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1.
The reaction of (CH3NPF3)2 with mono-and bissilylatedN,N-dimethylurea yields a crystalline solid which has been identified as a cuban-like P-N-compound with two dimethylurea-bridges. The conditions of formation and the NMR-spectra are discussed. 相似文献
2.
C. Holzner 《Monatshefte für Chemie / Chemical Monthly》1994,125(12):1353-1364
Zusammenfassung Cu(I) bildet mit zahlreichen nicht lumineszierenden Thionoliganden (N-monosubstituierten N-Sulfonylthioharnstoffen, N,N-Dialkyl-N-phenylthioharnstoffen und N,N-Dialkylmonothiocarbamaten) rot lumineszierende oktaedrische Cluster (CuL)6. Die Lumineszenz tritt sowohl im Festzustand als auch in Lösungen auf. Abklingzeiten von 10–5s deuten auf kurzlebige Phosphoreszenz hin. Der Einfluß verschiedener Strukturelemente auf die Lage der Emissionsmaxima wird diskutiert. Dabei bewirken Veränderungen in der Metall-Ligand-Koordination die stärkste Verschiebung der Lumineszenzbanden. Tetraedrische (CuL)4-Cluster mit den obigen Thionoliganden zeigen keine Lumineszenz. Generelle Unterschiede in der Struktur oktaedrischer und tetraedrischer Cluster werden diskutiert.Ag(I) bildet nur mit N-Alkyl-N-sulfonylthioharnstoffen lumineszierende Cluster (AgL)6. Die Lumineszenz ist im Gegensatz zu den Cu-Clustern auf den Festzustand beschränkt.
Luminescent Cu(I) and Ag(I) clusters with thiono ligands
Summary Octahedrical (CuL)6 clusters with several non luminescent thiono ligands (N-monosubstituted N-sulfonylthioureas, N,N-dialkyl-N-phenylthioureas and N,N-dialkylmonothiocarbamates) show red luminescence in the solid state and in solution. The luminescence lifetimes of 10–5s are typical of short lived phosphorescence. The emission bands are affected by structural variation of the ligand. Changes of the coordination bonds cause the strongest shifts of the luminescence maxima. Tetrahedrical (CuL)4 clusters with the same thiono ligands are not luminescent. General structural differences between octahedral and tetrahedral clusters are discussed.(AgL)6 clusters are only luminescent in the solid state and if the ligand is a N-monosubstituted N-sulfonylthiourea相似文献
3.
In the presence ofEt
3N·PF5, F4P–(CH3N)2PF2NHNH+(CH3)2 (I) looses one molecule of HF to yield F3P(CH3N)2PF2NHN(CH3)2 (II). The reaction ofI withDABCO (1,4-diazabicyclo[2.2.2]octane) yieldsDABCO·2H++(CH3NPF4)
2
––
(III) and [CH3NPF2NHN(CH3)2]2 (IV). Even in the presence of CsF,II does not react with HF. 相似文献
4.
Partial protection of diethyldithioketal ofN-acetylneuraminic acid--lactone using one or two equivalents oft-butyldimethylchlorosilane leads to the 9-O-silyletherderivative7 and the 8,9-bis-O-silylderivative5, resp. The reaction of1 as well as7 with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TIPSiCl2) yields selectively the protected products4 and9. The 9,8,7,6-tetra-O-acetyl-N-acetylneuraminic acid--lactone derivative3 is formed by the oxidative desulfurazation of the peracteylated form of1 (i. e.2) by means ofNBS. By reaction of5 withTPPDEAD the 6,7-carbonato compound6 arises instead of the expected 6,7-epoxyderivative. The analogous carbonate8 is formed by treating7 with bisimidazolylcarbonate. 相似文献
5.
Johannes Häusler 《Monatshefte für Chemie / Chemical Monthly》1986,117(2):269-273
Reaction of methyl 1-pyrroline-2-carboxylate (3 a) with N,N-Ditosylsulphur-diimide affords the pyrrol-2-carboxylic acid derivative7. The sulfenamide function in7 is cleaved by trimethyl phosphite leading to8. Presumably the reaction sequence (3 a 7) takes its course via the sulfinamidine4 a and the rearrangement product5 a followed by elimination of tosylamide. An analogous reaction starting with the dimethyl-1-pyrrolin-2-carboxylate3 b yields the stable sulfinamidine4 b, which undergoes a rearrangement reaction with base producing6 b with the thioaminal5 b as the intermediate.
