WO2011095277A1 - Phosphinyl hydrazides - Google Patents

Phosphinyl hydrazides Download PDF

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Publication number
WO2011095277A1
WO2011095277A1 PCT/EP2011/000189 EP2011000189W WO2011095277A1 WO 2011095277 A1 WO2011095277 A1 WO 2011095277A1 EP 2011000189 W EP2011000189 W EP 2011000189W WO 2011095277 A1 WO2011095277 A1 WO 2011095277A1
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Prior art keywords
fluorinated
independently
linear
another
perfluorinated
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PCT/EP2011/000189
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French (fr)
Inventor
Nikolai Ignatyev (/Mykola)
Wolfgang Hierse
Dana Bejan
Helge Willner
Dinoiu Vasile
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Merck Patent Gmbh
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Priority to EP11701010A priority Critical patent/EP2531513A1/en
Publication of WO2011095277A1 publication Critical patent/WO2011095277A1/en

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    • 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].

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Molecular Biology (AREA)

Abstract

This invention relates to fluorinated phosphinyl hydrazides, a process for their preparation, and the use of these compounds, especially in organic synthesis.

Description

Phosphinyl Hydrazides
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: Ph2P(O)NHNH2, Ph2P(O)NHN(CH3)2 (D.E.C. Corbridge, Phosphorus. An Outline of its Chemistry, Biochemistry and Technology (Second Edition), Elsvier, Amsterdam-Oxford-N.Y., 1980, p. 282), (CH3)2P(0)NHNHPh, Ph2P(O)NHNHPh (H. Bock and E. Baltin, Chemische Berichte, 98 (1965), S. 2844-2854), (CH3)2P(O)NHNH2 (E. Steininger et. al., Monatshefte fur Chemie, 97 (1966), S. 383-390),
(C2H5)2P(O)NHN(CH3)2, (C2H5)2P(O)NHNH(C4H9-t) (M. Negareche et. al., J of Organic Chemistry, 51 (1986), p. 342-346). All these phosphinyl hydrazides were obtained by the interaction of phosphinyl chlorides with corresponding hydrazines.
The present invention provides phosphinyl hydrazides of formula (I)
Figure imgf000002_0001
wherein 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, and R1 , R2 and R3 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
substituted by halogen, especially CI and/or F atoms.
Preferably, RF independently of one another are perfluorinated linear or perfluorinated branched alkyi or perfluorinated phenyl. Preferred alkyi derivatives are compounds wherein RF independently of one another are perfluorinated linear or perfluorinated branched Ci bis C2o alkyi, especially 0,2 bis Ci2 alkyi. Especially preferred are compounds wherein RF
independently of one another are perfluorinated linear or perfluorinated branched C2 bis C6 alkyi or perfluorinated phenyl.
R1 , R2 and R3 are preferably independently of one another linear or branched Ci bis C20 alkyi, especially Ci bis Ci2 alkyi, or substituted or unsubstituted phenyl or benzyl. Preferably phenyl and/or benzyl are substituted with one or more Ci bis C6 alkyi, especially with C-i bis C4 alkyi. Especially preferred are compounds with R1 = methyl, phenyl or 3,5-di-i- butyl-4-hydroxy-benzyl and R2 and R3 = H or compounds with R1 and R2 = linear Ci bis C4 alkyi, especially methyl or ethyl and R3 = H. Also preferred are compounds wherein R and R2 are the same and R3 = H.
