CN106866518A - A kind of synthetic method of the trifluoromethyl pyridine of 2 amino, 3 chlorine 5 - Google Patents

A kind of synthetic method of the trifluoromethyl pyridine of 2 amino, 3 chlorine 5 Download PDF

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Publication number
CN106866518A
CN106866518A CN201710246659.9A CN201710246659A CN106866518A CN 106866518 A CN106866518 A CN 106866518A CN 201710246659 A CN201710246659 A CN 201710246659A CN 106866518 A CN106866518 A CN 106866518A
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synthetic method
chloro
amino
fluoro
chlorine
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董永侠
向彬
李君�
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Inner Mongolia Ruimi Fine Chemical Co
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Inner Mongolia Ruimi Fine Chemical Co
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Priority to CN201710246659.9A priority Critical patent/CN106866518A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

The present invention relates to a kind of synthetic method of the trifluoromethyl pyridine of 2 amino, 3 chlorine 5, belong to organic chemistry filed.The synthetic method comprises the following steps：1. it is raw material with the trifluoromethyl pyridine of 2 fluorine, 3 chlorine 5, under water-soluble additive, is heated to 10 100 DEG C, 0.1 0.5MPa is forced into, through the 6h of aminating agent ammonification 1；2. step after 1. products obtained therefrom reclaims ammonia and auxiliary agent, is cooled to 0 DEG C, filtering obtains the trifluoromethyl pyridine of 2 amino, 3 chlorine 5.Specific synthetic method is as follows.The present invention substantially reduces the reaction time using high activity, the high selectivity of fluorine atom on the trifluoromethyl pyridine of 2 fluorine, 3 chlorine 5, meanwhile, reaction condition is more gentle.

