CN102875414A - Preparation method of 4-amino-2-trifluoromethyl cyanophenyl - Google Patents
Preparation method of 4-amino-2-trifluoromethyl cyanophenyl Download PDFInfo
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Abstract
The invention relates to a preparation method of 4-amino-2-trifluoromethyl cyanophenyl, which comprises the following steps: nitrifying the raw material o-chlorobenzotrifluoride positioned by easily lost halogen chlorine, directly substituting with cyano group, and finally, hydrogenating for reduction to obtain the target product 4-amino-2-trifluoromethyl cyanophenyl. The invention has the advantages of short route, high product quality, high yield, low production cost and fewer pollutants.
Description
Technical field
The present invention relates to the preparation method of a kind of 4-amino-2-4-trifluoromethylbenzonitrile, relate in particular to chlorobenzotrifluoride and be raw material prepares 4-amino-2-4-trifluoromethylbenzonitrile through nitrated, cyano group displacement and hydro-reduction method.
Background technology
Bicalutamide is the non-reflunomide of a kind of antiandrogen of Britain Zeneca company development and production, is widely used in treatment and prevention prostate cancer, carcinoma of the pancreas, mammary cancer etc.Bicalutamide has good tolerance, take rear effect without any steroidal activity, do not have the side effect of obvious blood vessel and metabolism aspect, patient is seldom arranged because of the untoward reaction of having taken medicine, and 4-amino-2-4-trifluoromethylbenzonitrile is the key intermediate of synthetic bicalutamide; The method of at present synthetic 4-amino-2-trifluoromethyl cyanobenzene (CAS 654-70-6) has two kinds:
1. take o-trifluoromethyl aniline as starting raw material, through diazotization, bromo, nitrated, cyano group displacement, synthetic this product of iron powder reducing four-step reaction; Technological line is as follows:
Can clearly be seen that from above-mentioned technological line, in diazotation step the raw material that uses many, need Hydrogen bromide, sodium hydroxide, the raw materials such as Sodium Nitrite, operate loaded down with trivial details, by product is many, must purify, and the yield of o-trifluoromethyl phenyl-bromide is low, only has about 60%, in the iron powder reducing step, must use the solvent extraction target compound, the amino 2-trifluoromethyl of 4-cyanobenzene is easy to mix three with iron powder in extraction process, not only needs a large amount of solvents, and color and luster and the purity of iron powder reducing technogenic influence after product, the reaction conditions of whole preparation process is wayward, and the target yield is low, only is about 30%, quality is unstable, product color is poor, production cost is obviously higher, produces large amount of sewage in the preparation process simultaneously, unsuitable suitability for industrialized production;
2. Chinese patent 200610038428 disclosed a kind of preparation methods:
Take the m-trifluoromethyl fluorobenzene as starting raw material, through the location bromination, the synthetic 4-amino of cyano group displacement and ammonia solution three-step reaction-2-4-trifluoromethylbenzonitrile.Technological line is as follows:
From the situation of patent disclosure, fluoride trifluoro toluene is more expensive between this route starting raw material, is unfavorable for saving cost, the first step location bromo is that solvent can produce a large amount of acid waste waters with Glacial acetic acid and sulfuric acid, adverse environment, it is large to process wastewater pressure, and second step cyano group replaces, with the such noxious solvent of quinoline, pyroreaction both consumed energy, and poisoned again environment, also have the production safety problem, also can produce large quantity of exhaust gas during the 3rd step ammonia solution aftertreatment.During this route industrialization, the power consumption of meet Lingao, the problem of high pollution.
Summary of the invention
For above-mentioned shortcoming, the object of the invention is to provide the preparation method of a kind of route weak point, good product quality, yield is high, production cost is low and pollutent is few 4-amino-2-4-trifluoromethylbenzonitrile.
