WO1995026340A1 - Procede d'obtention de cyanopyridine - Google Patents
Procede d'obtention de cyanopyridine Download PDFInfo
- Publication number
- WO1995026340A1 WO1995026340A1 PCT/JP1995/000587 JP9500587W WO9526340A1 WO 1995026340 A1 WO1995026340 A1 WO 1995026340A1 JP 9500587 W JP9500587 W JP 9500587W WO 9526340 A1 WO9526340 A1 WO 9526340A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- atom
- cyanopyridine
- trichloromethylpyridine
- reaction
- present
- Prior art date
Links
Classifications
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
Definitions
- the present invention relates to a method for producing cyanoviridines useful as intermediates for producing agricultural chemicals.
- a method for producing cyanopyridines for example, a method is known in which nicotinamide is reacted with phosphorus pentachloride to obtain 2-chloro-3-cyanopyridine in a yield of 30%. [Org. Syn., Coll. Vol. IV, 166 (1963)].
- this method uses phosphorus pentachloride, so the operation is complicated, and the reaction for converting an acid amide group into a nitrile group and the chlorination reaction of the nucleus simultaneously proceed to produce a perchlorinated product.
- the reaction involves many side reactions, and the yield of the desired product is not sufficient. Therefore, it was not a satisfactory method for selectively producing the desired cyanoviridines.
- An object of the present invention is to solve the conventional problems and to provide a method capable of producing a cyanopyridine safely, industrially, and inexpensively by suppressing side reactions.
- the present inventors have conducted intensive studies to achieve the above object, and found that trichloromethyl having at least one halogen atom at the 2- or 6-position of the pyridine ring as a raw material in the presence of an oxide or halide of copper or zinc. It was recognized that the conventional problems could be solved by reacting the compound with ammonium hydride using pyridines, and as a result of further research, the present invention was completed. Disclosure of the invention
- the present invention relates to the general formula
- M represents a copper atom or a zinc atom
- X represents a halogen atom or an oxygen atom
- m represents an integer of 2 or 1.
- R represents a hydrogen atom or a halogen atom
- XI and X 2 each represent a hydrogen atom or a halogen atom (at least one of X 1 and X 2 is a halogen atom)
- n is 1 or 2 Indicates the integer of.
- the present invention provides a method for producing cyanopyridines represented by
- the trichloromethylpyridines represented by the general formula (1) used in the method of the present invention may be any one of the general formula (1) wherein the substituents X 1 and X 2 are each a hydrogen atom, a chlorine atom, a fluorine atom, A halogen atom including a bromine atom and an iodine atom (hereinafter, may be simply referred to as a “halogen atom”) (provided that at least one of XI and X 2 is a halogen atom); Represents a hydrogen atom, or a halogen atom including a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom; ⁇ represents an integer of 1 or 2; therefore, trichloromethylpyridines which may have a plurality of substituents R (hereinafter, referred to as However, such trichloromethylpyridines may be simply described as “trichloromethylpyridines (1)”.
- any one usually used as such may be used, and specific examples thereof include ammonium chloride, ammonium bromide, and ammonium iodide. Among them, ammonium chloride is easily available and preferred.
- the amount of the ammonium halide used is in the range of 1 equivalent to 10 equivalents, preferably 1 equivalent to 3 equivalents, more preferably 1.2 equivalents to 1.5 equivalents to trichloromethylpyridines (1). Can be exemplified.
- metal compound (2) The metal compound represented by the general formula (2) used in the method of the present invention
- metal compound (2) may be simply referred to as “metal compound (2)”.
- copper halides such as cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide
- cupric oxide Copper oxides such as cuprous oxide
- zinc halides such as stannic chloride, zinc chloride, zinc bromide, zinc bromide, zinc zinc iodide, zinc zinc iodide
- acid or halides of copper or zinc such as zinc oxide.
- cupric chloride and cupric oxide are preferred because they are easily available and inexpensive.
- the amount of the metal compound (2) to be used is, for example, in the range of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on trichloromethylpyridines (1).
