CN103524319A - Synthesis method of benzoin - Google Patents
Synthesis method of benzoin Download PDFInfo
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- CN103524319A CN103524319A CN201310496165.8A CN201310496165A CN103524319A CN 103524319 A CN103524319 A CN 103524319A CN 201310496165 A CN201310496165 A CN 201310496165A CN 103524319 A CN103524319 A CN 103524319A
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- phenyl aldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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Abstract
The invention relates to a method for preparing benzoin from benzaldehyde, particularly a synthesis method of benzoin by using strong alkali weak acid salts as alkaline reagents under the catalytic action of VB1. According to the method, by using sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and other cheap strong alkali weak acid salts as alkaline reagents, the benzaldehyde is subjected to benzoic condensation reaction under the catalytic action of the VB1 to synthesize the benzoin. Compared with the method using the traditional sodium hydroxide, potassium hydroxide and other strong alkalis as the alkaline reagents, the method provided by the invention has the advantages of low price, high catalyst VB1 stability, easy reaction control and favorable reproducibility, does not have the possibility of Cannizzaro side reaction, and thus, is a simple and feasible benzoin preparation method.
Description
Technical field
The present invention relates to a kind of method of being prepared bitter almond oil camphor by phenyl aldehyde, particularly take inexpensive strong base-weak acid salt as alkaline reagents, the method for synthetic bitter almond oil camphor under VB1 catalysis.
Background technology
Bitter almond oil camphor is the important Organic Chemicals that two molecule phenyl aldehydes form by benzoic condensation coupling; be called again st-yrax, phenylbenzene ethanol ketone, 1; 2-hexichol hydroxyl ethyl ketone, 2-hydroxyl-1; 2-phenylbenzene ethyl ketone, benzoyl phenylcarbinol, Alpha-hydroxy-α-phenyl acetophenone, Alpha-hydroxy benzyl benzophenone etc.; being widely used in the photosensitizers of photosensitive resin, the anticrater agent of powder coating, is also simultaneously the synthetic intermediate of important medicinal intermediates, sterilant, other sensitive materials.For example, bitter almond oil camphor is the raw material of antiepileptic drug diphenyl hydantoin, is also for the benzil of photosensitizers, the reaction raw materials of benzoin ethers in printing and coatings industry.
Benzoic condensation reaction adopts hypertoxic sodium cyanide or potassium cyanide to make catalyzer the earliest, but along with people are to the improving constantly of environmental protection consciousness, and has the common concern that benzoic condensation reaction under the VB1 catalysis of thiazole ring structure has been subject to people.Benzoic condensation reaction method under VB1 catalysis comprises VB1 catalysis method, phase-transfer catalysis-VB1 method, ultrasonic wave-VB1 method, microwave-VB1 method.(university chemistry, 2010,25 (3): 58-61) by VB1 water dissolution, add 95% ethanol and new steam phenyl aldehyde, then dripping 10% the NaOH aqueous solution to pH value 9 ~ 10, reacting 120 min in 65 ℃, having obtained furoin such as He Qiangfang; (Guangdong chemical industry, 2006,33 (11): 27-30) take VB1 as catalyzer, utilize triethylamine for alkaline reagents, prepared thiophene acyloin such as Du Zhiyun.(Hubei Institute For Nationalities's journal natural science edition, 2008,26 (2): 206-208) in sodium hydroxide-VB1 catalyst system, add dodecyl dimethyl hexadecyldimethyl benzyl ammonium and synthesized bitter almond oil camphor as phase-transfer catalyst such as Jia Xiaohong; (Jiaying College journal, 2006,26 (3) such as Liu little Ling; 43-56.), in sodium hydroxide-VB1 catalyst system, adding PEG-6000 is that phase-transfer catalyst has synthesized hexichol hydroxyl ethyl ketone (bitter almond oil camphor); In addition; (the Shanghai chemical industry such as Chen Qiang; 2005; 30 (2): 19-21) studied in sodium hydroxide-VB1 catalyst system; the method of preparing bitter almond oil camphor by Ultrasonic Radiation, (Qufu Normal University's journal, 2008 such as Wang Shouxin; 34 (3): 93-95) studied in sodium hydroxide-VB1 catalyst system, adopted the method for the synthetic 2-pyridine acyloin of microwave irradiation.
