CN105837472A - Synthetic method for 4-(3-cyanobenzyl)phenylacetylimine - Google Patents
Synthetic method for 4-(3-cyanobenzyl)phenylacetylimine Download PDFInfo
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- CN105837472A CN105837472A CN201610196885.6A CN201610196885A CN105837472A CN 105837472 A CN105837472 A CN 105837472A CN 201610196885 A CN201610196885 A CN 201610196885A CN 105837472 A CN105837472 A CN 105837472A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
Abstract
The invention discloses a synthetic method for 4-(3-cyanobenzyl)phenylacetylimine, which belongs to the technical field of organic synthesis. The synthetic method of the invention has the advantages of low risks, high productivity and small influence on the environment and overcomes the disadvantages of low production yield, high risks, great influence on the environment, unsuitability for large-scale industrial production and the like of conventional synthetic methods for 4-(3-cyanobenzyl)phenylacetylimine.
Description
Technical field
The invention discloses the synthetic method of a kind of 4-(3-cyanobenzyl) phenylacetyl imines, belong to organic conjunction
Become technical field.
Background technology
Acetimide compound is widely used in polymeric material additive, the synthesis of heterocyclic compound, life at present
Materialization work, pharmacy, the manufacture of industrial dye intermediate and new type functional (insulation, fire-retardant) material, meanwhile,
It is also the low temperature dewatering synthesizing the compounds such as aldehyde, ketone, aminoacid, anhydride, ester that industry is conventional with laboratory
Agent, is carboxylic acid and amine (or alcohol) carries out one of of paramount importance reagent of acylation reaction, valuable in synthesis and originate dilute
Few macrolide and Macrocyclic lactams reaction also play the effect of uniqueness.
At present the synthetic method of 4-(3-cyanobenzyl) phenylacetyl imines exist to some extent production yield low,
The shortcomings such as dangerous height, effect on environment are big, are not suitable for large-scale industrial production.
Summary of the invention
The technical problem that present invention mainly solves: for the conjunction of current 4-(3-cyanobenzyl) phenylacetyl imines
There is the shortcomings such as production yield height low, dangerous, effect on environment are big in one-tenth method, is not suitable for big to some extent
The problem of the industrialized production of scale, the invention provides a kind of dangerous low, productivity ratio is high and effect on environment
The synthetic method of little 4-(3-cyanobenzyl) phenylacetyl imines.
For reaching above-mentioned purpose, the synthetic method of 4-(3-cyanobenzyl) the phenylacetyl imines of the present invention is:
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) in 50mL flask, 10～15mL aniline and the formalin of 4～7mL mass fractions 50% are added,
Mix homogeneously, then moves to be heated in water-bath 40～50 DEG C by flask, preheats 5～10min, uses subsequently
Dropping funnel is added thereto to the dehydrated alcohol of 5～10mL, loads onto reflux simultaneously, is warming up to 80～90 DEG C,
Keep temperature, backflow 30～40min；
(2) after above-mentioned backflow terminates, it is added thereto to 2～5mL lewis acids, after stirring, flask is moved
Lowering the temperature to ice-water bath, cooling is until separating out without white crystal, then by the crystal of precipitation through buchner funnel
Sucking filtration, re-uses absolute ether and carries out recrystallization, collect crystal, i.e. can get 3,4 ,-diphenyl-methane diamino
Base methyl formate；
(3) in 50mL is dried round-bottomed flask, the crystal of 1～2g above-mentioned gained, 60～70mg titanium dioxide are put into
Titanium and 5～10mL dichloromethane, then it is added thereto to 3 zeolites, it is subsequently mounted fractionating device, uses taper
Bottle, as receptor, is put in ice-water bath, is then heated as in water-bath by flask, and temperature is set as
124～136 DEG C, keep temperature 50～60min；
(4) after above-mentioned distillation terminates, distillate is poured into separatory in separatory funnel and takes upper organic layer, then to having
Machine layer adds the sodium chloride solution that isopyknic mass fraction is 40%, stratification after shaking, takes upper strata
Liquid, i.e. can get 3,4 '-diphenyl methane diamino acid methyl ester；
(5) in round-bottomed flask add the upper liquid of 10～15mL above-mentioned gained, 15～20mL glacial acetic acid,
60～70mgPd/C catalyst and 3 zeolites, and connect reflux, reflux temperature is set as
105～115 DEG C, reflux 1～2h, upon a drop in temperature, stopping stirring, filtered while hot, then filtrate is fallen
Enter to fill in the beaker of 150mL cold water, sucking filtration after cooling 1～2min, washs sucking filtration thing with cold water, by sucking filtration
Thing moves in 400mL beaker, adds 200mL water and heating makes it be completely dissolved, be cooled to deposit-free and produce
Raw, press dry after sucking filtration, i.e. can get 4-(3-cyanobenzyl) phenylacetyl imines, yield reaches 60～68.9%.
