CN114262252B - Method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt - Google Patents

Method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt Download PDF

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CN114262252B
CN114262252B CN202111321933.7A CN202111321933A CN114262252B CN 114262252 B CN114262252 B CN 114262252B CN 202111321933 A CN202111321933 A CN 202111321933A CN 114262252 B CN114262252 B CN 114262252B
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quaternary ammonium
ammonium salt
alkyne
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alkane
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樊保敏
周永云
陈景超
徐建斌
和振秀
樊瑞峰
孙蔚青
郭琪
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Yunnan Minzu University
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Abstract

The invention discloses a method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt, which comprises the following steps: 1) Alkyne is taken as an initial raw material, alkyne and quaternary ammonium salt catalyst are added into a reaction tube in a glove box, a certain amount of organic solvent is added, and then hydrogen with the pressure of 0.5-3MPa is introduced into the reaction tube to carry out stirring reaction at constant temperature to obtain reaction liquid; 2) And removing volatile solvents from the reaction liquid, and purifying by column chromatography to obtain olefin or alkane. The invention takes the cheap and easily available hydrogen as a hydrogen source, adopts the organic micromolecular quaternary ammonium salt as a catalyst, can realize the hydrogenation of alkyne compounds without transition metal and oxidant, not only reduces the cost required by experiments, greatly reduces the production cost, but also has high atom utilization rate and does not generate any byproducts. The catalyst adopted by the invention has the advantages of mild reaction conditions, simple catalytic system, high reaction selectivity, environment friendliness, stable catalysis, easy acquisition and easy recovery, is environment-friendly, and is worthy of popularization and application.

