1992 Volume 3 Issue 8
1992, 3(8): 579-582
Abstract:
In order to study the polar substituent effect almost with no steric effect in organophosphoruschemistry,a series of 4-substituted-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane 1-oxides (1) and p-substitutedphenylphosphonates (2) and corresponding mono hexyl esters (3) as model were synthesized.31P-NMR chemicalshifts of compounds (1) in methanol and deuterioacetone were determined.The Δδ values reflect 4-sbstituent po-lar effect.The 31P-NMR of compounds (2) and (3) and the pKa of compounds (3) were also measured.The results showed that the trend of polar effects of substituents in both carboxylic and organophosphates chemistry are similar.and the change of polar effects in variation with the alkyl groups is not significant.
In order to study the polar substituent effect almost with no steric effect in organophosphoruschemistry,a series of 4-substituted-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane 1-oxides (1) and p-substitutedphenylphosphonates (2) and corresponding mono hexyl esters (3) as model were synthesized.31P-NMR chemicalshifts of compounds (1) in methanol and deuterioacetone were determined.The Δδ values reflect 4-sbstituent po-lar effect.The 31P-NMR of compounds (2) and (3) and the pKa of compounds (3) were also measured.The results showed that the trend of polar effects of substituents in both carboxylic and organophosphates chemistry are similar.and the change of polar effects in variation with the alkyl groups is not significant.
1992, 3(8): 583-584
Abstract:
2-Fluoroalkyl-4-hydroxy-quinolines were easily obtained from thereactions of 2-(F-alkyl) acetates with aromatic amines in the presence of Et3N,followed by cyclization of the intermediates with PPA.
2-Fluoroalkyl-4-hydroxy-quinolines were easily obtained from thereactions of 2-(F-alkyl) acetates with aromatic amines in the presence of Et3N,followed by cyclization of the intermediates with PPA.
1992, 3(8): 585-588
Abstract:
This paper reports a new method for oxidizing the α-methyl or α-methylene groups in carbonyl compounds into 1,2-dicarbonyl compoundsby ammonium chlorochromate (ACC).
This paper reports a new method for oxidizing the α-methyl or α-methylene groups in carbonyl compounds into 1,2-dicarbonyl compoundsby ammonium chlorochromate (ACC).
1992, 3(8): 589-592
Abstract:
The syntheses of a new type of heteromacrocyclic polyether-2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene (L),and its pla-tinum complex (PtL2Cl2) were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.
The syntheses of a new type of heteromacrocyclic polyether-2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene (L),and its pla-tinum complex (PtL2Cl2) were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.
1992, 3(8): 593-594
Abstract:
The chlorination of O,O-dialkyl N,N-dialkyl thiophosphoramidates with phosphorus oxychloride proceeds with isomerization to give S-alkyl N,N-dialkyl thiophosphoramidochloridates,which react further with various nucleophiles in the presence of base to give the title compounds.
The chlorination of O,O-dialkyl N,N-dialkyl thiophosphoramidates with phosphorus oxychloride proceeds with isomerization to give S-alkyl N,N-dialkyl thiophosphoramidochloridates,which react further with various nucleophiles in the presence of base to give the title compounds.
1992, 3(8): 595-596
Abstract:
This paper describes the indirect electrooxidation of the side chain of aromatic com. pounds with a Ce(Ⅳ)/Ce(Ⅲ) redox system.The reaction has the following advantages:favourable selectivity,high yield,nonpollution and economy.
This paper describes the indirect electrooxidation of the side chain of aromatic com. pounds with a Ce(Ⅳ)/Ce(Ⅲ) redox system.The reaction has the following advantages:favourable selectivity,high yield,nonpollution and economy.
1992, 3(8): 597-600
Abstract:
The synthesis of derivatives of 3-β-D-xylopyranosyl-1,2,4-oxadiazoles is accomplished by condensing protected β-D-xylopyranosyl amidoxime with acid anhydrides or various substituted benzoyl chlorides in good yield.The structures of now derivatives were identified by spectra and elemental analysis. The stability of 1,2,4-oxadiazole ring and mechanism of cyclization were investigated.
