Process for preparing phosphites and transition metal complexes
View Patent ↗The present invention relates to a process for preparing phosphites and their transition metal complexes and also to their use in catalytic processes.
1. Process for preparing compounds of the formula (I)
where
D is an unsubstituted or substituted 1,1′-biphenyl-2,2′-diyl- or 1,1′-binaphthyl-2,2′-diyl radical and
R 1 is a radical selected from the group of C 1 –C 12 -alkyl, C 2 –C 12 -alkenyl, C 1 –C 12 -halogenalkyl, C 5 –C 15 -arylalkyl and C 4 –C 14 -aryl, with the proviso that
R 1 has a molar mass of 215 or less,
comprising
in a step a) reacting
compounds of the formula (II),
PHal 3 (II)
where Hal is in each case independently chlorine, bromine or iodine,
with compounds of the formula (III),
R 1 —OH (III)
where
R 1 is as defined above
to give compounds of the formula (IV)
R 1 OPHal 2 (IV)
where
R 1 and Hal are each as defined above,
in a step b) ditillatively purifying
the compounds of the formula (IV) of a) and
in a step c), reacting
the compounds of the formula (IV), purified in step b)
with compounds of the formula (V)
D(OH) 2 (V)
where
D is as defined above
to give compounds of the formula (I).
2. Process according to claim 1 , characterized in that step c) is carried out in the presence of a base.
3. Process according to claim 1 , characterized in that
R 1 is a radical which is selected from the group of C 1 –C 8 -alkyl, C 5 –C 15 -arylalkyl and C 4 –C 14 -aryl, with the proviso that
R 1 has a molar mass of 200 or less.
4. Process according to claim 1 , characterized in that D is an unsubstituted or substituted 1,1′-biphenyl-2,2′-diyl radical of the formula (VI)
or is an unsubstituted or substituted 1,1′-binaphthyl-2,2′-diyl radical of the formula (VII)
where the radicals
R 2 to R 20 are in each case independently selected from the group of hydrogen, fluorine, chlorine, bromine, cyano, protected hydroxyl, C 1 –C 12 -alkyl, C 1 –C 12 -halogenalkyl, C 1 –C 12 -alkoxy, C 1 –C 8 -alkylthio, free or protected formyl, C 4 –C 14 -aryl, tri(C 1 –C 8 -alkyl)siloxyl or radicals of the formula (VIII)
A-B-E-F (VIII)
where, each independently,
A is absent or is a C 1 –C 8 -alkylene radical and
B is absent or is oxygen, sulphur or NR 21
where
R 21 is hydrogen, C 1 –C 12 -alkyl or C 4 –C 14 -aryl and
E is a carbonyl group and
F is R 22 , OR 22 , NHR 23 or NR 23 R 24
where
R 22 is C 1 –C 12 -alkyl or C 6 –C 10 -aryl and
R 23 and R 24 are each independently C 1 –C 8 -alkyl or C 4 –C 14 -aryl, or NR 23 R 24 together is a cyclic amino radical having 4 to 12 carbon atoms, and in each case two adjacent radicals from R 2 to R 20 together optionally form a nonaromatic ring and in each case two of the radicals from R 1 to R 20 optionally are bridging.
5. Process according to claim 1 , characterized in that enantiomerically enriched compounds of the formula (V) are used.
6. Process according to claim 1 , characterized in that the compounds of formula (I) are selected from the group consisting of:
((S)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)isopropyl phosphite
((R)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)isopropyl phosphite
((R)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)-(R)-1-phenylethyl phosphite
((R)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)-(S)-1-phenylethyl phosphite
((S)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)-(R)-1-phenylethyl phosphite
((S)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)-(S)-1-phenylethyl phosphite
((S)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)cyclohexyl phosphite
((R)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)cyclohexyl phosphite
((S)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)phenyl phosphite
((R)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)phenyl phosphite
((S)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)-2,6-dimethylphenyl phosphite
((R)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl-2,2′-diyl)-2,6-dimethylphenyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)isopropyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)isopropyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-(rac)-1-phenylethyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-(rac)-1-phenylethyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-(S)-1-phenylethyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-(S)-1-phenylethyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-(R)-1-phenylethyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-(R)-1-phenylethyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-diphenylmethyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-diphenylmethyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)methyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)methyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-2,6-dimethylphenyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-2,6-dimethylphenyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-2,6-diiso-propylphenyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-2,6-diiso-propylphenyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)phenyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)phenyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)ethyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)ethyl phosphite
((S)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-4-tert-butylphenyl phosphite
((R)-5,5′,6,6′-tetramethyl-3,3′-bis(tert-butyl)-1,1′-biphenyl-2,2′-diyl)-4-tert-butylphenyl phosphite
((S)-1,1′-binaphthyl-2,2′-diyl)isopropyl phosphite
((R)-1,1′-binaphthyl-2,2′-diyl)isopropyl phosphite
((S)-1,1′-binaphthyl-2,2′-diyl)neopentyl phosphite
((R)-1,1′-binaphthyl-2,2′-diyl)neopentyl phosphite
((S)-1,1′-binaphthyl-2,2′-diyl)phenyl phosphite
((R)-1,1′-binaphthyl-2,2′-diyl)phenyl phosphite
((S)-1,1,′-binaphthyl-2,2′-diyl)benzyl phosphite and
((R)-1,1′-binaphthyl-2,2′-diyl)benzyl phosphite.