Description

Method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt.
Background
Olefin compounds have wide industrial application in the fields of fine chemical industry, medicines, pesticides, dyes, fragrances, hydrogen storage materials and the like. Particularly in terms of materials. The olefin has wide prospect in the aspect of luminescent materials, and researches show that the electroluminescent device is prepared by taking an olefin compound as a luminescent layer, and has the structure as follows: ITO/CuPc/NPB/DPVBi/Alq 3 Electroluminescent properties of the device were studied/LiF/Al. The highest brightness of the device reaches 4373cd/cm 2 The maximum lumen efficiency was 124lm/W, and the brightness at 20mA/cm2 current density was 434cd/cm 2 The CIE color coordinates are (x=0 15, y=0 16), and the blue luminescence of the device has better color purity. In addition, olefin compounds are also very widely used in the medical field, and studies have shown that a bipolar adsorbent based on a super-crosslinked ethylene polymer can be effectively used for treating patients with bacteremia, sepsis and septic shock of different origins.
Alkane compounds have great contribution to human beings in industry, and lower alkanes such as methane are common civil fuels and industrial raw materials. Medium alkanes such as gasoline, kerosene, diesel and the like are common industrial dyes, and vaseline which we use as a lubricant is also a common alkane.
Since olefins and paraffin compounds have wide applications in life, their researches have been attracting attention. Researchers have employed a number of different hydrogenation processes to synthesize olefins and alkane compounds. The most commonly used method at present adopts the transition metal catalytic hydrogenation reaction to prepare, but common transition metal catalysts are expensive, have severe requirements on experimental conditions, such as sensitivity to water and air, and have great operation difficulty.
Therefore, it is highly desirable to develop a mild, low cost, and efficient process for preparing olefin compounds.
Disclosure of Invention
The invention aims to provide a method for efficiently preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt.
The invention aims at realizing the method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt, which comprises the following steps:
1) Alkyne is taken as an initial raw material, alkyne and quaternary ammonium salt catalysts are added into a reaction tube in a glove box, a certain amount of organic solvent is added, and then hydrogen with the pressure of 0.5-3MPa is introduced into the reaction tube to carry out stirring reaction at a constant temperature to obtain reaction liquid;
2) And removing volatile solvents from the reaction liquid, and purifying by column chromatography to obtain olefin or alkane.
The beneficial effects of the invention are as follows:
1. the invention takes the cheap and easily available hydrogen as a hydrogen source, adopts the organic micromolecular quaternary ammonium salt as a catalyst, can realize the hydrogenation of alkyne compounds without transition metal and oxidant, not only reduces the cost required by experiments, greatly reduces the production cost, but also has high atom utilization rate and does not generate any byproducts.
2. The catalyst adopted by the invention has the advantages of mild reaction conditions, simple catalytic system, high reaction selectivity, environment friendliness, stable catalysis, easy acquisition and easy recovery, is environment-friendly, and is worthy of popularization and application.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of example 11;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of example 17.
Detailed Description
The invention is further illustrated, but is not limited in any way, by the following examples, and any alterations or substitutions based on the teachings of the invention are within the scope of the invention.
The invention discloses a method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt, which comprises the following steps:
1) Alkyne is taken as an initial raw material, alkyne and quaternary ammonium salt catalyst are added into a reaction tube in a glove box, a certain amount of organic solvent is added, and then hydrogen with the pressure of 0.5-3MPa is introduced to carry out stirring reaction at constant temperature to obtain reaction liquid;
2) And removing volatile solvents from the reaction liquid, and purifying by column chromatography to obtain olefin or alkane.
The quaternary ammonium salt catalyst is Bu 4 NBr、Bu 4 NCl、Bu 4 NOTf、Bu 4 NI、Bu 4 NPF 6 Or Me 4 NI。
When the alkene is prepared, the mass ratio of alkyne to quaternary ammonium salt catalyst is 15-25:1.
When preparing alkane, the mass ratio of alkyne to quaternary ammonium salt catalyst is 0.1-4:1.
In the step 1, the organic solvent is tetrahydrofuran, toluene, dichloroethane or 1, 4-dioxane.
In the step 1, the reaction temperature in the reaction tube is 70-80 ℃.
In the step 2, ethyl acetate/petroleum ether is used as an eluent in the column chromatography.
In the step 2, the volatile solvent is volatilized by a rotary evaporator under reduced pressure.
The invention is further illustrated by the following examples.
Example 1
