[4 + 6]-cycloaddition von 1,3-butadien an hexacarbonyl-μ-η6:6-heptafulvalen-dichrom(0)

The thermal reaction of heptafulvalene (I) with [Cr(CO)₃(CH₃CH)₃] (II) gives the hexacarbonyl-η^6:6-heptafulvalenedichromium(0) complex (III). UV irradiation of complex III in THF solution, with 1,3-butadiene (IV) in successive [4 + 6]-cycloadditions and decomplexations gives the complexes tricarbonyl-η⁶-11-(2,4,6-cycloheptatrien-1-ylidene)bicyclo[4.4.1]undeca-2,4,8-trine-chromium(0) (V) and tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)-chromium(0) (VI). On warming, VI looses the bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene) hydrocarbon ligand (VII). The reaction of VII with [Mo(CO)₃(diglyme)] (VIII) gives the tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)molybdenum(0) complex (IX). The compounds III, V–VII and IX were characterized by IR and NMR spectra (¹H, ¹³C) and by C,H elemental analysis.     

Activation of a carbon—nitrogen triple bond in the presence of Ru3(CO)12 and H4Ru4(CO)12

The reaction of PhCN with Ru₃ (CO)₁₂ in the presence of acetic acid gives H₄Ru₄(CO)₁₂, (I), (μ-H)Ru₃(CO)₁₀(μ-NCHPh) (II) and (μ-H)Ru₃(CO)₁₀(μ-NH-CH₂Ph) (III) as the main products. Reaction under 110 atm of H₂ gives more III and also gives benzylamine. Replacement of acetic acid by H₂ at atmospheric pressure gives only II. When H₄Ru₄CO)₁₂ reacts with PhCN alone or in the presence of NaOH, II is formed as the only product.The structures of II and III have been fully elucidated by X-ray methods. The nitrogen atom of the NCHPh ligand in II and that of the NHCH₂Ph ligand in III, interact with the isosceles-triangular metal cluster, symmetrically bridging the shortest Ru(1)-Ru(2) edge. A hydride ligand in both II and III bridges the same Ru(1)-Ru(2) edge of the cluster. Under mild conditions acetic acid is an essential requirement for the activation of Ru₃(CO)₁₂ for reaction with PhCN to give III, which cannot be obtained under these conditions from II.     

4-Thiazolidines,derivatives and analogs

Heating thiazan-2, 4-dione (I) with P₂S₅ in xylene or toluene gives a hitherto unknown isomer of propiorhodanine (II), 4-thione-1, 3-thiazan-2-one (III), with an active thione group and more acidic properties than II. Reaction of I with P₂S₅ in dioxane gave 2, 4-dithionethiazane, (IV) in high yield, this being the most convenient method of preparing IV.     

Über in 6-Stellung basisch substituierte Morphanthridine. 8. Mitteilung über siebengliedrige Heterocyclen

Morphanthridines III with a basic substituent in position 6, which show neuroleptic activity, have been synthesised as follows: Chlorination of the lactams I with POCl₃ gave the iminochlorides II, which were converted by bases to the amidines III. The 11-oxo-morphanthridines VI and VII were synthesised using the same procedure, 2-(1-methylpiperazine-4-carbonyl)-2′-amino-benzophenone (XI) was obtained directly from the 6-chloro-11-oxo-morphanthridine (V) or by extended heating of VI with N-methylpiperazine. Reduction of the 11-oxo-compounds VI and VII with NaBH₄ gave the 11-hydroxy-compounds IX and X. 3-(2-aminophenyl)-phtalide (VIII) resulted from the acid hydrolysis of IX.     

