CN106748877B - The method that one-step method prepares propylidene benzylamine - Google Patents
The method that one-step method prepares propylidene benzylamine Download PDFInfo
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- CN106748877B CN106748877B CN201710040642.8A CN201710040642A CN106748877B CN 106748877 B CN106748877 B CN 106748877B CN 201710040642 A CN201710040642 A CN 201710040642A CN 106748877 B CN106748877 B CN 106748877B
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- benzylamine
- propylidene
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- benzyl chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of production technology of pesticide intermediate, the particularly production method of 2 chlorine, 5 picoline intermediate propylidene benzylamine.The deficiencies such as the present invention is complicated for existing propylidene benzylamine synthesis technology, by-product is more, yield is low, propose a kind of method of one-step synthesis method propylidene benzylamine.The technical problem to be solved by the present invention is to simplify operating process, reaction yield, Improving The Quality of Products are improved.
Description
Technical field
The present invention relates to a kind of production technology of pesticide intermediate, particularly chloro--methylpyridine intermediate Asia third
The production method of base benzylamine.
Background technology
Chloro--methylpyridine (CMP) is heterocyclic insecticides, the vital raw material of herbicide, with its prepare imidacloprid,
The novel pesticides such as Acetamiprid, fluazifop, due to its interior suction, efficiently, low toxicity the advantages that, be widely used commercially available.With
Benzylamine, propionic aldehyde are raw material, can prepare chloro--methylpyridine through reactions such as condensation, acetylation, chlorinations, this method yield exists
68%, by-product benzyl chloride.(EP0546418)
Propylidene benzylamine is the main intermediate for synthesizing CMP.Therefore, the ease of propylidene benzylamine synthesis technology, receipts
Rate height directly affects the production cost of CMP and industrialized feasibility.Existing propylidene benzylamine synthesis technology is divided into 2 steps：1)
Benzyl chloride amination prepares benzylamine；2) benzylamine is reacted with propionic aldehyde prepares propylidene benzylamine.Benzylamine is usually by benzyl chloride and 7% ammonium hydroxide
Reaction (EU0452952), methenamine (JP6335546) are made, and dibenzylamine, three are generated since benzylamine is easily reacted with benzyl chloride
Benzylamine causes synthesis yield there was only 70%.And the synthesis of propylidene benzylamine needs to carry out (see US5304651) under -10 DEG C of low temperature,
Reaction yield is 87%.Two step yields 60% or so.
It is insufficient existing for existing propylidene benzylamine technique：1. being prepared using two-step method, complex technical process increases production
Cost；2. by-product dibenzylamine, tribenzylamine cause benzylamine yield, selectivity low in benzylamine preparation process；3. propylidene benzylamine is condensed
Reaction process needs low temperature, freezing of high cost.
Invention content
The deficiencies such as the present invention is complicated for existing propylidene benzylamine synthesis technology, by-product is more, yield is low, propose one kind one
The method that footwork synthesizes propylidene benzylamine.The technical problem to be solved by the present invention is to simplify operating process, improve reaction yield,
(product content is more than 94% to Improving The Quality of Products, 88%) yield is more than.
The present invention includes the following steps：
1) into 500ml four-hole boiling flasks, it is uniform that a certain amount of benzyl chloride, propionic aldehyde and stirring solvent are put into；
2) solvent and catalyst in a certain amount of step 1) is added to 500ml four-hole boiling flasks, then is added simultaneously to reactor
Reaction solution in aminating agent and step 1) controls certain reaction temperature, reacts certain time, and reaction terminates reaction solution being down to
Room temperature；
3) reaction solution in step 2) is filtered out into catalyst.A certain amount of water is added in filtrate, washing is stood, layering,
Solvent extraction 1 time of the water layer in a certain amount of step 1), extract liquor merge with oil reservoir after washing；
4) precipitation under the oil reservoir normal pressure after merging is taken off under the conditions of pressure is -0.095MPa to end to cooling down after 100 DEG C
100 DEG C of temperature, continuation steam propylidene benzylamine under the conditions of pressure 5mmHg, 180 DEG C, analyze content, calculated yield.
