CN107973721A - A kind of synthetic method of N- methyl neighbour's fluoroaniline - Google Patents
A kind of synthetic method of N- methyl neighbour's fluoroaniline Download PDFInfo
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- CN107973721A CN107973721A CN201711183457.0A CN201711183457A CN107973721A CN 107973721 A CN107973721 A CN 107973721A CN 201711183457 A CN201711183457 A CN 201711183457A CN 107973721 A CN107973721 A CN 107973721A
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- fluoroaniline
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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
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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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
Abstract
The invention discloses a kind of synthetic method of N methyl neighbour's fluoroaniline, include the following steps：Include the following steps：(1) using adjacent fluoroaniline as raw material, toluene, paraformaldehyde and catalyst A is added, is dehydrated after insulation reaction, it is post-treated to obtain N methylene neighbour's fluoroanilines；(2) N methylene neighbours fluoroaniline, catalyst B are loaded into autoclave, after nitrogen displacement, is passed through hydrogen and keeps certain pressure, heating carries out hydrogenation reaction, post-treated N methyl neighbour's fluoroanilines.This method can be easy to get with raw material, and reaction condition is gentle, and cost of material is relatively low, avoid the huge advantages such as di-methylation impurity, have larger industrial applications prospect.
Description
Technical field
The invention belongs to pesticide, medicine intermediate preparation field, and in particular to the synthetic method of N- methyl neighbour's fluoroanilines.
Background technology
N- methyl neighbour's fluoroanilines belong to fluorinated N- alkylarylamines, are a kind of very important Organic Ingredients and fine chemistry industry
Intermediate, is widely used in the fields such as dyestuff, plastics, medicine and pesticide.With the continuous development of dyestuff and rubber industry, agriculture
Medicine, the dosage of medicine are also continuously increased, and the demand of N- methyl neighbour's fluoroanilines increases rapidly, and its corresponding synthesis exploitation is also standby
It is concerned.
Specifically, N- methyl neighbour fluoroaniline has many synthetic methods, according to the difference of reaction scheme, can be divided into following several
Kind：
(1) one kind is using adjacent fluoroaniline as raw material (document Catalysis Science＆Technology, 6 (22), 7956-
7966；2016) methylation reaction, occurs with dimethyl carbonate to be made.But compare appearance since dimethyl carbonate belongs to methylate
A kind of easy raw material, actual most of (84%) generate the N of dimethyl substitution, N- dimethyl neighbour's fluoroanilines, target product N-
Methyl neighbour's fluoroaniline only has 5%.
(2) one kind is using adjacent fluoroaniline as starting material (OrganicLetters, 14 (15), 3948-3951；2012), exist
Under n-BuLi catalytic action, tetrahydrofuran is solvent, and methylation reaction, which occurs, with dimethyl suflfate is made.This method needs
Carried out at -78 DEG C of low temperature, condition is harsher, and dimethyl suflfate is toxic articles, and n-BuLi is using needing to accomplish anhydrous nothing
Oxygen, security risk are larger.
(3) one kind is using adjacent fluoroaniline as starting material (Journal of Agricultural and Food
Chemistry,58(23),12357-12365；2010), under sodium hydride catalytic action, DMF is solvent, is occurred with iodomethane
Methylation reaction is made.But this method sodium hydride is equally very dangerous, and iodomethane is expensive, and cost of material remains high,
Industrial applications are more difficult.
Three of the above route belongs to methylation reaction, there is the drawbacks of respective, but have one it is common the shortcomings that, be exactly raw
Into dibasic N, N- dimethyl neighbour's fluoroanilines, the ratio simply generated is slightly different, since property is similar, removes difficult.
The content of the invention
For the above-mentioned prior art there are problem, in order to reduce the content of accessory substance N, N- dimethyl neighbour's fluoroaniline, this hair
Bright to provide a kind of synthetic method of N- methyl neighbour's fluoroaniline, this method can be easy to get with raw material, and reaction condition is gentle, cost of material
It is relatively low, avoid the huge advantages such as di-methylation impurity.
The technical solution adopted by the present invention is as follows：
A kind of synthetic method of N- methyl neighbour's fluoroaniline, includes the following steps：
(1) enamine reacts
Using adjacent fluoroaniline as raw material, toluene, paraformaldehyde and catalyst A are added, is dehydrated after insulation reaction, post-treated
N- methylene neighbour's fluoroanilines；
(2) hydrogenation reaction
N- methylene neighbours fluoroaniline, catalyst B are loaded into autoclave, after nitrogen displacement, hydrogen is passed through and keeps a level pressure
Power, heating carries out hydrogenation reaction, post-treated to obtain N- methyl neighbour's fluoroanilines.
