CN101177381B - Method for synthesizing 2-aryl allyl alcohol compound - Google Patents
Method for synthesizing 2-aryl allyl alcohol compound Download PDFInfo
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- CN101177381B CN101177381B CN2007101567762A CN200710156776A CN101177381B CN 101177381 B CN101177381 B CN 101177381B CN 2007101567762 A CN2007101567762 A CN 2007101567762A CN 200710156776 A CN200710156776 A CN 200710156776A CN 101177381 B CN101177381 B CN 101177381B
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- allyl alcohol
- alcohol compound
- aryl
- synthetic method
- anion exchange
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Abstract
The invention relates to a synthesis method of a 2-aryl allylalcohol compound, in particular to a preparation method using macropore alkalescent cinnamene system anion exchange resin as solid alkali and palladium acetate as catalyst to prepare the 2-aryl allylalcohol compound through Heck reaction of aryl halide and propyl alcohol compound. The invention adopts the technical proposal that with the existence of the palladium acetate and the macropore alkalescent cinnamene system anion exchange resin, the aryl halide and propyl alcohol in a non-protonic polarity solvent are stirred at 50 to 180 DEG C for chemical reaction for 1 to 30 hours; after the reaction, an acidization is carried out with the pH value of reaction liquid reaching 1 to 3; and finally the 2-aryl allylalcohol compound is prepared. Compared to prior art, the technical proposal has the advantages that the recyclability of resin in the resultant product, no need of organic ligand phosphine, easy commercial process and the environmental friendliness.
Description
(1) technical field
The present invention relates to a kind of synthetic method of 2-aryl allyl alcohol compound, relating in particular to a kind of is catalyzer with the macroreticular weakly base styrene series anion exchange resin as solid alkali, palladium, do not using under the organophosphite ligand concrete conditions in the establishment of a specific crime, utilizing the preparation method of Heck reaction by halogenated aryl hydrocarbon and propanol compounds prepared in reaction 2-aryl allyl alcohol compound.
(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.
In the patent (application number 200410067730.X) that we have declared, utilize the Heck reaction, set out by halogenated aryl hydrocarbon and vinyl carbinol, in the ion liquid system of organophosphorus ligand, organic amine, palladium or nickel acetate, prepared the 2-aryl allyl alcohol compound, solved the pollution problem of solvent environment.But, the organic amine that uses in the Heck reaction is difficult to reclaim, and uses organophosphorus ligand, for the clean production technology of further exploitation, utilize macroreticular weakly base styrene series anion exchange resin solid alkali to substitute organic amine in the present invention, and avoided the use organophosphorus ligand.This technology is convenient to operation and processing, and resin easily reclaims, and has solved the pollution and the emission problem of last handling process, also be a kind of have application prospect green synthesis techniques.
(3) summary of the invention
The object of the invention is to provide a kind of preparation technology simple, excellent catalytic effect, the operational path novelty, with the macroreticular weakly base styrene series anion exchange resin as alkali, no phosphine part exists down, utilizes Heck reaction high reactivity ground to synthesize novel method suc as formula the 2-aryl allyl alcohol compound shown in (I).
For achieving the goal the present invention by the following technical solutions:
Suc as formula halogenated aryl hydrocarbon shown in (II) and vinyl carbinol is raw material, in aprotic polar solvent, in the presence of palladium and macroreticular weakly base styrene series anion exchange resin (III), in 50 ℃～180 ℃ following stirring reactions 1～30 hour, being acidified with acid the pH value is 1～3, the reaction solution aftertreatment must be suc as formula 2-aryl allyl alcohol compound shown in (I); The amount of substance ratio of described halogenated aryl hydrocarbon, vinyl carbinol, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 1～5: 0.005～0.01: 1～2;
R among formula (I), (II)
1For-H ,-CHO ,-CN ,-F ,-COCH
3,-CF
3,-CH
3,-OCH
3,-OC
2H
5,-OC
3H
7,-COOCH
3,-Ph ,-OH or-NH
2
X in the formula (II) is chlorine, bromine or iodine;
R in the formula (III)
2, R
3Be methyl or hydrogen independently of one another, n represents contained number of repeat unit purpose mean value on the polymer macromolecule chain.
Aprotic polar solvent of the present invention is dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone or 1-methyl-2-pyrrolidone.
Macroreticular weakly base styrene series anion exchange resin of the present invention is a Styrene-DVB D301 type resin, can be commercially available Styrene-DVB (D301R), Styrene-DVB (D301T), Styrene-DVB (D301G), Styrene-DVB (D392) or Styrene-DVB (D380) resin.
