Diphosphines
AssigneeBayer Aktiengesellschaft
InventorsBirgit Driessen-Holscher, Joachim Kralik, Inga Ritzkopf, Christian Steffens, Guido Giffels, Claus Dreisbach, Thomas Prinz, Walter Lange
Life of this patent
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Abstract
The invention relates to the preparation and use as catalysts of diphosphines of the formula (I) 1 in which R is C6-C14-aryl or C4-C13-heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the aryl and heteroaryl radicals may optionally be substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, and/or trimethylsilyl, and R1 to R4, independently of one another, are each hydrogen, C1-C10-alkyl, C1-C10-alkoxy, F, Cl, or Br.
Claims14
A process for the preparation of racemic diphosphines of the formula (I)
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- in which
- R is C6-C14-aryl or C4-C13-heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the aryl and heteroaryl radicals may optionally be substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, and/or trimethylsilyl, and
- R1 to R4, independently of one another, are each hydrogen, C1-C10-alkyl, C1-C10-alkoxy, F, Cl, or Br, comprising
- (a) converting a phenol of the formula (II)
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- in which R1 to R4 have the meanings given for formula (I), into the corresponding phenoxide using a base,
- (b) reacting the phenoxide with dihalogenomethane to give a formaldehyde acetal of the formula (III)
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- in which R1 to R4 have the meanings given for formula (I),
- (c) intramolecularly oxidatively coupling the formaldehyde acetal of the formula (III) is to give a cycloheptadiene of the formula (IV),
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- in which R1 to R4 have the meanings given for formula (I),
- (d) converting the cycloheptadiene of the formula (IV) by treatment with an acid into a biphenyidiol of the formula (V)
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- in which R1 to R4 have the meanings given for formula (I),
- (e) preparing the corresponding triflate from the biphenyldiol of the formula (V), and
- (f) coupling the triflate compound with a secondary phosphine of the formula (VI)
- HPR2 (VI),
- in which R has the meaning given for formula (I),
- with the addition of a base and in the presence of a palladium(0), palladium(II), nickel(0), and/or Ni(II) compound, thereby giving a compound of the formula (I).
Enantiomerically pure diphosphines of the formula (IX)
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- in which the radicals R″ are in each case identical and are 2-furyl, 2-N-methylpyrrolyl, 4-fluorophenyl, 3,5-di-methoxyphenyl, or 3,5-dimethylphenyl, and of a formula that is analogous to formula (IX) but represents the other enantiomer.
A cycloheptadiene compound of the formula (IV)
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- where R1 and R2 are H, R3 is chlorine, and R4 is methoxy.
Racemic and enantiomerically pure biphenyldiols of the formula (V)
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- and the corresponding racemic and enantiomerically pure triflate compounds thereof, where R1 and R2 are H, R3 is chlorine, and R4 is methoxy.
Dependencies are inferred from the claim text.