The most sodium hydroxide that adopts of benzoic condensation reaction under VB1 catalysis is made alkaline reagents, and minority is made alkaline reagents with triethylamine.Although it is higher that sodium hydroxide is made alkaline reagents yield, VB1 structure is easily destroyed, and reacts unstable, and circulation ratio is low, and triethylamine is made alkaline reagents, and aftertreatment is complicated, and yield is on the low side.
Summary of the invention
The invention provides a kind of method of being prepared bitter almond oil camphor by phenyl aldehyde, feature is to utilize the strong base-weak acid salts such as inexpensive sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus to make alkaline reagents, under VB1 catalysis, by adding thermal synthesis bitter almond oil camphor.The use of strong acid weak base salt is not only conducive to the structural stability of VB1, make operation more convenient, circulation ratio is better, effectively reduce the possibility that phenyl aldehyde carries out Cannizzaro reaction simultaneously, its yield approaches sodium hydroxide and makes alkaline reagents, is a kind of simple and easy to do preparation method of bitter almond oil camphor.
Bitter almond oil camphor of the present invention synthetic comprises following content:
Phenyl aldehyde is the new phenyl aldehyde that steams, and ethanol is the ethanol of dehydrated alcohol or 95%;
Strong base-weak acid salt is sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus etc., its concentration 2% to saturated solution;
The consumption of VB1 is that every 10.5 g phenyl aldehydes add 0.5 ~ 3.0 g;
The consumption of solvent is respectively every 10.5 g phenyl aldehydes and adds 1.5 mL ~ 12.5 mL water and 2.0 mL ~ 18.5 mL dehydrated alcohol or 95% ethanol;
PH value in reaction scope is 8 ~ 11;
Temperature of reaction is that between 50 ℃～100 ℃, the reaction times is between 0.5～5 h;
Reactive mode is direct heating reaction.
VB1 is dissolved according to a certain ratio in the aqueous ethanolic solution mixing, adds strong base-weak acid salt to adjust pH, make VB1 Formed negative ion, add new steaming phenyl aldehyde reacting by heating a few hours.Reaction product, through fully cooling, filtration, dry, obtains bitter almond oil camphor crude product, and yield is up to 63.5%.Crude benzol acyloin product utilization 95% ethyl alcohol recrystallization, obtains white, needle-shaped crystals, and through digital melting point detector, measuring fusing point is 134.3 ~ 135.1 ℃ (temperature is not proofreaied and correct), conforms to literature value.
Acquisition of technology progress of the present invention:
The present invention is prepared in bitter almond oil camphor process in VB1 catalysis, with strong base-weak acid salt, replaces sodium hydroxide to make alkaline reagents, has guaranteed the structural stability of VB1, has improved the circulation ratio of reaction, has avoided the carrying out of Cannizzaro side reaction;
Sodium hydroxide is in the People's Republic of China (PRC) " hazardous goods product famous-brand clock " (GB 12268-90), belong to second alkaline corrosion product in the 8th class hazardous goods corrosives, the strong base-weak acid salts such as sodium carbonate that present method is used, sodium bicarbonate do not belong to hazardous chemical, therefore the present invention utilizes the strong base-weak acid salts such as sodium carbonate to replace the synthetic bitter almond oil camphor of sodium hydroxide, has improved synthetic security;
The present invention compares as alkaline reagents than sodium hydroxide, because of the alkalescence of strong base-weak acid salt a little less than, can significantly accelerate rate of addition, save the operating time, make the building-up process of bitter almond oil camphor more simple.
