Furka, Árpád

Széll, Tamás

English

Furka Árpád

Széll Tamás

University of Szeged

DECOMPOSITION OF NITROCOMPOUNDS IN THE PRESENCE OF ALUMINIUM CHLORIDE By A. F U R K A and T. SZELL Institute of Applied Chemistry, The University, Szeged (Received September 15, 1961) The thermal decomposition of different nitro-aroniatic compounds, observed in the presence of.anhydtous aluminium chloride,-has been studied. The behaviour of these comp'ounds-is due to the nitro group introduced into the nucleus. Other substituents have also influence on the tempe-rature of decomposition. In our previous paper [1] the decomposition of nitrophenols and their esters, observed on heating in the presence of aluminium chloride, were reported. In the present work the decomposition of phenyl and mononitrophenyl esters of mono-nitrobenzoic acids, further that of other compounds were studied. It is shown by these experiments that the thermal decomposition observed is the consequence of the presence of the nitro substituent, for decomposition never occurred-— under: our experimental conditions — with compounds (phenols, carboxylic acids, phenolic esters) not containing nitro group (cf. Tables II, III, and previous paper Table. I). Different substituents introduced into the same position on the nucleus of. nitro-benzene may either reduce or increase the temperature of decomposition. Table II shows that alone 2-nitrobenzoic acid decomposed of the mononitrobenzoic acids, i. e. not alone the quality of the substituents but also their position have influence on the temperature of decomposition. It is to be noted that while among the mono-nitrophenols the ortho and para isomers, among the mononitrobenzoic acids the meta and para isomers behaved almost identically. Summing up all these the tempe-rature of decomposition of the substituted nitrobenzene derivatives decreased in the following order : • -3-COOH ~ 4-COOH ~ 3-COOC6H5 ^ 4-COOC6H5 > 4-C1 > nitrobenzene > "> 3-OH > 2-COOH ~ 4-OH ~ 2-OH > 2-COOC6H5 . Among the studied nitro. derivatives of phenyl benzoates. the 2- and 4-nitro-phenolic esters,, and the esters of 2-nitrobenzoic acid decomposed at relatively low temperature (Table III). Compared this with the temperature of decomposition of .mononitrophenols and mononitrobenzoic acids it can be concluded that esters, derived from phenols or acids easily decomposing, have also a relatively low tem-perature of decomposition. 51 130 À. FURKA AND T. SZÉLL Table I AlCb-comp. ratio Comp, (g) A1C13 (g) Temp, of decomp. (°C) Nitrobenzene 2:1 0,9 . 1,95 200 4-hydroxy-nitrobenzene 2:1 0,9 1,70 165 4-carboxy-nitrobenzene 2:1 0,9 . 1,44 -4-c hloro-nitrobenzene 2:1 Table II 0,9 1,53 204 AlCl3-acid ratio Acid (g) AICI3 (g) Temp, of decomp. (°C) Benzoic acid 2:1 0,9 1,97 -2-Nitro-benzoic acid 2:1 0,9 1,44 166 3-Nitro-benzoic acid 2:1 0,9 1,44 -4-Nitro-benzoic acid 2:1 0,9 1,44 -Phenylacetic acid 2:1 0,9 1,76 ' -Chloroacetic acid 2:1 0,9 2,55 : -Experimental1 Materials Aluminium chloride anhydrous (B. D. H. preparate). Benzoic acid, nitrobenzoic acids, phenylacetic acid, choloroacetic acid, phenyl-benzoate, nitrobenzene and A-chloro-nitrobenzene. Commercial grade. Nitrophenyl benzoates. 2-Nitrophenyl benzoate, m. p.: 54°; 3-nitrophenyl ben-zoate, m. p. 4-nitrophenyl benzoate, m. p. : 142°. Phenyl nitrobenzoates. Phenyl 2-nitrobenzoate, m. p. : 52—53° ; phenyl 3-nitro-benzoate, m. p.; 95—97°; phenyl 4-nitrobenzoate, m. p.: 127—129°. Nitrophenyl nitrobenzoates. 2-Nitrophenyl 2-nitrobenzoate, m. p.: 124—126°; 2-nitrophenyl 3-nitrobenzoate, m. p.: 128—130°; 2-nitrophenyl 4-nitrobenzoate, m. p.: 141—142°; 3-nitrophenyl 2-nitrobenzoate, m. p.: 113—114°; 3-nitro-i Melting points are uncorrected. DECOMPOSITION OF NITROCOMPOUNDS IN THE PRESENCE OF ALUMINIUM CHLORIDE 131 phenyl,3-nitrobenzoate, m. p.: 130—131°; 3-nitrophenyl 4-nitrobenzoate, m. p.: 173—174°; 4-nitrophenyl 2-nitrobenzoate, m.^p.: 111—112°; 4-nitrophenyl 3-nitroberizoate, m. p.: 141—142°; 4-nitrophenyl 4-nitrobenzoate, m. p.: 155— 157°. Esters, mentioned above, were prepared from the corresponding sodium phenolates and benzoyl clorides in benzene. Determination of temperature of decomposition was the same as discribed in the previous paper [1]. * * * The authors are grateful to the Hungarian Academy of Sciences for a grant. Table in . AlCl-ester ratio Ester (g) " A1C13 (g) Temp, of decomp. (°C) Phenyl benzoate 2:1 0,9 ' 1,20 -Trt.: l i u riiouyi ¿.-iuiiuucii£.uai.c . 2*1 0 9 0 98 82 Phenyl. 3-nitrobenzoate 2:1 . 0,9 0,98 - . Phenyl 4-nitrobenzoate 2:1 0,9 0,98. - . 2-Nitrophenyl benzoate 2:1 0,9 0,98 129 2-Nitrophenyl 2-nitrobenzoate 2:1 0,9 - 0,83 . 120 2-Nitrophenyl 3-nitrobenzoate 2:1 . 0,9 0,83 128 2-Nitrophenyl 4-nitrobenzoate 2:1 0,9 0,83 128 3-Nitrophenyl benzoate 2:1 0,9 0,98 193 3-Nitrophenyl 2-nitrobenzoate ' . 2:1 0,9 0,83 . 125 • 3-Nitrophenyl 3-nitrobenzoate . 2:1 0,9 0,83 194 3-Nitrophenyl 4-nitrobenzoate 2:1 0,9 0,83 195 4-NitrophenyI benzoate 2:1 0,9 0,98 132 4-Nitrophenyl 2-nitrobenzoate 2:1 0,9 0,83 118 4-Nitrophenyl 3-nitrobenzoate 2:1 • ' 0,9 0,83 143 4-Nitrophenyl 4-nitrobenzoate 2:1 0,9 0,83 144 3* 132 Л. FURKA AND Т. SZÉLL Reference [1] Fur'ka, А., Т. Széli: Acta Phys. et Chem. Szeged 6, 116 (I960). .. РАЗЛОЖЕНИЕ НИТРОСОЕДИНЕНИИ В ПРИСУТСТВИИ ХЛОРИСТОГО • АЛЮМИНИЯ /1. Фурка и Т. Селл . ' . Было изучено разложение различных нитро-ароматическнх. соединении, каблюдае- * мое в присутствии хлористого алюминия. Такое поведение этих соединеннй является следствием введения в ароматическое ядро ниро-группы. Другие заместители кольца также влияют на температуру разложения. 

Decomposition of mononitrophenolic esters in the presence of aluminium chloride

http://acta.bibl.u-szeged.hu/23600/1/phys_chem_007_fasc_003_004_129-132.pdf

Decomposition of mononitrophenolic esters in the presence of aluminium chloride

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