Bis(triphenylphosphine)platinum acetylides from functionally substituted acetylenes. A new synthesis method

A general procedure, giving high yields for the synthesis of (Ph₃P)₂Pt(CCR)₂ complexes (R = C₆H₅, C(CH₂)CH₃, (CH₂)₆CCH, CH₂OH, CH(OH)CH₃, CH(OH)C₆H₅, CH₂CH(OH)CH₃, C(OH)(CH₃)CH₃, C₆H₁₀OH, C(OH)(CH₃)CH₂CH₃, CH₂NHCH₃, CH₂NHCH₂C₆H₅, CH₂N(CH₃)₂, CH₂N(C₂H₅)₂) is reported. On the basis of the low frequency IR spectra a trans structure is proposed for all complexes. UV spectra are also reported.     

Silicium-stickstoff-fluorverbidungen: V. Darstellung neuer silylaminofluorsilane

Compounds of the composition RR′SiFNR″Si(CH₃)₃ (R = H, F, CH₃, C₂H₅, C₃H₇, C₂H₃, C₆H₅, C(CH₃)₃; R = F, CH₃, C₆H₅; R″ = CH₃, C(CH₃)₃, Si(CH₃)₃) are obtained by the reaction of silicontetrafluoride or organo-substituted silicon-fluorides with the lithium salts of alkylsilylamines in a molar ratio of $\text{1}\text{1}$. The disubstituted compounds RSiF(NR′Si(CH₃)₃)₂ (R = H, F, CH₃, C₂H₃, C₆H₅; R′ = CH₃, C(CH₃)₃) result when the reactants are in a $\text{1}\text{2}$ molar-ratio. Likewise the unsymmetrical siliconfluorsilylamines of the formulae F₂Si(NRSi(CH₃)₃) (NR′Si(CH₃)₃) (R = CH₃, R′ = C(CH₃)₃), as well as the trisubstituted compounds FSi(NCH₃Si(CH₃)₃)₃ and FSi(NCH₃Si(CH₃)₃)₂(N(Si(CH₃)₃)₂) were made. By reacting phenyltrifluorsilane with dialkylamines ($\text{1}\text{2}$) C₆H₅SiF₂NR₂(R = CH₃, C₂H₅) was obtained. The IR-, mass-, ¹H and ¹⁹F NMR spectra of the above-mentioned compounds are reported.     

KRISTALLSTRUKTUR VON BIS(DIETHYLDITHIOCARBAMATO)-PHENYLPHOSPHAN UND SYNTHESE EINIGER MONO- UND BIS(DIORGANYLDITHIOCARBAMATO)PHOSPHANE

Abstract

By reaction of organylchlorophosphanes with sodium dithiocarbamates compounds of the type RP(S₂CNR₂′)₂ with R = CH₃, C₆H₅; R' = CH₃, C₂H₅, CH(CH₃)₂, C₆H₅ and of the type (C₆H₅)₂PS₂CNR₂′ with R' = CH₃, CH(CH₃)₂ as well as compound [(C₆H₅)₂PS₂CN(CH₃)CH₂-]₂ are obtained. The crystal structure of C₆H₅P(S₂CN(C₂H₅)₂)₂ shows that the trend from bidentate to monodentate bonding of the dithiocarbamate ligands in the homologous series RE(S₂CN(C₂H₅)₂)₂; E = Bi, Sb, As, P is continued for E = P.

Durch Umsetzung der jeweiligen Chlorophosphane mit den entsprechenden Natriumdithiocarbamaten können folgende Verbindungen erhalten werden: Verbindungen des Typs RP(S₂CNR₂′)₂ mit R = CH₃, C₆H₅; R' = CH₃, C₂H₅, CH(CH₃)₂, C₆H₅; Verbindungen des Typs (C₆H₅)₂PS₂CNR₂′ mit R' = CH₃, CH(CH₃)₂ sowie [(C₆H₅)₂PS₂CN(CH₃)CH₂-]₂. Die Kristallstruktur von C₆H₅P(S₂CN(C₂H₅)₂)₂ zeigt, daß sich der Trend zu schwächer ausgeprägter zweizähniger Bindungsweise der Dithiocarbamatliganden in der homologen Reihe RE(S₂CN(C₂H₅)₂)₂; E = Bi, Sb, As, P für E = P fortsetzt.     

