EP2531513A1 - Hydrazides de phosphinyle - Google Patents

Hydrazides de phosphinyle

Info

Publication number
EP2531513A1
EP2531513A1 EP11701010A EP11701010A EP2531513A1 EP 2531513 A1 EP2531513 A1 EP 2531513A1 EP 11701010 A EP11701010 A EP 11701010A EP 11701010 A EP11701010 A EP 11701010A EP 2531513 A1 EP2531513 A1 EP 2531513A1
Authority
EP
European Patent Office
Prior art keywords
fluorinated
independently
linear
another
perfluorinated
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11701010A
Other languages
German (de)
English (en)
Inventor
Nikolai Ignatyev (/Mykola)
Wolfgang Hierse
Dana Bejan
Helge Willner
Dinoiu Vasile
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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 Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to EP11701010A priority Critical patent/EP2531513A1/fr
Publication of EP2531513A1 publication Critical patent/EP2531513A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/36—Amides thereof

Definitions

  • This invention relates to fluorinated phosphinyl hydrazides, a process for their preparation, and the use of these compounds, especially in organic synthesis.
  • Acylhydrazides are common reagents in the synthesis of heterocyclic compounds and are well know buildings blocks in organic chemistry (The Chemistry of Heterocyclic Compounds, E.C. Teylor, P. Wipf (Eds.), John Wiley and Sons: New. Jersey, 2004). Only few phosphinyl hydrazides are described in the literature, namely: Ph 2 P(O)NHNH 2 , Ph 2 P(O)NHN(CH 3 ) 2 (D.E.C. Corbridge, Phosphorus. An Outline of its Chemistry, Biochemistry and Technology (Second Edition), Elsvier, Amsterdam-Oxford-N.Y., 1980, p.
  • the present invention provides phosphinyl hydrazides of formula (I)
  • RF independently of one another are fluorinated linear or fluorinated branched alkyl, optionally comprising one or more oxygen atoms, or fluorinated phenyl or fluorinated alkylphenyl
  • R 1 , R 2 and R 3 independently of one another are H, phenyl, substituted phenyl, alkylphenyl, linear or branched alkyi optionally comprising one or more aromatic rings, heteroaromatic ring, oxygen atoms, sulfur atoms, double bonds and/or triple bonds, whereby one or more H atoms may be
  • halogen especially CI and/or F atoms.
  • RF independently of one another are perfluorinated linear or perfluorinated branched alkyi or perfluorinated phenyl.
  • Preferred alkyi derivatives are compounds wherein R F independently of one another are perfluorinated linear or perfluorinated branched Ci bis C 2 o alkyi, especially 0,2 bis Ci 2 alkyi.
  • R F independently of one another are perfluorinated linear or perfluorinated branched Ci bis C 2 o alkyi, especially 0,2 bis Ci 2 alkyi.
  • R F independently of one another are perfluorinated linear or perfluorinated branched Ci bis C 2 o alkyi, especially 0,2 bis Ci 2 alkyi.
  • R F independently of one another are perfluorinated linear or perfluorinated branched Ci bis C 2 o alkyi, especially 0,2 bis Ci 2 alkyi.
  • R F independently of one another are perfluorinated linear or perfluorinated branched Ci bis C 2 o al
  • perfluorinated linear or perfluorinated branched C 2 bis C 6 alkyi or perfluorinated phenyl independently of one another are perfluorinated linear or perfluorinated branched C 2 bis C 6 alkyi or perfluorinated phenyl.
  • R 1 , R 2 and R 3 are preferably independently of one another linear or branched Ci bis C 20 alkyi, especially Ci bis Ci 2 alkyi, or substituted or unsubstituted phenyl or benzyl.
  • phenyl and/or benzyl are substituted with one or more Ci bis C 6 alkyi, especially with C-i bis C 4 alkyi.
  • R F and R 1 , R 2 and R 3 have the preferred meanings.
  • a second subject matter of this invention is the use of fluorinated
  • fluorinated phosphinyl hydrazides of formula (I) can be used as phase-transfer catalysts, surfactants, lubricants, plasticizers, flames retardants, foams forming agents, starting material for generating of stable radicals and synthesis of molecular magnetic materials for molecular recognition by spectroscopic methods, antioxidants, components or additives to polymeric or painting compositions, or as additives to
  • a further subject matter of this invention is a process for the preparation of fluorinated phosphiny! hydrazides of formula (I) via reaction of hydrazines of formula (II)
  • RF independently of one another are fluorinated linear or
  • fluorinated branched alkyl optionally comprising one or more oxygen atoms, or fluorinated phenyl or fluorinated alkylphenyl, R 1 , R 2 and R 3 independently of one another are H, phenyl, substituted phenyl,
  • alkylphenyl linear or branched alkyl optionally comprising one or more aromatic rings, heteroaromatic ring, oxygen atoms, sulfur atoms, double bonds and/or triple bonds, whereby one or more H atoms may be
  • halogen especially CI and/or F atoms
  • X is halogen, especially CI or F.
  • RF independently of one another are perfluorinated linear or perfluorinated branched alkyl or perfluorinated phenyl.
  • Preferred alkyl derivatives are compounds wherein R F independently of one another are perfluorinated linear or perfluorinated branched Ci bis C 20 alkyi, especially C 2 bis C 12 alkyi. Especially preferred are compounds wherein R F
  • perfluorinated linear or perfluorinated branched C 2 bis C-6 alkyi or perfluorinated phenyl independently of one another are perfluorinated linear or perfluorinated branched C 2 bis C-6 alkyi or perfluorinated phenyl.
  • R , R 2 and R 3 are preferably independently of one another linear or branched C-i bis C2 0 alkyi, especially Ci bis C 12 alkyi, or substituted or unsubstituted phenyl or benzyl.
  • phenyl and/or benzyl are substituted with one or more d bis C 6 alkyi, especially with Ci bis C 4 alkyi.
  • phosphinic acid derivatives especially chlorides, or fluorides, but also from less reactive corresponding phosphine oxides.
  • fluorinated bis(alkyl)- or fluorinated bis(phenyl)-phosphinic acid chlorides or fluorides may be used.
  • the preferred processes are:
  • RF independently of one another are perfluorinated linear or perfluorinated branched alkyl or perfluorinated phenyl.
  • R F independently of one another are perfluorinated linear or perfluorinated branched C 2 bis C 12 alkyl, optionally comprising one or more oxygen atoms are preferred.
  • R 1 , R 2 and R 3 are preferably independently of one another linear or branched Ci bis C 2 0 alkyl- Especially preferred are the compounds in which R F are identical.
  • R F and R 1 , R 2 and R 3 have the preferred meanings.
  • phosphinyl hydrazides of formula (I) are prepared via reaction of fluorinated tris(alkyl)- or fluorinated tris(phenyl)-phosphine oxides with corresponding hydrazines.
  • preferred starting materials for the application in the synthesis of bis(perfluoroalkyl)phosphinyl hydrazides are: tris(pentafluoroethyl)phosphine oxide, or bis(pentafluoroethyl)phosphinyl chloride in combination with methylhydrazine, phenylhydrazine, 1 ,1- dimethylhydrazine, or 3,5-di-f-butyl-4-hydroxy-benzyl hydrazine.
  • Tris(perfluoroalkyl)phosphine oxides can be easily prepared (V.Ya.
  • the process of the invention for the preparation of fluorinated phosphinyl hydrazides of formula (I) is preferably conducted at a temperature range of from -60°C up to 120°C, depending from the compounds used.
  • the reaction is carried out at a temperature range of from -40°C up to room temperature (approximately 25°C), wherein the reaction temperature is in a range of from -40°C up to -10°C, when phosphinic acid derivatives are used and in a range of from -10°C up to room temperature (approximately 25°C), when phosphine oxides are used.
  • the reaction time depends from the compounds used and it is usually between 10 minutes and 24 hours. The skilled man in the art can easily adapt the reaction temperature and time to the reactivity of the compounds used.
  • Preferred reaction solvents are organic solvents, preferably polar-aprotic solvents.
  • the reaction can be conducted in acetonitrile, N,N- dimethylformamide, ⁇ , ⁇ -dimethylacetamide, N-methylpyrrolidone and/or other amides of secondary amines.
  • acetonitrile is especially preferred.
  • the compounds of formula (I) are purified by usual methods, e.g. by destination, crystallization, extraction, filtration, etc.
  • NMR spectra were measured in CD 3 CN solution at room temperature on a Bruker Avance DRX-400 ( 1 H, 400.13 MHz; 19 F, 376.49 MHz; 31 P, 161.97 MHz) spectrometer. The chemical shifts were referenced to external TMS ( H), CFCI 3 ( 19 F) and H 3 P0 4 ( 31 P). UV-spectra were recorded on Lambda EZ210 Spectrophotometer with Deuterium (D2) lamp (UV) and Tungsten Iodide lamp (Vis).
  • D2 Deuterium
  • Vis Tungsten Iodide lamp
  • a dry 25 ml flask, equipped with PTFE Young valve, is charged with 0.47 g (4.3 mmol) of phenylhydrazine, 1 ml of dry acetonitrile and 1.9 g (4.7 mmol) of tris(pentafluoroethyl)phosphine oxide, (C 2 F 5 ) 3 P O. After one hour at room temperature the homogeneous solution is formed. To complete the reaction, the mixture is left stirred at room temperature for 20 hours and then all volatile products are removed under high vacuum (10 "3 mbar).
  • NMR spectra are recorded in the dry acetonitrile-D 3 and confirm the formation of bis(pentafluoroethyl)phosphinyl- N(3,5-di-i-butyl-4-hydroxy-benzyl)hydrazide, (C 2 F 5 ) 2 P(O)NHNHCH 2 [3,5-(f- C 4 H9) 2 -C 6 H 2 -4-OH].

