Preparation of trans-disubstituted alkene derivatives 3b
The synthetic route is as follows:
Figure BDA0001578415730000042
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1a (2mmol) and benzyl alcohol 2b (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 b. The product was a white solid in 63% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.58(d,J＝31.0Hz,2H),8.39(s,1H),7.72(d,J＝16.1Hz,1H),7.49(d,J＝7.9Hz,2H),7.20(d,J＝7.8Hz,2H),7.11(d,J＝16.1Hz,1H),2.38(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝123.0,127.3,129.6,133.3,135.2,139.2,142.5,143.7,144.2,151.5ppm.Elemental analysis calcd for C13H12N2(M:196.10)[％]:C,79.56；H,6.16；N,14.27found:C 79.77,H 6.62,N 13.75.CAS Registry Number:142772-03-0.
Example 3
Preparation of trans-disubstituted alkene derivatives 3c
The synthetic route is as follows:
Figure BDA0001578415730000051
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) and 1.0mL of toluene, stirring for two hours, adding 2-methylpyrazine 1a (2mmol) and benzyl alcohol 2c (1mmol), reacting at 135 deg.C for 48 hours, stopping the reaction, evaporating the solvent, and performing column chromatography on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 c. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.63(s,1H),8.54(s,1H),8.43(s,1H),7.69(d,J＝16.1Hz,1H),7.52(d,J＝8.5Hz,2H),7.45(d,J＝8.4Hz,2H),7.14(d,J＝16.1Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝124.4,128.4,129.0,133.7,134.4,134.6,142.9,143.7,144.3,150.8ppm.Elemental analysis calcd for C12H9ClN2(M:216.04)[％]:C,66.52；H,4.19；Cl,16.36；N,12.93found:C 67.00,H 3.73,N 12.57.
Example 4
Preparation of trans-disubstituted alkene derivatives 3d
The synthetic route is as follows:
Figure BDA0001578415730000061
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) and 1.0mL of toluene, stirring for two hours, adding 2-methylpyrazine 1a (2mmol) and benzyl alcohol 2d (1mmol), reacting at 135 deg.C for 48 hours, stopping the reaction, evaporating the solvent, and performing column chromatography on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 d. The product was a white solid in 68% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.63(s,1H),8.54(s,1H),8.43(s,1H),7.69(d,J＝16.1Hz,1H),7.52(d,J＝8.5Hz,2H),7.45(d,J＝8.4Hz,2H),7.14(d,J＝16.1Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝123.0,124.6,128.8,132.0,133.9,135.0,143.0,143.9,144.4ppm.CAS Registry Number:1810802-39-1.
Example 5
Preparation of trans-disubstituted alkene derivatives 3e
The synthetic route is as follows:
Figure BDA0001578415730000062
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylpyrazine 1a (2 m)mol) and benzyl alcohol 2e (1mmol), reacting at 135 deg.C for 48 hr, stopping reaction, evaporating solvent, and performing column chromatography with ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 e. The product was a white solid in 83% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.54(d,J＝17.7Hz,2H),8.39(s,1H),7.89(d,J＝15.8Hz,1H),7.31-7.30(m,1H),7.22–7.21(m,1H),7.07–7.03(m,1H),6.95(d,J＝15.8Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝123.1,126.4,127.9,128.0,128.7,141.6,142.6,143.7,144.3,150.9ppm.Elemental analysis calcd for C10H8N2S(M:188.04)[％]:C,63.80；H,4.28；N,14.88；S,17.03found:C 63.51,H 3.84,N 14.37.CAS:361444-92-0.
Example 6
Preparation of trans-disubstituted alkene derivatives 3f
The synthetic route is as follows:
Figure BDA0001578415730000071
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1b (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 f. The product was a white solid in 80% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝9.05(d,J＝4.8Hz,1H),7.69(d,J＝16.4Hz,1H),7.64–7.61(m,2H),7.59(s,1H),7.46–7.43(m,1H),7.41–7.36(m,3H),7.33(d,J＝5.2Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝124.0,125.2,126.4,127.4,128.9,129.1,135.2,135.9,149.7,158.3ppm.CAS:35782-26-4.
