WO2003101921A1 - Procede de synthetisation de cf3-chf-cf2-nr2 - Google Patents

Procede de synthetisation de cf3-chf-cf2-nr2 Download PDF

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Publication number
WO2003101921A1
WO2003101921A1 PCT/JP2003/005920 JP0305920W WO03101921A1 WO 2003101921 A1 WO2003101921 A1 WO 2003101921A1 JP 0305920 W JP0305920 W JP 0305920W WO 03101921 A1 WO03101921 A1 WO 03101921A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound represented
group
chf
substituent
Prior art date
Application number
PCT/JP2003/005920
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English (en)
Japanese (ja)
Inventor
Akihira Sugiyama
Tatsuya Ohtsuka
Original Assignee
Daikin Industries, 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 Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to AU2003235231A priority Critical patent/AU2003235231A1/en
Priority to JP2004509617A priority patent/JP5127114B2/ja
Publication of WO2003101921A1 publication Critical patent/WO2003101921A1/fr

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Classifications

    • 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
    • C07C209/74—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 by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation

Definitions

  • the present invention relates to a method for synthesizing CF 3 —CHF_CF 2 —NR 2
  • R is the same or different and is selected from the group consisting of an alkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an aryl group which may have a substituent At least one group represented by
  • the compound represented by is used as a 7K acid group fluoridating agent.
  • a compound in which R represents an ethyl group that is, a compound of the formula ( ⁇ ′)
  • CF 3 -CF CF 2 ⁇ Et 2 H ⁇ CF 3 -CHF-CF 2 -NEt 2 (III ')
  • the compound represented by is produced. However, since the compound represented by the formula ( ⁇ ) has a boiling point close to that of the compound represented by the formula ( ⁇ ), the compound represented by the formula ( ⁇ ) is obtained when the target product is isolated by distillation. Azeotropes with the desired product. For this reason, in the above reaction, isolation of the target substance by distillation was difficult or complicated.
  • the compound represented by the formula (1 ′) is mixed into the target product, the mixture can also be used as a fluorinating agent. Conversion ability was low.
  • CF 3 - CF CF- NR 2
  • CF 3 - CHF- CF 2 - NR 2 CF- from a mixture of NR 2, CF 3 - CHF- CF 2 - NR 2
  • One of the purposes is to provide a method for synthesizing.
  • the present invention provides the following synthesis method.
  • R is the same or different and includes an alkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an aryl group which may have a substituent Indicate at least one group selected from the group.
  • Item 2 The synthesis method according to Item 1, wherein a mixture of the compound represented by the formula (I) and the compound represented by the formula (II) is reacted with anhydrous HF.
  • the amount of anhydrous HF used is 0.5 to 1 per mole of the compound represented by the formula (I).
  • Item 3 The method according to Item 1 or 2, wherein the amount is 0 mol.
  • Item 4 The method according to Item 1, wherein R is an alkyl group which may have a substituent. 2. The synthesis method according to 2.
  • Item 5 The method according to Item 3, wherein R is an alkyl group which may have a substituent.
  • Item 6 The method for synthesizing the compound represented by the formula (II) according to Item 4, wherein R represents an ethyl group.
  • Item 7 The method for synthesizing the compound represented by the formula (II) according to Item 5, wherein R represents an ethyl group.
  • an alkyl group which may have a substituent means an alkyl group having a substituent and an alkyl group having no substituent.
  • R may be the same or different and may have an alkyl group which may have a substituent, a heterocyclic group which may have a substituent, and a substituent. Shows at least one selected from the group consisting of good aryl groups.
