CN109020834A - A kind of preparation method of 2,2- dichloro benzyl cyanide - Google Patents
A kind of preparation method of 2,2- dichloro benzyl cyanide Download PDFInfo
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- CN109020834A CN109020834A CN201811002905.7A CN201811002905A CN109020834A CN 109020834 A CN109020834 A CN 109020834A CN 201811002905 A CN201811002905 A CN 201811002905A CN 109020834 A CN109020834 A CN 109020834A
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- reaction kettle
- dichloro benzyl
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- benzyl cyanide
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
The invention discloses the preparation method of one kind 2,2- dichloro benzyl cyanide, benzene acetonitrile normal pressure leads to chlorine heating reaction, and the conversion ratio of benzene acetonitrile can reach >=99.3%, obtain 2,2- dichloro benzyl cyanide, yield >=99.1% of 2,2- dichloro benzyl cyanides finally by vacuum distillation.The present invention provides the extremely simple preparation method of one kind 2,2- dichloro benzyl cyanide: operation is easy, and equipment is simple, safe and efficient, avoids the unfavorable factors such as high pressurization chlorination appratus requirement, complicated for operation, inefficiency, safety difference.
Description
Technical field
The present invention relates to the technical fields of organic synthesis, and in particular to the easy preparation side of one kind 2,2- dichloro benzyl cyanide
Method.
Background technique
2,2- dichloro benzyl cyanides are one in chemical industry for the product that two hydrogen on benzene acetonitrile methylene is replaced by chlorine
Kind important source material, can be used for the preparation of rubber additive dichloro ethyl phenylacetate.
Currently, there is the synthesis of more document reports 2,2- dichloro benzyl cyanide, can be carried out using different chlorination reagents
The α position chlorination of benzene acetonitrile: hydrogen is pulled out as 2,2- dichloro benzyl cyanide can be reacted progress α by benzene acetonitrile with butyl lithium, then in chlorine
Change and obtained under reagent effect, yield is 87% (Synthesis, 2005,7,1136.), but butyl lithium, chlorination reagent are relatively more high
Expensive, requirement of the use of butyl lithium to anhydrous and oxygen-free is high, and reaction also needs -78 DEG C of low temperature；Pass through benzene acetonitrile and sodium hypochlorite
Reaction, also available 2,2- dichloro benzyl cyanide, yield are 80% (Indian Journal of Chemistry, Section
B:Organic Chemistry Including Medicinal Chemistry,1988,27B(7),666.)；Pass through benzene second
Nitrile and the reaction of chlorination sulfone, also available 2,2- dichloro benzyl cyanide, yield are 76% (Polish Journal of
Chemistry,1979,53(1),201.)。
It is directly reacted by benzene acetonitrile and the chlorine of cheap and simple, 2,2- dichloro benzyl cyanide can also be directly obtained, PCT is special
Benefit (PCT Int.Appl., 2003084918) is reported by the way that benzene acetonitrile is added, and HCl gas is then added, chlorine is subsequently added
Gas, available 2,2- dichloro benzyl cyanide, reaction yield are after a certain period of time for heating reaction under whole 3-3.5 kilograms of pressure
96.3%.But the reaction needs to be passed through two kinds of gases, needs to be passed through HCl gas early period, the later period needs to be passed through chlorine, Er Qieyou
HCl is constantly generated in reaction process, pressure can be continuously increased, and 3-3.5 kilograms of whole pressure maintaining reaction needs during the reaction
Continuous pressure release exhaust, it is very cumbersome, it is unfavorable for the control of reaction.And compressive reaction the high requirements on the equipment, it is desirable that resistance to densification
Envelope, at high cost energy consumption is high.Therefore, developing a kind of mild, easy to operate, the easily controllable new preparation method of reaction condition is mesh
The emphasis of preceding research.
Summary of the invention
The present invention provides the simple and convenient process for preparing of one kind 2,2- dichloro benzyl cyanide, and reaction condition is mild, equipment requirement is low, behaviour
Work is easy, easily controllable, and yield is very high.
