Oxidation of 4 bromo 1 hydroxymethylcubane and 1,4 bis(hydroxymethyl)cubane with the 2,2,6,6 tetramethylpiperidine N oxyl-trichloroisocyanuric acid-sodium bicarbonate sys tem afforded the corresponding aldehydes. 4 Bromocubanecarbaldehyde was also obtained in high yield by reduction of 4 bromocubanecarboxylic acid and its methyl ester with bis(N methylpiperazinyl)aluminum hydride.
The present study concerned with reduction of methyl 4 bromocubanecarboxylate (1) with lithium aluminum hydride and aluminum hydride in THF. An efficient procedure was devel oped for the synthesis of 4 bromo 1 hydroxymethylcubane (2) based on reduction of com pound 1 with aluminum hydride under mild conditions. The structure of 2 was established by X ray diffraction.Key words: methyl 4 bromocubanecarboxylate, 4 bromo 1 hydroxymethylcubane, hydroxymethylcubane, reduction, lithium aluminum hydride, aluminum hydride, X ray dif fraction study.Cubane derivatives attract considerable interest as po tential pharmaceuticals. 2-6 However, their synthesis in volves many steps. Hence, the development of efficient and selective methods for modifications of compounds containing the cubane fragment and investigation of their structures are of great importance.The present study continues our research on reduc tion of cubane derivatives containing different functional groups with light metal hydrides. 7-11The aim of the study was to develop a more efficient procedure (compared to a known method 12 ) for the syn thesis of 4 bromo 1 hydroxymethylcubane and establish its structure. This compound can be used as an intermedi ate for the synthesis of biologically active compounds, in particular, of nitrates of cubane containing alcohols.Since the synthesis of various cubane derivatives in volves many steps, it is necessary to elaborate procedures for the preparation of intermediates in high yields in indi vidual steps. Our attempts to increase the yield of carbinol 2 reported earlier (80%) in reduction of ester 1 with lithium aluminum hydride 12 by performing the reaction at higher temperature (65 °С) over a longer period of time with the use of an excess of LiAlH 4 failed. The yield of com pound 2 was no higher than 80%. When the reaction was performed for 48-300 h, the yield decreased due to hydrodebromination (Scheme 1).With the aim of developing a more efficient and selec tive procedure for the preparation of carbinol 2, we stud ied reduction of ester 1 with aluminum hydride. This reaction was found to occur under mild conditions (15-25 °С) and proceed much faster (4 h at 20 °С) than the reaction with LiAlH 4 to give the target product in higher yield (∼94%) (see Scheme 1). In addition, this process is highly selective. Thus, reduction of ester 1 with AlH 3 was not accompanied by hydrodebromination for several days.The structure of product 2 was established by X ray diffraction (Fig.
Synthesis of 4-Bromocubane-1-carbaldehyde. -(SHASTIN*, A. V.; ZAKHAROV, V. V.; BUGAEVA, G. P.; EREMENKO, L. T.; ROMANOVA, L. B.; LAGODZINSKAYA, G. V.; ALEKSANDROV, G. G.; EREMENKO, I. L.; Russ.
An efficient procedure for the preparation of 1,4-bis(hydroxymethyl)cuhane by mdoction of cubane-1,4-dicarboxylic acid or its dimethyl ester with aluminum hydride was developed. The molecular structure of 1,4-bis(hydroxymethyl)cubane was established by X-ray diffraction analysis.
1998 bridged compounds bridged compounds Q 0060 42 -085 Cubane Derivatives. Part 4. Synthesis and Molecular Structure of 1,4-Bis(hydroxymethyl)cubane. -Reduction of cubane-1,4-dicarboxylic acid or its dimethyl ester (I) with aluminum hydride represents an effective method for the synthesis of 1,4-bis(hydroxymethyl)cubane (II). Compound (II) is characterized using X-ray crystallography. -(ZAKHAROV, V. V.; BUGAEVA, G. P.; IVANOVA, M. E.; ROMANOVA, L. B.; EREMENKO, L. T.; NEFEDOV, S. E.; EREMENKO, I. L.; Izv.
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