Description

A kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-
Technical field
The present invention relates to a kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, belong to organic chemistry filed.
Background technology
Fluazinam (SHIRLAN, IKF-1216) is new substituted phenyl amines, the wide spectrum developed by Japanese Shi Yuan industry companies Bactericide, the various gray molds caused to Botrytis cinerea have special efficacy.Same benzimidazole, dicarboximide class and in the market Existing bactericide no interactions resistance.The germs such as interlink spore genus, Phytophthora, Plasmopara, Sclerotinia and Venturia are drawn The disease for rising also has good activity.Chloro- 5 trifluoromethyl pyridines of compound 2- amino -3- are the passes for preparing bactericide fluazinam Key intermediate.
It is that raw material and ammoniacal liquor carry out ammonification that United States Patent (USP) US4349681 is proposed with the chloro-5-trifluoromethylpyridines of 2,3- bis- Reaction, obtains required product 2- amino chloro- 5 trifluoromethyl pyridines of -3-, but yield only 50% or so, and existing country's patent is equal With the chloro-5-trifluoromethylpyridines of 2,3- bis- for raw material optimizes improvement, yield brings up to 90%, but based on the chloro- 5- of 2,3- bis- Trifluoromethyl pyridine activity is relatively low, and reaction temperature needs 80-120 DEG C, and pressure needs 0.6-1MPa, needs 10- reaction time 15h, prolonged HTHP energy resource consumption is high, while serious to equipment corrosion, industrialization safety requirements is high, is unfavorable for industry Metaplasia is produced.
The content of the invention
The present invention by with the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- as raw material, in more gentle reaction temperature and pressure Under the conditions of, 2- amino chloro- 5 trifluoromethyl pyridines of -3- are prepared, it is original with the chloro-5-trifluoromethylpyridines of 2,3- bis- to solve above-mentioned Material prepares chloro- 5 trifluoromethyl pyridines of 2- amino -3- needs HTHP, the problem of reaction for a long time.
The invention provides a kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, the synthetic method includes Following steps：
1. with the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- as raw material, under water-soluble additive, 10-100 DEG C, pressurization are heated to To 0.1-0.5MPa, through aminating agent ammonification 1-6h；
2. step after 1. products obtained therefrom reclaims ammonia and auxiliary agent, is cooled to 0 DEG C, filtering obtains 2- amino -3- chloro- 5 three Fluoromethylpyridin.
The ammonia and auxiliary agent of recovery of the present invention can be directly used for step reaction 1..
Water-soluble additive of the present invention is preferably C1-C8Alcohol, C1-C8Ether in one or two mixtures.
C of the present invention1-C8Alcohol be preferably in methyl alcohol, ethanol, propyl alcohol, isopropanol, n-butanol one or two mix Compound.
C of the present invention1-C8Ether be preferably one or two mixing in ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran Thing.
The addition of water-soluble additive of the present invention be preferably the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- 0.1-2 times is weighed Amount.
The addition of water-soluble additive of the present invention is more preferably the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- 0.5-0.8 times of weight.
0.5 times weight of the addition of water-soluble additive of the present invention less than the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- When, then poor fluidity when filtering；It is during 0.8 times of weight of 3- chloro-5-trifluoromethylpyridines fluoro- higher than 2-, then uneconomical.
Aminating agent of the present invention is preferably ammoniacal liquor or ammonia.
The addition of aminating agent of the present invention is preferably 1-10 times of material of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- Amount.
The addition of aminating agent of the present invention is more preferably 4-6 times of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- The amount of material.
Step of the present invention 1. in be preferably reaction temperature be 60-80 DEG C, reaction pressure is 0.15-0.2MPa, reaction Time is 2-4h.
Specific synthetic method of the present invention is as follows：
The present invention has the beneficial effect that：
1. the present invention is contracted significantly using high activity, the high selectivity of fluorine atom on the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- The short reaction time, meanwhile, reaction condition is more gentle.
2. the present invention has high income, low cost, it is easy to industrialized feature, can meet the need of fluazinam large-scale production Ask, have broad application prospects.
Specific embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with Any mode limits the present invention.
Embodiment 1
A kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, the synthetic method comprises the following steps：
1. to sequentially adding the chloro- 5 trifluoromethyl pyridine 200g of the fluoro- 3- of 2-, isopropanol 120g and 25% ammonia in 1L autoclaves Water 240g, airtight heating is forced into 0.3MPa, isothermal reaction 3h to 80 DEG C；
2. by step 1. products obtained therefrom cooling pressure release, excessive ammonia is absorbed with water, and reaction solution is added into 500mL four-hole bottles It is interior, 0 DEG C is cooled under agitation, filtering obtains chloro- 5 trifluoromethyl pyridines of 2- amino -3-, and its purity is 99.9%, receives Rate is 99.1%.
Embodiment 2
A kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, the synthetic method comprises the following steps：
1. to sequentially adding the chloro- 5 trifluoromethyl pyridine 200g of the fluoro- 3- of 2-, tetrahydrofuran 100g in 1L autoclaves and be passed through Ammonia 60g, airtight heating is forced into 0.15MPa, isothermal reaction 2h to 30 DEG C；
2. by step 1. products obtained therefrom cooling pressure release, excessive ammonia is absorbed with water, and reaction solution is added into 500mL four-hole bottles It is interior, it is cooled to 0 DEG C under agitation, filtering obtains chloro- 5 trifluoromethyl pyridines of 2- amino -3-, its purity is 99.95%, Yield is 98.5%.
Embodiment 3
A kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, with being distinguished as embodiment 1：1. step be：To The chloro- 5 trifluoromethyl pyridine 200g of the fluoro- 3- of 2-, isopropanol 120g are sequentially added in 1L autoclaves and ammonia 60g is passed through, it is closed plus Heat is forced into 0.15MPa, isothermal reaction 2h to 30 DEG C；The chloro- 5 trifluoromethyl pyridine purity of 2- amino -3- for obtaining is 99.9%th, yield is 99.5%.
Embodiment 4
A kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, with being distinguished as embodiment 2：1. step be：To The chloro- 5 trifluoromethyl pyridine 200g of the fluoro- 3- of 2-, tetrahydrofuran 100g and 25% ammoniacal liquor 240g are sequentially added in 1L autoclaves, it is closed 80 DEG C are heated to, 0.3MPa, isothermal reaction 3h is forced into；The chloro- 5 trifluoromethyl pyridine purity of 2- amino -3- for obtaining is 99.9%th, yield is 99.2%.

