1-Chlor-1-phosphirane

The title compounds are prepared by reaction of disubstituted diazomethanes with 1-chloro-2-phenyl-2-trimethylsilyl-1-phosphaalkene. The chemistry of the 1-chloro-1-phosphiranes is described.     

Synthesis of Ethyl 1-Phenyl- and 1-Alkyl-1-Indene-2-Carboxylates

The ethyl 1-phenyl and 1-alkyl-1-indene-2-carboxylates 2g and 2a-2f respectively were prepared in 68 - 83% yield by the reaction of phenyl- and alkylmagnesium halides with ethyl 1-methoxy-1-indene-2-carboxylate (1c).     

2 1 1At-tellurium colloid and Na2 1 1At injections,and their radiobiological effects

Na^{2 1 1}At and^{2 1 1}At–Te colloid injections were prepared. By comparison with tissue distribution of Na^{2 1 1}At and^{2 1 1}At–Te colloid injections it has been demonstrated that the^{2 1 1}At–Te colloid is stable in vivo. It has been shown that the radiohalogen,^{2 1 1}At, has huge and extensive radiobiological effects in studying on the changes in histopathology, enzyme histochemistry, chromosome aberration, micronucleus frequency of bone-marrow polychromatic erythrocytes and the injury effect of^{2 1 1}At on experimental Ehrlich ascites cells.     

Amidrazones 11. Rearrangement of 1-allyl-substituted-4,5-dihydro-1-methyl-1H-pyrazolium bromides

1-Methyl-2-(2-propenyl)-3-pyrazolidinimine ( 5 ) was obtained by treatment of 3-amino-4,5-dihydro-1-methyl- 1-(2-propenyl)-1H-pyrazolium bromide ( 4 ) with ethanolic sodium ethoxide. Similar treatment of the analogous 2-(2-butenyl) and 2-(3-phenyl-2-propenyl)-substituted salts 12 and 15 gave 1-methyl-2-(1-methyl-2-propenyl)-3- pyrazolidinimine ( 13 ) and 1-methyl-2-(1-phenyl-1-propenyl)-3-pyrazolidinimine ( 16 ) respectively.     

1-乙酰胺基丙叉-1,1-二膦酸和1-丙酰胺基乙叉-1,1-二膦酸与碱土金属离子的螯合作用

用pH电位法研究了1-乙酰胺基丙叉-1,1-二膦酸(S-186)和1-丙酰胺基乙叉-1,1-二膦酸(S-106)与碱土金属的螯合作用(30±O.1℃).当金属离子与配体的摩尔浓度比为10∶1、1∶1和1∶2时,在水溶液中形成了MHL、ML、ML_2和M_2L等几种类型的配合物.分别测定了它们的稳定常数,其中S-186配合物稍高于S-106,说明配合物稳定性与螯合剂的碱度有平行关系.值得注意的是,这两种螯合剂与Sr~(2 )形成的双核配合物的稳定性均较其它碱土金属离子的为高.     

Dispersed fluorescence spectroscopy of the CBr2A1B1-X1A1 transition

Dispersed fluorescence spectra following the excitation of the CBr2A1B1-X1A1 2 and 2 bands at visible wavelengths were acquired in a discharge supersonic free jet expansion using an intensified charge-coupled device (ICCD) detector. The dispersed fluorescence spectra show signal-to-noise ratios of up to 60 and extend out to a maximum red shift frequency of 6000 cm(-1). Complete and detailed vibrational structure of the ground singlet state (X1A1) was observed. Vibrational parameters including fundamental frequencies, anharmonicities, and coupling constants were determined for the CBr2 X1A1 state. Additional vibrational structure starting at approximately 3650 cm(-1) was observed and this indicates the singlet-triplet energy gap to be >10 kcal mol(-1).     

GAS PERMEABILITY OF COPOLY(1-TRIMETHYL-SILYL-1-PROPYNE-PENTAMETHYL-DISILYL-1-PROPYNE) MEMBRANE

The permeability of copoly (1-trimethylsilyl-1-propyne-pentamethyldisilyl-1-propyne) membrane for twelve gases (0_2, N_2, CO_2, H_2, D_2, He, At, CH_4, C_2H_4, C_2H_6, C_3H_6 and C_3H_8) was examined. The basic laws of solution and diffusion of the gases in the membrane were expounded preliminarily. It was found that a linear relationship between logarithm of diffusion coefficient (D) and critical molar volume (V_c) of the gases. The permeation characteristics of the gases in the copoly (1-trimethylsilyl-1-propyne-pentamethyldisilyl-1-propyne) membrane was also discussed.     

