Preparation of preparing substituted indanones

Details Preparation of preparing substituted indanones Preparation of preparing substituted indanones

1999-09-01

2002-12-10

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S012000, C556S053000, C502S103000, C502S117000, C526S160000, C526S943000, C568S312000, C568S314000, C585S025000, C585S026000

Reexamination Certificate

active

06492539

ABSTRACT:

The present invention relates to a simple and economically interesting process for preparing substituted indanones.
Substituted indanones are important intermediates for preparing active compounds in the fields of pharmacy and crop protection (cf. S. J. deSolms et al., J. Med. Chem., 1978, 21, 437) and for preparing metallocene complexes (cf. Chemie in unserer Zeit, 1994, 28, 204, 205). In particular, substituted indanones can be used to prepare bridged chiral metallocenes which are of great importance as highly active catalysts in olefin polymerization (cf. EP-A 129 368). The catalyst properties can be influenced in a targeted manner by variation of the ligand system, eg. by substitution. This makes it possible to achieve the desired degree of change in the polymer yield, the tacticity or the melting point of the polymers (New J. Chem., 1990, 14, 499; Organomet., 1990, 9, 3098; Angew. Chem., 1990, 102, 339; EP-A 316 155; EP-A 351 392). Bridged zirconocenes containing, as &pgr; ligands, substituted indenyl radicals which bear the bridge in: position 1, preferably a hydrocarbon radical in position 2 and a hydrocarbon radical, preferably an aryl radical, in position 4 have been found to be particularly active and stereoselective catalyst systems (EP 0 576 970 A1; EP 0 629 632 A2). The ligand systems used for these highly active metallocenes are prepared from the corresponding indenes which are in turn obtained from indanones which are substituted in the appropriate positions (EP 0 576 970 A1; EP 0 629 632 A2). These indanones are synthesized from commercially available precursors or precursors known in the literature, for example as follows:
EP 0 576 970 A1:
The 2-methyl-4-phenylindanone is converted into the corresponding indene, for example by reduction of the ketone function to the alcohol and subsequent dehydration.
The three synthetic routes shown by way of example go through 2-, 4-substituted indanones which have in each case been obtained by Friedel-Crafts cyclization of the corresponding 3-arylpropionic acids. The syntheses are multistage processes in which relatively expensive starting compounds are used. Furthermore, in the syntheses disclosed in EP 0 629 632, the introduction of a protective group cannot be avoided. The processes shown are thus very costly routes.
It is therefore an object of the present invention to find a simple, flexible, inexpensive process for preparing substituted indanones which are important intermediates for preparing active compounds and metallocene complexes.
We have now surprisingly found that substituted indanones which contain a leaving group can be used to prepare, in a simple manner, other indanones which can be used, inter alia, for preparing active compounds and metallocene complexes.
The present invention accordingly provides a process for the preparation of indanones of the formula II from indanones of the Formula I or of indanones of the formula IIa from indanones of the formula Ia
which comprises reacting an indanone of the formula I or Ia with a coupling component, where, in the formulae I, Ia, II and IIa,
R
1
is a C
1
-C
40
-group such as a C
1
-C
40
-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, eg. a linear, branched or cyclic C
1
-C
20
-alkyl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
6
-C
22
-aryl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
7
-C
20
-alkylaryl group or a C
7
-C
20
-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents and the aryl part may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
2
-C
10
-alkenyl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
2
-C
20
-alkynyl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
8
-C
12
-arylalkenyl group, where the alkenyl part may bear one or, more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents and the aryl part may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents,
or R
1
is an OR
2
, SR
2
, NR
2
2
, PR
2
2
, SiR
2
3
or OSiR
2
3
group, where R
2
are identical or different and are each a C
1
-C
20
-hydrocarbon group such as a C
1
-C
10
-alkyl group or C
6
-C
14
-aryl group which may each bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents or two radicals R
2
may be joined to form a ring system, or R
1
is a C
1
-C
20
-heterocyclic group which is bound via a carbon atom and may in turn bear C
1
-C
20
-radicals or heteroatoms as substituents,
x is a leaving group such as a diazonium group, a halogen atom or a C
1
-C
40
-, preferably C
1
-C
10
-group which is bound via a heteroatom such as an atom of Group 13, 14, 15 or 16 of the Periodic Table of the Elements, eg. boron, silicon, tin, oxygen or sulfur, for example C
1
-C
40
-alkylsulfonate, C
1
-C
40
-haloalkylsulfonate, C
6
-C
40
-arylsulfonate, C
6
-C
40
-haloarylsulfonate, C
7
-C
40
-arylalkysulfonate, C
7
-C
40
-haloarylalkylsulfonate, C
1
-C
40
-alkylcarboxylate, C
1
-C
40
-haloalkylcarboxylate, C
6
-C
40
-arylcarboxylate, C
6
-C
40
-haloarylcarboxylate, C
7
-C
40
-arylalkylcarboxylate, C
7
-C
40
-haloarylalkylcarboxylate, formate, C
1
-C
40
-alkyl carbonate, C
1
-C
40
-haloalkyl carbonate, C
6
-C
40
-aryl carbonate, C
6
-C
40
-haloaryl carbonate, C
7
-C
40
-arylalkyl carbonate, C
7
-C
40
-haloarylalkyl carbonate, C
1
-C
40
-alkyl phosphonate, C
1
-C
40
-haloalkyl phosphonate, C
6
-C
40
-aryl phosphonate, C
6
-C
40
-haloaryl phosphonate, C
7
-C
40
-arylalkyl phosphonate or C
7
-C
40
-haloarylalkyl phosphonate,
R
3
is a C
1
-C
40
-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, for example a linear, branched or cyclic C
1
-C
20
-alkyl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
, NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
6
-C
22
-aryl group which may bear one or more identical or different halogen, OR
2
, SR
2
, NR
2
2
—, NH
2
, —N
2
H
3
, NO
2
, CN, CO
2
R
2
, CHO, COR
2
, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
7
-C
15
-alkylaryl group or C
7
-C
15
-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents and the aryl part may bear one or more identical or different halogen, OR
2
, SR
2
NR
2
2
—, NH
2
, —N
2
H
3
, NO
2
, CN, CO
2
R
2
, CHO, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
2
-C
10
-alkenyl group which may bear one or more identical or different halogen, OR, OR
2
, CO
2
R
2
, COR
2
, SR
2
, NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
2
-C
10
-alkynyl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
, NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, a C
8
-C
12
-arylalkenyl group which may bear one or more identical or different halogen, OH, OR
2
, SR
2
, NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents,
or R
3
is a halogen atom or a PR
2
2
, B(OR
2
)
2
, SiR
2
3
or SnR
2
3
group, where R
2
are identical or different and are each a C
1
-C
20
-hydrocarbon group, eg. a C
1
-C
10
-alkyl group or C
6
-C
14
-aryl group which may each bear one or more identical or different halogen, OH, OR
2
, SR
2
NR
2
2
—, PR
2
2
—, —SiR
2
3
or —OSiR
2
3
substituents, or two radicals R
2
may be joined to f

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