Example 7
Preparation of 3g of Trans-disubstituted alkene derivative
The synthetic route is as follows:
Figure BDA0001578415730000072
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylpyrazine 1c (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, column chromatography was performed using ethyl acetate/petroleum ether (1:10) and 3g of trans-disubstituted olefin derivative. The product was a white solid in 60% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.59(d,J＝4.4Hz,2H),7.56-7.54(m,2H),7.40–7.35(m,5H),7.31(d,J＝10.7Hz,1H),7.03(d,J＝16.3Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝120.9,126.0,127.0,128.8,128.9,133.3,136.1,144.7,150.1ppm.CAS:5097-93-8.
Example 8
Preparation of trans-disubstituted alkene derivatives for 3h
The synthetic route is as follows:
Figure BDA0001578415730000081
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, stirred for two hours, added with 1d (2mmol) and 2a (1mmol), reacted at 135 ℃ for 48 hours, then the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative for 3 hours. The product was a white solid in 70% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.10(d,J＝8.5Hz,1H),8.06(d,J＝8.5Hz,1H),7.77(d,J＝8.0Hz,1H),7.70–7.69(m,1H),7.62–7.53(m,2H),7.51–7.48(m,2H),7.30–7.25(m,2H),6.55–6.54(m,1H),6.48–6.47(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝110.3,113.9,119.8,124.5,125.2,127.5,128.9,129.8,135.1,139.4,142.2,150.4,162.8ppm.CAS:59066-62-5.
Example 9
Preparation of trans-disubstituted alkene derivatives 3i
The synthetic route is as follows:
Figure BDA0001578415730000082
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1e (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 i. The product was a white solid in 57% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.57(d,J＝5.6Hz,1H),8.39(d,J＝8.4Hz,1H),8.01(s,2H),7.84(d,J＝8.2Hz,1H),7.72–7.63(m,4H),7.58(d,J＝5.6Hz,1H),7.45–7.40(m,2H),7.37–7.32(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝112.0,122.9,124.5,127.2,127.4,127.5,128.6,128.8,129.9,135.8,136.8,137.0,142.5,154.6ppm.CAS:59066-57-8.
Example 10
Preparation of trans-disubstituted alkene derivatives 3j
The synthetic route is as follows:
Figure BDA0001578415730000091
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) and 1.0mL of toluene, stirring for two hours, adding 1f (2mmol) and benzyl alcohol 2a (1mmol), reacting at 135 deg.C for 48 hours, stopping reaction, evaporating solvent, and performing column chromatography to obtain ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefinDerivative 3 j. The product was a white solid in 86% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.06–8.01(m,2H),7.77–7.76(m,1H),7.71(d,J＝11.8Hz,1H),7.68–7.63(m,4H),7.44–7.41(m,2H),7.39–7.32(m,2H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝120.2,126.2,127.4,127.9,128.4,128.9,130.7,131.8,135.0,135.5,136.3,146.6,156.2ppm.CAS:1139911-18-4.
Example 11
Preparation of trans-disubstituted alkene derivatives 3k
The synthetic route is as follows:
Figure BDA0001578415730000092
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1g (2mmol) of benzyl alcohol 2a (1mmol) was added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10), trans-disubstituted olefin derivative 3 k. The product was a white solid in 95% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.01(s,1H),7.98(s,1H),7.64(d,J＝5.9Hz,2H),7.62–7.59(m,2H),7.42–7.37(m,3H),7.36–7.27(m,2H),7.04(d,J＝2.8Hz,1H),3.92(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝55.6,105.3,119.6,122.4,127.2,128.3,128.4,128.8,130.6,135.2,136.7,153.6,157.7ppm.CAS:59066-58-9.
Example 12
Preparation of trans-disubstituted alkene derivative 3aa
The synthetic route is as follows:
Figure BDA0001578415730000101
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 aa. The product was a white solid in 94% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.15–8.07(m,2H),7.79(d,J＝8.0Hz,1H),7.64–7.72(m,5H),7.52–7.47(m,1H),7.45–7.39(m,3H),7.35–7.32(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.3,126.2,127.3,127.5,128.7,128.8,129.0,129.2,129.8,134.5,136.4,136.5,148.3 156.0ppm.CAS Registry Number:38101-69-8.
Example 13
Preparation of trans-disubstituted alkene derivatives 3ab
The synthetic route is as follows:
Figure BDA0001578415730000102
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2b (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ab. The product was a white solid in 92% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.12(d,J＝8.6Hz,1H),8.07(d,J＝8.5Hz,1H),7.78(d,J＝8.1Hz,1H),7.73–7.68(m,2H),7.65(d,J＝5.0Hz,1H),7.55(d,J＝8.0Hz,2H),7.52–7.47(m,1H),7.37(d,J＝16.3Hz,1H),7.22(d,J＝8.0Hz,2H),2.39(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝21.4,119.2,126.1,127.2,127.3,127.5,128.1,129.2,129.6,129.7,133.8,134.4,136.3,138.8,148.3,156.2ppm.CAS Registry Number:1289213-24-6.
