WO2004035529A1 - Procede de production de n-(2-amino-1,2-dicyanovinyl)formamidine - Google Patents

Procede de production de n-(2-amino-1,2-dicyanovinyl)formamidine Download PDF

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Publication number
WO2004035529A1
WO2004035529A1 PCT/JP2003/013113 JP0313113W WO2004035529A1 WO 2004035529 A1 WO2004035529 A1 WO 2004035529A1 JP 0313113 W JP0313113 W JP 0313113W WO 2004035529 A1 WO2004035529 A1 WO 2004035529A1
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WO
WIPO (PCT)
Prior art keywords
amd
reaction
hydrochloride
producing
added
Prior art date
Application number
PCT/JP2003/013113
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English (en)
Japanese (ja)
Inventor
Mitsuru Takase
Masami Hatano
Yoshikazu Itou
Original Assignee
Nippon Soda Co.,Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co.,Ltd. filed Critical Nippon Soda Co.,Ltd.
Priority to AU2003272991A priority Critical patent/AU2003272991A1/en
Priority to JP2004544941A priority patent/JP4356111B2/ja
Publication of WO2004035529A1 publication Critical patent/WO2004035529A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms

Definitions

  • the present invention relates to a compound of the formula (1) useful as an agrochemical intermediate: (1) A method for producing N- (2-amino-1,2-dicyanovinyl) formamidine
  • the present invention relates to a method for producing N- (amino-1,2-disocyanovinyl) formamidine (AMD) represented by the formula: Conventional technology:
  • Japanese Patent Application Laid-Open No. 2001-158776 discloses a method for producing an amidine derivative represented by the following reaction formula.
  • the substituent represented by is an alkyl group or the like, and the compound of the present invention is not disclosed.
  • This reaction is thought to be via an imidoyl chloride obtained by reacting a cyano compound with hydrogen chloride as an intermediate.
  • a compound of hydrogen that is, hydrogen cyanide
  • the corresponding imidoyl chloride is produced or It was not known whether the imidoyl chloride formed was stable or not, and it was not known at all as an AMD manufacturing method.
  • DISCLOSURE OF THE INVENTION The object of the present invention is to provide an industrially superior method for producing AMD.
  • the present inventors have conducted intensive studies on the industrial production process of AMD and found that the desired product can be obtained in high yield by reacting with an ether-based solvent such as dioxane, and completed the present invention.
  • the present invention is a method for producing AMD, which comprises reacting DAMN, hydrogen chloride, and hydrogen cyanide in an organic solvent.
  • the reaction is carried out by dissolving hydrogen cyanide in an organic solvent and blowing hydrogen chloride, and then adding DAMN.
  • the organic solvent used in the reaction is not particularly limited as long as it is a solvent inert to the reaction, and examples thereof include ether solvents such as dioxane and tetrahydrofuran, and halogen solvents such as chloroform, and methylene chloride. Solvents are preferred, and cyclic ethers such as dioxane are particularly preferred.
  • the reaction temperature is between ⁇ 20 and 30 ° C., preferably between 0 and 10 ° C. — If the temperature is lower than 20 ° C, the reaction speed becomes slow. If the temperature is higher than 30 ° C, generated AMD is decomposed and hydrogen cyanide escapes out of the system, which is not preferable.
  • the amount of the solvent used in the reaction is not particularly limited, but is 0.5 to 5 liters, preferably 1 to 2 liters per mole of DAMN.
  • the number of moles of the reaction is 1 to 5 moles, preferably 1.1 to 1.3 moles, of hydrogen cyanide per mole of DAMN, and hydrogen chloride is 2 to 3 moles, preferably 2 to 2.4 moles, based on hydrogen cyanide.
  • the reaction is usually completed in 1 to 10 hours. After the reaction is completed, the slurry is removed and dried to obtain the hydrochloride salt of AMD.However, when dioxane or the like is used, the solvent is incorporated into the crystals, so the crude crystals containing the solvent are once converted to alcohol, etc. After dissolving in water, the solvent is distilled off to obtain a high-purity AMD hydrochloride.