Herrn Prof. Dr. Dr. h. c.K. Kratzl zum 70. Geburtstag herzlich gewidmet. 相似文献
6.
Zdzisław Gałdecki Bernard Luciak Krzysztof Kaczmarek Mirosław T. Leplawy Adam S. Redliński 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):993-998
Summary Synthesis and X-ray structure analysis of N-acetyl-,-diethylglycine-N-methylamide [CH3-Co-NH-C(C2H5)2-CO-NHCH3] are described. The compound was obtained from the corresponding N-acetyl derivative [CH3-CO-NH-C(C2H5)2-COOH] through the mixed anhydride procedure. It crystallizes as monohydrate (C9H18N2O2·H2O) in space group P21/c,a=7.139(1),b=11.823(2),c=15.778(3) Å, =122.23(1)°,V=1126.53 Å3,D
m=1.20 Mgm–3 (room temperature),R=0.046 for 1523 reflections. The crystal packing is dominated by two strong hydrogen bonds between the water molecule and two carbonyl oxygen atoms and two weak H-bonds to two amide-N-atoms of symmetry-equivalent molecules. The molecular conformation is closer to a 310-helix then ana-helix.
Synthese, Kristallstruktur und Konformation von N-Acetyl-,-diethylglycin-N-methylamid
Zusammenfassung Es wird über Synthese und die röntgenographische Strukturbestimmung von N-Acetyl-,-diethylglycin-N-methyl-amid [CH3-CO-NH-C(C2H5)2-CO-NH-CH3] berichtet. Die Verbindung wurde unter Anwendung der Methode der gemischten Anhydride aus dem entsprechenden N-Acetylderivat [CH3-CO-NH-C(C2H5)2-COOH] erhalten. Sie kristallisiert als Monohydrat (C9H18N2O2·H2O) in der Raumgruppe P21/c mita=7.139(1),b=11.823(2),c=15.778(3) Å, =122.23(1)°,V=1126.53 Å3,D m=1.20 Mgm–3,D x=1.204 Mgm–3 (Raumtemperatur).R=0.046 für 1523 Reflexe. Die Kristallpackung ist dominiert durch zwei starke H-Brücken vom Wassermolekül zu zwei Carbonylsauerstoffatomen sowie zwei schwachen H-Brücken zu zwei Amid-N-atomen symmetrieequivalenter Moleküle. Die Konformation des Peptidgerüstes ist näher einer 310 als einera-Helix.相似文献
7.
Elisabeth Öhler Mahmoud El-Badawi Erich Zbiral 《Monatshefte für Chemie / Chemical Monthly》1985,116(1):77-86
Zusammenfassung -Substituierte -Acylvinylphosphonate3 mitE-Konfiguration [R
2CO-CH=C(R
1)-P(O)(OR)2], werden in guten Ausbeuten durchWittig-Reaktion von Acylphosphonsäureestern1 [R
1CO-P(O)(OR)2,R
1=Alkyl oder Aryl] mit (2-Oxoalkyliden)triphenylphosphoranen2 [R
2CO-CH=PPh
3,R
2=Alkyl, O-Alkyl oder CH2
X (X=Br, OMe, CO2
Et)] erhalten.
A convenient route to -substituted dialkyl (E)-3-oxo-1-alkenylphosphonates
-Substituted dialkyl (E)--acylvinylphosphonates [R 2CO-CH=C(R 1)-P(O)(OR)2,3], are easily obtained in good yields byWittig-reaction of dialkyl acylphosphonates1 [R 1CO-P(O)(OR)2,R 1=alkyl or aryl) with 2-oxoalkylidene triphenylphosphoranes2 [R 2CO-CH=PPh 3,R 2=alkyl, O-alkyl and CH2 X (X=Br, OMe, CO2 Et)].相似文献
8.