Technology contents of the present invention is as follows: the preparation method of a kind of 4-amino-2-4-trifluoromethylbenzonitrile, and its step is as follows:
(1), nitrated:
Add tosic acid and chlorobenzotrifluoride in ethylene dichloride (technical grade), the add-on of tosic acid is 0.01～1 times of weight of chlorobenzotrifluoride; The consumption of ethylene dichloride is 0.5～30 times of weight of chlorobenzotrifluoride; Be added in the 4A molecular sieve that soaked in the sulfuric acid that concentration is 20～40 % by weight 2～4 hours, the add-on of 4A molecular sieve is 0.1～5 times of weight of chlorobenzotrifluoride again; Solution temperature is remained on 30～40 ℃ and drip the nitric acid that concentration is 98 % by weight, the add-on of nitric acid is 0.1～5 times of weight of chlorobenzotrifluoride, dropwise rear insulation reaction 5～6 hours, be warming up to again backflow, after the HPLC detection reaction is complete, then be cooled to gradually 10～20 ℃, suction filtration gets filtrate, filtrate is added drop-wise to the aqueous sodium carbonate that concentration is 15～25 % by weight, and the consumption of aqueous sodium carbonate is 0.3～30 times of weight of chlorobenzotrifluoride; Standing demix is removed water, with pure water washing organic phase 2～3 times, and 0.5～5 times of the weight that each pure water consumption is chlorobenzotrifluoride; And then standing demix removes water, the organic layer concentrating under reduced pressure steamed desolventize ethylene dichloride, and pressure is less than 2500Pa, gets yellow liquid 2-chloro-5-nitro-trifluoromethyl toluene;
(2), cyano group displacement:
In the above-mentioned 2-chloro-5-nitro-trifluoromethyl toluene that makes, add N, dinethylformamide (DMF) and cuprous cyanide, the add-on of DMF is 0.5～30 times of 2-chloro-5-nitro-trifluoromethyl toluene weight, and the add-on of cuprous cyanide is 0.1～5 times of 2-chloro-5-nitro-trifluoromethyl toluene weight; Then be warming up to backflow, after the HPLC detection reaction is complete, filtered while hot, again with behind the filtrate decompression Distillation recovery DMF, be cooled to 45～55 ℃ and must distill end liquid, in distillation end liquid, add ethyl acetate (technical grade), the add-on of ethyl acetate is 0.4～30 times of 2-chloro-5-nitro-trifluoromethyl toluene weight, standing demix is removed water, then be the ammonia scrubbing organic phase 1～3 time of 5～12 % by weight with concentration, it is 0.1～30 times of 2-chloro-5-nitro-trifluoromethyl toluene weight that ammoniacal liquor washs consumption at every turn; Standing demix is removed water again, organic layer is evaporated to dried brown oil 4-nitro-2-trifluoromethyl cyanobenzene again, and pressure is less than 2500Pa;
(3), hydro-reduction:
The 4-nitro that makes in the step (2)-2-trifluoromethyl cyanobenzene is put in the hydriding reactor, add again simultaneously methyl alcohol (technical grade), W-4 type Raney's nickel and Dyhard RU 100, the methyl alcohol add-on is 0.5～30 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, W-4 type Raney's nickel add-on is 0.05～5 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, the Dyhard RU 100 add-on is 0.01～5 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, then carry out nitrogen replacement 2～5 times, carry out again hydrogen exchange 1～3 time, carry out hydrogenation, the control hydrogen pressure is 0.3～0.8Mpa, be warming up to 55～65 ℃, HPLC detects control 4-nitro-2-trifluoromethyl cyanobenzene less than the 0.1%(area normalization method), reaction finishes, get filtrate after filtering under the nitrogen protection, be that 10～50 ℃ of lower underpressure distillation are removed methyl alcohol and got end liquid with filtrate at bath temperature, pressure is less than 2500Pa; In end liquid, add again toluene (technical grade), the add-on of toluene is 0.5～30 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, standing demix is removed water, wash organic phase 1～5 time with pure water again, each pure water consumption is 0.5～5 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, and then standing demix is removed water, organic layer is cooled to 0～10 ℃, kept this temperature 1～3 hour, off-white color to light yellow solid is separated out, filter to get wet product, the product that will wet are dried the 4-amino-2-4-trifluoromethylbenzonitrile that gets product.
Reaction formula of the present invention is as follows:
The advantage that the present invention compared with prior art has is: one, this route adopts the bulk raw material that the halogens chlorine easily leave away has been had good positioning, and directly cyano group replaces, and rear restore nitrification gets target product, avoided diazotization halogen bromo after cyano group replace restore nitrification again; Make reaction scheme of the present invention short, the good product quality of preparation, yield height, preparation cost is low; Two, prior art adopts chemical reduction, and raw material consumption is high, goes back original reagent and can not regenerate, the refuse that produces is many, the green catalysis hydrogenation that the present invention adopts, and catalyzer is directly applied mechanically, after the catalyzer of inactivation reclaims again, recycling, reagent consumes low, basic contamination-free, three, adopt solid acid catalysis, catalyzer is directly applied mechanically, after the catalyzer of inactivation reclaims again, recycling only is the waste water 1/10th of sulphuric acid catalysis generation, have dirty production cost low, dye the few advantage of thing.
