CN103896737A - Method for preparing propargyl alcohol by utilizing microstructure reactor - Google Patents

Method for preparing propargyl alcohol by utilizing microstructure reactor Download PDF

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CN103896737A
CN103896737A CN201410127669.7A CN201410127669A CN103896737A CN 103896737 A CN103896737 A CN 103896737A CN 201410127669 A CN201410127669 A CN 201410127669A CN 103896737 A CN103896737 A CN 103896737A
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propargyl alcohol
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张利雄
邓秋林
沈如伟
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Nanjing Tech University
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/18Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
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    • C07C2601/14The ring being saturated
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00Systems containing at least three condensed rings
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    • C07C2603/04Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract

The invention provides a method for preparing propargyl alcohol by utilizing a microstructure reactor, which is characterized in that a simple Grignard reagent is used as a raw material to generate a Grignard exchange reaction of a gas-liquid phase with acetylene gas in the microstructure reactor to generate a high-quality acetenyl magnesium bromide Grignard reagent; and carrying out nucleophilic addition reaction on the obtained ethynyl magnesium bromide Grignard reagent and electrophilic reagent in another microstructure reactor under the condition of continuous flow, and separating and refining the product after hydrolysis to obtain the substituted propargyl alcohol product. The method has the advantages of simple operation, simple, cheap and easily obtained raw materials and reagents, continuous, rapid and controllable process, mild condition, good product selectivity and realization of industrial production.

Description

A kind of method of utilizing micro-structured reactor to prepare propargyl alcohol
Technical field
The present invention relates to a kind of method of preparing propargyl alcohol, relate in particular to a kind of method of utilizing micro-structured reactor to prepare propargyl alcohol.
Background technology
The replacement propargyl alcohol with following formula structure is the important synthetic intermediate of a class, is mainly used in the field such as medicine, synthetic materials, also can be used as the lustering agent of nickel plating or copper etc.Under high temperature, high pressure, concentrated acid condition, propargyl alcohol has the good ability that prevents metallic corrosion.
Figure BDA0000484714430000011
The synthetic method of Chinese patent CN102701911A mainly contains dry acetylene gas, pass into Grignard reagent or lithium reagent under low temperature (78 ℃) in, carry out Ge Shi exchange, or under liquefied ammonia environment, pass in sodium amide or Lithamide, or pass in the tetrahydrofuran solution of potassium tert.-butoxide, then ketone or aldehyde splashing in above-mentioned reaction solution slowly obtained to alkynol.Chinese patent CN102476978A, CN1769254A reacts and prepares alkynol based on Favorski, i.e. and alkynol is prepared in ketone and alkynes reaction under alkalescence (solid potassium hydroxide) catalyst action.At normal pressure and suitable temperature, acetylene is passed in the organic solvent (solid catalyst potassium hydroxide is with in the Powdered mixed solution that is suspended in organic solvent and ketone) that is dissolved with ketone and reacted.A kind of method that U.S. Pat 6147266, Chinese patent CN1247849A propose fixed bed and produce continuously alkynol, employing anionite-exchange resin is catalyzer, this process low conversion rate.Whole reaction process is difficult to realize operate continuously, condition harshness, and process is loaded down with trivial details, higher to operation and equipment requirements, is not suitable for suitability for industrialized production.
Micro-reaction technology has enhancement of heat transfer, mass transfer, easy handling, safe and reliable and without advantages such as scale effects; show wide application prospect at aspects such as the energy, chemical industry, organic synthesis and fine chemicals; especially aspect strong exothermal reaction type, also there are being many application (Chambers, R.D.; Spink, R.C.H.Chem.Commun.1999,10,883.; Wada, Y.; Schmidt, M.A.; Jensen, K.F.Ind.Eng.Chem.Res.2006,45,8036.).In micro-structured reactor, prepare Grignard reagent document and have been reported (Wakami H.; Yoshida J.Org.Process.Res.Dev.2005,9,787.), also do not have report but use gas to carry out Ge Shi exchange system as raw material with simple Ge Shi for the method for propargyl alcohol.
Summary of the invention
The object of this invention is to provide a kind of simple and direct, the micro-structured reactor that utilizes efficient, highly selective is prepared the method for propargyl alcohol rapidly, continuously.
