The catalytic preparation of substituted benzanilides by the reaction of substituted benzoic acids with aniline is an important model process that has been intensively developed recently, in the field of the «green chemistry» concept, direct catalytic amidation, and its study is an urgent scientific and practical task.
Within the framework of solving this problem, the catalysis of the acylation of aniline by substituted benzoic acids with trivalent phosphorus compounds P(III) was studied. It was established that P(III) in the amount of only 2% mol. from substituted benzoic acid effectively catalyze this reaction, which proceeds in boiling low-polar solvents with intensive water distillation in an air atmosphere, which leads to obtaining anilides of substituted benzoic acids with a yield close to quantitative. The new catalysts, phosphorus trichloride and tribromide, phosphorous acid, successfully complement the catalytic system tetrabutoxytitanate/polybutoxytitanate, previously used for these purposes, allowing to obtain anilides of aminobenzoic acids with greater selectivity, as well as anilides of oxybenzoic acids.
The study of the kinetic regularities of the reaction catalyzed by phosphorus trichloride showed a weak effect of substituents: |ρ| ≤ 0.61. Hammett dependences are represented by curves with a maximum, straight line segments are characteristic only for certain groups of substituents, both for meta- and para-substituted and for orthosubstituted benzoic acids.
One of the possible mechanisms of acylation is the formation in situ in the first minutes of the reaction of aniline phosphite, which can act as an oxygen-nucleophilic catalyst, and, upon interaction with substituted benzoic acid, forms the corresponding benzoyl phosphite, which is then attacked by a free aniline molecule to obtain substituted benzanilide.
The ortho effect for P(III) catalysis is absent or very weak, in the case of aminobenzoic acids. At the same time, anthranilic acid can form a phosphite with phosphorous acid, which directly participates in catalysis.
Irving C.D., Floreancig J.T., Laulhe S. Amide synthesis through the in situ generation of chloro- and imido-phosphonium salts.ACS Omega. 2020. 5: 15734.
Leggio А., Bagalа J., Belsito E.L., Comandu A., Greco M., Liguori A. Formation of amides: onе-pot condensation of carboxylic acids and amines mediated by TiCl4. Chem. Cent. J. 2017. 11(1): 87.
Chiriac С.I., Onciu M., Tanasa F. Synthesis of aromatic amides at room temperature using triphenyl phosphite-4-dimethylaminopyridine as reagent. Designed monomers and polymers. 2004. 7(4): 331.
Hu Chen, Xunfu Xu, Liu Liu, Guo Tang, YufenZhaoa. Phosphorus oxychloride as an efficient coupling reagent for the synthesis of esters, amides and peptides under mild conditions. RSC Adv. 2013. 3: 16247.
ShteinbergL.Ya., Boyko V.D., Kondratov S.A., Shein S.M., ShteinbergYa.B. Catalysis with phosphorus compounds in the reaction of benzoic acid with aniline. Zhurn. organ. khimii. 1992. 28(5): 1034.
ShteinbergL.Ya., Dibrova V.M.,Shein S.M. Phosphorous acid catalysis in the synthesis of benzanilide.Ukr. khim. zhurn. 2012. 78(2): 110.
ShteinbergL.Ya., Shein S.M. Phosphorus trichloride – catalyst and condensing agent in the synthesis of benzanilide. Ukr. khim. zhurn. 2012. 78(10): 120.
ShteinbergL.Ya., Kondratov S.A., Shein S.M. The influence of solvents in the catalyzed reaction of aniline with benzoic acid. Zhurn. organ. khimii. 2005. 41(7): 312.
ShteinbergL.Ya., Коndratov S.А.,Shein S.M. Metallocomplex catalysis in the acylation of aniline with substituted benzoic acids. Zhurn. organ. khimii. 1988. 24(9): 1968.
ShteinbergL.Ya., Kondratov S.A., Shein S.M., Marshalova V.V. Effect of water on the kinetics of the catalytic reaction of benzoic acid with aniline. Kinetics and сatalysis. 2007. 48(5): 1.
ShteinbergL.Ya.Influence of substituents on the reaction rate of meta- and parasubstituted benzoic acids with aniline, catalyzed by polybutoxytitanates.Ukr. khim. zhurn. 2020. 86(6): 3.
ShteinbergL.Ya.Influence of substituents on the reaction rate of оrthosubstituted benzoic acids with aniline, catalyzed by polybutoxytitanates.Ukr. khim. zhurn. 2021. 87(3): 18.
