CN108250153A - A kind of preparation method of trans- disubstituted alkene - Google Patents

A kind of preparation method of trans- disubstituted alkene Download PDF

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CN108250153A
CN108250153A CN201810144381.9A CN201810144381A CN108250153A CN 108250153 A CN108250153 A CN 108250153A CN 201810144381 A CN201810144381 A CN 201810144381A CN 108250153 A CN108250153 A CN 108250153A
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preparation
trans
disubstituted alkene
base
cdcl
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CN108250153B (en
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张春艳
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Qingdao University of Science and Technology
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Abstract

The present invention discloses a kind of preparation method of trans- disubstituted alkene, belongs to organic chemical synthesis technical field.This method uses simple alcohols and methyl nitrogen heterocyclic ring as starting material, by transition metal-catalyzed olefination, obtains trans- disubstituted olefin(e) compound.The reaction raw materials, catalyst and additive are cheap and easy to get, and synthesis technology is simple, greatly reduce synthesis cost；Reaction condition is mild, and yield is high, is easy to industrialize；Reaction raw materials and catalyst clean are nontoxic, and environmental pollution is small.The trans- disubstituted olefin(e) compound and its derivative are widely used as important fine chemicals in industries such as medicine, pesticide, fragrance and photoelectricity.

Description

A kind of preparation method of trans- disubstituted alkene
Technical field
The invention belongs to organic chemical synthesis technical fields, are related to a kind of preparation method of trans- disubstituted alkene.
Background technology
Alkene has extensive purposes as a kind of important fine chemicals in industries such as pesticide, medicine, fragrance.Alkene Hydrocarbyl group is common pharmacophoric group, is widely present in various natural products and synthetic drug with physiological activity, simultaneously It is also the segment for forming various functions material.For example, trans- disubstituted alkene --- montelukast was grown up suitable for 15 years old or more The prevention and long-term treatment of asthma, the asthma symptoms including prevention daytime and night treat the asthma trouble to aspirin sensitive Person and the bronchoconstriction for preventing exercise induced.Since this kind of use of a compound is special, it is developed in recent years a large amount of Synthetic method.
There are many kinds of the methods of the disubstituted alkene of traditional synthesis of trans：(1) many name reactions (Witting, Horner-Wadsworth-Emmons, Peterson olefination, Julia olefination etc.)；(2) it is catalyzed Heck reacts；(3) Suzuki coupling reactions；(4) olefin metathesis reaction.Although these methods have higher yield, on Stating method largely needs the phosphonate reagent, metal reagent or utilization aldehyde and the limit of equivalent initiator and various additives of equivalent System, practical application are greatly limited.
Before all reactions are all based on equivalents of metal reagent or phosphine Ye Lide reagents participate in reaction, inevitably A large amount of metal waste and organic phosphine compound are generated, economical in reaction is not high, while huge pressure is caused to environment, The requirement of Green Sustainable is not met.Due to the utilization of various additives, reaction substrate expansion is caused to be severely limited, Reaction substrate functional group compatibility is poor, economic and practical not high.
Therefore, directly using alcohol without aldehyde directly with methyl heterocycles compound by olefination, by-product is only For water and hydrogen, high atom economy prepares substrate applicability trans- disubstituted alkene derivatives in extensive range with important Theory significance and prospect is widely applied, meets the requirement of Green Chemistry.
Invention content
The purpose of the present invention is to provide a kind of preparation methods for being concisely and efficiently trans- disubstituted alkene.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
The method that the present invention prepares trans- disubstituted alkene is raw material using primary alcohol and methyl nitrogen heterocyclic ring, passed through It crosses metallic catalyst catalysis and olefination occurs, obtain the compound of trans- disubstituted alkene structures, react 23- under a nitrogen 48 hours；Solvent is drained after reaction, and column chromatography can obtain trans- disubstituted olefin(e) compound；
Its reaction formula is：
The nitrogenous heterocyclic structural formula of methyl is：
Wherein：
X, Y, Z are independent carbon atom or nitrogen-atoms, R1Group is independently selected from hydrogen, halogen or methoxyl group.