Technical scheme of the present invention is: a kind of method of utilizing micro-structured reactor to prepare propargyl alcohol, and its concrete steps are as follows:
(1) Ge Shi exchange: in micro-structured reactor, Ge Shi permutoid reaction occurs for acetylene gas and Grignard reagent;
(2) nucleophilic addition(Adn): in micro-structured reactor, by step (1) product and electrophilic reagent generation nucleophilic addition;
(3) hydrolysis reaction: in micro-structured reactor, step (2) product, through hydrating solution generation hydrolysis reaction, is obtained replacing the thick product of propargyl alcohol;
(4) replace the thick product of propargyl alcohol through separation, purification, obtain replacing propargyl alcohol.
Preferably above-mentioned Grignard reagent is methyl-magnesium-bromide, ethylmagnesium bromide, normal-butyl bromination magnesium or allyl group bromination magnesium; More preferably Grignard reagent is ethylmagnesium bromide or methyl-magnesium-bromide.
Preferably above-mentioned electrophilic reagent is aldehydes or ketones solution, and the structural formula of aldehydes or ketones is as R 1c (O) R 2, wherein R 1for alkyl C nh 2n+1(n=1~5) or aromatic base, aromatic base is p-methoxy-phenyl, bromophenyl, chloro-phenyl-, fluorophenyl, trimethoxyphenyl or styryl; R2 alkyl C nh 2n+1(n=1~5) or aromatic base, aromatic base is p-methoxy-phenyl, bromophenyl, chloro-phenyl-, fluorophenyl, trimethoxyphenyl or styryl.Solvent in electrophilic reagent is preferably tetrahydrofuran (THF), normal hexane or ether.Preferably the concentration of aldehydes or ketones solution is 0.01~5mol/L.
Preferably above-mentioned hydrating solution is proton type solvent, more preferably ammonium chloride, dilute hydrochloric acid, ammonium sulfate or ammonium nitrate.For can there is hydrolysis reaction in the amount of hydrating solution.
Preferably the micro-structured reactor in above-mentioned steps (1), (2) and (3) includes micro mixer and micro passage reaction, and micro mixer and micro passage reaction link together.Preferably above-mentioned micro passage reaction passage internal diameter (diameter) is 0.1~10mm; Micro mixer internal diameter (diameter) is of a size of 0.021~10mm.Be characterized in that internal flow contact area is large, conduct heat, mass transfer velocity is fast, process can realize operate continuously.Can realize number and increase amplification, produce as required, without scale effect.
Temperature of reaction in preferred steps (1) is-20~30 ℃; Be preferably-5~0 ℃; Temperature of reaction in step (2) is 20~40 ℃; Temperature of reaction in step (3) is 20~40 ℃.
Preferably the Ge Shi permutoid reaction time is 5s~30min; The nucleophilic addition residence time is 6s~50min; The hydrolysis reaction residence time is 10s~10min.
In the method for synthetic replacement propargyl alcohol of the present invention, in Ge Shi permutoid reaction, acetylene gas flow velocity and Grignard reagent velocity ratio are 4~300, the Ge Shi permutoid reaction time is that 5s~30min(does not calculate the reaction times at micro mixer, the reaction times of micro mixer ignores), the nucleophilic addition residence time is 6s~50min, and the mol ratio of Grignard reagent and electrophilic reagent is 1:1.2~1:0.5; The hydrolysis reaction residence time is 10s~10min.
The selectivity of the replacement propargyl alcohol that the present invention synthesizes is all greater than 91%, yield 87~96%.
Beneficial effect:
The present invention has overcome the drawback of traditional method, has the following advantages: 1) reaction conditions gentleness; 2) product has the selectivity of height; 3) simple to operate, can realize continuous, controllable operating; 4), according to Production requirement, can realize the production of mass-producing and without scale effect.
Innovative point of the present invention is to provide a kind of multiple micro-structured reactor series connection to use, and realized mild condition, the process method of the synthetic replacement propargyl alcohol of controlled, highly selective continuously.Mass transfer, heat-transfer capability that the present invention utilizes micro-structured reactor to have advantages of are strong, the ultra-low temperature surroundings requirement of having avoided traditional Ge Shi clearing house to need, and realized continuous operation.