Especially advantageous are combinations wherein RF and R1 , R2 and R3 have the preferred meanings. Particularly preferred are compounds with RF = perfluorinated C2 bis C6 alkyi, preferably C2F5, R and R3 = H, and R2 = linear Ci bis C4 alkyi, prefereably CH3, phenyl or 3,5-di-f-butyl-4-hydroxy- benzyl. Also prefereed are compounds with R3 = H and R1 and R2 = alkyi, preferably CH3. A second subject matter of this invention is the use of fluorinated
phosphinyl hydrazides of formula (I) for the synthesis of organic compounds comprising (Rf)2 (0) groups, wherein Rf has the meaning described in the foregoing.
Furthermore, 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
electrolytes in electrochemical cells.
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)
R R2N-NHR3 (II)
with fluorinated phosphine oxides of formula (III) or fluorinated phosphinic acid derivatives of formula (IV)
(RF)3P=0 (RF)2P(0)X
(III) (IV)
wherein 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, R1 , R2 and R3 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
substituted by halogen, especially CI and/or F atoms, and X is halogen, especially CI or F.
Preferably, RF independently of one another are perfluorinated linear or perfluorinated branched alkyl or perfluorinated phenyl. Preferred alkyl derivatives are compounds wherein RF independently of one another are perfluorinated linear or perfluorinated branched Ci bis C20 alkyi, especially C2 bis C12 alkyi. Especially preferred are compounds wherein RF
independently of one another are perfluorinated linear or perfluorinated branched C2 bis C-6 alkyi or perfluorinated phenyl.
R , R2 and R3 are preferably independently of one another linear or branched C-i bis C20 alkyi, especially Ci bis C12 alkyi, or substituted or unsubstituted phenyl or benzyl. Preferably phenyl and/or benzyl are substituted with one or more d bis C6 alkyi, especially with Ci bis C4 alkyi. Especially preferred are compounds with R1 = methyl, phenyl or 3,5-di-i- butyl-4-hydroxy-benzyl and R2 and R3 = H or compounds with R1 and R2 = linear Ci bis C4 alkyi, especially methyl or ethyl and R3 = H. Also preferred are compounds wherein R and R2 are the same and R3 = H. Surprisingly, it has been found that fluorinated phosphinyl hydrazides of formula (I) can be easily synthesized not only from corresponding
phosphinic acid derivatives, especially chlorides, or fluorides, but also from less reactive corresponding phosphine oxides. Especially fluorinated bis(alkyl)- or fluorinated bis(phenyl)-phosphinic acid chlorides or fluorides may be used.
The preferred processes are:
(RF)3P=0 + R1R2N- NHR3 (RF)2P(0)N- NR1 R2 + RFH
( in ) ( >· )
(RF)2P(0)CI + R1 R2N- N(H)R3 (RF)2P(0)N- NR1R2 + HCI
(trapped with CaH2,
( V ) ( II ) ^3 or other base)
(RF)2P(0)F + R1 R2N- N(H)R3 - (RF)2P(0)N- NR-,R2 + HF
! j L (trapped with CaH2,