Example 14
Preparation of trans-disubstituted alkene derivatives 3ac
The synthetic route is as follows:
Figure BDA0001578415730000111
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2c (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ac. The product was a white solid in 94% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.13(d,J＝8.6Hz,1H),8.08(d,J＝8.5Hz,1H),7.79(d,J＝8.1Hz,1H),7.74–7.68(m,2H),7.65(d,J＝7.8Hz,1H),7.52–7.38(m,4H),7.30(t,J＝7.5Hz,1H),7.15(d,J＝7.4Hz,1H),2.41(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝21.5,119.2,124.5,126.1,127.5,128.0,128.7,128.90,129.2,129.5,129.7,134.5,136.3,136.5,148.3,156.1ppm.CAS Registry Number:1318193-16-6.
Example 15
Preparation of trans-disubstituted alkene derivative 3ad
The synthetic route is as follows:
Figure BDA0001578415730000112
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2d (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ad. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.14(t,J＝8.5Hz,2H),7.97(d,J＝16.2Hz,1H),7.82–7.69(m,4H),7.55–7.50(m,1H),7.35(d,J＝16.2Hz,1H),7.28–7.27(m,1H),2.55(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝19.9,119.2,125.7,126.1,126.2,127.4,128.4,129.2,129.6,130.1,130.5,132.0,136.2,148.2,156.1ppm.CAS Registry Number:1318193-18-8.
Example 16
Preparation of trans-disubstituted alkene derivative 3ae
The synthetic route is as follows:
Figure BDA0001578415730000121
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2e (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ae. The product was a white solid in 80% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.15–8.08(m,2H),7.81–7.66(m,4H),7.53–7.48(m,1H),6.98–6.92(m,3H),2.44(s,6H),2.32(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝21.1,21.3,119.0,126.1,127.4,127.5,129.0,129.3,129.7,132.9,134.1,136.3,136.5,137.0,148.3,156.3ppm.Elemental analysis calcd for C20H19N(M:273.15)[％]:C,87.87；H,7.01；N,5.12found:C 88.04,H 7.11,N 5.55.CAS Registry Number:848232-91-7
Example 17
Preparation of trans-disubstituted alkene derivatives 3af
The synthetic route is as follows:
Figure BDA0001578415730000122
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2f (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted alkene derivative 3 af. The product was a white solid in 86% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.16(d,J＝8.6Hz,1H),8.11(d,J＝8.5Hz,1H),7.82(d,J＝8.0Hz,1H),7.76–7.68(m,3H),7.62(d,J＝8.3Hz,2H),7.55–7.50(m,1H),7.48–7.39(m,3H),1.39(s,9H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝31.3,34.8,119.2,125.8,126.1,127.1,127.3,127.5,128.3,129.2,129.7,133.8,134.3,136.3,148.3,152.0,156.3ppm.Elemental analysis calcd for C20H19N(M:287.17)[％]:C,87.76；H,7.37；N,4.87found:C 87.22,H 7.72,N 5.00.CAS Registry Number:801231-11-8.
Example 18
Preparation of trans-disubstituted alkene derivative 3ag
The synthetic route is as follows:
Figure BDA0001578415730000131
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2g (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ag. The product was a white solid in 92% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.15(d,J＝8.5Hz,1H),8.10(d,J＝8.5Hz,1H),7.80(d,J＝8.1Hz,1H),7.77–7.72(m,4H),7.69–7.63(m,5H),7.54–7.49(m,2H),7.45(d,J＝7.2Hz,2H),7.39–7.34(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.4,126.2,127.0,127.4,127.5,127.6,127.8,128.9,129.0,129.2,129.8,134.0,135.6,136.4,140.5,141.4,148.3,156.0ppm.CAS Registry Number:190437-73-1
Example 19
Preparation of trans-disubstituted alkene derivative 3ah
The synthetic route is as follows:
Figure BDA0001578415730000132
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2h (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ah. The product was a white solid in 96% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.11(d,J＝8.5Hz,1H),8.06(d,J＝8.5Hz,1H),7.78(d,J＝8.1Hz,1H),7.72–7.67(m,2H),7.64-7.58(m,3H),7.48(t,J＝7.4Hz,1H),7.31–7.26(m,2H),6.94(d,J＝7.3Hz,2H),3.85(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝55.4,114.3,119.2,125.9,126.9,127.2,127.5,128.7,129.1,129.3,129.7,134.0,136.2,148.3,156.4,160.1ppm.CAS Registry Number:190437-90-2.