  • AMD can be a raw material for various compounds as shown below. 1. Synthesis of 4 (5) -amino-5 (4) -cyanoimidazole (AICN)
  • the desired product When reacting with AMD hydrochloride, the desired product can be obtained in high yield by suspending the mixture in an organic solvent or an aqueous solvent and dropping an aqueous solution of sodium hydroxide such as aqueous sodium hydroxide.
  • the organic solvent used in the reaction is not particularly limited as long as it is a solvent inert to the reaction, and the same solvents as those used in the production of AMD can be used.
  • the reaction is carried out without isolating AMD hydrochloride, it is advantageous to use the solvent used for producing AMD as it is.
  • the reaction temperature is -20 to 30 ° C, preferably 10 to 20 ° C. If the temperature is lower than -20 ° C, the reaction speed will be slow.
  • the amount of the solvent used in the reaction is not particularly limited, but is 0.5 to 5 liters, preferably:! To 2 liters per mole of AMD hydrochloride.
  • the number of moles of the reaction is 3 to 5 moles, preferably 3.2 to 3.8 moles of alkali per mole of AMD hydrochloride.
  • the reaction is usually completed in 1 to 5 hours. After completion of the reaction, the product is neutralized with an acid, extracted with an organic solvent, and concentrated to obtain crude crystalline AICN.
  • the target product After cooling in an organic solvent of AMD hydrochloride and adding dropwise an aqueous solution of sodium hydroxide or the like, the target product can be obtained in high yield by heating to reflux.
  • the number of moles of the reaction is 4 to 10 moles, preferably 5 moles per mole of AMD hydrochloride. ⁇ 6 moles.
  • crude crystals AICA can be obtained by neutralizing with an acid and extracting with an organic solvent, or concentrating as it is.
  • the target compound can be obtained in high yield by heating and refluxing the AMD hydrochloride dissolved or suspended in an organic solvent.
  • the amount of hydrochloric acid used to produce AMD hydrochloride is 2.5 to 3.5 moles per mole of DAMN, which is higher than the usual AMD manufacturing conditions, so that it can be manufactured in one pot. Is possible.
  • DCI When AMD is isolated, DCI can also be obtained by heating in a polar solvent such as acetic acid.
  • a polar solvent such as acetic acid.
  • the production method of the present invention is, as is clear from the above-mentioned Reference Examples, capable of producing AMD which can be used as various agrochemical intermediates under mild conditions and in a high yield, and thus is industrially excellent. It is a manufacturing method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé, efficace du point de vue industriel, de production de N-(2-amino-1,2-dicyanovinyl)formamidine (AMD) qui est représentée par la formule (I) et qui est utile en tant qu'intermédiaire pour des produits chimiques à usage agricole et pour des médicaments. Dans le procédé selon l'invention, on fait réagir, dans un solvant organique, du diaminomaléonitrile (DAMN) avec du chlorure d'hydrogène et du cyanure d'hydrogène pour produire de l'hydrochlorure AMD à un rendement élevé. Formule (I)
PCT/JP2003/013113 2002-10-16 2003-10-14 Procede de production de n-(2-amino-1,2-dicyanovinyl)formamidine WO2004035529A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003272991A AU2003272991A1 (en) 2002-10-16 2003-10-14 Process for producing n-(2-amino-1,2-dicyanovinyl)formamidine
JP2004544941A JP4356111B2 (ja) 2002-10-16 2003-10-14 Ｎ−（２−アミノ−１，２−ジシアノビニル）ホルムアミジンの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002301978 2002-10-16
JP2002-301978 2002-10-16

Publications (1)

Publication Number Publication Date
WO2004035529A1 true WO2004035529A1 (fr) 2004-04-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/013113 WO2004035529A1 (fr) 2002-10-16 2003-10-14 Procede de production de n-(2-amino-1,2-dicyanovinyl)formamidine