The results of X-ray diffraction analysis of novel triethylallylammonium chloride compounds with copper(I) chloride, copper(I) bromide, and copper(II) chloride are reported. The [(CH3CH2)3(CH2=CHCH2xN]Cu
3
I
Cl4 and [(CH3CH2)3(CH2=CHCH2Cu
3
I
Br3.86)Cl0.14 -complexes are isostructural: space group P21/a; a= 17.58(1) Å, b = 12.059(8)Å, c = 7.184(4) Å, = 98.37(5)° and a = 17.972(9) Å, b=12.479(8) Å, c = 7.290(5) Å, = 98.81(5)°, respectively. 2-Coordination of the copper atom by the olefinic bond plays a key role in the structural ordering of the tetraalkylammonium cation. In contrast, the structure of {(CH3CH2)3x(CH2=CHCH2)N}2CuIICl4 (P42/nmc; a = 8.839(3) Å, c =15.660(9) Å) follows the ionic salt pattern.Original Russian Text Copyright © 2004 by L. M. Babkov, I. I. Gnatyuk, G. A. Puchkovskaya, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 398–405, May–June, 2004. 相似文献
9.
Chun-Kiu Kwok Thomas C. W. Mak 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(5):461-471
N,N-DicyclohexylpiperazineN,N-dioxide octahydrate, C16H46N2O10,M
r=426.55, monoclinic, space groupC2/m (No. 12),a=12.961(4),b=11.533(4),c=7.907(1) Å, =98.37(2)o,V=1169.3(6) Å3,Z=2. The structure was solved by the direct method and refined toR=0.045 for 1192 observed MoK
reflections. TheN,N-dioxide molecule occupies a site of symmetry 2/m. The piperazine ring takes the chair form with the two N–O bonds oriented axially in atrans configuration. Hydrogen bonding between the water molecules, as well as between theN-oxide groups and water molecules, gives rise to a puckered layer composed of edge-sharing four-membered, five-membered, six-membered, and eight-membered rings. Adjacent layers are cross-linked by theN,N-dicyclohexylpiperazine moieties lying between them, thereby generating a sandwich structure consolidated by covalent and hydrogen bonding.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82062 (8 pages). 相似文献
10.
The least-energy dissociation path of the ground state of CH2N2 was determined fromab initio calculations using in a complementary way basis sets of minimal size (STO-3G) and double-zeta (DZ) quality. The results indicate that the least-energy point of attack of the N2 molecule on CH2 (1
A
1) is roughly perpendicular to the molecular plane (93 °), the C and N atoms being almost co-linear (angle C-N-N203 ° with outermost N atom pointing away from CH2). The potential barrier of 1.2 eV found previously on theC
2v
dissociation path, disappears completely along the least-energy dissociation path (point groupC
s
(out-of-plane)). These findings corroborate the Woodward-Hoffman rules for this process since the outermost orbitals of the two intersecting states found in point groupC
2v
(...2b
1 and ...8a
1) both correlate to the same irreducible representation (10á) in point groupC
s
(out-of-plane).Larger basis set calculations (DZ + polarization functions on all centers, 3d
c and 3d
N developed here), were also carried out on CH2N2 (1
A
1,3
A
2 and1
A
2) at the1
A
1 equilibrium geometry and on CH2 (3
B
1) and N2 (1
g
+
) at their respective equilibrium geometries. These calculations, together with consideration of correlation energy differences, yieldD
0
0
(CH2N2,1
A
1) = 19 kcal/mole and vertical excitation energies of 67 and 73 kcal/mole for the3
A
2 and1
A
2 states respectively. The latter value is in good agreement with the measured experimental value: 72.4 kcal/mole corresponding to the maximum of intensity in the1
A
21
A
1 absorption band. 相似文献
11.
From1b, 1c and1d no 1,4-oxazines are available under dehydrating conditions. Only reaction of1c withPPA at room temperature yields7, while1 d in dependence of the reaction time withPPA at 100°C undergoes cyclisation to the indoles3 b and3 c and the pyrroloindole4 b, resp.
Teile der DiplomarbeitHaubold G., Wien 1977. Teile der DissertationHaubold G., Wien 1980. 相似文献
12.