Example 20
Preparation of trans-disubstituted alkene derivative 3ai
The synthetic route is as follows:
Figure BDA0001578415730000141
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol), 1.0mL of formazan was addedAfter stirring in benzene for two hours, 2-methylquinoline 4(2mmol) and 2i (1mmol) were added, the reaction was stopped after 48 hours at 135 ℃, the solvent was evaporated to dryness, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted alkene derivative 3 ai. The product was a white solid in 93% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.10(t,J＝8.0Hz,2H),8.03(d,J＝16.6Hz,1H),7.79–7.67(m,4H),7.51–7.41(m,2H),7.34–7.24(m,1H),7.01(t,J＝7.5Hz,1H),6.94(d,J＝8.3Hz,1H),3.93(s,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝55.6,111.0,119.0,120.8,125.5,126.0,127.2,127.3,127.5,129.2,129.3,129.6,129.8,136.2,148.3,156.8,157.4ppm.CAS Registry Number:77669-18-2.
Example 21
Preparation of trans-disubstituted alkene derivative 3aj
The synthetic route is as follows:
Figure BDA0001578415730000142
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2j (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 aj. The product was a white solid in 85% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.17(d,J＝8.5Hz,1H),8.11(d,J＝8.5Hz,1H),7.82(d,J＝8.1Hz,1H),7.77–7.67(m,3H),7.61–7.51(m,3H),7.42–7.37(m,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.4,126.3,127.4,127.5,128.4,129.0,129.2,129.5,129.8,133.0,134.3,135.0,136.4,148.3,155.6ppm.CAS Registry Number:38101-91-6.
Example 22
Preparation of trans-disubstituted alkene derivative 3ak
The synthetic route is as follows:
Figure BDA0001578415730000151
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2k (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ak. The product was a white solid in 86% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.18-8.05(m,2H),7.87–7.72(m,3H),7.54(t,J＝7.5Hz,1H),7.47–7.41(m,1H),7.36–7.31(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝118.9,126.3,126.9,127.0,127.4,129.2,129.4,129.7,129.9,130.1,131.7,134.5,136.3,148.1,155.7ppm.CAS Registry Number:14174-62-0.
Example 23
Preparation of trans-disubstituted alkene derivatives 3al
The synthetic route is as follows:
Figure BDA0001578415730000152
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2l (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 al. The product was a white solid in 72% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.14(d,J＝8.6Hz,1H),8.08(d,J＝8.5Hz,1H),7.79(d,J＝8.1Hz,1H),7.74-7.69(m,1H),7.66-7.66(m,1H),7.62(d,J＝5.8Hz,1H),7.55–7.48(m,5H),7.39(d,J＝16.3Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.3,122.5,126.3,127.4,127.5,128.6,129.1,129.5,129.8,131.9,133.1,135.4,136.5,148.1,155.5ppm.CAS Registry Number:1220212-12-3.
Example 24
Preparation of trans-disubstituted alkene derivative 3am
The synthetic route is as follows:
Figure BDA0001578415730000161
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2m (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 am. The product was a white solid in 69% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.13(d,J＝8.5Hz,1H),8.07(d,J＝8.9Hz,1H),7.79(d,J＝8.1Hz,1H),7.71(t,J＝8.4Hz,3H),7.65–7.59(m,2H),7.50(t,J＝7.5Hz,1H),7.42–7.35(m,3H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.3,126.2,127.3,127.5,128.3,128.9,129.2,129.4,129.8,132.9,134.2,135.0,136.4,148.2,155.5ppm.CAS Registry Number:1391817-61-0.