Alcoholysis of (2-methoxycarbonyl)ethyltin compounds

Under acid or base catalysis, di(2-alkoxycarbonylethyl)tin dichlorides of various R groups, (ROCOCH₂CH₂)₂SnCl₂, can be prepared conveniently in high yield by alcoholysis of (CH₃OCOCH₂CH₂)₂SnCl₂ in various alcohols, ROH (R = C₂H₅, C₄H₉, iso-C₄H₉, C₅H₁₁, C₆H₅CH₂, C₄H₉CH(C₂H₅)CH₂). When excess acid or base is present in the aqueous solution, (ROCOCH₂CH₂)₂SnCl₂ eliminate ROH and precipitate as C₆H₈O₄Sn regardless of the R group. C₆H₈O₄Sn can be converted into various (ROCOCH₂CH₂)₂SnCl₂ derivatives on dissolving in alcoholic HCl solutions.     

Optisch aktive übergangsmetall-komplexe LXIV. Neue optisch aktive Cp(CO)Fe-acyl-komplexe mit

The novel complexes CpFe(CO)(COR)P(C₆H₅)₂NR'R^* with Cp = C₅H₅,C₉H₇ (indenyl); R = CH₃, C₂H₅, CH(CH₃)₂, CH₂C₆H₅;R` = H, CH<sub>3</sub>, C<sub>2</sub>H<sub>5</sub>, CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub> and R<sup>*</sup> = (S)-CH(CH<sub>3</sub>)(C<sub>6</sub>H<sub>5</sub>), have been synthesized by reaction of CpFe(CO)<sub>2</sub>R wiht P(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>NR`R^* and characterized analytically as well as spectroscopically. The pairs of diastereoisomers RS/SS have been separated by preparative liquid chromatography and fractional crystallization, respectively. The optically pure complexes (+)₄₃₆- und ()₄₃₆-CpFe(CO)(COR)P(C₆H₅)₂NR`R^* are configurationally stable at room temperature. At higher temperatures they equilibrate with CpFe(CO)₂R and epimerize with respect to the Fe configuration.     

Synthesis of formamidines from 2-amino-3-methylquinazolin-4-one and its 6-nitro derivative

The condensation of 2-amino-3-methylquinazolin-4-one and its 6-nitro derivative with dialkyl-, arylalkyl-, and heterylformamides has given the corresponding formamidines of the quinazolinone series. The details of the compounds synthesized are as follows X, R, R′, yield (%), mp (°C, ethanol), R_f (chloroform-methanol (20:1) Al₂O₃): empirical formula: H, CH₃, CH₃, 77, 238–240, 0.49, C₁₂H₁₄ON₄; H, C₂H₅, C₂H₅, 65, 208–210, 0.96, C₁₄H₁₈ON₄; H, CH₃, C₆H₅, 84, 162–164, 0.54, C₁₇H₁₆ON₄; H, (CH₂)₂O(CH₂)₂, 60, 196–197, 0.43, C₁₄H₁₆O₂N₄; H, (CH₂)₅, 6.6, 196–198, 0.4, C₁₅H₁₈·ON₄; NO₂, CH₃, CH₃, 64. 194–196, 0.83, C₁₂H₁₃O₃N₅; NO₂, C₂H₅, C₂H₅, 37, 142–144, 0.8, C₁₄H₁₇O₃N₅; NO₂; CH₃, C₆H₅, 38, 298, 0.88, C₁₇H₁₅O₃N₅; NO₂, (CH₂)₂O(CH₂)₂, 60, 148–150, 0.7, C₁₄H₁₅O₄N₅. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 680–684, September–October, 1980.     