Pokhodenko V.D., Degtyarev L.S., Koshechko V.G., Kuts V.S. Free radical chemistry problems. (Kyiv: Naukovadumka, 1981) [in Russian].
Koshechko V.G., Khizhny V.A., Pokhodenko V.D. Kinetics and mechanism of oxidation of stable radicals by Lewis acids.Zhurn. organ. khimii. 1976. 12(1): 103.
Gireva R.N. On the use of phosphorus trichloride for the acylation reaction of aromatic amines. Bulletin of the Tomsk Polytechnic Institute. 1956. 83: 129.
Van Wazer J.R. Phosphorus and its compounds. (Мoscow: IL, 1962) [in Russian].
ShteinbergL.Ya., Kondratov S.A., Shein S.M., Mishchenko S.E., Dolmat V.M., Dibrova V.M. Water as a regulator of the catalytic activity of tetrabutoxytitanium in the amide formation reaction. Kinetics and сatalysis. 1999. 40(4): 566.
Nagy D.I., Grün A., Greiner I., Keglevich G. The Role of phosphorus trichloride and phosphorous acid in the formation of α-hydroxymethylenebisphosphonic acids from the corresponding carboxylic acids – a mechanistic overview.Current Organic Chemistry. 2017. 21(16):1567.
Kirby A.J, Warren S.G. TheOrganic chemistry of phosphorus. (Мoscow: Mir, 1971) [in Russian].
Hudson R.F. Structure and mechanism of reactions of organophosphorus compounds. (Мoscow: Mir, 1967) [in Russian].
Cabral J., Laszlo P., Montaufier M.-T., Randriamahefa S.L. The phosphazo route to 2-alkenamides from acrylic acid and its derivatives. Tetrahedron Letters. 1990. 31(12): 1705.
Panchenkov G.M., Lebedev V.P. Chemical kinetics and catalysis. Training for universities. Мoscow: Chimiya, 1985 [in Russian].
Zhdanov Yu.А., Minkin V.I. Correlation analysis in organic chemistry. Rostov: Publishing house of Rostov University, 1966 [in Russian].
Zhongwen Li, Jianyu Dong, Xiuling Chen, Qiang Li, Yongbo Zhou, Shuang-Feng Yin. Metal- and oxidant-free synthesis of quinazolinones from β-ketoesters with o-aminobenzamides via phosphorous acid-catalyzedcyclocondensation and selective C−C bond cleavage. J. Org. Chem. 2015. 80: 9392.
Аlbert А., Serjeаnt Е. Acid and base ionization constants. M.-L.: Khimiya, 1964 [in Russian].
Litvinenko L.M., Oleynik N.M. Organic catalysts and homogeneous catalysis. Kyiv: Naukovadumka, 1981 [in Russian].
Titsky G.D., Stepko O.P., Litvinenko L.M. Bifunctional catalysis by organic acids of pentavalent phosphorus in the formation of N-arylamides. Quantitative assessment of the mutual influence of substituents in the catalyst and arylamine. Zhurn. organ. khimii. 1975. 11(5): 1021.
Titsky G.D., Litvinenko L.M., Stepko O.P. Catalytic activity of amides of organophosphorus acids in the reaction of benzoyl chloride with m-chloroaniline in benzene. Ibid. 1974. 44(8): 1688.
Oberlander E. A., Tebby J. C. Reactions of phosphoric anhydride with acyclic amides. Synthesis of amidines and imides. Heteroatom Chemistry. 1998. 9(2): 261.
Efremov D.A., Oberlander E.A., Tebby J.C. Phosphorylation of benzanilides by phosphoric anhydride. Phosphorus, sulfur, and silicon and the related Elements. 1994. 86(1–4): 81.
Fife T.H., Singh R., Bembi R. Intramolecular general base catalyzed ester hydrolysis. The Hydrolysis of 2-aminobenzoate esters. J. Org. Chem. 2002. 67(10): 3179.
Benali-Cherif N., Allouche F., Direm A., Soudani K. Hydrogen bonding in 2-carboxyanilinium dihydrogen phosphite at 100 K. Actacrystallographica. Section E. Structure Reports. 2009. 65(Pt.4): o664.
Lecomte M., Lipshultz J.M., Kim-Lee S.-H.,Li G.,Radosevich A.T. Driving recursive dehydration by PIII/PV catalysis: annulation of amines and carboxylic acids by sequential C–N and C–C bond formation. J Am Chem Soc. 2019. 141(32): 12507.