The present invention, as raw material, N- methyl neighbour's fluoroanilines, energy is obtained through enamine, hydrogenation two-step reaction using adjacent fluoroaniline
N is effectively avoided, the generation of N- dimethyl neighbour's fluoroanilines, purity is high, and this method cost of material is low, is adapted to industrialized production.
The synthetic route of the present invention is as follows：
In step (1), the catalyst A is triethylamine, the dosage of catalyst A be adjacent fluoroaniline quality 5 ‰~
2%；
Neighbour's fluoroaniline and paraformaldehyde add molar ratio as 1：1.0~2.0；Paraformaldehyde dosage deficiency, meeting
Raw material reaction is caused to be not thorough, yield is relatively low, preferably, the molar ratio that adds of adjacent fluoroaniline and paraformaldehyde is 1：1.3~
1.5；
Neighbour's fluoroaniline and toluene add mass ratio as 1：1.0~3.0；Toluene is used as water entrainer, first in system
The dosage deficiency of benzene, is easy to cause dehydration and is not thorough, and accessory substance increases, and yield is relatively low, preferably, adjacent fluoroaniline and toluene
Add mass ratio as 1：1.5~2.0；
In step (1), the temperature of insulation reaction is 80~100 DEG C, and the time of insulation reaction is 1~4h；Reaction temperature mistake
Low then reaction speed is slower, and reaction temperature is excessive, and accessory substance increase, preferably, the temperature of insulation reaction is 85~90 DEG C, is protected
The time of temperature reaction is 1~2h；
In step (1), dehydration temperaturre is 100~110 DEG C, and dewatering time is 1~4h；Dehydration temperaturre is too low, is dehydrated not thorough
Bottom, dehydration temperaturre is excessive, then extends the reaction time.
In step (2), the catalyst B is Raney's nickel or palladium carbon, and the dosage of catalyst B is N- methylene neighbour's fluoroanilines
5 ‰~the 2% of quality；
In step (2), the temperature of hydrogenation reaction is 100~150 DEG C, and the time of hydrogenation reaction is 2~4h；Reaction temperature mistake
Low then reaction speed is slower, and after reaction temperature is higher than 150 DEG C, impurity showed increased, conversion ratio and yield are relatively low, as excellent
Choosing, the temperature of hydrogenation reaction is 110~120 DEG C；
In step (2), the pressure of hydrogenation reaction is 0.3~3MPa；The too low then reaction speed of reaction pressure is slower, reaction pressure
Power is excessive, and the reaction time extends, preferably, the pressure of hydrogenation reaction is 0.5~1.5MPa.
Compared with prior art, the invention has the advantages that：The present invention provides N- methyl neighbour's fluoroaniline
New synthetic method, raw material are easy to get, and reaction condition is gentle, and cost of material is relatively low, have larger industrial applications prospect.
Embodiment
Embodiment 1
(1) enamine reacts
100g neighbour's fluoroaniline is mixed with 150g toluene, adds 40.5g paraformaldehydes, 2g triethylamines, are warming up to 85~90
DEG C, insulation reaction 2h, is warming up to 100~110 DEG C of dehydration 3h, when temperature rises to 110 DEG C, is cooled to 60 DEG C, decompression steams first
Benzene and excess formaldehyde, then collect 120~130 DEG C of cuts, up to N- methylene neighbour's fluorobenzene under the conditions of -0.09~-0.1MPa
Amine 95.4g, gas phase purity are 98.3%, molar yield 86.1%.
(2) hydrogenation reaction
By 250g N- methylene neighbour's fluoroanilines, 2.5g Raney's nickels are fitted into 1L autoclaves, first with nitrogen displacement three times, then
With hydrogen displacement three times, 120 DEG C, pressure 1.0MPa, when insulation 3 is small are warming up to, is cooled to room temperature, hydrogen is discharged, by upper strata
Clarified solution is transferred in flask, and vacuum distillation, collects 85~90 DEG C of (20mmHg) cuts, up to N- methyl neighbour's fluoroanilines
245.4g, gas phase purity are 96.5%, molar yield 96.6%.
Embodiment 2
(1) enamine reacts
100g neighbour's fluoroaniline is mixed with 150g toluene, adds 32.4g paraformaldehydes, 2g triethylamines, are warming up to 85~90
DEG C, insulation reaction 2h, is warming up to 100~110 DEG C of dehydration 3h, when temperature rises to 110 DEG C, is cooled to 60 DEG C, decompression steams first
Benzene and excess formaldehyde, then collect 120~130 DEG C of cuts, up to N- methylene neighbour's fluorobenzene under the conditions of -0.09~-0.1MPa
Amine 87.1g, gas phase purity are 98.0%, molar yield 78.6%.
