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1.
Zusammenfassung Die Umsetzung von Diphenylphosphinigsäurechlorid mit Alkalisalzen aromatischer Sulfinsäuren führt unter Reduktion am Schwefel, Oxydation am Phosphor und Ausbildung einer Bindung zwischen Phosphor und Schwefel, zu Diphenylthiophosphinsäure-S-arylestern: (C6H5)2P(O)–S–Ar (Ar=C6H5, 4-CH3C6H4, 4-ClC6H4, 2-Cl-5-CH3-C6H3, 2-C10H7). Die besten Ausbeuten (40–85%) wurden mitDMF als Lösungsmittel erhalten. Aliphatische Phosphinigsäurechloride geben keine Bindung zwischen P und S. Ebenso tritt keine Umsetzung ein, wenn im Säurechlorid eine P–O-Struktur vorliegt. Auch die Umsetzung von (C6H5)2PCl und (C6H5)2P(O)Cl mit Sulfonsäuren anstelle der Sulfinsäuren führt zu keiner P–S-Verknüpfung. Diese Phosphor-Schwefel-Bindung in den Thiophosphinsäure-S-estern stellt die schwächste Stelle im Molekül dar, da ein hydrolytischer, oxydativer oder reduktiver Angriff diese Bindung wieder löst.
Reaction of diphenylchlorophosphine with alkali salts of aromatic sulfinic acids leads to diphenylthiophosphinates; reduction occurs at the sulfur atom, oxidation at the phosphorus atom and a bond between phosphorus and sulfur is formed: (C6H5)2P(O)–S–Ar, Ar=C6H5, 4-CH3C6H4, 2-ClC6H4, 2-Cl-5-CH3-C6H3, 2-C10H7. The best yields were obtained in dimethyl formamide as solvent. With aliphatic chlorophosphines no bond formation beetween sulfur and phosphorus occurred. Similarly no reaction was observed, when a phosphorus atom in a higher state of oxidation was present, as for example in diphenylphosphonylchloride. Also, no reaction took place when sulfonic instead of sulfinic acids were used. The weakest bond found to exist in the diphenylthiophosphinates was the P–S-linkage, which readily undergoes hydrolytic, oxidative or reductive cleavage.相似文献
2.
η6-o-Chlorotoluene-η5-cyclopentadienyliron hexafluorophosphate undergoes nucleophilic substitution of the chlorine atom with anions generated (K2CO3/DMF) from methyl thioglycolate, diethyl malonate, dimethyl malonate, methyl acetoacetate and 2,4-pentanedione. The compounds prepared were o-CH3C6H4SCH2CO2CH3FeCp+PF6−, o-CH3C6H4CH(CO2C2H5)2FeCp+PF6−, o-CH3C6H4CH(CO2CH3)2FeCp+PF6−, o-CH3C6H4CH(COCH3)CO2CH3FeCp+PF6− and o-CH3C6H4CH2COCH3FeCp+PF6
. Similarly, the reaction of diethyl malonate, dimethyl malonate, methyl acetoacetate anions and methylamine with η6-2,6-dichlorotoluene-η5-cyclopentadienyliron hexafluorophosphate yielded monosubstitution of one of the chloro groups. The complexes prepared in this study were η6-diethyl(3-chloro-2-methyl) phenylmalonate- η5-cyclopentadienyliron hexafluorophosphate, η6-dimethyl(3-chloro-2-methyl)phenylmalonate-η5-cyclopentadienyliron