A. F. Oleinik

Aryl- and aryloxyfurans as components of the diene synthesis with dimethyl acetylenedicarboxylate

The diene synthesis of 2-aryl- and 2-aryloxyfurans with dimethyl acetylenedicarboxylate gives adducts, the aromatizatio of which under the influence of acetic acid leads to esters of 3-aryl- and 3-aryloxy-6-hydroxyphthalic acids.

Arylation of furylglyoxylic acid by the meerwein reaction

We also used the Meerwein reaction to synthesize in addition to acids (la) and (Ib), the hitherto unknown glyoxylic acids (Ic)-(le). We isolated 2,5-bis(p-ethoxycarbonylphenyl)furan as a by-product from the arylation of furylglyoxylic acid with the p-(ethoxycarbonyl)benzene diazonium cation. We have already reported the formation of 2,5-bisarylfurans in the arylation of pyromucic acid [2] and acylfurans [I].

2-Acetylfuran in the Meerwein reaction

Abstract2,5-Diarylfurans are formed along with 2-acetyl-5-arylfurans in the Meerwein arylation of 2-acetylfuran.

Synthesis and tuberculostatic activity of 3-and 5-substituted 2-arylfurans

Aminomethylation was accomplished by boiling the components of the mixture for 5 to i0 h in isoamyl alcohol. The reaction proceeded only at 4 < pH < 7. Arylfurans with electron donor groups or a substituent chlorine atom in the benzene ring were successfully introduced in the Mannich reaction. The attempt to aminomethylate Ie led to the formation of bis[2(p-nitrophenyl)furyl-5]methane (IIle). Analogous compounds (IIIa, b) were obtained asside products in the Mannich reaction with Ia, b. The quantity of IIIa, b produced depended upon the acidity of the reaction mixture and increased with rise in pH. The formation of these kinds of compounds has been previously observed in the radical arylation of 2-hydroxymethylfuran [2]. The structure of compounds IIa-d and IIIb, e was confirmed by EPR spectra (Table i).

Arylation of furan derivatives via the Meerwein reaction

Meerwein arylation of 2-arylfurans and 2-furylnitroethylene gave 2,5-diarylfurans and 5-aryl-2-furylnitroethylenes. Meerwein arylation of 2-acylfurans gives 2,5-diarylfurans and substituted azobenzenes in addition to 2-acyl-5-arylfurans.

Antimicrobial activity of 2-arylfuran derivatives and their structural analogs

To examine the dependence of the biological activity of the arylfuran derivatives that we studied on their structure, we synthesized the structural analogs of these compounds. We prepared derivatives of 2-arylthiophene and also of 2-aryltetrahydrofuran with a structure analogous to that of the corresponding 2-arylfuran derivatives, which, as already found [3], exhibit a marked tuberculostatic activity.

Investigation of the stereochemistry of adducts of aryloxyfurans with maleic acid derivatives by PMR spectroscopy

The stereochemistry of adducts of aryloxyfurans with maleic acid derivatives was studied by PMR spectroscopy. It was shown that adducts with maleic anhydride are produced only in the form of exo isomers, whereas adducts with N-phenyl-maleinimide are isolated from the reaction in the form of mixtures of endo and exo forms. Bromination of the adducts was realized. The orientation of the bromine atoms in the bromination products was established by PMR spectroscopy: The bromine atoms in the dibromo derivative of the adduct with maleic anhydride are cis-oriented (endo-4-Br, endo-5-Br), whereas the bromine atoms have a trans configuration (endo-4-Br, exo-5-Br) in the dibromo derivative of the adduct with N-phenylmaleinimide.

Synthesis and antimicrobial activity of derivatives of 2-aryl-3,4-bis(carboxy)furans

Derivatives of 2-aryl-3,4-bis(carbomethoxy)furans (Ilia and 5) gave the corresponding acids la and b, which with thionyl chloride in the presence of a catalytic amount of DMFA were converted to the acid dichlorides (lla and b). In the absence of DMFA, Ib formed the anhydride of 2-(p-anisyl)-3,4-bis(carboxy)furan. The diamines (IVa and b) were obtained from lla and b. With hydrazine, lla and b were converted into the cyclic hydrazides (Va and b).

Synthesis and tuberculostatic activity of 5-aryl-2-(2-hydroxyethyl)furans and their carbamoyl derivatives

Arylfuryllithium, formed by the interaction of arylfurans with butyl lithium, was treated in si~ with ethylene oxide to give the hydroxyethyl derivatives la-d. The structure of the compounds obtained was confirmed by the presence of absorption bands in the 3350-3500 and 1028-1055 cm -I regions of the IR, and of proton signals for the OH at 2.19 ppm (s),* and for the methylene group at 2.85 ppm (B-CH2, t) and 3.82 ppm (a-CHu, t) in the NMR spectrum.

Synthesis and germistatic activity of syn and anti isomers of arylfurfural oxime acetates

i. M. A. Iradyan, R. A. Aroyan, and A. A. Aroyan, Arm. Khim. Zh., No. i0, 851 (1973). 2. A. A. Aroyan, M. A. Iradyan, and R. A. Aroyan, Arm. Khim. Zh,, No. 2, 136 (1973). 3. US Patent No. 3775478 (1973); Chem. Abstr., 80, 36,880 (1974). 4. US Patent No. 3714179 (1973); Chem, Abstr., 78, 111,325 (1973). 5. West German Patent No. 2104158 (1971); Chem. Abstr., 75, 151,791 (1971). 6. US Patent No. 3715367 (1973); Chem. Abstr., 78, 136295 (1973). 7. Canadian Patent No. 736484 (1966); Chem. Abstr., 65, 12211 (1966). 8. R. T. Aplin, M. Fisher, and D. Becner, J. Am. Chem. Soc., 21, 4888 (1965). 9. A. A. Aroyan, T. R. Ovsepyan, R. G. Melik-Ogandzhanyan, et al., Arm. Khim. Zh., No. 5, 406 (1969). i0. A. S. Azaryan, Sh. A. Avetyan, and A. A. Aroyan, Arm. Khim. Zh., No. 2, 151 (1972). ii. P. R. Ovsepyan and A. A. Aroyan, Arm. Khim. Zh., No. i, 42 (1972). 12. A. A. Aroyan, To R. Ovsepyan, and P. R. Akopyan, Arm. Khim. Zh., No. 7, 629 (1970).