Specific embodiment
Ethylene dichloride is technical grade in lower routine embodiment, and toluene is technical grade, and methyl alcohol is technical grade, and ethyl acetate is technical grade.
Example 1,
(1), nitrated:
In with the glass four-hole boiling flask of churned mechanically 500ml, add the 200ml ethylene dichloride, in ethylene dichloride, add again tosic acid 0.2 gram and chlorobenzotrifluoride 36.1 grams, be added in again 4A molecular sieve 20 grams that soaked 2.5 hours in the sulfuric acid that concentration is 30 % by weight; Solution temperature is remained on 35 ℃ and drip nitric acid 15.1 gram that concentration is 98 % by weight, dropwise rear insulation reaction 5 hours, be warming up to again backflow, after the HPLC detection reaction is complete, then be cooled to gradually 15 ℃, suction filtration gets filtrate, and filtrate is added drop-wise to rear standing demix and place to go water in the 100 gram aqueous sodium carbonates that concentration is 20 % by weight, wash organic phase 2 times with pure water, each pure water consumption 30 grams; And then standing demix removes water, the organic layer concentrating under reduced pressure steamed desolventize ethylene dichloride, and pressure is 2000Pa, gets yellow liquid 2-chloro-5-nitro-trifluoromethyl toluene 39 grams;
(2), cyano group displacement:
In with the glass four-hole boiling flask of churned mechanically 500ml, add the above-mentioned 2-chloro-5-nitro-trifluoromethyl toluene that makes 39 grams, 100mlN, dinethylformamide and cuprous cyanide 19 grams, then be warming up to backflow, after the HPLC detection reaction is complete, filtered while hot, again with behind the filtrate decompression Distillation recovery DMF, be cooled to 50 ℃, in distillation end liquid, add the 100ml ethyl acetate, standing demix is removed water, then be the ammonia scrubbing organic phase 2 times of 10 % by weight with concentration, the each washing amount of ammoniacal liquor is 20 grams; And then standing demix removes water, organic layer is evaporated to dried brown oil 4-nitro-2-trifluoromethyl cyanobenzene 33 grams again, and pressure is 2000Pa;
(3), hydro-reduction:
The 33 gram 4-nitro-2-trifluoromethyl cyanobenzenes that make in the step (2) are put in the hydriding reactor of 500ml; add again simultaneously methyl alcohol 200ml; W-4 type Raney's nickel 5 grams and Dyhard RU 100 2 grams; then carry out nitrogen replacement 3 times; carry out again hydrogen exchange 2 times; carry out hydrogenation; the control hydrogen pressure is 0.5Mpa; be warming up to 60 ℃, HPLC detects control 4-nitro-2-trifluoromethyl cyanobenzene less than the 0.1%(area normalization method), reaction finishes; filter to get filtrate under the nitrogen protection; filtrate is carried out underpressure distillation 40 ℃ of bath temperatures and is removed methyl alcohol and get end liquid, and pressure is 2000Pa, adds 100ml toluene in end liquid again; standing demix is removed water; wash organic phase 2 times with pure water again, each pure water consumption is 100ml, and then standing demix is removed water; just organic phase is cooled to 3 ℃ again; kept this temperature 2 hours, off-white color to light yellow solid is separated out, and filters to get wet product; wet product oven dry is namely got the finished product 4-amino of content 99.2 % by weight-2-4-trifluoromethylbenzonitrile 27 restrain yield 95%.