hexafluorophosphate, η6-methyl(3-chloro-2-methyl)phenylacetoacetate-η5-cyclopentadienyliron hexafluorophosphate and η6-3-chloro(2-methyl-N-methyl)aniline-η5-cyclopentadienyliron hexafluorophosphate. Reaction of η6-2,6-dichlorotoluene-η5-cyclopentadienyliron hexafluorophosphate with excess methanol as well as methyl thioglycolate in the presence of K2CO3 resulted in disubstitution of both chloro groups to yield new complexes, η6-2,6-dimethoxytoluene-η5-cyclopentadienyliron hexafluorophosphate and η6-methyl[(2-methylphenyl)1,3-dithio] diacetate-η55-cyclopentadienyliron hexafluorophosphate, respectively. Complexes o-CH3C6H4CH(CO2C2H5)2FeCp+PF6−, o-CH3C6H4CH(CO2CH3)2FeCp+PF6− and o-CH3C6H4CH2 COCH3FeCp+ PF6− react with excess K2CO3 and benzyl bromide in refluxing methylene chloride to give 80–90% yields of complexes o-CH3C6H4C(CH2C6H5)(CO2C2H5)2FeCp+PF6−, o-CH3C6H4C(CH2C6H5)(CO2CH3)2FeCp+PF6− and o-CH3C6H4CH(CH2C6H5)COCH3FeCp+PF6−, respectively. Reaction of complex, o-CH3C6H4C(CH2C6H5)(CO2C2H5)2FeCp+PF6− with one molar equivalent of t-BuOK followed by acidic work-up gives o-(C2H5CO2CH2)C6H4CH(CO2C2H5)CH2C6H5FeCp+PF6−. Similarly, reactions of complexes o-CH3C6H4C(CH2C6H5)(CO2C2H5)2FeCp+PF6− and o-CH3C6H4C(CH2C6H5)(CO2CH3)2FeCp+PF6− with t-BuOK in THF followed by alkylation with methyl iodide gave the new complexes, o-(C2H5O2C(CH3)CH)C6H4CH(CH2C6H5)CO2C2H5FeCp+PF6− and o-(CH3O2C(CH3)CH)C6H4CH(CH2C6H5)CO2CH3FeCp+PF6−, respectively. Vacuum sublimation of the new complexes, o-CH3C6H4C(CH2C6H5)(CO2C2H5)2FeCp+PF6− and o-(C2H5O2CCH2)C6H4CH(CH2C6H5)CO2C2H5FeCp+PF6− gives o-CH3C6H4C(CH2C6H5)(CO2C2H5)2 and O-(C2H5O2CCH2)C6H4CH(CH2C6H5)CO2C2H5, respectively. 相似文献
3.
Helio G. Bonacorso Guilherme P. Bortolotto Jussara Navarini Liliane M.F. Porte Carson W. Wiethan Nilo Zanatta Marcos A.P. Martins Alex F.C. Flores 《Journal of fluorine chemistry》2010,131(12):1297-1301
This study describes a simple and efficient procedure to synthesize a novel series of fourteen 4-substituted N-(5-pyridinyl-1H-1,2,4-triazol-3-yl)-6-(trifluoromethyl)pyrimidin-2-amines, where the 4-substituents are H, CH3, C6H5, 4-FC6H4, 4-CH3C6H4, 4-CH3OC6H4 and 2-Furyl; from the cyclocondensation reaction of N-[5-(pyridinyl)-1H-1,2,4-triazol-3-yl]guanidines with 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trifluoroalk-3-en-2-ones. The reactions were carried out in ethanol under reflux for 18 h and led to 40-68% yields. N-(Pyridyl-triazolyl)guanidine precursors were further obtained from reactions of cyanoguanidine with nicotinic or isonicotinic acid hydrazides and the halogenated enones from trifluoroacetylation of enolethers or acetals. 相似文献
4.
