CN103387519A - Preparation method for 4-hydroxybenzyl cyanide - Google Patents
Preparation method for 4-hydroxybenzyl cyanide Download PDFInfo
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- CN103387519A CN103387519A CN201310276145XA CN201310276145A CN103387519A CN 103387519 A CN103387519 A CN 103387519A CN 201310276145X A CN201310276145X A CN 201310276145XA CN 201310276145 A CN201310276145 A CN 201310276145A CN 103387519 A CN103387519 A CN 103387519A
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Abstract
The invention belongs to the field of organic chemistry synthesis, and specifically relates to the field of preparation of 4-hydroxybenzyl cyanide. A preparation method for 4-hydroxybenzyl cyanide comprises preparation of benzylalcohol and preparation of 4-hydroxybenzyl cyanide by employing 4-hydroxybenzaldehyde as a raw material and potassium borohydride as a reducing agent. The preparation method for 4-hydroxybenzyl cyanide is performed at normal temperature and normal pressure; the operation process is fast, simple and easy to control; the reaction time in the preparation process is shorter; and the yield of the finished product of 4-hydroxybenzyl cyanide is 95% or more.
Description
Technical field
The invention belongs to the organic chemical synthesis field, relate in particular a kind of preparation field of p-hydroxybenzylcyanide.
Technical background
The multiplex intermediate of doing organic synthesis of p-hydroxybenzylcyanide, commonly for the synthesis of the Target medicine, the former many employing autoclaves of the preparation of p-hydroxybenzylcyanide are reaction vessel, hydrogen is reductive agent, reaction process is difficult to control, operating process is easily caused danger, and last p-hydroxybenzylcyanide yield rate is lower; The former diazotization legal system that also adopts of the preparation of p-hydroxybenzylcyanide is standby, this preparation method's cost is high, p-hydroxybenzylcyanide finished product yield rate is low, and the preparation method of existing p-hydroxybenzylcyanide all can not well meet on present market the demand for p-hydroxybenzylcyanide.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the p-hydroxybenzylcyanide under a kind of normal temperature environment simple to operate efficiently.
For solving the problems of the technologies described above, the invention provides the preparation method of p-hydroxybenzylcyanide, the preparation method of p-hydroxybenzylcyanide comprises following two steps:
(1) preparation of benzylalcohol
1. add reactor take p-Hydroxybenzaldehyde as raw material, take methyl alcohol as solvent, add in reactor, then add appropriate water in reactor, stir;
2. to above-mentioned (1) 1. the reactor in step slowly add POTASSIUM BOROHYDRIDE, the temperature of monitoring reactor is at 30-35 ℃, reaction;
3. 2. add acidic solution in the reactor in step to above-mentioned (1), conditioned reaction still solution is to neutral;
4. with above-mentioned (1) 3. in step the material after the reactor internal reaction carry out centrifugally, remove solution, obtain the benzylalcohol crude product, with the oven dry of benzylalcohol crude product, standby.
(2) preparation of p-hydroxybenzylcyanide
1. the benzylalcohol crude product that above-mentioned (1) is 4. obtained in step is placed in reactor, and adds methyl alcohol, ethyl formate, sodium cyanide in reactor, stir,
2. the solution in 1. is heated to 53-54 ℃ with above-mentioned steps (2), and keeps 53-54 ℃ of reaction 2 hours, obtains p-hydroxybenzylcyanide solution crude product, stops stirring;
3. the p-hydroxybenzylcyanide solution crude product in 2. carries out stirring heating to above-mentioned steps (2), sloughs the methyl alcohol in solution, then adds appropriate water, and is cooling;
4. add appropriate ethylene dichloride extraction in the cooling solution in 3. to above-mentioned steps (2);
5. the solution that the extraction in 4. obtains with above-mentioned steps (2) carries out the normal temperature crystallization, and filtration drying, obtain p-hydroxybenzylcyanide.