Country Status (3)

Country Link
JP (1) JP4356111B2 (fr)
AU (1) AU2003272991A1 (fr)
WO (1) WO2004035529A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008266202A (ja) * 2007-04-19 2008-11-06 Nippon Soda Co Ltd アミノイミダゾール誘導体の製造方法
WO2008133169A1 (fr) 2007-04-19 2008-11-06 Nippon Soda Co., Ltd. Procédé de production de n-(2-amino-1,2-dicyanovinyl)imidate, procédé de production de n-(2-amino-1,2-dicyanovinyl)formamidine et procédé de production d'un dérivé d'amino-imidazole
CN111362875A (zh) * 2020-04-23 2020-07-03 西安瑞联新材料股份有限公司 一种4-氨基-5-咪唑甲酰胺的工业化生产方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002155059A (ja) * 2000-11-17 2002-05-28 Nippon Soda Co Ltd ４−アミノ−５−シアノイミダゾール誘導体及びその中間体の製造方法
EP1215206A1 (fr) * 1999-09-20 2002-06-19 Nippon Soda Co., Ltd. Procede de preparation de 4(5)-amino-5(4)-carboxamidoimidazoles et de leurs produits intermediaires

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1215206A1 (fr) * 1999-09-20 2002-06-19 Nippon Soda Co., Ltd. Procede de preparation de 4(5)-amino-5(4)-carboxamidoimidazoles et de leurs produits intermediaires
JP2002155059A (ja) * 2000-11-17 2002-05-28 Nippon Soda Co Ltd ４−アミノ−５−シアノイミダゾール誘導体及びその中間体の製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008266202A (ja) * 2007-04-19 2008-11-06 Nippon Soda Co Ltd アミノイミダゾール誘導体の製造方法
WO2008133169A1 (fr) 2007-04-19 2008-11-06 Nippon Soda Co., Ltd. Procédé de production de n-(2-amino-1,2-dicyanovinyl)imidate, procédé de production de n-(2-amino-1,2-dicyanovinyl)formamidine et procédé de production d'un dérivé d'amino-imidazole
KR101156497B1 (ko) * 2007-04-19 2012-06-18 닛뽕소다 가부시키가이샤 아미노이미다졸 유도체의 제조 방법
US8258333B2 (en) 2007-04-19 2012-09-04 Nippon Soda Co., Ltd. Method for production of N-(2-amino-1,2-dicyanovinyl)imidates, method for production of N-(2-amino-1,2-dicyanovinyl)formamidine, and method for production of aminoimidazole derivatives
US8273899B2 (en) 2007-04-19 2012-09-25 Nippon Soda Co., Ltd. Method for production of N-(2-amino-1,2-dicyanovinyl)imidates, method for production of N-(2-amino-1,2-dicyanovinyl)formamidine, and method for production of aminoimidazole derivatives
CN102850238A (zh) * 2007-04-19 2013-01-02 日本曹达株式会社 N-（2-氨基-1,2-二氰基乙烯基）甲脒的制造方法
CN102850277A (zh) * 2007-04-19 2013-01-02 日本曹达株式会社 氨基咪唑衍生物的制造方法
US8785654B2 (en) 2007-04-19 2014-07-22 Nippon Soda Co., Ltd. Method for production of N-(2-amino-1,2-dicyanovinyl)imidates, method for production of N-(2-amino-1,2-dicyanovinyl)formamidine, and method for production of aminoimidazole derivatives
CN111362875A (zh) * 2020-04-23 2020-07-03 西安瑞联新材料股份有限公司 一种4-氨基-5-咪唑甲酰胺的工业化生产方法

Also Published As

Publication number Publication date
JPWO2004035529A1 (ja) 2006-02-16
JP4356111B2 (ja) 2009-11-04
AU2003272991A1 (en) 2004-05-04

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