Accompanying drawing explanation
It in figure, is the synthetic device schematic flow sheet that replaces propargyl alcohol of micro-structured reactor; A1, A2, A3 are high pressure syringe pump, A4 is ram pump, B1, B2, B3 are micro mixer, and C1, C2, C3 are micro passage reaction, and D1, D2 are thermostat container, E is product-collecting bottle, F is mass flow controller, and R1 is Grignard reagent, and R2 is acetylene, R3 aldehyde solution or ketone solution, R4 is hydrating solution.
Embodiment
Following examples contribute to understand the present invention, but are not limited to summary of the invention.In this area, the simple replacement that technician does the present invention or improve and all belong to the technical scheme that the present invention protects within.
Embodiment 1
As shown in Figure 1: ethylmagnesium bromide is injected micro mixer B1(intersection toe type micro mixer by high pressure syringe pump A1, HPIMM, IMM, Germany, length×width×height=25 × 21 × 37 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:300, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into micro mixer B2(V2 by ram pump A4, IMM, Germany) with the tetrahydrofuran (THF) mixed solution (0.1mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:1, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 56%, 1-phenyl-2-propargyl alcohol selectivity 59%.The test data of embodiment 1~16 is: 1h NMR (400MHz, CDCl 3): δ 7.55-7.53 (d, 2H, J=7.2Hz), 7.40-7.32 (m, 3H), 5.40 (d, 1H, J=1.2Hz), 2.65 (d, 1H, J=2Hz), 2.55 (s, 1H). 13c NMR (400MHz, CDCl 3): δ 140.0,128.7,128.5,126.6,83.5,74.8,64.4.
Embodiment 2
As shown in Figure 1: ethylmagnesium bromide is injected micro mixer B1(Caterpillar by high pressure syringe pump A1, IMM, Germany, length x width=300 × 300 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:100, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 0.5mm) continuation reaction 5s, product ethynyl bromination magnesium pumps into micro mixer B2(intersection toe type micro mixer by ram pump A4, HPIMM, IMM, Germany, length×width×height=25 × 21 × 37 μ m) with the tetrahydrofuran (THF) mixed solution (1mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:1.2, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 6s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammoniumsulphate soln at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 5mm) continue reaction 10min enter product-collecting bottle E.Product G C analyzes transformation efficiency 45%, 1-phenyl-2-propargyl alcohol selectivity 77%.
Embodiment 3
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:50, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 3mm) continuation reaction 2min, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (3mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.8, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 2min, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 6mm) with pump into dilute hydrochloric acid solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 10mm) continue reaction 8min enter product-collecting bottle E.Product G C analyzes transformation efficiency 46%, 1-phenyl-2-propargyl alcohol selectivity 95%.
Embodiment 4
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 5min, product ethynyl bromination magnesium pumps into micro mixer B2(Caterpillar by ram pump A4, IMM, Germany, length x width: 300 × 300 μ m) with the tetrahydrofuran (THF) mixed solution (5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:1, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 5min, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium nitrate solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 10mm) continue reaction 10min enter product-collecting bottle E.Product G C analyzes transformation efficiency 50%, 1-phenyl-2-propargyl alcohol selectivity 93%.
Embodiment 5
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:10, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 5mm) continuation reaction 10min, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.8, then enter micro passage reaction C2(internal diameter: 5mm) continuation reaction 30min, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 0.5mm) continue reaction 10s enter product-collecting bottle E.Product G C analyzes transformation efficiency 47%, 1-phenyl-2-propargyl alcohol selectivity 96%.
Embodiment 6
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 10mm) continuation reaction 30min, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.75, then enter micro passage reaction C2(internal diameter: 8mm) continuation reaction 30min, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 4min enter product-collecting bottle E.Product G C analyzes transformation efficiency 82%, 1-phenyl-2-propargyl alcohol selectivity 91%.
Embodiment 7
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 100%, 1-phenyl-2-propargyl alcohol selectivity 94%.
Embodiment 8
As shown in the figure: ethylmagnesium bromide is injected micro mixer B1(V2 by high pressure syringe pump A1, IMM, Germany) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 100%, 1-phenyl-2-propargyl alcohol selectivity 75%.
Embodiment 9
As shown in the figure: ethylmagnesium bromide is injected the threeway of micro mixer B1(T-type by high pressure syringe pump A1, internal diameter: 10mm) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 100%, 1-phenyl-2-propargyl alcohol selectivity 58%.
