CN109422620A - A kind of alkynes high-selectivity reduction at Z- type alkene method - Google Patents
A kind of alkynes high-selectivity reduction at Z- type alkene method Download PDFInfo
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
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Abstract
The invention discloses a kind of alkynes high-selectivity reductions into the method for Z- type alkene: stannous chloride, ligand and potassium tert-butoxide being added in Schlenk reaction tube, vacuumized, under the conditions of protective gas, organic solvent A is added, stirs evenly at room temperature；After dibenzenyl class compound and connection boric acid pinacol ester shown in Formulas I are dissolved in organic solvent B again, it is added drop-wise in the reaction tube, is stirred to react at room temperature 1~12 hour, gained reaction solution is post-treated to obtain Z- type olefin and its derivatives shown in formula II；The ligand is bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3-, bis- (2,6- diisopropyl phenyl) imidazolitm chlorides of 1,3-；The ethyl alcohol cheap using safety is as hydrogen source；Reaction condition is mild, saves energy consumption；The features such as in addition, also having yield high, selectivity is high, and substrate universality is strong, easy to operate.
Description
(1) technical field
The present invention relates to a kind of synthetic method of organic compound, relate in particular to a kind of alkynes high-selectivity reduction at
The method of Z- type alkene.
(2) background technique
Alkenes compounds are a kind of important organic synthesis intermediates, are widely used in medicine, pesticide and material science
Equal fields.They are widely used in polymerization reaction, metathesis reaction, epoxidation reaction, hydroformylation reaction, hydrogen in chemical engineering
Aminating reaction etc..With this, the related synthetic technology for studying alkene has broad prospect of application.
Currently, the most common method of the synthetic method for the related alkene reported both at home and abroad be still using corresponding halogenated hydrocarbons or
The elimination reaction of alcohol.In recent decades, also become a kind of substitution of synthesis functional group using the cross-coupling reaction of aryl olefin
The important method of complicated alkene.In addition, alkynes is exactly reduced to alkene by most important method.Wherein transition metal-catalyzed alkynes
The transfer hydrogenation of hydrocarbon causes the extensive concern of synthesis chemists.In in the past few decades, Pd, Rh, Ru, Fe, Ni
The transfer hydrogenation of equal metal catalytics has obtained significant development.Copper catalyst shows extensive function in such reaction
Group tolerance, from the side for, copper catalyst is a kind of very promising selection, but correlative study is seldom.Copper is urged
The transfer hydrogenation of change first has to form hydrogen copper complex [LCu-H], and hydrogen source common at present is silane, hydrogen, ammonia borine
Deng, and had not been reported by hydrogen source of alcohol.On the other hand, the selectivity of the reduction reaction of alkynes is unavoidable key, such as
It is the key that reaction that obtains Z- or E- product equally with high selectivity.
To sum up, develop it is a kind of with cheap metal replace noble metal, with the cheap hydrogen source of safety, it is highly selective, reaction
The synthetic route that time is short, easy to operate, reaction is mild and there is no over-hydrogenation is come to synthesize alkenes compounds be very
It is necessary to.
(3) summary of the invention
For the deficiencies in the prior art, the present invention is intended to provide a kind of method for preparing alkene analog derivative.
A kind of alkynes high-selectivity reduction at Z- type alkene method, it is characterised in that: the method is specifically pressed as follows
Step carries out:
Stannous chloride, ligand and potassium tert-butoxide are added in Schlenk reaction tube, vacuumized, under the conditions of protective gas,
Organic solvent A is added, stirs evenly at room temperature；Again by dibenzenyl class compound and connection boric acid pinacol ester shown in Formulas I
After being dissolved in organic solvent B, it is added drop-wise in the reaction tube, is stirred to react 1~12 hour (preferably 5 hours) at room temperature, institute
Reaction solution is post-treated obtains Z- type olefin and its derivatives shown in formula II；The ligand is the bis- (2,4,6- tri- of 1,3-
Aminomethyl phenyl) imidazolitm chloride, bis- (2,6- diisopropyl phenyl) imidazolitm chlorides of 1,3-；The stannous chloride, ligand,
The ratio between dibenzenyl class compound, amount of substance of connection boric acid pinacol ester shown in potassium tert-butoxide, Formulas I are as follows: 0.025~
05~0.15:1:1:1~1.2 0.1:0.；
In Formulas I or formula II,
R1Or R2Respectively stand alone as H, CH3、OCH3、F、Cl、Br、CF3, CN or COOCH3；
n1~n2Represent the number of substituent group, n1Or n2Respectively stand alone as 1~5.
