摘要:

Derivatives of Thioureas and Metal Complexes from N‐Thiocarbamoyl‐benzimidoyl Chlorides.The reactions of nickel(II)‐coordinated N‐benzoyl‐thioureas with acid chlorides are described. With different nucleophiles the title compounds N‐thiocarbamoyl‐benzimidoyl‐chlorides yield N‐thiobenzoyl‐thioureas, N‐thiocarbamoyl‐benzimido(thio)esters and N‐thiocarbamoyl‐benzamidines as chelating agents, respectively. By cyclisation 1,3,5‐thiadiazin‐2‐thiones and 1,2,4‐triazoles were obtained. The formation, structure and bonding situation of the ligands and the transition metal complexes are discussed. 1,2,4‐Dithiazolium‐halometalates, 1,3,5‐oxadiazinium salts and selen

ISSN:0021-8383    

DOI:10.1002/prac.19913330302

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

AbstractBy replacement of methanol in the Cu4OX6(MeOH)4(X  Cl, Br) complexes with thiourea (tu), N,N′‐diphenylthiourea (diftu), N,N′‐dimethlthiourea (dimtu), tetramethylthiourea (tmtu) and acetylthiourea (actu), the complexes Cu4OCl6L4where L  tu, tu(0.3 Et2O), diftu, dimtu, tmtu, actu (0.5Et2O) and the complexes Cu4OBr6L4, where L  tu, diftu, dimtu, tmtu have been prepared. Their infrared and electronic spectra indicate the presence of Cu4O grouping and the trigonal bipyramidal coordination of copper(II). These complexes exhibit e.p.r. signals in the temperature range 100–260 K, in contrast to other known complexes of this structural type, which showed the e.p.r. signals at significantly lower temperatures. Thiourea and its derivatives are not able to reduce copper(II) in reaction with the tetranuclear Cu4OX6(MeOH)4complexes in methanol‐ether solution due to the redox stabilizing effect of the tetra

ISSN:0021-8383    

DOI:10.1002/prac.19913330303

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

Synthesis and Properties of Novel Alkali Metal Alkoxo‐ and Aroxocobaltates(II).By reaction of CoBr2or CoBr2· 2THF with 4–5 moles of MOR in THF, M  Li, Na, K, R = iso‐propyl (iPr), phenyl (Ph), 2‐naphthyl (2‐Naph), the following novel alkali metal alkoxo‐ and aroxocobaltates(II) have been prepared.Li2Co(OiPr)4· LiBr · 3THF (1), Na2Co(OiPr)4· THF (2), KCo(OiPr)3· THF (3), Li2Co(OPh)4· 4THF (4), Na2Co(OPh)4· 5THF (5), K2Co(OPh)4·0,75THF (6), Li2Co(O‐2‐Naph)4· 4THF (7), Na2Co(O‐2‐Naph)4· 5THF (8), K2Co(O‐2‐Naph)4· 2THF (9), and K3Co(O‐2‐Naph)5· 2THF (10).The blue and violet, crystalline and very air‐sensitive (i.e. protolytically sensitive) compounds, some with good solubilities in organic solvents, eliminate THF in vacuo at temperatures between 50 and 100°C to yield the corresponding THF‐free compounds (1a) to (10a).Electronic spectra (VIS/NIR) and the results of magnetic measurements at 293 K point to preferred (but not exc

ISSN:0021-8383    

DOI:10.1002/prac.19913330304

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

Synthesis of 2‐Amino‐Substituted 4,5‐Dihydro‐1,3‐thiazoles.The reaction of 2‐substituted 4‐methallylthiosemicarbazides1with carbonyl compounds catalyzed by weak acids gives thiosemicarbazones2and 1,2,4‐triazolidine‐3‐thiones3. By contrast under strong acidic conditions the reaction occurs by electrophilic cyclisation with participation of the methallyl and thiono groups, and 4,5‐dihydro‐1,3‐thiazoles5are formed after neutralisation. The electrophilic cyclisation of N‐methallyl substituted thioureas6and 1,4‐disubstituted thiosem

ISSN:0021-8383    

DOI:10.1002/prac.19913330305

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

Liquid‐Liquid‐Extraction of Metal Ions with Lariat Ethers.Lariat ethers of various ring size and substitution are synthesized and characterized by physical data and chemical analysis. The extraction behaviour of the crown compounds towards Na+, K+, Cs+and Ag+in a picric acid solution has been investigated. The extraction contants for 1:1 and 1:2 complexes are determined using the equilibrium distribution data. The results show that the flexible side chain in the investigated compounds has in no case a positive effect on the metal picrate extract

