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US 2004/0006235 A1Published application
Process for the preparation of ring compounds
AssigneeMerck Patent GmbH
InventorsDetlef Pauluth, Peer Kirsch, Peter Baeuerle, Oliver Deeg
Life of this patent
Estimating the term…
Abstract
In a process for the preparation of ring compounds via a combinatorial synthesis, the reaction procedure is based on a Suzuki coupling, subsequent halo-demetallation and finally a further Suzuki coupling. The Suzuki couplings are each carried out with a boronic acid or a boronic acid ester. The reaction procedure uses provides novel ring compounds and uses novel synthesis units used for this purpose. The novel ring compounds are suitable for use as constituents in liquid-crystalline mixtures.
Claims20
A process for preparation of a ring compound of formulae I to IV
- 63
- wherein one or two CH groups in the aromatic ring systems of the formulae I to IV may each be replaced by N;
- m and n, independently of one another, are identical or different and are each 0 or 1, and the sum m+n is 1 or 2;
- X is a single bond,
- 64
- the L groups, independently of one another, are identical or different and are each R, F, Cl, Br, I, OH, OR, SH, SR, CN, NO2, NO, CHO, COOH, COOR, CONH2, CONHR, CONR2, CF3, NH2, NHR or NR2;
- R is an alkyl, alkenyl or acyl group having from up to 12 carbon atoms or an aryl group having 6 carbon atoms, which is optionally substituted by an alkyl group having from 1 to 12 carbon atoms;
- a, b, c, d, e and f, independently of one another, are identical or different and are each 0, 1 or 2, and the sum a+b+c+d+e+f is 1 to 8;
- R1 and R2, independently of one another, are identical or different and are each H, F, Cl, CN, NCS, a straight-chain or branched, optionally chiral alkyl radical or alkoxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkynyl radical having from 2 to 8 carbon atoms, in each of which, in addition, one CH2 group may be replaced by —O—, —CO—, —O—CO— or —COO— in such a way that heteroatoms are not linked directly to one another and/or one or more H may be replaced by halogen;
- and
- in the case where m is 0 one CH2 group in R1 may be replaced by one of the following groups, or in the case where n is 0 one CH2 group in R may be replaced by one of the following groups:
- a) trans-1,4-cyclohexylene, in which, in addition, one or more non-adjacent CH2 groups may each be replaced by —O— or —S—,
- b) a radical from the group consisting of 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or
- c) 1,4-cyclohexenylene,
- and in which the radicals a), b) and c) are unsubstituted or substituted by CN, halogen, or combinations thereof;
- said process comprising subjecting a compound of formulae V to VIII
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- wherein
- Z is I, Cl, Br or triflate,
- M is Si, Ge or Sn, and
- R3, R4 and R5, independently of one another, are identical or different and are each H, C1-C12-alkyl or C1-C12-alkoxy,
- via combinatorial synthesis, to the following reaction steps which are carried out in a matrix-like arrangement of reaction vessels:
- A) Suzuki coupling with a boronic acid or a boronic acid ester of formula X
- 66
- wherein
- R6 and R7, independently of one another, are identical or different and are each H, C1-C12-alkyl, C2-C12-alkenyl or aryl, and where R6 and R7 can also be bridged in a cyclic manner;
- B) subsequent halo-demetallation;
- and
- C) Suzuki coupling with a boronic acid or a boronic acid ester of formula XI
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- wherein one or two CH groups in the aromatic ring systems of formulae V to VIII, X and XI may each also be replaced by N.