Example 25
Preparation of trans-disubstituted alkene derivatives 3an
The synthetic route is as follows:
Figure BDA0001578415730000171
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) is added into 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and,2n (1mmol), reacting at 135 deg.C for 48 hr, stopping reaction, evaporating solvent, and performing column chromatography with ethyl acetate/petroleum ether (1:10) and trans-disubstituted alkene derivative 3 an. The product was a white solid in 70% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.57(d,J＝16.0Hz,1H),8.39(d,J＝8.2Hz,1H),8.19(t,J＝8.8Hz,2H),7.97–7.89(m,3H),7.85(d,J＝8.1Hz,1H),7.80–7.75(m,2H),7.65–7.57(m,3H),7.56–7.49(m,2H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.6,123.7,124.2,125.7,125.9,126.2,126.3,127.5,128.6,128.9,129.3,129.7,136.4,148.3,156.0ppm.CAS Registry Number:190437-71-9.
Example 26
Preparation of trans-disubstituted alkene derivative 3ao
The synthetic route is as follows:
Figure BDA0001578415730000172
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2o (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ao. The product was a white solid in 67% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝7.81(d,J＝16.4Hz,1H),7.75–7.71(m,1H),7.63–7.60(m,2H),7.56–7.53(m,1H),7.47–7.39(m,3H),7.36–7.33(m,2H),7.09(d,J＝15.7Hz,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝111.2,112.0,120.0,121.7,126.0,126.8,127.3,127.5,129.2,129.7,136.3,143.2,148.4,152.9,155.6ppm.CAS Registry Number:1318193-21-3.
EXAMPLE 27 preparation of the Trans-disubstituted alkene derivative 3ap
The synthetic route is as follows:
Figure BDA0001578415730000181
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2p (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ap. The product was a white solid in 93% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.09(dd,J＝14.8,8.5Hz,2H),7.86(d,J＝16.1Hz,1H),7.77–7.69(m,2H),7.54(d,J＝8.6Hz,1H),7.49(t,J＝8.0,3.9Hz,1H),7.30(d,J＝5.1Hz,1H),7.25–7.21(m,2H),7.08–7.05(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝119.2,125.9,125.9,127.1,127.4,127.7,128.0,128.1,129.0,129.6,136.1,141.9,148.1,155.4ppm.CAS Registry Number:73010-95-4.
Example 28
Preparation of trans-disubstituted alkene derivative 3aq
The synthetic route is as follows:
Figure BDA0001578415730000182
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2q (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 aq. The product was a white solid in 69% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.67–8.64(m,1H),8.19–8.14(m,2H),7.87–7.85(m,2H),7.81–7.79(m,1H),7.75–7.67(m,3H),7.61–7.59(m,1H),7.55–7.50(m,1H),7.25–7.19(m,1H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝109.9,120.3,122.8,122.9,126.6,127.5,123.0,136.7,149.7,154.9,155.1ppm.CAS Registry Number:16552-20-8.
Example 29
Trans-disubstituted alkene derivatives 3ar
The synthetic route is as follows:
Figure BDA0001578415730000191
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2r (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was carried out using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ar. The product was a white solid in 74% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.06(d,J＝8.5Hz,2H),7.76(d,J＝8.1Hz,1H),7.71–7.66(m,1H),7.54(d,J＝8.5Hz,1H),7.50–7.45(m,1H),6.85–6.78(m,1H),6.71(d,J＝16.1Hz,1H),2.28(s,1H),1.94–1.72(m,5H),1.45–1.23(m,5H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝26.0,26.1,32.5,41.1,118.6,125.7,127.0,127.3,128.6,129.0,129.4,136.0,143.3,148.0,156.7ppm.CAS Registry Number:1318193-26-8.
Example 30
Preparation of trans-disubstituted alkene derivatives 3as
The synthetic route is as follows:
Figure BDA0001578415730000192
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2s (1mmol) were added theretoAfter 48 hours at 135 ℃, the reaction was stopped, the solvent was evaporated to dryness, and column chromatography was performed on ethyl acetate/petroleum ether (1:10), trans-disubstituted olefin derivative 3 as. The product was a white solid in 85% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.03-7.99(m,2H),7.72(d,J＝8.1Hz,1H),7.68–7.62(m,1H),7.53–7.33(m,2H),6.77(d,J＝15.7Hz,1H),6.42–6.34(m,1H),1.75–1.63(m,1H),0.95–0.88(m,2H),0.69–0.64(m,2H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝8.1,14.9,118.9,125.6,127.0,127.4,128.3,129.0,129.5,136.1,142.0,148.1,156.2ppm.CAS Registry Number:2042682-91-5.
