Esters of diphenic acid
Abstract Generated abstract
A series of aryl monoesters of diphenic acid was synthesized as part of a search for new biologically active compounds. The esters were prepared by reacting diphenic anhydride with substituted phenols in dry xylene, then isolated through alkaline dissolution, acid precipitation, and recrystallization, with melting points and elemental analyses reported for eight compounds. The products were colorless crystalline substances insoluble in water but soluble in organic solvents, and their sodium and ammonium salts were also examined. Insecticidal testing against flies and rice weevils indicated that only the p-cresyl monoester showed some contact activity, while some water-soluble salts showed increased toxicity in intestinal-action tests.
Full Text
Esters of Diphenic Acid
IV. Monoaryl Esters of Diphenic Acid and Their Insecticidal Activity
L. P. Kulev, R. N. Gireva, A. P. Belyaeva
In continuation of investigations aimed at finding new biologically active substances, we have obtained a series of acidic aryl esters of diphenic acid. All the esters were prepared by the reaction of diphenic anhydride with the corresponding phenols according to scheme [1].
\[ \begin{aligned} &\text{diphenic anhydride} + \mathrm{HO{-}AzX} \longrightarrow \text{HOOC–diphenyl–COO–AzX} \end{aligned} \]
where \(X = \mathrm{H}, \mathrm{CH_3}, \mathrm{Cl}, \mathrm{NO_2}\).
Monoesters are colorless crystalline substances, insoluble in water but soluble in alcohol and other organic solvents; with alkali metals they give salts readily soluble in water. Testing of insecticidal activity, carried out by A. V. Kovalenok at Tomsk State University on flies and rice weevils, showed that only the p-cresyl ester of diphenic acid possesses some activity.
Experimental Part
0.05 mole of diphenic anhydride, 0.05 mole of phenol, and 50 ml of dry xylene are heated in a flask equipped with a reflux condenser and a stirrer, in an oil bath at a temperature of \(145^\circ\), for 4 hours.
The precipitate that separates upon cooling of the reaction mixture is filtered off, dried, and dissolved in a 10% solution of soda. The solution is filtered. The monoester is precipitated from the filtrate with hydrochloric acid. The precipitate is recrystallized from alcohol or from a mixture of alcohol with dioxane.
The characteristics of the monoesters obtained are given in Table 1.
In addition to the esters themselves, which were tested for insecticidal activity by the contact method, water-soluble sodium and ammonium salts of the esters were obtained. Testing the latter as intestinal-action insecticides in some cases showed an increase in toxicity.
Table 1
\[ \begin{array}{c} \text{Esters}\\[4pt] \text{(general structure: } \mathrm{R{-}OOC{-}C_6H_4{-}C_6H_4{-}COOH}\text{)} \end{array} \]
| \(R\) | m.p., °C | Empirical formula | Analysis: found, % | Analysis: calculated, % |
|---|---|---|---|---|
| Phenyl | 136—137 | \(\mathrm{C_{20}H_{14}O_4}\) | C—76,23 H—4,07 |
C—75,47 H—4,40 |
| 2-Methylphenyl | 187—190 | \(\mathrm{C_{21}H_{16}O_4}\) | C—75,80 H—5,29 |
C—75,90 H—4,82 |
| 4-Methylphenyl | 161—162 | \(\mathrm{C_{21}H_{16}O_4}\) | C—75,86 H—4,87 |
C—75,90 H—4,82 |
| 4-Chlorophenyl | 158—159 | \(\mathrm{C_{20}H_{13}O_4Cl}\) | Cl—9,91 | Cl—10,07 |
| 2-Chlorophenyl | 167 | \(\mathrm{C_{20}H_{13}O_4Cl}\) | Cl—9,27 | Cl—10,07 |
| 4-Nitrophenyl | 208—209 | \(\mathrm{C_{20}H_{12}O_6N}\) | N—3,91 | N—3,86 |
| 3-Nitrophenyl | 140—141 | \(\mathrm{C_{20}H_{12}O_6N}\) | N—4,10 | N—3,86 |
| 1-Naphthyl | 201 | \(\mathrm{C_{24}H_{16}O_4}\) | C—78,19 H—4,35 |
C—78,26 H—4,35 |
Conclusions
Eight aryl monoesters of 2,2′-diphenic acid not described in the literature have been synthesized. Only the p-cresyl monoester of diphenic acid possesses some insecticidal activity.
LITERATURE
- R. E. Dean, E. N. White, A. D. McNell. J. Appe. Ch. 3, 439, 1953.