Saccharin derivatives

Plant protecting and regulating compositions – Plant growth regulating compositions – Organic active compound containing

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548210, A01N 4380, C07D27506, C07D41710

Patent

active

057169063

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/EP95/02975 filed Jul. 27, 1995, published as WO96/05198 Feb. 22, 1996.
The present application relates to saccharin derivatives of the formula I ##STR3## where the substituents have the following meanings: L and M are hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, chlorine, cyano, methylsulfonyl, nitro or trifluoromethyl; C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.5 -alkynyl, C.sub.1 -C.sub.4 -acyl, benzyl or phenyl, the phenyl rings in each case being unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 -alkyl; ##STR4## where R.sup.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl and 1-methylthiocyclopropyl; -C.sub.4 -acyl or a chlorine atom;
The invention further relates to herbicidal compositions, containing the compounds I, and methods of controlling undesired plant growth using the saccharin derivatives I. Moreover, the present invention also encompasses intermediates for preparing the final products I according to the invention and preparation processes for the products I, using the novel intermediates of the formulae B2 and IV ##STR5##
Saccharin derivatives having herbicidal action cannot be inferred from the prior art. However, unsubstituted saccharin (o-sulfobenzimide, ie. L, M, Q and Z in formula I=H) has been known as a synthetic sweetener for a long time. 4-Hydroxysaccharin is further known as a sweetener (German Offenlegungsschrift 3 607 343). The use of saccharin derivatives in pest control is also known, eg. JP publication 72/00419, 73/35457 (fungicides) and in pharmacy, eg. EP-A 594 257 and patents further mentioned therein.
Heterocyclic compounds having a sulfonamide-containing ring have been disclosed as herbicides, a typical representative which can be mentioned here being bentazone ##STR6##
It is an object of the present invention to make available novel herbicides having a basic structure which was hitherto unknown for this indication. We have found that this object is achieved by the compounds I and the intermediates B2 defined at the outset.
Compounds of the formula I where R.sup.1 =H are obtained by acylating 2087! with an acid chloride of the formula IV to give an ester of the formula B1, converting this by reaction with p-toluenesulfonic acid in toluene to a 1,3-diketone of the formula C1, then either converting the 1,3-diketone C1 to an enol ether D1 using ethyl orthoformate or to an enamine D2 using dimethylformamide dimethyl acetal and reacting D1 or D2 with hydroxylamine to give the saccharin derivative of the formula I.1. The reaction sequence is summarized in the following reaction scheme: ##STR7##
The .beta.-ketoesters of the formula A1 used as starting materials are known and can be obtained eg. by reaction of Meldrum's acid with acid chlorides of the formula R.sup.2 --COCl and subsequent reaction with tert-butanol. ##STR8##
The reaction of .beta.-ketoesters of the formula A1 with benzoyl chlorides and the subsequent acid-catalyzed decomposition to 1,3-diketones is known, eg. from EP-A 527 037 and EP-A 560 483. Both the condensation of 1,3-diketones with triethyl orthoformate and the reaction of the enol ethers D1 formed in this case with hydroxylamine to give isoxazoles is known, eg. from EP-A 527 036 and EP-A 560 483. The reaction of 1,3-diketones with orthoamides such as dimethylformamide dimethyl acetal and the subsequent reaction of the enamines D2 formed in this case with hydroxylamine to give isoxazoles is described by Menozzi in J. Het. Chem. 20 (1983), 645.
If, however, R.sup.1 has the meaning C.sub.1 -C.sub.4 -alkyl, the compounds of the formula I are obtained by reacting saccharincarbonyl chlorides of the formula IV with alkynylstannanes of the formula A2 to give benzoylalkynes of the formula B2 and then subjecting these to a cycloaddition with nitrile oxides of the formula C2 to give the isoxazoles of the formula I.2: ##STR9##
In the formulae mentioned above, L and M have the meaning given at the outset and Z is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.3 -C.s

REFERENCES:
patent: 1937521 (1933-12-01), Limburg
patent: 5457106 (1995-10-01), Takatani et al.
Liebigs Ann. 669, (1963), 85--Die Asymmetrische . . . Von Walter Theilacker et al.
Kastle, Amer. Chem. Jrl. 11 (1889), 177-99.
Weber, Chem. Ber. 25 (1892), 1737-45.
Zincke, Liebigs Ann. 427 (1922) 221-55.
Crisp, Synth. Comm. 19 (1989), 1745.
Menozzi, J. Het. Chem. 20 (1983), 645.
Chem. Abstr. of JP 73/35457 (1970).

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