EXAMPLE 31 preparation of trans-disubstituted alkene derivative 3at
The synthetic route is as follows:
Figure BDA0001578415730000201
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2t (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was carried out using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 at. The product was a white solid in 70% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.04(d,J＝8.5Hz,2H),7.73(d,J＝8.1Hz,1H),7.66(t,J＝7.7Hz,1H),7.55(d,J＝8.7Hz,1H),7.45(t,J＝7.5Hz,1H),6.83(d,J＝16.2Hz,1H),6.66(d,J＝16.3Hz,1H),1.19(s,9H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝29.4,33.8,118.5,125.7,126.4,127.0,127.3,129.0,129.4,136.0,148.0,148.1,156.8ppm.CAS Registry Number:1639897-71-4.
Example 32
Preparation of trans-disubstituted alkene derivative 3au
The synthetic route is as follows:
Figure BDA0001578415730000202
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2u (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 au. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ＝8.07–8.02(m,2H),7.74(d,J＝8.1Hz,1H),7.69–7.64(m,1H),7.56(d,J＝8.6Hz,1H),7.48–7.43(m,1H),6.70(d,J＝16.0Hz,1H),6.55(dd,J＝16.0,8.6Hz,1H),2.15–2.04(m,1H),1.64–1.36(m,4H),0.93(t,J＝7.4Hz,6H)ppm；13C NMR(75.41MHz,23.0℃,CDCl3):δ＝11.9,27.5,46.9,118.6,125.8,127.2,127.4,129.2,129.5,131.4,136.1,141.9,148.1,156.5ppm.Elemental analysis calcd for C16H19N(M:225.15)[％]:C,85.28；H,8.50；N,6.22found:C 85.12,H 8.99,N 6.70.

Claims (4)

1. A preparation method of trans-disubstituted alkene is characterized in that primary alcohol and methyl nitrogen-containing heterocycle are used as raw materials, and an olefination reaction is carried out under the condition of ligand, alkali and solvent by catalysis of a transition metal catalyst to obtain a compound with a trans-disubstituted alkene structure;
the general reaction formula is as follows:
Figure FDA0002673848260000011
wherein: x, Y, Z is an independent carbon atom or nitrogen atom, R1And R2Each independently selected from the following groups: hydrogen, halogen, methoxy, straight or branched C1～C20An aromatic group, the aromatic ring represented by the dotted line may be present or absent;
or the like, or, alternatively,
Figure FDA0002673848260000012
wherein: x 'and Y' are independent carbon atoms or nitrogen atoms, R3And R4Each independently selected from the following groups: hydrogen, halogen, methoxy, straight or branched C1～C20An aromatic group, the aromatic ring represented by the dotted line may be present or absent;
or the like, or, alternatively,
Figure FDA0002673848260000013
wherein: r5Selected from the following groups: straight or branched C1～C20An aromatic group;
the transition metal catalyst is Mn (CO)2Br or Mn2(CO)10；
The ligand is (E) -1- (2-pyridyl) -N- (2-picolyl) azomethine [ (E) -1- (pyridine-2-yl) -N- (pyridine-2-ylmethyi) methanimine ], (E) -1- (2-pyridyl) -N- (2-picolyl) ethylenimine [ (E) -1- (pyridine-2-yl) -N- (pyridine-2-ylmethyi) ethane-1-imine ], (E) -2- ((2- (2-pyridyl) hydrazono) methyl) pyridine [ (E) -2- ((2- (pyridine-2-yl) hydrazono) methyl) pyridine ] or [ (E) -2- (2- (1- (2-pyridyl) ethylidene) hydrazono) pyridine ] [ (E) -1- (2-pyridyl) ethylidene) pyridine ] (E) ) -2- (2- (1- (pyridine-2-yl) ethylidene) hydrazinyl) pyridine ];
the alkali is inorganic alkali or organic alkali;
the organic solvent is one or two of benzene, nitromethane, toluene, benzotrifluoride, xylene, mesitylene, 1, 4-dioxane, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, diethyl ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol and tert-amyl alcohol.
2. The method according to claim 1, wherein the linear or branched C is1～C20The group is methyl, ethyl, propyl, isopropyl or butyl.
3. The method according to claim 1, wherein the aromatic group is a phenyl group, a substituted phenyl group, a pyridyl group, a furyl group, a thienyl group, a 1-naphthyl group, a 2-naphthyl group or a substituted naphthyl group.
4. The method according to claim 1, wherein the base is potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium hydride, sodium hydride, lithium hydride, potassium carbonate, or sodium carbonate.
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