In a glove box, 4-acetylenic hydrocarbon biphenyl (35.6 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium bromide (3.3 mg,0.01 mmol) was weighed, 2ml of tetrahydrofuran was taken out by a pipette and 0.5MPa of hydrogen gas was introduced, and the mixture was placed in a magnetic stirrer to stir at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-vinylbiphenyl (32.0 mg,91% yield).
1 H NMR (400MHz，CDCl3)：δ7.69-7.55(m，4H)，7.54-7.41(m，4H),7.40-7.33(m，1H)，6.79(dd，J=17.6，10.9Hz，1H)，5.83(dd，J=17.6，1Hz，1H)，5.31(dd，J=10.8，0.9Hz，1H)，1.29(s，1H)
The reaction formula is as follows:
。
example 2
In a glove box, 3-fluorobiphenyl alkyne (39.2 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium iodide (5.6 mg,0.01 mmol) was weighed, 2ml toluene was taken out by a pipette and 0.5MPa hydrogen gas was introduced, and the reaction was stirred in a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain 2-fluorobiphenyl (34 mg,89% yield).
1 H NMR (400MHz，CDCl3)：δ8.35-8.55(m，4H)，8.25-8.30(m，4H)，7.40-7.33(m，1H)，5.23(dd，J=17.6，10.9Hz，1H)，5.12(dd，J=17.6，1Hz，1H)，3.31(dd，J=10.8，0.9Hz，1H)
The reaction formula is as follows:
。
example 3
In a glove box, 2-methoxybiphenyl ethyne (41.6 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium triflate (7.8 mg,0.01 mmol) was weighed, 2ml toluene was taken out by a pipette, 1.0MPa of hydrogen was introduced, and the reaction was stirred in a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain 2-methoxybiphenyl ethylene (35 mg,86% yield).
1 H NMR (400MHz，CDCl3)：δ7.25(t，J=8.3Hz，2H)，7.17(d，J=7.8Hz，2H)，6.66-6.59(m，2H)，6.59-6.53(m，2H)，4.43(dd，J=8.2，3.1Hz，1H)，3.42(dd，J=11.1，3.1Hz，1H)，3.29(dd，J=11.0，8.2Hz，1H)，2.35(s，3H)
The reaction formula is as follows:
。
example 4
In a glove box, phenylacetylene (20.4 mg,0.2 mmol) was accurately weighed and charged into a stirred reaction tube, tetramethyl ammonium iodide (4.0 mg,0.01 mmol) was weighed, 2ml toluene was taken from a pipette, 3.0MPa of hydrogen gas was introduced, and the reaction tube was placed in a magnetic stirrer and stirred at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain styrene (18.9 mg,93% yield).
1 H NMR (400MHz，CDCl3)：δ7.42-7.40(m，2H)，7.34-7.30(m，2H)，7.26-7.23(m，1H)，6.63(dd，J=17.6，10.92Hz，1H)，5.61(d，J=17.6Hz，1H)，5.18(d，J=10.9Hz，1H)
The reaction formula is as follows:
。
example 5
In a glove box, 2-naphthylacetylene hydrocarbon (30.4 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium tetrafluoroborate (3.2 mg,0.01 mmol) was weighed, 2ml of tetrahydrofuran was taken out by a pipette, 0.5MPa of hydrogen gas was introduced, and the mixture was placed in a magnetic stirrer and stirred at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain 2-naphthylethylene (28.5 mg,93% yield).
1 H NMR (400 MHz，CDCl3 )：δ7 .81-7.77(m，3H)，7 .44(S，1H)，7 .64-7 .62(m，1H)， 7 .47-7 .40(m，2H)，6 .87(dd，J = 17 .6Hz，10 .9HZ，1H)，5.18(d，J = 10 .9Hz，1H)
The reaction formula is as follows:
。
example 6
In a glove box, 2-acetylene hydrocarbon anthracene (40.4 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetraphenyl phosphine iodide (4.6 mg,0.01 mmol) was weighed, 2ml of tetrahydrofuran was taken out by a pipette, 2.5MPa of hydrogen gas was introduced, and the mixture was placed in a magnetic stirrer and stirred at 85 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain acetylene hydrocarbon anthracene (38.5 mg,94% yield).
1 H NMR (400 MHz，CDCl3 ) ：δ8.36(s，2H)，7 .85(S，1H)，7.65(dd，J=8 .9，1 .6 Hz， 1H)，7 .51-7.40(m，2H)，6 .92(dd，J= 17 .6Hz，10.9HZ，1H)，5 .18(d，J = 10 .9Hz，1H)
The reaction formula is as follows:
。
example 7
In a glove box, 4-methoxycarbonyl phenylacetylene (32 mg,0.2 mmol) was accurately weighed and placed in a reaction tube with a stirrer, tetraphenyl phosphine iodide (4.6 mg,0.01 mmol) was weighed, 2ml of tetrahydrofuran was taken out by a pipette, 1.5MPa of hydrogen gas was introduced, and the mixture was placed in a magnetic stirrer and stirred at 75 ℃. After the reaction was completed, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give methyl 4-vinylbenzoate (28.0 mg,90% yield).
1 H NMR (400 MHz，CDCl3 ) ：δ8 .03-7.81(m，2H)，7 .59-7 .43(m，2H)，6.65(dd,J= 8 .9，1 .6 Hz，1H)，7 .51-7 .40(m，2H)，6 .92(dd，J = 17 .6Hz，10 .9HZ，1H)，5 .18(d，J = 10 .9Hz，1H)
The reaction formula is as follows:
。
example 8
In a glove box, 4-methylphenylacetylene hydrocarbon (23.2 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium chloride (2.8 mg,0.01 mmol) was weighed, 2ml of a tetradioxane was taken out by a pipette, 2.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 75 ℃. After the reaction was completed, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain 20.0mg of 4-methylstyrene (20 mg,85% yield).
1 H NMR (400 MHz，CDCl3 ) ：δ7 .37-7.35(m，2H)，7 .19-7 .17(m，2H)，6 .77-6.70(m， 0.1H) 5 .77-5 .72(m，2H)，2 .39(s，3H)
The reaction formula is as follows:
。
example 9
In a glove box, 4-chlorobenzeneethyne (27.2 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium chloride (2.8 mg,0.01 mmol) was weighed, 2ml of a tetradioxane was taken out by a pipette, 0.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-chlorostyrene yield (24.8 mg,91% yield).
1 H NMR (400 MHz，CDCl3 )：δ7 .37-7.28(m，2H)，7 .19-7 .17(m，2H)，6 .77-6.70(m，1 H) 5 .77-5 .72(m，2H)，2 .39(s，3H)
The reaction formula is as follows:
。
example 10
In a glove box, 4-bromophenylacetylene hydrocarbon (36.0 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium chloride (2.8 mg,0.01 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 3.0MPa of hydrogen gas was introduced, and the mixture was stirred in a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-bromostyrene (27.8 mg,91% yield).
