CN1284756C - Process for preparing 2-aryl allyl alcohol - Google Patents
Process for preparing 2-aryl allyl alcohol Download PDFInfo
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- CN1284756C CN1284756C CN 200410067730 CN200410067730A CN1284756C CN 1284756 C CN1284756 C CN 1284756C CN 200410067730 CN200410067730 CN 200410067730 CN 200410067730 A CN200410067730 A CN 200410067730A CN 1284756 C CN1284756 C CN 1284756C
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- allyl alcohol
- preparation
- aryl
- aryl allyl
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Abstract
The present invention discloses a preparation method of 2-aryl allyl alcohol, which comprises the following steps: halogenated aryl hydrocarbon and allyl alcohol are stirred to carry out reactions for 1 to 50 hours in ionic liquid under the existence of catalysts, ligands and organic amine at 20 to 150 DEG C, and the product of 2-aryl allyl alcohol is obtained by post treatment. The preparation method of the present invention has the advantages of simple preparation technology, high yield, easy operation and little environmental pollution, and catalytic systems are easy for circulatory use.
Description
(1) technical field
The present invention relates to a kind of preparation method of 2-aryl allyl alcohol.
(2) background technology
The oxy-compound that is connected with terminal olefin on aromatic ring is the important intermediate of many medicines, be one and have polyfunctional compound, carry out the transformation of traditional technology by this compound developing new drug or to relative medicine, important academic significance and wide application prospect are arranged.
Utilize Friedel-Crafts Synthetic 2-aryl allyl alcohol by product more, reaction preference is poor, is difficult to carry out suitability for industrialized production.The Heck reaction is an important supplement of Friedel-Crafts reaction, utilizes this reaction to combine with ionic liquid, can solve recycling of catalyst system, reaches the purpose of suitability for industrialized production.
The Heck reaction is the important method of being synthesized the alkenyl substituted aromatic hydroxy compound under catalyzing by metal palladium by halogenated aryl hydrocarbon.Ionic liquid is as emerging Green Chemistry solvent, and is non-volatile, nonflammable explosive, and organism and inorganics are had good solubility, and reaction can be carried out at homogeneous phase, stable to water and air, is convenient to operation and processing, easily reclaims.But ionic liquid also catalysis quickens the process of chemical reaction and improves the selectivity of reaction.Use ionic liquid to be reaction medium simultaneously, synthetic compound with terminal olefin also is a kind of green synthesis techniques that application prospect is arranged.
(3) summary of the invention
For overcoming complicated process of preparation in the prior art, low, the environmental pollution important disadvantages of yield, the invention provides a kind of preparation method of 2-aryl allyl alcohol.The technical solution used in the present invention is:
A kind of preparation method of 2-aryl allyl alcohol may further comprise the steps: halogenated aryl hydrocarbon and vinyl carbinol are in ionic liquid, and in the presence of catalyzer, part, organic amine, in 20 ℃～150 ℃ following stirring reactions 1～50 hour, aftertreatment got product 2-aryl allyl alcohol;
Described ionic liquid is suc as formula the 3-Methylimidazole inorganic acid salt shown in (I) or 1-alkyl-3-Methylimidazole inorganic acid salt [Bmim]
+L
-, R in the formula (I)
1Expression H or carbon atom quantity are 1～18 alkyl, and L is one of following: BF
4, PF
6, OA
C, CF
3SO
3, N (SO
2CF
3)
2Ionic liquid is preferably 3-methyl imidazolium tetrafluoroborate or 1-alkyl-3-methyl imidazolium tetrafluoroborate, and alkyl is the alkyl of carbon atom quantity n=1～18; More preferably 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methyl imidazolium tetrafluoroborate.
Described catalyzer is divalence or non-valent nickel or palladium compound, as Ni (Oac)
2, NiCl
2, Pd (OAc)
2, PdCl
2, Pd (dba)
2Deng, be preferably nickel acetate or palladium;
Described part is 1, two (diphenylphosphine) ethane or 1 of 2-, two (diphenylphosphine) propane (DPPP) or 1 of 3-, two (diphenylphosphine) butane of 4-.