H. Schindlbauer 《Monatshefte für Chemie / Chemical Monthly》1965,96(6):2051-2057
Zusammenfassung Die Umsetzung von Alkalidiphenylphosphid mit Methylaryl-sulfonaten zu tert. Phosphinen gelingt umso leichter, je weniger Methylgruppen der Arylrest enthält. Folgende Phosphine (C6H5)2PR wurden dargestellt: R=2-CH3C6H4–, 4-CH3C6H4–, 2,4-(CH3)2C6H3– und 4-Methyl--naphthyl. Ebenso wurden die Phosphine mit R=3-(CH3)2NC6H4– und 2-(CH3)2NC6H4– aus den Dimethylanilinsulfonaten erhalten. Die Umsetzung von (C6H5)2PK mit Na-1,4-Chlorbenzolsulfonat im Molverhältnis 2:1 gibt fast quantitativ 1,4-Phenylen-bis-diphenylphosphin, im Molverhältnis 1:1 aber entsteht (bei tieferen Temperaturen) Diphenylphosphin-p-benzolsulfonat. Diphenyl-(2,4,6-trimethyl-phenyl)phosphin wird am besten aus Diphenylchlorphosphin und Mesitylmagnesiumbromid hergestellt.Zusammenfassung Alkali diphenylphosphides react with methylarylsulfonates giving tert. phosphines. The yield increases with decreasing number of methyl groups in the arylsulfonate. The following phosphines (C6H5)2PR were prepared: R=2-CH3C6H4, 4-CH3C6H4, 2,4-(CH3)2C6H3, and 4-methyl--naphthyl. Similarly the phosphines with R=3-(CH3)2NC6H4 and 2-(CH3)2NC6H4 were prepared from dimethylaniline sulfonates. The reaction of (C6H5)2PK with sodium 1,4 chlorophenyl sulfonate at a molar ratio of 2:1 yields nearly quantitatively 1,4-phenylene-bis(diphenylphosphine); however at a mole ratio of 1:1 and at lower temperatures sodium diphenylphosphine-p-phenyl sulfonate is obtained. The best way to prepare diphenyl(2,4,6-trimethyl-phenyl)phosphine was to use diphenyl-chloro phosphine and mesitylmagnesium bromide. 相似文献
5.
The half-sandwich type compounds C5H5Rh[P(OR)3]2 (R = CH3, C2H5, C6H5, p-CH3C6H4, p-ClC6H4) have been prepared from [(P(OR)3)2RhCl]2 and NaC5H5. The NMR. data as well as the IR. and mass spectra of the new compounds will be discussed. The preparation of C5H5Rh(CO)P(OC2H5)3 is also reported. 相似文献
6.
Guo-Cang Wang Lin Yu Jing-Rong Cui Fu-Xiang Ran 《Journal of organometallic chemistry》2004,689(9):1631-1638
A series of novel arylantimony derivatives of analogues of demethylcantharimide with the formulae ArnSbL(5−n) and ArnSbL′(5−n)(LH=N-hydroxy-demethyldehydrogencantharimide, L′H=N-hydroxy-demethylcantharimide, n=3, 4; ArC6H5, 4-CH3C6H4, 3-CH3C6H4, 2-CH3C6H4, 4-ClC6H4, 4-FC6H4) were synthesized and characterized by elemental analysis, IR, 1H NMR and mass spectroscopy. The crystal structures of (C6H5)4SbL, (4-CH3C6H4)3SbL2 and (3-CH3C6H4)3SbL′2 were determined by X-ray diffraction. The in vitro antitumor activities of all compounds against six cancer cells are reported. 相似文献
7.
Some new bimetallic carboxylates of tin and germanium with general formula where R1 = m-CH3C6H4, p-CH3C6H4, C6H5, R2 = o-CH3C6H4, p-CH3C6H4, o-CH3OC6H4, C6H5, CH3, have been prepared by the condensation reaction of diethyltin oxide and triarygermyl(substituted)propanoic acid in 1:2 mole ratio, respectively, and characterized by multinuclear (1H, 13C, 119Sn) NMR, 119mSn Mössbauer and IR spectroscopy. The X-ray crystal structure of the ligand I4 [(C6H5)3GeCH(o-CH3OC6H4)CH2COOH] delineate four coordinated germanium atom with a peculiarity of having a molecule of solvent (CHCl3). The chiral center in the synthesized compounds was identified on the basis of 1H NMR data and measurements of angle of rotations. 相似文献
8.