Preferably, 2. the time of middle reaction is 330-380 minute to step (1).
Preferably, the acidic solution of step (1) in 3. is dilute hydrochloric acid.
Preferably, in step (1), the p-Hydroxybenzaldehyde mass component is 5 components, and the POTASSIUM BOROHYDRIDE mass component is 1 part.
Preferably, in step (2), the benzylalcohol mass component is 4 components, and sodium cyanide quality component is 2 components, and ethyl formate quality component is 7 components, and the quality component of methyl alcohol is 10 components.
adopt the beneficial effect of technique scheme to be: p-Hydroxybenzaldehyde is colourless needle crystal, be slightly soluble in cold water, be soluble in hot water, pure and mild ether, take p-Hydroxybenzaldehyde as raw material, be easy to control and operation, take methyl alcohol as solvent, make p-Hydroxybenzaldehyde be dissolved in methyl alcohol, and methanol prices is cheap, cost is lower, utilize potassium borohydride reduction, POTASSIUM BOROHYDRIDE is xln or crystalline powder, POTASSIUM BOROHYDRIDE is water-soluble and discharge hydrogen, POTASSIUM BOROHYDRIDE is added reactor slowly, make hydrogen produce slowly, safe operation process, the preparation method of p-hydroxybenzylcyanide of the present invention, whole operating process is all carried out at normal temperatures and pressures, operating process simply is easy to control, and the preparation method's finished product yield rate compared to original p-hydroxybenzylcyanide is high.
Embodiment
Below technical scheme of the present invention is described, so that those skilled in the art understand.
The preparation method of p-hydroxybenzylcyanide, the preparation method of p-hydroxybenzylcyanide comprise following two steps:
(1) preparation of benzylalcohol
1. add reactor take p-Hydroxybenzaldehyde as raw material, take methyl alcohol as solvent, add in reactor, then add appropriate water in reactor, stir;
2. to above-mentioned (1) 1. the reactor in step slowly add POTASSIUM BOROHYDRIDE, the temperature of monitoring reactor is at 30-35 ℃, reaction;
3. 2. add acidic solution in the reactor in step to above-mentioned (1), conditioned reaction still solution is to neutral;
4. with above-mentioned (1) 3. in step the material after the reactor internal reaction carry out centrifugally, remove solution, obtain the benzylalcohol crude product, with the oven dry of benzylalcohol crude product, standby.
(2) preparation of p-hydroxybenzylcyanide
1. the benzylalcohol crude product that above-mentioned (1) is 4. obtained in step is placed in reactor, and adds methyl alcohol, ethyl formate, sodium cyanide in reactor, stir,
2. the solution in 1. is heated to 53-54 ℃ with above-mentioned steps (2), and keeps 53-54 ℃ of reaction 2 hours, obtains p-hydroxybenzylcyanide solution crude product, stops stirring;
3. the p-hydroxybenzylcyanide solution crude product in 2. carries out stirring heating to above-mentioned steps (2), sloughs the methyl alcohol in solution, then adds appropriate water, and is cooling;
4. add appropriate ethylene dichloride extraction in the cooling solution in 3. to above-mentioned steps (2);
5. the solution that the extraction in 4. obtains with above-mentioned steps (2) carries out the normal temperature crystallization, and filtration drying, obtain p-hydroxybenzylcyanide.
2. the time of middle reaction is 330-380 minute to step (1), the acidic solution of step (1) in 3. is dilute hydrochloric acid, in step (1), the p-Hydroxybenzaldehyde mass component is 5 components, the POTASSIUM BOROHYDRIDE mass component is 1 part, in step (2), the benzylalcohol mass component is 4 components, sodium cyanide quality component is 2 components, and ethyl formate quality component is 7 components, and the quality component of methyl alcohol is 10 components.