Übergangsmetall—carbin-komplexe LIV. Neue metallocenylcarben- und - carbinkompexe der VI. Nebengruppe – darstellung,vergleich und elektrochemisches verhalten

The lithiated metallocenes ruthenocene (C₅H₅)₂Ru and 1,1′ -dimethylferrocene (C₅H₄CH₃)₂Fe react with the metal hexacarbonyls of Group VIB to yield acylato complexes, from which, by subsequent alkylation with [Et₃O][BF₄], the corresponding pentacarbonylethoxyrunthenocenylcarbene (I—III) as well as pentacarbonylethoxydimethylferrocenylcarbene complexes (IV—VI) of chromium, molybdenum and tungsten are obtained. The reaction of the new tungsten complexes III + VI with boron and aluminium halides (MX₃; X = Cl, Br) at low temperatures yields trans-halogenotetracarbonylruthenocenylcarbyne (VII, VIII) and trans-bromotetracarbonyldimethylferrocenylcarbyne complexes (IX). The reaction conditions, the results of spectroscopic and electrochemical measurements, compared to previously discussed ferrocenylcarbene- and -carbyne complexes and the X-ray structure of III are reported.     

The reaction of malononitrile with thioglycolic acid. A novel procedure for the synthesis of thiazolone derivatives

Malononitrile (I) reacted with thioglycolic acid to yield the thiazolin-4-one derivatives II or III depending on the molar ratio of the reactants. Compound II reacted with benzaldehyde in refluxing pyridine to yield the arylidene derivative IV. On the other hand, the benzylidine bis derivative VIII was obtained when II was reacted with benzaldehyde in refluxing ethanol. The structure of IV was established via its synthesis from the reaction of benzylidenemalononitrile (VI) and thioglycolic acid in refluxing acetic acid. Similar to II, compound III condensed with benzaldehyde to yield the benzylidene derivative IX.     

Beiträge zur Chemie der Trifluormethylquecksilber-Verbindungen

Contribution to the Chemistry of Trifluoromethylmercury (II) Compounds CF₃HgI (I) has been obtained in appreciable amount by a newly modified method, The reaction of I with silver salts AgX or AgY₂ (X = CN, NCO, SCN, SeCN, N₃, SCF₃, IO₃; Y = O, C₂O₄, NCN) gives corresponding CF₃HgX derivatives (II–VIII, XI, XII, XVII) mostly in good yield. The synthesis of (CF₃Hg)₂S (IX) has been attained by the reaction of I with Tl₂CS₃, while it gives with Ag₂O (CF₃Hg)₂O (VIII) instead of the hydroxide. VIII reacts in ethereal solution with H₂Se giving (CF₃Hg)₂Se (X). Stable CF₃HgN and (CF₃Hg)₂N derivatives (XIII–XVII) could only be obtained when at least one more substituent on N atom, which reduces its basicity, is present. I.r., ¹⁹F-n.m.r. and mass spectroscopic data for the prepared compounds have been reported.     

The reaction of allene with β-diketonatoiridium(I) complexes: synthesis,properties and crystal structures of bis(η3-allyllic) complexes of iridium(III) and of iridocyclopentane derivatives

Allene reacts with compounds of the type (β-diketonato)Ir(η-C₈H₁₄)₂| (I) to give iridium(III) derivatives of formula (β-diketonato)IrC₁₂H₁₆ (II) in which an allene tetramer i.e. the 2,3,6,7-tetramethyleneoctane-1,8-diyl group, is bonded to the iridium atom by two η₃-allylic groups. The molecular structures of these complexes were deduced by ¹H NMR studies and by single-crystal X-ray analysis of (hfacac)IrC₁₂H₁₆ (IIb). The reactions of the complexes II with hydrogen and with CO are described.The reaction of (acac)Ir(η-C₈H₁₄)₂ with allene, at -78°C, gives a thermally unstable compound of probable stoichiometry (acac)Ir(C₃H₄)₄ (VI). Its low-temperature IR spectrum and its reaction with bromine indicate that VI contains two η²-bonded allene molecules and teh 3,4-dimethyleneiridocyclopentane moiety. VI reacts with pyridine with loss of an allene molecule to give an iridium(III) derivative of formula (acac)Ir(C₆H₈)(C₃H₄)py (IX). Complex IX was shown by single-crystal X-ray analysis to contain the 3,4-dimethyleneiridocyclopentane moiety and one η²-bonded allene molecule.The role of irido cycles as precursors of the bis(allylic) complexes II is discussed.     