Diiod(methylthio)gallan. Darstellung und reaktivität

Different synthetic routes for the preparation of diiodo(methylthio)gallane are given. Some reactions of this compound with Lewis bases, such as O(CH₃)₂, S(CH₃)₂, S₂(CH₃)₂, N(CH₃)₃, P(CH₃)₃, and other compounds, such as CH₃I, CH₃OH, C₂H₅OH, C₂H₅SH, i-C₃H₇SH, and C₂H₅SeH are investigated. Spectra and some physical and chemical properties of the new compounds are reported. The structure of diiodo(methylthio)gallane is discussed in view of some interesting differences of this molecule in solution and in crystal form.     

Mass spectrometry of transition metal π-complexes. XV—The effect of substituents on the fragmentation of benchrotrenyls under electron impact

Mass spectra of substituted benchrotrenyls RC₆H₅Cr(CO)₃ where R?H, F, CI, I, CH₃, OCH₃, COOCH₃, C₂H₅, N(CH₃)₂, NH₂, C₆H₅, C(CH₃)₃, p-C₆H₄NH₂, CH₂C₆H₅, CH₂CH₂C₆H₅), 1,3,5-(CH₃)₃C₆H₃Cr(CO)₃ and 1,2,3,5-(CH₃)₄C₆H₂Cr(CO)₃ have been studied. It has been found that for monosubstituted benchrotrenyls there is a linear dependence of the parameter log [Cr]⁺/[RC₆H₅Cr]⁺) on the number of degrees of freedom of the [RC₆H₅Cr]⁺ ion. Decarbonylation of the molecular ions is not affected by the nature of the substituent R. The results are interpreted in terms of the quasi-equilibrium theory of mass spectra.     

Local surrounding of cobalt(II) in dithiocarbamate complexes,their magnetic and spectral properties

[Co(S₂CNRR’)₂] complexes [R = R’ = CH₃, C₂H₅, C₃H₇, C₄H₉, or CH₂C₆H₅; RR’ = (CH₂)₅, (CH₂)₆, or (CH₂)₂O(CH₂)₂] were prepared via interaction of CoCl₂ with sodium dithiocarbamates in aqueous medium (pH 6–7). [Co(S₂CNRR’)₂] are low-spin compounds (μ_eff 2.19–2.45 μ_B) with distorted square-planar geometry of the CoS₄ coordination node. The Co-S bonds length is 2.22–2.26 Å, and the distance between cobalt and carbon atoms is 2.73–2.74 Å.     

Die komplexchemie polyfunktioneller liganden : XXVIII. Über die selektive spaltung von arsenphenyl-bindungen mit jodwasserstoff in nichtwässrigen systemen

The phenylalkyl arsines (CH₃)₂AsC₆H₅, CH₃As(C₆H₅)₂, C₂H₅As(C₆H₅)₂, (CH₂)_n [As(C₆H₅)₂]₂ (n = 1, 2), and C[CH₂As(C₆H₅)₂]₄ react with liquid or gaseous HI in nonaqueous solvents by selective cleavage of the arsenicphenyl bonds yielding (CH₃)₂AsI, CH₃AsI₂, C₂H₅AsI₂, (CH₂)_n(AsI₂)₂ and C(CH₂AsI₂)₄. The latter forms the tetradentate ligand C[CH₂As(CH₃)₂]₄ with CH₃MgI. The electron impact mass spectra of these compounds show clear fragmentation patterns resulting mainly from the formation of fragments with AsAs bonds or (As)_n clusters (_n = 3, 4). From CH₃AsI₂ and C₂H₅AsI₂ the iodine-free cycloarsines (AsCH₃)₃, (AsC₂H₅)₃, (AsC₂H₅)₄, As₃(C₂H₅)₂CH₃ and As₄(C₂H₅)₃CH₃ are formed by thermal secondary reactions in the high temperature inlet systems of the mass spectrometer. The fragmentations of the cycloarsines and the other compounds are discussed. The infrared spectral absorptions of all the alkyl iodoarsines can be completely assigned in the range of 4000 – 250 cm^?1. The IR data of C₂H₅AsI₂ indicate the existence of trans and gauche rotational isomers.     