The synthesis of derivatives of 3-β-D-xylopyranosyl-1,2,4-oxadiazoles is accomplished by condensing protected β-D-xylopyranosyl amidoxime with acid anhydrides or various substituted benzoyl chlorides in good yield.The structures of now derivatives were identified by spectra and elemental analysis. The stability of 1,2,4-oxadiazole ring and mechanism of cyclization were investigated.
1992, 3(8): 601-604
Abstract:
The ccndensation reactions occurred when heating bis (perfluoroalkane-sulfonyl) methanes with aromatic aldehydes in acetic acid anhydride and gave high yields of 1-aryl-2,2-di (perfluoroalkanesulfonyl) ethylenes.
The ccndensation reactions occurred when heating bis (perfluoroalkane-sulfonyl) methanes with aromatic aldehydes in acetic acid anhydride and gave high yields of 1-aryl-2,2-di (perfluoroalkanesulfonyl) ethylenes.
1992, 3(8): 605-606
Abstract:
A novel tricomponental condensation leading to p-nitrophenyl-ethyl hydrogen substituted benzylphosphonates was described.The use of these compounds for the synthesis of phosphonopeptide with phosphonamide moiety was demonstrated.
A novel tricomponental condensation leading to p-nitrophenyl-ethyl hydrogen substituted benzylphosphonates was described.The use of these compounds for the synthesis of phosphonopeptide with phosphonamide moiety was demonstrated.
1992, 3(8): 607-610
Abstract:
The title compound 1b has been synthesized from the chiralbuilding block 2 through five steps.
The title compound 1b has been synthesized from the chiralbuilding block 2 through five steps.
1992, 3(8): 611-612
Abstract:
Electron transfer reactions between O-benzoyl t-butylhydroxyl-amine,t-BuNHOCOPh (1) and perfluorodiacyl peroxides (RfCO2)2 (2) mayserve as a novel method for generating useful t-hutyl perfluoroalkylnitroxldes at room temperature in CFCl2-CF2Cl.
Electron transfer reactions between O-benzoyl t-butylhydroxyl-amine,t-BuNHOCOPh (1) and perfluorodiacyl peroxides (RfCO2)2 (2) mayserve as a novel method for generating useful t-hutyl perfluoroalkylnitroxldes at room temperature in CFCl2-CF2Cl.
1992, 3(8): 613-614
Abstract:
The reaction of benzyl alcohol and ethanol cannot take place with quaternary ammonium salt,but will be carried out smoothly if benzyl halide is added.
The reaction of benzyl alcohol and ethanol cannot take place with quaternary ammonium salt,but will be carried out smoothly if benzyl halide is added.
1992, 3(8): 615-618
Abstract:
Oilless alkyd resin modified with the silicoorganic compounds has been obtained successfully by polymerization.At appropriate proportion of silicoorganic compounds,the polymerized product has higher hardness and lustre than that of oilless alkyd resin.
Oilless alkyd resin modified with the silicoorganic compounds has been obtained successfully by polymerization.At appropriate proportion of silicoorganic compounds,the polymerized product has higher hardness and lustre than that of oilless alkyd resin.
1992, 3(8): 619-620
Abstract:
A new series of MR-IPN polyacrylamide-poly (vinyl-ethylenediamine) chelate sorbents were prepared by the reaction of ethylenediamine with MR-IPN matrixes.The new chelate sorbent showed good sorption properties for auric and platinic ions.
A new series of MR-IPN polyacrylamide-poly (vinyl-ethylenediamine) chelate sorbents were prepared by the reaction of ethylenediamine with MR-IPN matrixes.The new chelate sorbent showed good sorption properties for auric and platinic ions.
1992, 3(8): 621-624
Abstract:
Ion-containing segmented polyetherurethanes with well defined structures were synthesized by using ion-containing extenders.Structure characteristics,thermal behavior and surface mobility were examined.
Ion-containing segmented polyetherurethanes with well defined structures were synthesized by using ion-containing extenders.Structure characteristics,thermal behavior and surface mobility were examined.
1992, 3(8): 625-628
Abstract:
Three new β-dihydroagarofuran sesquiterpene polyol esters,one alkaloid and two non-alkaloids,were isolated from the MeOH extract of seed oil of Celastrus angulatus. Their structures were elucidated on the basis of UV,IR,mass,NOE difference,1H-NMR,13C-NMR and 1H-13C long-range correlation spectroscopy.