- the reaction is carried out in a temperature range of 100 ° C. to 250 ° C., preferably 170 ° C. to 230 ° C., under normal pressure or pressurized condition.
- a cyanopyridine represented by the general formula (3) [hereinafter, such a cyanopyridine may be simply referred to as “cyanoviridine (3)”. ] Can be obtained.
- the order of adding the trichloromethylpyridines (1), the ammonium halide, and the metal compound (2) to the reaction vessel is arbitrary, and any of the raw materials may be added first.
- the use of a solvent is optional, and the reaction proceeds smoothly even without the use of a solvent. It is sufficient to consider whether to use a solvent or not, but it is preferable to use a solvent in terms of yield.
- a solvent inert to the reaction for example, sulfolane is suitable.
- Examples of the cyanopyridines (3) produced by the method of the present invention include 2-chloro-5-cyanopyridine, 2-chloro-3-cyanopyridine, 2-bromo-5-cyanopyridine, 2-bromo-3-cyanopyridine and 3-cyanopyridine.
- Fluoropyridine 5-cyano 2-fluoropyridine, 2,3-dichloro-1-5-cyanopyridine, 2,6-dichloro-3-cyanopyridine, 3-bromo-12-chloro-5-cyanopyridine, 2,6-dibromo-13-cyanopyridin , 2,3,6-trichloro-5-cyanopyridine, 3-bromo-2,6-dichloro-5-cyanopyridine, 2,3,4,6-tetrachloro-5-cyanoviridine, 5-cyano 2,3, 4, 6-tetrafluoropyridine, 2, 6-di Black mouth 1-cyano 3-fluoropyridine and the like.
- the raw material trichloromethylpyridines (1) used in the method of the present invention are partially commercially available, and those which are not may be obtained by halogenating 3-trichloromethylpyridin by a known method. Can be.
- the cyanopyridines (3) obtained by the method of the present invention can be derivatized to aminomethyl pyridines by reducing the cyano group by a known method to form an aminomethyl group. According to the method described in Japanese Patent Laid-Open No. Hei 41-15454741, it is also possible to easily induce a compound to be an active ingredient of an insecticide.
- the use of a compound having at least one halogen atom at the 2- or 6-position of the pyridine ring as a raw material allows the polymer to be formed or to be produced depending on the temperature or operating conditions during the reaction.
- the objective reaction can proceed smoothly by suppressing a side reaction which is likely to occur in the reaction of the compound having a pyridine ring.
- 3-trichloromethylpyridines in which the 2-position and the 6-position of the pyridine ring are all hydrogen atoms are used as a raw material for the present method, favorable results are obtained as described below as a reference example. Absent.
- the present invention will be described more specifically with reference to Examples and Reference Examples.
- the obtained toluene layer was subjected to gas chromatography to remove sulfolane. After thoroughly washing with water and drying over anhydrous sodium sulfate, the extraction solvent was distilled off under reduced pressure. Further, the obtained residue was subjected to distillation under reduced pressure to obtain 21.1 g of the desired product as a fraction having a boiling point of 134 ° CZ 23 mmHg. (Yield 76%)
- the present invention by a simple method of reacting trichloromethylpyridines (1) with an ammonium halide in the presence of a metal compound (2), side reactions such as nuclear halogenation can be suppressed, and the cyanopyridines can be industrially produced. Now you can get it. Since the method of the present invention does not include a diazotization step, it is an industrially safe method with no danger of explosion and the like, and is useful as an industrial production method of cyanopyridines (3).
- the cyanopyridines (3) obtained by carrying out the method of the present invention can be reduced with hydrogen or the like to give aminos, which are important intermediates of insecticides described in JP-A-4-154571, for example. It can be easily converted to methylpyridines.