Above-mentioned 2-aryl allyl alcohol is preferably the vinyl carbinol suc as formula the compound shown in (II) or 2-(2 '-naphthyl), and correspondingly, described halogenated aryl hydrocarbon is suc as formula compound shown in (III) or 2-bromonaphthalene;
R in its Chinese style (II) and the formula (III)
2For electrophilic or push away electron substituent group, as-H ,-CHO ,-CN ,-F ,-COCH
3,-CF
3,-CH
3,-OCH
3,-OC
2H
5,-OC
3H
7,-COOCH
3,-Ph ,-OH ,-NH
2, be preferably one of following: 1.-H, 2.-COCH
3, 3.-CN, 4.-CH
3X in the formula (III) is chlorine or bromine or iodine.
Described organic amine is preferably triethylamine.
Above-mentioned product postprocessing can be that dichloromethane extraction gets product 2-aryl allyl alcohol with reaction solution layering deionizing liquid.
Described temperature of reaction is preferably 50 ℃～140 ℃, and the reaction times is preferably 5～40 hours.
Each material of the present invention is recommended to react by following proportioning:
The mol ratio of halogenated aryl hydrocarbon, vinyl carbinol, catalyzer, part, organic amine is 1: 2～5: 0.04～0.1: 0.08～0.2: 0.16～0.4, and the ionic liquid that uses based on the 1mol halogenated aryl hydrocarbon is 2L.
2-aryl allyl alcohol described in the present invention is preparation according to the following steps preferably:
With halogenated aryl hydrocarbon 1 mmole, palladium 0.04 mmole or nickel acetate 0.1,1, two (diphenylphosphine) propane 0.08 mmoles of 3-or 0.2 mmole, vinyl carbinol 3 mmoles, triethylamine 0.16 mmole or 0.2 mmole, 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 10 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 12 hours.After reaction finishes, cooling, aftertreatment is identified product with nuclear magnetic resonance spectrum and mass spectrum.
The reaction formula of above-mentioned reaction is:
After described catalyzer and ionic liquid reaction finish, recyclable recycling.
Preparation method of the present invention, preparation technology is simple, yield is high, and is easy to operate, and environmental pollution is little.
(4) embodiment
Below in conjunction with specific embodiment preparation method of the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1 prepares 2-phenyl vinyl carbinol by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (diphenylphosphine) propane (0.08 mmole) of 3-, 290 milligrams of vinyl carbinols (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 121 milligrams of product 2-phenyl vinyl carbinols, yield 90%.
1H?NMR(CDCl
3)δppm：1.5(s，1H)，3.70(d，J＝6.5Hz，2H)，5.16(m，1H)，5.42(s，1H)，7.25～7.33(m，3H)，7.40～7.45(m，2H)；
13C?NMR(CDCl
3)δppm：65.14，112.65，126.13，127.97，128.55，138.58，147.42。
MS(m/z)：134(M
+)。
Embodiment 2 prepares 2-phenyl vinyl carbinol by chlorobenzene
With 113 milligrams of chlorobenzenes (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (diphenylphosphine) propane (0.08 mmole) of 3-, 290 milligrams of vinyl carbinols (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating was 115 ℃ of reactions 20 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 118 milligrams of product 2-phenyl vinyl carbinols, yield 88%.
Embodiment 3 prepares 2-(4 '-acetylphenyl) vinyl carbinol by the 4-bromoacetophenone
With 198 milligrams of 4-bromoacetophenones (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (diphenylphosphine) propane (0.08 mmole) of 3-, 290 milligrams of vinyl carbinols (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating was 120 ℃ of reactions 10 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 157 milligrams of product 2-(4 '-acetylphenyl) vinyl carbinols, yield 89%.
1H?NMR(CDCl
3)δppm：1.55(s，1H)，2.60(s，3H)，4.57(s，2H)，5.48(dd，J＝2.3，1.3Hz，1H)，5.59(d，J＝0.75Hz，1H)，7.50～7.57(m，3H)，7.93～7.96(m，2H)；
13C?NMR(CDCl
3)δppm：26.94，65.25，115.23，126.64，128.98，136.89，143.59，146.85，197.91。
MS(m/z)：176(M
+)。
Embodiment 4 utilizes and reclaims ionic liquid, prepares 2-phenyl vinyl carbinol by bromobenzene
Ionic liquid reclaims by embodiment 1 and obtains, and other reactants, consumption and step get 115 milligrams of product 2-phenyl vinyl carbinols, yield 86% with embodiment 1.