Three new β-dihydroagarofuran sesquiterpene polyol esters,one alkaloid and two non-alkaloids,were isolated from the MeOH extract of seed oil of Celastrus angulatus. Their structures were elucidated on the basis of UV,IR,mass,NOE difference,1H-NMR,13C-NMR and 1H-13C long-range correlation spectroscopy.
1992, 3(8): 629-632
Abstract:
Two cyclopeptides,heterophyllin A and B,have been isolated from the roots of Pseudostellaria heterophylla.Their structures were elucidated by chemical,spectroscopic,and enzymatic methods.
Two cyclopeptides,heterophyllin A and B,have been isolated from the roots of Pseudostellaria heterophylla.Their structures were elucidated by chemical,spectroscopic,and enzymatic methods.
1992, 3(8): 633-634
Abstract:
On the basis of chemical and spectroscopic evidence,the structure of parvifolinwas established as ent-7β,20-epoxy-kaurane-15-oxo-1α,6β,7β,11β,16α-pentaol.
On the basis of chemical and spectroscopic evidence,the structure of parvifolinwas established as ent-7β,20-epoxy-kaurane-15-oxo-1α,6β,7β,11β,16α-pentaol.
1992, 3(8): 635-636
Abstract:
Two new bicyclo[3,2,1] octanoid neolignans,named as kadsurenin I and kadsurenin J were isolated from Piper kadsura (Choiey) Ohwi.Based on the spectros-copic analysis (UV,IR,MS and NMR) and chemical derivatization,their structures were established as 7R,8R,1'R,2'S,3'R-Δs'-3,4,5'-trimethoxy-2'-hydroxy-1',2',3',4'-tetrahydro-4'-oxo-7.3',8.1'-neolignan and 7R,8R,1'R,2'S,3'R-Δs'-3,4,5'-trimethoxy-2'-acetoxy-1',2',3',4'-tetrabydro-4'-oxo-7.3',8.1'-neolignan respectively.
Two new bicyclo[3,2,1] octanoid neolignans,named as kadsurenin I and kadsurenin J were isolated from Piper kadsura (Choiey) Ohwi.Based on the spectros-copic analysis (UV,IR,MS and NMR) and chemical derivatization,their structures were established as 7R,8R,1'R,2'S,3'R-Δs'-3,4,5'-trimethoxy-2'-hydroxy-1',2',3',4'-tetrahydro-4'-oxo-7.3',8.1'-neolignan and 7R,8R,1'R,2'S,3'R-Δs'-3,4,5'-trimethoxy-2'-acetoxy-1',2',3',4'-tetrabydro-4'-oxo-7.3',8.1'-neolignan respectively.
1992, 3(8): 637-640
Abstract:
The program system described in this paper is a microcomputer analytic system for X-ray crystal structure used in chemical laboratories.The abbreviated name is NOMCSDP.NOMCSDP has been developed on the basis of NRCVAX and SHELXS-86.It is a software for X-ray crystal structure analysis of organic molecules,especially natural organic molecules (1-7).
The program system described in this paper is a microcomputer analytic system for X-ray crystal structure used in chemical laboratories.The abbreviated name is NOMCSDP.NOMCSDP has been developed on the basis of NRCVAX and SHELXS-86.It is a software for X-ray crystal structure analysis of organic molecules,especially natural organic molecules (1-7).
1992, 3(8): 641-644
Abstract:
Acidic hydrogen peroxide solution,in the presence of a certain metal cation,can react with alkaline solution and produce chemiluminescence light emission.The present paper firstly reports this novel kind of chemiluminescence reaction.The effect of some factors and metal ions on the chemiluminescence reaction has been tested and studied.
Acidic hydrogen peroxide solution,in the presence of a certain metal cation,can react with alkaline solution and produce chemiluminescence light emission.The present paper firstly reports this novel kind of chemiluminescence reaction.The effect of some factors and metal ions on the chemiluminescence reaction has been tested and studied.