Gerald W Fowles David A Rice Thomas G Sheehan 《Journal of organometallic chemistry》1977,135(3):321-326
RTiBr3 (R = CH3, C6H5 and (4-CH3)C6H4) forms 1/2 adducts, RTiBr32L, with a number of monodentate ligands containing nitrogen, oxygen ad sulphur donor atoms. Bidentate ligands normally give 1/1 adducts, as do the bulky monodentate ligands (C6H5)3PO. Dioxan gives 1/1 adducts with CH3TiBr3 and C6H5TiBr5 but a 1/2 adduct with (4-CH3)C6H4TiBr3.Structures are assigned on the basis of IR and NMR data. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(3):121-126
Abstract Thirty compounds of the type (ZC6H4)3PM(CO)5 where Z is 3-CH3, 4-CH3, 3-CH3O, 4-CH3O, 3-CF3, 4-CF3, 4-Cl, 4-F, 4-CH3S, or 4-(CH3) C and M is Cr, Mo, or W are reported, in addition to [4-(CH3)3SiC6H4]3 PW(CO)5 and [(2-CH3C6H4)n(C6H5)3–n P] M(CO)5 where n is 1 or 2 and M is Cr, Mo, or W. Phosphorus-31 NMR and infrared data are presented. In general, the compounds containing the more effective electron withdrawing substituents on the tertiary arylphosphines exhibit the larger 31P coordination chemical shifts, the higher carbonyl stretching frequencies, and the larger phosphorus-31-tungsten-183 coupling constants. 相似文献
10.
Guo-Cang Wang Jian Xiao Hai-Bin Song Jing-Rong Cui Fu-Xiang Ran 《Journal of organometallic chemistry》2005,690(1):151-156
A series of novel organoantimony arylhydroxamates with the formulae [Ar3SbL2]−[HNEt3]+ (LH = arylhydroxamic acid; Ar = C6H5, 4-CH3C6H4, 3-CH3C6H4, 4-ClC6H4, 4-FC6H4) and (4-CH3C6H4)4SbL were synthesized and characterized by elemental analysis, IR, 1H NMR and mass spectroscopy. The crystal structures of (4-CH3C6H4)4SbL and [Ph3SbL2]−[HNEt3]+ were determined by X-ray diffraction. The in vitro antitumor activities of all compounds against three human cancer cells are reported. 相似文献
11.
Maud Brink 《Monatshefte für Chemie / Chemical Monthly》1973,104(3):619-623
Zusammenfassung Die magnetische Nichtäquivalenz der Methylenprotonen in 2-R-Benzo-1,3-dioxanen, mit R=C6H5,o-ClC6H4,m-ClC6H4,p-ClC6H4,o-BrC6H4,m-BrC6H4,p-BrC6H4,o-NO2C6H4,m-NO2C6H4,p-NO2C6H4,o-CH3OC6H4,m-CH3OC6H4,p-CH3OC6H4, -Naphthyl, -Naphthyl, -Thienyl und -Thienyl, wurde in (CD3)2CO, CDCl3, CCl4, CS2 und C6D6 untersucht.
Magnetic non equivalent methylenic protons of some 2-substituted 1.3-benzodioxanes
The magnetic non equivalence of the methylenic protons in 2-R-1.3-benzodioxanes, with R=C6H5,o-ClC6H4,m-ClC6H4,p-ClC6H4,o-BrC6H4,m-BrC6H4,p-BrC6H4,o-NO2C6H4,m-NO2C6H4,p-NO2C6H4,o-CH3OC6H4,m-CH3OC6H4,p-CH3OC6H4, -naphthyl, -naphthyl, -thienyl and -thienyl were studied in (CD3)2CO, CDCl3, CCl4, CS2 and C6D6.相似文献
12.
13.