adopt the beneficial effect of technique scheme to be: p-Hydroxybenzaldehyde is colourless needle crystal, be slightly soluble in cold water, be soluble in hot water, pure and mild ether, take p-Hydroxybenzaldehyde as raw material, be easy to control and operation, take methyl alcohol as solvent, make p-Hydroxybenzaldehyde be dissolved in methyl alcohol, and methanol prices is cheap, cost is lower, utilize potassium borohydride reduction, POTASSIUM BOROHYDRIDE is xln or crystalline powder, POTASSIUM BOROHYDRIDE is water-soluble and discharge hydrogen, POTASSIUM BOROHYDRIDE is added reactor slowly, make hydrogen produce slowly, safe operation process, the preparation method of p-hydroxybenzylcyanide of the present invention, whole operating process is all carried out at normal temperatures and pressures, operating process simply is easy to control, and the preparation method's finished product yield rate compared to original p-hydroxybenzylcyanide is high.
Adopt the preparation method of the p-hydroxybenzylcyanide of technical solution of the present invention, carry out at normal temperatures and pressures, quick and easy being easy to of operating process controlled, and the reaction preparation process time is shorter, and p-hydroxybenzylcyanide finished product yield rate can reach more than 95%.
Above-mentioned invention is exemplarily described; obviously specific implementation of the present invention is not subject to the restrictions described above; as long as this non-substantially improved that has adopted method design of the present invention and technical scheme to carry out; or without improving the design that will invent and technical scheme, directly apply to other occasions, all within protection scope of the present invention.
Claims (5)
1. the preparation method of p-hydroxybenzylcyanide, it is characterized in that: the preparation method of p-hydroxybenzylcyanide comprises following two steps:
(1) preparation of benzylalcohol
1. add reactor take p-Hydroxybenzaldehyde as raw material, take methyl alcohol as solvent, add in reactor, then add appropriate water in reactor, stir;
2. to above-mentioned (1) 1. the reactor in step slowly add POTASSIUM BOROHYDRIDE, the temperature of monitoring reactor is at 30-35 ℃, reaction;
3. 2. add acidic solution in the reactor in step to above-mentioned (1), conditioned reaction still solution is to neutral;
4. with above-mentioned (1) 3. in step the material after the reactor internal reaction carry out centrifugally, remove solution, obtain the benzylalcohol crude product, with the oven dry of benzylalcohol crude product, standby.
(2) preparation of p-hydroxybenzylcyanide
1. the benzylalcohol crude product that above-mentioned (1) is 4. obtained in step is placed in reactor, and adds methyl alcohol, ethyl formate, sodium cyanide in reactor, stir,
2. the solution in 1. is heated to 53-54 ℃ with above-mentioned steps (2), and keeps 53-54 ℃ of reaction 2 hours, obtains p-hydroxybenzylcyanide solution crude product, stops stirring;
3. the p-hydroxybenzylcyanide solution crude product in 2. carries out stirring heating to above-mentioned steps (2), sloughs the methyl alcohol in solution, then adds appropriate water, and is cooling;
4. add appropriate ethylene dichloride extraction in the cooling solution in 3. to above-mentioned steps (2);
5. the solution that the extraction in 4. obtains with above-mentioned steps (2) carries out the normal temperature crystallization, and filtration drying, obtain p-hydroxybenzylcyanide.
2. the preparation method of p-hydroxybenzylcyanide according to claim 1 is characterized in that: described step (1) 2. in time of reaction be 330-380 minute.
3. the preparation method of p-hydroxybenzylcyanide according to claim 1 is characterized in that: the acidic solution of described step (1) in 3. is dilute hydrochloric acid.
4. the preparation method of p-hydroxybenzylcyanide according to claim 1 is characterized in that: in described step (1), the p-Hydroxybenzaldehyde mass component is 5 components, and the POTASSIUM BOROHYDRIDE mass component is 1 part.
