Reactions that occur during the synthesis of 3-phenyl-5-phenoxymethyl-2-N-phenyliminooxazolidine

Conclusions 3-Phenyl-5-phenoxymethyl-2-N-phenyliminooxazolidine, formed by the reaction of diphenyl-carbodiimide with phenyl glycidyl ether, reacts with an excess of the latter to give 3-phenyl-5-phenoxymethyl-2-oxazolidone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2152–2153, September, 1983.     

Synthesis and X-ray crystallographic investigation of 3-phenyl-3-phenoxymethyl-2-oxazolidinone

Conclusions 3-Phenyl-5-phenoxymethyl-2-oxazolidinone is the product of interaction of phenylisocyanate with phenylglycidyl ether. Its molecule has a less strained conformation than the molecule of related 2-N-phenylimino-3-phenyl-5-phenoxymethyloxazolidine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 870–874, April, 1986.     

Formylation of 2-phenyl- and 3-phenyl-5-hydroxybenzofuran derivatives

The Vilsmeier formylation of 2-phenyl- and 3-phenyl-5-hydroxybenzofuran derivatives was studied. It is shown that 2-phenyl-5-methoxybenzofuran is formylated in the 4 position, whereas 3-phenyl-5-methoxybenzofuran is formylated in the 2 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1023–1024, August, 1976.     

5-Hydroxy-3-phenyl-5-vinyl-2-isoxazoline and 3-phenyl-5-vinylisoxazole: synthesis and reactivity

5-Hydroxy-3-phenyl-5-vinyl-2-isoxazoline has been synthesized by reacting benzonitrile oxide with the enolate ion of methyl vinyl ketone. From 5-hydroxy-5-vinyl-2-isoxazoline, 5-vinylisoxazole was then quantitatively obtained by dehydration-aromatization under acidic conditions. Similar results, though not quantitative, were also found by treatment in 2-propanol under basic conditions (i-PrOH/H₂O, Na₂CO₃, reflux). In contrast to 2-propanol, reactions performed in methanol (and, in part, those carried out in ethanol) revealed a more complex behaviour, the nucleophilic addition of ROH onto the vinyl group being mainly observed. Nucleophilic addition was also found with alkyllithiums. The mechanism of the nucleophilic addition is discussed. Epoxidation and further reaction with benzonitrile oxide of both 3-hydroxy-5-phenyl-5-vinyl-2-isoxazoline and 3-phenyl-5-vinylisoxazole are also described.     

Studies on 5-arylidene-3-phenyl-2-methylmercaptohydantoins

The action of ammonium acetate on 5-arylidene-3-phenyl-2-methylmercaptohydantoins 1g,h in acetic acid led to the formation of the 5-arylidene-3-phenylhydantoin derivatives 4a,b . In absence of a solvent, ring opening and rearrangement took place with the formation of the 5-arylidene-N²-phenylglycocyamidine derivatives 7a-c . Compounds 7a-c reacted with methyl iodide to afford the corresponding 3-methyl derivatives 9a-c . The structures of the synthesised products were established and the mechanism proposed for the rearrangement reaction was discussed.     

Ultraviolet spectra of 2-phenyl-4- and 2-phenyl-5-azaindan-1, 3-diones

The UV spectra of 2-phenyl-4-azaindan-1, 3-dione (I), 2-phenyl-5-azaindan-1, 3-dione (II), and their N-methylbetaines are investigated. 2×10^–5 M aqueous alcoholic solutions of 2-phenyl-4-azaindan-1, 3-dione (I) contain the anionic form (IA), and in solutions of 2-phenyl-5-azaindan-1, 3-dione (II) the betaine form (IIB) is also in equilibrium with the anion (IIA). Solutions of I and II in 0.1 M sulfuric acid are characterized by a wide and rather intense absorption band at about 500 m, indicating the presence of a betaine form (IB and IIB). In 2M hydrochloric acid solution 2-phenylazaindan-1, 3-diones and their N-methylbetaines (III and IV) are protonated at the oxygen atom, giving the enol forms of the N-protonated or corresponding N-methylated 2-phenylazaindandiones.     

