CN102126988A - Preparation method of 4-(4-chlorophenyl)-2-bromomethyl-2-phenylbutanenitrile - Google Patents
Preparation method of 4-(4-chlorophenyl)-2-bromomethyl-2-phenylbutanenitrile Download PDFInfo
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- CN102126988A CN102126988A CN201010592816XA CN201010592816A CN102126988A CN 102126988 A CN102126988 A CN 102126988A CN 201010592816X A CN201010592816X A CN 201010592816XA CN 201010592816 A CN201010592816 A CN 201010592816A CN 102126988 A CN102126988 A CN 102126988A
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Abstract
The invention discloses a preparation method of 4-(4-chlorophenyl)-2-bromomethyl-2-phenylbutanenitrile. The method comprises the following preparation steps: a) synthetizing 2-(4-chlorophenyl)-1-chloroethane; b) synthetizing 4-(4-chlorophenyl)-2-phenylbutanenitrile; and c) synthetizing 4-(4-chlorophenyl)-2-bromomethyl-2-phenylbutanenitrile. The preparation method uses cheap raw materials and has simple operations and high yield.
Description
Technical field
The invention belongs to the organic synthesis field, relate to the preparation method of 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile specifically.
Background technology
Triazole bactericidal agent is the sterilant that class people comparatively are familiar with.After Beyer Co., Ltd in 1973 releases the sterilant triazolone that first commercialization has chiral carbon, triazole bactericidal agent development is fast, more than the quantity, is that any in the past sterilant is incomparable, at present existing about 40 kind commercializations, RH-7592 are exactly wherein a kind of.
The mechanism of action of triazole bactericidal agent is the formation that influences fungal cell wall by the biosynthesizing that hinders the fungi ergosterol, and most fungal diseases that damage to crops is grown all have good prevention effect.Most triazole bactericidal agents have efficiently, wide spectrum, long-acting, strong interior absorption and stereoselectivity isoreactivity characteristics.Triazole bactericidal agent also has certain plant growth regulating simultaneously, and it eliminates the plant apical dominance by suppressing the synthetic of plant materials inner gibberellin, and multiple functions such as having volume increase, precocity, resist, be degeneration-resistant is closed.
Therefore 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, seeks a kind of raw material cheapness as the important intermediate of preparation RH-7592, and simple to operate, the preparation method that productive rate is high is very necessary.
Summary of the invention
Technical problem to be solved by this invention is: a kind of raw material cheapness is provided, and simple to operate, the preparation method of the 4-that productive rate is high (4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, and its preparation process is as follows:
A) 2-(4-chloro-phenyl-)-1-monochloroethane is synthetic, and reaction equation is as follows:
In reactor, add sulfur oxychloride, the mixing solutions with pyridine and 4-chlorophenethylol is added drop-wise in the reactor then, dropwise, backflow 5 ~ 6 h, reaction finishes, underpressure distillation, excessive sulfur oxychloride is steamed, remaining extremely neutral with 30 ~ 50wt.% aqueous sodium hydroxide solution adjusting pH, ethyl acetate extraction, organic layer merges washing, dry, precipitation get product 2-(4-chloro-phenyl-)-1-monochloroethane;
B) 4-(4-chloro-phenyl-)-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:
In reactor, add sodium hydride, exsiccant N, dinethylformamide, nitrogen or protection of inert gas, controlled temperature＜25 ℃, drip benzyl cyanide and N, the mixed solution of dinethylformamide dropwises, and continues reaction 20 ~ 30 min, drip 2-(4-chloro-phenyl-)-1-chlorine and N again, the mixed solution of dinethylformamide, after dropwising, 25 ± 3 ℃ are continued to stir 2 ~ 3 h, reaction finishes, make reacting liquid temperature be no more than 30 ℃, add trash ice, be stirred to trash ice and all melt, with 10 ~ 15wt.% aqueous hydrochloric acid, transfer pH to neutral, use ethyl acetate extraction, organic layer merges washing, dry, precipitation, crude product steams excessive benzyl cyanide through underpressure distillation, gets product: 4-(4-chloro-phenyl-)-2-phenylbutyronitrile;
C) 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:
In reactor, add 4-(4-chloro-phenyl-)-2-phenylbutyronitrile, dimethyl sulfoxide (DMSO), methylene bromide, stir,, drip 40 ~ 50wt.% aqueous sodium hydroxide solution at 20 ± 2 ℃, be warming up to 50 ~ 60 ℃ then, insulation reaction 2 ~ 3 h under this temperature, reaction adds entry after finishing, and transfers pH to neutral, use ethyl acetate extraction again, organic layer merges washing, and dry, precipitation get target product: 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile.
The 4-chlorophenethylol in the described step a) and the mol ratio of sulfur oxychloride and pyridine are 1:4.0 ~ 5.0:0.1 ~ 0.15.