■^3 or other base) wherein RF independently of one another are perfluorinated linear or perfluorinated branched alkyl or perfluorinated phenyl. Especially, compounds wherein RF independently of one another are perfluorinated linear or perfluorinated branched C2 bis C12 alkyl, optionally comprising one or more oxygen atoms are preferred. R1 , R2 and R3 are preferably independently of one another linear or branched Ci bis C20 alkyl- Especially preferred are the compounds in which RF are identical.
Especially advantageous are combinations wherein RF and R1 , R2 and R3 have the preferred meanings.
Preferably phosphinyl hydrazides of formula (I) are prepared via reaction of fluorinated tris(alkyl)- or fluorinated tris(phenyl)-phosphine oxides with corresponding hydrazines. Especialy, 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.
Semenii, V.A. Stepanov, N.V. Ignatyev, G.G. Furin, L.M. Yagupolskii, Zh. Obshch. Khim., 55 (1985), S. 2716-2720) from industrially available tris(perfluoroalkyl)difluorophosphoranes (N. Ignatyev und P. Sartori, J.
Fluorine Chem., 103 (2000), S. 57-61 ; and WO 2000/21969).
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. Preferably 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, Ν,Ν-dimethylacetamide, N-methylpyrrolidone and/or other amides of secondary amines. Especially preferred is acetonitrile.
The compounds of formula (I) are purified by usual methods, e.g. by destination, crystallization, extraction, filtration, etc.
Apart from the preferred compounds, methods, compositions and processes mentioned in the description, the claims disclose further preferred combinations of the subject-matters according to the invention. The disclosures in the cited references are explicitly part of the content of the present application. The following examples explain the present invention in greater detail without restricting the scope of protection. In particular, the features, properties and advantages, described in the examples, of the compounds on which the relevant examples are based can also be applied to other substances and compounds which are not described in detail, but fall within the scope of protection, unless stated otherwise elsewhere. In addition, the invention can be carried out throughout the range claimed and is not restricted to the examples mentioned here.
NMR spectra were measured in CD3CN solution at room temperature on a Bruker Avance DRX-400 (1H, 400.13 MHz; 19F, 376.49 MHz; 31P, 161.97 MHz) spectrometer. The chemical shifts were referenced to external TMS ( H), CFCI3 (19F) and H3P04 (31P). UV-spectra were recorded on Lambda EZ210 Spectrophotometer with Deuterium (D2) lamp (UV) and Tungsten Iodide lamp (Vis).
Examples
Example 1 : Bis(pentafluoroethyl)phosphinyl-N-(methyl)hydrazide,
(C2F5)2P(0)NHNHCH3
(C2F5)3P=O + NH2-NHCH3 (C2F5)2P(0)NH-NHCH3 + C2F5H t
A dry 25 ml flask, equipped with PTFE Young valve, is charged with 0.10 g (2.1 mmol) of methylhydrazine, 1 ml of dry acetonitrile and 1.3 g (3.2 mmol) of tris(pentafluoroethyl)phosphine oxide, (C2F5)3P=0. The reaction mixture is left stirred at room temperature for 16 hours and then all volatile products are removed under high vacuum (10"3 mbar). The white solid product (0.58 g; yield is 84 % calculating on methylhydrazine) is moved into the glove-box to take the NMR probe and to measure the melting point (M.p. = 72° C). NMR spectra are recorded in the dry acetonitrile-D3 and confirm the formation of bis(pentafluoroethyl)-phosphinyl N-(methyl)hydrazide,