7. Process according to claim 1 , characterized in that the distillation in step b) is carried out a pressure from 0.001 to 1000 hPa.
8. Process according to claim 1 further comprising as step d), reacting the compounds of the formula (I) obtained in steps a) to c) with transition metal compounds.
9. Process according to claim 8 , characterized in that solutions of compounds of the formula (I), as obtained in step c), are used directly in step d), optionally after removing precipitates.
10. Process according to claim 8 , characterized in that solutions of compounds of the formula (I), as obtained in step c), are concentrated, optionally after removing precipitates, the compounds of the formula (I) are taken up again in solvents and subsequently provided for reaction in step d).
11. Process according to claim 8 , characterized in that transition metal compounds containing compounds of the formula (I) are those of the formula (Xa),
[(I) 4 M 1 ]An 1 (Xa)
where
(I) is in each case independently, a compound of the formula (I) and
M 1 is rhodium or iridium and
An 1 is methanesulphonate, trifluoromethanesulphonate, tetrafluoroborate, hexafluorophosphate, perchlorate, hexafluoroantimonate, tetra(bis 3,5-trifluoromethylphenyl)borate or tetraphenylborate or
those of the formula (Xb)
[(I) 2 L 2 M 1 ]An 1 (Xb)
where
(I) is in each case independently a compound of the formula (I) and
M 1 is rhodium or iridium and
An 1 is methanesulphonate, trifluoromethanesulphonate, tetrafluoroborate, hexafluorophosphate, perchlorate, hexafluoroantimonate, tetra(bis 3,5-trifluoromethylphenyl)borate or tetraphenylborate and
L is in each case a C 2 –C 12 -alkene, or
L 2 together is a (C 4 –C 12 )-diene and
those of the formula (XI)
[(I) 4 Hal 2 M 1 2 ] (XI)
where
(I) is in each case independently a compound of the formula (I) and
M 1 is rhodium or iridium and
Hal is chlorine, bromine or iodine or
those of the formula (XII)
[(I) 2 (arene)Hal 2 Ru] (XII),
where
(I) is in each case independently a compound of the formula (I) and
arene is a coordinated aromatic compound having 6 to 12 ring carbon atoms which is optionally substituted by up to 6 radicals which are each independently selected from the group of C 1 –C 8 -alkyl, benzyl and phenyl and
Hal is chlorine, bromine or iodine, or
those of the formula (XIII)
[(I) 2 (XIV)Hal 2 Ru] (XIII)
where
(I) is in each case independently a compound of the formula (I) and
Hal is chlorine, bromine or iodine,
(XIV) represents compounds of the formula (XIV)
where
R 25 , R 26 , R 27 and R 28 are each independently hydrogen, C 1 –C 12 -alkyl, C 4 –C 14 -aryl or C 5 –C 15 -arylalkyl radicals, or in each case two radicals together are a straight-chain or branched C 3 –C 12 -alkylene radical.
12. A transition metal complex having the formula (Xa)
[(I) 4 M 1 ]An 1 (Xa),
where
(I) is in each case independently a compound of the formula (I) as defined in claim 1 and
M 1 is rhodium or iridium and
An 1 is methanesulphonate, trifluoromethanesulphonate, tetrafluoroborate, hexafluorophosphate, perchlorate, hexafluoroantimonate, tetra(bis 3,5-trifluoromethylphenyl)borate or tetraphenylborate.
13. A transition metal complex having the formula (Xb)
[(I) 2 L 2 M 1 ]An 1 (Xb)
where
(I) is in each case independently a compound of the formula (I) as defined in claim 1 and
M 1 is rhodium or iridium and
An 1 is methanesulphonate, trifluoromethanesulphonate, tetrafluoroborate, hexafluorophosphate, perchlorate, hexafluoroantimonate, tetra(bis 3,5-trifluoromethylphenyl)borate or tetraphenylborate and
L is in each case a C 2 –C 12 -alkene, or a nitrile, or
L 2 together is a (C 4 –C 12 )-diene.
14. A transition metal complex having the formula (XI)
[(I) 4 Hal 2 M 1 2 ] (XI),
where
(I) is in each case independently, a compound of the formula (I) as defined in claim 1 and
M 1 is rhodium or iridium and
Hal is chlorine, bromine or iodine.
15. A transition metal complex having the formula (XII)
[(I) 2 (arene)Hal 2 Ru] (XII),
where
(I) is in each case independently a compound of the formula (I) as defined in claim 1 and
arene is a coordinated aromatic compound having 6 to 12 ring carbon atoms which is optionally substituted by up to 6 radicals which are each independently selected from the group of C 1 –C 8 -alkyl, benzyl and phenyl.
Hal is chlorine, bromine or iodine.
16. A transition metal complex having the formula (XIII)
[(I) 2 (XIV)Hal 2 Ru] (XIII),
where
(I) is in each case independently, a compound of the formula (I) and
Hal is chlorine, bromine or iodine,
(XIV) represents compounds of the formula (XIV)
where
R 25 , R 26 , R 27 and R 28 are each independently hydrogen, C 1 –C 12 -alkyl, C 4 –C 14 -aryl or C 5 –C 15 -arylalkyl, or in each case two radicals together are a straight-chain or branched C 3 –C 12 -alkylene radical.