Reaktionsverhalten des Diäthylamino-divinylphosphines

Behaviour of Diethylamino-divinylphosphine The preparation of diethylamino-divinylphosphine 1 and its reaction with S_x, Br₂, CH₃J, HCl, HP(C₆H₅)₂, and HSn(C₄H₉)₃ are described. Whereas 1 and (C₆H₅)₂P? CH?CH₂ do'nt polymerize by a radical mechanism, (C₂H₅)₂N? P(S)(CH?CH₂)₂ yields an unburnable polymerisation product. Copolymerisation of (C₆H₅)₂P? CH?CH₂ or 1 , respectively, and styrene results in a polymeric substance with a molecular weight of about 2600.     

Alkaline hydrolysis of diaryl ditellurides under phase transfer conditions; synthesis of alkyl aryl tellurides

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, CH₂CHCH₂, C₆H₅CHCHCH₂, C₆H₅SeCH₂, $\text{CH}{}_2\text{CH}{}_2\text{CH}{}_2\text{CHCHC}$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.     

Untersuchungen an Selen-Verbindungen. LXIV. Darstellung und Eigenschaften von Säurederivaten von Phenylselen(IV) -Verbindungen (C6Hs) 2SeX2, (C6H5) 3SeX

Studies on Selenium Compounds. LXIV. Preparation and Properties of Acid Derivatives of Phenylselenium(IV) Compounds (C₆H₅) ₂SeX₂ and (C₆H₅) ₃SeX. Reactions of (C₆H₅) ₂SeBr₂ and (C₆H₅) ₃SeCl with silver salts of acids are investigated. From (C₆H₅) ₂SeBr₃ and AgY (Y = N0₃, CH₃CO₃, CF₃CO₂, 1/2 SO₄, CH₃SO₃, NCO) the compounds (C₆H₅) ₂Se(NO₃) ₂ (C₆H₅) ₂Se(CH₃CO₂) ₂, (C₆H_s) ₂Se(CF₃CO₂) ₂, (C₆H₅) ₂SeSO₄, (C₆H₅) ₂Se(CH₃SO₃) ₂ and (C₆H₅) ₂Se(NCO) ₂ are prepared. They are characterized by solubility, molecular weight and conductivity. Reaction of (C₆H₅) ₃SeCl and AgX (X = NO₃, CH₃CO₂) yields (C₆H₅) ₃SeNO₃ and (C₆H₅) ₃SeCH₃CO₂.     

Schwingungsspektroskopische Untersuchungen an den Organohydrogensilanen (XCH2)(CH3)2SiH (X = Cl,Br, J), X(YO)2SiH (X = CH3, C2H5/Y = CH3, C2H5 … tert.-C4H9), (C6H5)2SiH2 und C6H5SiH3

Infrared and Raman Spectroscopic Investigations on the Organosubstituted Silicon Hydrides (XCH₂)(CH₃)₂SiH (X = Cl, Br, J), X(YO)₂SiH (X = CH₂, C₂H₅/Y = CH₃, C₂H₅ … tert.-C₄H₉), (C₆H₅)₂SiH₂ and C₆H₅SiH₃ Typical band splittings, specially for the SiH stretching vibration, are shown in the infrared and Raman spectra of the silicon hydrides (XCH₂)(CH₃)₂SiH (X = Cl, Br, J), and X(YO)₂SiH (X = CH₃, C₂H₅/Y = CH₃, C₂H₅ … tert.-C₄H₉). The cause of this behavior is in all probability the existence of rotational isomers. Raman polarization measurements at organosubstituted silicon di- and trihydrides demonstrate the accidental degeneracy of the SiH valence vibrations.     

A novel synthesis of carbene complexes of manganese and molybdenum containing the trichlorogermyl group

A number of carbene complexes of formulas Cl₃GeMn(CO)₄C(OR′)R and C₅H₅Mo(CO)₂(GeCl₃)C(OR′)CH₃ (R = CH₃, C₆H₅; R′ = CH₃, C₂H₅) have been prepared by the reaction of [N(C₂H₅)₄]GeCl₃ with CH₃Mn(CO)₅, C₆H₅Mn(CO)₅, or C₅H₅Mo(CO)₃CH₃ followed by alkylation of the resulting trichlorogermylacylcarbonylmetallate ion. The compound C₅H₅Mo(CO)₂(GeCl₃)$\text{COCH}{}_2\text{CH}{}_2\text{C}$H₂ has been prepared directly by the reaction of [N(C₂H₅)₄]GeCl₃ with C₅H₅Mo(CO)₃(CH₂)₃Br.     