Reactions of some sterically-hindered organosilicon hydrides and iodides with halogens

The reaction of TsiSiMe₂H (I) (Tsi = (Me₃Si)₃C) with I₂ or with a molar equivalent of ICl gives the iodide TsiSiMe₂I (II) in hydroxylic media (MeOH, CH₃CO₂H, CF₃CO₂H) as it does in CCl₄. The reaction with I₂ is very fast in CF₃CO₂H, but in MeOH is only about as fast as in CCl₄. The iodide II reacts with ICl in MeOH to give a mixture of TsiSiMe₂OMe (III) and TsiSiMe₂Cl (IV), but the reaction is markedly slower than that in CCl₄ (in which IV is formed). The hydride I also reacts with INO₃ in MeOH to give II, and the latter reacts with INO₃ to give III. The reactions of TsiSiPh₂H (V) and TsiSiPh₂I (VI) with ICl in MeOH are markedly slower than those of I and II; even with one equivalent of ICl in MeOH, V gives a mixture of VI and the (rearranged) methoxide (Me₃Si)₂C(SiPh₂Me)(SiMe₂OMe) (VII). Reaction of VI with ICl in MeOH gives VII and the rearranged chloride (Me₃Si)₂C(SiPh₂Me)(SiMe₂Cl). The formation of methoxides in the reactions of the iodides II and VI with ICl in MeOH, and the rearrangements observed in the case of VI, are consistent with a mechanism involving an intermediate silicocation. Other mechanistic aspects are discussed.     

Kinetics of reaction of alkynes with some cobalt carbonyls

Pt(CO)₂Cl₂ reacts in benzene, toluene or tetrahydrofuran with 3-hexyne to give carbonylplatinumbis[di-μ-chloro,chloro(tetraethylcyclobutadiene)platinum](I), bis[dichloro(tetraethylcyclopentadienone)platinum] (III), dichloro-(tetraethyl-p-benzoquinone)platinum (IV) and dichloro(tetraethylcyclobutadiene)platinum (II). This last compound is also obtained by treating I with 1 to 3 moles of triphenylphosphine or p-toluidine. p ]The structure and reactions of III are discussed; the anion exchange reaction gives the iodo-analogue, while treatment with donor ligands gives adducts of formula [(C₂H₅)₄C₄CO]PtCl₂L(L = triphenylphosphine, p-toluidine, benzylamine and pyridine) and [(C₂H₅)₄C₄CO]PtCl₂L₂(L = benzylamine, 3-methylpyridine). p ]2-Butyne reacts with dichlorodicarbonylplatinum to give the methyl analogous of compounds I–III.     

Über die natur der übergangsmetall-kohlenstoff-σ-bindung: IX. Über die darstellung und charakterisierung von η5-cyclopentadienyl-triphenylphosphin-nickel-η1-thioanisolyl und seine thermische zersetzung in nickelthiophenolatokomplexe

The reaction of Cp(PPh₃)NiCl (Cp = η⁵-C₅H₅) with PhSCH₂Li gives Cp(PPh₃)Ni(η¹-CH₂SPh) (I), which has been isolated as green crystals and characterized by elemental analysis, magnetic measurement, ¹H NMR and mass spectroscopic investigations and by protolysis to form PhSCH₃. Cp₂Ni also reacts with PhSCH₂Li in the presence of PPh₃ to give I containing 5–10% of Cp(PPh₃)NiSPh (II) and about 1% of [CpNiSPh]₂ (III) as impurities. In the absence of PPh₃, III is formed, with the release of ethylene and cyclopropane, even at a temperature of ?20°C. For comparison, II has been synthesized from Cp₂Ni, PPh₃ and LiSPh and from the reaction of III with PPh₃.I decomposes in boiling benzene to give II (ca. 33%) and III (ca. 13%). The conversion of the thioanisolyl into thiophenolato complexes can be understood on assuming that {CpNi(η²-CH₂SPh)} is formed as an unstable intermediate.     