R in the formula of the present invention (II)
1Be preferably-H-COCH
3,-CN, or-CH
3
Acidifying of the present invention is for adding hcl acidifying.
Product postprocessing of the present invention is with the reaction solution dichloromethane extraction, and the extraction liquid anhydrous magnesium sulfate drying concentrates, and column chromatography for separation gets product 2-aryl allyl alcohol.
The volumetric usage of aprotic polar solvent of the present invention is counted 10～100mL/mmol with halogenated aryl hydrocarbon.
Temperature of reaction of the present invention is preferably 50 ℃～140 ℃, and the reaction times is preferably 5～20 hours.
The amount of substance ratio of halogenated aryl hydrocarbon of the present invention, vinyl carbinol, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 1～5: 0.005～0.01: 1～2, is preferably 1: 2: 0.005: 1.5.
The synthetic method of 2-aryl allyl alcohol compound of the present invention, it is characterized in that may further comprise the steps, halogenated aryl hydrocarbon and vinyl carbinol are dissolved in the aprotic polar solvent, be added in palladium and macroreticular weakly base styrene series anion exchange resin, stirring heating, 100 ℃ of down reactions 15 hours, the cooling reaction solution, add hcl acidifying to pH be 3, use dichloromethane extraction, the extraction liquid anhydrous magnesium sulfate drying concentrates, and enriched material gets the 2-aryl allyl alcohol compound through column chromatography for separation; The amount of substance ratio of described halogenated aryl hydrocarbon, vinyl carbinol, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 2: 0.005: 1.5; Described aprotic polar solvent is the 1-methyl-2-pyrrolidone, and volumetric usage is counted 30mL/mmo1 with halogenated aryl hydrocarbon, R in the described halogenated aryl hydrocarbon
1For-H ,-COCH
3,-CN, or-CH
3
After macroreticular weakly base styrene series anion exchange resin reaction described in the present invention finishes, 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), 290 milligrams of vinyl carbinols (5 mmole), 1.12 milligrams of (0.005 mmole) Styrene-DVB of palladium (D301 R) resin, 0.3 gram (1.5 mmole), 10 milliliters of dimethyl sulfoxide (DMSO), place 200 milliliters of there-necked flasks, stirring heating was 100 ℃ of reactions 15 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying concentrates, and column chromatography for separation gets 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), 116 milligrams of vinyl carbinols (2 mmole), 1.12 milligrams of (0.005 mmole) Styrene-DVB of palladium (D301R) resin, 0.4 gram (2 mmole), 100 milliliters of dimethyl formamides, place 200 milliliters of there-necked flasks, stirring heating was 50 ℃ of reactions 30 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying concentrates, and column chromatography for separation gets 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), 58 milligrams of vinyl carbinols (1 mmole), 2.24 milligrams of (0.01 mmole) Styrene-DVB of palladium (D301G) resin, 0.24 gram (1 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 120 ℃ of reactions 10 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying, concentrated, column chromatography for separation gets 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 Styrene-DVB (D301G) resin, prepares 2-phenyl vinyl carbinol by bromobenzene
Other operations are with embodiment 1, and reaction obtains 115 milligrams of product 2-phenyl vinyl carbinols, yield 86%.
Embodiment 5 prepares 2-phenyl vinyl carbinol by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 116 milligrams of vinyl carbinols (2 mmole), 1.12 milligrams of palladium (0.005 mmole), Styrene-DVB (D301T) resin 0.3 gram (1.5 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 15 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying concentrates, and column chromatography for separation gets 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), 2.24 milligrams of 290 milligrams of (0.01 mmole) vinyl carbinols of palladium (5 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 100 milliliters of dimethyl sulfone, place 200 milliliters of there-necked flasks, stirring heating was 150 ℃ of reactions 1 hour.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying, concentrated, column chromatography for separation gets 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), 290 milligrams of vinyl carbinols (5 mmole), 1.12 milligrams of palladium (0.01 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 100 milliliters of N,N-DIMETHYLACETAMIDEs, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying, concentrated, column chromatography for separation gets 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), 290 milligrams of vinyl carbinols (5 mmole), 2.24 milligrams of palladium (0.01 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 100 milliliters of tetramethylene sulfone, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, the dilute hydrochloric acid of adding 10% is acidified to pH=3, stirred 50 milliliters of extractions of methylene dichloride three times, extraction liquid anhydrous magnesium sulfate drying 30 minutes, concentrate, column chromatography for separation gets 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), 2.24 milligrams of palladium (0.01 mmole), 145 milligrams of vinyl carbinols (2.5 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 100 milliliters of tetramethylene sulfone, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying concentrates, and column chromatography for separation gets 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), 290 milligrams of vinyl carbinols (5 mmole), 1.12 milligrams of palladium (0.005 mmole), Styrene-DVB (D301T) resin 0.3 gram (1.5 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finished, cooling added hcl acidifying to pH=3, stirred 30 minutes, and 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying concentrates, and column chromatography for separation gets 122 milligrams of product 2-phenyl vinyl carbinols, yield 91%.