The structure of the 01 derivatives is：
Wherein：
R2Group is selected from C1~C10Fat group (such as ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4~ C10Interior aromatic group (such as furyl, furan derivatives base, pyridyl group, pyridine derivate base, thienyl, thiophene derivant base, Phenyl, substituted-phenyl, 1- naphthalenes, 2- naphthalenes).
Or,
The nitrogenous heterocyclic structural formula of methyl is：
Wherein：
X', Y' are independent carbon atom or nitrogen-atoms, R3Group is independently selected from hydrogen, halogen or methoxyl group；
The structure of the 01 derivatives is：
Wherein：
R4Group is selected from C1~C10Fat group (such as ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4~ C10Interior aromatic group (such as furyl, furan derivatives base, pyridyl group, pyridine derivate base, thienyl, thiophene derivant base, Phenyl, substituted-phenyl, 1- naphthalenes, 2- naphthalenes).
Or,
The nitrogenous heterocyclic structural formula of methyl is：
The structure of the contracting amine aldehyde derivatives is：
Wherein：
R5Group is selected from C1~C10Fat group (such as ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4~ C10Interior aromatic group (such as furyl, furan derivatives base, pyridyl group, pyridine derivate base, thienyl, thiophene derivant base, Phenyl, substituted-phenyl, 1- naphthalenes, 2- naphthalenes).
The alkali is potassium tert-butoxide, sodium tert-butoxide, tert-butyl alcohol lithium, bis- (trimethylsilyl) potassamides, bis- (trimethyl silicanes Alkyl) Sodamide, bis- (trimethylsilyl) lithium amides, sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrofining, sodium hydride, Lithium hydride, potassium carbonate or sodium carbonate；It is preferred that potassium hydroxide, sodium hydroxide or hydrofining.
The catalyst is pentacarbonyl manganous bromide (Mn (CO)2Br) or ten carbonyls close manganese (Mn2(CO)10), the use of catalyst Measure 0.5%~10% for contracting amine aldehyde derivatives mole.
The ligand is (E) -1- (2- pyridyl groups)-N- (2- picolyls) azomethine
[(E) -1- (pyridin-2-yl)-N- (pyridin-2-ylmethyl) methanimine], (E) -1- (2- pyrroles Piperidinyl)-N- (2- picolyls) ethyleneimine [(E) -1- (pyridin-2-yl)-N- (pyridin-2-ylmethyl) ethan- 1-imine], (E) -2- ((2- (2- pyridyl groups) hydrazono-) methyl) pyridine [(E) -2- ((2- (pyridin-2-yl) Hydrazono) methyl) pyridine] or [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyridine] [(E) -2- (2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)pyridine]。
The organic solvent for benzene, nitromethane, toluene, benzotrifluoride, dimethylbenzene, mesitylene, 1,4- dioxane, Acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1,2- dichloroethanes, ether, glycol dimethyl ether, methyl tertiary butyl ether(MTBE), Methylcyclopentyl ether, tetrahydrofuran, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), methanol, ethyl alcohol One or both of with tertriary amylo alcohol.It is preferred that tertriary amylo alcohol and toluene Mixed Solvent.
The present invention has the following advantages relative to the prior art：
1st, the present invention is carried out anti-industrially under the catalysis of metallic catalyst cheap and easy to get by alcohol and methyl nitrogen heterocyclic ring Should, by the method for alkenyl, an only step can efficiently prepare trans- disubstituted olefin(e) compound, the reaction raw materials and catalysis Agent is cheap and easy to get, and synthesis technology is simple, greatly reduces synthesis cost；
2nd, the present invention can efficiently synthesize trans- disubstituted alkene with a step, this is to be obtained for the first time using alcohol by olefination To trans- disubstituted olefin(e) compound.
3rd, reaction condition of the present invention is mild, easy to operate, and yield is high, and substrate applicability range is wide, is easy to industrialize.
