DERIVATIVES OF DIPHENIC ACID

I. Substituted amides of 2,2′-diphenic acid

L. P. KULEV, G. M. STEPNOVA

The problem of using phenanthrene in industrial organic synthesis has still not been solved. The most promising direction, as follows from an analysis of recent literature data, is the preparation of phenanthrene oxidation products, chiefly diphenic acid and its anhydride, which may be of considerable interest for the production of polymeric materials of the alkyd-resin type [1, 2, 3], plasticizers [4], and other valuable products.

We set ourselves the goal of obtaining a series of amides of diphenic acid and testing them for herbicidal activity. Only a few representatives of this series have been described in the literature. Thus, A. Chandra, Sirkar, and R. Ranjan obtained the incomplete amide of diphenic acid and benzidine [5].

V. Baran and R. Britz synthesized the incomplete anilide and phenylimide of the same acid [6]. The authors give no data on the physiological activity of the compounds they obtained.

By analogy with known herbicides and plant-growth stimulants of the benzoic- and phthalic-acid series [7], we synthesized substituted monoamides (I) from diphenic anhydride and the corresponding amine, substituted diamides (II), and imides (III) from diphenic acid and an amine in the presence of phosphorus trichloride.

\[ \begin{array}{ccc} \mathrm{I} & \mathrm{II} & \mathrm{III} \\[4pt] \text{(structural formula)} & \text{(structural formula)} & \text{(structural formula)} \end{array} \]

\[ X = \mathrm{Cl},\ \mathrm{NO_2},\ \mathrm{CH_3} \]

All the compounds are crystalline substances, soluble in alcohol, xylene, and chlorobenzene; the monoamides give alkali-metal salts that are readily soluble in water.

Tests for herbicidal activity were carried out by the senior research associate of the Botanical Garden of Tomsk State University, A. V. Polozhii. According to preliminary data, the most active against weeds (creeping chamomile, foxtail grass, orache) proved to be—

2- and 3-nitro-substituted diphenylamides (3 kg/ha) and the sodium salt of 1-naphthylamide of diphenic acid (3 kg/ha), somewhat surpassing, apparently, the analogous derivatives of phthalic acid.

Experimental Part

Mono-2-nitroanilide of diphenic acid (I). In a flask fitted with a reflux condenser and stirrer are placed 11.2 g of diphenic anhydride, 6.9 g of 2-nitroaniline, and 100 ml of dry xylene, and the mixture is heated with stirring at 145° for 3 hours. It is cooled, the precipitated solid is filtered off, dried, and recrystallized from xylene. A light-yellow crystalline powder with m.p. 185°, soluble in hot xylene and chlorobenzene, sparingly soluble in alcohol. Found, %: N 7.78. C\(_{20}\)H\(_{14}\)O\(_5\)N\(_2\). Calculated, %: N 7.73. The sodium salt was obtained by dissolving 7.24 g of the monoanilide in soda (1.06 g in 20 ml of water) and evaporating the solution on a water bath. Very readily water-soluble bright-yellow crystals. Found, %: N 7.34. C\(_{20}\)H\(_{13}\)O\(_5\)N\(_2\)Na. Calculated, %: N 7.28.

Mono-3-nitroanilide of diphenic acid (II). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 6.9 g of 3-nitroaniline. Colorless needles with m.p. 221–222°. Found, %: N 7.76. C\(_{20}\)H\(_{14}\)O\(_5\)N\(_2\). Calculated, %: N 7.73. The sodium salt—cream-colored crystals readily soluble in water. Found, %: N 7.38. C\(_{20}\)H\(_{13}\)O\(_5\)N\(_2\)Na. Calculated, %: N 7.28.

Mono-4-nitroanilide of diphenic acid (III). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 6.9 g of 4-nitroaniline. Small, almost colorless crystals with m.p. 180–181°. Found, %: N 7.69. C\(_{20}\)H\(_{14}\)O\(_5\)N\(_2\). Calculated, %: N 7.73. The sodium salt—yellow crystals. Found, %: N 7.19. C\(_{20}\)H\(_{13}\)O\(_5\)N\(_2\)Na. Calculated, %: N 7.28.

Mono-4-chloroanilide of diphenic acid (IV). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 6.37 g of 4-chloroaniline. Colorless crystals with m.p. 169°. Found, %: N 3.96; Cl 10.36. C\(_{20}\)H\(_{14}\)O\(_3\)NCl. Calculated, %: N 3.98; Cl 10.11. The sodium salt—colorless crystals. Found, %: N 3.68. C\(_{20}\)H\(_{14}\)O\(_3\)NClNa. Calculated, %: N 3.74.