《Journal of Coordination Chemistry》2012,65(13):1165-1171
In an attempt to obtain chiral single crystals of a two-dimensional (2D) bimetallic oxalate-based material by enantioselective auto-assembling of Mn2+ and (rac)-[Cr(C2O4)3]3? templated by the optically active complex (+)-(Rp)-[1-CH2(n-C3H7)3-2-CH3(C5H3)Fe(C5H5)]+, we obtained the unexpected 2D network species {NH(n-C3H7)3[MnCr(C2O4)3]}. X-ray diffraction determination of the structure reveals that the complex crystallizes in the enantiomorphous space group P63. The interlayer spacing of 7.93?Å?is the lowest found so far for 2D, bimetallic, oxalate-bridged compounds. 相似文献
14.
J.V. Comasseto J.T.B. Ferreira J.A.Fontanillas Val 《Journal of organometallic chemistry》1984,277(2):261-266
The disproportionation reaction of diaryl ditellurides [(C6H5Te)2, (p-CH3C6H4Te)2, (p-CH3OC6H4Te)2, (p-C2H5OC4Te)2, (2-naphthyl-Te)2] with sodium hydroxide under phase transfer conditions at room temperature is described for the first time. The phase transfer catalyst used is 2HT-75, a trade name for a mixture of dialkyldimethylammonium chlorides. The intermediates aryl tellurolates react “in situ” with alkyl halides to give the corresponding alkyl aryl tellurides (ArTeR) in 52–72% yield. The following compounds were prepared: Ar C6H5, R=CH3(CH2)3CH2, (CH3)2CHCH2CH2, (CH3)2CHCH2, CH3CHBrCH2CH2, CH3(CH2)8CH2, C6H5CH2, ClCH2, C6H5CH2CH2, CH2CHCH2, C6H5CHCHCH2, C6H5SeCH2, H; Ar=p-CH3C6H4, R = CH3(CH2)2CH2; Ar=p-CH3OC6H4, R = CH3(CH2)2CH2; Ar = p-CH2H5OC6H4, R= CH3(CH2)2CH2; Ar = 2-naphthyl, R = CH3(CH42)2CH2. 相似文献
15.
The syntheses and properties of the titanium(III) complexes Cp2Tir · R′CN (R = C6H5, o-, m-, p-CH3C6H4, CH2C6H5, C6F5, Cl; R′ = CH3, t-C4H9, C6H5, o-CH3C6H4, 2,6-(CH3)2C6H3) are described. In the complexes the nitrogen atom of the cyanide ligands is coordinated to the metal. The thermal stabilities of the complexes depend markedly on R and R′; on heating they undergo a novel reaction in which two cyanide ligands are coupled by formation of a CC bond, while the metal is oxidized to titanium(IV). 相似文献
16.
Abstract The reaction of primary amine hydrochlorides with phosphorus oxychloride in the presence of 1/4 mole of H20 yields the title compounds I (R = C6H5-, 4-CH3CH6H4 ?′ 4-CH3CH6H4 ?, 3-CH3CH6H4 ? CF3CH2-). Hydrochlorides Of more basic amines do not yield any cyclic material. The compound I (R = C6H5) was isolated as one isomer. An X-ray crystallographic study has shown an open ring structure in which the two chlorine atoms are positioned on the same face of the P4N4 ring as the P-O-P bridge. 相似文献
17.