Preparation of 3(5)-phenyl-1-hydroxypyrazole 2-oxide and 4-methyl-3(5)-phenyl-1-hydroxypyrazole 2-oxide

Nitrosation of acrylophenone oxime or of methacrylophenone oxime with n-butyl nitrite in the presence of pyridine and copper(II) sulfate gives the copper complexes of the title compounds. The free 1-hydroxypyrazole 2 -oxides are isolated by treating the copper complexes with dilute sodium hydroxide, filtration, and acidification of the basic filtrates. The title compounds are the first examples of 1-hydroxypyrazole 2 -oxides in which the C3(5) ring position is unsubstituted.     

Alkyldithiocarboxylation of 3-hydroxy-1-phenyl-2-pyrazolin-5-one

4-Alkyldithiocarboxylate-3,5-dihydroxy-1-phenylpyrazoles 2, are prepared in good yield by the reaction of 3-hydroxy-1-phenyl-2-pyrazolin-5-one 1 with sodium acetate in dimethylformamide (DMF), carbon disulfide and alkyl halides.     

O-Alkylation of 3-hydroxy-1-phenyl-2-pyrazolin-5-one

3-Hydroxy-1-phenyl-2-pyrazolin-5-one 1 reacts with primary, secondary and allylic alcohols under catalytic acidic conditions and in the presence of 3 Å molecular sieves, to afford 3-alkoxy-1-phenyl-2-pyrazolin-5-ones 3 .     

Bridged 1,4-benzoxazocines from 5-hydroxy-3-phenyl-2-benzofuranone

A previously described neighboring group reaction has been extended to the synthesis of hydroxy-substituted bridged 1,4-benzoxazocines (i.e., 7, 8 ) bearing a structural analogy to potent analgetics of the hydroxy-6,7-benzomorphan series. In contrast to the latter, the presence of a hydroxyl group in the aromatic ring of the present series destroys all analgesic activity possessed by the unsubstituted system.     

Cycloaddition to aminomethylene derivatives of 1-phenyl-3-methylpyrazole-5-thione and 1-phenyl-3-methylpyrazole-5-selenone

Addition products — anhydrides of 1-phenyl-3-methyl-4-alkylamino-4,5,6-tetrahydrothio(seleno)pyrano-3, 2-pyrazole-5,6-dicarboxylic acids — were obtained by cycloaddition of maleic anhydride to aminomethylene derivatives of 1-phenyl-3-methylpyrazole-5-thione and 1-phenyl-3-methylpyrazole-5-selenone, while anhydrides of the corresponding dihydrothio(seleno)pyranopyrazoledicarboxylic acids were obtained by splitting out of an amine. The oxygen-containing analog does not undergo cycloaddition. An oxanol dye is formed from 1-phenyl-3-methyl-4-dimethylaminomethylene-5-pyrazolone, whereas the corresponding acyl derivative was isolated from the monomethyl derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 527–529, April, 1979.     

3-N-乙酰基-2-芳基-5-苯基-1,3,4-噁唑啉类化合物的合成与表征

以自制的苯甲酰腙与乙酸酐环合,高收率地合成了3-N-乙酰基-2-芳基-5-苯基-1,3,4-噁唑啉类化合物。其结构经^1H NMR,IR,MS和元素分析表征,并对其质谱碎片裂解途径进行了探讨。     

Spirobutyrolactone derived from 1-phenyl-3-methyl-2-pyrazolin-5-one

X-ray diffraction and NMR spectral examination have shown that 1-phenyl-3-methyl-2-pyrazolin-5-one reacts with methyl acrylate in methanol to give spiro[(1-phenyl-3-methyl-2-pyrazolin-5-one)-4,5-butyrolactone]. The conformation has been shown to be the same in the crystal and in solution, the pyrazoline ring has been found to be nonplanar, the reasons for the acoplanarity established, stabilizing and destabilizing interactions studied, and the orientation of the phenyl substituent relative to the pyrazolin-5-one ring determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 909–913, July, 1988.