1992, 3(8): 645-648
Abstract:
The electronic spectroscopic properties of several meso-substituted zinc tetrabenzoporphyrins (ZnTBP,ZnTMTBP,ZnTPTBP,ZnTTTBP and ZnTNTBP) have been investigated in toluene.The lifetimes determined showed that the fluorescence of these compounds decay with good double exponentials.
The electronic spectroscopic properties of several meso-substituted zinc tetrabenzoporphyrins (ZnTBP,ZnTMTBP,ZnTPTBP,ZnTTTBP and ZnTNTBP) have been investigated in toluene.The lifetimes determined showed that the fluorescence of these compounds decay with good double exponentials.
1992, 3(8): 649-650
Abstract:
The electronic structure and chemical bonding of the title complexes have been studied by an unrestricted INDO program made applicable for the lanthanoid compounds.The results indicated: (1) In coordinated bonds O-Ln and N-Ln,5d orbitals of Ln have large contribution in all valence orbitals of Ln and 4f orbitals have very small contribution. (2) The covalent character and ionic character are almost equal in the chemical bond which is comparatively weak between phen,C2H5OH and Ln are mainly ionic with some covalent character.
The electronic structure and chemical bonding of the title complexes have been studied by an unrestricted INDO program made applicable for the lanthanoid compounds.The results indicated: (1) In coordinated bonds O-Ln and N-Ln,5d orbitals of Ln have large contribution in all valence orbitals of Ln and 4f orbitals have very small contribution. (2) The covalent character and ionic character are almost equal in the chemical bond which is comparatively weak between phen,C2H5OH and Ln are mainly ionic with some covalent character.
1992, 3(8): 651-652
Abstract:
Ab initio electronic structure calculations are reported for low-lying electronic states,X 1Σ+ and A 1Π of the N2F+ molecule.Geometric parameters for the ground state X 1Σ+ are predicted by means of mul-tireference single and double excitation configuration interaction (MRSDCI) calculations with a double zeta plus polarization (DZ+P) basis set.Vertical excitation energy for these two electronic states is determined using MRSDCI/DZ+P calculations at the ground state equilibrium geometry.The oscillator strength for the X 1Σ+→A 1Π transition and the radiative lifetime for the A 1Π state are calculated based on the MRSDCI wavefunctions.
Ab initio electronic structure calculations are reported for low-lying electronic states,X 1Σ+ and A 1Π of the N2F+ molecule.Geometric parameters for the ground state X 1Σ+ are predicted by means of mul-tireference single and double excitation configuration interaction (MRSDCI) calculations with a double zeta plus polarization (DZ+P) basis set.Vertical excitation energy for these two electronic states is determined using MRSDCI/DZ+P calculations at the ground state equilibrium geometry.The oscillator strength for the X 1Σ+→A 1Π transition and the radiative lifetime for the A 1Π state are calculated based on the MRSDCI wavefunctions.
1992, 3(8): 653-656
Abstract:
The stability of the complexes of four pyridine-like ligands with Cu(ATP)2- was studied and by comparing the stability constants of the ternary complexes [Cu(ATP)L]2- with those of the binary complexes [CuL]2+,a stacking interaction between the pyridine ring and the purine ring of ATP is indicated.It is possible to interpret the antitumor mechanism of[Pt(NH3)8 (N-het)Cl]Cl in terms of this stacking interaction.
The stability of the complexes of four pyridine-like ligands with Cu(ATP)2- was studied and by comparing the stability constants of the ternary complexes [Cu(ATP)L]2- with those of the binary complexes [CuL]2+,a stacking interaction between the pyridine ring and the purine ring of ATP is indicated.It is possible to interpret the antitumor mechanism of[Pt(NH3)8 (N-het)Cl]Cl in terms of this stacking interaction.
1992, 3(8): 657-658
Abstract:
New tanthanide comptexes of acetylacetonate-meso-tetra-(4-pyridyt) porphyrin (LnTpypacac,Ln=Dy,Ho,Yb,Lu,H2Tpyp=tetra-(4-pyridyl)-porphyrin,Hacac=acetylacetone) were prepared by reaction of Ln (acac)3·3H2O with H2Tpyp and were characterized by elemental analyses,ultra-viotet spectra,infrared spectra and thermal analyses.