Embodiment
Embodiment 1:
1.75 g (0.005 mol) VB1 is dissolved with 5 mL distilled water, add 15 mL 95% ethanol to shake up, drip 10% NaHCO
3the aqueous solution is adjusted pH 9-10, loads onto reflux condensing tube, is placed in 70 ℃ of water-baths and reacts 2.0 h.Reaction finishes, by the abundant cooling st-yrax solid of separating out of product, and filtration under diminished pressure, by a small amount of 95% cold washing with alcohol, dry, obtain 1.55 g st-yraxes, productive rate is 14.76%.NaHCO
3in-VB1 catalyst system, due to NaHCO
3alkalescence very weak, be unfavorable for VB1 Formed negative ion, make effectively catalysis benzoic condensation reaction of VB1; On the other hand, need to add a large amount of alkaline solutions, make phenyl aldehyde and alkaline solution layering, so the yield of bitter almond oil camphor be very low.
Embodiment 2:
1.75 g (0.005 mol) VB1 is dissolved with 3.5 mL distilled water, add 16.5 mL 95% ethanol to shake up, drip 10% Na
2cO
3the aqueous solution is adjusted pH 9-10, loads onto reflux condensing tube, is placed in 70 ℃ of water-baths and reacts 2.0 h.Reaction finishes, by the abundant cooling st-yrax solid of separating out of product, and filtration under diminished pressure, by a small amount of 95% cold washing with alcohol, dry, obtain 5.36 g st-yraxes, productive rate is 51.05%.Na
2cO
3in-VB1 catalyst system, Na
2cO
3alkalescence compare NaHCO
3contribute to VB1 Formed negative ion, so yield is higher than NaHCO by force,
3make alkaline reagents.
Embodiment 3:
1.75 g (0.005 mol) VB1 is dissolved with 6 mL distilled water, add 15 mL 95% ethanol to shake up, drip 20% Na
2cO
3the aqueous solution is adjusted pH 9-10, loads onto reflux condensing tube, is placed in 75 ℃ of water-baths and reacts 1.5 h.Reaction finishes, by the abundant cooling st-yrax solid of separating out of product, and filtration under diminished pressure, by a small amount of 95% cold washing with alcohol, dry, obtain 6.87 g st-yraxes, productive rate is 65.40%.
Embodiment 4:
1.75 g (0.005 mol) VB1 is dissolved with 5 mL distilled water, add 15 mL 95% ethanol to shake up, drip 20% Na
2cO
3the aqueous solution is adjusted pH 9-10, loads onto reflux condensing tube, is placed in 75 ℃ of water-baths and reacts 2.0 h.Reaction finishes, by the abundant cooling st-yrax solid of separating out of product, and filtration under diminished pressure, by a small amount of 95% cold washing with alcohol, dry, obtain 6.15 g st-yraxes, productive rate is 58.57%.
Claims (10)
1. a method of being prepared bitter almond oil camphor by phenyl aldehyde, particularly take inexpensive strong base-weak acid salt as alkaline reagents, the synthetic method of the bitter almond oil camphor under VB1 catalysis, it is characterized in that: by VB1 water dissolution, add appropriate ethanol, after utilizing strong base-weak acid salt adjustment pH value for alkalescence, add phenyl aldehyde, by reacting by heating certain hour, prepare bitter almond oil camphor.
2. according to letter of authorization, require the strong base-weak acid salt described in 1 to refer to sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus etc.
3. according to letter of authorization, requiring the phenyl aldehyde described in 1 is the new phenyl aldehyde that steams.
4. according to letter of authorization, require the strong base-weak acid salt described in 2, its concentration 2% to saturated solution.
5. according to letter of authorization, requiring the consumption of the VB1 described in 1 is that every 10 mL (10.5 g) phenyl aldehyde adds 0.5 ~ 3.0 g.
6. according to the ethanol described in letter of authorization requirement 1, refer to the ethanol of dehydrated alcohol or 95%.
7. according to the consumption of the water described in letter of authorization requirement 1 and ethanol, be respectively every 10 mL (10.5 g) phenyl aldehyde and add 1.5 mL ~ 12.5 mL water and 2.0 mL ~ 18.5 mL dehydrated alcohol or 95% ethanol.
8. according to letter of authorization, requiring the adjustment pH value scope described in 1 is 8 ~ 11.