4th, reaction raw materials (alcohol) of the present invention and catalyst (manganese) cleaning are nontoxic cheap, and environmental pollution is small.
5th, reaction process cleaning of the present invention, more meets the requirement of Green Chemistry.
6th, the reaction transformation efficiency is higher, can realize a gram grade amplification test, it is easy to accomplish industrialization.
Specific embodiment
The invention will be further described below.
Embodiment 1
The preparation of trans- disubstituted alkene derivatives 3a
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylpyrazines 1a (2mmol), benzylalcohol 2a (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3a of formula.Product is white solid, yield 81%.
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.
Embodiment 2
The preparation of trans- disubstituted alkene derivatives 3b
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 1a (2mmol), benzylalcohol 2b (1mmol), after Stop reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours in 135 DEG C:10), trans- disubstituted alkene Hydrocarbon derivative 3b.Product is white solid, yield 63%.
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.
Embodiment 3
The preparation of trans- disubstituted alkene derivatives 3c
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylpyrazines 1a (2mmol), benzylalcohol 2c (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3c of formula.Product is white solid, yield 81%.
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.
Embodiment 4
The preparation of trans- disubstituted alkene derivatives 3d
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylpyrazines 1a (2mmol), benzylalcohol 2d (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3d of formula.Product is white solid, yield 68%.
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.
Embodiment 5
The preparation of trans- disubstituted alkene derivatives 3e
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylpyrazines 1a (2mmol), benzylalcohol 2e (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3e of formula.Product is white solid, yield 83%.
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.
Embodiment 6
The preparation of trans- disubstituted alkene derivatives 3f
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 1b (2mmol), benzylalcohol 2a (1mmol), after Stop reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours in 135 DEG C:10), trans- disubstituted alkene Hydrocarbon derivative 3f.Product is white solid, yield 80%.
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.
Embodiment 7
The preparation of trans- disubstituted alkene derivatives 3g
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylpyrazines 1c (2mmol), benzylalcohol 2a (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3g of formula.Product is white solid, yield 60%.
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.
Embodiment 8
The preparation of trans- disubstituted alkene derivatives 3h
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, 1d (2mmol), 2a (1mmol) is added in, after 135 DEG C reaction 48 hours after stop reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1:10), trans- disubstituted alkene spreads out Biological 3h.Product is white solid, yield 70%.
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 =110.3,113.9,119.8,124.5,125.2,127.5,128.9,129.8,135.1,13 9.4,142.2,150.4, 162.8ppm.CAS:59066-62-5.
Embodiment 9
The preparation of trans- disubstituted alkene derivatives 3i
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 1e (2mmol), benzylalcohol 2a (1mmol), after Stop reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours in 135 DEG C:10), trans- disubstituted alkene Hydrocarbon derivative 3i.Product is white solid, yield 57%.
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.
Embodiment 10
The preparation of trans- disubstituted alkene derivatives 3j
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 1f (2mmol), benzylalcohol 2a (1mmol), after Stop reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours in 135 DEG C:10), trans- disubstituted alkene Hydrocarbon derivative 3j.Product is white solid, yield 86%.
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.
Embodiment 11
The preparation of trans- disubstituted alkene derivatives 3k
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 1g (2mmol), benzylalcohol 2a (1mmol), after Stop reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours in 135 DEG C:10), trans- disubstituted alkene Hydrocarbon derivative 3k.Product is white solid, yield 95%.
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.
Embodiment 12
The preparation of trans- disubstituted alkene derivatives 3aa
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), benzylalcohol 2a (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3aa of formula.Product is white solid, yield 94%.
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.
Embodiment 13
The preparation of trans- disubstituted alkene derivatives 3ab
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2b (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ab of formula.Product is white solid, yield 92%.
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.
Embodiment 14
The preparation of trans- disubstituted alkene derivatives 3ac
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2c (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ac of formula.Product is white solid, yield 94%.
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=21.5,119.2,124.5,126.1,127.5,128.0,128.7,128.90,129.2,12 9.5,129.7, 134.5,136.3,136.5,148.3,156.1ppm.CAS Registry Number:1318193-16-6.
