Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1998-05-20
2000-09-19
Shah, Mukund J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C07D48722
Patent
active
061214426
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to 1,2-dialkynylated compounds, especially dialkynyl-1,2-diones, a method of their production and their use as synthetic structural units to produce NIR dyes, pigments, thermostable polymers, charge-transfer complexes, heterocycles or pharmaceuticals.
1,2-dialkynylated compounds represent synthons for chemical synthesis which can be transformed by very many different reactions in pharmaceutically effective compounds, dyes or pigments, thermostable polymers, electron acceptors in charge-transfer complexes or in other valuable chemical substances.
Up to the present, no vicinal diketones were known in the state of the art which are substituted on both carbonyl carbon atoms by alkynyl groups (called "dialkynyl-1,2-diones" in the following). This is surprising since such compounds are especially well-suited according to theoretical considerations for the production of .alpha.,.beta.-dialkynyl-substituted heterocycles. Experiments to produce these desired compounds in a manner analogous to the synthesis of other 1,2-dione derivatives from oxalic acid derivatives (F. Babudri, V. Fiandanese, G. Marchese, A. Punzi: Tetrahedron Lett. (1995), 36, 7305-7308) such as e.g. from oxalylchloride or from 1,4-dimethylpiperazine-2, 3-dione (U. T. Mueller-Westerhoff, M. Zhou; J. Org. Chem. (1994) 59, 4988-4992) failed. In particular, no conversion of the metalated acetylides took place at low temperatures or overaddition to the tetra-alkinylated compounds, that is to the 1,2-diols, occurred under more vigorous conditions. Even the synthesis from trimethylsilyloxymethane phosphonates as masked equivalents of the corresponding acyl anions did not produce satisfactory results.
Thus, the present invention solves the problem of making available 1,2-dialkynylated synthons which can be used in the production of pharmaceutically effective compounds, dyes or pigments, thermostable polymers, electron acceptors in charge-transfer complexes or of other valuable chemical substances, as well as a method by which these synthons can be produced in a simple manner and in good yields.
This problem is solved by the embodiment characterized in the claims. In particular, compounds with the general formula (I) are made available ##STR1## in which the groups R.sup.1 and R.sup.2 can be identical or different and represent a hydrogen atom, a halogen atom, a straight-chain or branched-chain alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 7 carbon atoms which can comprise one or more heteroatoms, a substituted or unsubstituted aryl group which can comprise one or more heteroatoms, a mono-, di- or trialkylsilyl group with 1 to 6 carbon atoms independently of each other in each instance in the straight-chain or branched-chain alkyl group, a mono-, di- or triarylsilyl group with substituted or unsubstituted aryl groups independently of each other in each instance, an aralkyl group, an alkenyl group, an alkynyl group, an alkylthio group, an arylthio group, a trifluoromethyl-, ester-, carboxyl-, sulfonyl-, cyan-, alcohol-, aldehyde-, amino- or nitro group, or R.sup.1 and R.sup.2 form a ring together with 4 to 8 optionally substituted CH.sub.2 groups, at least one CH.sub.2 group of which can be replaced by an oxygen atom, a sulfur atom or an NR.sup.3 group, with R.sup.3 defined as defined below, X and Y can be identical or different and represent an oxygen atom, a sulfur atom, a dibromomethylene group, a dicyanomethylene group, an acyclic or cyclic O,O-ketenacetal group containing 2 to 3, optionally substituted, CH.sub.2 groups, a substituted or unsubstituted 2-(1,3-dithiol-2-ylidene) group, a methylidene group substituted with a straight-chain or branched-chain alkyl group or with a cycloalkyl group or with a substituted or unsubstituted aryl group, a group with the following structures, ##STR2## a PR.sup.3 group or an NR.sup.3 group in which the group R.sup.3 represents a hydrogen atom, a straight-chain or branched-chain alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 7 carbon atoms which c
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Faust Rudiger
Weber Christian
Shah Mukund J.
Sripada Pavanaram K
University of Heildelberg
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