Claims (9)
1. the synthetic method of 2-aryl allyl alcohol compound shown in the formula (I), it is characterized in that described method comprises the steps: being raw material suc as formula halogenated aryl hydrocarbon shown in (II) and vinyl carbinol, in aprotic polar solvent, in the presence of palladium and macroreticular weakly base styrene series anion exchange resin (III), in 50 ℃～180 ℃ following stirring reactions 1～30 hour, being acidified with acid pH value is 1～3, and the reaction solution aftertreatment must be suc as formula 2-aryl allyl alcohol compound shown in (I); The amount of substance ratio of described halogenated aryl hydrocarbon, vinyl carbinol, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 1～5: 0.005～0.01: 1～2; Described macroreticular weakly base styrene series anion exchange resin is a Styrene-DVB D301 type resin;
R among formula (I), (II)
1For-H ,-CHO ,-CN ,-F ,-COCH
3,-CF
3,-CH
3,-OCH
3,-OC
2H
5,-OC
3H
7,-COOCH
3,-Ph ,-OH or-NH
2X in the formula (II) is chlorine, bromine or iodine; R in the formula (III)
2, R
3Be methyl or hydrogen independently of one another, n represents contained number of repeat unit purpose mean value on the polymer macromolecule chain.
2. the synthetic method of 2-aryl allyl alcohol compound according to claim 1 is characterized in that described aprotic polar solvent is dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone or 1-methyl-2-pyrrolidone.
3. the synthetic method of 2-aryl allyl alcohol compound according to claim 1 is characterized in that the R in the described formula (II)
1For-H ,-COCH
3,-CN, or-CH
3
4. the synthetic method of 2-aryl allyl alcohol compound according to claim 1 is characterized in that described Styrene-DVB D301 type resin is the resin of Styrene-DVB D301R, Styrene-DVB D301T or Styrene-DVB D301G model.
5. the synthetic method of 2-aryl allyl alcohol compound according to claim 1 is characterized in that described reaction solution aftertreatment is with the reaction solution dichloromethane extraction, and the extraction liquid drying concentrates, and column chromatography for separation gets product 2-aryl allyl alcohol.
6. as the synthetic method of 2-aryl allyl alcohol compound as described in one of claim 1～5, it is characterized in that the volumetric usage of described aprotic polar solvent is counted 10～100mL/mmol with halogenated aryl hydrocarbon.
7. the synthetic method of 2-aryl allyl alcohol compound according to claim 1 is characterized in that described temperature of reaction is 50 ℃～140 ℃, and the reaction times is 5～20 hours.
8. the synthetic method of 2-aryl allyl alcohol compound according to claim 1 is characterized in that the amount of substance ratio of described halogenated aryl hydrocarbon, vinyl carbinol, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 2: 0.005: 1.5.
9. the synthetic method of 2-aryl allyl alcohol compound according to claim 1, it is characterized in that may further comprise the steps, halogenated aryl hydrocarbon and vinyl carbinol are dissolved in the aprotic polar solvent, add palladium and macroreticular weakly base styrene series anion exchange resin, stirring heating, reacted 15 hours down at 100 ℃, the cooling reaction solution, adding 10% dilute sulphuric acid, to be acidified to PH be 3, use dichloromethane extraction, the extraction liquid anhydrous magnesium sulfate drying concentrates, and enriched material gets the 2-aryl allyl alcohol compound through column chromatography for separation; The amount of substance ratio of described halogenated aryl hydrocarbon, vinyl carbinol, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 2: 0.005: 1.5; Described aprotic polar solvent is the 1-methyl-2-pyrrolidone, and volumetric usage is counted 30mL/mmol with halogenated aryl hydrocarbon, R in the described halogenated aryl hydrocarbon
1For-H ,-COCH
3,-CN, or-CH
3
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Assignee: Zhejiang Liaoyuan Pharmaceutical Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2011330000108 Denomination of invention: Method for synthesizing 2-aryl allyl alcohol compound Granted publication date: 20100915 License type: Exclusive License Open date: 20080514 Record date: 20110318 |
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