Embodiment 15
The preparation of trans- disubstituted alkene derivatives 3ad
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2d (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ad of formula.Product is white solid, yield 81%.
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.
Embodiment 16
The preparation of trans- disubstituted alkene derivatives 3ae
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2e (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ae of formula.Product is white solid, yield 80%.
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
Embodiment 17
The preparation of trans- disubstituted alkene derivatives 3af
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2f (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3af of formula.Product is white solid, yield 86%.
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.
Embodiment 18
The preparation of trans- disubstituted alkene derivatives 3ag
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2g (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ag of formula.Product is white solid, yield 92%.
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
Embodiment 19
The preparation of trans- disubstituted alkene derivatives 3ah
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2h (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ah of formula.Product is white solid, yield 96%.
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.
Embodiment 20
The preparation of trans- disubstituted alkene derivatives 3ai
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2i (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ai of formula.Product is white solid, yield 93%.
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.
Embodiment 21
The preparation of trans- disubstituted alkene derivatives 3aj
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2j (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3aj of formula.Product is white solid, yield 85%.
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.
Embodiment 22
The preparation of trans- disubstituted alkene derivatives 3ak
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2k (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ak of formula.Product is white solid, yield 86%.
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=118.9,126.3,126.9,127.0,127.4,129.2,129.4,129.7,129.9,13 0.1,131.7, 134.5,136.3,148.1,155.7ppm.CAS Registry Number:14174-62-0.
Embodiment 23
The preparation of trans- disubstituted alkene derivatives 3al
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2l (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3al of formula.Product is white solid, yield 72%.
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.
Embodiment 24
The preparation of trans- disubstituted alkene derivatives 3am
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2m (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3am of formula.Product is white solid, yield 69%.
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.
Embodiment 25
The preparation of trans- disubstituted alkene derivatives 3an
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2n (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3an of formula.Product is white solid, yield 70%.
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.
Embodiment 26
The preparation of trans- disubstituted alkene derivatives 3ao
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2o (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ao of formula.Product is white solid, yield 67%.
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.
The preparation of the trans- disubstituted alkene derivatives 3ap of embodiment 27
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2p (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ap of formula.Product is white solid, yield 93%.
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=119.2,125.9,125.9,127.1,127.4,127.7,128.0,128.1,129.0,12 9.6,136.1, 141.9,148.1,155.4ppm.CAS Registry Number:73010-95-4.
Embodiment 28
The preparation of trans- disubstituted alkene derivatives 3aq
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2q (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3aq of formula.Product is white solid, yield 69%.
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.
Embodiment 29
Trans- disubstituted alkene derivatives 3ar
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2r (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3ar of formula.Product is white solid, yield 74%.
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.
Embodiment 30
The preparation of trans- disubstituted alkene derivatives 3as
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2s (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3as of formula.Product is white solid, yield 85%.
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.
The preparation of the trans- disubstituted alkene derivatives 3at of embodiment 31
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2t (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3at of formula.Product is white solid, yield 70%.
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.
Embodiment 32
The preparation of trans- disubstituted alkene derivatives 3au
Its synthetic route is as follows：
In glove box, by Mn (CO)5Br (0.005mmol), [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyrrole Pyridine] (0.006mmol), it adds in 1.0mL toluene, after stirring two hours, adds in 2- methylquinolines 4 (2mmol), 2u (1mmol) stops reaction, solvent evaporated, column chromatography ethyl acetate/petroleum ether (1 after being reacted 48 hours after 135 DEG C:10), instead The disubstituted alkene derivatives 3au of formula.Product is white solid, yield 81%.
