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WO2009112349A1 - Procédé de préparation de monoxydes de diphosphine - Google Patents

Procédé de préparation de monoxydes de diphosphine Download PDF

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Publication number
WO2009112349A1
WO2009112349A1 PCT/EP2009/052053 EP2009052053W WO2009112349A1 WO 2009112349 A1 WO2009112349 A1 WO 2009112349A1 EP 2009052053 W EP2009052053 W EP 2009052053W WO 2009112349 A1 WO2009112349 A1 WO 2009112349A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
alkyl
group
aryl
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.)
Ceased
Application number
PCT/EP2009/052053
Other languages
German (de)
English (en)
Inventor
Hartmut Denecke
Alexander Tishkov
Norbert Gutfrucht
Matthias Maase
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2009112349A1 publication Critical patent/WO2009112349A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5341—Organo-phosphine oxides or thioxides containing a P-P bond

Definitions

  • the object of the present invention relates to a process for the preparation of diphosphine monoxides by reaction of dialkyl- or diarylphosphine chloride with alkoxydialkyl- or diarylphosphine without solvent and subsequent removal of the product.
  • TPDM 1, 2,2-Tetraphenyldiphosphinmonoxid
  • diphosphines are usually carried out by coupling the corresponding halophosphine with an alkoxyphosphine with elimination and simultaneous removal of the haloalkane in an inert solvent.
  • TPDM tetraphenyldiphosphine
  • metals such as sodium, lithium or magnesium
  • subsequent oxidation of the tetraphenyldiphosphine with air or other oxidizing agents as described by A. J Blake, G. P McQuillan, I.A. Oxton, D. Troy, J. Mol. Struct. 1982, 78, at pages 265 to 272.
  • a disadvantage of this method is not only the two-step process control, but also the increased safety measures that must be made for the production of tetraphenyldiphosphine, as must be taken to handle the air-sensitive alkali metals and the handling of the air-sensitive products. Furthermore, in the coupling reaction large amounts of heat are released, which must be removed accordingly. Further disadvantages are that the oxidation proceeds only with low selectivity and in the reaction the formation of by-products such as tetraphenyldiphosphine dioxide can not be avoided.
  • diphosphine monoxide Another method for preparing diphosphine monoxide is described by Inorg. Nucl. Chem. Letters 1967, Vol.3, at page 313. In this case, diphenylphosphine chloride is reacted in the presence of methoxydiphenylphosphine and benzene as the solvent.
  • the procedure of the synthesis of TPDM from E-thoxydiphenylphosphine, which is accessible on an industrial scale, and diphenylch- lorphosphin according to the E. Fluck and H. Binder Inorg. Nucl. Chem. Letters 1967, Vol. 3, at page 313 showed that the resulting product has a purity of ⁇ 90% and that the crystallization does not lead to a reduction in the content of tetraphenyldiphosphine dioxide. Due to this procedure in a solvent, however, because of the dilution (about 1 M) and the low reaction rate, the space-time yield at about 6 g / L * h is low.
  • the object of the present invention is therefore to provide a process which makes it possible selectively to produce diphosphine monoxides which produce less than 10% of secondary components, which allows a simplified work-up and also has an improved reaction time.
  • R 1 -R 4 are independently selected from the group of C 1 -C 16 -alkyl, C 1 -C 16 -alkenyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkyl-NR 2 R 3 , Cs-do -cycloalkyl, C3-C10-cycloalkoxy, C ⁇ -Cio-aryl, C ⁇ -C-io-aryloxy, C ⁇ -Cio-aryl-Ci-Ci ⁇ -alkyl, C6-Cio-aryl-Ci-Ci6- alkoxy, NR 2 R 3 , COR 2 , COOR 2 and CONR 2 R 3 comprising the step
  • R 5 is selected from the group of C 2 -C 16 -alkyl, C 1 -C 16 -alkenyl, C 3 -C 10 -cycloalkyl or C ⁇ -do-aryl !.
  • radicals R 1 to R 4 are phenyl groups.
  • step a) is carried out at a temperature in the range from 110 to 130 ° C.
  • the process according to the invention is advantageous if the separation of the compound of the formula I in step c) takes place by filtration or centrifugation.
  • radicals R 1 to R 4 are independently selected from the group of C 1 -C 18 -alkyl, C 1 -C 18 -alkenyl, C 1 -C 4 -alkoxy, d-
  • Preferred C 1 -C 16 -alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, isobutyl, hexyl, octyl, decyl, dodecyl, tetradecyl, 2-ethylhexyl and 2-methyl.
  • C ⁇ -Cio-aryl groups are phenyl and naphthyl. Particularly preferred
  • radicals R 1 and R 2 and R 3 and R 4 are identical. Especially preferred for R 1 and R 2 is the phenyl group and for R 3 and R 4 is the phenyl, ethyl and allyl group. Especially preferred is especially when R 1 to R 4 are phenyl groups.
  • the group R 5 is selected from the group of C 2 -C 16 -alkyl, C 1 -C 16 -alkenyl, C 3 -C 10 -cycloalkyl or C 6 -C 10 -aryl.
  • Preferred C2-C16 alkyl groups are selected from the group of ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, i-butyl, decyl, dodecyl, tetradecyl or 2-ethylhexyl.
  • the ethyl group is very particularly preferred.
  • the preferred C 1 -C 16 -alkenyl group is AIIyI.
  • Preferred C 3 -C 10 -cycloalkyl groups are selected from the group of cyclopentyl and cyclohexyl.
  • Preferred C ⁇ -C-io-arvl groups are selected from the group of phenyl, naphthyl, ToIyI, dimethylphenyl and methoxyphenyl.
  • the group R 5 is selected from the group of ethyl and
  • the reaction is carried out in the presence of temperatures in the range from 50 to 180 ° C., more preferably in the range from 80 to 160 ° C., very particularly preferably in the range from 110 to 130 ° C.
  • step a an excess of the compound of formula III is added to the compound of formula II.
  • the ratio of compounds of the formula II to III is thus 1: 5, more preferably 1: 2.4.
  • the process according to the invention can be operated both batchwise, semi-batch and continuously. Preference is given to a semi-batch or continuous procedure. Quite particularly preferred is a continuous mode of operation.
  • the product R 5 Cl formed during the reaction in addition to the compound of the formula I is removed from the reaction mixture.
  • the removal can be carried out by methods known to those skilled in the art, such as stripping, distillation, extraction or phase separation.
  • the process procedure is preferably selected such that the R 5 Cl formed in the reaction is gaseous and is produced in such amounts that it can be distilled off safely during the reaction. This is preferably realized by a controlled addition of the compound of formula II to the compound of formula III.
  • the compound of the formula I which is formed by this process is preferably precipitated as a solid. Some compounds of formula I are also oils.
  • the compound of formula I is then separated from the reaction solution obtained after step b). The separation can be carried out by the methods known to those skilled in the art, such as filtration, centrifuging, extraction, distillation and sublimation.
  • the product obtained by the process according to the invention may, if appropriate, be subjected to a further purification step once more.
  • Possible purification steps here are recrystallization, washing of the crystallizate, followed by removal of the wash solution under reduced pressure, distillation, sublimation. Preference is given to washing the crystals under ISb or Ar atmosphere, followed by removal of the washing solution under reduced pressure. All organic solvents selected from the group of toluene, xylene, dibutyl ether, alkanes such as hexane, heptane and petroleum ether or mixtures thereof are suitable for washing the crystals.
  • Example 1 (according to the invention) Ethoxydiphenylphosphine (552.6 g, 2.40 mol) is placed in a stirred flask and heated to 120 0 C internal temperature. Within 1 h chlorodiphenylphosphine (220.6 g, 1, 0mol) is added dropwise so that the resulting ethyl chloride can be safely removed. It is stirred for a further hour at reaction temperature and then cooled. The crystals are filtered off and washed with toluene. It is dried at the best possible oil pump vacuum and 100 0 C.