Further, the organic solvent A and the organic solvent B are simultaneously methanol, ethyl alcohol, isopropanol or tertiary fourth
Alcohol；Further, while preferably ethyl alcohol.
Further, the addition total amount of organic solvent A and the organic solvent B is with diphenyl shown in the Formulas I
The amount of the substance of acetylene compound is calculated as 15ml/mmol.
Further, the protective gas is nitrogen.
Further, the preferably described ligand is bis- (2,4, the 6- trimethylphenyl) imidazolitm chlorides of 1,3-.
Further, the preferably described stannous chloride, ligand, potassium tert-butoxide, dibenzenyl class chemical combination shown in Formulas I
The ratio between object, amount of substance of connection boric acid pinacol ester are as follows: 0.1:0.15:1:1:1.2.
Further, recommend the post-processing approach of the reaction solution are as follows: after reaction, be added into gained reaction solution
The column chromatography silica gel of 100-200 mesh is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and with body
Product is than being that the petroleum ether of 50:1 and the mixture of ethyl acetate are eluted as eluant, eluent, and TLC tracks elution process, and collection contains
There is the eluent of target product, merges the eluent solvent is evaporated off and obtain Z- type alkene shown in the formula II and its spread out
Biology.
Further, method of the present invention is recommended specifically to carry out as follows:
Stannous chloride, ligand and potassium tert-butoxide are added in Schlenk reaction tube, is vacuumized, is filled and change nitrogen 3 times, is added
Ethyl alcohol stirs 15min at room temperature；Dibenzenyl class compound and connection boric acid pinacol ester shown in Formulas I are dissolved in ethyl alcohol again
In, then be added drop-wise in the reaction tube, it is stirred to react 5 hours, after reaction, is added into gained reaction solution at room temperature
The column chromatography silica gel of 100-200 mesh is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and with body
Product is than being that the petroleum ether of 50:1 and the mixture of ethyl acetate are eluted as eluant, eluent, and TLC tracks elution process, and collection contains
There is the eluent of target product, merges the eluent solvent is evaporated off and obtain Z- type olefin and its derivatives shown in formula II；
The ligand is bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3-；The stannous chloride, ligand, potassium tert-butoxide,
The ratio between dibenzenyl class compound, amount of substance of connection boric acid pinacol ester shown in Formulas I are as follows: 0. 1:0.15:1:1:1.2；
The addition total amount of the ethyl alcohol is calculated as 10ml/mmol with the amount of the substance of dibenzenyl class compound shown in the Formulas I.
The raw material dibenzenyl class compound that the present invention uses can be by corresponding iodobenzene and phenylacetylene through Sonoga
Shira coupling is made, and specifically refers to document [Fu Shaomin et al, Journal of the American C
hemical Society,2016,138,8588-8594].2570863438
Compared with prior art, the beneficial effects of the present invention are:
The present invention passes through alkynes under stannous chloride/ligand/potassium tert-butoxide/connection boric acid pinacol ester catalyst system effect,
It is reduced to alkene by the transfer hydrogenation of alkynes, noble metal is replaced with cheap metal；The ethyl alcohol cheap using safety is as hydrogen
Source；Reaction condition is mild, saves energy consumption；In addition, also having yield high, selectivity is high, and substrate universality is strong, easy to operate
The features such as.
