CN109651193A - A kind of synthetic method of benzoyl cyanide - Google Patents
A kind of synthetic method of benzoyl cyanide Download PDFInfo
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- CN109651193A CN109651193A CN201910056947.7A CN201910056947A CN109651193A CN 109651193 A CN109651193 A CN 109651193A CN 201910056947 A CN201910056947 A CN 201910056947A CN 109651193 A CN109651193 A CN 109651193A
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- Prior art keywords
- benzoyl cyanide
- cyanide
- benzoyl
- synthetic method
- chlorobenzoyl chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of benzoyl cyanide, using Cymag and chlorobenzoyl chloride as raw material, using the mixture of Macrogol 600 and tri-n-octyl methyl ammonium chloride as phase transfer catalyst, using water or glycerol as cocatalyst, it reacts at 60 DEG C -110 DEG C with chlorobenzoyl chloride, benzoyl cyanide crude product and byproduct of reaction are made after reaction time 3-5 hour, under the action of the solvent, benzoyl cyanide fine work is made after the crude product is washed, separation.The present invention synthesizes the technique of benzoyl cyanide by simple method, in order to reduce pollution, turns harm into good, and need to be handled using alkaline chlorination process, cyanide is made by active oxychloride, destruction, to generate nontoxic sodium chloride under strongly alkaline conditions.And solvent is recyclable applies, therefore the synthetic method has the characteristics that pollute small, high conversion rate, easy to operate.
Description
Technical field
The present invention relates to field of fine chemical more particularly to a kind of synthetic methods of benzoyl cyanide.
Background technique
It is colourless squamous crystal under benzoyl cyanide room temperature, is a kind of important fine-chemical intermediate, is widely used in
The synthesis of pesticide and medicine, such as: herbicide metamitron, benzene piperazine are net, medical gastrodyn etc..The synthetic method of benzoyl cyanide has:
Chlorobenzoyl chloride and cuprous cyanide reaction method, chlorobenzoyl chloride and benzoyl oxide and Cymag reaction method, dimethylamine catalysis hydrogen cyanide method,
Cymag and chlorobenzoyl chloride reaction method.But chlorobenzoyl chloride and reaction temperature needed for cuprous cyanide reaction method are about 210 DEG C high, are taken
Between longer and yield it is low, improved method be added ultra-fine grain diameter Cymag and a certain amount of second cyanogen, cuprous cyanide can be reduced
Dosage, reaction temperature is reduced, but still can not solve the problems, such as mantoquita recycling and heavy metal pollution, so its industrialized production
Value is little.Chlorobenzoyl chloride and benzoyl oxide and Cymag reaction method are the problem is that benzoyl cyanide and benzoyl oxide are difficult to point
From.Dimethylamine catalysis hydrogen cyanide method need to use the hydrogen cyanide of severe toxicity, and the more difficult and risk of operation is very big, and the requirement ratio to equipment
It is more harsh.Cymag and when chlorobenzoyl chloride reaction method newer synthetic method its need phase transfer catalyst and a small amount of polar object
Matter, the method mild condition and pollution it is small.The selection of its phase transfer catalyst is emphasis.
The type of phase transfer catalyst has very much, again includes quaternary ammonium salt, quaternary alkylphosphonium salt, sulfonium salt such as father-in-law's salt, this is a kind of
Use phase transfer catalyst earlier；Polyether class comprising crown ether, polyethylene glycol and its derivative, big ring type amidogen polyether.In view of
Application of the phase transfer catalyst in organic synthesis is more and more wider, and the effect of the phase transfer catalyst of unifunctional base cannot expire
The existing demand of foot, therefore there are a series of multi-functional phase transfer catalysis (PTC)s being made of the phase transfer catalyst of single function base
Agent, such as: polyethylene glycol, the combination of father-in-law's salt, polyethylene glycol, crown ether combination, quaternary ammonium salt, crown ether combination etc. optimize organic conjunction with this
At route.
