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1.
The decomposition of various symmetric and unsymmetric azo-initiators (1,1-dichloro-1,1-diphenyl-1,1-azoethane, 2,2-dichloro-2,2-azopropane, 1,1-dichloro-1,1-azocyclohexane, 2,2-diacetoxy-2,2-azopropane, 1,1-diacetoxy-1,1-diphenyl-1,1-azoethane, 1,1-diacetoxy-1,1-azocyclohexane, 2,2-dipropionoxy-2,2-azopropane, 2,2-dicapronoxy-2,2-azopropane, 4,4-dimethyl-1,4-azobutyrolactone, azoisobutyronitrile, 2-t-butylazo-2-cyanobutan, 2-t-bytylazo-1-cyanocyclohexan) in solution was studied in dependence of temperature. Volumetry and differential-scanning-calorimetry (DSC) were used to determine decomposition rates; first order kinetics was found in all cases.
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2.
3-(2-Chloroalkyl)-2,2-dihaloaziridines were synthesized via cycloaddition of dihalocarbenes to the CN double bond of β-chloroimines. Under the action of Lewis acids or HCl, N-C3 bond cleavage occurred, giving rise to N-substituted 2,4-dichloro-3,3-dimethylbutanamides, which were further converted to 3-chloropyrrolidin-2-ones under alkaline conditions. When 2,2-dichloro-3-(2-chloro-1,1-dimethylethyl)-1-phenylaziridine was reacted with sodium methoxide, aziridine ring opening with N-C2 bond cleavage took place, leading to methyl 4-chloro-3,3-dimethyl-2-(phenylamino)butanoate.  相似文献   

3.
Summary 2,2-Disubstituted 1,1-biferrocenyls have been prepared by coupling of appropriate ferrocene derivatives. The stereochemistry of the diastereoisomers obtained thereby is discussed on the basis of n.m.r.-spectroscopy and in two cases (2a, b) from X-ray structure analyses. Chiroptical properties of optically active 1,1-biferrocenyls — obtained from (+)(R)-1-ferrocenyl-N,N-dimethylaminoethane — are reported. Attempts to prepare 2,2,5,5-tetrasubstituted biferrocenyls failed.Dedicated to Prof. Dr. Edwin Hengge on the occasion of his 60th birthday  相似文献   

4.
Several ruthenium procatalysts were tested in the transfer hydrogenation of acetophenone with 2-propanol using the chiral imine ligand (S)-2-(2-pyridinylmethyleneamino)-2-hydroxy-1,1-binaphthyl and the corresponding amine (S)-2-(2-pyridinylmethylamino)-2-hydroxy-1,1-binaphthyl. Ru(PPh 3)3Cl2 was the best procatalyst. Its triphenylphosphane ligands were crucial for the catalytic activity and take part in the chirality transfer. Triphenylphosphane removing reagents such as copper(I) chloride, TEMPO, or TMAO improved the catalytic performance to enantioselectivities up to 99% ee. The findings led to a mechanistic proposal including dissociation equilibria of triphenylphosphane and chelate ring opening of the tridentate chiral binaphthyl ligand. New ligands with an additional chiral center were synthesized and tested as cocatalysts. The nature of catalytically active intermediates was examined by MS and NMR spectroscopy.  相似文献   

5.
Conclusions The primary product during the acylation of N,N-dimethylhydrazine with anhydrides of,-unsaturated acids is the N,N-dimethylhydrazide of the acid, which at elevated temperatures rearranges to its tautomer — the corresponding 1,1-dimethylpyrazolin-3-oxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 917–918, April, 1970.`  相似文献   

6.
Summary Ethylferrocene was subjected to dimethylaminomethylation. The isolated products were the 1,2-,1,3- and l,l'-(N,N-dimethyIaminomethyl)ethylferrocenes, and the 1,1-di(N,N-dimethylaminomethyl)-2- and -3-ethylferrocenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2239–2240, December, 1966.  相似文献   

7.
Conclusions 1-Methoxyferrocene-2-carboxylic acid, 1,1-dimethoxyferrocene-2-carboxylic acid, and 2-methoxy-ferrocenyl diphenyl carbinol have been obtained via the lithium derivatives of methoxy- and 1,1-dimeth-oxyferrocenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1867–1869, August, 1967.The authors express their thanks to V. N. Drozd for much valuable advice in the performance of this work.  相似文献   

8.
9.
Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.  相似文献   

10.
Conclusions Both the nucleophilic and the free radical addition of n-butyl mercaptan to acetylenic-hydroxy ketones (1,1-disubstituted derivatives of 2-pentyn-1-ol-4-one) lead to the formation of the corresponding 1,1-disubstituted derivatives of 2-butylthio-2-penten-1-ol-4-one in 41–65% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1669–1670, July, 1973.  相似文献   

11.
Summary An investigation of the infrared spectra showed that the salts (potassium, sodium, ammonium, and lithium) of 1,1-dinitroalkanes and trinitromethane have three absorption bands: 1480, 1210, and 1120 cm–1. The infrared spectra do not contain absorption bands characteristic of the C=N double bond or an uncharged nitro group. Therefore, it is confirmed that salts of 1,1-dinitroalkanes and trinitromethane do not contain a C=N bond, and that all the nitro groups are equivalent and participate equally in the formation of the anion.  相似文献   

