Preparation of phosphorus compounds

1. Process for preparing compounds of the formula (I)

in which

R 1 and R 2 are each independently a monovalent radical which in each case has 1 to 30 carbon atoms or

PR 1 R 2 as a whole is a 5- to 9-membered heterocyclic radical which contains a total of 2 to 50 carbon atoms and optionally contains up to three further heteroatoms which are selected from the group of oxygen and nitrogen, and

A 1 and A 2 are each independently a substituted or unsubstituted ortho-arylene radical and

E is E 1 or E 2 where E 1 is an unsubstituted, monosubstituted or disubstituted vicinal cis-alkenediyl radical and E 2 is a vicinal alkanediyl radical in which the two yl carbon atoms each bear one or two hydrogen atoms,

comprising

in a step a), reacting compounds of the formula (II)

in which A 1 , A 2 and E are each as defined above with compounds of the formula (III)

R 1 R 2 P-Hal  (III)

in which R 1 and R 2 are each as defined above and

Hal 1 is chlorine, bromine or iodine,

in the presence of acid or base,

to form compounds of the formula (IV)

in which A 1 , A 2 , E, R 1 and R 2 are each as defined above and

in a step b), reducing the compounds of the formula (IV) to compounds of the formula (I).

2. Process according to claim 1 , characterized in that R 1 and R 2 are each independently C 1 –C 18 -alkyl, C 3 –C 12 -alkenyl, C 1 –C 18 -perfluoroalkyl, C 1 –C 18 -perfluoroalkoxy, C 1 –C 18 -alkoxy, C 5 –C 24 -aryl, C 5 –C 24 -aryloxy, C 5 –C 25 -arylalkyl, C 5 –C 25 -arylalkoxy or NR 4 R 5 where R 4 and R 5 are each independently C 1 –C 12 -alkyl, C 5 –C 14 -aryl or C 6 –C 15 -arylalkyl, or NR 4 R 5 as a whole is a 5- to 7-membered cyclic amino radical having a total of 4 to 12 carbon atoms, or

PR 1 R 2 as a whole is a 5- to 7-membered heterocyclic radical of the formula (V)

in which

Het 1 and Het 2 are each independently absent, or are each oxygen or NR 5 where R 5 is C 1 –C 12 -alkyl, C 5 –C 14 -aryl or C 6 –C 15 -arylalkyl and

K is an alkanediyl radical having 2 to 25 carbon atoms, a divalent arylalkyl radical having 5 to 15 carbon atoms, an arylene radical having a total of 5 to 14 carbon atoms or a 2,2′-(1,1′-bisarylene) radical having a total of 10 to 30 carbon atoms.

3. Process according to claim 1 , characterized in that A 1 and A 2 are each independently an ortho-phenylene radical of the formula (VI)

in which

n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and

R 6 is in each case independently selected from the group of fluorine, chlorine, bromine, iodine, nitro, free and protected formyl, C 1 –C 12 -alkyl, C 1 –C 12 -alkoxy, C 1 –C 12 -haloalkoxy, C 1 –C 12 -haloalkyl, C 5 –C 14 -aryl, C 6 –C 15 -arylalkyl or radicals of the formula (VII)

L-Q-T-W  (VII)

in which, each independently,

L is absent or is C 1 –C 8 -alkylene or C 2 –C 8 -alkenylene and

Q is absent or is oxygen, sulphur or NR 7

where

R 7 is hydrogen, C 1 –C 8 -alkyl, C 6 –C 15 -arylalkyl or C 5 –C 14 -aryl and

T is a carbonyl-group and

W is R 8 , OR 8 , NHR 9 or N(R 9 ) 2 ,

where

R 8 is C 1 –C 8 -alkyl, C 5 –C 15 -arylalkyl or C 5 –C 14 -aryl and

R 9 is in each case independently C 1 –C 8 -alkyl, C 5 –C 14 -arylalkyl or C 4 –C 15 -aryl, or N(R 9 ) 2 together is a 5- or 6-membered cycloamino radical,

or a radical of the formulae (VIIIa–g)

L-W  (VIIIa)

L-SO 2 -W  (VIIIb)

L-NR 12 SO 2 R 12   (VIIIc)

L-SO 3 Z  (VIIId)

L-PO 3 Z 2   (VIIIe)

L-COZ  (VIIIf)

L-CN  (VIIIg)

in which L, Q, W and R 8 are each as defined under the formula (VII) and Z is hydrogen or M 1 where M 1 is as defined under the definition of R 7 .