In conclusion traditional technique has the problem of heavy metal pollution, simultaneously because temperature and time demand is higher, institute
It is low to cause conversion ratio, and benzoyl cyanide is difficult to separate with benzoyl oxide, and dimethylamine catalysis hydrogen cyanide method need to use severe toxicity
Hydrogen cyanide, operate more difficult and risk it is very big.
Summary of the invention
The purpose of the present invention is to solve disadvantages existing in the prior art, such as: traditional technique has heavy metal-polluted
The problem of dye, simultaneously because temperature and time demand is higher, so it is low to cause conversion ratio, and benzoyl cyanide and benzoyl oxide
It is difficult to separate, dimethylamine catalysis hydrogen cyanide method need to use the hydrogen cyanide of severe toxicity, and it is very big to operate more difficult and risk.
To achieve the goals above, present invention employs following technical solutions:
A kind of synthetic method of benzoyl cyanide, using Cymag and chlorobenzoyl chloride as raw material, using toluene as solvent, with poly- second two
Alcohol 600 and tri-n-octyl methyl ammonium chloride are mixing phase transfer catalyst, using water or glycerol as cocatalyst, at 60 DEG C -110 DEG C
Chlorobenzoyl chloride is added dropwise in temperature range, after chlorobenzoyl chloride is added dropwise, heat preservation reflux, and tracking reaction process is composed with gas, to
It can stop flowing back when the mass fraction of chlorobenzoyl chloride is less than 0.1% in reaction solution, benzoyl cyanide crude product is obtained by filtration simultaneously in about 4h
Filter residue is washed with toluene, merging filtrate simultaneously isolates solvent and benzoyl cyanide, and solvent is recyclable to be applied, the matter of gained benzoyl cyanide
Measuring score is 99%, yield 96%-97%.
Further, phase transfer catalyst used in the synthesis process of benzoyl cyanide is the catalysis of different single function bases
The novel and multifunctional base phase transfer catalyst of agent composition, the i.e. combination of polyethylene glycol and father-in-law's salt.It is preferred that Macrogol 600 is pungent with three
The mixture of methyl ammonium, Macrogol 600 dosage are the 0.1%-0.5% of chlorobenzoyl chloride quality, and Macrogol 600
Mass ratio with tri-n-octyl methyl ammonium chloride is 1:1.
Further, using toluene as solvent in the synthesis process of benzoyl cyanide, using water or glycerol as cocatalyst.Benzoyl
The dropping temperature of chlorine is 60 DEG C -110 DEG C.
Compared with prior art, the beneficial effects of the present invention are: the present invention synthesizes benzoyl cyanide by simple method
Technique is turned harm into good to reduce pollution, need to be handled using alkaline chlorination process, make cyanide under strongly alkaline conditions by
Active oxychloride, destruction generate nontoxic sodium chloride.And solvent is recycled and applies, therefore the synthetic method is small with pollution, turns
The features such as rate is high, easy to operate.
Detailed description of the invention
Fig. 1 is a kind of synthetic method response diagram of benzoyl cyanide proposed by the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
In the description of the present invention, it is to be understood that, term " on ", "lower", "front", "rear", "left", "right", "top",
The orientation or positional relationship of the instructions such as "bottom", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, merely to just
In description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation, with
Specific orientation construction and operation, therefore be not considered as limiting the invention.
The synthetic method of one benzoyl cyanide of embodiment
By 100mL toluene, the solid sodium cyanide of 23.7g 97%, 0.06g Macrogol 600,0.06g tricaprylmethyl chlorine
Change ammonium, 0.1g water is put into 250mL four-hole boiling flask, unlatching device for absorbing tail gas, stirring, recirculated cooling water.Heating device is opened,
It begins to warm up.When the temperature of reaction solution rises to 60 DEG C, the cock of constant pressure funnel is opened, starts that 57.4g benzoyl is added dropwise
Chlorine pays attention to maintaining reaction temperature between 60 DEG C to 85 DEG C.Chlorobenzoyl chloride about 1.5h is dripped off, and after being added dropwise, it is anti-to continue reflux
Tracking reaction process should and be sampled, when the mass fraction of chlorobenzoyl chloride in reaction solution is less than 0.1%, reaction terminates, and about needs 4h.