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  • 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

L'invention concerne un procédé de préparation de monoxydes de diphosphine par réaction de chlorure de dialkylphosphine ou de diarylphosphine avec une alcoxydialkylphosphine ou une alcoxydiarylphosphine sans solvant et séparation consécutive du produit.
PCT/EP2009/052053 2008-03-11 2009-02-20 Procédé de préparation de monoxydes de diphosphine Ceased WO2009112349A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08152559.4 2008-03-11
EP08152559 2008-03-11

Publications (1)

Publication Number Publication Date
WO2009112349A1 true WO2009112349A1 (fr) 2009-09-17

Family

ID=40548868

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/052053 Ceased WO2009112349A1 (fr) 2008-03-11 2009-02-20 Procédé de préparation de monoxydes de diphosphine

Country Status (1)

Country Link
WO (1) WO2009112349A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011009876A1 (fr) * 2009-07-24 2011-01-27 Basf Se Dérivés de diphosphines en tant qu’ignifugeants dans des résines époxy aromatiques et/ou hétéroaromatiques

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AL'FONSOV, V. A. ET AL: "Ligand exchange reactions in a series of phosphorus(III) derivatives. Characteristics of exchange in a series of phosphinous derivatives", J. GEN. CHEM. USSR, vol. 51, 1981, pages 8 - 15, XP008105745 *
DEMIK, N. N. ET AL: "Synthesis of diphosphine monoxides", J. GEN. CHEM USSR, vol. 61, 1991, pages 460 - 461, XP008105746 *
FLUCK ET AL: "Darstellung von verbindungen MIT P---P ? und P---P---P ? gerüsten", INORGANIC AND NUCLEAR CHEMISTRY LETTERS, vol. 3, no. 8, 1967, pages 307 - 313, XP002524721 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011009876A1 (fr) * 2009-07-24 2011-01-27 Basf Se Dérivés de diphosphines en tant qu’ignifugeants dans des résines époxy aromatiques et/ou hétéroaromatiques

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