The reaction of (CH3NPF3)2 with substituted hydrazines yields a new type of a P/N/P/N ring system by addition of one molecule hydrogenfluorid to the substituted molecule. These betain-like compounds are the first examples of a P/N/P/N ring system with one P-atom in 5- and the other in 6-conformation. 相似文献
13.
14.
Summary The bifunctional title compounds2 react with acylating, carbamoylating and sulfonylating reagents mostly at the primary amino group of the hydrazine function. Both functional groups of2 are attacked by N,N-carbonyldiimidazole converting it into 1H-1,2,4,5-tetrazepin-3-one derivatives8. The acid-induced 1,4-elimination of phenylhydrazine from2 gives rise to the formation of phenylosazones3. In the presence of thiocyanic acid the intermediately formed phenylazo-alkenes1 undergo [3+2]-cycloaddition furnishing 1-anilino-imidazoline-2-thiones13.
Additionsprodukte von Hydrazin-Derivaten an Phenylazo-alkene, 5. Mitt.: Umsetzung von -(1-Phenylhydrazino)alkanon phenylhydrazonen mit Säuren und Säurederivaten
Zusammenfassung Die bifunktionellen Titelverbindungen2 reagieren mit Acylierungs-, Carbamoylierungs-und Sulfinylierungs-Reagenzien meist an der primären Amino-Gruppe der Hydrazin-Funktion. N,N-Carbonyldiimidazol greift beide funktionelle Gruppen von2 an und bedingt die Umwandlung in 1H-1,2,4,5-Tetrazepin-3-on-Derivate8. Die säureinduzierte 1,4-Eliminierung von Phenylhydrazin aus2 führt zur Bildung der Phenylosazone3. In Gegenwart von Thiocyansäure erfolgt [3+2]-Cycloaddition an die intermediär gebildeten Phenylazo-alkene1, sodaß 1-Anilino-imidazolin-2-thione13 entstehen.相似文献
15.
Reactions of the isopropoxides of some of the lighter lanthanons with bidentate -ketoimines, such asAAH-n-C4H9 andAAH-C6H5 (donor system: N,OH) and tridentate -ketoimines such asAA(CH2CH2)H2 andAA(CH2CHCH3)H2 (donor system: HO,N.OH) have led to products of the typesLn(O-i-C3H7)3n
(AA-R)
n
,Ln(Oi-C3H7) (AAR') andLn
2(AAR')3 [Ln=La(III), Pr(III) or Nd(III);n=1 or 2;R=-n-C4H9 or-C6H5 andR'=-CH2CH2-or-CH2CHCH3-]. Some undergo exchange reactions with an excess oftert-butanol, leading to the corresponding complexesLn(O-tert-C4H9)3n
(AA-n-C4H9)
n
andLn(O-tert-C4H9) (AA-CH2CH2). All these have been characterised by elemental analysis, molecular weight determinations and their ir spectra. A thermogravimetric analysis of the diisopropoxy derivatives has also been carried out.
Schiff-Basen Derivate von Lanthaniden-Synthese von La(III), Pr(III) und Nd(III) chelaten mit -Ketoiminen
Zusammenfassung Reaktionen von Lanthanid-Isopropoxiden mit zweizähnigen -Ketoiminen [AAH-n-C4H9 undAAH-C6H5; Donorsystem: N,OH] und dreizähnigen -Ketoiminen [AA(CH2CH2)H2 undAA(CH2CHCH3)H2; Donorsystem: OH, N,OH] führten zu Produkten vom, TypLn(O-i-C3H7)3-n (AA-R) n ,Ln(O-i-C3H7) (AAR') undLn 2(AAR')3 [Ln=La(III), Pr(III) oder Nd(III);n=1 oder 2;R=n-C4H9 oder C6H5 undR'=CH2CH2 oder CH2CHCH3]. Einige Komplexe unterliegen bei Behandlung mit einem Überschuß vontert-Butanol einer Austauschreaktion, die zu den entsprechenden Butoxid-Komplexen führt [Ln(O-tert-C4H9)3-n , (AA-n-C4H9) n undLn(O-tert-C4H9) (AACH2CH2)]. Alle Derivate wurden mittels Elementaranalyse, Molgewichtsbestimmung und IR-Spektroskopie charakterisiert. Eine thermogravimetrische Analyse der Diisopropoxi-Derivate wurde ebenfalls ausgeführt.相似文献
16.