12.
The reaction of N-(pyrid-2-yl) and N-(5-methyipyrid-2-yl) cyanoacetamides with butylthiodibutylborane in a 23 ratio leads to the formation of trinuclear complex boron compounds, the alcoholysis of which gave N,N-di(pyrid-2-yl) 3-amino-2-cyanopent-2-ene-1,5-diamides. The latter are dimers of the starting cyanamides, which are capable of acting as hexadentate chelating agents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 168–173, January, 1991.  相似文献   

13.
1-Amino-2-R-benzimidazoles are oxidized by lead tetraacetate to give, depending on the substituent in the 2-position, either to 1,1-azobenzimidazoles (R=H, CH3, C6H5, Cl, N(CH3)2) or 3-R-benzo-1,2,4-triazines (R=NH2, NHCH3, NHC6H5, OH). The factors affecting the course of the reaction are discussed. The physicochemical properties of the 1,1-azobenzimidiazoles obtained have been examined.For preliminary communication, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1486–1499, November, 1989.  相似文献   

14.
Two new copper(II) azido complexes, namely bis-(tetraethylammonium)[tetraazidocuprate(II)] (1) and catena-di--1,1-azido-[di--1,1-azido-bis-(2,4-dimethylpyridine)dicopper(II)] (2), have been prepared and characterized by spectroscopic and crystallographic methods. Complex (1) consists of isolated NEt+ 4 cations and [Cu(N3)4]2– anions. The site symmetry around the copper atom in the anion is 4/m. Complex (2) features a 1 D chain structure, five coordinated square pyramidal copper(II) atoms with both azides functioning as -1,1-bridges. The i.r. spectra reveal that both complexes contain asymmetric azido ligands. The solid and solution electronic spectra of (1) and (2) show very strong absorption bands in the visible region associated with N 3 CuII charge-transfer transitions. The e.p.r. spectra of powder samples and solutions at room temperature were recorded and discussed.  相似文献   

15.
Conclusions Upon reaction of perfluoro-3-methylindene and perfluoro-1-methyleneindane with hexafluoropropylene oxide at 225°C the corresponding cyclopropane derivatives are formed: perfluoro-la-methyl-1,1a,6,6a-tetrahydrocycloprop[a]indene and perfluorospiro[indane-1,1-cyclopropane], which are transformed during thermolysis in the presence of bromine into 1-bromo-2-difluorobromomethylperfluoro-1-methylindane and 1-bromo-1-(2-bromotetrafluoroethyl)perfluoroindane respectively, and in the absence of bromine into the starting olefins.Deceased.For previous report, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1839–1845, August, 1988.  相似文献   

16.
Five kinds of solid coordination complexes of uranium(VI) and thorium(IV) with the diamide (N,N,N,N-tetrabutylmalon-amide (TBMA), N,N,N,N-tetrabutylsuccinylamide (TBSA), N,N,N,N-tetrabutylglutaramide (TBGA), N,N,N,N-tetrabutyl-adipicamide (TBAA)) were synthesized. All these complexes of UO2(NO3)2·TBMA, UO2(NO3)2· TBSA, [UO2(NO3)2·(TBGA1/2)2] x , UO2(NO3)2·TBAA and Th(NO3)4·2TBMA were characterized by elemental analysis, UV spectra, IR spectra and 13C NMR spectra. The coordination form and proposed structures of the complexes are also discussed.  相似文献   

17.
With excess acyl halide 1-methyl-3-acyl-2-(1-methyl-2-benzimidazolyl)-4-benzimidazoline is converted to an unstable 1-methyl-3-acyl-2-(1-methyl-3-acyl-4-benzimidazolin-2-yl)benzimidazolium chloride, which undergoes intramolecular redox cleavage with the formation of 1,1-dimethyl-2,2-dibenzimidazolyl and an aldehyde and dissociates at the C-C bond that connects the benzimidazolium and benzimidazoline fragments into a carbene yield and a 1-methyl-3-acylbenzimidazolium chloride.See [1] for communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 339–342, March, 1987.  相似文献   

18.
Conclusions The reactions of 1,1-dimethylhydrazine hydrochloride with ,-unsaturated acid chlorides were studied. In this reaction l,1-dimethyl-3-oxopyrazolidinium chlorides are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 162–164, January, 1967.  相似文献   

19.
Substituted 2-pyrazolines were synthesized from 5-aryl-1,1-dichloro-1,3-pentadien-5-ones and 6-aryl-2pyrones. A detailed analysis of the1H and13C NMR spectra of the starting compounds and final products was carried out.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Khimiya Geterolsiklicheskikh Soedineii, No. 11. pp. 1511–1524. November, 1995. Original article submitted November 14, 1995.  相似文献   

20.
Condensation of the trimethylsilyl derivatives of theophyllin and 3-isobutyl-1-methylxanthine with -D-glucofuranourono-6,3-lactone in the presence of trimethylsilyl trifluoromethanesulfonate has given N(7)--D-glucofuranouronosides. Their hydrolytic stability has been examined at pH 1.4 and 7.4.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 241–245, February, 1989.  相似文献   

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