Example 2,
(1), nitrated:
In with churned mechanically 10 liters glass four-hole boiling flask, add 4 liters of ethylene dichloride, in ethylene dichloride, add again tosic acid 4 grams and chlorobenzotrifluoride 722 grams, be added in again 4A molecular sieve 400 grams that soaked 2.5 hours in the sulfuric acid that concentration is 30 % by weight; Solution temperature is remained on 35 ℃ and drip nitric acid 302 gram that concentration is 98 % by weight, dropwise rear insulation reaction 5 hours, be warming up to again backflow, after the HPLC detection reaction is complete, then be cooled to gradually 15 ℃, suction filtration gets filtrate, and filtrate is added drop-wise to rear standing demix and place to go water in the 200 gram aqueous sodium carbonates that concentration is 10 % by weight, wash organic phase 2 times with pure water, each pure water consumption 1000 grams; And then standing demix removes water, the organic layer concentrating under reduced pressure steamed desolventize ethylene dichloride, and pressure is 2000Pa, gets yellow liquid 2-chloro-5-nitro-trifluoromethyl toluene 760 grams;
(2), cyano group displacement:
In with churned mechanically 10 liters glass four-hole boiling flask, add the above-mentioned 2-chloro-5-nitro-trifluoromethyl toluene that makes 760 grams, 2 liters of N, dinethylformamide and cuprous cyanide 370 grams, then be warming up to backflow, after the HPLC detection reaction is complete, filtered while hot, again with behind the filtrate decompression Distillation recovery DMF, be cooled to 50 ℃, add 2 liters of ethyl acetate in distillation end liquid, standing demix is removed water, then be the ammonia scrubbing organic phase 2 times of 10 % by weight with concentration, the each washing amount of ammoniacal liquor is 400 grams; And then standing demix removes water, organic layer is evaporated to dried brown oil 4-nitro-2-trifluoromethyl cyanobenzene 640 grams again, and pressure is 2000Pa;
(3), hydro-reduction:
The 640 gram 4-nitro-2-trifluoromethyl cyanobenzenes that make in the step (2) are put in 10 liters the hydriding reactor; add again simultaneously methyl alcohol 4000ml; W-4 type Raney's nickel 100 grams and Dyhard RU 100 40 grams; then carry out nitrogen replacement 3 times; carry out again hydrogen exchange 1 time; carry out hydrogenation; the control hydrogen pressure is 0.5Mpa; be warming up to 60 ℃; HPLC detects control 4-nitro-2-trifluoromethyl cyanobenzene less than the 0.1%(area normalization method), reaction finishes, and filters to get filtrate under the nitrogen protection; filtrate is 40 ℃ of bath temperatures; pressure is that 2000Pa carries out distillation for removing methanol and gets end liquid; add 2 liters of toluene in end liquid, standing demix is removed water, washs organic phase 2 times with pure water more again; each pure water consumption is 2 liters; and then standing demix removes water, and just organic phase is cooled to 3 ℃ again, keeps this temperature 2 hours; off-white color to light yellow solid is separated out; filter to get wet product, wet product oven dry is namely got the finished product 4-amino of content 99.2 % by weight-2-4-trifluoromethylbenzonitrile 511 restrain yield 93%.
Claims (1)
1. the preparation method of 4-amino-2-4-trifluoromethylbenzonitrile, its step is as follows:
(1), nitrated:
Add tosic acid and chlorobenzotrifluoride in ethylene dichloride, the add-on of tosic acid is 0.01～1 times of weight of chlorobenzotrifluoride; The consumption of ethylene dichloride is 0.5～30 times of weight of chlorobenzotrifluoride; Be added in the 4A molecular sieve that soaked in the sulfuric acid that concentration is 20～40 % by weight 2～4 hours, the add-on of 4A molecular sieve is 0.1～5 times of weight of chlorobenzotrifluoride again; Solution temperature is remained on 30～40 ℃ and drip the nitric acid that concentration is 98 % by weight, the add-on of nitric acid is 0.1～5 times of weight of chlorobenzotrifluoride, dropwise rear insulation reaction 5～6 hours, be warming up to again backflow, after the HPLC detection reaction is complete, then be cooled to gradually 10～20 ℃, suction filtration gets filtrate, filtrate is added drop-wise to the aqueous sodium carbonate that concentration is 15～25 % by weight, and the consumption of aqueous sodium carbonate is 0.3～30 times of weight of chlorobenzotrifluoride; Standing demix is removed water, with pure water washing organic phase 2～3 times, and 0.5～5 times of the weight that each pure water consumption is chlorobenzotrifluoride; And then standing demix removes water, the organic layer concentrating under reduced pressure steamed desolventize ethylene dichloride, and pressure is less than 2500Pa, gets yellow liquid 2-chloro-5-nitro-trifluoromethyl toluene;