The mol ratio of the 2-in the described step b) (4-chloro-phenyl-)-1-chlorine and sodium hydride and benzyl cyanide is 1:4 ~ 5:5 ~ 6.
The mol ratio of the 4-in the described step c) (4-chloro-phenyl-)-2-phenylbutyronitrile and methylene bromide and sodium hydroxide is 1:2.2 ~ 2.5:1.5 ~ 1.8.
Described preparation process b) rare gas element in is a kind of in helium, neon, the argon gas.
Beneficial effect of the present invention: the preparation method of this 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, the raw material cheapness, simple to operate, the productive rate height.
Embodiment
Describe specific embodiments of the present invention below in detail, but not as limitation of the present invention:
Embodiment 1:
A) 2-(4-chloro-phenyl-)-1-monochloroethane is synthetic, and reaction equation is as follows:
In reactor, add sulfur oxychloride (228 mL, 1.245 mol), then the mixing solutions of pyridine (2.9 g, 37.05 mmol) with 4-chlorophenethylol (45.0 g, 0.285 g) is added drop-wise in the reactor, dropwise, 5 h that reflux, reaction finishes, underpressure distillation, excessive sulfur oxychloride is steamed, remaining extremely neutral with 30wt.% aqueous sodium hydroxide solution adjusting pH, ethyl acetate (500 mL * 3) extraction, organic layer merges to be washed, dry, precipitation, get product 2-(4-chloro-phenyl-)-1-monochloroethane, content 97.3%, yield 96.7%;
B) 4-(4-chloro-phenyl-)-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:
In reactor, add the sodium hydride (43.8 g, 1.096 mol) of 60.0wt.%, exsiccant N, dinethylformamide (450 mL), nitrogen protection, controlled temperature＜25 ℃ drip benzyl cyanide (170.1 g, 1.452 mol) and N, the mixed solution of dinethylformamide (200 mL), dropwise, continue reaction 20 ~ 30 min, drip 2-(4-chloro-phenyl-)-1-chlorine (48.4 g again, 0.274 mol) and N, the mixed solution of dinethylformamide (500 mL), after dropwising, 25 ℃ are continued to stir 2.5 h, reaction finishes, make reacting liquid temperature be no more than 30 ℃, add trash ice (450 g), be stirred to trash ice and all melt, use the 10wt.% aqueous hydrochloric acid, transfer pH to neutral, with ethyl acetate (500 mL * 3) extraction, organic layer merges washing, dry, precipitation, crude product steams excessive benzyl cyanide through underpressure distillation, gets product: 4-(4-chloro-phenyl-)-2-phenylbutyronitrile, content 93.4%, yield: 87.2%;
C) 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:
In reactor, add 4-(4-chloro-phenyl-)-2-phenylbutyronitrile (61.0 g, 0.238 mol), dimethyl sulfoxide (DMSO) (300 mL), methylene bromide (37 mL, 0.531 mol) stirs, at 20 ℃, drip 40 ~ 50wt.% sodium hydroxide (14.3 g) water (20 mL) solution, be warming up to 50 ℃ then, insulation reaction 2.5 h under this temperature, reaction adds entry after finishing, transfer pH to neutral, use ethyl acetate (600 mL * 3) extraction again, organic layer merges washing, dry, precipitation, get target product: 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, content 95.3%, yield 95.4%.
Embodiment 2:
A) 2-(4-chloro-phenyl-)-1-monochloroethane is synthetic, and reaction equation is as follows:
In reactor, add sulfur oxychloride (478 mL, 6.605 mol), then the mixing solutions of pyridine (16 mL, 198.12 mmol) with 4-chlorophenethylol (206.9 g, 1.321 mol) is added drop-wise in the reactor, dropwise, 6 h that reflux, reaction finishes, underpressure distillation, excessive sulfur oxychloride is steamed, remaining extremely neutral with 50wt.% aqueous sodium hydroxide solution adjusting pH, ethyl acetate (2000 * 3) extraction, organic layer merges to be washed, dry, precipitation, get product 2-(4-chloro-phenyl-)-1-monochloroethane, content 96.9%, yield 97.4%;
B) 4-(4-chloro-phenyl-)-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:
In reactor, add the sodium hydride (256.2 g, 6.405 mol) of 60.0wt.%, exsiccant N, dinethylformamide (2000 mL), helium gas protection, controlled temperature＜25 ℃, drip benzyl cyanide (900.4 g, 7.686 mol) and N, the mixed solution of dinethylformamide (8000 mL) dropwises, continue reaction 30 min, drip 2-(4-chloro-phenyl-)-1-chlorine (226.9 g, 1.281 mol) and N again, the mixed solution of dinethylformamide (1500 mL), after dropwising, 28 ℃ are continued to stir 3 h, and reaction finishes, and makes reacting liquid temperature be no more than 30 ℃, add trash ice (1800 g), be stirred to trash ice and all melt, use the 15wt.% aqueous hydrochloric acid, transfer pH to neutral, extract with ethyl acetate (2000 mL * 3), organic layer merges washing, drying, precipitation, crude product is through underpressure distillation, steam excessive benzyl cyanide, get product: 4-(4-chloro-phenyl-)-2-phenylbutyronitrile; Content 95.1%, yield: 86.7%;
C) 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:
In reactor, add 4-(4-chloro-phenyl-)-2-phenylbutyronitrile (281.7 g, 1.101 mol), dimethyl sulfoxide (DMSO) (1400 mL), methylene bromide (192 mL, 2.753 mol) stirs, at 22 ℃, drip 40 ~ 50wt.% sodium hydroxide (79.3 g) water (82 mL) solution, be warming up to 50 ~ 60 ℃ then, insulation reaction 3 h under this temperature, reaction adds entry after finishing, transfer pH to neutral, use ethyl acetate (3000 mL * 3) extraction again, organic layer merges washing, dry, precipitation, get target product: 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, content 96.2%, yield 94.3%.