Solvent in step 1) of the present invention is any one of dichloroethanes, chlorobenzene, chloroform, thiacyclohexane, preferably
Solvent is chloroform, dichloroethanes, more preferable chloroform；
Solvent in step 1) of the present invention is that the mass ratio that feeds intake of benzyl chloride is 10~2:1, preferable amount is 8~2:
1, more preferably 6~3:1；
The molar ratio of step 1) propionic aldehyde and benzyl chloride of the present invention is 0.9~1.2:1, preferable amount be 0.9~
1.1:1, more preferably 0.95~1.05:1；
Catalyst in step 2) of the present invention be metallic copper, metallic nickel, metallic iron, metallic aluminium any one, preferably
Catalyst be metallic copper, metallic iron, more preferable metallic copper；
The mass ratio that feeds intake of step 2) catalyst and benzyl chloride of the present invention is 0.5~2.5:100, preferable amount is
0.8~2:100, more preferable dosage 1~1.5:100；
Aminating agent type is ammonia and ammonium hydroxide, preferably ammonia in step 2) of the present invention；
The molar ratio of aminating agent and benzyl chloride in step 2) of the present invention is 4~20:1, preferred molar ratio
It is 8~15:1, more preferably 10~12:1；
Step 2) reaction temperature of the present invention be 20~100 DEG C, preferable temperature be 30~80 DEG C, more preferably 40~70
℃；
2~10hr of reaction time in step 2) of the present invention, preferably time are 3~8hr, more preferably 4~7hr.
Specific implementation mode
Example 1：
Benzyl chloride 50.6g, propionic aldehyde 24.3g, chloroform 200g are weighed into 500ml glass four-hole boiling flasks, are uniformly mixed.
10g chloroforms and 0.6g catalytic metal coppers are added into 500ml glass four-hole boiling flasks, after stirring is warming up to 60 DEG C,
Benzyl chloride propionic aldehyde chloroform solution is added dropwise, is passed through ammonia, reacts 5 hours, then keep the temperature 1 hour, reaction terminates, and drops to room temperature, and filtering is urged
50g washings, stratification is added in agent, filtrate.Water layer 50g chloroform aqueous layer extracteds, stratification, extract liquor and oil after washing
It is laminated simultaneously.
Precipitation is to cooling down after 100 DEG C under oil reservoir normal pressure, is taken off under the conditions of pressure is -0.095Mpa to 100 DEG C of final temperature.It is pressing
Distillation obtains 53.2 grams of product to 180 DEG C under conditions of power is 5mmHg.Through high performance liquid chromatography detection content 94.5%, yield
88.6%.
Example 2-5：
In order to investigate the influence that ammonia usage synthesizes propylidene benzylamine, the experiment that different ammonias participate in reaction has been carried out,
Remaining condition is the same as embodiment 1.Data such as following table：
As seen from the above table, under same reaction condition, when ammonia and benzyl chloride molar ratio are 10, propylidene benzylamine yield is most
Height is 88.7%.Ammonia usage it is excessive or it is very few can all cause propylidene benzylamine yield decline.
Example 6-8：
In examples detailed above 1, ammonia is replaced with ammonium hydroxide, remaining is constant.It is that knot is tested in the case of different ammonia volumes below
Fruit：
As seen from the above table, under same reaction condition, when ammonium hydroxide and benzyl chloride molar ratio are 10, propylidene benzylamine yield is most
Height is 88.1%.And ammonia volume is excessively high or height yield is all declined.
Example 9-13：
Catalyst selects 0.6g metallic coppers, reaction yield 88% in example 1.It is difference under same reaction condition below
(wherein, catalyst amount refers to catalyst and benzyl chloride and feeds intake mass ratio the contrast and experiment of catalyst effect, below
It is identical)
As seen from the above table, under same reaction condition, metallic copper catalytic effect is best, followed by metallic iron, metallic aluminium, metal
Nickel.
Example 14-18：
On the basis of example 1, different solvents are used instead, 30-60 DEG C of reaction temperature, remaining is constant.Experimental result is as follows：
As seen from the above table, under same reaction condition, chloroform, dichloroethanes effect are preferable, followed by hexamethylene, chlorobenzene
Example 19-21：
On the basis of example 1, different propionic aldehyde dosages are used instead, remaining is constant.Experimental result is as follows：
As seen from the above table, different propionic aldehyde dosage, reaction yield is different, and mainly benzylamine can be reacted with benzyl chloride, propylidene
Benzylamine can also be reacted with propionic aldehyde.
Example 22-24：
On the basis of example 1, different propionic aldehyde dosages are used instead, remaining is constant.Experimental result is as follows：
As seen from the above table, different reaction time, reaction yield are different.
Example 25-26：
Benzyl chloride, propionic aldehyde, chloroform, catalyst are put bottom of bottle, the mode of logical ammonia is reacted.Experimental result is as follows：
As seen from the above table, under same reaction condition, effect is too late by the way of independent logical ammonia feeds simultaneously.
