Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Patent
1997-01-21
1998-07-21
Ambrose, Michael G.
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
544389, 546245, 560 24, 560 25, 560 27, 560 28, 560157, 560158, C07D295205, C07D21106, C07C26904
Patent
active
057836973
DESCRIPTION:
BRIEF SUMMARY
This application is a national stage filing under 35 USC 371 and was based upon PCT International Application No. PCT/EP95/02805, which was filed Jul. 18, 1995.
The present invention relates to a process for preparing vinyl esters of carbamic acid compounds. In particular, the present invention relates to a process for preparing compounds of this type, in which the reaction of secondary amines with carbon dioxide and acetylene compounds is carried out in the presence of catalysts from the group of platinum metals.
The preparation of vinyl carbamates from vinyl chloroformate and amines is a reaction which has been described in detail (R. A. Olofson et al.; THL 18, 1563-1566 (1977)).
Two variants are known for the preparation of vinyl chloroformate starting from carbon oxychloride. On the one hand reaction with mercury enolate (R. A. Olofson et at.; JOC, 43, 752, (1978)), and on the other hand reaction with ethylene glycol to give ethylene glycol bischloroformate which is subsequently cleaved thermally to vinyl chloroformate (L. H. Lee, JOC 30, 3943, (1965); U.S. Pat. No. 2,377,095).
Besides the great safety precautions necessary when working with carbon oxychloride, there is a highly toxic risk in the use of organomercury compounds.
Thermal elimination on ethylene glycol bischloroformate takes place only with poor selectivity and the formation of toxicologically objectionable byproducts.
P. H. Dixneuf has described a synthesis of vinyl carbamates from secondary amines, carbon dioxide and acetylene (J. Org. Chem. 54, 1518 (1989)). This entailed acetylene being dissolved in a solvent at -50.degree. C. and reacted in an autoclave with carbon dioxide and a secondary amine with catalysis by ruthenium trichloride at 80.degree. C. to give the vinyl carbamate. The yields in this process are moderate.
J. of Organic Chemistry, Vol. 54, No. 7, p. 1518 (1989) relates to a process for preparing vinyl carbamates by reacting secondary amine with carbon dioxide and acetylene, vinylacetylene or hexyne, with vinyl carbamates being obtained in the presence of ruthenium compounds with or without catalytic amounts of a free phosphine.
It is an object of the present invention to improve the process as known from the prior art in such a way that high yields and/or high selectivity, preferably both, is achieved.
We have found that this object is achieved by a process for preparing vinyl carbamate compounds. These compounds have the formulae (I) and (II) ##STR1## where R.sup.1 and R.sup.2 each monovalent hydrocarbon radicals with 1 to 6 carbon atoms, in particular alkyl or aryl- and/or cycloalkyl-substituted alkyl with 1 to 6 carbon atoms, aryl or alkyl- and/or cycloalkyl-substituted aryl with 6 to 10 carbon atoms and cycloalkyl or alkyl- and/or aryl-substituted cycloalkyl with 3 to 10 carbon atoms, or bonded, a heterocyclic group with 5 to 7 ring members and I to 3 hetero atoms from the group of O, N, S, 10 carbon atoms, aryl or alkaryl with 6 to 10 carbon atoms, particular alkylene or aryl- and/or cycloalkyl-substituted alkylene with 1 to 6 carbon atoms, arylene or alkyl- and/or cycloalkyl-substituted arylene with 6 to 10 carbon atoms and cycloalkylene or alkyl- and/or aryl-substituted cycloalkylene with 3 to 10 carbon atoms, or R.sup.1 form, with the particular nitrogen atoms to which they are bonded, a heterocyclic group with 5 to 7 ring members and 1 to 3 hetero atoms from the group of O, N, S.
In the process, the appropriate secondary amines of the formulae (III) and (IV) ##STR2## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the abovementioned meanings, are reacted with carbon dioxide and acetylenically unsaturated compounds of the formula (V) the presence of a compound of a metal from the platinum group, in particular a ruthenium compound.
In this reaction, according to the invention process step (b) with or without process step (a), or, preferably both, are carried out:
It has been found, surprisingly, that secondary amines can be reacted with carbon dioxide and acetylene to give the vinyl carbamates in distinctly highe
REFERENCES:
patent: 2377085 (1945-05-01), Kung
Mahe, Roger et al. "Catalytic Synthesis of Vinyl Carbamates from Carbon Dioxide and Alkynes with Ruthenium Complexes," J. Org. Chem. 1989, 54, 1518-1523, Mar. 1989.
Olofson et al., Tetrahedron Letters, No. 18, pp. 1563-1566, 1977.
Olofson et al., J. Org. Chem., vol. 43, No. 4, 1978.
Lee, J. Org. Chem., vol. 30, pp. 3943-3945, 1965.
Mahe et al., J. Org. Chem. vol. 54, pp. 1518-1523, 1989.
Chem. Abst., vol. 114, No. 20, AN 186109t (1991).
Heider Marc
Henkelmann Jochem
Karcher Michael
Ruhl Thomas
Ambrose Michael G.
BASF - Aktiengesellschaft
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