Claims (5)
- The preparation method of (1.4-4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, its preparation process is as follows:A) 2-(4-chloro-phenyl-)-1-monochloroethane is synthetic, and reaction equation is as follows:In reactor, add sulfur oxychloride, the mixing solutions with pyridine and 4-chlorophenethylol is added drop-wise in the reactor then, dropwise, backflow 5 ~ 6 h, reaction finishes, underpressure distillation, excessive sulfur oxychloride is steamed, remaining extremely neutral with 30 ~ 50wt.% aqueous sodium hydroxide solution adjusting pH, ethyl acetate extraction, organic layer merges washing, dry, precipitation get product 2-(4-chloro-phenyl-)-1-monochloroethane;B) 4-(4-chloro-phenyl-)-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:In reactor, add sodium hydride, exsiccant N, dinethylformamide, nitrogen or protection of inert gas, controlled temperature＜25 ℃, drip benzyl cyanide and N, the mixed solution of dinethylformamide dropwises, and continues reaction 20 ~ 30 min, drip 2-(4-chloro-phenyl-)-1-chlorine and N again, the mixed solution of dinethylformamide, after dropwising, 25 ± 3 ℃ are continued to stir 2 ~ 3 h, reaction finishes, make reacting liquid temperature be no more than 30 ℃, add trash ice, be stirred to trash ice and all melt, with 10 ~ 15wt.% aqueous hydrochloric acid, transfer pH to neutral, use ethyl acetate extraction, organic layer merges washing, dry, precipitation, crude product steams excessive benzyl cyanide through underpressure distillation, gets product: 4-(4-chloro-phenyl-)-2-phenylbutyronitrile;C) 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is synthetic, and reaction equation is as follows:In reactor, add 4-(4-chloro-phenyl-)-2-phenylbutyronitrile, dimethyl sulfoxide (DMSO), methylene bromide, stir,, drip 40 ~ 50wt.% aqueous sodium hydroxide solution at 20 ± 2 ℃, be warming up to 50 ~ 60 ℃ then, insulation reaction 2 ~ 3 h under this temperature, reaction adds entry after finishing, and transfers pH to neutral, use ethyl acetate extraction again, organic layer merges washing, and dry, precipitation get target product: 4-(4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile.
- 2. the preparation method of 4-according to claim 1 (4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is characterized in that, the 4-chlorophenethylol in the described step a) and the mol ratio of sulfur oxychloride and pyridine are 1:4.0 ~ 5.0:0.1 ~ 0.15.
- 3. the preparation method of 4-according to claim 1 (4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is characterized in that, the mol ratio of the 2-in the described step b) (4-chloro-phenyl-)-1-chlorine and sodium hydride and benzyl cyanide is 1:4 ~ 5:5 ~ 6.
- 4. the preparation method of 4-according to claim 1 (4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile, it is characterized in that the mol ratio of the 4-in the described step c) (4-chloro-phenyl-)-2-phenylbutyronitrile and methylene bromide and sodium hydroxide is 1:2.2 ~ 2.5:1.5 ~ 1.8.