ISSN:0021-8383    

DOI:10.1002/prac.19913330306

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

Substituted Alkinyles as Axial Ligands at Hemine Like Bound Iron(III) ‐ Incorporation into a Spectrochemical Series.Substituted lithium alkynyles LiCCR (R =tBu, Ph, p‐ClC6H4, Me3Si,iPr3Si, Ph3Si) react with the hemine like macrocyclic iron(III) complex 6,13‐di(ethoxycarbonyl)‐5, 14‐dimethyl‐1, 4, 8, 11‐tetraazatetradeca‐4,6,12,14‐tetraenato[2−]iron(III)‐iodide (formula2;) in tetrahydrofuran to form anionic low‐spin di‐adducts [fe(CCR)2]−. The incorporation of the alkynyles into a spectrochemical series of the axial ligands (studied by the sharp equatorial‐ligand‐to‐metal CT absorption band) results in the wavelength‐sequence (nm): OH−(≈︁ 510) « N3−(≈︁ 625)

ISSN:0021-8383    

DOI:10.1002/prac.19913330307

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

Photometric Investigations in Transition of the Dianions in the Trianions of o,ó‐Dihydroxyazodyes and to the Forming of Associates with Cationic Surfactants in this pH‐range.In transition of the dianions in the trianions of the investigated dyes take place preferred the deprotonation of the tautomeric form A12−by forming of the equilibrium H 1/2 2−⇄ A3−. The addition of cationic surfactants to the dye solution caused the increase of the pKa3‐values of the dyes. That proved among other things the formation of associates is dye and cationic surfactants dete

ISSN:0021-8383    

DOI:10.1002/prac.19913330308

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

New Pyrazol Derivatives. IV. Preparation and Cyclization of Some Acceptor‐Substituted N‐(Pyrazol‐3‐yl)‐thioureas.3‐Aminopyrazol‐4‐carboxylic acid derivatives (1,2) were transformed by reaction with different isothiocyanates R2NCS to N‐(pyrazol‐3‐yl)‐N.‐substituted thioureas (5,6).Ethyl 3‐amino‐1‐benzylpyrazol‐4‐carboxylate reacts with CSCl2to form ethyl 1‐benzyl‐3‐isothiocyanatopyrazol‐4‐carboxylate (3) which yields with amines the corresponding N‐(pyrazol‐3‐yl)‐N.‐substituted thioureas (5). As a byproduct in the reaction with CSCl2N,N.‐di‐(pyrazol‐3‐yl)‐thiourea (4) is formed. With hydrazine or phenylhydrazine N‐(pyrazol‐3‐yl)‐thiosemicarbazides (7a,b) are obtained.The thioureas (5,6) can be cyclized in basic solution to 4,5,6,7‐tetrahydropyrazolo[3,4‐d]pyrimidin‐4‐on‐6‐thiones (8) which on alkylation form 6‐alkylthio‐4,5‐dihydropyrazolo[3,4‐d]pyrimidin‐4‐ones (9). Methyl‐N‐(pyrazol‐3‐yl)‐N.‐benzoylisothiourea (10) reacts with ethylamine to form N‐benzoyl‐N.‐ethyl‐N‥‐(pyrazol‐3‐yl)‐guanidine derivative (11) which on treatment with NaH in dimethylformamide yields 6‐benzoylamino‐5‐ethyl‐4,5‐dihydropyrazolo[3,4‐d]pyrimidin‐4‐one (12).By tr

ISSN:0021-8383    

DOI:10.1002/prac.19913330309

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

摘要:

Three Component Reactions. XX. Methoxymercuration of Cyclohexa‐1,4‐dienes.The methoxymercuration of several cyclohexa‐1,4‐dienes leads to insoluble mixtures of mono‐ and bismercuricompounds2–4and5–7. After reduction with NaBH4/NaOH mixtures of methoxycyclohexenes and bismethoxycyclohexanes result. The result of capillary gaschromatographic analyses and n.m.r. spectra allow a semiquantitative evaluation of the reac

ISSN:0021-8383    

DOI:10.1002/prac.19913330310

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY

ISSN:0021-8383    

DOI:10.1002/prac.19913330311

出版商:WILEY‐VCH Verlag GmbH    

年代:1991

数据来源: WILEY