(C2F5)2P(0)NHNHCH3.
19F NMR (Solvent: CD3CN; Reference substance: CCI3F), δ, ppm: -81.4 m (CF3), 122.4 (centre of A,B doublet) d.d.m (FA, CF2), 124.6 (centre of A,B doublet) d.d.m (Fb> CF2), 2JP,F(A) = 73 Hz, 2JP,F(B) = 80 Hz, JF(A),F(B) = 322 Hz.
31 P NMR (Solvent: CD3CN; Reference substance: 85 % Η3Ρ04), δ, ppm: 9.0 m.
1H NMR (Solvent: CD3CN; Reference substance: TMS), δ, ppm
(CH3), 4.12 br.s (NH). 6.75 br.d (NH); 2 P,H = 40 Hz. Example 2: Bis(pentafluoroethyl)phosphinyl-N-(phenyl)hydrazide, (C2F5)2P(0)NHNHC6H5
(C2F5)3P=0 + NH2-NHC6H5 - (C2F5)2P(0)NH-NHC6H5 + C2F5H |
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, (C2F5)3P=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). The resulting slightly yellow crystalline solid material (1.37 g; yield is 81 % calculating on phenylhydrazine) is purified by sublimation in a high vacuum at 82° C and moved into the glove-box to take the NMR probe and to measure the melting point (M.p. = 88° C). NMR spectra are recorded in the dry acetonitrile-D3 and confirm the formation of
bis(pentafluoroethyl)phosphinyl N-(phenyl)hydrazide,
(C2F5)2P(O)NHNHC6H5.
19F NMR (Solvent: CD3CN; Reference substance: CCI3F), δ, ppm: -81.2 m (CF3), 121.9 (centre of A,B doublet) d,d,m (FA, CF2), 124.6 (centre of A,B doublet) d.d.rn (Fb, CF2), 2JP,F(A) = 74 Hz, 2 P,F(B) = 83 Hz, JF(A),F(B) = 340 Hz.
31 P NMR (Solvent: CD3CN; Reference substance: 85 % H3PO4), δ, ppm: 8.9 t.t.d.d, 2JP,H = 44 Hz, 3JP,H = 4 Hz, 2JP,F(A) = 78 Hz, 2JP,F(B) = 82 Hz.
1H NMR (Solvent: CD3CN; Reference substance: TMS), δ, ppm: 6.47 d (NH), 6.92 - 7.00 m (3H), 7.24 - 7.31 m (2H). 7.46 br.d (NH); 2JP,H = 44 Hz, 3JP,H = 4 Hz. Example 3: Bis(pentafluoroethyl)phosphinyl-N-(phenyl)hydrazide,
(C2F5)2P(0)NH HC6H5
(C2F5)2P(0)CI + NH2-NHC6H5 » (C2F5)2P(0)NH-NHC6H5 + HCI
2 HCI + CaH2 — - CaCI2 + H2 1
A dry 25 ml flask, equipped with PTFE Young valve, is charged with 0.15 g CaH2, 0.34 g (3.1 mmol) of phenylhydrazine, 1 ml of dry acetonitrile and cooled down to -30° C. 1.5 g (4.6 mmol) of bis(pentafluoroethyl)phosphinyl chloride, (C2F5)2P(0)CI are condensed to the reaction mixture. After
warming up to the room temperature, the reaction mixture is left stirred for 20 hours and filtered. All volatile products are removed then under high vacuum (10~3 mbar). The resulting yellow crystalline solid material (0.94 g; yield is 77 % calculating on phenylhydrazine) is moved into the glove-box to take the NMR probe. NMR spectra, which are recorded in the dry
acetonitrile-D3, coincides with the spectra of
bis(pentafluoroethyl)phosphinyl-N-(phenyl)hydrazide,
(C2F5)2P(O)NHNHC6H5, obtained in the Example 2
Example 4: Bis(pentafluoroethyl)phosphinyl N,N-di(methyl)hydrazide,
Figure imgf000010_0001
(C2F5)3P=0 + NH2-N(CH3)2 - (C2F5)2P(0)NH-N(CH3)2 + C2F5H |
A dry 25 ml flask, equipped with PTFE Young valve, is charged with 0.23 g (3.8 mmol) of 1 ,1-dimethylhydrazine, 1 ml of dry acetonitrile and 1.78 g (4.4 mmol) of tris(pentafluoroethyl)phosphine oxide, (C2F5)3P=O at 0° C. After 5-10 min of exothermic reaction at room temperature, the reaction mixture becomes homogeneous. The reaction mixture is left stirred at room