Embodiment 5 prepares 2-phenyl vinyl carbinol by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 26 milligrams of nickel acetates (0.1 mmole), 1, two 49 milligrams in (diphenylphosphine) propane (0.12 mmole) of 3-, 500 milligrams of n-butyl vinyl ether (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 107 milligrams of product 2-phenyl vinyl carbinols, yield 80%.
Embodiment 6 prepares 2-(3 '-cyano-phenyl) vinyl carbinol by the 3-bromobenzylcyanide
With 182 milligrams of 3-bromobenzylcyanides (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (diphenylphosphine) propane (0.08 mmole) of 3-, 290 milligrams of vinyl carbinols (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 129 milligrams of product 2-(3 '-cyano-phenyl) vinyl carbinols, yield 81%.
1H?NMR(CDCl
3)δppm：1.67(s，1H)，4.53(d，J＝5.3Hz，2H)，5.47(d，J＝0.57Hz，1H)，5.53(d，J＝0.58Hz，1H)，7.44～7.76(m，4H)；
13C?NMR(CDCl
3)δppm：61.34，111.65，117.63，119.17，127.35，132.68，144.42，145.72。
MS(m/z)：159(M
+)。
Embodiment 7 prepares 2-(4 '-aminomethyl phenyl) vinyl carbinol by the 4-toluene bromide
With 171 milligrams of 4-toluene bromides (1 mmole), 26 milligrams of nickel acetates (0.1 mmole), 1, two 49 milligrams in (diphenylphosphine) propane (0.12 mmole) of 3-, 500 milligrams of n-butyl vinyl ether (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 131 milligrams of product 2-(4 '-aminomethyl phenyl) vinyl carbinols, yield 89%.
1H?NMR(CDCl
3)δppm：1.51(s，1H)，2.35(s，3H)，4.54(m，2H)，5.29(dd，J＝1.3，3.1Hz，1H)，5.43(d，J＝1.3Hz，1H)，7.15～7.47(m，4H)；
MS(m/z)：148(M
+)。
Embodiment 8 prepares 2-(2 '-naphthyl) vinyl carbinol by the 2-bromonaphthalene
With 207 milligrams of 2-bromonaphthalenes (1 mmole), 26 milligrams of nickel acetates (0.1 mmole), 1, two 49 milligrams in (diphenylphosphine) propane (0.12 mmole) of 3-, 500 milligrams of n-butyl vinyl ether (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 170 milligrams of product 2-(4 '-aminomethyl phenyl) vinyl carbinols, yield 92%.
1H?NMR(CDCl
3)δppm：1.76(s，1H)，4.63(s，2H)，5.44(d，J＝1.2，Hz，1H)，5.6(s，1H)，7.42～7.86(m，7H)；
MS(m/z)：184(M
+)。
Embodiment 9 prepares 2-phenyl vinyl carbinol by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 18 milligrams of palladium (0.08 mmole), 1, two 68 milligrams of (diphenylphosphine) butane (0.16 mmole) of 4-, 145 milligrams of vinyl carbinols (2.5 mmole), 34 milligrams of triethylamines (0.32 mmole), 2 milliliters of 1-ethyls-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 20 ℃ of reactions 50 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 114 milligrams of product 2-phenyl vinyl carbinols, yield 85%.
Embodiment 10 prepares 2-phenyl vinyl carbinol by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 45 milligrams of palladium (0.2 mmole), 1, two 68 milligrams in (diphenylphosphine) propane (0.16 mmole) of 4-, 145 milligrams of vinyl carbinols (2.5 mmole), 42.5 milligrams of triethylamines (0.4 mmole), 2.5 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 80 ℃ of reactions 40 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 122 milligrams of product 2-phenyl vinyl carbinols, yield 91%.
Embodiment 11 prepares 2-phenyl vinyl carbinol by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 18 milligrams of palladium (0.08 mmole), 1, two 33 milligrams in (diphenylphosphine) propane (0.08 mmole) of 3-, 145 milligrams of vinyl carbinols (2.5 mmole), 34 milligrams of triethylamines (0.32 mmole), 2 milliliters of 1-ethyls-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 150 ℃ of reactions 1.5 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 118 milligrams of product 2-phenyl vinyl carbinols, yield 88%.