Claims (18)
1. the method that one-step method prepares propylidene benzylamine, which is characterized in that include the following steps：
1) into 500ml four-hole boiling flasks, it is uniform that a certain amount of benzyl chloride, propionic aldehyde and stirring solvent are put into；
2) solvent and catalyst in a certain amount of step 1) is added to 500ml four-hole boiling flasks, then amination is added simultaneously to reactor
Reaction solution in agent and step 1) controls certain reaction temperature, reacts certain time, and reaction terminates reaction solution being down to room
Temperature；
3) reaction solution in step 2) is filtered out into catalyst, a certain amount of water is added in filtrate, washing is stood, layering, water layer
With the solvent extraction 1 time in a certain amount of step 1), extract liquor merges with oil reservoir after washing；
4) precipitation under the oil reservoir normal pressure after merging is taken off under the conditions of pressure is -0.095MPa to final temperature to cooling down after 100 DEG C
100 DEG C, continuation steams propylidene benzylamine under the conditions of pressure 5mmHg, 180 DEG C, analyzes content, calculated yield；The step 1)
In solvent be the mass ratio that feeds intake of benzyl chloride be 10~2:1, the molar ratio of propionic aldehyde and benzyl chloride is 0.9~1.2:1, institute
State catalyst in step 2) be metallic copper, metallic nickel, metallic iron, metallic aluminium any one, the step 2) catalyst and chlorine
The mass ratio that feeds intake for changing benzyl is 0.5~2.5:100.
2. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that in the step 1)
Solvent is any one of dichloroethanes, chlorobenzene, chloroform, thiacyclohexane.
3. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that in the step 1)
Solvent is that the amount ratio that feeds intake of benzyl chloride is 8~2:1.
4. the method that one-step method according to claim 3 prepares propylidene benzylamine, which is characterized in that in the step 1)
Solvent is that the amount ratio that feeds intake of benzyl chloride is 6~3:1.
5. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that the step 1) propionic aldehyde
Molar ratio with benzyl chloride is 0.9~1.1:1.
6. the method that one-step method according to claim 5 prepares propylidene benzylamine, which is characterized in that the step 1) propionic aldehyde
Molar ratio with benzyl chloride is 0.95~1.05:1.
7. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that the step 2) catalysis
The mass ratio that feeds intake of agent and benzyl chloride is 0.8~2:100.
8. the method that one-step method according to claim 7 prepares propylidene benzylamine, which is characterized in that the step 2) catalysis
The mass ratio that feeds intake of agent and benzyl chloride is 1~1.5:100.
9. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that amine in the step 2)
Agent type is ammonia and ammonium hydroxide.
10. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that in the step 2)
Aminating agent and benzyl chloride molar ratio be 4~20:1.
11. the method that one-step method according to claim 10 prepares propylidene benzylamine, which is characterized in that in the step 2)
Aminating agent and benzyl chloride molar ratio be 8~15:1.
12. the method that one-step method according to claim 11 prepares propylidene benzylamine, which is characterized in that in the step 2)
Aminating agent and benzyl chloride molar ratio be 10~12:1.
13. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that the step 2) is anti-
It is 20~100 DEG C to answer temperature.
14. the method that one-step method according to claim 13 prepares propylidene benzylamine, which is characterized in that the step 2) is anti-
It is 30~80 DEG C to answer temperature.
15. the method that one-step method according to claim 14 prepares propylidene benzylamine, which is characterized in that the step 2) is anti-
It is 40~70 DEG C to answer temperature.
16. the method that one-step method according to claim 1 prepares propylidene benzylamine, which is characterized in that in the step 2)
2~10hr of reaction time.
17. the method that one-step method according to claim 16 prepares propylidene benzylamine, which is characterized in that in the step 2)
Reaction time is 3~8hr.
18. the method that one-step method according to claim 17 prepares propylidene benzylamine, which is characterized in that in the step 2)
Reaction time is 4~7hr.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330592A (en) * | 2015-11-23 | 2016-02-17 | 上海晋景化学有限公司 | Preparation method of 2-chloro-5-picoline |
| CN105837499A (en) * | 2016-03-31 | 2016-08-10 | 常州大学 | Synthetic method for 2,3-chloro-5-chloromethylpyridine |
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2017
- 2017-01-20 CN CN201710040642.8A patent/CN106748877B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330592A (en) * | 2015-11-23 | 2016-02-17 | 上海晋景化学有限公司 | Preparation method of 2-chloro-5-picoline |
| CN105837499A (en) * | 2016-03-31 | 2016-08-10 | 常州大学 | Synthetic method for 2,3-chloro-5-chloromethylpyridine |
Non-Patent Citations (1)
| Title |
|---|
| "Mild Electrochemical Deprotection of N-Phenylsulfonyl N-Substituted Amines Derived from (R)-Phenylglycinol";Vincent Coeffard et al.;《Eur. J. Org. Chem.》;20071016;第390页左栏第4段 * |
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