Benzaldehyde synthesis was described by the interaction of dibromomethylbenzene with diisopropylphosphinic acid esters [1]. We supposed that this reaction is perspective for synthesis of various functionally substituted benzaldehydes including benzenedicarbaldehydes.
We studied the reactuions of dibromomethylbenzenes containing acetoxy group in m- and p- positions (1) or second dibromomethyl group in p-position (2) with diethylphosphinic, methylphosphonic and phosphoric acid esters (3). The corresponding aldehydes (4), P(IV) acid anhydrides (5) and alkyl bromide (6) were formed. Interaction of the reagents (1) and (3) or (2) and (3) was carried out by heating of their mixture in sealed ampule. Reaction course was controlled by dynamic 1H NMR spectroscopy.
Hydrolisis of dibromide (1) for the purpose of generating of aldehyde function was accompanied with splitting of ester group. It transformed into hydroxybenzenecarbaldehyde (7) [2]. Our new method allowed to save hydrolitic sensitive ester group and obtain acetoxybenzenecarbaldehyde (8). In the case of 1,4-bis (dibromomethyl)benzene (2) depending on ratio of reagents (2) and (3) terephthalic aldehyde (9) or its mixture with 4-(dibromomethyl)benzenecarbaldehyde (10) are formed. Aldehyde (10) was separated using column chromatography and transformed into 4-(dibromomethyl)benzenecarbimine (11). In conclusion, new type substances (8), (10) and (11) obtained by new method are very perspective starting materials for synthesis of polyfynctional compounds. They contain various pharmacophoric groups and therefor they are potential biologically active substances.
The work was supported by the Russian Foundation for Basic Research and Tatarstan Republic government (grant no. 13-03-7098) and by the Ministry of Education and Science of Russian Federation (within the basic part of task # 2014/56).
Literature
M.B. Gazizov, T.N. Kachalov, R.F. Karimova ect. // Journal of General Chemistry. – 1997. – V.97, № 12. – P.2005-2006.
E.L. Elied, K.W. Nelson // J.Chem.Soc. - 1955.-P.1628-1629