Derivatives of 9-Fluorenone-4-carboxylic Acid
Abstract Generated abstract
Several derivatives of 9-fluorenone-4-carboxylic acid and related diphenic acid compounds were synthesized as part of a search for biologically active substances. Methyl 9-fluorenone-4-carboxylate was condensed with selected aromatic amines to give crystalline anils, which were characterized by melting points and nitrogen analyses, while additional chloral-derived amides and trichloroacetic acid hydrazide were prepared by heating the corresponding starting materials. Preliminary insecticidal tests on houseflies showed limited activity for the anils, with the phenylimine derivative giving the highest recorded mortality, whereas the three additional compounds tested did not show positive results.
Full Text
DERIVATIVES OF 9-FLUORENONE-4-CARBOXYLIC ACID
L. P. Kulev, R. N. Gireva, A. P. Belyaeva
(Presented by the Organic Section of the Scientific Seminar of the Chemical-Technological Faculty)
Previously we obtained esters and some oximes of 9-fluorenone-4-carboxylic acid [1, 2].
In order to search for new biologically active preparations, several additional compounds of this series were synthesized; they were obtained by condensation of methyl 9-fluorenone-4-carboxylate with amines according to the following scheme:
\[ \mathrm{CH_3OOC}\text{-fluorenone-}C{=}O + \mathrm{AzNH_2} \longrightarrow \mathrm{CH_3OOC}\text{-fluorene-}C{=}N{-}\mathrm{Az} \]
Anils are crystalline substances, insoluble in water but soluble in organic solvents.
The characteristics of the anils obtained are given in the table.
Preliminary tests of insecticidal activity were carried out on houseflies placed in a glass vessel dusted with the preparation. Mortality of the flies was recorded after 24 hours.
Experimental Part
A mixture of 0.02 M methyl 9-fluorenone-4-carboxylate and 0.02 M of the corresponding amine is heated in an oil bath at a temperature of \(125^\circ\) for 1 hour. After completion of the reaction, a solid mass forms in the flask; it is washed with alcohol and then recrystallized from xylene. Condensation with other amines could not be carried out.
Several additional derivatives of diphenic acid amide and 9-fluorenone-4-carboxylic acid were also obtained.
\[ \begin{array}{c} \text{diphenyl fragment}-\mathrm{CONHCH(OH)-CCl_3}\\ \text{diphenyl fragment}-\mathrm{COOH} \end{array} \]
\[ \%\,N \text{ calculated } 3.6. \]
\[ \%\,N \text{ found } 3.7. \]
A mixture of 0.05 M diphenic acid amide and 0.05 M chloral was heated in a water bath at a temperature of 33°.
After completion of the synthesis, the reaction mass was dissolved in boiling chloroform and filtered. After evaporation of the chloroform, the mass was cooled in a refrigerator, washed with cold water, and recrystallized from alcohol.
Table
| Ester formula | m.p. | Analysis for N, % found | Analysis for N, % calculated | % mortality of flies |
|---|---|---|---|---|
| Methyl ester of 9-fluorenone-4-carboxylic acid phenylimine: \( \mathrm{CH_3OOC}\)-fluorene-\(\mathrm{C{=}N{-}C_6H_5}\) | 162 | 4.18 | 4.46 | 26 |
| Methyl ester of 9-fluorenone-4-carboxylic acid \(p\)-tolylimine: \( \mathrm{CH_3OOC}\)-fluorene-\(\mathrm{C{=}N{-}C_6H_4CH_3}\) | 112 | 3.98 | 4.28 | 5 |
| Methyl ester of 9-fluorenone-4-carboxylic acid \(p\)-anisylimine: \( \mathrm{CH_3OOC}\)-fluorene-\(\mathrm{C{=}N{-}C_6H_4OCH_3}\) | 159 | 3.91 | 4.08 | 13 |
\[ \mathrm{ 9\text{-}fluorenone\text{-}4\text{-}CONHCH(OH)\text{-}CCl_3 } \]
\[ \begin{aligned} \%\,\mathrm{Cl}\ \text{calculated} &\ 28.74\\ \%\,\mathrm{Cl}\ \text{found} &\ 28.86\\ \%\,\mathrm{N}\ \text{calculated} &\ 3.78\\ \%\,\mathrm{N}\ \text{found} &\ 3.82 \end{aligned} \]
was obtained by the method described above.
\[ \mathrm{Cl_3CC(=O)-NH-NH_2} \]
\[ \begin{aligned} \%\,\mathrm{N}\ \text{calculated} &\ 15.78\\ \%\,\mathrm{N}\ \text{found} &\ 15.47 \end{aligned} \]
A mixture of 0.1 M trichloroacetic acid was heated with an excess of hydrazine hydrate at a temperature of 130° for 4 hours. After completion of the synthesis, the mass was washed with water, then recrystallized from dioxane.
Preliminary tests for insecticidal activity of these three compounds did not give positive results.
LITERATURE
- L. P. Kulev, R. N. Gireva, G. M. Stepnova. Derivatives of 2,2′-diphenic acid, communication I, ZhOKh, 32, 2812, 1962.
- L. P. Kulev, R. N. Gireva, G. M. Stepnova. Derivatives of 2,2′-diphenic acid, communication II, ZhOKh, 33, 411, 1963.