Mono-2-toluidide of diphenic acid (V). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 5.35 g of 2-toluidine. Colorless crystals with m.p. 209–210°. Found, %: N 4.63. C\(_{21}\)H\(_{17}\)O\(_3\)N. Calculated, %: N 4.23. The sodium salt—colorless crystals. Found, %: N 3.98. C\(_{21}\)H\(_{16}\)O\(_3\)NNa. Calculated, %: N 3.96.

Mono-4-toluidide of diphenic acid (VI). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 5.35 g of 4-toluidine. Colorless needles with m.p. 179–180°. Found, %: N 4.30. C\(_{21}\)H\(_{17}\)O\(_3\)N. Calculated, %: N 4.23. The sodium salt—colorless crystals. Found, %: N 3.98. C\(_{21}\)H\(_{16}\)O\(_3\)NNa. Calculated, %: N 3.96.

Mono-1-naphthylamide of diphenic acid (VII). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 7.15 g of 1-naphthylamine. Colorless crystals with m.p. 227–228°. Found, %: N 3.71. C\(_{24}\)H\(_{17}\)O\(_3\)N. Calculated, %: N 3.81. The sodium salt—colorless crystals. Found, %: N 3.83. C\(_{24}\)H\(_{16}\)O\(_3\)NNa. Calculated, %: N 3.75.

Mono-4-antipyrilamide of diphenic acid (VIII). Obtained analogously to (I) from 11.2 g of diphenic anhydride and 10.15 g of 4-aminoantipyrine. Colorless crystals with m.p. 214°. Found, %: N 9.73. C\(_{25}\)H\(_{21}\)O\(_4\)N\(_3\). Calculated, %: N 9.83.

Bis(2-toluidide) of diphenic acid (IX). In a flask fitted with a reflux condenser, dropping funnel, and stirrer are placed 12.1 g of diphenic acid, 10.7 g of 2-toluidine, 100 ml of dry xylene, ...

dropwise add 9.1 g of phosphorus trichloride and heat with stirring for 3 hours. Cool; filter off the precipitate that has separated; dry, neutralize with soda, and recrystallize from xylene. Colorless crystals, m.p. 235–236°. Found, %: N 6.50. C\(_{28}\)H\(_{22}\)O\(_2\)N\(_2\). Calculated, %: N 6.67.

Bis(4-toluidide) of diphenic acid (X). Obtained analogously to (IX) from 12.1 g of diphenic acid, 10.7 g of 4-toluidine, and 9.1 g of phosphorus trichloride. Colorless needles, m.p. 180–181°. Found, %: N 6.67. C\(_{28}\)H\(_{24}\)O\(_2\)N\(_2\). Calculated, %: N 6.67.

Bis(anilide) of diphenic acid (XI). Obtained analogously to (IX) from 12.1 g of aniline and 9.1 g of phosphorus trichloride. Colorless crystals, m.p. 235°. Found, %: N 7.28. C\(_{26}\)H\(_{20}\)O\(_2\)N\(_2\). Calculated, %: N 7.14.

Bis(2-nitroanilide) of diphenic acid (XII). Obtained analogously to (IX) from 12.1 g of diphenic acid, 13.8 g of 2-nitroaniline, and 9.1 g of phosphorus trichloride. Fine bright-yellow crystals, m.p. 205–206°. Found, %: N 11.71. C\(_{26}\)H\(_{18}\)O\(_4\)N\(_4\). Calculated, %: N 11.62.

Bis(3-nitroanilide) of diphenic acid (XIII). Obtained analogously to (IX) from 12.1 g of diphenic acid, 13.8 g of 3-nitroaniline, and 9.1 g of phosphorus trichloride. Fine cream-colored crystals, m.p. 220–221°. Found, %: N 11.65. C\(_{26}\)H\(_{18}\)O\(_4\)N\(_4\). Calculated, %: N 11.62.

Bis(4-nitroanilide) of diphenic acid (XIV). Obtained analogously to (IX) from 12.1 g of diphenic acid, 13.8 g of 4-nitroaniline, and 9.1 g of phosphorus trichloride. Light-yellow crystals, m.p. 234–235°. Found, %: N 11.53. C\(_{26}\)H\(_{18}\)O\(_4\)N\(_4\). Calculated, %: N 11.62.