(4) specific implementation method
Invention is further described in detail combined with specific embodiments below, but protection scope of the present invention is not limited to
This:
The synthetic method for the raw material dibenzenyl class compound that the present invention uses:
Iodine benzene-like compounds (10mmol) and phenylacetylene class compound (11mmol) are weighed into there-necked flask, 40mL tri- is added
Ethamine.Liquid nitrogen frozen substitutes nitrogen three times, then is added at one time bis-triphenylphosphipalladium palladium dichloride under nitrogen protection
Reaction mixture is stirred to react until raw material conversion is complete by (0.25mmol) and cuprous iodide (0.1mmol) at 50 DEG C
(TLC detection).It is cooled to room temperature, filters, petroleum ether after reaction, the column of 100-200 mesh is added into gained filtrate
Chromatographic silica gel is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and using petroleum ether as elution
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain dibenzenyl class compound shown in formula 3.
Embodiment 1
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by 0.2mmol dibenzenyl (35.6mg) and 0.24mmol connection boric acid frequency
That alcohol ester molten (61mg) is in 2mL ethyl alcohol, then is added drop-wise in reaction tube, is stirred to react at room temperature 5 hours.After reaction, to
The column chromatography silica gel of 100-200 mesh is added in gained reaction solution and is evaporated under reduced pressure removing solvent, gained crude product is subjected to silica gel
Column chromatography for separation, and eluted using volume ratio for the petroleum ether of 50:1 and the mixture of ethyl acetate as eluant, eluent, T LC
Elution process is tracked, the eluent containing target product is collected, merges the eluent solvent is evaporated off and obtain pure product.It should
Substance is colourless liquid, yield 95%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.29–7.13(m,10H),6.60(s,2H).13C NMR
(101MHz,CDCl3)δ137.2,130.2,128.9,128.2,127.1.
Embodiment 2
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.01mmol stannous chloride (1mg), 0.02mmol 1,3-
(6.9mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, and 1ml is added
Ethanol as solvent stirs 15min at room temperature.Again by 0.2mmol dibenzenyl (35.6mg) and 0.24mmol connection boric acid frequency that
Alcohol ester (61mg) is dissolved in 2mL ethyl alcohol, then is added drop-wise in reaction tube, is stirred to react at room temperature 5 hours.After reaction, to institute
It obtains the column chromatography silica gel that 100-200 mesh is added in reaction solution and is evaporated under reduced pressure removing solvent, gained crude product is subjected to silicagel column
Chromatography, and being eluted using volume ratio for the petroleum ether of 50:1 and the mixture of ethyl acetate as eluant, eluent, T LC with
Track elutes process, collects the eluent containing target product, merges the eluent solvent is evaporated off and obtain pure product.The object
Matter is colourless liquid, yield 75%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.29–7.13(m,10H),6.60(s,2H).13C NMR
(101MHz,CDCl3)δ137.2,130.2,128.9,128.2,127.1.
Embodiment 3
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.005mmol stannous chloride (0.5mg), 0.01mmol 1,3-
(3.4mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.0.2mm ol dibenzenyl (35.6mg) and 0.24mmol are joined into boric acid again
Pinacol ester (61mg) is dissolved in 2mL ethyl alcohol, then is added drop-wise in reaction tube, is stirred to react at room temperature 5 hours.After reaction,
The column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, gained crude product is subjected to silicon
Plastic column chromatography separation, and eluted using volume ratio for the petroleum ether of 50:1 and the mixture of ethyl acetate as eluant, eluent, TLC
Elution process is tracked, the eluent containing target product is collected, merges the eluent solvent is evaporated off and obtain pure product.It should
Substance is colourless liquid, yield 55%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.29–7.13(m,10H),6.60(s,2H).13C NMR
(101MHz,CDCl3)δ137.2,130.2,128.9,128.2,127.1.
Embodiment 4
By bis- (2,6- diisopropyl phenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(12.8mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by 0.2mmol 1- methyl -4- (phenylacetylene base)-benzene (38.4mg) and
0.24mmol connection boric acid pinacol ester (61mg) is dissolved in 2mL ethyl alcohol, then is added drop-wise in reaction tube, and it is small to be stirred to react 5 at room temperature
When.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, by institute
Crude product carry out silica gel column chromatography separation, and using volume ratio for 50:1 petroleum ether and ethyl acetate mixture as elute
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain pure product.The substance is colourless liquid, yield 81%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.32–7.18(m,5H),7.16–7.10(m,2H), 7.02
(d, J=7.6Hz, 2H), 6.55 (s, 2H), 2.30 (s, 3H)13C NMR(101MHz,CDCl3)δ 137.5,136.8,
134.2,130.2,129.5,128.9,128.8,128.8,128.2,126.9,21.2.
