Synthesis of 1-(2,4,6-trichlorophenyl)-3-(3-nitro- and 2-chloro-5-nitroanilino)-5-pyrazolones

A convenient one flask synthesis of 1-aryl-3-nitroanilino-5-pyrazolones in yields of 60–65% is described. Synthesis involves initial reaction of ethyl 3-ethoxy-3-iminopropionate hydrochloride and a nitroaniline in methanol producing an imidate ester. The imidate ester is then reacted with an arylhydrazine forming an amidine. The amidine is then cyclized with base.     

Phospha-s-triazines. IV. Degradation studies of 1-diarylphospha-3,5-bis(perfluoroaliphatic)-2,4,6-triazines and 1,3,-bis(diarylphospha)-5-perfluoroaliphatic-2,4,6-triazines

Thermal and thermal oxidative stability evaluations were performed on mono- and diphospha-s-triazines at 235 and 316°C using sealed Pyrex ampoules. The specific compounds studied were: 1-diphenylphospa-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis(perfluoro-alkylether)-2,4,6-triazines, their respective pentafluorophenyl analogues, 1,3-bis(diphenylphospha)-5-perfluoro-n-heptyl-2,4,6-triazine and 1,3-bis(diphenylphospha)-5-perfluoroalkylether-2,4,6-triazine. All the compounds wherein phenyl groups were present on the phosphorous exhibited good thermal stability up to 316°C; the analogous pentafluorophenyl substituted materials were degraded extensively at these temperatures. The oxidative stability of both the mono- and diphospha-s-triazines was excellent at 235°C, but at 316°C some degradation was observed. This was more pronounced in compounds containing the perfluoroalkyl moiety on carbon than in the perfluoroalkylether substituted members of the series.     

Synthesis of 3-(2-chloro-5-nitroanilino and 4-nitroanilino)-1-(2,4,6-trichlorophenyl)-2-pyrazolin-5-ones

A new synthesis of 3-anilino-1-aryl-2-pyrazolin-5-ones in which the pyrazolinone ring is built via N? N bond formation is described. 2-Cyano-2′,4′,6′-trichloroacetanilide 1 was converted to imino ether hydrochloride 2 which was reacted with anilines in methanol to produce N-arylimino ether 3a,b. Reaction of these N-arylimino ethers with hydroxylamine gave N-arylamidoximes 4a,b . An 1,2,4-oxadiazol-5-one 6a was prepared from the N-arylamidoxime 4a and subjected to base-induced rearrangement. The desired 3-anilino-pyrazolinone 7a was obtained only in a very low yield. However, O-acetylation of the N-arylamidoximes 4a,b followed by acid-catalyzed ring closure and rearrangement in the presence of excess acetic anhydride gave a mixture of N-acetylanilinopyrazolinones (e.g. 10 ) and 4-acetyloxy-3-N-acetylanilinopyrazoles (e.g. 12 ) which upon acid hydrolysis afforded the 3-anilinopyrazolinones 7a,b in better yield.     

Reaction 5-(Arylmethylidene)-2,4,6-pyrimidine-2,4,6(1H,3H,5H)-triones with Arenecarbaldehyde Phenylhydrazones in the Presence of Sodium N-Chlorobenzenesulfonamide

Russian Journal of Organic Chemistry - The reactions of 5-(arylmethylidene)-2,4,6-pyrimidine-2,4,6(1H,3H,5H)-triones with arenecarbaldehyde phenylhydrazones in the presence of sodium...     