Embodiment 10
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 99%, 1-phenyl-2-propargyl alcohol selectivity 90%.
Embodiment 11
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:4, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 1min, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 99%, 1-phenyl-2-propargyl alcohol selectivity 59%.
Embodiment 12
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(-20 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 2min, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (0.5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(40 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 0.1mm) with pump into ammonium chloride solution at thermostat container D2(40 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 1min enter product-collecting bottle E.Product G C analyzes transformation efficiency 97%, 1-phenyl-2-propargyl alcohol selectivity 91%.
Embodiment 13
As shown in the figure: ethylmagnesium bromide is injected falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 1200 × 400 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(30 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (2mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(20 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(20 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 99%, 1-phenyl-2-propargyl alcohol selectivity 64%.
Embodiment 14
As shown in the figure: allyl group bromination magnesium injects falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 10s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the tetrahydrofuran (THF) mixed solution (2mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 99%, 1-phenyl-2-propargyl alcohol selectivity 90%.
Embodiment 15
As shown in the figure: normal-butyl bromination magnesium injects falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 600 × 200 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 30s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the normal hexane mixed solution (1mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:0.5, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 90%, 1-phenyl-2-propargyl alcohol selectivity 74%.
Embodiment 16
As shown in the figure: methyl-magnesium-bromide injects falling liquid film micro-structured reactor B1(length x width by high pressure syringe pump A1: 300 × 100 μ m) be metered into acetylene gas by F and react, ethylmagnesium bromide is than acetylene gas velocity ratio 1:25, at thermostat container D1(0 ℃) in there is Ge Shi permutoid reaction, enter micro passage reaction C1(internal diameter: 1mm) continuation reaction 50s, product ethynyl bromination magnesium pumps into the threeway of micro mixer B2(T-type by ram pump A4, internal diameter: 1mm) with the ether mixed solution (5mol/L) that is pumped into phenyl aldehyde by high pressure syringe pump A2 at thermostat container D2(25 ℃) in mix, the mol ratio of Grignard reagent and phenyl aldehyde is 1:2, then enter micro passage reaction C2(internal diameter: 1mm) continuation reaction 20s, the product obtaining enters the threeway of micro mixer B3(T-type, internal diameter: 1mm) with pump into ammonium chloride solution at thermostat container D2(25 ℃ by syringe pump A3) in react, then enter micro passage reaction C3(internal diameter: 1mm) continue reaction 2min enter product-collecting bottle E.Product G C analyzes transformation efficiency 90%, 1-phenyl-2-propargyl alcohol selectivity 89%.
Embodiment 17
Press method described in embodiment 10, different is is raw materials usedly: aubepine.Product is through concentrated, and flash chromatography post separates, yield 95%, 1-p-methoxyphenyl-2-propargyl alcohol selectivity 99%. 1HNMR(400MHz,CDCl 3):δ7.48(d,2H,J=8.8Hz),6.91(d,2H,J=8.8Hz),5.42(d,1H,J=3.6Hz),3.81(d,3H,J=4.0Hz),2.66(d,1H,J=2.4Hz),2.24(d,1H,J=6.0Hz). 13C?NMR(100MHz,CDCl 3):δ159.8,132.4,128.0,114.0,83.7,74.6,64.0,55.3.
Embodiment 18
Press method described in embodiment 10, different is is raw materials usedly: p-bromobenzaldehyde.Product is through concentrated, and chromatography column separates, yield 87%, and 1-is to bromophenyl-2-propargyl alcohol selectivity 97%. 1H?NMR(400MHz,CDCl 3):δ 1H?NMR(400MHz,CDCl 3)7.80-7.78(m,1H),7.59-7.56(m,1H),7.40-7.36(m,1H),7.23-7.20(m,1H),5.82-5.80(m,1H),2.67(d,1H,J=2.4Hz),2.52(d,1H,J=5.6Hz). 13C?NMR(100MHz,CDCl 3):δ138.9,133.0,130.0,128.5,128.0,122.7,82.4,75.0,63.9.