  • alkyl group examples include, but are not particularly limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Chain or branched J 2 to C 2 .
  • An alkyl group is exemplified.
  • linear or branched An alkyl group and more preferably an ethyl group.
  • the heterocyclic group is not particularly limited, piperidyl, furyl, thienyl, imidazolyl, Okisazoriru, thiazolyl, pyrrolyl, pyrrolidinyl, Toria Zoriru, benzothiazolyl, benzimidazolyl, Okisajiazoriru, Chiajia Zoriru, indolyl, pyrazolyl, pyridazinyl, cinnolinyl, quinolyl, Isoquinolyl, quinoxalinyl, pyrazinyl, pyridyl, benzofuryl, benzophenyl, tetrazolyl and the like.
  • Ariru group is not particularly limited, phenyl, naphthyl, ant Lil, is C 6 -C 24 Ariru groups such Fuenantoriru are exemplified. Preferably C fi ⁇ C 14 a ⁇ Li Ichiru group.
  • the number of the substituents is not particularly limited, it is 1 to 5, preferably 1 to 3.
  • Ariru groups and substituents having a substituent Examples of the substituent of the group include a C ⁇ Ce alkyl group, a halogen atom, ( ⁇ to (: 6 alkoxy group, cyano group, nitro group, amino group and the like).
  • the compound represented by the formula (I) is a known compound and can be obtained by the reaction of the formula (III).
  • anhydrous HF may be reacted with a mixture of the compound represented by the formula (I) and the compound represented by the formula (II).
  • This mixture can be obtained by the reaction of the formula (III), but is not limited thereto.
  • the mixing ratio is not particularly limited.
  • the compound represented by the above formula (II) produced by the synthesis method of the present invention is useful as a fluorinating agent (particularly, a fluorinating agent for a hydroxyl group).
  • R is as described above.
  • it is an alkyl group, more preferably, an ethyl group.
  • anhydrous HF is reacted with a compound represented by the formula (I) or a mixture of a compound represented by the formula (I) and a compound represented by the formula (II).
  • Various reaction conditions in this reaction are as follows.
  • the amount of anhydrous HF to be used is not particularly limited as long as the reaction proceeds, but is preferably 0.5 to 10 mol, more preferably 0.5 to 2 mol, per 1 mol of the compound represented by the formula (I). It is.
  • reaction solvent for example, CH 3 CN, DMS0, glyme solvents, CH 2 C1 2, and ether solvents, CH Cl 3, CC, NMP , DMF, CFC-, HCFC-, HFC- flon non solvent such as Protic solvent Etc.
  • the reaction solvent for example, CH 3 CN, DMS0, glyme solvents, CH 2 C1 2, and ether solvents, CH Cl 3, CC, NMP , DMF, CFC-, HCFC-, HFC- flon non solvent such as Protic solvent Etc.
  • the reaction temperature is not particularly limited as long as the reaction proceeds, but is not less than 78 ° to 150 ° (: preferably 0 ° C to 100 ° C, more preferably 10 ° C to 30 ° C.
  • the time can be set as appropriate according to other reaction conditions
  • the reaction pressure may be any of normal pressure, pressure, and reduced pressure, but is preferably normal pressure in view of the simplicity of the reaction system. May be any of an HF atmosphere, an air atmosphere, a nitrogen substitution atmosphere, an Ar atmosphere, and the like, but is preferably an HF atmosphere.
  • CF generated during the synthesis of CF 3 -CHF-CF 2 -NR 2 as a by-product 3 - CF CF- the NR 2 as a raw material, further CF 3 - CHF - CF 2 - NR 2 can be synthesized.
  • the overall yield of CF 3 —CHF—CF 2 —NR 2 is improved, and the amount of the by-products can be extremely reduced, so that CF 3 —CHF—CF 2 —NR 2 It is possible to omit the step of separating the two.
  • CF 3 -CHF-CF 2 -NE t 2 gives a result of azeotrope in the ratio of 80:20, and the mixture is rectified to obtain CF 3 — CHF—CF 2 -NE t 2 alone could not be recovered.
  • CF 3 —CHF_CF 2 —NR 2 is useful as a fluorinating agent (particularly a hydroxyl group fluorinating agent).