9. according to letter of authorization, require reacting by heating temperature described in 1 between 50 ℃～100 ℃, the reaction times is between 0.5～5 h.
10. according to letter of authorization, requiring the reacting by heating mode described in 1 is direct heating reaction.
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| CN201310496165.8A CN103524319A (en) | 2013-10-22 | 2013-10-22 | Synthesis method of benzoin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936578A (en) * | 2014-04-01 | 2014-07-23 | 常州大学 | Method for preparing benzoin product in mother liquor recycling manner |
| CN105906499A (en) * | 2016-06-20 | 2016-08-31 | 赵三虎 | Environment-friendly synthesis method for cyclically preparing benzoin |
| CN105985218A (en) * | 2015-01-27 | 2016-10-05 | 李坚 | Method and application of reaction of carboxylate or carboxylic acid and water for synthesizing acyloin and alcohol (ketone) organics |
| CN110746279A (en) * | 2019-10-30 | 2020-02-04 | 阜阳市诗雅涤新材料科技有限公司 | Continuous synthesis method of benzoin |
| CN110773223A (en) * | 2019-12-06 | 2020-02-11 | 南京理工大学 | g-C 3N 4Supported transition metal oxide and application thereof in synthesis of α -hydroxyketone |
| CN111018681A (en) * | 2019-12-31 | 2020-04-17 | 天津久日新材料股份有限公司 | Method for preparing benzoin in micro-reaction device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5780338A (en) * | 1980-11-07 | 1982-05-19 | Sumitomo Chem Co Ltd | Preparation of benzoin |
| CN101774900A (en) * | 2010-01-27 | 2010-07-14 | 扬州大学 | Method for synthesizing benzoin ketone in water phase |
-
2013
- 2013-10-22 CN CN201310496165.8A patent/CN103524319A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5780338A (en) * | 1980-11-07 | 1982-05-19 | Sumitomo Chem Co Ltd | Preparation of benzoin |
| CN101774900A (en) * | 2010-01-27 | 2010-07-14 | 扬州大学 | Method for synthesizing benzoin ketone in water phase |
Non-Patent Citations (4)
| Title |
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| 何强芳等: "安息香缩合反应的影响因素", 《大学化学》, vol. 25, no. 3, June 2010 (2010-06-01) * |
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| 林洁: "不同缓冲溶液对臭氧分解影响的研究", 《四川大学学报（工程科学版）》, vol. 44, December 2012 (2012-12-01) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936578A (en) * | 2014-04-01 | 2014-07-23 | 常州大学 | Method for preparing benzoin product in mother liquor recycling manner |
| CN103936578B (en) * | 2014-04-01 | 2016-01-27 | 常州大学 | A kind of Recycling Mother Solution prepares the method for st-yrax product |
| CN105985218A (en) * | 2015-01-27 | 2016-10-05 | 李坚 | Method and application of reaction of carboxylate or carboxylic acid and water for synthesizing acyloin and alcohol (ketone) organics |
| CN105906499A (en) * | 2016-06-20 | 2016-08-31 | 赵三虎 | Environment-friendly synthesis method for cyclically preparing benzoin |
| CN110746279A (en) * | 2019-10-30 | 2020-02-04 | 阜阳市诗雅涤新材料科技有限公司 | Continuous synthesis method of benzoin |
| CN110773223A (en) * | 2019-12-06 | 2020-02-11 | 南京理工大学 | g-C 3N 4Supported transition metal oxide and application thereof in synthesis of α -hydroxyketone |
| CN110773223B (en) * | 2019-12-06 | 2022-09-09 | 南京理工大学 | g-C 3 N 4 Supported transition metal oxide and application thereof in synthesis of alpha-hydroxy ketone |
| CN111018681A (en) * | 2019-12-31 | 2020-04-17 | 天津久日新材料股份有限公司 | Method for preparing benzoin in micro-reaction device |
| CN111018681B (en) * | 2019-12-31 | 2022-10-14 | 天津久日新材料股份有限公司 | Method for preparing benzoin in micro-reaction device |
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Application publication date: 20140122 |