Embodiment 19
Press method described in embodiment 10, different is is raw materials usedly: o-bromobenzaldehye.Product is through concentrated, and flash chromatography post separates, yield 92%, 1-o-bromophenyl-2-propargyl alcohol selectivity 98%. 1H?NMR(400MHz,CDCl 3):δ7.53-7.42(m,4H),5.43(dd,1H,J=2.0,4.0Hz),2.68(d,1H,J=2.4Hz),2.28(d,1H,J=6.0Hz). 13C?NMR(100MHz,CDCl 3):δ139.0,131.8,128.3,122.6,83.0,75.2,68.0,63.8,25.6.
Embodiment 20
Press method described in embodiment 10, different is is raw materials usedly: 4-chloro-benzaldehyde.Product is through concentrated, and flash chromatography post separates, yield 88%, 1-rubigan-2-propargyl alcohol selectivity 96%. 1H?NMR(400MHz,CDCl 3):δ7.48(d,2H,J=8.8Hz),7.35(d,2H,J=8.4Hz),5.43(s,1H),2.67(d,1H,J=2.4Hz),2.49(s,1H). 13C?NMR(100MHz,CDCl 3):δ138.4,134.4,128.8,128.0,83.0,75.2,63.7.
Embodiment 21
Press method described in embodiment 10, different is is raw materials usedly: p-Fluorobenzenecarboxaldehyde.Product is through concentrated, and flash chromatography post separates, yield 92%, and 1-is to fluorophenyl-2-propargyl alcohol selectivity 95%. 1H?NMR(400MHz,CDCl 3):δ7.54-7.51(m,2H),7.08-7.04(m,2H),5.44(s,1H),2.68(d,1H,J=2.0Hz),2.45(d,1H,J=3.2Hz). 13C?NMR(100MHz,CDCl 3):δ162.8(J=245.4Hz),135.8(J=3.3Hz),128.5(J=8.6Hz),115.5(J=21.7Hz),83.3,75.1,63.8.
Embodiment 22
Press method described in embodiment 10, different is is raw materials usedly: 3,4,5-Trimethoxybenzaldehyde.Product, through concentrated, separated and is obtained product, yield 92%, 1-(3,4,5-trimethoxy) phenyl-2-propargyl alcohol selectivity 93% by flash chromatography post. 1H?NMR(400MHz,CDCl 3):δ6.78(s,2H),5.42-5.40(m,1H),3.89(s,6H),3.85(s,3H),2.69(d,1H,J=2.4Hz),2.26(d,1H,J=6.4Hz). 13C?NMR(100MHz,CDCl 3):δ153.4,138.1,135.6,103.6,83.4,74.9,64.5,60.8,56.1.
Embodiment 23
Press method described in embodiment 10, different is is raw materials usedly: phenylacrolein.Product is through concentrated, and flash chromatography post separates and obtains product, yield 92%, 1-styryl-2-propargyl alcohol selectivity 98%. 1H?NMR(400MHz,CDCl 3):δ7.42-7.27(m,5H),6.83-6.80(dd,1H,J=14.8,0.8Hz),6.34-6.28(dd,1H,J=10.0,6.0Hz),5.09-5.05(m,1H),2.65(d,1H,J=2.4Hz),2.05-2.04(m,1H). 13C?NMR(100MHz,CDCl 3):δ135.9,132.3,128.6,128.2,127.4,126.8,82.7,74.6,62.7.
Embodiment 24
Press method described in embodiment 10, different is is raw materials usedly: 9-Fluorenone, the nucleophilic addition(Adn) residence time is 50min.Product is through concentrated, and flash chromatography post separates and obtains product, yield 90%, 1-(9H-fluorenyl)-2-propargyl alcohol selectivity 95%. 1H?NMR(400MHz,CDCl 3):δ7.72(d,2H,J=6.8Hz),7.62(d,2H,J=7.2Hz),7.43-7.34(m,4H),2.54(s,1H),2.48(s,1H). 13C?NMR(100MHz,CDCl 3):δ146.6,139.1,129.9,128.6,124.3,120.2,83.8,74.6,71.4.
Embodiment 25
Press method described in embodiment 10, different is is raw materials usedly: pimelinketone.Product is through extraction, concentrated, adds internal standard substance sym-trimethylbenzene, gas chromatographic analysis yield 98%, 1-ethynylcyclohexanol selectivity 92%.