(2) hydrogenation reaction
By 250g N- methylene neighbour's fluoroanilines, 2.5g Raney's nickels are fitted into 1L autoclaves, first with nitrogen displacement three times, then
With hydrogen displacement three times, 100 DEG C, pressure 1.0MPa, when insulation 3 is small are warming up to, is cooled to room temperature, hydrogen is discharged, by upper strata
Clarified solution is transferred in flask, and vacuum distillation, collects 80~85 DEG C of (20mmHg) cuts, up to N- methyl neighbour's fluoroanilines
240.1g, gas phase purity are 96.3%, molar yield 94.5%.
Embodiment 3
(1) enamine reacts
100g neighbour's fluoroaniline is mixed with 150g toluene, adds 40.5g paraformaldehydes, 2g triethylamines, are warming up to 90~100
DEG C, insulation reaction 2h, is warming up to 100~110 DEG C of dehydration 3h, when temperature rises to 110 DEG C, is cooled to 60 DEG C, decompression steams first
Benzene and excess formaldehyde, then collect 120~130 DEG C of cuts under the conditions of -0.09~-0.1MPa, are N- methylene neighbour's fluorobenzene
Amine 91.1g, gas phase purity are 98.3%, molar yield 82.2%.
(2) it is hydrogenated with
By 250g N- methylene neighbour's fluoroanilines, 2.5g Raney's nickels are fitted into 1L autoclaves, first with nitrogen displacement three times, then
With hydrogen displacement three times, 130 DEG C, pressure 1.0MPa, when insulation 3 is small are warming up to, is cooled to room temperature, hydrogen is discharged, by upper strata
Clarified solution is transferred in flask, and vacuum distillation, collects 80~85 DEG C of (20mmHg) cuts, up to N- methyl neighbour's fluoroanilines
230.7g, gas phase purity are 96.0%, molar yield 90.8%.
Embodiment 4
(1) enamine reacts
100g neighbour's fluoroaniline is mixed with 150g toluene, adds 40.5g paraformaldehydes, 2g triethylamines, are warming up to 85~90
DEG C, insulation reaction 2h, is warming up to 100~105 DEG C of dehydration 3h, when temperature rises to 105 DEG C, is cooled to 60 DEG C, decompression steams first
Benzene and excess formaldehyde, then collect 120~130 DEG C of cuts, up to N- methylene neighbour's fluorobenzene under the conditions of -0.09~-0.1MPa
Amine 78.1g, gas phase purity are 98.2%, molar yield 70.5%.
(2) hydrogenation reaction
By 250g N- methylene neighbour's fluoroanilines, 1.5g Raney's nickels are fitted into 1L autoclaves, first with nitrogen displacement three times, then
With hydrogen displacement three times, 120 DEG C, pressure 1.0MPa, when insulation 3 is small are warming up to, is cooled to room temperature, hydrogen is discharged, by upper strata
Clarified solution is transferred in flask, and vacuum distillation, collects 80~85 DEG C of (20mmHg) cuts, up to N- methyl neighbour's fluoroanilines
237.6g, gas phase purity are 96.5%, molar yield 93.5%.
Embodiment 5
(1) enamine reacts
100g neighbour's fluoroaniline is mixed with 100g toluene, adds 40.5g paraformaldehydes, 2g triethylamines, are warming up to 85~90
DEG C, insulation reaction 2h, is warming up to 100~110 DEG C of dehydration 3h, when being warming up to 110 DEG C, is cooled to 60 DEG C, decompression steams toluene
And excess formaldehyde, 120~130 DEG C of cuts are then collected under the conditions of -0.09~-0.1MPa, up to N- methylene neighbour's fluoroanilines
86.2g, gas phase purity are 98.1%, molar yield 77.8%.
(2) hydrogenation reaction
By 250g N- methylene neighbour's fluoroanilines, 1.5g Raney's nickels are fitted into 1L autoclaves, first with nitrogen displacement three times, then
With hydrogen displacement three times, 120 DEG C, pressure 0.5MPa, when insulation 5 is small are warming up to, is cooled to room temperature, hydrogen is discharged, by upper strata
Clarified solution is transferred in flask, and vacuum distillation, collects 80~85 DEG C of (20mmHg) cuts, is N- methyl neighbour's fluoroanilines
245.2g, gas phase purity are 96.5%, molar yield 96.5%.
Embodiment 6
Compared with Example 1, differ only in step (2), the catalyst of addition is 1.3g palladium carbons, remaining condition phase
Together, N- methyl neighbour fluoroaniline 245.2g are obtained, gas phase purity is 96.8%, molar yield 96.5%.