New tanthanide comptexes of acetylacetonate-meso-tetra-(4-pyridyt) porphyrin (LnTpypacac,Ln=Dy,Ho,Yb,Lu,H2Tpyp=tetra-(4-pyridyl)-porphyrin,Hacac=acetylacetone) were prepared by reaction of Ln (acac)3·3H2O with H2Tpyp and were characterized by elemental analyses,ultra-viotet spectra,infrared spectra and thermal analyses.
1992, 3(8): 659-662
Abstract:
A new method of preparing electrical conductive molybdenum oxide by thermal decomposition from hydrazine-containing molybdenum salt was described.The process of the thermal decomposition of hydrazine-containing molybdemum salt was investigated by thermal analysis (TG and DTA) and the thermally decomposed product was studied by S.E.M.and chemical analysis.The result indicated that the molybdenum oxide obtained in this way was electrical conductive.
A new method of preparing electrical conductive molybdenum oxide by thermal decomposition from hydrazine-containing molybdenum salt was described.The process of the thermal decomposition of hydrazine-containing molybdemum salt was investigated by thermal analysis (TG and DTA) and the thermally decomposed product was studied by S.E.M.and chemical analysis.The result indicated that the molybdenum oxide obtained in this way was electrical conductive.
1992, 3(8): 663-664
Abstract:
A new three-arms-nine-chains discotic molecule has been synthesized,and the aggregation structure of the compound was measured by x-ray diffraction,infrared spectra,polarizing microscope,etc.From these evidences,the new discotic liquid crystal is found to have the discotic lammelar phase.
A new three-arms-nine-chains discotic molecule has been synthesized,and the aggregation structure of the compound was measured by x-ray diffraction,infrared spectra,polarizing microscope,etc.From these evidences,the new discotic liquid crystal is found to have the discotic lammelar phase.
1992, 3(8): 665-666
Abstract:
The reaction of [CpMo(CO)2]2 with 8,8'-diquinolyl disulphide C9H6NSSNC9H6 resulted in the cleavage of Mo≡Mo triple bond to give a new mononuclear complex CpMo(CO)2(N,S-C9H6NS) which was refluxed with PPh3 in THF to form the title complex.The crystal structure of the title complex was determined by X-ray diffraction.
The reaction of [CpMo(CO)2]2 with 8,8'-diquinolyl disulphide C9H6NSSNC9H6 resulted in the cleavage of Mo≡Mo triple bond to give a new mononuclear complex CpMo(CO)2(N,S-C9H6NS) which was refluxed with PPh3 in THF to form the title complex.The crystal structure of the title complex was determined by X-ray diffraction.
1992, 3(8): 667-668
Abstract:
The structures of Nylon-1010 with different draw ratios have been investigated by using Small-Angle X-ray Scattering (SAXS).It is shown that by using a simple geometrical construction the following structure parameters can be directly derived from the correlation function,the long period (L),the thickness of the crystal amorphous interphase (dtr),the lamellar thickness (do),the "invariant" (Q),the specific inner surface (Os),and the electron density difference between the core of the crystallite and the amorphous matrix (ηc-ηa).
The structures of Nylon-1010 with different draw ratios have been investigated by using Small-Angle X-ray Scattering (SAXS).It is shown that by using a simple geometrical construction the following structure parameters can be directly derived from the correlation function,the long period (L),the thickness of the crystal amorphous interphase (dtr),the lamellar thickness (do),the "invariant" (Q),the specific inner surface (Os),and the electron density difference between the core of the crystallite and the amorphous matrix (ηc-ηa).
1992, 3(8): 669-672
Abstract:
Urea can be sorbed by complexation with metal-polyaerylic acid complex.The experimental results indicate that the coordination occurs in the 0 atom of urea with Cu(Ⅱ) in Cu(Ⅱ)-polyaerylic acid complex and the sorption capacity of urea can reach about 60 mg per gram of the Cu(Ⅱ)-polyacrylic acid complex.
Urea can be sorbed by complexation with metal-polyaerylic acid complex.The experimental results indicate that the coordination occurs in the 0 atom of urea with Cu(Ⅱ) in Cu(Ⅱ)-polyaerylic acid complex and the sorption capacity of urea can reach about 60 mg per gram of the Cu(Ⅱ)-polyacrylic acid complex.