The technical solution adopted by the present invention is that:
The preparation method of one kind 2,2- dichloro benzyl cyanide, includes the following steps:
(1) benzene acetonitrile is added to the first reaction kettle, normal heating is to 80-135 DEG C；
(2) it is passed through chlorine into the first reaction kettle, continues normal heating reaction, the first reaction kettle reacts the tail gas generated,
Finally pass in hydrochloric acid absorption tower；
After fully reacting in (3) first reaction kettles, the product liquid in the first reaction kettle is taken out, by being evaporated under reduced pressure to
To product 2,2- dichloro benzyl cyanide.
The preparation method of 2,2- dichloro benzyl cyanide disclosed by the invention, uses the benzene acetonitrile of commercialization for raw material, benzene acetonitrile
The mass ratio of the material with chlorine is 1:2.05~1:2.1.
In step (1), the reaction temperature is 80-135 DEG C, preferably 100-110 DEG C.
In step (2), the time of the reaction is usually 20-30 hours, preferably 27-29 hours.
In step (3), fully reacting refers to, the liquid in the first reaction kettle passes through vapor detection, the conversion ratio of benzene acetonitrile
Reach 99.3% or more.
Further, due to containing HCl and micro chlorine in the tail gas of the first reaction kettle, second level chlorine is can be used in the method for the present invention
Change method improves yield.
The step (2) preferably operates by the following method:
It is passed through chlorine into the first reaction kettle, continues normal heating reaction, the tail gas that the reaction of the first reaction kettle generates is passed through
In second reaction kettle, equipped with the benzene acetonitrile with the inventory equivalent of the first reaction kettle in step (1) in second reaction kettle, often
Pressure is heated to 80-135 DEG C and is reacted, and the tail gas of the second reaction kettle is passed through in hydrochloric acid absorption tower.
Further, the method also includes step (4) and (5):
(4) raw material in the second reaction kettle is transferred to the first reaction kettle, and into the second reaction kettle in addition and step (1)
The benzene acetonitrile of the inventory equivalent of first reaction kettle, the first reaction kettle and the second reaction kettle all normal heatings are to 80-135 DEG C；
(5) circulate operation step (2)~(4), are prepared 2,2- dichloro benzyl cyanide.
Specifically, it is preferred that the preparation method of 2,2- dichloro benzyl cyanides operates according to the following steps:
(1) benzene acetonitrile is added to the first reaction kettle, normal heating is to 80-135 DEG C；
(2) it is passed through chlorine into the first reaction kettle, continues normal heating reaction, the first reaction kettle reacts the tail gas generated,
It is passed through in the second reaction kettle, equipped with the benzene second with the inventory equivalent of the first reaction kettle in step (1) in second reaction kettle
Nitrile, normal heating are reacted to 80-135 DEG C, and the tail gas of the second reaction kettle is passed through in hydrochloric acid absorption tower；
After fully reacting in (3) first reaction kettles, the product liquid in the first reaction kettle is taken out, by being evaporated under reduced pressure to
To product 2,2- dichloro benzyl cyanide；
(4) raw material in the second reaction kettle is transferred to the first reaction kettle, and into the second reaction kettle in addition and step (1)
The benzene acetonitrile of the inventory equivalent of first reaction kettle, the first reaction kettle and the second reaction kettle all normal heatings are to 80-135 DEG C；
(5) circulate operation step (2)~(4), are prepared 2,2- dichloro benzyl cyanide.
The fully reacting of step (3) refers to that the liquid in the first reaction kettle is reached by vapor detection, the conversion ratio of benzene acetonitrile
To 99.3% or more.
Further, in the step (3), after the fully reacting in the first reaction kettle, the liquid in the first reaction kettle is taken out
Body product, the product liquid after merging repeatedly circulation, obtains product 2,2- dichloro benzyl cyanide by vacuum distillation.
Further, the preferably heating temperature of the first reaction kettle and the second reaction kettle is identical.
The conversion ratio and yield of the method for the present invention are all very high, and the conversion ratio of benzene acetonitrile is >=99.3%, 2,2- dichloro-benzenes second
Yield >=99.1% of nitrile.
Operation of the present invention is easy, and equipment is simple, safe and efficient, avoids pressurization chlorination appratus requirement height, operation again
The unfavorable factors such as miscellaneous, inefficiency, safety difference.
Compared with prior art, the invention has the following advantages that
1, reaction is whole only needs to be passed through a kind of gas of chlorine, and convenient and simple, chlorination efficiency is high.
