ISSN print edition: 0366-6352
ISSN electronic edition: 1336-9075
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Synthesis of O-substituted N-hydroxy-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-en-e2,3-dicarboximides and their herbicide and insecticide activity

Laboratorium für Chemie der Naturwissenschaftlichen Fakultät an der Komensky-Universität, Bratislava

Abstract: The synthesis of not yet described N-alkoxy, N-alkenyloxy, N-aralkyloxy, and N-acyloxy derivs. from N-hydroxy-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (I) was described. The title activity as related to the structural formula was studied. I was prepd. by a modified procedure applied for the prepn. of the tetrahydrophthaloxime with an aq. medium instead of MeOH, but only with 1 hr. refluxing. N-Alkoxy, N-alkenyloxy, and N-aralkyloxy derivs. were prepd. by the reaction of Na salt of I with the corresponding halide in the aq.-alc. medium with the yields, dependent on the reactivity of the halide, in the range from 61.8-95.8%. The N-acetoxy deriv. was prepd. by the reaction of I and Ac2O, yield 75.7%. The other N-acyloxy derivs. were prepd. by the reaction of I with the corresponding acyl chlorides in C6H6 and with the addn. of PhNEt2. The yields were from 83.0% to 96.5%. These N-alkoxy derivs. were prepd. (m.p. given): methoxy (II), 197.5-8.5°; ethoxy (III), 134-6°, propoxy (IV), 123-5°; isopropoxy (V), 137-8°; allyloxy (VI), 92.5-4.5°; butoxy (VII), 94.5-6.5°; 3-chloro-2-butenyloxy (VIII), 123.5-5.0°; amyloxy (IX), 143-5°; isoamyloxy (X), 105-7°; hexyloxy (XI), 100.5-2.5°; benzyloxy (XII), 194.5-6.5°; acetoxy (XIII), 195.5-6.5°; benzoyloxy (XIV), 193.5-4.5°; 3,4,5-trimethoxybenzoyloxy (XV), 249-51°; 2-chlorobenzoyloxy (XVI), 229.5-30.5°; 4-chlorobenzoyloxy (XVII), 216-17°, and furoyloxy (XVIII), 215.5-17.5°. Alkyl iodides were applied in the formation of II, III, IV, VII, IX, X and XI, alkyl chlorides in the formation of VIII and XII, and alkyl bromides in the formation of V and VI. The general procedure for the prepn. of the N-alkoxy derivs. II to XII is given in the prepn. of VI: 0.05 mole I is dissolved in the soln. of NaOH in 50 ml. H2O and 100 ml. EtOH. After adding 0.05 mole of allyl bromide, the mixt. is refluxed 1 hr., decolorized with active C and concd. in vacuo to give VI. To prep. XIII, 0.04 mole I is dissolved in 50 ml. Ac2O and refluxed 1 hr., the mixt. decolorized as above, and poured into 500 ml. H2O at 40° to give (after cooling) XIII. XIV to XVIII are prepd. by the procedure given for XVI: a mixt. of 0.05 mole I, 0.05 mole 2-ClC6H4COCl, and 0.05 mole PhNEt2 is refluxed 1 hr. in 50 ml. C6H6, decolorized, and concd. in vacuo, poured into 200 ml. H2O at 50°, and cooled to give XVI. The substitution with 6 atoms of Cl in the positions 1, 4, 5, 6, 7, 7 caused a considerable decrease in the herbicide activity in II to XVIII. The insecticide activity (tested on Musca domestica) is also low.

Full paper in Portable Document Format: 215a340.pdf (in Slovak)

Chemical Papers 21 (5) 340–349 (1967)