5. the preparation method of p-hydroxybenzylcyanide according to claim 1, it is characterized in that: in described step (2), the benzylalcohol mass component is 4 components, sodium cyanide quality component is 2 components, and ethyl formate quality component is 7 components, and the quality component of methyl alcohol is 10 components.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788342A (en) * | 2015-04-07 | 2015-07-22 | 湖南大学 | Method for preparing aromatic nitrile compound from aromatic methanol |
| CN109160873A (en) * | 2018-08-14 | 2019-01-08 | 重庆市化工研究院 | A kind of aromatic series allyl ether and its synthetic method and application |
Citations (4)
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| US4378319A (en) * | 1981-10-29 | 1983-03-29 | A. H. Marks & Co., Limited | Process for the manufacture of aromatic cyanides |
| PL194989B1 (en) * | 1999-09-21 | 2007-07-31 | Inst Farmaceutyczny | Method of obtaining genisteine |
| CN102180810A (en) * | 2011-03-10 | 2011-09-14 | 青岛科技大学 | Preparation method of 4-hydroxyphenylacetonitrile |
| CN102675148A (en) * | 2012-04-23 | 2012-09-19 | 嘉兴学院 | Preparation method of hydroxybenzyl cyanide |
-
2013
- 2013-07-01 CN CN201310276145.XA patent/CN103387519B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378319A (en) * | 1981-10-29 | 1983-03-29 | A. H. Marks & Co., Limited | Process for the manufacture of aromatic cyanides |
| PL194989B1 (en) * | 1999-09-21 | 2007-07-31 | Inst Farmaceutyczny | Method of obtaining genisteine |
| CN102180810A (en) * | 2011-03-10 | 2011-09-14 | 青岛科技大学 | Preparation method of 4-hydroxyphenylacetonitrile |
| CN102675148A (en) * | 2012-04-23 | 2012-09-19 | 嘉兴学院 | Preparation method of hydroxybenzyl cyanide |
Non-Patent Citations (2)
| Title |
|---|
| BRAITHWAITE MALCOLM J.: "A novel synthesis of para-hydroxybenzyl", 《SPECIALITY CHEMICALS MAGAZINE》, vol. 6, no. 3, 31 December 1986 (1986-12-31) * |
| 贺新等: "一锅法合成2,4-二氟苯乙腈", 《应用化工》, vol. 38, no. 08, 28 August 2009 (2009-08-28) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788342A (en) * | 2015-04-07 | 2015-07-22 | 湖南大学 | Method for preparing aromatic nitrile compound from aromatic methanol |
| CN109160873A (en) * | 2018-08-14 | 2019-01-08 | 重庆市化工研究院 | A kind of aromatic series allyl ether and its synthetic method and application |
| CN110330411A (en) * | 2018-08-14 | 2019-10-15 | 重庆市化工研究院 | A kind of aromatic series allyl ether and its synthetic method and application |
| CN110407674A (en) * | 2018-08-14 | 2019-11-05 | 重庆市化工研究院 | 4- allyloxy benzyl alcohol, synthetic method and application |
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Effective date of registration: 20190320 Address after: 300 000 No. 11 Xingyuan Road, Xianshuigu Town Industrial Zone, Jinnan District, Tianjin Patentee after: TIANJIN KERMEL CHEMICAL REAGENT Co.,Ltd. Address before: 300110 Xindu Building 1-1-505-1 on the southwest side of the intersection of Weijin Road and Wandezhuang Street, Nankai District, Tianjin Patentee before: HUIJIAWANG (TIANJIN) TECHNOLOGY CO.,LTD. Effective date of registration: 20190320 Address after: 300110 Xindu Building 1-1-505-1 on the southwest side of the intersection of Weijin Road and Wandezhuang Street, Nankai District, Tianjin Patentee after: HUIJIAWANG (TIANJIN) TECHNOLOGY CO.,LTD. Address before: 242000 Guanyin Pavilion, Jingyang Town, Jingde County, Xuancheng, Anhui, China Patentee before: ANHUI PROVINCE JINGDE COUNTY TIANYI MEDICINE CHEMICAL PLANT |
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