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Home Molecular Biology Converting-enol-ester-precursor-of-a-benzoyl-1-3-cycloalkyldione-to-a-benzoyl-1-3-cycloalkyldione

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 Converting enol ester precursor of a benzoyl-1,3-cycloalkyldione to a benzoyl-1,3-cycloalkyldione

Details
Inventors: Bay, Elliott;
Assignee: Stauffer Chemical Company (Westport, CT)
Primary Examiner: Reamer; James H.
Assistant Examiner:
Attorney, Agent or Firm: Ackerman; Joel G., Fennelly; Richard P.

Enol ester precursors of benzoyl-1,3-cycloalkyldiones (e.g., the enol ester precursors of 2-(2'-nitrobenzoyl)-1,3-cyclohexanedione compounds) are converted to the desired benzoyl-1,3-cycloalkyldiones by heating the precursor in the presence of base and a catalytic amount of a trialkylsilylcyanohydrin as a cyanide source.

DETAILED DESCRIPTION OF THE PRESENT INVENTION The enol ester precursor of the benzoyl-1,3-cycloalkyldione has the general formula: ##STR1## where R is a substituted or unsubstituted phenyl group and A is a substituted or unsubstituted hydrocarbyl ring with a C.
dbd.
O moiety forming the ring two carbons removed from the carbon linked to the single bonded benzoyl oxygen atom and a carbon-carbon double bond from the carbon linked to that benzoyl oxygen and the carbon of the ring between that carbon and the one forming the aforementioned C.
dbd.
O moiety of the ring.
Particularly preferred compounds of this type are more fully described in the aforementioned published European Patent Application No.
186,118 and in its U.
S.
counterpart (U.
S.
Ser.
No.
802,135, filed Nov.
29, 1985, which is incorporated herein by reference), which is a continuation-in-part of U.
S.
Ser.
No.
683,900, filed Dec.
20, 1984.
Such compounds are herbicides and are defined as 2-(2'-nitrobenzoyl)-1,3-cyclohexanediones.
The conversion of the aforementioned enol ester precursor of the benzoyl-1,3-cycloalkyldione yields the desired benzoyl-1,3-cycloalkyldione which has the formula: ##STR2## where R is as defined before and A' is a 1,3-cycloalkyldione having two C.
dbd.
O moieties as part of its ring structure, each flanking each side of the ring carbon bonded to the single bonded benzoyl oxygen atom.
The cycloalkyl group is preferably cyclohexyl.
Some representative benzoyl-1,3-cycloalkyldione end products include 2-(2'-nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione, 2-(2'-nitro-4'-trifluoromethylbenzoyl)-1,3-cyclohexanedione, and 2-(2'-nitrobenzoyl)-1,3-cyclohexanedione.
The conversion of the enol precursor described before to the desired end product is achieved by reacting one mole of the enol ester precursor with about one to about four moles (preferably 2 moles) of base and about 0.
01 mole to about 0.
5 mole or higher of trialkylsilylcyanohydrin as a cyanide source).
The mixture can be stirred until the conversion (or arrangement) reaction is substantially complete at a temperature of below about 50



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