Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1994-11-17
1996-04-16
Ivy, C. Warren
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
549285, 549299, 549354, 549389, 560128, 558428, 558430, 554111, 554221, C07D31300, C07C 6974
Patent
active
055084443
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT/GB93/00523 filed Mar. 12, 1993.
This invention relates to cyclic compounds and to a process for making them. The compounds are useful intermediates in the fields of agrochemicals and pharmaceuticals.
Certain cis 1,2-dihydroxycylohexadienes are useful in the preparation of novel polymers. In our European Patent Specification No. 76606 B we disclose a process for the production of such dihydroxy cyclohexadienes from aromatic compounds using mutant strains of the species Pseudomonas putida, in particular mutants of P. putida strains NCIB 11767 and NCIB 11680. The enzyme which catalyses the reaction involved in this process is an aromatic dioxygenase which catalyses a reaction between certain aromatic compounds and oxygen for example, the reaction below between benzene and oxygen ##STR1##
When strains such as P. putida NCIB 11767 and NCIB 11680 are fed with aromatics, the dihydroxy cyclohexadiene compounds do not accumulate since they are rapidly further oxidised via catechols to products of intermediary metabolism. However, in our European Patent No. 76606-B we describe how mutants of these microorganisms may be produced which are unable to oxidise the dihydroxy cyclohexadienes and these as a result accumulate when such mutants are exposed to aromatic substrates. Some of these mutants must be grown in the presence of benzene or toluene if the activity of the aromatic dioxygenase enzyme needed to convert aromatics to dihydroxy cyclohexadienes is to be induced.
The process of our European Patent 76606-B, particularly when carried out using microbial cells produced by the method of European Patent No. 250 122 B, enables conversions of aromatic compounds to be achieved to produce some interesting new cyclic dihydroxy compounds. In our EP-A-364 152 we disclose compounds of the formula ##STR2## where R is an alkyl or substituted alkyl group, and a process for preparation of such compounds using P. putida.
The process of EP-A-364 152 involves crystalising the cyclic dihydroxy compounds under conditions of extremely low temperatures (for example, -78.degree. C.) which are not practical or economic for the preparation of large quantities of the compounds for use in the preparation of, for example, agrochemicals or pharmaceuticals.
Surprisingly, it has been found that preparation of the novel compounds of the present invention can by achieved with much less difficulty and more economically by the process of the present invention.
According to the invention there is provided a cyclohexadiene compound of formula (I) or (II) ##STR3## wherein A is a carboxylic ester or CN; R.sup.1 is lower alkylene in formula (II) and methylene in formula (I) both optionally carrying one or more non-interfering substituents; R.sup.2 is 0 or NH or NR.sup.3 ; R.sup.3 is C.sub.1-4 alkyl; X is a non-interfering substituent; Z is an optional group comprising a 5- or 6-membered carbocyclic ring which is optionally substituted; m is 0 or 1; and n is 0-3.
In the compounds of formula (I) A is a carboxylic ester having the formula --C(O)--O--R, preferred examples are those in which R is straight or branched chain C.sub.1 -C.sub.10 alkyl, particularly C.sub.1-4 alkyl, for example, methyl, ethyl, n- and iso-propyl, n-, iso-,sec- and tertiary-butyl.
In the compounds of formula (I) R.sup.1 is methylene and is optionally substituted one or more non-interfering substituents including halogen, particlularly fluorine, chlorine, bromine and iodine, C.sub.1-6 alkyl, particularly, methyl, ethyl, n-, isopropyl, n-, iso-, sec- and tertiary-butyl, C.sub.3-6 cycloalkyl especially cyclohexyl, CF.sub.3, CN, NO.sub.2, phenyl or phenyl substituted with substituents as defined for X below, CO.sub.2 R where R is as defined above, OH, OR.sup.4, SH, SR.sup.4, NHR.sup.4, NR.sup.4 R.sup.4, O, NOH, NOR.sup.4, CH.sub.2, CR.sup.4 H and CR.sup.4 R.sup.4.
Where R.sup.1 in formula (II) is lower alkylene it is preferably C.sub.1-4 alkylene, especially methylene or ethylene. R.sup.1 is optionally substituted with suitable non-interfering substituent
REFERENCES:
patent: 5216083 (1993-06-01), Grubbs et al.
Demarinis et al: "Synthesis of trans-2, 3-dihydroxy-2, 3-dihydrobenzoic acid and related substances from 4-carbo-tert-butoxyoxepin", Journal of the American Chemical Society, vol. 96, No. 4, Feb. 20, 1974, pp. 1193-1197.
Gibson, et al: "Microbial Degradation of Aromatic Hydrocarbons", The Microbial Degradation of Oil Pollutants, pp. 33-38 (1973).
Joseph-Nathan, P et al CA: 5430a (1966).
Blacker Andrew J.
Bowden Martin C.
Brown Martin
Ivy C. Warren
Owens Amelia
Zeneca Limited
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