2, reaction whole process carries out under normal pressure, does not need to pressurize, it is low for equipment requirements, low energy consumption, it is artificial save, safety
Property is good.
3, the high conversion rate of benzene acetonitrile and yield height, the conversion ratio of benzene acetonitrile are >=99.3%, 2,2- dichloro benzyl cyanides
Yield >=99.1%.
Detailed description of the invention
Fig. 1 2,2- dichloro benzyl cyanide nuclear magnetic spectrogram.
Specific embodiment
Technical solution of the present invention is described in further detail with reference to embodiments, but protection scope of the present invention is not
It is limited to this.
Embodiment 1:
1171g (10mol) benzene acetonitrile is added to the first reaction kettle, is heated to 110 DEG C, while by other 1171g
(10mol) benzene acetonitrile is added to the second reaction kettle, is also heated at 110 DEG C, and chlorine 1455g (20.5mol) is passed through the first reaction
Kettle continues 110 DEG C of normal heating and reacts 20 hours；The tail gas that reaction generates first is passed through in the second reaction kettle, finally passes to hydrochloric acid
Absorption tower.Liquid in first reaction kettle is detected by GC, and wherein the conversion ratio of benzene acetonitrile is 99.4%, will be in the first reaction kettle
Liquid by vacuum distillation obtain product 2,2- dichloro benzyl cyanide 1843g, yield 99.1%.
The identification of 2,2- dichloro benzyl cyanide nuclear-magnetisms, map is as shown in Figure 1:1H NMR(400MHz,CDCl3,δ,ppm):7.89-
7.80(m,2H),7.55-7.45(m,3H).
Embodiment 2:
1171g (10mol) benzene acetonitrile is added to the first reaction kettle, is heated to 100 DEG C, while by other 1171g
(10mol) benzene acetonitrile is added to the second reaction kettle, is also heated at 100 DEG C, and chlorine 1475g (20.8mol) is passed through the first reaction
Kettle continues normal heating and reacts 28 hours；The tail gas that reaction generates first is passed through in the second reaction kettle, finally passes to absorption by Hydrochloric Acid
Tower.Liquid in reaction kettle is detected by GC, and wherein the conversion ratio of benzene acetonitrile is 99.6%, and the liquid in the first reaction kettle is led to
It crosses vacuum distillation and obtains product 2,2- dichloro benzyl cyanide 1850g, yield 99.5%.
Embodiment 3:(round-robin method)
Material in the second reaction kettle in embodiment 2 (is had already been through into the 1171g of last time the first reaction kettle tail gas
(10mol) benzene acetonitrile) it is transferred in the first reaction kettle, 100 DEG C are heated to, while other 1171g (10mol) benzene acetonitrile being added
Enter to the second reaction kettle, be also heated at 100 DEG C, chlorine 1475g (20.8mol) is passed through the first reaction kettle, continues normal heating
Reaction 28 hours；The tail gas that reaction generates first is passed through in the second reaction kettle, finally passes to hydrochloric acid absorption tower.Liquid in reaction kettle
It is detected by GC, wherein the conversion ratio of benzene acetonitrile is 99.8%, and the liquid in the first reaction kettle is produced by vacuum distillation
Object 2,2- dichloro benzyl cyanide 1850g, yield 99.6%.
Claims (8)
1. one kind 2, the preparation method of 2- dichloro benzyl cyanide, which is characterized in that described method includes following steps:
(1) benzene acetonitrile is added to the first reaction kettle, normal heating is to 80-135 DEG C；
(2) it is passed through chlorine into the first reaction kettle, continues normal heating reaction, the first reaction kettle reacts the tail gas generated, finally
It passes in hydrochloric acid absorption tower；
After fully reacting in (3) first reaction kettles, the product liquid in the first reaction kettle is taken out, is produced by vacuum distillation
Object 2,2- dichloro benzyl cyanide.
2. the preparation method of 2,2- dichloro benzyl cyanide according to claim 1, which is characterized in that in the step (2), institute
The time for the reaction stated is 20-30 hours.
3. the preparation method of 2,2- dichloro benzyl cyanide according to claim 1, which is characterized in that in first reaction kettle
The ratio between benzene acetonitrile and the amount of substance of chlorine to feed intake are 1:2.05~1:2.1.