Zvjezdana Lazarević Jasna Vorkapić-Furač Jasenka Mühl 《Monatshefte für Chemie / Chemical Monthly》1992,123(12):1175-1179
Summary Stable enolic isomers of 2-aroyl-4-aracyl-1,3-cyclopentanediones such as3 and4 were prepared by condensation of aryl methyl ketones and diethyl maleate using an excess of sodium ethoxide (Aryl=C6H5, 4-C6H4CH3, 4-C6H4Br and 4-C6H4Cl).
-Tricarbonyl Verbindungen. I. 2,4-Disubstituierte 1,3-Cyclopentandione
Zusammenfassung Stabile Enol-Isomere von 2-Aroyl-4-aracyl-1,3-cyclopentandionen wie3 und4 wurden durch Kondensation von Arylmethylketonen und Diethylmaleat mit einem Überschuß von Natriumethoxid dargestellt (Aryl=C6H5, 4-C6H4CH3, 4-C6H4Br und 4-C6H4Cl).相似文献
17.
Pei Hongxia Lu Sheming Ke Yanxiong Li Jianmin Qin Shoubo Zhou Shuxi Wu Xintao Du Wenxin 《Structural chemistry》2004,15(3):207-210
A new Cu(II)PMIDA compound [Cu(H2PMIDA)(phen)] 3H2O (1) (H4PMIDA = H2O3PCH2N (CH2CO2H)2,phen = 1,10-phenanthroline) has been successfully synthesized and structurally characterized. In complex 1, Cu (II) is six coordinated by chelation in a tetradentate fashion by a PMIDA ligand and by two N atoms of a phen ligand. Every phen–Cu(II)–PMIDA group connects with each other via a hydrogen bond and the edge-to-face -stacking interaction. Complex 1 crystallized in triclinic P-1 with cell dimensions of a = 7.5817(6) Å, b = 10.6980(8) Å, c = 13.1852(10) Å, =82.350(2)°, = 84.151(2)°, =78.4250(2), V= 1035.25(14) Å3, Z = 2, Dc = 1.677 Mg/m3. 相似文献
18.
Horst K. Neudeck 《Monatshefte für Chemie / Chemical Monthly》1989,120(6-7):597-621
Summary The spiroketones19, 21, 24, 27, and31 were prepared by cyclisation of the dicarboxylic acids and their acid chlorides, resp., (18, 20, 22, 23, 25, 26, 28, and30) with polyphosphoric acid (PPA) or SnCl4. The latter compounds were synthesized by alkylation of the appropriate -keto esters10, 11, 12, and13 with the benzyl chlorides14, 15, 16, and subsequent retro-Claisen-reaction. The spiro compounds21a and39 were obtained byPPA-cyclisation of the keto acids35 and38, which in turn were prepared by aldol-reaction of the ketoness-hydrindacen-1-on and9a with phthalaldehydic acid to the olefinic keto acids33 and36 followed by catalytic hydrogenation. 相似文献
19.
By reaction of several N-phenyl-benzamidrazones with SO2F2 2-phenyl-2,5-dihydro-1,2,3,5-thiatriazole-1,1-dioxides2 a–c are formed. By reaction of N,N-diethyl-N-chlorosulfonyl-chloroformamidine8 with hydrazines the corresponding 4-diethylamino-substituted derivatives9 a–d are obtained. Methylation of2 b yields two isomeric products5 and6, whereas by methylation of9 d only one product9 b is obtained. 相似文献
20.
Reaction of (RNPF3)2 compounds (R=CH3, C2H5,n-C3H7,n-C4H9,i-C4H9) withN-trimethylsilyl-methylamine leads to nucleophilic substitution of one or two fluorine atoms by the methylamino group, depending on the molar amounts of the reactants. In the case ofR=CH3, two by-products are formed: in the first step a compound with coordination numbers IV, V and VI for the three phosphorus atoms in C5H17F7N5P3 and in the second step a monospiroflourodiaza-5, 5-diphosphetidine.
9. Mitteilung:Utvary, K., Kubjacek, M., Varmuza, K. Z. anorg. allg. Chem.458, 281 (1979). 相似文献