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69501029T DE69501029T2 (de) | 1994-03-29 | 1995-03-29 | Verfahren zur herstellung von cyanopyridin |
KR1019950705052A KR100332140B1 (ko) | 1994-03-29 | 1995-03-29 | 시아노피리딘류의제조방법 |
US08/549,667 US5675012A (en) | 1994-03-29 | 1995-03-29 | Process for production of cyanopyridine |
JP52509795A JP3805788B2 (ja) | 1994-03-29 | 1995-03-29 | シアノピリジン類の製造方法 |
EP95913365A EP0700903B1 (en) | 1994-03-29 | 1995-03-29 | Process for producing cyanopyridine |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6/82276 | 1994-03-29 | ||
JP8227694 | 1994-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995026340A1 true WO1995026340A1 (fr) | 1995-10-05 |
Family
ID=13769980
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1995/000587 WO1995026340A1 (fr) | 1994-03-29 | 1995-03-29 | Procede d'obtention de cyanopyridine |
Country Status (7)
Country | Link |
---|---|
US (1) | US5675012A (ja) |
EP (1) | EP0700903B1 (ja) |
JP (1) | JP3805788B2 (ja) |
KR (1) | KR100332140B1 (ja) |
DE (1) | DE69501029T2 (ja) |
ES (1) | ES2109819T3 (ja) |
WO (1) | WO1995026340A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998043958A1 (de) * | 1997-04-01 | 1998-10-08 | Bayer Aktiengesellschaft | Verfahren zur herstellung von 2,6-dichlor-5-fluornicotinonitril und die chemische verbindung 3-cyano-2-hydroxy-5-fluorpyrid-6-on-mononatriumsalz sowie dessen tautomere |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19647527C1 (de) * | 1996-11-16 | 1998-03-12 | Degussa | Verfahren zur Herstellung von Cyanoverbindungen durch Ammonoxidation |
US6781666B2 (en) * | 1999-07-16 | 2004-08-24 | Minolta Co., Ltd. | Liquid crystal display and method to manufacture the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6028938A (ja) * | 1983-07-27 | 1985-02-14 | Sumitomo Chem Co Ltd | ナイトロオキシデ−ションによるニトリル類の製造方法 |
-
1995
- 1995-03-29 JP JP52509795A patent/JP3805788B2/ja not_active Expired - Fee Related
- 1995-03-29 ES ES95913365T patent/ES2109819T3/es not_active Expired - Lifetime
- 1995-03-29 KR KR1019950705052A patent/KR100332140B1/ko not_active IP Right Cessation
- 1995-03-29 WO PCT/JP1995/000587 patent/WO1995026340A1/ja active IP Right Grant
- 1995-03-29 DE DE69501029T patent/DE69501029T2/de not_active Expired - Lifetime
- 1995-03-29 US US08/549,667 patent/US5675012A/en not_active Expired - Lifetime
- 1995-03-29 EP EP95913365A patent/EP0700903B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6028938A (ja) * | 1983-07-27 | 1985-02-14 | Sumitomo Chem Co Ltd | ナイトロオキシデ−ションによるニトリル類の製造方法 |
Non-Patent Citations (2)
Title |
---|
Ann. Chem., Vol. 487 (1931), pages 127 to 133. * |
Org. Syn., Col. 1, Vol. IV (1963), page 166. * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998043958A1 (de) * | 1997-04-01 | 1998-10-08 | Bayer Aktiengesellschaft | Verfahren zur herstellung von 2,6-dichlor-5-fluornicotinonitril und die chemische verbindung 3-cyano-2-hydroxy-5-fluorpyrid-6-on-mononatriumsalz sowie dessen tautomere |
Also Published As
Publication number | Publication date |
---|---|
EP0700903B1 (en) | 1997-11-12 |
EP0700903A4 (en) | 1996-07-31 |
KR960702441A (ko) | 1996-04-27 |
DE69501029T2 (de) | 1998-03-05 |
EP0700903A1 (en) | 1996-03-13 |
DE69501029D1 (de) | 1997-12-18 |
US5675012A (en) | 1997-10-07 |
JP3805788B2 (ja) | 2006-08-09 |
KR100332140B1 (ko) | 2002-09-05 |
ES2109819T3 (es) | 1998-01-16 |
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