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151.
Carbophilic Additions of Organocuprates and 1,3-Thiazole-5(4H)-thiones Organocuprates and 1,3-thiazole-5(4H)-thiones 1 react in THF at 0° via carbophilic addition onto the C? S bond to give 4,5-dihydro-1,3-thiazole-5-thiols 3 (Scheme 3). This observation is in marked contrast to the previously described reaction of organolithium compounds and 1 , which undergo a thiophilic addition onto the exocyclic S-atom. As an exception, treatment of the 1,3-thiazole-5(4H)-thione 1a with tert-butyl cuprate leads to 7a (Scheme 3). 相似文献
152.
153.
FTIR-spectroscopic investigations of catalytic reactions yield detailed information about the interaction of adsorbed molecules with the catalyst and kinetic data of the surface reaction, if the participating molecules show vibrations whose position and intensity in the IR-spectrum depend on the sorption state and the quantity adsorbed. In this paper, the possibilities and limitations of the method are represented by two examples. 相似文献
154.
155.
Polycyclic ‘cage’ ketones, such as pentacyclo[5.4.0.02,6.03,10.05,9]undecan‐8‐one ( 10 ), pentacyclo[5.4.0.02,6.03,10.05,9]undecane‐8,11‐dione ( 11 ), and adamantan‐2‐one ( 16 ) were treated with the nucleophilic dimethoxycarbene (DMC; 1 ), which was generated thermally from 2,5‐dihydro‐2,2‐dimethoxy‐5,5‐dimethyl‐1,3,4‐oxadiazole ( 4a ) in boiling toluene. In this ‘one‐pot’ procedure, the α‐hydroxycarboxylic acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes 4–7). Additionally, ‘cage’ thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme 8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave α‐mercaptocarboxylate 25 and the corresponding desulfurized ester 24 , respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo‐face is postulated to explain the structures of the isolated products. 相似文献
156.
Radical Cyclizations of Alkenyl-Substituted 4,5-Dihydro-1,3-thiazole-5-thiols Heating of 5-alkenyl- or 5-alkinyl-4,5-dihydro-1,3-thiazole-5-thiols of type 5 in the presence of a radical initiator gave dithiaspirobicycles in fair-to-excellent yield (Scheme 3). Under analogous conditions, the 4,5-dihydro-4-vinyl-1,3-thiazole-5-thiol 5d underwent a cyclization to give the annellated dithiabicycle 7 (Scheme 4). In this reaction, a minor product 8 was formed by an unknown reaction mechanism. The structure of 8 was established by X-ray crystallography. The starting 1,3-thiazole-5-thiols 5 have been synthesized by carbophilic alkylation of me C?S group of 1,3-thiazole-5(4H)-thiones with Grignard-reagents or alkylcuprates. The thiazolethiones were obtained by the reaction of 3-amino-2H-azirines with thiobenzoic acid followed by sulfurization and cyclization. The 4-benzyl derivative 1b was thermally rearranged via 1,3-benzyl migration to yield the benzyl (1,3-thiazol-5-yl) sulfide 11 (Scheme 5). 相似文献
157.
Herbert Schumann Kerstin Zietzke Frank Erbstein Roman Weimann 《Journal of organometallic chemistry》1996,520(1-2):265-268
LnCl3 reacts with Na(C5Me41Bu) in THF to form the organolanthanoid chlorides [(C5Me41Bu)2LnCl(THF)] (Ln = La (1a), Lu (1b)). Compounds 1a and 1b yield in reaction with NaO2CCH3 the monomeric organolanthanoid acetates [(C5Me41Bu)2LnO2CCH3] (Ln = La (2a), Lu (2b)). The single crystal X-ray structure analysis of 2b as well as the cryoscopic molecular weight investigation of 2a verify the monomeric structure of these complexes. 相似文献
158.
Grzegorz Mlosto Jaroslaw Romaski Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》1995,78(6):1499-1510
1,3-Dipoles with a Central S-Atom from the Reaction of Azides and Thiocarbonyl Compounds: An Unexpected MeS Migration in the Trapping Product of a ‘Thiocarbonyl-aminide’ with Methyl Dithiobenzoate Reaction of PhN3 with O-methyl thiobenzoate ( 11a ) and thioacetate ( 11c ) as well as with the dithio esters 11b,d at 80° yields the corresponding imidates and thioimidates 12 (Scheme 3). The formation of 12 is rationalized by a 1,3-dipolar cycloaddition of the azide and the C?S group followed by successive elimination of N2 and S. In the three-component reaction of 11b , PhN3, and the sterically crowded thioketone 1a , 1,2,4-trithiolane 13a and 1,4,2-dithiazolidine 3a are formed in addition to 12b (Scheme 4). The heterocycles 13a and 3a are trapping products of 1a and ‘thiocarbonyl-thiolate’ 5a and ‘thiocarbonyl-aminide’ 2a (Ar?Ph), respectively (Scheme 6). These 1,3-dipoles are formed as reactive intermediates. Surprisingly, in the presence of catalytic amounts of acids, the major product is the (methyldithio)cyclobutyl thioimidate of type 14 (Scheme 5), formed by an acid-catalyzed MeS migration in dithiazolidine 17 . A reaction mechanism is proposed in Scheme 7. 相似文献
159.
Transition Metal Substituted Acylphosphanes and Phosphaalkenes. 17. Synthesis and Structure of the μ-Isophosphaalkyne Complexes [(η5-C5H5)2(CO)2Fe2(μ-CO)(μ-C?PC6H2R3)] (R = Me, iPr, tBu) . Condensation of (η5-C5H5)2(CO)2Fe2(μ-CO)(μ-CSMe)}+SO3CF3? ( 6 ) with 2,4,6-R3C6H2PH(SiMe3) ( 7 ) ( a : R = Me, b : R = iPr, c : R = tBu) affords the complexes (η5-C5H5)2(CO)2Fe2(μ-CO)(η-C?PC6H2R3-2,4,6) ( 9 a–c ) with edge-bridging isophosphaalkyne ligands as confirmed by the x-ray structure analysis of 9 a . 相似文献
160.
The geometric structure of (CF3S)2C=C(SCF3)2 in the vapour phase was determined by electron diffraction. The molecule possesses D2 symmetry with the S---CF3 bonds oriented perpendicular to the ethene plane, in alternating directions up-down-up-down. The following skeletal geometric parameters were obtained (ra distances and angles, experimental uncertainties are 3σ values): C=C = 1.34Å (ass.), C(sp2---S = 1.761(5)Å, S---C(sp3) = 1.832(5)Å, S---C---C = 119.6(4)°, C---S---C = 100.6(13)°, and ø(C=C---S---C) = 90.9(11)°. The gas phase conformation differs considerably from the crystal structure, where the molecule possesses Ci symmetry and the CF3 groups, which are bonded to cis-standing sulfur atoms, lie on the same side of the ethene plane with dihedral angles ø(C=C---S---C) of 117° and 127°. 相似文献