Embodiment 27
Press method described in embodiment 10, different is is raw materials usedly: valeral.Product is through extraction, concentrated, adds internal standard substance sym-trimethylbenzene, gas chromatographic analysis yield 98%, 1-amyl group-2-propargyl alcohol selectivity 91%.
Embodiment 26
Press method described in embodiment 10, different is is raw materials usedly: acetone.Product is through extraction, concentrated, adds internal standard substance sym-trimethylbenzene, gas chromatographic analysis, 2-methyl-3-butyne-2-alcohol yield 91%, selectivity 93%.Embodiment 27
Press method described in embodiment 10, different is is raw materials usedly: cinnamophenone.Product, through concentrated, separated and is obtained product, yield 96%, 1-phenyl-1-styryl-2-propargyl alcohol selectivity 95% by flash chromatography post. 1H?NMR(400MHz,CDCl 3):δ7.41-7.24(m,8H),7.69-7.67(m,2H),6.97(d,1H,J=16.0Hz),6.39-6.35(m,1H),2.87(s,1H),2.65(s,1H). 13C?NMR(100MHz,CDCl 3):δ142.8,136.0,132.3,129.4,128.6,128.4,128.1,128.0,126.9,125.7,84.7,75.8,72.7.

Claims (10)

1. utilize micro-structured reactor to prepare a method for propargyl alcohol, its concrete steps are as follows:
(1) Ge Shi exchange: in micro-structured reactor, Ge Shi permutoid reaction occurs for acetylene gas and Grignard reagent;
(2) nucleophilic addition(Adn): in micro-structured reactor, by step (1) product and electrophilic reagent generation nucleophilic addition;
(3) hydrolysis reaction: in micro-structured reactor, step (2) product, through hydrating solution generation hydrolysis reaction, is obtained replacing the thick product of propargyl alcohol;
(4) replace the thick product of propargyl alcohol through separation, purification, obtain replacing propargyl alcohol.
2. the method for claim 1, is characterized in that described Grignard reagent is methyl-magnesium-bromide, ethylmagnesium bromide, normal-butyl bromination magnesium or allyl group bromination magnesium.
3. method as claimed in claim 2, is characterized in that described Grignard reagent is ethylmagnesium bromide or methyl-magnesium-bromide.
4. the method for claim 1, is characterized in that described electrophilic reagent is aldehydes or ketones solution, and the structural formula of aldehydes or ketones is as R 1c (O) R 2, wherein R 1for alkyl C nh 2n+1(n=1~5) or aromatic base, aromatic base is p-methoxy-phenyl, bromophenyl, chloro-phenyl-, fluorophenyl, trimethoxyphenyl or styryl; R2 alkyl C nh 2n+1(n=1~5) or aromatic base, aromatic base is p-methoxy-phenyl, bromophenyl, chloro-phenyl-, fluorophenyl, trimethoxyphenyl or styryl.
5. the method for claim 1, is characterized in that described hydrating solution is ammonium chloride, dilute hydrochloric acid, ammonium sulfate or ammonium nitrate.
6. the method for claim 1, is characterized in that the micro-structured reactor in step (1), (2) and (3) includes micro mixer and micro passage reaction, and micro mixer and micro passage reaction link together.
7. method as claimed in claim 6, is characterized in that described micro passage reaction passage internal diameter is 0.1~10mm; Micro mixer internal diameter is 0.021~10mm.
8. the synthetic method of replacement propargyl alcohol as claimed in claim 1, is characterized in that described Ge Shi permutoid reaction acetylene gas flow velocity and Grignard reagent velocity ratio are 4~300:1; The mol ratio of Grignard reagent and electrophilic reagent is 1:(0.5-1.2).
9. the method for claim 1, it is characterized in that the temperature of reaction in described step (1) is-20~30 ℃; Temperature of reaction in step (2) is 20~40 ℃; Temperature of reaction in step (3) is 20~40 ℃.
10. the method for claim 1, is characterized in that the described Ge Shi permutoid reaction time is 5s~30min; The nucleophilic addition residence time is 6s~50min; The hydrolysis reaction residence time is 10s~10min.