Claims (10)

1. a kind of synthetic method of chloro- 5 trifluoromethyl pyridines of 2- amino -3-, it is characterised in that：The synthetic method includes as follows Step：
1. with the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- as raw material, under water-soluble additive, 10-100 DEG C is heated to, is forced into 0.1-0.5MPa, through aminating agent ammonification 1-6h；
2. step after 1. products obtained therefrom reclaims ammonia and auxiliary agent, is cooled to 0 DEG C, filtering obtains chloro- 5 fluoroforms of 2- amino -3- Yl pyridines.
2. synthetic method according to claim 1, it is characterised in that：The water-soluble additive is C1-C8Alcohol, C1-C8's One or two mixtures in ether.
3. synthetic method according to claim 2, it is characterised in that：The C1-C8Alcohol be methyl alcohol, it is ethanol, propyl alcohol, different One or two mixtures in propyl alcohol, n-butanol.
4. synthetic method according to claim 2, it is characterised in that：The C1-C8Ether for ether, methyl tertiary butyl ether(MTBE), One or two mixtures in tetrahydrofuran.
5. synthetic method according to claim 1, it is characterised in that：The addition of the water-soluble additive is the fluoro- 3- of 2- 0.1-2 times of weight of chloro-5-trifluoromethylpyridine.
6. synthetic method according to claim 5, it is characterised in that：The addition of the water-soluble additive is the fluoro- 3- of 2- 0.5-0.8 times of weight of chloro-5-trifluoromethylpyridine.
7. synthetic method according to claim 1, it is characterised in that：The aminating agent is ammoniacal liquor or ammonia.
8. synthetic method according to claim 1, it is characterised in that：The addition of the aminating agent is that the fluoro- 3- of 2- are chloro- The amount of 1-10 times of material of 5- trifluoromethyl pyridines.
9. synthetic method according to claim 8, it is characterised in that：The addition of the aminating agent is that the fluoro- 3- of 2- are chloro- The amount of 4-6 times of material of 5- trifluoromethyl pyridines.
10. synthetic method according to claim 1, it is characterised in that：The step 1. in reaction temperature be 60-80 DEG C, reaction pressure is 0.15-0.2MPa, and the reaction time is 2-4h.
CN201710246659.9A 2017-04-16 2017-04-16 A kind of synthetic method of the trifluoromethyl pyridine of 2 amino, 3 chlorine 5 Pending CN106866518A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108003093A (en) * 2017-12-07 2018-05-08 山东汇盟生物科技有限公司 Preparation method of 2-hydroxy-3-trifluoromethylpyridine
CN112321496A (en) * 2020-11-20 2021-02-05 内蒙古佳瑞米精细化工有限公司 Method for synthesizing 2-amino-3-chloro-5-trifluoromethylpyridine
CN113527194A (en) * 2021-03-15 2021-10-22 武威广达科技有限公司 Preparation method of 2-amino-3-chloro-5-trifluoromethylpyridine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750705A (en) * 1995-08-21 1998-05-12 Basf Aktiengesellschaft Substituted trifluoromethylpyridines
CN101081833A (en) * 2006-05-29 2007-12-05 山东广恒化工有限公司 Preparation method of 2-amido-3-5-trifluoro picoline
WO2011092618A1 (en) * 2010-01-28 2011-08-04 Finchimica S.P.A. Method for the preparation of fluazinam

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750705A (en) * 1995-08-21 1998-05-12 Basf Aktiengesellschaft Substituted trifluoromethylpyridines
CN101081833A (en) * 2006-05-29 2007-12-05 山东广恒化工有限公司 Preparation method of 2-amido-3-5-trifluoro picoline
WO2011092618A1 (en) * 2010-01-28 2011-08-04 Finchimica S.P.A. Method for the preparation of fluazinam

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Title
SOLTAN Z. KUSOV ET AL.,: "Direct di- and triamination of polyfluoropyridines in anhydrous ammonia", 《JOURNAL OF FLUORINE CHEMISTRY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108003093A (en) * 2017-12-07 2018-05-08 山东汇盟生物科技有限公司 Preparation method of 2-hydroxy-3-trifluoromethylpyridine
CN112321496A (en) * 2020-11-20 2021-02-05 内蒙古佳瑞米精细化工有限公司 Method for synthesizing 2-amino-3-chloro-5-trifluoromethylpyridine
CN112321496B (en) * 2020-11-20 2022-03-04 内蒙古佳瑞米精细化工有限公司 Method for synthesizing 2-amino-3-chloro-5-trifluoromethylpyridine
CN113527194A (en) * 2021-03-15 2021-10-22 武威广达科技有限公司 Preparation method of 2-amino-3-chloro-5-trifluoromethylpyridine
CN113527194B (en) * 2021-03-15 2023-10-03 武威广达科技有限公司 Preparation method of 2-amino-3-chloro-5-trifluoromethyl pyridine

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Application publication date: 20170620