CS257137B1 - Process for preparing 3-aryloxymetylenphlhalides with pesticide activity - Google Patents

Description

The invention relates to a process for the preparation of pesticidally active 3-aryloxymethylenephthalides of the general formula I

in which

R ¹ is hydrogen or nitro and R ² is methyl, fluoro, chloro, bromo, iodo or nitro, n is an integer from 0 to 3.

It is known that the previously described methods for the preparation of 3-aryloxymethylenephthalides are based on the reaction of phthalic anhydride with aryloxyacetic acid under base catalysis such as potassium acetate, pyridine or trlethylamine (Gabriel S .: Ber. 14, 921, 1881; Furdík M., Lácová M) , Livař M .: Acta Facult, Rer., Nature Univ. Comen., Tom XII 265, 1968; Lácová M .: Chem. Rumors 27, 525, 1973;

M., Brondos M .: Chem. rumors 36, 245, 1982).

A disadvantage of the above-mentioned syntheses mainly from 257137 in terms of production technology is that the reaction yields are low, ranging from 10-25% and the end product is very contaminated with starting materials and decomposition products, since the reaction is carried out at temperatures of 220-250 ° C. a high percentage of brown oily decomposition products are formed.

The above drawbacks are solved by the process according to the invention. In the proposed process according to the invention, an equimolar mixture of melted phthalic anhydride of the formula II is condensed

R ¹ is hydrogen or a nitro group and a mixed acetic and aryloxyacetic anhydride of the general formula III ωco - o - co - (- ₎ where:

R ² and n are as defined above, in the presence of 2-5% K ₂ CO ₃ at a temperature of 170-200 degrees Celsius when condensation water escapes. Said process can be favored by stirring the reaction mixture, thereby reducing the reaction time. After completion of the reaction time (30-90 minutes), the reaction mixture was poured into water, NaHCO 3 was added, stirred for 1-2 h and then the precipitate was filtered off with suction. The yield of the crude product is 60-97% depending on R ¹ and R ² . The crude product can be used as a herbicidal preparation.

It is known that the 3-aryloxymethylene phthalides of the formula I are herbicidally active substances (Tácová M., Exclusive S .: US 135352, 1970), are insecticidal active substances of the juvenoid type (Lácová M., Paulov Š., Paulovová J. , J., J., Paulovová, J., Paulov, S., Lácová, M .: Effects of 3-aryloxymethylenephthalides on the development of Culex pipiens Molestus mosquitoes, Biologia (Bratislava) 33, 2, 127, 1978).

The following example illustrates but does not limit the scope of the invention. Example

A mixture of aryloxyacetic acid (0.1 mol) and acetic anhydride (30-40 cm ³ ) is heated to 150-200 ° C with distillation of AcOH. After distilling about 20 cm ³ , the hot mixture is poured into remelted phthalic anhydride (0.11 mol), K 2 CO 3 (1 g) is added and heated to 170-200 ° C with stirring while distilling off the condensed water. If water is no longer distilled, the mixture is cooled to 100-130 ° C and water is added with stirring (500 cm ³ ) and NaHCO 3 (3 g), stirred for 1 h at room temperature. The precipitate formed is filtered off with suction. It can be crystallized from ethanol, acetic acid, acetone or dimethylsulfoxide. Further prepared phthalides are in Table 1.

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Claims (1)

A process for the preparation of pesticidally active 3-aryloxymethylenephthalides of the general formula I wherein R ² and n are as defined above, with a phthalic anhydride of the formula III wherein: R ¹ is hydrogen or nitro and R ² is methyl, chloro, fluoro, bromo, iodo or nitro; n is an integer of 0-3, characterized by condensing a mixed aryloxyacetic anhydride and acetic acid of formula II R ¹ is as defined above, in the presence of K ₂ CO ₃ , at a temperature of 170-200 ° C. O-CH ₂ CO-O ~ COC / - / ₃ (II) Severografla, n. p. Race 7, Most 0SM *, 40 K * p