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 (7)

1. a kind of preparation method of trans- disubstituted alkene, which is characterized in that using primary alcohol and methyl nitrogen heterocyclic ring it is raw material, It is catalyzed by transition-metal catalyst and olefination occurs, obtain the compound of trans- disubstituted alkene structures；
Its reaction formula is：
Wherein：X, Y, Z are independent carbon atom or nitrogen-atoms, R1And R2It is independently selected from following groups：Hydrogen, halogen, methoxy Base, linear chain or branch chain C1~C20, aromatic group；
Or,
Wherein：X', Y' are independent carbon atom or nitrogen-atoms, R3And R4It is independently selected from following groups：Hydrogen, halogen, methoxy Base, linear chain or branch chain C1~C20, aromatic group；
Or,
Wherein：R5Selected from following groups：Linear chain or branch chain C1~C20, aromatic group.
2. preparation method according to claim 1, which is characterized in that the linear chain or branch chain C1~C20Group for methyl, Ethyl, propyl, isopropyl, butyl, benzyl, cyclohexyl or cyclopropyl.
3. preparation method according to claim 1, which is characterized in that the aromatic group is phenyl, substituted-phenyl, pyridine Base, pyridine derivate base, furyl, furan derivatives base, thienyl, thiophene derivant base, 1- naphthalenes, 2- naphthalenes or substitution naphthalene Base.
4. preparation method according to claim 1, which is characterized in that the transition-metal catalyst is Mn (CO)2Br or Mn2(CO)10。
5. preparation method according to claim 1, which is characterized in that the ligand is (E) -1- (2- pyridyl groups)-N- (2- Picolyl) azomethine [(E) -1- (pyridin-2-yl)-N- (pyridin-2-ylmethyl) methanimine], (E) - 1- (2- pyridyl groups)-N- (2- picolyls) ethyleneimine [(E) -1- (pyridin-2-yl)-N- (pyridin-2-ylmethyl) Ethan-1-imine], (E) -2- ((2- (2- pyridyl groups) hydrazono-) methyl) pyridine [(E) -2- ((2- (pyridin-2-yl) Hydrazono) methyl) pyridine] or [(E) -2- (2- (1- (2- pyridines) ethylidene) connects diazanyl) pyridine] [(E) -2- (2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)pyridine]。
6. preparation method according to claim 1, which is characterized in that the alkali is inorganic base or organic base；It is preferred that tertiary fourth Potassium alcoholate, sodium tert-butoxide, tert-butyl alcohol lithium, bis- (trimethylsilyl) potassamides, bis- (trimethylsilyl) Sodamides, bis- (front threes Base silane base) lithium amide, sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrofining, sodium hydride, lithium hydride, potassium carbonate or carbonic acid Sodium.
7. preparation method according to claim 1, which is characterized in that the organic solvent for benzene, nitromethane, toluene, Benzotrifluoride, dimethylbenzene, mesitylene, 1,4- dioxane, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1,2- bis- Chloroethanes, ether, glycol dimethyl ether, methyl tertiary butyl ether(MTBE), methylcyclopentyl ether, tetrahydrofuran, N,N-dimethylformamide, One or both of DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), methanol, ethyl alcohol and tertriary amylo alcohol.
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CN112300085A (en) * 2020-11-17 2021-02-02 温州大学 Alkenyl method of methyl heterocyclic compound

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CN111253305A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Alkenyl or alkylation reaction method of alkyl substituted azaarene
CN111253305B (en) * 2018-11-30 2022-09-02 中国科学院大连化学物理研究所 Alkenyl or alkylation reaction method of alkyl substituted azaarene
CN109678854A (en) * 2019-01-22 2019-04-26 陕西师范大学 A kind of method that manganese catalyzes and synthesizes pyrido [1,2-a] indoles -6 (1H) -one class compound
CN109678854B (en) * 2019-01-22 2021-04-09 陕西师范大学 Method for synthesizing pyrido [1,2-a ] indole-6 (1H) -ketone compound by manganese catalysis
CN110804015A (en) * 2019-11-12 2020-02-18 河北科技大学 Preparation method of trans-disubstituted olefin
CN110804015B (en) * 2019-11-12 2021-08-20 河北科技大学 Preparation method of trans-disubstituted olefin
CN112300085A (en) * 2020-11-17 2021-02-02 温州大学 Alkenyl method of methyl heterocyclic compound

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