temperature for 15 hours and then all volatile products are removed under high vacuum (10"3 mbar). The white solid product (1.45 g; yield is 82 % calculating on 1 ,1-dimethylhydrazine) is moved into the glove-box to take the NMR probe and to measure the melting point (M.p. = 71° C). NMR spectra are recorded in the dry acetonitrile-D3 and confirm the formation of bis(pentafluoroethyl)phosphinyl N,N-di(methyl)hydrazide,
(C2F5)2P(O)NHN(CH3)2.
19F NMR (Solvent: CD3CN; Reference substance: CCI3F), δ, ppm: -81.2 m (CF3), 121.4 (centre of A,B doublet) d,d (FA, CF2), 124.9 (centre of A,B doublet) d,d (Fb, CF2), 2JP,F(A) = 72 Hz, 2JP,F(B) = 82 Hz, JF(A),F(B) = 338 Hz.
3 P NMR (Solvent: CD3CN; Reference substance: 85 % Η3Ρ04), δ, ppm: 6.5 t,t,d, 2JP,H = 42 Hz, 3JP,H = 4 Hz, 2JP,F(A) = 74 Hz, 2JP,F(B) = 82 Hz.
1H NMR (Solvent: CD3CN; Reference substance: TMS), δ, ppm: 2.61 s (CH3), 6.90 br.d (NH); 2JP,H = 42 Hz.
Example 5: Bis(pentafluoroethyl)phosphinyl-N(3,5-di-f-butyl-4- hydroxy-benzyl)hydrazide,
(C2F5)2P(0)NHNHCH2[3,5-(i-C4H9)2-C6H2-4-OH]
A dry 25 ml flask, equipped with PTFE Young valve, is charged with 0.80 g (3.2 mmol) of 3,5-di-f-butyl-4-hydroxy-benzyl hydrazine, 1 ml of dry acetonitrile and 1.5 g (3.7 mmol) of tris(pentafluoroethyl)phosphine oxide, (C2F5)3P=0 at 0° C. After stirring for 30 min at room temperature the homogeneous solution is formed. To complete the reaction, the mixture is left stirred at room temperature for 21 hours and then all volatile products are removed under high vacuum (10"3 mbar). The white solid product (1.5 g; yield is 88 % calculating on3,5-di-f-butyl-4-hydroxy-benzyl hydrazine) is moved into the glove-box to take the NMR probe and to measure the melting point (M.p. = 106 - 108° C). NMR spectra are recorded in the dry acetonitrile-D3 and confirm the formation of bis(pentafluoroethyl)phosphinyl- N(3,5-di-i-butyl-4-hydroxy-benzyl)hydrazide, (C2F5)2P(O)NHNHCH2[3,5-(f- C4H9)2-C6H2-4-OH].
19F NMR (Solvent: CD3CN; Reference substance: CCI3F), δ, ppm: -81 .2 m (CF3), 122.0 (centre of A,B doublet) d,d,m (FA, CF2), 124.3 (centre of A,B doublet) d,d,m (Fb, CF2), 2JP,F(A) = 72 Hz, 2JP,F(B) = 81 Hz, JF(A).F<B) = 335 Hz.
3 P NMR (Solvent: CD3CN; Reference substance: 85 % H3PO4), δ, ppm: 9.2 quin.d, 2JP,H = 37 Hz, 2JP,F = 76 Hz.
1H NMR (Solvent: CD3CN; Reference substance: TMS), δ, ppm: 1.38 br.s (18H, 6CH3), 3,82 s (2H, CH2), 4.38 br.s (OH), 5.41 s (NH), 6.69 br.d (NH), 7.10 s (2H, ArH); 2JP,H = 39 Hz. Example 6: Oxidation of Bis(pentafluoroethyl)phosphinyl-N(3,5-di-f- butyl-4-hydroxy-benzyl)hydrazide to stable radical, (C2F5)2P(O)NHNHCH2[3,5-(f-C4H9)2-C6H2-4-O ]
Figure imgf000012_0001
0.084 g (0.16 mmol) of bis(pentafluoroethyl)phosphinyl-N(3,5-di-i-butyl-4- hydroxy-benzyl)hydrazide, (C2F5)2P(0)NHNHCH2[3,5-(f-C4H9)2-C6H2- -OH] is dissolved in 1.5 ml of dry toluene and 0.10 g (0.46 mmol) of PbO2 is added in inert atmosphere. The reaction mixture is stirred for 30 min at room temperature. The colouring of the solution changes to yellow that indicates the formation of radical species. The UV-spectra (see Figure 1) also confirmes the formation of stable radical. The colour of the solution in closed flask remains unchanged for several weeks.