The behaviour of beryllium μ4-oxo-μ-carboxylates under electron impact

The electron impact mass spectra of eight polynuclear beryllium complexes Be₄O(RCO₂)₆ (R?H, CH₃, C₂H₅) and Be₄O(RCO₂)₅OR′ (R?CH₃, R′?H, CH₃, C₂H₅, C₃H₇; R?C₂H₅, R′?C₂H₅) are reported. The major fragmentations involve the elimination of (RCO)₂O (RCOOR′) or Be(RCO₂)₂ (Be(RCO₂)OR′) from the ions [M? L]⁺ and of {(R? H)CO}, (R′? H), H₂O and BeO from the lighter ions. The fragmentation patterns are practically independent of the organic groups present and can be rationalized by stereochemical considerations.     

Conversion kinetics of ozone complexes with arenes

The kinetics of conversion of ozone complexes with a series of substituted benzene ArX.O₃ (ArX=C₆H₅CH₃, C₆H₅C₂H₅, C₆H₅CH(CH₃)₂, C₆H₅C(CH₃)₃, C₆H₅F, C₆H₅Cl,m-BrC₆H₄CH₃, C₆H₅CH₂Cl have been studied by spectrophotometry. The rate of ArX.O₃ consumption in CH₂Cl₂-ArX solutionis W=k₀ [ArX. O₃]+k₁ [ArX. O₃] [ArX].     

Photochemische Darstellung von Hexaalkylborazol-und Aromaten-chromtricarbonylen

The half-sandwich type complexes LCr(CO)₃ (L=(C₂H₅)₃B₃N₃(CH₃)₃, (CH₃)₃B₃N₃(C₂H₅)₃, C₆H₆, sym-C₆H₃(CH₃)₃) have been prepared by photochemical reaction of Cr(CO)₆ with the appropriate ligand L at highly reduced pressure. This new method is of particular advantage for the synthesis of the hexaalkylborazole complexes.     

Synthesis of 3-alkyl-6-phenyl-4(3H)-pteridinones and their 8-oxides. Potential substrates of xanthine oxidase

Synthetic routes for the preparation of 3-alkyl-6-phenyl-4(3H)-pteridinones 6 and their corresponding 8-oxides 5 (R = CH₃, C₂H₅, (CH₂)₂CH₃, (CH₂)₃CH₃, CH(CH₃)C₂H₅, CH(CH₃)₂ and CH(C₂H₅)CH₂OCH(OC₂H₅)₂ are described and their reactivities towards xanthine oxidase from Arthrobacter M-4 are determined. Only the 3-methyl derivative of 6-phenyl-4(3H)-pteridinone and its 8-oxide i. e. 6a and 5a are found to be substrates although their reactivities are still very low. Oxidation takes place at C-2 of the pteridinone nucleus. All the 3-alkyl derivatives are less tightly bound to the enzyme than 6-phenyl-4(3H)-pteridinone. Introduction of the N-oxide at N-8 considerably lowers the binding of the substrates. Inhibition studies have revealed that 3-methyl-6-phenyl-4(3H)-pteridinone ( 6a ) is a non-competitive inhibitor with a Ki-value of 47 μM and the 3-ethyl derivative ( 6b ) an uncompetitive one with a Ki-value of 19.6 μM.     

Neue Synthesewege für Organohalogenstibane

New Methods for Synthesis of Organohalogenostibanes Organohalogenostibanes RSbX₂ (R = CH₃, C₆H₅; X = Cl, Br) and R₂SbX (R = C₆H₅; X = Cl) are received in good yields by alkylation or arylation of the corresponding antimony halides with Pb(CH₃)₄, Sn(CH₃)₄, Sb(CH₃)₃, or Sb(C₆H₅)₃. These methods are better than those, described in the literature for preparation of the compounds.