Embodiment 12 prepares 2-(2 '-naphthyl) vinyl carbinol by the 2-bromonaphthalene
With 207 milligrams of 2-bromonaphthalenes (1 mmole), 13 milligrams of nickel acetates (0.05 mmole), 1, two 47 milligrams in (diphenylphosphine) ethane (0.12 mmole) of 2-, 500 milligrams of n-butyl vinyl ether (5 mmole), 40 milligrams of triethylamines (0.4 mmole), 2 milliliters of 1-dodecyls-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 90 ℃ of reactions 25 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 170 milligrams of product 2-(4 '-aminomethyl phenyl) vinyl carbinols, yield 92%.
Claims (9)
1, a kind of preparation method of 2-aryl allyl alcohol, it is characterized in that may further comprise the steps: halogenated aryl hydrocarbon and vinyl carbinol are in ionic liquid, in the presence of catalyzer, part, organic amine, in 20 ℃～150 ℃ following stirring reactions 1～50 hour, aftertreatment got product 2-aryl allyl alcohol;
Described ionic liquid is suc as formula the 3-Methylimidazole inorganic acid salt shown in (I) or 1-alkyl-3-Methylimidazole inorganic acid salt [Bmim]
+L
-, R in the formula (I)
1Expression H or carbon atom quantity are the alkyl of n=1～18, and L is one of following: BF
4, PF
6, OAc, CF
3SO
3, N (SO
2CF
3)
2
Described catalyzer is divalence or non-valent nickel or palladium compound;
Described part is 1, two (diphenylphosphine) ethane or 1 of 2-, two (diphenylphosphine) propane or 1 of 3-, two (diphenylphosphine) butane of 4-.
2, the preparation method of 2-aryl allyl alcohol according to claim 1 is characterized in that described 2-aryl allyl alcohol and halogenated aryl hydrocarbon are respectively suc as formula the compound shown in (II) and the formula (III);
R in its Chinese style (II) and the formula (III)
2For electrophilic or push away electron substituent group, the X in the formula (III) is chlorine or bromine or iodine.
3, the preparation method of 2-aryl allyl alcohol according to claim 1 is characterized in that described 2-aryl allyl alcohol and halogenated aryl hydrocarbon are respectively 2-(2 '-naphthyl) vinyl carbinol and 2-bromonaphthalene.
4, the preparation method of 2-aryl allyl alcohol according to claim 2 is characterized in that described R
2For one of following: 1.-H, 2.-COCH
3, 3.-CN, 4.-CH
3
5, the preparation method of 2-aryl allyl alcohol according to claim 1 is characterized in that described catalyzer is nickel acetate or palladium.
6, the preparation method of 2-aryl allyl alcohol according to claim 1 is characterized in that described organic amine is a triethylamine.
7, the preparation method of 2-aryl allyl alcohol according to claim 1 is characterized in that described ionic liquid for being 3-methyl imidazolium tetrafluoroborate or 1-alkyl-3-methyl imidazolium tetrafluoroborate, and alkyl is the alkyl of carbon atom quantity n=1～18.
8, the preparation method of 2-aryl allyl alcohol according to claim 7 is characterized in that described ionic liquid is for being 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methyl imidazolium tetrafluoroborate.
9, according to the preparation method of the described 2-aryl allyl alcohol of one of claim 1～8, it is characterized in that described aftertreatment is: with reaction solution layering deionizing liquid, dichloromethane extraction gets the 2-aryl allyl alcohol.
10, the preparation method of 2-aryl allyl alcohol according to claim 9 is characterized in that described temperature of reaction is 50 ℃～140 ℃, and the reaction times is 5～40 hours; The mol ratio of described halogenated aryl hydrocarbon, vinyl carbinol, catalyzer, part, organic amine is 1: 2～5: 0.04～0.1: 0.08～0.2: 0.16～0.4, and the ionic liquid that uses based on the 1mol halogenated aryl hydrocarbon is 2L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161617B (en) * | 2007-11-15 | 2010-06-02 | 浙江工业大学 | A method for preparing 2-(6'-methoxy group-2'-naphthyl) propenol |
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| CN101792414B (en) * | 2010-03-18 | 2012-06-13 | 浙江工商大学 | Method for preparing 2-(3'-quinolyl) propenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101161617B (en) * | 2007-11-15 | 2010-06-02 | 浙江工业大学 | A method for preparing 2-(6'-methoxy group-2'-naphthyl) propenol |
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