The invention has the beneficial effects as follows:
(1) present invention is easily operated, and cost of manufacture is low；
(2) product obtained by the present invention, yield reaches 60～68.9%.
Detailed description of the invention
10～15mL aniline and the formalin of 4～7mL mass fractions 50% is added in 50mL flask,
Mix homogeneously, then moves to be heated in water-bath 40～50 DEG C by flask, preheats 5～10min, uses subsequently
Dropping funnel is added thereto to the dehydrated alcohol of 5～10mL, loads onto reflux simultaneously, is warming up to 80～90 DEG C,
Keep temperature, backflow 30～40min；After above-mentioned backflow terminates, it is added thereto to 2～5mL lewis acids,
After stirring, moving to flask lower the temperature in ice-water bath, cooling, until separating out without white crystal, then will
The crystal separated out, through buchner funnel sucking filtration, re-uses absolute ether and carries out recrystallization, collect crystal,
To 3,4 '-diphenyl methane diamino acid methyl ester；In 50mL is dried round-bottomed flask, put into 1～2g above-mentioned institute
The crystal, 60～the 70mg titanium dioxide that obtain and 5～10mL dichloromethane, then it is added thereto to 3 zeolites,
It is subsequently mounted fractionating device, uses conical flask as receptor, put in ice-water bath, then by flask as water
Heating in bath, temperature is set as 124～136 DEG C, keeps temperature 50～60min；Treat that above-mentioned distillation is tied
Shu Hou, pours distillate separatory in separatory funnel into and takes upper organic layer, then add isopyknic in organic layer
Mass fraction is the sodium chloride solution of 40%, stratification after shaking, takes upper liquid, i.e. can get 3,4 '-two
Phenylmethane diamino-methyl formate；In round-bottomed flask add 10～15mL above-mentioned gained upper liquid,
15～20mL glacial acetic acid, 60～70mgPd/C catalyst and 3 zeolites, and connect reflux, backflow
Temperature is set as 105～115 DEG C, reflux 1～2h, upon a drop in temperature, stopping stirring, filtered while hot, then
Filtrate is poured in the beaker filling 150mL cold water, sucking filtration after cooling 1～2min, washs sucking filtration with cold water
Thing, moves to sucking filtration thing in 400mL beaker, adds 200mL water and heating makes it be completely dissolved, be cooled to
Deposit-free produces, and press dry, i.e. can get 4-(3-cyanobenzyl) phenylacetyl imines after sucking filtration, and yield reaches
60～68.9%.
Example 1
Addition 12mL aniline and the formalin of 6mL mass fraction 50% in 50mL flask, mix homogeneously,
Then flask moves to be heated in water-bath 45 DEG C, preheat 8min, use Dropping funnel to add wherein subsequently
Entering the dehydrated alcohol of 8mL, load onto reflux simultaneously, be warming up to 85 DEG C, keep temperature, reflux 35min；
After above-mentioned backflow terminates, it is added thereto to 4mL lewis acid, after stirring, flask is moved to frozen water
Lowering the temperature in bath, cooling is until separating out without white crystal, then by the crystal of precipitation through buchner funnel sucking filtration,
Re-use absolute ether and carry out recrystallization, collect crystal, i.e. can get 3,4 '-diphenyl methane diamino formic acid
Methyl ester；In 50mL is dried round-bottomed flask, put into the crystal of the above-mentioned gained of 1g, 65mg titanium dioxide and
8mL dichloromethane, then it is added thereto to 3 zeolites, it is subsequently mounted fractionating device, uses conical flask conduct
Receptor, puts in ice-water bath, is then heated as in water-bath by flask, and temperature is set as 128 DEG C,
Keep temperature 55min；After above-mentioned distillation terminates, distillate is poured into separatory in separatory funnel, and to take upper strata organic
Layer, then in organic layer, add the sodium chloride solution that isopyknic mass fraction is 40%, stand after shaking and divide
Layer, takes upper liquid, i.e. can get 3,4 '-diphenyl methane diamino acid methyl ester；15mL is added in round-bottomed flask
The upper liquid of above-mentioned gained, 15mL glacial acetic acid, 60mgPd/C catalyst and 3 zeolites, and connect back
Stream device, reflux temperature is set as 110 DEG C, and reflux 1h, upon a drop in temperature, stops stirring, filtered while hot,
Then filtrate is poured in the beaker filling 150mL cold water, sucking filtration after cooling 2min, take out with cold water washing
Screening, moves to sucking filtration thing in 400mL beaker, adds 200mL water and heating makes it be completely dissolved, cooling
Producing to deposit-free, press dry, i.e. can get 4-(3-cyanobenzyl) phenylacetyl imines after sucking filtration, yield reaches
To 63.8%.