Embodiment 5
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml methanol as solvent, stirs 15min at room temperature.Again by 0.2mmol 1- methyl -4- (phenylacetylene base)-benzene (38.4mg) and
0.24mmol connection boric acid pinacol ester (61mg) is dissolved in 2m L methanol, then is added drop-wise in reaction tube, and it is small to be stirred to react 5 at room temperature
When.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, by institute
Crude product carry out silica gel column chromatography separation, and using volume ratio for 50:1 petroleum ether and ethyl acetate mixture as elute
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain pure product.The substance is colourless liquid, yield 29%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.32–7.18(m,5H),7.16–7.10(m,2H), 7.02
(d, J=7.6Hz, 2H), 6.55 (s, 2H), 2.30 (s, 3H)13C NMR(101MHz,CDCl3)δ 137.5,136.8,
134.2,130.2,129.5,128.9,128.8,128.8,128.2,126.9,21.2.
Embodiment 6
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml isopropanol makees solvent, stirs 15min at room temperature.Again by 1-methyl of 0.2mmol-4- (phenylacetylene base)-benzene (38.4mg) and
0.24mmol connection boric acid pinacol ester (61mg) is dissolved in 2m L isopropanol, then is added drop-wise in reaction tube, is stirred to react 5 at room temperature
Hour.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, it will
Gained crude product carries out silica gel column chromatography separation, and using volume ratio be the petroleum ether of 50:1 and the mixture of ethyl acetate as washing
De- agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merge the eluent be evaporated off it is molten
Agent obtains pure product.The substance is colourless liquid, yield 15%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.32–7.18(m,5H),7.16–7.10(m,2H), 7.02
(d, J=7.6Hz, 2H), 6.55 (s, 2H), 2.30 (s, 3H)13C NMR(101MHz,CDCl3)δ 137.5,136.8,
134.2,130.2,129.5,128.9,128.8,128.8,128.2,126.9,21.2.
Embodiment 7
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
The 1ml tert-butyl alcohol makees solvent, stirs 15min at room temperature.Again by 0.2mmol 1-chloro- 4- (phenylacetylene base)-benzene (42.4mg) and
0.24mmol connection boric acid pinacol ester (61mg) is dissolved in the 2mL tert-butyl alcohol, then is added drop-wise in reaction tube, is stirred to react 5 at room temperature
Hour.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, it will
Gained crude product carries out silica gel column chromatography separation, and using volume ratio be the petroleum ether of 50:1 and the mixture of ethyl acetate as washing
De- agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merge the eluent be evaporated off it is molten
Agent obtains pure product.The substance is colourless liquid, yield 5%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.32-7.10 (m, 9H), 6.62 (d, J=12.2Hz, 1H),
6.52 (d, J=12.2Hz, 1H)13C NMR(101MHz,CDCl3)δ136.8,135.6,132.7, 130.9,130.2,
128.9,128.8,128.4,128.3,127.3
Embodiment 8
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by the chloro- 4- of 0.2mmol 1- (phenylacetylene base)-benzene (42.4mg) and
0.24mmol connection boric acid pinacol ester (61mg) is dissolved in 2mL ethyl alcohol, then is added drop-wise in reaction tube, and it is small to be stirred to react 2 at room temperature
When.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, by institute
Crude product carry out silica gel column chromatography separation, and using volume ratio for 50:1 petroleum ether and ethyl acetate mixture as elute
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain pure product.The substance is colourless liquid, yield 67%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.32-7.10 (m, 9H), 6.62 (d, J=12.2Hz, 1H),
6.52 (d, J=12.2Hz, 1H)13C NMR(101MHz,CDCl3)δ136.8,135.6,132.7, 130.9,130.2,
128.9,128.8,128.4,128.3,127.3
Embodiment 9
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by the chloro- 4- of 0.2mmol 1- (phenylacetylene base)-benzene (42.4mg) and
0.24mmol connection boric acid pinacol ester (61mg) is dissolved in 2mL ethyl alcohol, then is added drop-wise in reaction tube, is stirred to react 12 at room temperature
Hour.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, it will
Gained crude product carries out silica gel column chromatography separation, and using volume ratio be the petroleum ether of 50:1 and the mixture of ethyl acetate as washing
De- agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merge the eluent be evaporated off it is molten
Agent obtains pure product.The substance is colourless liquid, yield 93%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.32-7.10 (m, 9H), 6.62 (d, J=12.2Hz, 1H),
6.52 (d, J=12.2Hz, 1H)13C NMR(101MHz,CDCl3)δ136.8,135.6,132.7, 130.9,130.2,
128.9,128.8,128.4,128.3,127.3
Embodiment 10
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by 0.2mmol 1- (phenylacetylene base) -4- trifluoromethyl-benzene (49.2mg)
It is dissolved in 2m L ethyl alcohol, then is added drop-wise in reaction tube with 0.2mmol connection boric acid pinacol ester (61mg), be stirred to react 5 at room temperature
Hour.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, it will
Gained crude product carries out silica gel column chromatography separation, and using volume ratio be the petroleum ether of 50:1 and the mixture of ethyl acetate as washing
De- agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merge the eluent be evaporated off it is molten
Agent obtains pure product.The substance is yellow liquid, yield 80%.
Characterize data:1H NMR(400MHz,CDCl3):δ7.70–7.58(m,4H),7.57–7.50(m,2H), 7.43–
7.31(m,3H).13C NMR(101MHz,CDCl3)δ131.8,131.8,129.9(q,JC-F=32.7Hz), 128.8,
128.5,127.2,125.3(q,JC-F=3.7Hz), 124.0 (q, JC-F=272.6Hz), 122.6,91.8,88.0.
Embodiment 11
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by 0.2mmol 1- methoxyl group -4- (phenylacetylene base)-benzene (41.6mg) and
0.24mmol connection boric acid pinacol ester molten (61mg) is in 2 mL ethyl alcohol, then is added drop-wise in reaction tube, and it is small to be stirred to react 5 at room temperature
When.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, by institute
Crude product carry out silica gel column chromatography separation, and using volume ratio for 50:1 petroleum ether and ethyl acetate mixture as elute
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain pure product.The substance is colourless liquid, yield 88%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.38-7.20 (m, 7H), 6.82 (d, J=7.6Hz, 2H),
6.59(s,2H),3.83(s,3H).13C NMR(101MHz,CDCl3)δ158.6,137.6,130.1, 129.7,129.6,
128.8,128.7,128.2,126.9,113.5,55.1.
Embodiment 12
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by the fluoro- 4- of 0.2mmol 1- (phenylacetylene base)-benzene (39.2mg) and
0.24mmol connection boric acid pinacol ester molten (61mg) is in 2mL ethyl alcohol, then is added drop-wise in reaction tube, and it is small to be stirred to react 5 at room temperature
When.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, by institute
Crude product carry out silica gel column chromatography separation, and using volume ratio for 50:1 petroleum ether and ethyl acetate mixture as elute
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain pure product.The substance is colourless liquid, yield 92%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.30-7.14 (m, 7H), 6.90 (t, J=8.7Hz, 2H),
6.59 (d, J=12.2Hz, 1H), 6.54 (d, J=12.2Hz, 1H)13C NMR (101MHz, CDCl3) δ 161.8 (d, J=
247.6Hz), 137.0,133.1 (d, J=3.4Hz), 130.5 (d, J=7.9Hz), 130.2 (d, J=1.2Hz), 129.0,
(128.8,128.3,127.2,115.1 d, J=21.4Hz)
Embodiment 13
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by 0.2mmol 4- (phenylacetylene base) cyanophenyl (40.6mg) and 0.24mmol
Connection boric acid pinacol ester molten (61mg) is in 2mL ethyl alcohol, then is added drop-wise in reaction tube, is stirred to react at room temperature 5 hours.Reaction knot
Shu Hou, into gained reaction solution be added 100-200 mesh column chromatography silica gel and be evaporated under reduced pressure removing solvent, by gained crude product into
The separation of row silica gel column chromatography, and washed using volume ratio for the petroleum ether of 50:1 and the mixture of ethyl acetate as eluant, eluent
De-, TLC tracks elution process, collects the eluent containing target product, merges the eluent solvent is evaporated off and obtain product
Sterling.The substance is colourless liquid, yield 98%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.52 (d, J=8.2Hz, 2H), 7.34 (d, J=8.2 Hz,
2H), 7.31-7.18 (m, 5H), 6.79 (d, J=12.2Hz, 1H), 6.60 (d, J=12.2Hz, 1H)13C NMR(101MHz,
CDCl3)δ142.1,136.2,133.3,132.0,129.5,128.8,128.5,128.4, 127.8,119.0,110.5.