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Abstract

Hydrazides de phosphinyle fluorés, leur procédé de préparation, et leur utilisation, notamment en synthèse organique.
EP11701010A 2010-02-02 2011-01-18 Hydrazides de phosphinyle Withdrawn EP2531513A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11701010A EP2531513A1 (fr) 2010-02-02 2011-01-18 Hydrazides de phosphinyle

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10001011 2010-02-02
PCT/EP2011/000189 WO2011095277A1 (fr) 2010-02-02 2011-01-18 Hydrazides de phosphinyle
EP11701010A EP2531513A1 (fr) 2010-02-02 2011-01-18 Hydrazides de phosphinyle

Publications (1)

Publication Number Publication Date
EP2531513A1 true EP2531513A1 (fr) 2012-12-12

Family

ID=43770442

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11701010A Withdrawn EP2531513A1 (fr) 2010-02-02 2011-01-18 Hydrazides de phosphinyle

Country Status (2)

Country Link
EP (1) EP2531513A1 (fr)
WO (1) WO2011095277A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH594042A5 (fr) * 1973-10-31 1977-12-30 Ciba Geigy Ag
DE19846636A1 (de) 1998-10-09 2000-04-13 Merck Patent Gmbh Elektrochemische Synthese von Perfluoralkylfluorophosphoranen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011095277A1 *

Also Published As

Publication number Publication date
WO2011095277A1 (fr) 2011-08-11

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