Example 2
Addition 15mL aniline and the formalin of 7mL mass fraction 50% in 50mL flask, mix homogeneously,
Then flask moves to be heated in water-bath 50 DEG C, preheat 10min, use Dropping funnel to add wherein subsequently
Entering the dehydrated alcohol of 10mL, load onto reflux simultaneously, be warming up to 90 DEG C, keep temperature, reflux 40min；
After above-mentioned backflow terminates, it is added thereto to 5mL lewis acid, after stirring, flask is moved to frozen water
Lowering the temperature in bath, cooling is until separating out without white crystal, then by the crystal of precipitation through buchner funnel sucking filtration,
Re-use absolute ether and carry out recrystallization, collect crystal, i.e. can get 3,4 '-diphenyl methane diamino formic acid
Methyl ester；In 50mL is dried round-bottomed flask, put into the crystal of the above-mentioned gained of 2g, 70mg titanium dioxide and
10mL dichloromethane, then it is added thereto to 3 zeolites, it is subsequently mounted fractionating device, uses conical flask conduct
Receptor, puts in ice-water bath, is then heated as in water-bath by flask, and temperature is set as 136 DEG C,
Keep temperature 50min；After above-mentioned distillation terminates, distillate is poured into separatory in separatory funnel, and to take upper strata organic
Layer, then in organic layer, add the sodium chloride solution that isopyknic mass fraction is 40%, stand after shaking and divide
Layer, takes upper liquid, i.e. can get 3,4 '-diphenyl methane diamino acid methyl ester；15mL is added in round-bottomed flask
The upper liquid of above-mentioned gained, 20mL glacial acetic acid, 70mgPd/C catalyst and 3 zeolites, and connect back
Stream device, reflux temperature is set as 115 DEG C, and reflux 2h, upon a drop in temperature, stops stirring, filtered while hot,
Then filtrate is poured in the beaker filling 150mL cold water, sucking filtration after cooling 2min, take out with cold water washing
Screening, moves to sucking filtration thing in 400mL beaker, adds 200mL water and heating makes it be completely dissolved, cooling
Producing to deposit-free, press dry, i.e. can get 4-(3-cyanobenzyl) phenylacetyl imines after sucking filtration, yield reaches
To 68.1%.
Example 3
Addition 10mL aniline and the formalin of 4mL mass fraction 50% in 50mL flask, mix homogeneously,
Then flask moves to be heated in water-bath 40 DEG C, preheat 5min, use Dropping funnel to add wherein subsequently
Entering the dehydrated alcohol of 5mL, load onto reflux simultaneously, be warming up to 80 DEG C, keep temperature, reflux 30min；
After above-mentioned backflow terminates, it is added thereto to 2mL lewis acid, after stirring, flask is moved to frozen water
Lowering the temperature in bath, cooling is until separating out without white crystal, then by the crystal of precipitation through buchner funnel sucking filtration,
Re-use absolute ether and carry out recrystallization, collect crystal, i.e. can get 3,4 '-diphenyl methane diamino formic acid
Methyl ester；In 50mL is dried round-bottomed flask, put into the crystal of the above-mentioned gained of 1g, 60mg titanium dioxide and
5mL dichloromethane, then it is added thereto to 3 zeolites, it is subsequently mounted fractionating device, uses conical flask conduct
Receptor, puts in ice-water bath, is then heated as in water-bath by flask, and temperature is set as 124 DEG C,
Keep temperature 50min；After above-mentioned distillation terminates, distillate is poured into separatory in separatory funnel, and to take upper strata organic
Layer, then in organic layer, add the sodium chloride solution that isopyknic mass fraction is 40%, stand after shaking and divide
Layer, takes upper liquid, i.e. can get 3,4 '-diphenyl methane diamino acid methyl ester；10mL is added in round-bottomed flask
The upper liquid of above-mentioned gained, 15mL glacial acetic acid, 60mgPd/C catalyst and 3 zeolites, and connect back
Stream device, reflux temperature is set as 105 DEG C, and reflux 1h, upon a drop in temperature, stops stirring, filtered while hot,
Then filtrate is poured in the beaker filling 150mL cold water, sucking filtration after cooling 1min, take out with cold water washing
Screening, moves to sucking filtration thing in 400mL beaker, adds 200mL water and heating makes it be completely dissolved, cooling
Producing to deposit-free, press dry, i.e. can get 4-(3-cyanobenzyl) phenylacetyl imines after sucking filtration, yield reaches
To 60%.