28 more elements
A ring compound of formula XIII
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- wherein
- one or two CH groups in the aromatic ring systems of formula XIII may each be replaced by N;
- Y is a group of formulae XIV to XVII
- 70
- in which one or two CH groups in the aromatic ring systems may each be replaced by N;
- m and n, independently of one another, are identical or different and are each 0 or 1, and the sum m+n is 1 or 2;
- X is a single bond,
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- L, independently of one another, are identical or different and are each R, F, Cl, Br, I, OH, OR, SH, SR, CN, NO2, NO, CHO, COOH, COOR, CONH2, CONHR, CONR2, CF3, NH2, NHR or NR2;
- R is an alkyl, alkenyl or acyl group having up to 12 carbon atoms or an aryl group having 6 carbon atoms which is optionally substituted by an alkyl group having from 1 to 12 carbon atoms;
- and
- a, b, c, d, e and f, independently of one another, are identical or different and are each 0, 1 or 2, and the sum a+b+c+d+e+f is 1 to 8;
- R1 and R2, independently of one another, are identical or different and are each H, F, Cl, CN, NCS, a straight-chain or branched, optionally chiral alkyl radical or alkoxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkynyl radical having from 2 to 8 carbon atoms, in each of which, in addition, one CH2 group may be replaced by —O—, —CO—, —O—CO—, —COO— or —CH═CH— in such a way that heteroatoms are not linked directly to one another and/or one or more H may be replaced by halogen;
- and
- in the case where m is 0 or n is 0, one CH2 group in R1 or R2 may be replaced by one of the following groups:
- a) trans-1,4-cyclohexylene, in which, in addition, one or more non-adjacent CH2 groups may each be replaced by —O— or —S—,
- b) a radical from the group consisting of 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or
- c) 1,4-cyclohexenylene,
- and in which the radicals a), b) and c) may also be substituted by CN and/or halogen.
17 more elements
A boronic acid or boronic acid ester compound of formula XIX
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- wherein
- one or two CH groups in the aromatic ring system may each be replaced by N;
- r is 1 or 2;
- R is H, F, Cl, CN, NCS, a straight-chain or branched, optionally chiral, alkyl radical or alkoxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkynyl radical having from 2 to 8 carbon atoms, in each of which, in addition, one CH2 group may be replaced by —O—, —CO—, —O—CO— or —COO— in such a way that heteroatoms are not linked directly to one another and/or one or more H may be replaced by halogen;
- the L groups, independently of one another, are identical or different and are each R′, F, Cl, Br, I, OH, OR′, SH, SR′, CN, NO2, NO, CHO, COOH, COOR′, CONH2, CONHR′, CONR′2, CF3, NH2, NHR′ or NR′2;
- R′ is an alkyl, alkenyl or acyl group having from up to 12 carbon atoms or an aryl group having 6 carbon atoms, which is optionally substituted by an alkyl group having from 1 to 12 carbon atoms;
- a, is 0, 1 or 2;
- R6 and R7,independently of one another, are identical or different and are each H, C1-C12-alkyl, C2-C12-alkenyl or aryl, and where R6 and R7 can also be bridged in a cyclic manner.
6 more elements
A boronic acid or boronic acid ester compound of formula XXI
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- wherein
- one or two CH groups in the aromatic ring system may each be replaced by N;
- r is 1 or 2;
- R3, R4 and R5, independently of one another, are identical or different and are each H, C1-C12-alkyl or C1-C12-alkoxy;
- R6 and R7,independently of one another, are identical or different and are each H, C1-C12-alkyl, C2-C12-alkenyl or aryl, and where R1 and R7 can also be bridged in a cyclic manner;
- M is Si, Ge or Sn;
- the L groups, independently of one another, are identical or different and are each R′, F, Cl, Br, I, OH, OR′, SH, SR′,CN, N2, NO;
- CHO, COOH, COOR′, CONH2, CONHR′, CONR′2, CF3, NH2, NHR′ or NR2;
- R′ is an alkyl, alkenyl or acyl group having from up to 12 carbon atoms or an aryl group having 6 carbon atoms, which is optionally substituted by an alkyl group having from 1 to 12 carbon atoms;
- and
- a, is 0, 1 or 2.
9 more elements
Dependencies are inferred from the claim text.