1 H NMR (400 MHz，CDCl3 )：δ7 .45-7.42(m，2H)，7 .28-7 .25(m，2H)，6 .68-6.61(m， 1H) 5 .77-5 .72(m ,2H)，5 .30-5 .25(s，3H)
The reaction formula is as follows:
。
example 11
In a glove box, 4-tert-butylphenylacetylene (31.6 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetraphenylphosphine iodide (4.6 mg,0.01 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 1.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 80 ℃. After the completion of the reaction, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-t-butylstyrene (28.4 mg,90% yield).
1 H NMR(400 MHz ,CDCl3 )：δ7 .44-7 .40(m，4 H)，6 .83-6 .74(m，2H)，5 .77-5 .75(m，1 H)，5 .42-5 .26(m，1H)
The reaction formula is as follows:
。
example 12
In a glove box, 4-acetylene hydrocarbon benzonitrile (25.4 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium bromide (3.3 mg,0.01 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 0.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 80 ℃. After the completion of the reaction, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-vinylbenzonitrile (23.6 mg,93% yield).
1 H NMR(400 MHz，CDCl3 )：δ7 .61-7.60(m，2H)，6 .77-6 .74(m，1H)，5 .77-5.76(m， 1H)，5 .42-5 .26(m，1H)
The reaction formula is as follows:
。
example 13
In a glove box, 3, 5-Ditrifluoromethylphenylacetylene (47.6 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium bromide (3.3 mg,0.01 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 2.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain 3, 5-bistrifluoromethyl styrene (44.3 mg,93% yield).
1 H NMR(400 MHz，CDCl3 )：δ7 .38-7.36(m，2H)，6 .77-6 .74(m ,1H)，5 .77-5 .76(m， 1H)，5 .42-5 .26(m，1H)
The reaction formula is as follows:
。
example 14
In a glove box, m-tolueneethyne (23.2 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium bromide (3.3 mg,0.01 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 1.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain m-toluylene (21.5 mg,93% yield).
1 HNMR(400 MHz，CDCl3 )：δ7 .38-7.33(m，2H)，7 .18-7 .15(m，2H)，6 .77-6.74(m，1H)，5 .07-5 .00(m，1H)
The reaction formula is as follows:
。
example 15
In a glove box, ethyl phenylpropionate (32.0 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium triflate (7.8 mg,0.01 mmol) was weighed, 2ml toluene was taken out by a pipette, 2.5MPa hydrogen gas was introduced, and the reaction was stirred in a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain ethyl benzoate (28 mg,88% yield).
1 H NMR (400 MHz，CDCl3 )：δ7 .25(t，J = 8 .3 Hz，2H) , 7 .17(d，J = 7 .8 Hz，2H)， 6.66-6 .59(m，2H)，6 .59-6 .53(m，2H)，4.43(dd，J = 8 .2，3 .1 Hz，1H)，3.42(dd，J = 11 .1， 3 .1 Hz，1H)，3.29(dd，J = 11 .0，8 .2 Hz，1H)，2.35(s，3H)
The reaction formula is as follows:
。
example 16
In a glove box, ethyl propiolate (20.0 mg,0.2 mmol) was accurately weighed and charged into a stirred reaction tube, tetraphenyl phosphine iodide (4.6 mg,0.01 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 0.5MPa of hydrogen gas was introduced, and the reaction was stirred in a magnetic stirrer at 80 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain ethyl acrylate (18.2 mg,90% yield).
1 H NMR(400 MHz ,CDCl3 ) ：δ7 .44-7 .40(m，4 H)，6 .83-6 .74(m，2H)，5 .77-5 .75(m，1 H)，5 .42-5 .26(m，1H)
The reaction formula is as follows:
。
example 17
In a glove box, p-nitroacetylene (29.4 mg,0.2 mmol) was accurately weighed and charged into a stirred reaction tube, tetrabutylammonium bromide (16.5 mg,0.05 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 0.5MPa of hydrogen was introduced, and the reaction was stirred under a magnetic stirrer at 70 ℃. After the reaction was completed, the reactor was opened and volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to obtain p-ethylnitrobenzene (27.3 mg,93% yield).
1 H NMR(400 MHz ,CDCl3 ) ：δ7 .61-7 .60(m，2H)，6 .77-6 .74(m，1H)，5 .77-5 .76(m， 1H)，5 .42-5 .26(m，1H)
The reaction formula is as follows:
。
example 18
In a glove box, 4-acetylene hydrocarbon benzonitrile (25.4 mg,0.2 mmol) was accurately weighed and charged into a stirred reaction tube, tetrabutylammonium bromide (33 mg,0.1 mmol) was weighed, 2mL of tetrahydrofuran was taken out by a pipette, 1.5MPa of hydrogen gas was introduced, and the reaction was stirred in a magnetic stirrer at 80 ℃. After the completion of the reaction, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-ethylbenzonitrile (23.6 mg,93% yield).
1 H NMR(400 MHz ,CDCl3 ) ：δ7 .61-7 .60(m，2H)，6 .77-6 .74(m，1H)，5 .77-5 .76(m， 1H)，5 .42-5 .26(m，1H)
The reaction formula is as follows:
。
example 19
In a glove box, 4-chlorobenzeneethyne (27.2 mg,0.2 mmol) was accurately weighed and charged into a reaction tube with a stirrer, tetrabutylammonium chloride (14.0 mg,0.05 mmol) was weighed, 2ml of a tetradioxane was taken out by a pipette, 2.5MPa of hydrogen gas was introduced, and the reaction was stirred under a magnetic stirrer at 80 ℃. After the completion of the reaction, the reactor was opened and the volatile matters were removed under reduced pressure using a rotary evaporator, and then purified by column chromatography using ethyl acetate and petroleum ether as eluent to give 4-chlorophenyl ethane (24.8 mg,91% yield).
1 H NMR (400 MHz，CDCl3)：δ7 .37-7.28(m，2H)，7 .19-7 .17(m，2H)，6 .77-6.70(m，1 H)，5 .77-5 .72 (m ,2H)，2 .39 (s ,3H)
The reaction formula is as follows:
。