Claims (1)
1. the synthetic method of 4-(3-cyanobenzyl) phenylacetyl imines, it is characterised in that concrete synthesis step is:
(1) in 50mL flask, 10～15mL aniline and the formalin of 4～7mL mass fractions 50% are added,
Mix homogeneously, then moves to be heated in water-bath 40～50 DEG C by flask, preheats 5～10min, uses subsequently
Dropping funnel is added thereto to the dehydrated alcohol of 5～10mL, loads onto reflux simultaneously, is warming up to 80～90 DEG C,
Keep temperature, backflow 30～40min；
(2) after above-mentioned backflow terminates, it is added thereto to 2～5mL lewis acids, after stirring, flask is moved
Lowering the temperature to ice-water bath, cooling is until separating out without white crystal, then by the crystal of precipitation through buchner funnel
Sucking filtration, re-uses absolute ether and carries out recrystallization, collect crystal, i.e. can get 3,4 ,-diphenyl-methane diamino
Base methyl formate；
(3) in 50mL is dried round-bottomed flask, the crystal of 1～2g above-mentioned gained, 60～70mg titanium dioxide are put into
Titanium and 5～10mL dichloromethane, then it is added thereto to 3 zeolites, it is subsequently mounted fractionating device, uses taper
Bottle, as receptor, is put in ice-water bath, is then heated as in water-bath by flask, and temperature is set as
124～136 DEG C, keep temperature 50～60min；
(4) after above-mentioned distillation terminates, distillate is poured into separatory in separatory funnel and takes upper organic layer, then to having
Machine layer adds the sodium chloride solution that isopyknic mass fraction is 40%, stratification after shaking, takes upper strata
Liquid, i.e. can get 3,4 '-diphenyl methane diamino acid methyl ester；
(5) in round-bottomed flask add the upper liquid of 10～15mL above-mentioned gained, 15～20mL glacial acetic acid,
60～70mgPd/C catalyst and 3 zeolites, and connect reflux, reflux temperature is set as
105～115 DEG C, reflux 1～2h, upon a drop in temperature, stopping stirring, filtered while hot, then filtrate is fallen
Enter to fill in the beaker of 150mL cold water, sucking filtration after cooling 1～2min, washs sucking filtration thing with cold water, by sucking filtration
Thing moves in 400mL beaker, adds 200mL water and heating makes it be completely dissolved, be cooled to deposit-free and produce
Raw, press dry after sucking filtration, i.e. can get 4-(3-cyanobenzyl) phenylacetyl imines, yield reaches 60～68.9%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567881A2 (en) * | 1992-05-01 | 1993-11-03 | Bayer Ag | Process for the preparation of polyamine mixtures of the polyamino-polyaryl-polymethylene series |
| CN102399155A (en) * | 2011-12-29 | 2012-04-04 | 河南省华鼎高分子合成树脂有限公司 | Method for preparing 4,4-methylenedianiline |
| KR101142576B1 (en) * | 2004-02-04 | 2012-05-03 | 바이엘 머티리얼사이언스 아게 | Production of di- and polyisocyanates of the diphenylmethane series with defined acidity |
| CN102516128A (en) * | 2011-12-19 | 2012-06-27 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
-
2016
- 2016-03-31 CN CN201610196885.6A patent/CN105837472A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567881A2 (en) * | 1992-05-01 | 1993-11-03 | Bayer Ag | Process for the preparation of polyamine mixtures of the polyamino-polyaryl-polymethylene series |
| KR101142576B1 (en) * | 2004-02-04 | 2012-05-03 | 바이엘 머티리얼사이언스 아게 | Production of di- and polyisocyanates of the diphenylmethane series with defined acidity |
| CN102516128A (en) * | 2011-12-19 | 2012-06-27 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102399155A (en) * | 2011-12-29 | 2012-04-04 | 河南省华鼎高分子合成树脂有限公司 | Method for preparing 4,4-methylenedianiline |
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Application publication date: 20160810 |