Researches on pyranes,their analogs,and related compounds

Condensation of 2, 4-diacetylphenol with diethyl oxalate serves as a basis for preparing 2-carbethoxy- and 2-carboxy-6-acetylchromones (I, II), 2-carbethoxy-6-ethoxyoxalyacetylchromone (V), and 2-carboxy-6-hydroxyoxalylacetylchromone (VI). The Mannich reaction is used to synthesize 6-(ω-dialkylaminopropionyl)-2-carboxychromones (VII, VIII) from compound I. Reaction of chromone-2-carbonyl chloride with enamines prepared from cyclohexanone and tetrahydrothiopyrone-4- gives syntheses of 2-(chromonoyl-2)cyclohexanone (III) and 3-(chromonoyl-2)tetrahydrothiopyrone-4 (IV). Hydrazine hydrate and compound III give the pyrazole derivative IX, while hydrazine hydrate and compound IV give pyrazole derivative X along with pyrazolylpyrazole derivative XI, which results from a second molecule of hydrazine hydrate opening the chromone ring. For Part XX see [11].     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. III. Die Reaktion zwischen Acrylnitril und PCl3

On Trichlorophosphazo Compounds from Nitriles. III. The Reaction between Acrylonitrile and PCl₃. The reaction of PCl₃ with acrylonitrile at higher temperatures gives CH₂Cl? CCl₂? CCl₂? N? PCl₃ ( II ). On pyrolysis of (II), CH₂Cl? CCl₂? CN (IV) is form- ed. Treatment of (II) with SO, results in CHzCL? CCl₂? CCl?N-P(0)Cl₂ ( III ). At lower temperatures and/or in the presence of PCl₃, acrylonitrile reacts with PCl₃ to give the cis/ trans isomers VIa and VIb .     

Insect pheromones and their analogues. XVIII. Regiospecific synthesis of (±)-15,19-dimethyltritriacontane — A component of the pheromone of Stomoxys calcitrans

(±)-15,19-Dimethyltritriacontane (II) — a component of the pheromone of the stable fly — has been obtained by a five-stage synthesis from dimethylcyclooctadiene (I). The coupling of 1,1-dimethoxy-4-methyl-8-oxonon-4Z-ene [the product of the ozonolysis of (I)] with n-C₁₃H₂₇CH=PPh₃ (THF; ?30°, 2 h; 25°, 15 h; Ar) gave 1,1-dimethoxy-4,8-dimethyldocosa-4Z,8Z(E)-diene (III). The hydrolysis of (III) (TsOH·Py, H₂O-Ac, boiling, 4 h) gave the corresponding aldehyde (IV). The condensation of (IV) with n-C₁₀H₂₁CH=PPh₃ (THF; ?60° to ?30°C, 2 h, 25°C, 15 h) led to 15,19-dimethyltritriaconta-11Z(E),15Z,19Z(E)-triene (V), the exhaustive hydrogenation of which (ethanol, H₂, 5% Pd/C, 25°C) gave (II). The substance, the yield in %, and R_f values are given, respectively: (II), 95, 0.92; (III), 29, 0.74; (IV), 80, 0.72; (V) 50, 0.8. The IR and PMR spectra of compounds (II)–(V) and the mass spectra of (II) and (III) are given.     

Synthesis of 1,2-disubstituted naphth [1,2-d]imidazole-4,5-diones

A convenient synthesis of 3-acylamino-1,2-naphthoquinones (I) is presented. The addition of aromatic and aliphatic amines to I followed by exposure to oxygen gives the corresponding 4-arylamino- or 4-alkylamino-3-acylamino-1,2-naphthoquinones (II). The addition of 4-cyclo-hexylbutylamine to 3-trichloroacetamino-1,2-naphthoquinone took an anomalous course and 1-(4′-cyclohexylbutyl)-3(H)-naphth[1,2-d]imidazoline-2,4,5-trione (VII) was obtained. Treatment of II with refluxing acetic acid gave 1,2-disubstituted naphth[1,2-d]imidazole-4,5-diones (III). The reaction was successful with a variety of 4-substituted amino-3-acylamino-1,2-naphthoquinones (II) and usually occurred in excellent yield. However, the cyclization of II to III is subject to steric limitation and attempts to cyclize 4-tert-butylamino-3-acetamino-1,2-naphthoquinone to the corresponding imidazole derivative was unsuccessful. The infrared, ultraviolet and nuclear magnetic resonance spectra of I, II, and III are discussed in relation to their structures.     

Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen. XCI. Dekamethylcyclotetrasilazan

Decamethylcyclotetrasilazane (I) was prepared starting with 1,3-dichloropentamethyldisilazane (II), 1.3-dichlorotetramethyldisilazane (III) and 1,3-bis-(methylamino)tetramethyldisilazane (IV). respectively, according to scheme 1, equ. (1), (2) and (3) in the text. (I) does not form, as given in the literature (equ. 4)⁵, by thermal transformation of bis(methylaminodimethylsilyl)-tetramethylcyclodisilazane (V); in this case exclusively – in equ. (2) and (3) only in side steps – the reaction products are a mixture of N-methylcyclotrisilazanes (scheme 2, VI–IX).     

Synthesis and Spatial Structure of the Derivatives of 2,5-Dioxo-3,3-Bis(Trifluoromethyl)-6,7-Benzo-1,4,2-and 2,5-Dioxo-4,4-Bis(Trifluoromethyl)-6,7-Benzo-1,3,2-Oxazaphosphepines

Abstract

Hexafluoroacetone imine easily interacts with compounds (I, R = OMe, OCH₂CF₂CHF₂, NEt₂, Ph) in two directions unlike hexafluoroacttone and gives 1,4,2-oxazaphosphepines (II) (pathway I) or 1,3,2-oxszaphosphepines (III) (pathway 2). The compound (II) (R = NEt₂) lightly hydrolyzes to yield the salt (IV). The structure of heterocycles II-IV) has been confirmed by X-ray analysis (see fig. I, II, R = OMe; fig. 2, IV). The detail structural peculiarities of the compounds am discussed.     

Pyrans,their analogs,and related compounds

Reaction of 4, 4-dichloroflavine (I) with sulfurylchloride affords 2, 3, 3, 4, 4-pentachloroflavan (II). Hydrolysis of II gives 2-hydroxy-3, 3-dichloro-4-flavanone (III), while alcoholysis with aqueous alcohols yields 2-alkoxy-3,3-dichloro-4-flavanones (IVa, b). Treatment of III with SOCl₂ gives 2,3,3-trlchloro-4-flavanone (V), which with caustic alkali or sodium ethoxide is converted into o-(1-phenyl-2, 2-dichlorovinyloxy)benzoic acid (VIc) or its ethyl ester (VIb), respectively.For Part XLII, see [7].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1167–1170, September, 1970.     

Treatment of dimethyl (+)-L-tartrate with sulfur tetrafluoride

Treatment of dimethyl (+)-L-tartrate (I) with sulfur tetrafluoride results in the formation of an intermediate, 2-fluoro-1,2-bis(methoxycarbonyl)ethyl fluorosulfite (II), which under the action of hydrogen fluoride, present in the reaction mixture, is converted into dimethyl (?)(2S:3S)-2-fluoro-3-hydroxysuccinate (III). The reaction of the latter with SF₄ leads to dimethyl meso-2,3-difluorosuccinate (IV). The structure and configurations of the compounds obtained were established by ¹H and ¹⁹F NMR. Treatment of dimethyl (+)-L-tartrate (I) with sulfur tetrafluoride in the presence of excessive hydrogen fluoride gave dimethyl meso-2,3-difluorosuccinate in 96% yield.     

Dicyclopentadienyl-niobium(iii) and -niobium(iv) complexes

The reduction of (η-C₅H₅)₂NbCl₂ (I) under various conditions gives the dimer (η-C₅H₅)₄Nb₂Cl₃ (II) containing niobium(III) and niobium(IV). Reaction of II with AgClO₄ gives [(η-C₅H₅)₄Nb₂Cl₂]⁺ ClO₄^- (III). FeCl₃ and (C₆F₅)₂ TlBr displace I from II to give (η-C₅H₅)₂Nb(μ-Cl)(μ-X)MY₂, where MFe, XYCl(IV) and MTl, XBr, YC₆F₅ (V). Reactions of I with metal halides MXY₂ give (η-C₅H₅)₂ClNb(μ-Cl)MXY₂ where XYCl, MAl (VI), Fe (VII), Tl (VIII) and XBr, YC₆F₅, MTl (IX). The chemical behaviour of all these compounds is described.