Process for preparing aromatic olefins in the presence of...

Details Process for preparing aromatic olefins in the presence of... Process for preparing aromatic olefins in the presence of...

1999-06-04

2001-09-18

Shah, Mukund J. (Department: 1611)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

Reexamination Certificate

active

06291383

ABSTRACT:

The present invention relates to a process for preparing aromatic olefins using palladium catalyst systems comprising phosphite ligands.
Olefins, in particular aromatic olefins such as cinnamic acid derivatives, styrenes or stilbenes, are of industrial importance as fine chemicals, starting materials for polymers, UV absorbers, agrochemicals and precursors of active compounds.
A frequently employed method of synthesizing aromatic olefins in the university sector is the Heck reaction in which iodoaromatics or bromoaromatics and, in exceptional cases, chloroaromatics are reacted with olefins in the presence of palladium catalysts. Reviews which describe this methodology may be found, for example, in R. F. Heck, Org. React. 1982, 27, 345 and in B. Cornils, W. A. Herrmann, Applied homogeneous catalysis with organometallic compounds, Vol. 2, p. 712, VCH, Weinheim 1996.
Catalysts which are used for the purposes of the Heck reaction are palladium compounds. Although both palladium(II) and palladium(0) complexes can be used in Heck reactions, it is generally accepted that palladium(0) compounds are the actual catalysts in the reaction. In particular, co-ordinatively unsaturated 14 and 16 electron palladium(0) species which are stabilized by means of donor ligands such as phosphines are formulated in the literature. When using aryl iodides as starting materials in Heck reactions, it is also possible to dispense with phosphine ligands. However, aryl iodides are very expensive starting compounds which, moreover, produce stoichiometric amounts of waste iodide salts. Less expensive starting materials for the Heck reaction, e.g. aryl bromides or aryl chlorides, require the addition of stabilizing ligands for them to be catalytically activated and reacted.
The catalyst systems described for Heck reactions frequently give satisfactory catalytic turnover numbers (=TONs) only when uneconomical starting materials such as iodoaromatics and activated bromoaromatics are used. Otherwise, in the case of deactivated bromoaromatics and particularly in the case of chloroaromatics, it is generally necessary to add large amounts of catalyst, customarily from 1 to 5 mol%, in order to achieve industrially useful conversions. In addition, owing to the complexity of the reaction mixtures, simple catalyst recycling is not possible, so that the catalyst costs generally also stand in the way of industrial implementation. Although newer catalyst systems based on cyclometallated phosphines give satisfactory catalyst activities for a series of bromoaromatics, the catalyst have to be prepared separately from expensive alkylated phosphines. Furthermore, chloroaromatics cannot yet be activated in an industrially satisfactory manner using these catalysts (W. A. Herrmann, C. Bro&bgr;mer, K. Öfele, T. Priermeier, M. Beller, H. Fischer,
Angew. Chem
. 1995, 107, 1989, Strukturell definierte Katalysatoren f{umlaut over (u )}r die Heck-Olefinierung von Chlor—und Bromaromaten). Where high yields were achieved, it was necessary to use very high and thus very expensive amounts of catalyst since the catalyst TON has hitherto been low even using these systems.
For these reasons, there is a great need for a new palladium catalyst system which comprises inexpensive ligands and which does not display the disadvantages of the known catalytic processes, which is suitable for industrial-scale use and which gives olefins in high yield and purity with a high catalyst TON.
This object is achieved by a process for preparing monofunctional, bifunctional or/and polyfunctional olefins of the formulae (Ia), (Ib), (Ic) or/and (Id),
where R
1
to R
3
are, independently of one another, hydrogen, (C
1
-C
8
)-alkyl, CN, COOH, COO-alkyl-(C
1
-C
8
), CO-alkyl-(C
1
-C
8
), aryl-(C
6
-C
10
), COO-aryl-(C
6
-C
10
), CO-arly-(C
6
-C
10
),
O-alkyl-(C
1
-C
8
), O—CO-alkyl-(C
1
-C
8
), N-alkyl
2
-(C