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

Abstract

L'invention concerne un processus de production de CF3-CHF-CF2-NR2 utilisé comme agent fluorant. Cette invention concerne également un procédé de synthétisation de ce composé représenté par la formule (II), dans laquelle les R sont identiques ou différents et représentent chacun au moins un élément sélectionné dans le groupe constitué par des alkyles éventuellement substitués, des groupes hétérocycliques éventuellement substitués et des aryles éventuellement substitués, lequel procédé consiste à faire réagir un composé représenté par la formule (I), dans laquelle les R ont la même définition que celle mentionnée ci-dessus, avec du fluorure d'hydrogène anhydre.
PCT/JP2003/005920 2002-05-30 2003-05-13 Procede de synthetisation de cf3-chf-cf2-nr2 WO2003101921A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003235231A AU2003235231A1 (en) 2002-05-30 2003-05-13 Method of synthesizing cf3-chf-cf2-nr2
JP2004509617A JP5127114B2 (ja) 2002-05-30 2003-05-13 Ｃｆ３−ｃｈｆ−ｃｆ２−ｎｒ２合成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-156742 2002-05-30
JP2002156742 2002-05-30

Publications (1)

Publication Number Publication Date
WO2003101921A1 true WO2003101921A1 (fr) 2003-12-11

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PCT/JP2003/005920 WO2003101921A1 (fr) 2002-05-30 2003-05-13 Procede de synthetisation de cf3-chf-cf2-nr2

Country Status (3)

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JP (1) JP5127114B2 (fr)
AU (1) AU2003235231A1 (fr)
WO (1) WO2003101921A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7196226B2 (en) * 2003-12-18 2007-03-27 Lanxess Deutschland Gmbh Fluoraminoolefins and fluorination reagents which can be prepared therefrom
JP2009196939A (ja) * 2008-02-22 2009-09-03 Tosoh F-Tech Inc フッ素化試薬組成物およびｇｅｍ−ジフルオロ化合物の製造方法
CN104478732A (zh) * 2014-12-18 2015-04-01 山东国邦药业股份有限公司 一种连续制备Ishikawa氟化剂的方法及实现该方法的反应装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0773206A1 (fr) * 1994-07-14 1997-05-14 Daikin Industries, Ltd. Procede de production de 1,1,1,2,3,3,3-heptafluoropropane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0773206A1 (fr) * 1994-07-14 1997-05-14 Daikin Industries, Ltd. Procede de production de 1,1,1,2,3,3,3-heptafluoropropane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AKIO TAKAOKA ET AL.: "Alcohol oyobi karubon-san no fusso-ka-zai to shiteno hexafluoropropene-dialkyl amine fukatai no yuko riyo - tetrafluoropropionic amidine, tetrafluoroethyl chikan benzo shukugo fukusokan kagobutsu oyobi fluorocytosine yudotai no gosei", JOURNAL OF THE CHEMICAL SOCIETY OF JAPAN, no. 11, 1985, pages 2161 - 2168, XP002954033 *
TAKAOKA A. ET AL.: "F-propene-dialkylamine reaction products as fluorinating agents", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 52, no. 11, 1979, pages 3377 - 3380, XP002971347 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7196226B2 (en) * 2003-12-18 2007-03-27 Lanxess Deutschland Gmbh Fluoraminoolefins and fluorination reagents which can be prepared therefrom
JP2009196939A (ja) * 2008-02-22 2009-09-03 Tosoh F-Tech Inc フッ素化試薬組成物およびｇｅｍ−ジフルオロ化合物の製造方法
CN104478732A (zh) * 2014-12-18 2015-04-01 山东国邦药业股份有限公司 一种连续制备Ishikawa氟化剂的方法及实现该方法的反应装置
CN104478732B (zh) * 2014-12-18 2017-01-11 山东国邦药业股份有限公司 一种连续制备Ishikawa氟化剂的方法及实现该方法的反应装置

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JPWO2003101921A1 (ja) 2005-09-29
AU2003235231A1 (en) 2003-12-19
JP5127114B2 (ja) 2013-01-23

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