Bicyclo[4,1,0]heptane-2,4-dion derivatives, its synthetic interm

Details Bicyclo[4,1,0]heptane-2,4-dion derivatives, its synthetic interm Bicyclo[4,1,0]heptane-2,4-dion derivatives, its synthetic interm

1994-05-25

1995-11-21

Reamer, James H.

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

568374, 560119, 560124, C07C 4548

Patent

active

054689058

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/JP92/00084, filed Jan. 28, 1992.


FIELD OF THE INVENTION

The present invention relates to bicyclo[4,1,0]heptane-2,4-dion derivatives useful as an intermediate, the intermediates for the synthesis thereof and the process for the manufacture thereof.


BACKGROUND ARTS

2-substituted benzoyl-1,3-cyclohexanediones have been known effective as weed killers, and the ones having various subsituents and/or chemical structures have been proposed.
It is an object of the present invention to provide effective compounds as the intermediates for synthesizing herbicidal compounds.


DISCLOSURE OF THE INVENTION

The present invention is directed to a compound represented by the general formula (I): ##STR1## wherein R.sup.1, R.sup.2 denotes each independently hydrogen, alkyl or --COOR.sup.3, and R.sup.3 denotes alkyl, and the process for the manufacture thereof, and a compound represented by the general formula (II): ##STR2## wherein R.sup.1, R.sup.2 are as defined above and R.sup.4 denotes alkyl, and the process for the manufacture thereof.
The compound of the general formula (I) is prepared from the compound of the general formula (II) according to the process shown below; ##STR3## wherein R.sup.1, R.sup.2 and R.sup.4 are as defined above.
The reaction shown above is accomplished by reacting a cyclopropane derivative of the general formula (II) in an adequate solvent and in the presence of a base.
As the solvent described above, alcohols such as methanol and ethanol can be used, and the sodium alcoholate or potassium alcoholate thereof can be used as the base described above.
The reaction can be accomplished at a temperature in a range of from room temperature to 150.degree. C., and preferably at the boiling point of the alcohol used. One to five times amount in mole of the base relatively to the mole of the cyclopropane derivative used, and preferably 1 to 2 times in mole, is used for the reaction.
Them cyclopropane derivatives of the general formula (II) can be manufactured by reacting a ketone of the general formula (III) with an ester of the general formula(IV) in the presence of a base according to the process shown below; ##STR4## wherein R.sup.1, R.sup.2 and R.sup.4 are as defined above, and Hal denotes halogen.
The foregoing reaction is normally accomplished in an adequate solvent. As the solvent, benzene, toluene and the like can be used besides alcohols, however, it is the most preferable to use alcoholate as a base in alcohol. In the reaction, bicyclic compounds represented by the general formula (I) can be prepared without isolating cyclopropane derivatives of the formula (II) when more than 2 moles of alcoholate is used. The halogen is preferably chlorine.
As shown below, a compound of the general formula (VI) having herbicidal activity can be readily prepared by reacting the bicyclic compound of the general formula (I) with chloride benzoate of the general formula (V). ##STR5## wherein Xn denotes a substituent.
It is described in the International Publication No. WO 91/00260 Gazette that the compound represented by the general formula (VI) shows herbicidal activity.
The compound specified in this invention may have the tautomers as shown below. ##STR6##
The chemical structures of the compounds according to the invention and other compounds were determined by using IR, NMR, MS and other analytical apparatuses.


BEST MODE FOR CARRYING OUT THE INVENTION

Now, the present invention is practically explained with reference to Examples and Practical Examples.


EXAMPLE 1



(2-acetylcyclopropyl)diethyl methylmalonate
##STR7##
In 25 ml of ethanol was added 5.15 g of powdered sodium ethylate, then dissolved. To the solution, 13.2 g of diethyl methylmalonate was added at room temperature, then 9.5 g of 5-chloro-3-pentane-2-on (90% purity) was further fed dropwise thereto for 30 min. at a temperature of from 0.degree. to 10.degree. C. After reacting the solution for 3 hours at room temperature, ethanol therein was removed by distillation under reduced pressure, then an extraction

REFERENCES:
patent: 3932511 (1976-01-01), Schaafsma et al.
patent: 4399310 (1983-08-01), Greco
patent: 4414418 (1983-11-01), Lehky
patent: 5228898 (1993-07-01), Ueda et al.
Enda et al, J.A.C.S., vol. 107, pp. 5495-5501 (1985).
Kutney et al, Can. J. Chem., vol. 59, pp. 3162-3167 (1981).

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