CN201410127669.7A 2014-03-31 2014-03-31 Method for preparing propargyl alcohol by utilizing microstructure reactor Pending CN103896737A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106397106A (en) * 2015-07-28 2017-02-15 浙江省化工研究院有限公司 Method for performing olefin addition reaction by using microchannel reactor
CN106588958A (en) * 2015-10-14 2017-04-26 上虞新和成生物化工有限公司 Production system and method for continuously preparing alkynol di-Grignard reagent
CN108121317A (en) * 2018-02-07 2018-06-05 重庆消烦多新材料有限公司 A kind of ECS hot spot multiple unit control systems for preparing alkynol based compound
CN109897010A (en) * 2019-03-04 2019-06-18 天津凯莱英制药有限公司 A kind of method for continuously synthesizing of 1,2,3- triazole compound
CN110483243A (en) * 2019-09-17 2019-11-22 西安近代化学研究所 A kind of 1-(2- chlorphenyl) -2-(1- chlorine cyclopropyl) the chloro- 2- propyl alcohol of -3- preparation method
CN111302971A (en) * 2018-12-12 2020-06-19 上海奥博生物医药技术有限公司 Method for continuously preparing 5-cyanodiol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101495488A (en) * 2006-07-18 2009-07-29 隆萨股份公司 Method fro grignard type reactions in microreactors
US20090275627A1 (en) * 2008-05-05 2009-11-05 Allergan, Inc. Alpha2b and alpha2c agonists
CN102701911A (en) * 2011-03-28 2012-10-03 河北百灵威超精细材料有限公司 A method for purification and enhanced stability of alkynol compounds
CN102993133A (en) * 2013-01-08 2013-03-27 南京工业大学 Method for preparing epoxy fatty acid methyl ester by one-step method through microreactor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101495488A (en) * 2006-07-18 2009-07-29 隆萨股份公司 Method fro grignard type reactions in microreactors
US20090275627A1 (en) * 2008-05-05 2009-11-05 Allergan, Inc. Alpha2b and alpha2c agonists
CN102701911A (en) * 2011-03-28 2012-10-03 河北百灵威超精细材料有限公司 A method for purification and enhanced stability of alkynol compounds
CN102993133A (en) * 2013-01-08 2013-03-27 南京工业大学 Method for preparing epoxy fatty acid methyl ester by one-step method through microreactor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李洪钟: "《过程工程 物质.能源.智慧》", 31 December 2010 *
穆金霞等: "微通道反应器在合成反应中的应用", 《化学进展》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106397106A (en) * 2015-07-28 2017-02-15 浙江省化工研究院有限公司 Method for performing olefin addition reaction by using microchannel reactor
CN106397106B (en) * 2015-07-28 2019-02-12 浙江省化工研究院有限公司 A method of alkene addition reaction is carried out using micro passage reaction
CN106588958A (en) * 2015-10-14 2017-04-26 上虞新和成生物化工有限公司 Production system and method for continuously preparing alkynol di-Grignard reagent
CN106588958B (en) * 2015-10-14 2018-09-28 上虞新和成生物化工有限公司 A kind of continuous production system and method for preparing alkynol di Grignard reagent
CN108121317A (en) * 2018-02-07 2018-06-05 重庆消烦多新材料有限公司 A kind of ECS hot spot multiple unit control systems for preparing alkynol based compound
CN111302971A (en) * 2018-12-12 2020-06-19 上海奥博生物医药技术有限公司 Method for continuously preparing 5-cyanodiol
CN113329994A (en) * 2018-12-12 2021-08-31 浙江华海药业股份有限公司 Method for continuously preparing 5-cyanodiol
CN111302971B (en) * 2018-12-12 2023-08-22 上海奥博生物医药股份有限公司 Method for continuously preparing 5-cyanodiol
CN113329994B (en) * 2018-12-12 2023-09-19 浙江华海药业股份有限公司 Method for continuously preparing 5-cyanodiol
US11845710B2 (en) 2018-12-12 2023-12-19 Zhejiang Huahai Pharmaceutical Co., Ltd Method for continuously preparing citalopram diol
CN109897010A (en) * 2019-03-04 2019-06-18 天津凯莱英制药有限公司 A kind of method for continuously synthesizing of 1,2,3- triazole compound
CN110483243A (en) * 2019-09-17 2019-11-22 西安近代化学研究所 A kind of 1-(2- chlorphenyl) -2-(1- chlorine cyclopropyl) the chloro- 2- propyl alcohol of -3- preparation method

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