Reaction of 1, 1-Di-p-methoxyphenyl-2, 2-dinitroethylene and 1, 1-Di-O-methoxyphenyl-2, 2-dinitroethylene with 1-Benzyl-1, 4-dihydronicotinamide： Evidence for Concerted Electron-hydrogen Atom Transfer Mechanism

1,1-Di-p-methoxyphenyl-2, 2-dinitroethylene reacts with 1-benzyl-1, 4-dihydronicotinamide (BNAH) in deaerated acetonitrile to give 1,1-di-p-methoxyphenyl-2, 2-dinitroethane,while 1,1-di-O-methoxyphenyl-2, 2-dinitroethylene fails to react with BNAH under the same conditions, which provides evidence for a concerted electron-hydrogen atom transfer mechanism.     

The mechanism of thermal dehydrochlorination. Pyrolysis of 1-Chloro-1-fluoroethane and 1-chloro-1, 1-difluoroethane

The thermal decompositions of 1-chloro-1-fluoroethane and 1-chloro-1,1-difluorethane at atmospheric pressure have been studied in the temperature range 500–600°C in a flow system. The dehydrochlorinations are homogenous in a carbonaceous reactor and unimolecular. The rate constants are given by and The criteria for molecular or chain processes in thermal dehydrochlorinations are discussed.     

Synthesis Of 1-Benzazepines as Precursors of 1-Benzazepinediones

The synthesis of 6-hydroxy-7-nitro-1-benzazepine-2-one 7 from 5-hydroxy-1-tetralone 1 and 6-hydroxy-1-benzazepine-2-one 2 is described. Bromination of 6-hydroxy-1-benzazepine-2-one 2 with NBS in ethyl acetate afforded 7-bromo-6-hydroxy-1-benzazepine-2-one 13 and 7,9-dibromo-6-hydroxy-1-benzazepine-2-one 14. Oxidation of benzazepinone 13 with (diacetoxyiodo)benzene provided 7-bromo-1-benzazepine-2,6,9-trione 5.     

Allylic oxidation of 1-methyl-1-cycloheptene

Conclusions The oxidation of 1-methylcycloheptene by SeO₂ and Hg(OAc)₂ gave a mixture of 1-hydroxymethyl-2-cyclohepten-1-ol and 3-methyl-2-cyclohepten-1-ol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2134–2136, September, 1986.     

1, 1-Difluoro-1H-cyclopropa[a]naphthalene

1, 1-Difluorocyclopropa[a]naphthalene ( 1b ) is prepared in three steps from 4-bromo-1,2-dihydronaphthalene ( 7 ) via carbene addition, benzylic bromination and bidehydrohalogenation. Structural evidence for formation of 1b is based on ¹H- and ¹⁹F-NMR spectroscopy. Compound 1b is stable in solution at ?30°. Upon reaction with MeOH/H⁺ it is converted to a 1:2 mixture of 1- and 2-methylnaphthoate ( 10 and 11 , respectively).     

1-Trimethylsilyl-, 1-Trimethylgermyl- und 1-Trimethylstannyl-3,4-dimethylphospholen

1-Trimethylsilyl-, 1-Trimethylgermyl-, and 1-Trimethylstannyl-3,4-dimethylphospholene 1-Lithium-3,4-dimethylphospholen reacts with Me₃SiCl and Me₃GeCl yielding 1-trimethylsilyl-3,4-dimethylphospholene ( 1 ) and 1-trimethylgermyl-3,4-dimethylphospholene ( 2 ) respectively. 2 and 1-trimethylstannyl-3,4-dimethylphospholene ( 3 ) are formed using the reaction of 1 with Me₃GeCl and Me₃SnCl respectively. The ¹H, ¹³C and ³¹PNMR-spectra as well as the mass spectra of the new compounds are discussed.     

Molecular and crystal structure of 1-amino-3,5-diphenyl-2,4,4,6,6-Pentacyano-cyclohex-1-ene and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene

Molecular and crystal structures of 1-amino-3,5-diphenyl-2,4,4,6,6-pentacyano-cyclohex-1-ene (I) and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene (II) are studied to examine intermolecular interactions. Crystal data for (I): space group P2₁, a=11.172(3), b=6.561(2), c=16.390(4) Å, β=100.25(2)⁰, V=1182.1 ų, Z=2, R=0.046; for (II): space group P1, a=10.756(3), b=10.890(3), c=12.999(3) Å, α=62.20(2), β=70.73(2), γ=65.42(2)⁰, V=1207.2 ų, Z=2, R=0.074. Intermolecular bonds via the aminonitrile fragment in (I) lead to formation of chains along they axis: N1…N6′ (1?x, ?1/2+y, 1?z) of 3.465(8) Å, N6…N1″ (1?x, 1/2+y, 1?z), and the contact with the solvent (acetone) O1…N1 of 2.984(7) Å. In compound (II), the intermolecular contacts N1…N5′ (?x+1, ?y, ?z+1) of 3.064(7) Å link the molecules into dimeric associates.     