(2), cyano group displacement:
In the above-mentioned 2-chloro-5-nitro-trifluoromethyl toluene that makes, add N, dinethylformamide and cuprous cyanide, the add-on of DMF is 0.5～30 times of 2-chloro-5-nitro-trifluoromethyl toluene weight, and the add-on of cuprous cyanide is 0.1～5 times of 2-chloro-5-nitro-trifluoromethyl toluene weight; Then be warming up to backflow, after the HPLC detection reaction is complete, filtered while hot, again with filtrate decompression Distillation recovery N, behind the dinethylformamide, be cooled to 45～55 ℃ and must distill end liquid, in distillation end liquid, add ethyl acetate, the add-on of ethyl acetate is 0.4～30 times of 2-chloro-5-nitro-trifluoromethyl toluene weight, standing demix is removed water, then be the ammonia scrubbing organic phase 1～3 time of 5～12 % by weight with concentration, it is 0.1～30 times of 2-chloro-5-nitro-trifluoromethyl toluene weight that ammoniacal liquor washs consumption at every turn; Standing demix is removed water again, organic layer is evaporated to dried brown oil 4-nitro-2-trifluoromethyl cyanobenzene again, and pressure is less than 2500Pa;
(3), hydro-reduction:
The 4-nitro that makes in the step (2)-2-trifluoromethyl cyanobenzene is put in the hydriding reactor, add again simultaneously methyl alcohol, W-4 type Raney's nickel and Dyhard RU 100, the methyl alcohol add-on is 0.5～30 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, W-4 type Raney's nickel add-on is 0.05～5 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, the Dyhard RU 100 add-on is 0.01～5 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, then carry out nitrogen replacement 2～5 times, carry out again hydrogen exchange 1～3 time, carry out hydrogenation, the control hydrogen pressure is 0.3～0.8Mpa, be warming up to 55～65 ℃, HPLC detects control 4-nitro-2-trifluoromethyl cyanobenzene less than 0.1%, reaction finishes, get filtrate after filtering under the nitrogen protection, be that 10～50 ℃ of lower underpressure distillation are removed methyl alcohol and got end liquid with filtrate at bath temperature, pressure is less than 2500Pa; In end liquid, add toluene again, the add-on of toluene is 0.5～30 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, standing demix is removed water, wash organic phase 1～5 time with pure water again, each pure water consumption is 0.5～5 times of 4-nitro-2-trifluoromethyl cyanobenzene weight, and then standing demix is removed water, organic phase is cooled to 0～10 ℃, kept this temperature 1～3 hour, off-white color to light yellow solid is separated out, filter to get wet product, the product that will wet are dried the 4-amino-2-4-trifluoromethylbenzonitrile that gets product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278409A (en) * | 2021-06-22 | 2021-08-20 | 西南石油大学 | High-temperature acidizing corrosion inhibitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012058A (en) * | 1958-05-15 | 1961-12-05 | Pennsalt Chemicals Corp | Nitrile compounds |
| EP0365763A1 (en) * | 1988-09-30 | 1990-05-02 | Agouron Pharmaceuticals, Inc. | Antiproliferative cyclic compounds |
| CN101759597A (en) * | 2009-12-31 | 2010-06-30 | 上海康鹏化学有限公司 | Preparation method of 2-trifluoromethyl-4-aminobenzonitrile |
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- 2012-10-16 CN CN2012103914706A patent/CN102875414A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012058A (en) * | 1958-05-15 | 1961-12-05 | Pennsalt Chemicals Corp | Nitrile compounds |
| EP0365763A1 (en) * | 1988-09-30 | 1990-05-02 | Agouron Pharmaceuticals, Inc. | Antiproliferative cyclic compounds |
| CN101759597A (en) * | 2009-12-31 | 2010-06-30 | 上海康鹏化学有限公司 | Preparation method of 2-trifluoromethyl-4-aminobenzonitrile |
Non-Patent Citations (3)
| Title |
|---|
| 《Journal of Medicinal Chemistry》 20080228 Olivier Payen et al. Synthesis and Structure-Activity Relationships of the First Ferrocenyl-Aryl-Hydantoin Derivatives of the Nonsteroidal Antiandrogen Nilutamide 1 第51卷, 第6期 * |
| OLIVIER PAYEN ET AL.: "Synthesis and Structure–Activity Relationships of the First Ferrocenyl-Aryl-Hydantoin Derivatives of the Nonsteroidal Antiandrogen Nilutamide", 《JOURNAL OF MEDICINAL CHEMISTRY》 * |
| 刘雅茹 等: "3-三氟甲基-4-氰基苯胺的合成", 《广东药学院学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278409A (en) * | 2021-06-22 | 2021-08-20 | 西南石油大学 | High-temperature acidizing corrosion inhibitor |
| CN113278409B (en) * | 2021-06-22 | 2022-04-29 | 西南石油大学 | High-temperature acidizing corrosion inhibitor |
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Application publication date: 20130116 |