CN106748877A - 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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- CN106748877A CN106748877A CN201710040642.8A CN201710040642A CN106748877A CN 106748877 A CN106748877 A CN 106748877A CN 201710040642 A CN201710040642 A CN 201710040642A CN 106748877 A CN106748877 A CN 106748877A
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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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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of production technology of pesticide intermediate, the particularly production method of the picoline intermediate propylidene benzylamine of 2 chlorine 5.The present invention for existing propylidene benzylamine synthesis technique it is complicated, accessory substance is more, the low deficiency of yield, a kind of method of one-step synthesis method propylidene benzylamine of proposition.The technical problems to be solved by the invention are to simplify operating process, improve reaction yield, Improving The Quality of Products.
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, by inhaling in the inner, efficiently, low toxicity the advantages of, widely used commercially available.With
Benzylamine, propionic aldehyde are raw material, and chloro--methylpyridine can be prepared through the reaction such as condensation, acetylation, chlorination, and the 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 technique, receipts
Rate height directly affects the production cost and industrialized feasibility of CMP.Existing propylidene benzylamine synthesis technique is divided into 2 steps：1)
Benzyl chloride amination prepares benzylamine；2) benzylamine prepares propylidene benzylamine with propionic aldehyde reaction.Benzylamine is generally by benzyl chloride and 7% ammoniacal liquor
Reaction (EU0452952), methenamine (JP6335546) are obtained, because benzylamine easily generates dibenzylamine, three with benzyl chloride reaction
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.
The deficiency that existing propylidene benzylamine technique is present：1. prepared using two-step method, complex technical process increased production
Cost；2. by-product dibenzylamine, tribenzylamine cause benzylamine yield, selectivity low in benzylamine preparation process；3. propylidene benzylamine condensation
Course of reaction needs low temperature, freezes high cost.
The content of the invention
The present invention for existing propylidene benzylamine synthesis technique it is complicated, accessory substance is more, the low deficiency of yield, proposes one kind one
Footwork synthesizes the method for propylidene benzylamine.The technical problems to be solved by the invention are to simplify operating process, raising reaction yield,
(product content is more than 94% to Improving The Quality of Products, and yield is more than 88%).
The present invention is comprised the following steps：
1) in 500ml four-hole boiling flasks, a certain amount of benzyl chloride, propionic aldehyde and stirring solvent are put into uniform；
2) add a certain amount of step 1 to 500ml four-hole boiling flasks) in solvent and catalyst, then added simultaneously to reactor
Aminating agent and step 1) in reaction solution, control certain reaction temperature, react certain hour, reaction terminates to be down to reaction solution
Room temperature；
3) by step 2) in reacting liquid filtering go out catalyst.A certain amount of water is added in filtrate, is washed, stands, is layered,
Water layer is with a certain amount of step 1) in solvent extraction 1 time, extract merges with oil reservoir after washing；
4) by precipitation under the oil reservoir normal pressure after merging to cooling after 100 DEG C, taken off to end under the conditions of pressure is -0.095MPa
100 DEG C of temperature, continuation steams propylidene benzylamine under the conditions of pressure 5mmHg, 180 DEG C, analyzes content, calculated yield.
Step 1 of the present invention) in solvent for dichloroethanes, chlorobenzene, chloroform, thiacyclohexane any one, preferably
Solvent is chloroform, dichloroethanes, more preferably chloroform；
Step 1 of the present invention) in solvent be the mass ratio that feeds intake of benzyl chloride for 10~2:1, preferable amount is 8~2:
1, more preferably 6~3:1；
Step 1 of the present invention) molar ratio of propionic aldehyde and benzyl chloride is 0.9~1.2:1, preferable amount be 0.9~
1.1:1, more preferably 0.95~1.05:1；
Step 2 of the present invention) in catalyst for metallic copper, metallic nickel, metallic iron, metallic aluminium any one, preferably
Catalyst be metallic copper, metallic iron, more preferably metallic copper；
Step 2 of the present invention) mass ratio that feeds intake of catalyst and benzyl chloride is 0.5~2.5:100, preferable amount is
0.8~2:100, more preferably consumption 1~1.5:100；
Step 2 of the present invention) in aminating agent species be ammonia and ammoniacal liquor, preferably ammonia；
Step 2 of the present invention) in the molar ratio of aminating agent and benzyl chloride be 4~20:1, preferred mol ratio
It is 8~15:1, more preferably 10~12:1；
Step 2 of the present invention) reaction temperature be 20~100 DEG C, preferable temperature be 30~80 DEG C, more preferably 40~70
℃；
Step 2 of the present invention) in 2~10hr of reaction time, preferably the time be 3~8hr, more preferably 4~7hr.
Specific embodiment
Example 1：
To benzyl chloride 50.6g, propionic aldehyde 24.3g, chloroform 200g is weighed in 500ml glass four-hole boiling flasks, it is well mixed.