1
-C
8
) and aryl is an aromatic radical containing up to 14 carbon atoms,
where this radical may bear up to five substituents which are, independently of one another, hydrogen, (C
1
-C
8
)-alkyl, O-alkyl-(C
1
-C
8
), OCO-alkyl-(C
1
-C
8
), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO
2
, Si(alkyl-(C
1
-C
8
))
3
, CN, COOH, CHO, SO
3
H, NH
2
, NH-alkyl-(C
1
-C
8
),
N-alkyl
2
-(C
1
-
8
), P-alkyl
2
-(C
1
-C
6
), SO
2
-alkyl-(C
1
-C
6
), SO-alkyl-(C
1
-C
6
), CF
3
, NHCO-alkyl-(C
1
-C
4
), COO-alkyl-(C
1
-C
8
), CONH
2
, CO-alkyl-(C
1
-C
8
), NHCOH, NHCOO-alkyl-(C
1
-C
4
), CO-phenyl, COO-phenyl, CHCH—CO
2
-alkyl-(C
1
-C
8
), P(phenyl)
2
, CHCHCO
2
H, PO-phenyl
2
, POalkyl
2
-(C
1
-C
4
), PO
3
H
2
, PO(O-alkyl-(C
1
-C
6
))
2
, SO
3
-alkyl-(C
1
-C
4
), where aryl is as defined above,
and where R
1a
to R
7a
are, independently of one another, hydrogen, (C
1
-C
8
)-alkyl, O-alkyl-(C
1
-C
8
),
OCO-alkyl-(C
1
-C
8
), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO
2
, Si(alkyl-(C
1
-C
8
))
3
, CN, COOH, CHO, SO
3
H, NH
2
, NH-alkyl-(C
1
-C
8
), N-alkyl
2
-(C
1
-C
8
), P-alkyl
2
-(C
1
-C
8
),
SO
2
-alkyl-(C
1
-C
6
), SO-alkyl-(C
1
-C
6
), CF
3
, NHCO-alkyl-(C
1
-C
4
), COO-alkyl-(C
1
-C
8
), CONH
2
, CO-alkyl-(C
1
-C
8
), NHCOH, NHCOO-alkyl-(C
1
-C
4
), CO-phenyl, COO-phenyl,
CHCH—CO
2
-alkyl-(C
1
-C
8
), P(phenyl)
2
, CHCHCO
2
H, PO-phenyl
2
-(C
1
-C
4
), PO
3
H
2
, PO(O-alkyl-(C
1
-C
6
))
2
, SO
3
-alkyl-(C
1
-C
4
), where aryl is as defined above
and where Ar is a heteroaromatic,
where the heteroaromatic Ar can be a substituted five-, six- or seven-membered ring containing, if desired, nitrogen, oxygen or sulfur atoms in the ring,
where further aromatic, heteroaromatic and/or aliphatic rings can be fused onto the ring, and
where the heteroaromatic can have substituents which are, independently of one another, hydrogen, (C
1
-C
8
)-alkyl, O-aryl, aryl, fluorine, chlorine, OH, NO
2
, CN, CO
2
H, CHO, SO
3
H, NH
2
, NH-alkyl-(C
1
-C
2
), N-alkyl
2
-(C
1
-C
12
), CHCHCO
2
H, NHCO-alkyl-(C
1
-C
12
), CO-alkyl-(C
1
-C
12
), NHCHO, COaryl, CO
2
aryl, CF
3
, CONH
2
, POaryl
2
, POalkyl
2
-(C
1
-C
12
), Si(alkyl-(C
1
-C
12
))
3
, O-alkyl-(C
1
-C
8
), OCO-alkyl-O-phenyl, phenyl, NH-alkyl-(C
1
-C
4
), COO-alkyl-(C
1
-C
8
), NHCOO-alky-(C
1
-C
4
), CO-phenyl, COO-phenyl, CHCH—CO
2
-alkyl-(C
1
-C
8
), PO-phenyl
2
, PO
3
H
2
, SO
3
-alkyl-(C
1
-C
4
), SO
2
-alkyl-(C
1
-C
4
), SO-alkyl-(C
1
-C
4
),
where aryl is as defined above,
and where
R
8a
to R
l0a
are, independently of one another, hydrogen, CN, CO
2
H, CO
2
-alkyl-(C
1
-C
8
), CONH
2
, CONH-alkyl-(C
1
-C
4
), CON-(alkyl)
2
-(C
1
-C
4
), fluorine, CO
2
-phenyl, alkyl-(C
1
-C
8
), phenyl, aryl, PO(phenyl)
2
, PO[alkyl-(C
1
-C
4
)]
2
, CO-phenyl, CO-alkyl-(C
1
-C
4
), O-alkyl-(C
1
-C
4
),
CONH-alkyl-(C
1
-C
8
), CON[alkyl-(C
1
--C
8
)]
2
, NH-alkyl-(C
1
-C
4
), PO
3
H
2
, SO
3
H, SO
3
-alkyl-(C
1
-C
4
), SO
2
-alkyl-(C
1
-C
4
), O-phenyl, where aryl is as defined above,
by reacting haloaromatics, haloolefins or/and heterohaloaromatics of the formulae (IIa), (IIb), (IIc) or/and (IId)
with olefins of the formula (II),
where, in the formulae of the type II and III, R
1
to R
3
and R
1a
to R
10a
are as defined above for the forrnulae of the type (I) and where X is iodine, bromine, chlorine, OSO
2
CF
3
, OSO
2
-phenyl, OSO
2
-tolyl, OSO
2
-alkyl-(C
1
-C
8
),
wherein a mixture of a palladium(0) complex or a palladium(II) salt with phosphylite ligands of the formulae (IVa) or/and (IVb),
where the fornula (IVb) represents a chelating phosphite ligand and where the radicals R
11a
to R
14a
are identical or different and are each, independently of one another, (C
1
-C
18
)-alkyl or/and a substituted (C
1
-C
18
)-alkyl group having the substituents hydrogen, O-alkyl-(C
1
-C
8
), O—CO-alkyl-(C
1
-C
8
), O-phenyl, phenyl, fluorine, chlorine, OH, NO
2
, CN, COOH, CHO, SO
3
H, SO
2
-alkyl-(C
1
-C
8
), SO-alkyl-(C
1
-C
8
), NH
2
, NH-alkyl-(C
1
-C
8
), N-alkyl
2
-(C
1
-C
8
), NHCO-alkyl-(C
1
-C
4
), CF
3
, COO-alkyl-(C
1
-C
8
), CONH
2
, CO-alkyl-(C
1
-C
8
), NHCOH, NHCOO-alkyl-(C
1
-C
4
), CO-phenyl, COO-phenyl, CHCH—CO
2
-alkyl-(C
1
-C
8
), CHCHCO
2
H, PO-phenyl
2
, POalkyl
2
-(C
1
-C
8
),

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