Embodiment 14
By bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 0.02mmol stannous chloride (2mg), 0.03mmol 1,3-
(10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) are added in Schlenk reaction tube, vacuumize, fill and change nitrogen 3 times, are added
1ml ethanol as solvent, stirs 15min at room temperature.Again by 0.2mmol 4- (phenylacetylene base) methyl benzoate (47.2mg) and
0.24mmol connection boric acid pinacol ester molten (61mg) is in 2mL ethyl alcohol, then is added drop-wise in reaction tube, and it is small to be stirred to react 5 at room temperature
When.After reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and is evaporated under reduced pressure removing solvent, by institute
Crude product carry out silica gel column chromatography separation, and using volume ratio for 50:1 petroleum ether and ethyl acetate mixture as elute
Agent is eluted, and TLC tracks elution process, collects the eluent containing target product, merges the eluent and solvent is evaporated off
Obtain pure product.The substance is colourless liquid, yield 90%.
Characterize data:1H NMR (400MHz, CDCl3): δ 7.80 (d, J=8.2Hz, 2H), 7.20 (d, J=8.2 Hz,
2H), 7.12 (s, 5H), 6.61 (d, J=12.2Hz, 1H), 6.50 (d, J=12.3Hz, 1H), 3.79 (s, 3H) .13C NMR
(101MHz,CDCl3)δ166.9,142.1,136.6,132.2,129.5,129.2,128.8, 128.5,128.3,127.5,
52.0。
Claims (10)
1. a kind of alkynes high-selectivity reduction is at the method for Z- type alkene, it is characterised in that: the method specifically presses following step
It is rapid to carry out:
Stannous chloride, ligand and potassium tert-butoxide are added in Schlenk reaction tube, vacuumizes, is added under the conditions of protective gas
Organic solvent A stirs evenly at room temperature；Dibenzenyl class compound and connection boric acid pinacol ester shown in Formulas I are dissolved in again
It after organic solvent B, is added drop-wise in the reaction tube, is stirred to react at room temperature 1~12 hour, gained reaction solution is post-treated to be obtained
To Z- type olefin and its derivatives shown in formula II；The ligand is bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3-
Or bis- (2,6- diisopropyl phenyl) imidazolitm chlorides of 1,3-；The stannous chloride, ligand, potassium tert-butoxide, two shown in Formulas I
The ratio between phenylacetylene class compound, amount of substance of connection boric acid pinacol ester are as follows: 0.025~0.1:0.05~0.15:1:1:1~
1.2；
In Formulas I or formula II,
R1Or R2Respectively stand alone as H, CH3、OCH3、F、Cl、Br、CF3, CN or COOCH3；
n1~n2Represent the number of substituent group, n1Or n2Respectively stand alone as 1~5.
2. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: described
Organic solvent A and the organic solvent B are while being methanol, ethyl alcohol, isopropanol or the tert-butyl alcohol.
3. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: described
The addition total amount of organic solvent A and organic solvent B is with the meter of the substance of dibenzenyl class compound shown in the Formulas I
For 15ml/mmol.
4. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: described
Protective gas is nitrogen.
5. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: described
Ligand is bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3-.
6. alkynes high-selectivity reduction as claimed in claim 2 is at the synthetic method of Z- type alkene, it is characterised in that: described
Organic solvent A and organic solvent B are simultaneously ethyl alcohol.
7. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: described
Stannous chloride, ligand, potassium tert-butoxide, dibenzenyl class compound, connection boric acid pinacol ester shown in Formulas I substance amount it
Than are as follows: 0.1:0.15:1:1:1.2.
8. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: n1Or n2
It is 1.
9. alkynes high-selectivity reduction as described in claim 1~8 is at the synthetic method of Z- type alkene, it is characterised in that: institute
State the post-processing approach of reaction solution are as follows: after reaction, the column chromatography silica gel of 100-200 mesh is added into gained reaction solution and subtracts
Solvent is distilled off in pressure, gained crude product is carried out silica gel column chromatography separation, and be the petroleum ether and acetic acid of 50:1 with volume ratio
The mixture of ethyl ester is eluted as eluant, eluent, and TLC tracks elution process, collects the eluent containing target product, is merged
The eluent is evaporated off solvent and obtains Z- type olefin and its derivatives shown in the formula II.
10. alkynes high-selectivity reduction as described in claim 1 is at the synthetic method of Z- type alkene, it is characterised in that: described
Method specifically carry out as follows:
Stannous chloride, ligand and potassium tert-butoxide are added in Schlenk reaction tube, is vacuumized, is filled and change nitrogen 3 times, ethyl alcohol is added,
15min is stirred at room temperature；After dibenzenyl class compound and connection boric acid pinacol ester shown in Formulas I are dissolved in ethyl alcohol again, drop
It is added in the reaction tube, is stirred to react at room temperature 5 hours, after reaction, 100-200 mesh is added into gained reaction solution
Column chromatography silica gel and be evaporated under reduced pressure removing solvent, by gained crude product carry out silica gel column chromatography separation, and with volume ratio be 50:
1 petroleum ether and the mixture of ethyl acetate are eluted as eluant, eluent, and TLC tracks elution process, are collected and are produced containing target
The eluent of object, merges the eluent solvent is evaporated off and obtain Z- type olefin and its derivatives shown in formula II；Described matches
Body is bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3-；The stannous chloride, ligand, potassium tert-butoxide, shown in Formulas I
The ratio between dibenzenyl class compound, amount of substance of connection boric acid pinacol ester are as follows: 0.1:0.15:1:1:1.2；The ethyl alcohol
Total amount is added, 10ml/mmol is calculated as with the amount of the substance of dibenzenyl class compound shown in the Formulas I.
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| CN110256192A (en) * | 2019-06-25 | 2019-09-20 | 南通大学 | It is a kind of using alcohol be hydrogen source Photocatalysis selectivity synthesis cis and trans olefins process |
| CN111423304A (en) * | 2020-05-09 | 2020-07-17 | 合肥工业大学 | Synthesis method of 1, 1-difluoroolefin compound |
| CN111454286A (en) * | 2020-05-09 | 2020-07-28 | 合肥工业大学 | Synthetic method of difluoroalkenyl boron compound |
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| CN114085242A (en) * | 2021-12-08 | 2022-02-25 | 南京林业大学 | Synthesis method of iron-catalyzed alkyl internal alkyne compound |
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| CN111423304A (en) * | 2020-05-09 | 2020-07-17 | 合肥工业大学 | Synthesis method of 1, 1-difluoroolefin compound |
| CN111454286A (en) * | 2020-05-09 | 2020-07-28 | 合肥工业大学 | Synthetic method of difluoroalkenyl boron compound |
| CN111423304B (en) * | 2020-05-09 | 2023-02-28 | 合肥工业大学 | Synthetic method of 1,1-difluoroolefin compound |
| CN111454286B (en) * | 2020-05-09 | 2023-08-08 | 合肥工业大学 | Synthesis method of difluoro alkenyl boron compound |
| CN113101977A (en) * | 2021-03-25 | 2021-07-13 | 杭州师范大学 | Preparation method and application of visible light response composite photocatalyst |
| CN114085242A (en) * | 2021-12-08 | 2022-02-25 | 南京林业大学 | Synthesis method of iron-catalyzed alkyl internal alkyne compound |
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| CN115626863B (en) * | 2022-10-18 | 2023-06-23 | 南京工业大学 | Method for preparing chloroethylene by hydrochlorination of acetylene in fixed bed by using low-content ruthenium-based catalyst |
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