Claims

Claims
1. Compounds of formula (I)
Figure imgf000014_0001
wherein
RF independently of one another are fluorinated linear or fluorinated branched alkyl or fluorinated phenyl, optionally comprising one or more oxygen atoms, or fluorinated alkylphenyl, and
R1, R2 and R3 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 substituted by halogen, especially CI and/or fluorine atoms.
2. Compounds according to claim 1 , wherein RF independently of one another are perfluorinated linear or perfluorinated branched alkyl or perfluorinated phenyl.
3. Compounds according to any of claims 1 or 2, wherein RF
independently of one another are perfluorinated linear or
perfluorinated branched C2 bis Ci2 alkyl, optionally comprising one or more oxygen atoms.
4. Compounds according to any of claims 1 to 3, wherein R , R2 and R3 independently of one another are linear or branched Ci bis C20 alkyl.
5. Use of compounds according to any of claim 1 to 4 for synthesis of organic compounds comprising (Rf)2P(O) groups, wherein Rf has the meaning according to claims 1 to 4.
6. Use of compounds according to any of claim 1 to 4 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 electrolytes in electrochemical cells.
7. Process for preparation of compounds to any of claims 1 to 4 via interaction of hydrazines of formula (II)
R1R2N-NHR3 (II)
with fluorinated tris(alkyl)phosphine oxides of formula (III) or fluorinated phosphinic acid derivatives of formula (IV)
Figure imgf000015_0001
wherein 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,
R1, R2 and R3 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 substituted by halogen, especially CI and/or F atoms, and X is halogen, especially CI or F.
8. Process according to claim 7, wherein RF independently of one
another are perfluorinated linear or perfluorinated branched alkyl or perfluorinated phenyl.
9. Process according to any of claims 7 or 8, wherein RF independently of one another are perfluonnated linear or perfluonnated branched C2 bis C12 a'kyl, optionally comprising one or more oxygen atoms.
10. Process according to any of claims 7 to 9, wherein R1 , R2 and R3 independently of one another are linear or branched Ci bis C20 alkyl.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2451178A1 (en) * 1973-10-31 1975-05-07 Ciba Geigy Ag BENZYLATED PHOSPHORIC ACID HYDRACIDES
WO2000021969A1 (en) 1998-10-09 2000-04-20 Merck Patent Gmbh Electrochemical synthesis of perfluoroalkylfluorophosphoranes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2451178A1 (en) * 1973-10-31 1975-05-07 Ciba Geigy Ag BENZYLATED PHOSPHORIC ACID HYDRACIDES
WO2000021969A1 (en) 1998-10-09 2000-04-20 Merck Patent Gmbh Electrochemical synthesis of perfluoroalkylfluorophosphoranes

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
"Chemistry, Biochemistry and Technology", 1980, ELSVIER
BAGROV ET AL, RUSS. J. GEN. CHEM., vol. 63, no. 7, 1993, pages 1109 - 1111, XP008135036 *
BEJAN ET AL, J. FLUOR. CHEM., vol. 131, 14 November 2009 (2009-11-14), pages 325 - 332, XP002630528 *
H. BOCK; E. BALTIN, CHEMISCHE BERICHTE, vol. 98, 1965, pages 2844 - 2854
JOHN. A. GLADYSZ, DENNIS P. CURRAN, ISTVÁN T. HORVÁTH: "Handbook of Fluorous Chemistry", 30 June 2005 (2005-06-30), pages I - xxix, XP002630708, ISBN: 9783527603909, Retrieved from the Internet <URL:http://onlinelibrary.wiley.com/doi/10.1002/3527603905.fmatter/pdf> [retrieved on 20110331], DOI: 10.1002/3527603905 *
M. NEGARECHE, J. OF ORGANIC CHEMISTRY, vol. 51, 1986, pages 342 - 346
MOSKALEV ET AL, RUSS. J. ORG. CHEM., vol. 30, no. 5, 1994, pages 785 - 789, XP008135035 *
N. IGNATYEV; P. SARTORI, J. FLUORINE CHEM., vol. 103, 2000, pages 57 - 61
STEININGER, MONATSHEFTE FUR CHEMIE, vol. 97, 1966, pages 383 - 390
V.YA. SEMENII; V.A. STEPANOV; N.V. IGNATYEV; G.G. FURIN; L.M. YAGUPOLSKII, ZH. OBSHCH. KHIM., vol. 55, 1985, pages 2716 - 2720

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