- 5. the preparation method of 4-according to claim 1 (4-chloro-phenyl-)-2-brooethyl-2-phenylbutyronitrile is characterized in that described preparation process b) in rare gas element be a kind of in helium, neon, the argon gas.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8822727B2 (en) | 2008-03-04 | 2014-09-02 | Arena Pharmaceuticals, Inc. | Processes for the preparation of intermediates related to the 5-HT2C agonist (R)-8-chloro-1-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine |
| US8952197B2 (en) | 2009-06-18 | 2015-02-10 | Arena Pharmaceuticals, Inc. | Processes for the preparation of 5-HT2C receptor agonists |
| US8999970B2 (en) | 2010-09-01 | 2015-04-07 | Arena Pharmaceuticals, Inc. | Administration of an anti-obesity compound to individuals with renal impairment |
| US9045431B2 (en) | 2010-06-02 | 2015-06-02 | Arena Pharmaceuticals, Inc. | Processes for the preparation of 5-HT2C receptor agonists |
| US9169213B2 (en) | 2012-10-09 | 2015-10-27 | Arena Pharmaceuticals, Inc. | Method of weight management |
| US9248133B2 (en) | 2010-09-01 | 2016-02-02 | Arena Pharmaceuticals, Inc. | Salts of lorcaserin with optically active acids |
| US9365521B2 (en) | 2010-09-01 | 2016-06-14 | Arena Pharmaceuticals, Inc. | Non-hygroscopic salts of 5-HT2C agonists |
| CN106083652A (en) * | 2016-06-12 | 2016-11-09 | 阜阳欣奕华材料科技有限公司 | A kind of synthetic method of 2,3,5,6 tetrafluoro 7,7 ', 8,8 ' four cyanogen dimethyl-parabenzoquinone |
| US10226471B2 (en) | 2010-09-01 | 2019-03-12 | Arena Pharmaceuticals, Inc. | Modified-release dosage forms of 5-HT2C agonists useful for weight management |
| CN116621730A (en) * | 2023-07-24 | 2023-08-22 | 山东国邦药业有限公司 | Synthesis method of cyclopropylnitrile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125822A (en) * | 2007-08-22 | 2008-02-20 | 江苏丰登农药有限公司 | Method for preparing 2-bromomethyl-2-phenyl-4-(4-chlorophenyl)-butyronitrile |
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- 2010-12-17 CN CN201010592816XA patent/CN102126988A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125822A (en) * | 2007-08-22 | 2008-02-20 | 江苏丰登农药有限公司 | Method for preparing 2-bromomethyl-2-phenyl-4-(4-chlorophenyl)-butyronitrile |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8822727B2 (en) | 2008-03-04 | 2014-09-02 | Arena Pharmaceuticals, Inc. | Processes for the preparation of intermediates related to the 5-HT2C agonist (R)-8-chloro-1-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine |
| US8952197B2 (en) | 2009-06-18 | 2015-02-10 | Arena Pharmaceuticals, Inc. | Processes for the preparation of 5-HT2C receptor agonists |
| US9045431B2 (en) | 2010-06-02 | 2015-06-02 | Arena Pharmaceuticals, Inc. | Processes for the preparation of 5-HT2C receptor agonists |
| US9365521B2 (en) | 2010-09-01 | 2016-06-14 | Arena Pharmaceuticals, Inc. | Non-hygroscopic salts of 5-HT2C agonists |
| US9248133B2 (en) | 2010-09-01 | 2016-02-02 | Arena Pharmaceuticals, Inc. | Salts of lorcaserin with optically active acids |
| US8999970B2 (en) | 2010-09-01 | 2015-04-07 | Arena Pharmaceuticals, Inc. | Administration of an anti-obesity compound to individuals with renal impairment |
| US9770455B2 (en) | 2010-09-01 | 2017-09-26 | Arena Pharmaceuticals, Inc. | Administration of an anti-obesity compound to individuals with renal impairment |
| US10226471B2 (en) | 2010-09-01 | 2019-03-12 | Arena Pharmaceuticals, Inc. | Modified-release dosage forms of 5-HT2C agonists useful for weight management |
| US10463676B2 (en) | 2010-09-01 | 2019-11-05 | Arena Pharmaceuticals, Inc. | Modified-release dosage forms of 5-HT2C agonists useful for weight management |
| US9169213B2 (en) | 2012-10-09 | 2015-10-27 | Arena Pharmaceuticals, Inc. | Method of weight management |
| CN106083652A (en) * | 2016-06-12 | 2016-11-09 | 阜阳欣奕华材料科技有限公司 | A kind of synthetic method of 2,3,5,6 tetrafluoro 7,7 ', 8,8 ' four cyanogen dimethyl-parabenzoquinone |
| CN106083652B (en) * | 2016-06-12 | 2017-11-21 | 阜阳欣奕华材料科技有限公司 | A kind of synthetic method of the cyanogen dimethyl-parabenzoquinone of 2,3,5,6 tetrafluoro 7,7 ', 8,8 ' four |
| CN116621730A (en) * | 2023-07-24 | 2023-08-22 | 山东国邦药业有限公司 | Synthesis method of cyclopropylnitrile |
| CN116621730B (en) * | 2023-07-24 | 2023-12-15 | 山东国邦药业有限公司 | Synthesis method of cyclopropylnitrile |
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Application publication date: 20110720 |