After being cooled to 35 DEG C -45 DEG C, filtering, filter residue is washed in two times with 40mL toluene, collects filtrate.51.4g matter is obtained after handling filtrate
Measure the benzoyl cyanide that score is 99%, yield 96.1%.The solvent toluene isolated is recyclable to be applied.
The cyanide (predominantly Cymag) that byproduct sodium chloride contains is handled with alkaline chlorination process, makes cyanide strong
By active oxychloride, destruction under alkaline condition, nontoxic available sodium chloride is generated.
The synthetic method of embodiment dibenzoyl cyanogen
By 100mL toluene, the solid sodium cyanide of 23.7g 97%, 0.3g Macrogol 600,0.3g tricaprylmethyl chlorination
In ammonium, 0.6g water investment 250mL four-hole boiling flask, device for absorbing tail gas, stirring, recirculated cooling water are opened.Heating device is opened, is opened
Begin to heat.When the temperature of reaction solution rises to 60 DEG C, the cock of constant pressure funnel is opened, starts that 57.4g chlorobenzoyl chloride is added dropwise,
Pay attention to maintaining reaction temperature between 60 DEG C to 85 DEG C.Chlorobenzoyl chloride about 1.5h is dripped off, and after being added dropwise, continues back flow reaction simultaneously
Sampling tracking reaction process, when the mass fraction of chlorobenzoyl chloride in reaction solution is less than 0.1%, reaction terminates, and about needs 4h.Cooling
To after 35 DEG C -45 DEG C, filtering, filter residue is washed in two times with 40mL toluene, collects filtrate.51.8g mass point is obtained after handling filtrate
The benzoyl cyanide that number is 99%, yield 96.9%.The solvent toluene isolated is recyclable to be applied.
The cyanide (predominantly Cymag) that byproduct sodium chloride contains is handled with alkaline chlorination process, makes cyanide strong
By active oxychloride, destruction under alkaline condition, nontoxic available sodium chloride is generated.
The synthetic method of embodiment dibenzoyl cyanogen
By 100mL toluene, the solid sodium cyanide of 23.7g 97%, 0.06g Macrogol 600,0.06g tricaprylmethyl chlorine
Change ammonium, 0.1g water is put into 250mL four-hole boiling flask, unlatching device for absorbing tail gas, stirring, recirculated cooling water.Heating device is opened,
It begins to warm up.When the temperature of reaction solution rises to 85 DEG C, the cock of constant pressure funnel is opened, starts that 57.4g benzoyl is added dropwise
Chlorine pays attention to maintaining reaction temperature between 85 DEG C to 110 DEG C.Chlorobenzoyl chloride about 1.5h is dripped off, and after being added dropwise, it is anti-to continue reflux
Tracking reaction process should and be sampled, when the mass fraction of chlorobenzoyl chloride in reaction solution is less than 0.1%, reaction terminates, and about needs 4h.
After being cooled to 35 DEG C -45 DEG C, filtering, filter residue is washed in two times with 40mL toluene, collects filtrate.51.7g matter is obtained after handling filtrate
Measure the benzoyl cyanide that score is 99%, yield 96.7%.The solvent toluene isolated is recyclable to be applied.
The cyanide (predominantly Cymag) that byproduct sodium chloride contains is handled with alkaline chlorination process, makes cyanide strong
By active oxychloride, destruction under alkaline condition, nontoxic available sodium chloride is generated.
The synthetic method of example IV benzoyl cyanide
By 100mL toluene, the solid sodium cyanide of 23.7g 97%, 0.3g Macrogol 600,0.3g tricaprylmethyl chlorination
In ammonium, 0.6g water investment 250mL four-hole boiling flask, device for absorbing tail gas, stirring, recirculated cooling water are opened.Heating device is opened, is opened
Begin to heat.When the temperature of reaction solution rises to 85 DEG C, the cock of constant pressure funnel is opened, starts that 57.4g chlorobenzoyl chloride is added dropwise,
Pay attention to maintaining reaction temperature between 85 DEG C to 110 DEG C.Chlorobenzoyl chloride about 1.5h is dripped off, and after being added dropwise, continues back flow reaction
And tracking reaction process is sampled, when the mass fraction of chlorobenzoyl chloride in reaction solution is less than 0.1%, reaction terminates, and about needs 4h.Drop
To after 35 DEG C -45 DEG C, filtering, filter residue is washed temperature in two times with 40mL toluene, collects filtrate.51.5g mass is obtained after handling filtrate
The benzoyl cyanide that score is 99%, yield 96.3%.The solvent toluene isolated is recyclable to be applied.