Claims (7)

1. a method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt, which is characterized by comprising the following steps:
1) Alkyne is taken as an initial raw material, alkyne and quaternary ammonium salt catalysts are added into a reaction tube in a glove box, a certain amount of organic solvent is added, and then hydrogen with the pressure of 0.5-3MPa is introduced into the reaction tube to carry out stirring reaction at a constant temperature to obtain reaction liquid; the quaternary ammonium salt catalyst is Bu 4 NBr、Bu 4 NCl、Bu 4 NOTf、Bu 4 NI、Bu 4 NPF 6 Or Me 4 NI；
2) And removing volatile solvents from the reaction liquid, and purifying by column chromatography to obtain olefin or alkane.
2. The method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt according to claim 1, wherein the mass ratio of alkyne to quaternary ammonium salt catalyst is 15-25:1 when alkene is prepared.
3. The method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt according to claim 1, wherein the mass ratio of alkyne to quaternary ammonium salt catalyst is 0.1-4:1 when alkane is prepared.
4. The method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt according to claim 1, wherein in the step 1), the organic solvent is tetrahydrofuran, toluene, dichloroethane or 1, 4-dioxane.
5. The method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt according to claim 1, wherein in the step 1), the reaction temperature in the reaction tube is 70-80 ℃.
6. The method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt according to claim 1, wherein in the step 2), the column chromatography uses ethyl acetate/petroleum ether as eluent.
7. The method for preparing alkene and alkane by catalyzing alkyne with quaternary ammonium salt according to claim 1, wherein in the step 2), the volatile solvent is volatilized by a rotary evaporator under a reduced pressure condition.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102060714A (en) * 2010-06-25 2011-05-18 天津市有机化工一厂 Method for preparing 4-aminodiphenylamine
CN102639470A (en) * 2009-10-19 2012-08-15 雪佛龙美国公司 Hydroisomerization and selective hydrogenation of feedstock in ionic liquid-catalyzed alkylation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2623509A1 (en) * 2012-02-01 2013-08-07 Kanto Kagaku Kabushiki Kaisha Method of producing an optically active amine compound by catalytic asymmetric hydrogenation using a ruthenium-diphosphine complex

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102639470A (en) * 2009-10-19 2012-08-15 雪佛龙美国公司 Hydroisomerization and selective hydrogenation of feedstock in ionic liquid-catalyzed alkylation
CN102060714A (en) * 2010-06-25 2011-05-18 天津市有机化工一厂 Method for preparing 4-aminodiphenylamine

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BMIm-PF6@SiO2 Microcapsules: Particulated Ionic Liquid as A New Material for the Heterogenization of Catalysts;Ester Weiss等;《Chem. Mater.》;第26卷;第4781-4787页 *
双吗啉手性季铵盐相转移催化剂的合成;谢兵等;《化学试剂》;第34卷(第12期);第1111-1113, 1136页 *
季按盐相转移催化剂的合成及其应用进展;官仕龙等;《广西师范大学学报》;第82-90页 *
负载型季铵盐相转移催化剂的研究进展;徐帅帅等;《应用化工》;第49卷(第9期);第2324-2327, 2333页 *

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