Bis(4-chloroanilide) of diphenic acid (XV). Obtained analogously to (IX) from 12.1 g of diphenic acid, 12.75 g of 4-chloroaniline, and 9.1 g of phosphorus trichloride. Colorless crystals, m.p. 236–237°. Found, %: N 6.36. C\(_{26}\)H\(_{18}\)O\(_2\)N\(_2\)Cl\(_2\). Calculated, %: N 6.07.

Bis(1-naphthylamide) of diphenic acid (XVI). Obtained analogously to (IX) from 12.1 g of diphenic acid, 14.30 g of 1-naphthylamine, and 9.1 g of phosphorus trichloride. Colorless crystals, m.p. 260°. Found, %: N 5.73. C\(_{34}\)H\(_{24}\)O\(_2\)N\(_2\). Calculated, %: N 5.89.

2-Tolylimide of diphenic acid (XVII). 12.1 g of diphenic acid, 5.35 g of 2-toluidine, 4.55 g of phosphorus trichloride, and 100 ml of dry xylene are heated in a flask with a reflux condenser and stirrer on a water bath for 3 hours. Cool, filter off the precipitate that has separated, neutralize with soda, dry, and recrystallize from alcohol. Fine colorless crystals, m.p. 189–190°. Found, %: N 4.35. C\(_{21}\)H\(_{15}\)O\(_2\)N. Calculated, %: N 4.47.

4-Tolylimide of diphenic acid (XVIII). Obtained analogously to (XVII) from 12.1 g of diphenic acid, 5.35 g of 4-toluidine, and 4.55 g of phosphorus trichloride. Colorless needles, m.p. 147–148°. Found, %: N 4.63. C\(_{21}\)H\(_{15}\)O\(_2\)N. Calculated, %: N 4.47.

4-Chlorophenylimide of diphenic acid (XIX). Obtained analogously to (XVII) from 12.1 g of diphenic acid, 6.37 g of 4-chloroaniline, and 4.55 g of phosphorus trichloride. Colorless crystals, m.p. 219–220°. Found, %: N 4.25; Cl 10.90. C\(_{20}\)H\(_{12}\)O\(_2\)NCl. Calculated, %: N 4.19; Cl 10.64.

2-Nitrophenylimide of diphenic acid (XX). Obtained analogously to (XVII) from 12.1 g of diphenic acid, 6.90 g of 2-nitroaniline, and 4.55 g of phosphorus trichloride. Bright-yellow crystals, m.p. 224.5°. Found, %: N 8.21. C\(_{20}\)H\(_{12}\)O\(_4\)N\(_2\). Calculated, %: N 8.14.

3-Nitrophenylimide of diphenic acid (XXI). Obtained analogously to (XVII) from 12.1 g of diphenic acid, 6.90 g of 3-nitroaniline, and 4.55 g of phosphorus trichloride. Light-yellow needles, m.p. 257°. Found, %: N 8.16. C\(_{20}\)H\(_{12}\)O\(_4\)N\(_2\). Calculated, %: N 8.14.

4-Nitrophenylimide of diphenic acid (XXII). Obtained analogously to (XVII) from 12.1 g of diphenic acid, 6.90 g of 4-nitroaniline, and 4.55 g of phosphorus trichloride. Colorless needles with m.p. 261°. Found, %: N 8.20. $\mathrm{C}_{20}\mathrm{H}_{12}\mathrm{O}_{4}\mathrm{N}_{2}$. Calculated, %: N 8.14.

Conclusions

A series of substituted amides of diphenic acid has been obtained. It has been established that the fully nitro-substituted anilides and 1-naphthylamide of diphenic acid possess the strongest herbicidal action.

Literature

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5. Anukul Chandra Sircar und Prem Ranjan Sen Gupta, Studien über Ringbildung. III. Kondensation von Bensidin mit Anhydriden zweibasischer Säuren. Chem. Zbl. 1928, II, 2248.

6. W. H. Warran und R. A. Briggs, Über die Einwirkung von Thionilchlorid auf einige Anilsäuren. Ber. Dtsch. chem. Ges. 64, 26—30, 1931.

7. Basakov Yu. A. Results of Science. Biological Sciences, 2. Chemical agents for stimulating and inhibiting physiological processes in plants. Publishing House of the Academy of Sciences of the USSR, 123, 1958.