Comparative example 1
Compared with Example 1, differ only in step (1), do not add catalyst of triethylamine, remaining condition is identical, knot
Fruit finds that generation water is less, and vapor detection, adjacent fluoroaniline conversion ratio only has 5% or so.
Claims (9)
1. a kind of synthetic method of N- methyl neighbour's fluoroaniline, it is characterised in that include the following steps：
(1) enamine reacts
Using adjacent fluoroaniline as raw material, toluene, paraformaldehyde and catalyst A are added, is dehydrated after insulation reaction, it is post-treated that N- is sub-
Methyl neighbour's fluoroaniline；
(2) hydrogenation reaction
N- methylene neighbours fluoroaniline, catalyst B are loaded into autoclave, after nitrogen displacement, hydrogen is passed through and keeps certain pressure, rise
Temperature carries out hydrogenation reaction, post-treated to obtain N- methyl neighbour's fluoroanilines.
2. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that described to urge in step (1)
Agent A is triethylamine, and the dosage of catalyst A is 5 ‰~the 2% of adjacent fluoroaniline quality.
3. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that it is described neighbour fluoroaniline with it is more
Polyformaldehyde adds molar ratio as 1：1.0~2.0.
4. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that neighbour's fluoroaniline and first
Benzene adds mass ratio as 1：1.0~3.0.
5. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that in step (1), insulation is anti-
The temperature answered is 80~100 DEG C, and the time of insulation reaction is 1~4h.
6. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that in step (1), dehydration temperature
Spend for 100~110 DEG C, dewatering time is 1~4h.
7. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that described to urge in step (2)
Agent B is Raney's nickel or palladium carbon, and the dosage of catalyst B is 5 ‰~the 2% of N- methylene neighbour's fluoroaniline quality.
8. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that in step (2), hydrogenation is anti-
The temperature answered is 100~150 DEG C, and the time of hydrogenation reaction is 2~4h.
9. the synthetic method of N- methyl neighbour's fluoroaniline according to claim 1, it is characterised in that in step (2), hydrogenation is anti-
The pressure answered is 0.3~3MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053486A (en) * | 2018-08-16 | 2018-12-21 | 江苏中旗科技股份有限公司 | A kind of synthetic method of N- methyl -2- fluoroaniline |
| CN112374998A (en) * | 2020-12-04 | 2021-02-19 | 阜新睿光氟化学有限公司 | Preparation method of N-methyl o-fluoroaniline |
| CN112851518A (en) * | 2019-11-28 | 2021-05-28 | 江苏中旗科技股份有限公司 | Synthesis method of N-methyl o-fluoroaniline |
| CN113429297A (en) * | 2021-07-08 | 2021-09-24 | 江西汇和化工有限公司 | Method for synthesizing N-methyl o-fluoroaniline by one-pot method |
| CN113480434A (en) * | 2021-07-12 | 2021-10-08 | 浙江捷达科技有限公司 | Synthesis method of N, N' -di-tert-butyl ethylenediamine |
| CN114031519A (en) * | 2021-12-08 | 2022-02-11 | 浙江工业大学 | Method for synthesizing N-aryl imine |
| CN114031519B (en) * | 2021-12-08 | 2024-04-26 | 浙江工业大学 | Method for synthesizing N-aryl imine |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053486A (en) * | 2018-08-16 | 2018-12-21 | 江苏中旗科技股份有限公司 | A kind of synthetic method of N- methyl -2- fluoroaniline |
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| CN112851518A (en) * | 2019-11-28 | 2021-05-28 | 江苏中旗科技股份有限公司 | Synthesis method of N-methyl o-fluoroaniline |
| CN112851518B (en) * | 2019-11-28 | 2023-02-14 | 江苏中旗科技股份有限公司 | Synthesis method of N-methyl o-fluoroaniline |
| CN112374998A (en) * | 2020-12-04 | 2021-02-19 | 阜新睿光氟化学有限公司 | Preparation method of N-methyl o-fluoroaniline |
| CN113429297A (en) * | 2021-07-08 | 2021-09-24 | 江西汇和化工有限公司 | Method for synthesizing N-methyl o-fluoroaniline by one-pot method |
| CN113480434A (en) * | 2021-07-12 | 2021-10-08 | 浙江捷达科技有限公司 | Synthesis method of N, N' -di-tert-butyl ethylenediamine |
| CN114031519A (en) * | 2021-12-08 | 2022-02-11 | 浙江工业大学 | Method for synthesizing N-aryl imine |
| CN114031519B (en) * | 2021-12-08 | 2024-04-26 | 浙江工业大学 | Method for synthesizing N-aryl imine |
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Application publication date: 20180501 |