The cyanide (predominantly Cymag) that byproduct sodium chloride contains is handled with alkaline chlorination process, makes cyanide strong
By active oxychloride, destruction under alkaline condition, nontoxic available sodium chloride is generated.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of synthetic method of benzoyl cyanide, it is characterised in that step are as follows: using Cymag and chlorobenzoyl chloride as raw material, with poly- second
The mixture of glycol 600 and tri-n-octyl methyl ammonium chloride is phase transfer catalyst, using water or glycerol as cocatalyst, 60 DEG C-
It reacts at 110 DEG C with chlorobenzoyl chloride, benzoyl cyanide crude product and byproduct of reaction is made after reaction time 3-5 hour,
Under the action of solvent, benzoyl cyanide fine work is made after the crude product is washed, separation.
2. a kind of synthetic method of benzoyl cyanide according to claim 1, which is characterized in that the solvent is toluene.
3. a kind of synthetic method of benzoyl cyanide according to claim 1, which is characterized in that the Macrogol 600 and
The mass ratio of tri-n-octyl methyl ammonium chloride is 1:1.
4. a kind of synthetic method of benzoyl cyanide according to claim 1, which is characterized in that the Macrogol 600 is used
Amount is the 0.1%-0.5% of chlorobenzoyl chloride quality.
5. a kind of synthetic method of benzoyl cyanide according to claim 1, which is characterized in that the cocatalyst dosage is
The 0.2%-1.0% of chlorobenzoyl chloride quality.
6. a kind of synthetic method of benzoyl cyanide according to claim 1, which is characterized in that the byproduct of reaction uses
Alkaline chlorination process is handled.
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| CN201910056947.7A CN109651193A (en) | 2019-01-22 | 2019-01-22 | A kind of synthetic method of benzoyl cyanide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880729A (en) * | 2021-10-29 | 2022-01-04 | 邯郸市瑞田农药有限公司 | Preparation method for synthesizing benzoyl cyanide by catalyst catalysis |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4069252A (en) * | 1975-06-25 | 1978-01-17 | Bayer Aktiengesellschaft | Process for the preparation of certain acyl cyanide compounds |
| JPS5337639A (en) * | 1976-09-20 | 1978-04-06 | Degussa | Production of benzoyl cyanide |
| US4143068A (en) * | 1976-04-02 | 1979-03-06 | Bayer Aktiengesellschaft | Process for the preparation of acyl cyanide compounds |
| US4144269A (en) * | 1977-04-18 | 1979-03-13 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of benzoyl cyanide (IV) |
| JPS5484547A (en) * | 1977-12-02 | 1979-07-05 | Degussa | Manufacture of cyanobenzoyl |
| US4209461A (en) * | 1977-12-02 | 1980-06-24 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of benzoyl cyanide (I) |
| US4284584A (en) * | 1976-04-02 | 1981-08-18 | Bayer Aktiengesellschaft | Process for the preparation of acyl cyanides |
| JPS6310754A (en) * | 1986-07-02 | 1988-01-18 | Nippon Tokushu Kagaku Kogyo Kk | Production of acyl cyanide |
| CN1027258C (en) * | 1989-05-19 | 1995-01-04 | 阿托化学公司 | Process for synthesising acyl cyanides |
| CN1027260C (en) * | 1989-05-19 | 1995-01-04 | 阿托化学公司 | Process for preparing acyl cyanides in anhydrous medium |
| WO2003070666A2 (en) * | 2002-02-15 | 2003-08-28 | Value Recovery, Inc. | Process for making organic products from non-product streams using phase transfer catalysis |