Studies on 1, 2, 4-Benzothiadiazine 1, 1-Dioxide IX.1 Synthesis and Pharmacological Evaluation of 1, 2, 4-Benzothiadiazine 1, 1-Dioxide Biphenyl Tetrazoles as Angiotensin II Antagonists

In the course of our investigations on the development of cardiovascular agents, 3-butyl-2-[2′-(2H-tetrazol-5-yl)bipheny]-4-yl]methyl-2H-1, 2, 4-benzothiadiazine 1, 1-dioxide ( 2 ) was considered as a potential angiotensin II antagonist on the basis of bioisosteric replacement of the quinazoline ring of compound 1 with a 1, 2, 4-benzothiadiazine 1, 1-dioxide ring system. Alkylation of 6 with 4 afforded 7 and 8 in 24% and 28% yields, respectively. An attempt to remove the trityl group of compounds 7 and 8 under acidic condition gave the ring opened products 9 and 11 in 28% and 36% yields, respectively. However, compounds 2 and 10 were obtained in 46% and 85% yields when compounds 7 and 8 were refluxed in methanol. Preliminary assays of compounds 9 and 11 against angiotensin II receptors revealed weak activity with IC₅₀ values of 3.6 μM and 5.4 μM, respectively. Compound 10 (IC₅₀ = 87 nM) exhibited stronger binding affinity than compound 2 (IC₅₀ = 750 nM).     

1, 5-Rearrangement of enol acylates of aryl 1H.-1, 2, 4-triazol-1-ylmethyl ketones

The rearrangement of enol acylates of aryl 1H-1, 2, 4-triazol-1-ylmethyl ketones at 140–150°C in acetic anhydride is studied. The migration of the acyl group to the C(5) atom of the heterocycle is found to be intramolecular. The characteristics of the original and final products are presented. X-ray structural studies of the enol acetates of 2, 4-dichlorophenyl 1H-1, 2, 4-triazol-1-ylmethyl ketone and 2, 4-dichlorophenyl 5-acetyl-1H-1, 2, 4-triazol-1-ylmethyl ketone are carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 560–564, March, 1993.     

Angular distributions of photoelectrons in resonantly enhanced multiphoto ionization via the 7s[1 1/2]0 1 and 8s[1 1/2]0 1 states of Xe

Photoelectron angular distributions have been measured for the three-photon resonant one-photon ionization, (3+1), of Xe via the 7s[1 1/2]⁰ ₁ and 8s[1 1/2]⁰ ₁ states. The results are in good agreement with the theoretical predictions of Tang and Lambropoulos [13] for the 8s[1 1/2]⁰ ₁, but not for the 7s[1 1/2]⁰ ₁ state. Furthermore, the results are compared to those which have been obtained by Blazewicz et al. [1] for the three-photon resonant two-photon ionization, (3+2), of Xe via the 6s[1 1/2]⁰ ₁ state.     

New synthesis of chalcogenolactones. 1H,3H-benzo[c]selenophen-1-one, 1H,3H-benzo[c]tellurophen-1-one and the related 3,4-dihydro-1H-2-benzoselenin-1-one and 3,4-dihydro-1H-2-benzotellurin-1-one

The synthesis of three new basic heterocyclic systems namely, 1H,3H-benzo[c]tellurophen-1-one (2-tellurophthalide), 3,4-dihydro-1H-2-benzoselenin-1-one (3,4-dihydro-2-isoselenocoumarin) and 3,4-dihydro-1H-2-benzotellurin-1-one (3,4-dihydro-2-isotellurocoumarin), is reported through the cyclisation of o-(bromoalkyl)benzoyl chlorides.     

3-Ferrocenyl-1-methyl- and 1-ferrocenyl-3-methylcyclopropenes

Dehydrobromination of isomeric 3-bromo-1-ferrocenyl-2-methylcyclopropanes afforded 3-ferrocenyl-1-methyl- and 1-ferrocenyl-3-methylcyclopropenes. These undergo smooth opening of the three-membered ring to give 1- and 2-ferrocenylbuta-1,3-dienes and 1- and 2-methyl-1H-cyclopentaferrocenes; with 1,3-diphenylisobenzofuran they give the classical Diels-Alder adducts.     

Syntheses of Heterocycles from the Sodium Salts of 3-(1-Adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-Adamantyl)-1-hydroxy-1-buten-3-one

The interaction of the sodium salts of 3-(1-adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-adamantyl)-1-hydroxy-1-buten-3-one with hydroxylamine, hydrazine, and guanidine leads to the synthesis of 5-(1-adamantyl)-5-hydroxy- and 5-(1-adamantylmethyl)-5-hydroxy-2-isoxazolines, 3-(1-adamantyl)- and 3-(1-adamantylmethyl)pyrazoles, 3-(1-adamantyl)-2-phenylpyrazole, and 4-(1-adamantyl)-2-amino- and 4-(1-adamantylmethyl)-2-aminopyrimidines.