Katsuhiko Kawakami Masa-aki Haga Toshio Tanaka 《Journal of organometallic chemistry》1973,60(2):363-373
Several isocyanide complexes [Ir(RNC)4]X (I) (R = p-CH3C6H4, X = I; R = p-CH3OC6H4, X = I and PF6) and [Ir(RNC)2(PPh3)3] ClO4(II) (R = p-CH3C6H4 and p-CH3OC6H4) have been prepared by the reactions of [Ir(COD)Cl]2 and [Ir(COD)(PPh3)2]ClO4 (COD = l,5-cyclooctadiene) with aryIisocyanides, respectively. Oxidative addition reactions of I and II with halogens, and II with π-acids such as tetracyanoethylene(TCNE), fumaronitrile, maleic anhydride, dimethyl fumarate, acrylonitrile, and dimethyl acetylenedicarboxylate are described. The structures of I, II and the π-acid addition products of II, [Ir(p-CH3C6H4NC)2 (PPh3)2 (π-acid)]ClO4 (IV) (π-acid = TCNE, fumaronitrile, maleic anhydride, and acetylene dicarboxylate), are discussed on the basis of their electronic, IR, and NMR spectra. Especially, I is suggested to have an unusual layer structure involving Ir to Ir interaction, the result of which is relatively low reactivity in oxidative addition reactions. Trigonal bipyramidal configurations are suggested for IV with the two isocyanides in the trans and cis positions for the olefin and acetylene adducts, respectively. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(11):937-945
Reactions of singly-bonded dinuclear complexes [(η5-CH3O2CC5H4)2M2(CO)6] (I, M?=?Mo; II, M?=?W) with the diarenylditelluride [4-CH3C6H4Te]2 in refluxing toluene for 4–6?h afforded dinuclear complexes 1 and 2 trans/ae-[(η5-RC5H4)2M2(CO)4(μ-ArTe)2] (Ar?=?4-CH3C6H4Te). Complexes 1 and 2 were also synthesized by reactions of triply-bonded dinuclear complexes [(η5-CH3O2CC5H4)2M2(CO)4] (III, M?=?Mo; IV, M?=?W) with [4-CH3C6H4Te]2 in refluxing toluene for 1?h. Both complexes have been characterized by elemental analysis, 1H NMR, 13C NMR and IR spectroscopy and X-ray diffraction. Preliminary low-temperature NMR experiments on complexes 1 and 2 have revealed that in solution each complex goes through a rapid inversion of the butterfly four-membered ring M2Te2. 相似文献
19.
Aryl(chloromethyl)thallium chlorides, Ar(ClCH2)TlCl (Ar=C6H5, p-CH3C6H4) have been prepared by treatment of arylthallium dichlorides with diazomethane. The derived carboxylates, Ar(ClCH2)TlX, react with HgX2 to give the dicarboxylates, (ClCH2)TlX2 (X = OCOCH3, OCOC3H7-i) and with tetramethyltin to give CH3(ClCH2)TlX compounds. R(ClCH2)TIX compounds (R = CH3, C6H5, p-CH3C6H4) undergo disproportionation in methanol to R2TlX and (ClCH2)2TlX compounds. 相似文献
20.
2,4-Bismethylthio-1,3,2,4-dithiadiphosphetane 2,4- disulfide, IIa, is prepared from 0,0-dimethyldithiophosphoric acid, Ia, and P4S10 at 160°C. 2,4-Bis(4-phenoxyphenyl)-1,3,2,4- dithiadiphsophetane 2,4-disulfide, IIc, and 2,4-bis(4-phenylthiolophenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, IId, are prepared at l60°C from P4 S10 and diphenylether and diphenylsulfides, respectively. Carboxylic acids RCOOH(R = CH3 C2H5, n-C3H7, n-C4H9, C6H5CH2, C6H8) react with compound Ia at 130°C to give the corresponding methyl dithioesters. Carboxylic acids RCOOH (R = C6H8-CH2, C6H8) react with compound Ib at 200°C for 15 min to give the corresponding ethyl dithioesters, while low boiling acids (R = CH3, C2H8, n-C3H7) yielded mixtures of the corresponding ethyl dithioester and ethyl carboxylate. Carboxylic acid chlorides RCOCl (R = ClCH2, C2H5, t-C4H5 C6H5CH2, C6H5, P-NO2C6H4) react with compound IIa at 80°C to give the corresponding methyl dithioesters in good yields. S-Substituted thioesters react with IIC at 85°C to give the corresponding dithioesters in good yields. Dihydro2(3H)-furanone, VI, and 5-methyl-2(3H)-furanone, VII, react with IIa at 80°C; to dihydro-2(3H)-thiophenethione, VIII and 2,2'-dithiobis(5-methyl thiophene),IX, respectively. Also XI reacts with IIa,IIc, and IId to give VIII in nearly quantitative yields. 相似文献