| WO2003074448A2 (en) * | 2002-03-01 | 2003-09-12 | Value Recovery, Inc. | Process for making organic products from non-product streams using a catalyst |
| SE526672C2 (en) * | 2003-11-14 | 2005-10-25 | Biosynth Svenska Ab | Preparation of acyl cyanides, useful for producing herbicides, by reacting hydrogen cyanide with formyl or tertiary amine group polymer and then with acyl halide |
| CN103304444A (en) * | 2013-06-27 | 2013-09-18 | 江苏省农用激素工程技术研究中心有限公司 | Preparation method of benzoyl cyanide |
| CN104387292A (en) * | 2014-10-27 | 2015-03-04 | 河北诚信有限责任公司 | Process for synthesizing acyl nitrile |
-
2019
- 2019-01-22 CN CN201910056947.7A patent/CN109651193A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4069252A (en) * | 1975-06-25 | 1978-01-17 | Bayer Aktiengesellschaft | Process for the preparation of certain acyl cyanide compounds |
| US4284584A (en) * | 1976-04-02 | 1981-08-18 | Bayer Aktiengesellschaft | Process for the preparation of acyl cyanides |
| US4143068A (en) * | 1976-04-02 | 1979-03-06 | Bayer Aktiengesellschaft | Process for the preparation of acyl cyanide compounds |
| JPS5337639A (en) * | 1976-09-20 | 1978-04-06 | Degussa | Production of benzoyl cyanide |
| US4144269A (en) * | 1977-04-18 | 1979-03-13 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of benzoyl cyanide (IV) |
| US4209461A (en) * | 1977-12-02 | 1980-06-24 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of benzoyl cyanide (I) |
| JPS5484547A (en) * | 1977-12-02 | 1979-07-05 | Degussa | Manufacture of cyanobenzoyl |
| JPS6310754A (en) * | 1986-07-02 | 1988-01-18 | Nippon Tokushu Kagaku Kogyo Kk | Production of acyl cyanide |
| CN1027258C (en) * | 1989-05-19 | 1995-01-04 | 阿托化学公司 | Process for synthesising acyl cyanides |
| CN1027260C (en) * | 1989-05-19 | 1995-01-04 | 阿托化学公司 | Process for preparing acyl cyanides in anhydrous medium |
| WO2003070666A2 (en) * | 2002-02-15 | 2003-08-28 | Value Recovery, Inc. | Process for making organic products from non-product streams using phase transfer catalysis |
| WO2003074448A2 (en) * | 2002-03-01 | 2003-09-12 | Value Recovery, Inc. | Process for making organic products from non-product streams using a catalyst |
| SE526672C2 (en) * | 2003-11-14 | 2005-10-25 | Biosynth Svenska Ab | Preparation of acyl cyanides, useful for producing herbicides, by reacting hydrogen cyanide with formyl or tertiary amine group polymer and then with acyl halide |
| CN103304444A (en) * | 2013-06-27 | 2013-09-18 | 江苏省农用激素工程技术研究中心有限公司 | Preparation method of benzoyl cyanide |
| CN104387292A (en) * | 2014-10-27 | 2015-03-04 | 河北诚信有限责任公司 | Process for synthesizing acyl nitrile |
Non-Patent Citations (3)
| Title |
|---|
| ROMAN BIELSKI ETAL: "Conversion of Pollutants in Dilute Aqueous Waste Streams to Useful Products: a Potential Method Based on Phase-Transfer Catalysis", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》 * |
| 南向竹等: "苯甲酰腈的合成优化研究", 《山东化工》 * |
| 章非娟: "《工业废水污染防治》", 31 December 2001 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880729A (en) * | 2021-10-29 | 2022-01-04 | 邯郸市瑞田农药有限公司 | Preparation method for synthesizing benzoyl cyanide by catalyst catalysis |
| CN113880729B (en) * | 2021-10-29 | 2024-04-26 | 邯郸市瑞田农药有限公司 | Preparation method for synthesizing benzoyl cyanide by catalyst catalysis |
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