After adding 10g chloroforms and 0.6g catalytic metal coppers, stirring to be warming up to 60 DEG C in 500ml glass four-hole boiling flasks,
Benzyl chloride propionic aldehyde chloroform solution is added dropwise, ammonia is passed through, reacts 5 hours, then be incubated 1 hour, reaction terminates, and drops to room temperature, and filtering is urged
Agent, filtrate adds 50g washings, stratification.Oil after water layer 50g chloroform aqueous layer extracteds, stratification, extract and washing
It is laminated simultaneously.
Precipitation is lowered the temperature to 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.In pressure
Power obtains 53.2 grams of product to be distilled to 180 DEG C under conditions of 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 to propylidene benzylamine, the experiment that different ammonias participate in reaction is carried out,
Remaining condition is with embodiment 1.Data such as following table：
As seen from the above table, under same reaction condition, when ammonia is 10 with benzyl chloride mol ratio, 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 ammoniacal liquor, remaining is constant.Tied the following is being tested in the case of different ammonia volumes
Really：
As seen from the above table, under same reaction condition, when ammoniacal liquor is 10 with benzyl chloride mol ratio, propylidene benzylamine yield is most
Height, is 88.1%.And ammonia volume is too high or height yield has all declined.
Example 9-13：
Catalyst selects 0.6g metallic coppers, reaction yield 88% in example 1.It is different the following is under same reaction condition
(wherein, catalyst amount refers to that catalyst and benzyl chloride feed intake mass ratio to 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 optimal, next to that 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, next to that hexamethylene, chlorobenzene
Example 19-21：
On the basis of example 1, different propionic aldehyde consumptions are used instead, remaining is constant.Experimental result is as follows：
As seen from the above table, different propionic aldehyde consumptions, reaction yield is different, and mainly benzylamine can react with benzyl chloride, propylidene
Benzylamine can also react with propionic aldehyde.
Example 22-24：
On the basis of example 1, different propionic aldehyde consumptions are used instead, remaining is constant.Experimental result is as follows：
As seen from the above table, different reaction time, reaction yield is 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 not as good as charging simultaneously by the way of independent logical ammonia.
Claims (10)
1. the method that one-step method prepares propylidene benzylamine, it is characterised in that comprise the following steps：
1) in 500ml four-hole boiling flasks, a certain amount of benzyl chloride, propionic aldehyde and stirring solvent are put into uniform；
2) add a certain amount of step 1 to 500ml four-hole boiling flasks) in solvent and catalyst, then add amination simultaneously to reactor
Agent and step 1) in reaction solution, control certain reaction temperature, react certain hour, reaction terminates for reaction solution to be down to room
Temperature；
3) by step 2) in reacting liquid filtering go out catalyst.A certain amount of water, washing, standing, layering, water layer are added in filtrate
With a certain amount of step 1) in solvent extraction 1 time, extract merges with oil reservoir after washing；
4) by precipitation under the oil reservoir normal pressure after merging to cooling after 100 DEG C, taken off to final temperature under the conditions of pressure is -0.095MPa
100 DEG C, continuation steams propylidene benzylamine under the conditions of pressure 5mmHg, 180 DEG C, analyzes content, calculated yield.
2. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 1) in
Solvent is any one of dichloroethanes, chlorobenzene, chloroform, thiacyclohexane, and preferred solvent is chloroform, dichloroethanes, more preferably chlorine
It is imitative.
3. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 1) in
Solvent is 10~2 for the mass ratio that feeds intake of benzyl chloride:1, preferable amount is 8~2:1, more preferably 6~3:1.
4. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 1) propionic aldehyde
It is 0.9~1.2 with the molar ratio of benzyl chloride:1, preferable amount is 0.9~1.1:1, more preferably 0.95~1.05:1.
5. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 2) in
Catalyst be metallic copper, metallic nickel, metallic iron, metallic aluminium any one, preferred catalyst be metallic copper, metallic iron, it is more excellent
Select metallic copper.
6. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 2) catalysis
Agent is 0.5~2.5 with the mass ratio that feeds intake of benzyl chloride:100, preferable amount is 0.8~2:100, more preferably consumption 1~1.5:
100。
7. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 2) in amine
Agent species is ammonia and ammoniacal liquor, preferably ammonia.
8. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 2) in
Aminating agent is 4~20 with the molar ratio of benzyl chloride:1, preferred mol ratio is 8~15:1, more preferably 10~12:1.
9. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 2) reaction
Temperature is 20~100 DEG C, and preferable temperature is 30~80 DEG C, more preferably 40~70 DEG C.
10. the method that one-step method according to claim 1 prepares propylidene benzylamine, it is characterised in that the step 2) in
2~10hr of reaction time, preferably time are 3~8hr, more preferably 4~7hr.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285771A (en) * | 2020-04-28 | 2020-06-16 | 杭州益至生物科技有限公司 | Method for synthesizing N-isopropylamine |
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 |
-
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 |
|---|
| VINCENT COEFFARD ET AL.: ""Mild Electrochemical Deprotection of N-Phenylsulfonyl N-Substituted Amines Derived from (R)-Phenylglycinol"", 《EUR. J. ORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285771A (en) * | 2020-04-28 | 2020-06-16 | 杭州益至生物科技有限公司 | Method for synthesizing N-isopropylamine |
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