Synthesis of 1-(4-butoxyphenyl)-1-cyclohexyl-3-(4-arylpiperazin-1-yl)-2-phenylpropan-1-ols and their dihydrochlorides

Aminomethylation of 1-(4-butoxyphenyl)-2-phenylethanone with paraformaldehyde and substituted piperazines in ethanol medium results in 1-(4-butoxyphenyl)-3-(4-R-piperazin-1-yl)-2-phenylpropan-1-ones. The latter react with cyclohexylmagnesium halide to give 1-(4-butoxyphenyl)-1-cyclohexyl-3-(4-arylpiperazin-1-yl)-2-phenylpropan-1-ols. Reduction of the prepared β-aminoketones with lithium aluminum hydride in absolute diethyl ether leads to the secondary aminopropanols. The prepared compounds could be converted into the corresponding dihydrochlorides.     

Preparation of 2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutenes from 2-(2,4,6-tri-tert-butylphenyl)-1-phosphaethyne and alkyllithiums

2-(2,4,6-Tri-tert-butylphenyl)-1-phosphaethyne was allowed to react with 0.5 eq. of alkyllithium to afford 2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutenes through an intramolecular cyclisation of a 1,3-diphosphabuta-1,3-diene intermediate.     

Crystal and Molecular Structure of Acylalmino Derivatives of 1-(2,4,6-Trichlorophenyl)-4,5-dihydropyrazol-5-one

The structure of acylamino derivatives of 1-(2,4,6-trichlorophenyl)-4,5-dihydropyrazol-5-one was studied by X-ray diffraction. 3-Acetylamino-1-(2,4,6-trichlorophenyl)-4,5-dihydropyrazol-5-one and 3-benzoylamino-1-(2,4,6-trichlorophenyl)-4,5-dihydropyrazol-5-one exist in crystal as CH tautomers. The nature and number of acylamino groups were found to affect the nature of intermolecular hydrogen bonds in the crystals studied.     

Reaction of dichlorocarbene with 1-(2,4,6-tri-t-butylphenyl)-1-phosphaallenes

1-(2,4,6-Tri-t-butylphenyl)-1-phosphaallene reacted with dichlorocarbene to give 2-dichloromethylene-1-(2,4,6-tri-t-butylphenyl)-1-phosphirane. The structure was confirmed by X-ray crystal structure analysis. A similar isomerization product was obtained in the reaction of dichlorocarbene with 3-phenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaallene.     

Synthesis of the diastereomeric 2-aryl-1-cyclohexyl-3-(2,3-epoxypropionyl)aziridines

The reaction of cinnamoyloxiranes with an iodine-cyclohexylamine complex in the presence of an excess of amine led to a mixture of the four diastereomeric epoxypropionylaziridines the ratio of which depended on steric and electronic factors in the substrate and reactants.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 456–459, April, 1986.     

Synthesis and Structure of E-2- (2,4,6-tri-tert-butylphenylphosphinyl ) - 2- [N- (tert-butyldimethylsilyl) - N- (p-chrolophenyl ) ] amino- 1- (2,4,6-tri-tert- butyl-phenyl ) phosphacthylene

The title compound E-2-(2, 4, 6-tri-tert-butylphenylphosphinyl)-2-[ N- ( tert-butyldimethylsilyl )-N- ( p-chrolophenyl )] amino-l- ( 2, 4, 6-tri-tert-butylphenyl)phosphacthylene (C49H78NClP2Si, Mr= 806.65) was synthesized and characterized by X-ray diffraction analysis. The crystal is monoclinic, space group P 21 /n with a=10.319(3), b=23.309(5), c=21.41(1) A, β=99.64(5)°, V=5078(3)A3, Z =4, Dc=1. 05g/cm3, F(000)=1760, μ=1. 92cm-1. Due to the steric hindrance from substituents around phosphaethylene, the P = C bond length is significantly longer than those observed in its analogues. The values of the three bond angles involved in the sp2-hybridized carbon atom (C(1)) of the phosphaethylene are 133.4, 115.1 and 111.4° respectively, deviating significantly from the ideal value of 120°. In addition,although 5 sp2- hybridized atoms (C(2), P(1), C(1), N and C(44)) are sequentially bonded in this molecule, no interaction is observed among the remaining pz orbits of these atoms on the string.