4. Process according to claim 1 , characterized in that E is a radical of the formulae (IXa) or (IXb) where, in formula (IXa)

R 10 and R 11 are each independently hydrogen, cyano, fluorine, chlorine, bromine, iodine, C 1 –C 18 -alkyl, C 4 –C 24 -aryl, C 5 –C 25 -arylalkyl, CO 2 M, CONH 2 , SO 2 N(R 12 ) 2 , SO 3 M 1 , where R 12 is in each case independently as defined above or is a radical of the formula (X),

T 2 -Het 3 -R 13   (X)

in which

T 2 is absent or is carbonyl,

Het 3 is oxygen or NR 12 where R 12 is hydrogen, C 1 –C 12 -alkyl, C 5 –C 14 -aryl or C 6 –C 15 -arylalkyl and

R 13 is C 1 –C 18 -alkyl, C 5 –C 24 -aryl or C 5 –C 25 -arylalkyl,

and, in formula (IXb),

R 14 and R 15 are each independently hydrogen, C 1 –C 18 -alkyl, C 5 –C 24 -aryl or C 5 –C 25 -arylalkyl.

5. Process according to at least one of claims 1 to 4 , characterized in that

10-cyano-5-diphenylphosphinyl-5H-dibenzo[a,d]cycloheptene ( CN tropp Ph ) 5-(2S,5S-2,5-dimethylphospholanyl)-5H-dibenzo[a,d]cycloheptene (S,S-tropphos Me )

5-(2R,5R-2,5-dimethylphospholanyl)-5H-dibenzo[a,d]cycloheptene (R,R-tropphos Me )

(10-methoxy-5H-dibenzo[a,d]cyclohepten-5-yl)diphenylphosphine ( MeO tropp Ph )

(10-methoxy-5H-dibenzo[a,d]cyclohepten-5-yl)dicyclohexylphosphine ( MeO tropp Cyc )

[(5S)-10-[(−)-menthyloxy]-5H-dibenzo[a,d]cyclohepten-5-yl]diphenylphosphine, (S- menthyloxy tropp Ph ) and [(5R)-10-[(−)-menthyloxy]-5H-dibenzo[a,d]cyclohepten-5-yl]-diphenylphosphine (R- menthyloxy tropp Ph ) are prepared.

6. Process according to claim 1 , characterized in that acids are used for step a).

7. Process according to claim 1 , characterized in that the acids used are those which, based on an aqueous reference scale and 25° C., have a pKa value of 5.5 or less.

8. Process according to claim 1 , characterized in that step a) is carried out at a temperature of −20° C. to 100° C.

9. Process according to claim 1 , characterized in that stereoisomer mixtures of compounds of the formula (IV), are separated before carrying out step b).

10. Process according to at least one of claims 1 to 9 , characterized in that at least one of the R 1 , R 2 , A 1 , A 2 and E radicals in the compounds of the formula (IV) is converted to another R 1 , R 2 , A 1 , A 2 and E radical.

11. Process according to claim 1 , characterized in that the reduction in step b) is carried out in the presence of hydrosilicon compounds.

12. Process according to claim 1 , characterized in that the reduction in step b) is carried out at a temperature of 20° C. to 200° C.

13. Process according to claim 1 , characterized in that the resulting compounds are reduced to the free phosphines in a further step.

14. Compounds of the formula (IVa)

in which A 1 , A 2 and E are each as defined in claim 1 .

15. 5-Dichlorooxyphosphoryl-5H-dibenzo[a,d]cycloheptene (troppo Cl ) and 5-dibromooxyphosphoryl-5H-dibenzo[a,d]cycloheptene (troppo Br ).

16. Process for preparing compounds of the formula (IVa)

in which A 1 , A 2 and E are each as defined in claim 1 and

Hal is in each case chlorine, bromine or iodine,

comprising reacting

compounds of the formula (II) as defined in claim 1 in the presence of acid or base with compounds of the formula (IIIa)

PHal 3   (IIIa)

in which

Hal is in each case independently chlorine, bromine or iodine.

17. Process according to claim 16 , characterized in that the compounds of the formula (IVa) are also reacted with compounds of the formula (XII)

R 1/2 -M  (XII)

in which R 1 and R 2 are each as defined in claim 1 , and M, in the case that

R 1 or R 2 are to be bonded to the phosphorus atom via an oxygen atom, is hydrogen or 1/n equivalent of a metal or of a metal fragment having the valency n, and, in the case that

R 1 or R 2 are to be bonded to the phosphorus atom via a nitrogen atom, is hydrogen, and, in the case that

R 1 or R 2 are to be bonded to the phosphorus atom via a carbon atom, is 1/n equivalent of a metal or of a metal fragment having the valency n,

the same also applying in a similar manner to radicals in which R 1 R 2 as a whole is a divalent radical.

18. Process according to claim 17 , characterized in that the resulting compounds are reduced to the free phosphines in a further step.

19. A process for preparing ligand for metals or conducting catalytic processes comprising providing the compounds of claim 14 .

20. The process of claim 19 , characterized in that the catalytic processes are hydrogenations and hydrosilylations.