The method of obtaining tris-formylrifamycin

 

(57) Abstract:

The invention relates to organic chemistry, namely, the method of production of triptycene derivatives, in particular the production of Tris-formylrifamycin with substituents in positions of three different rings triptycene fragment. The objective of the invention is to develop a simple and convenient method of obtaining new Tris-formylrifamycin. The proposed method is that trypticon first formuliruut ,-dichlorodimethyl ether in nitromethane in the presence of aluminum chloride and hydrogen chloride at a molar ratio trypticon: aluminium chloride:hydrogen chloride:dichlorodimethyl ether, equal 1:3 - 6:0,10 - 0,89:4 - 7, and then spend further formirovanie when the molar ratio of the same reagents, equal 1:7 - 11:0,27 - 0,089:8 - 12 with subsequent chromatographic selection of product. The total yield in two stages was 37 - 57%. The proposed method allows for the first time to get a new reformulation two-stage synthesis on the basis of triptycene with exit 37 - 57%. table 1.

The invention relates to organic chemistry, namely, the method of production of triptycene derivatives, in particular the production of Tris-formylrifamycin with C the drive to get photoresists, and also can serve as the starting material for the synthesis of reticulated polymers.

Tris-formylrifamycin previously not described in literature. It cannot be retrieved by the method previously described in the literature for Tris-acetyltryptamine.

Object of the invention is the disassembly is simple and convenient method of obtaining new Tris-formylrifamycin.

The proposed method is that trypticon first formuliruut a,-dichlormethane ether in nitromethane in the presence of aluminum chloride and hydrogen chloride at a molar ratio triptycene a,-dichlorodimethyl ether hydrogen chloride is 1:4-7:0,010-0,089, then conduct further formirovanie when the molar ratio of the same reagents, equal to 1:8-12: 0,027-0,089, with subsequent chromatographic selection of product. The total yield in two stages was 37 57%

The formation deforestation in the presence of aluminum chloride leads, apparently, to the formation of the complex of this aldehyde with aluminium chloride that due to the electron-withdrawing nature of aluminum chloride deactivates the aromatic system and eliminates further formirovanie.

Hydrogen chloride displaces aluminum from complexlist hydrogen chloride, to regulate the depth of formirovaniya. In the absence of hydrogen chloride deforestation further formuliruetsya.

Example 1. In the solution 0,508 g (2 mmol) triptycene in 2 ml of nitromethane in the presence of 1.17 g (9 mmol) of aluminium chloride at 0oC under stirring on a magnetic stirrer miss 1.2 ml (0,054 mmol) of gaseous hydrogen chloride, is then added dropwise with stirring 1 ml in (11.2 mmol) a-dichlorodimethyl ether, after 120 min, treated with 10 ml of water, extracted with chloroform (3x5 ml). The residue after removal of solvent in vacuo chromatographic on a column of silica gel. Elute with chloroform.

Examples 2-16 was carried out analogously to example 1.

Conditions of the experiments are shown in the table.

Tris-formylrifamycin: So pl. above 350oC (heptane), Rf0,1 (Silufol, chloroform). An NMR spectrum1H (60 MHz, CDCl3d M. D.): 5,7 (2H), 7.5 m (6N), 7,95 (3H), 9,9 s (3H). Tris-formylrifamycin characterized by recovering hydrazine hydrate in Tris-methyltryptamine: So pl. 57-61oC (sublimates at 1-2 mm RT. Art.), Rf0,36 (Silufol, hexane-benzene, 2:1). An NMR spectrum1H (60 MHz, CCl4d, M. D.): 2.2 s (N), a 5.1 (2H), 6,7 d (3H), 7,15, 7,3 l (6N).

Found, C 93.32 per, N 6,90

the th Tris-formylrifamycin with a total output 37-57%

The method of obtaining Tris-formylrifamycin, namely, that trypticon first formuliruut ,-dichlorodimethyl ether in nitromethane in the presence of aluminum chloride and gaseous hydrogen chloride at a molar ratio trypticon aluminium chloride hydrogen chloride ,-dichlorodimethyl ether 1 3 6 0,010 0,089 4 7, and then conduct further formirovanie when the molar ratio of the same reagents 1 7 11 0,027 0,089 8 12, with subsequent chromatographic selection of product.

 

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