4. the preparation method of 2,2- dichloro benzyl cyanide according to claim 1, which is characterized in that the step (2) press with
Lower method operation:
It is passed through chlorine into the first reaction kettle, continues normal heating reaction, the tail gas that the reaction of the first reaction kettle generates is passed through second
In reaction kettle, equipped with the benzene acetonitrile with the inventory equivalent of the first reaction kettle in step (1) in second reaction kettle, normal pressure adds
Heat is reacted to 80-135 DEG C, and the tail gas of the second reaction kettle is passed through in hydrochloric acid absorption tower.
5. the preparation method of 2,2- dichloro benzyl cyanide according to claim 4, which is characterized in that the method also includes steps
Suddenly (4) and (5):
(4) raw material in the second reaction kettle is transferred to the first reaction kettle, and is added and in step (1) first into the second reaction kettle
The benzene acetonitrile of the inventory equivalent of reaction kettle, the first reaction kettle and the second reaction kettle all normal heatings are to 80-135 DEG C；
(5) circulate operation step (2)~(4), are prepared 2,2- dichloro benzyl cyanide.
6. the preparation method of 2,2- dichloro benzyl cyanide according to claim 1, which is characterized in that the method is according to following
Step operation:
(1) benzene acetonitrile is added to the first reaction kettle, normal heating is to 80-135 DEG C；
(2) it is passed through chlorine into the first reaction kettle, continues normal heating reaction, the tail gas that the reaction of the first reaction kettle generates is passed through
In second reaction kettle, equipped with the benzene acetonitrile with the inventory equivalent of the first reaction kettle in step (1) in second reaction kettle, often
Pressure is heated to 80-135 DEG C and is reacted, and the tail gas of the second reaction kettle is passed through in hydrochloric acid absorption tower；
After fully reacting in (3) first reaction kettles, the product liquid in the first reaction kettle is taken out, is produced by vacuum distillation
Object 2,2- dichloro benzyl cyanide；
(4) raw material in the second reaction kettle is transferred to the first reaction kettle, and is added and in step (1) first into the second reaction kettle
The benzene acetonitrile of the inventory equivalent of reaction kettle, the first reaction kettle and the second reaction kettle all normal heatings are to 80-135 DEG C；
(5) circulate operation step (2)~(4), are prepared 2,2- dichloro benzyl cyanide.
7. the preparation method of 2,2- dichloro benzyl cyanide according to claim 1, which is characterized in that the step (3) it is anti-
It should be all referring to for the liquid in the first reaction kettle by vapor detection, the conversion ratio of benzene acetonitrile reaches 99.3% or more.
8. the preparation method of 2,2- dichloro benzyl cyanide according to claim 6, which is characterized in that in the step (3), the
After fully reacting in one reaction kettle, the product liquid in the first reaction kettle is taken out, the product liquid after merging repeatedly circulation leads to
It crosses vacuum distillation and obtains product 2,2- dichloro benzyl cyanide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184410A (en) * | 2007-01-29 | 2008-08-14 | Central Glass Co Ltd | Method for producing 2,2-difluoro-phenylacetoacetate |
| CN100516015C (en) * | 2002-04-04 | 2009-07-22 | Dsm精细化学奥地利Nfg两合公司 | Method for producing 2,2-dichloro or dibromo-phenyl alkyl acetates |
-
2018
- 2018-08-30 CN CN201811002905.7A patent/CN109020834A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100516015C (en) * | 2002-04-04 | 2009-07-22 | Dsm精细化学奥地利Nfg两合公司 | Method for producing 2,2-dichloro or dibromo-phenyl alkyl acetates |
| JP2008184410A (en) * | 2007-01-29 | 2008-08-14 | Central Glass Co Ltd | Method for producing 2,2-difluoro-phenylacetoacetate |
Non-Patent Citations (3)
| Title |
|---|
| YONG-DAE PARK，等: "2-Chloropyridazin-3(2H)-ones as Electrophilic Chlorinating Agents: Effective a-Chlorination of Active Methylene/Methine Compounds", 《SYNTHESIS》 * |
| 彭天成，等: "间-(三氟甲基)苯甲酸的合成", 《精细化工》 * |
| 陈应祥: "《工业化学过程及计算》", 31 December 1989, 成都科技大学出版社 * |
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Application publication date: 20181218 |