The anionic polymerization behavior of 2‐methyl‐4‐phenyl‐1‐buten‐3‐yne (2) was investigated to get information on the effect of substituent at the 2‐position. The polymerization of 2 did not proceed in tetrahydrofuran at –78°C by lithium initiators, while sodium initiators can conduct the polymerization smoothly to give polymers consisting of a specific 1,2‐polymerized unit. The living nature of the polymerization of 2 by diphenylmethylsodium was supported by the post‐polymerization experiment. 相似文献
This work deals with the in‐depth investigation of thiol‐yne based network formation and its effect on thermomechanical properties and impact strength. The results show that the bifunctional alkyne monomer di(but‐1‐yne‐4‐yl)carbonate ( DBC ) provides significantly lower cytotoxicity than the comparable acrylate, 1,4‐butanediol diacrylate ( BDA ). Real‐time near infrared photorheology measurements reveal that gel formation is shifted to higher conversions for DBC /thiol resins leading to lower shrinkage stress and higher overall monomer conversion than BDA . Glass transition temperature (Tg), shrinkage stress, as well as network density determined by double quantum solid state NMR, increase proportionally with the thiol functionality. Most importantly, highly cross‐linked DBC /dipentaerythritol hexa(3‐mercaptopropionate) networks (Tg ≈ 61 °C) provide a 5.3 times higher impact strength than BDA , which is explained by the unique network homogeneity of thiol‐yne photopolymers.
Summary: ω‐Styryl‐polystyrene macromonomers were synthesized by anionic induced deactivation reactions. Their homopolymerization in the presence of a fluorinated half‐sandwich metallocene catalyst (CpTiF3/MAO) was investigated. In spite of the intrinsic lower reactivity of these macromonomers with respect to the micromolecular monomer, coordination homopolymerization was possible. The influence of several experimental parameters on the polymerization yield and degree could be demonstrated. In most cases, under identical experimental conditions, higher polymerization yields and degrees were observed with respect to the CpTiCl3/MAO catalyst.
The synthesis of p‐polystyryl‐substituted styrene derivatives by the homopolymerization of ω‐styryl‐polystyrene macromonomers in the presence of CpTiF3. 相似文献
1‐Thiacyclooct‐4‐yne (=5,6‐didehydro‐3,4,7,8‐tetrahydro‐2H‐thiocin; 9 ) can be prepared from thiocan‐5‐one ( 6 ) in three steps by applying the so‐called selenadiazole method. The heterocyclic alkyne can be oxidized to the corresponding sulfoxide 16 and sulfone 17 . Due to their geometrical strain, all three cyclic alkynes show high reactivities in Diels? Alder and 1,3‐dipolar cycloadditions. Moreover, tetrathiafulvalenes can be prepared from 9 and 16 by the reaction with CS2. 相似文献
Quaternary Cesium Copper(I) Lanthanoid(III) Selenides of the Type CsCu3M2Se5 (M = Sm, Gd — Lu) By oxidation of mixtures of copper and lanthanoid metal with elemental selenium in molar ratios of 1 : 1 : 2 and in addition of CsCl quaternary cesium copper(I) lanthanoid(III) selenides with the formula CsCu3M2Se5 (M = Sm, Gd — Lu) were obtained at 750 °C within a week from torch‐sealed evacuated silica tubes. An excess of CsCl as flux helps to crystallize golden yellow or red, needle‐shaped, water‐resistant single crystals. The crystal structure of CsCu3M2Se5 (M = Sm, Gd — Lu) (orthorhombic, Cmcm, Z = 4; e. g. CsCu3Sm2Se5: a = 417.84(3), b = 1470.91(8), c = 1764.78(9) pm and CsCu3Lu2Se5: a = 407.63(3), b = 1464.86(8), c = 1707.21(9) pm, respectively) contains [MSe6]9— octahedra which share edges to form double chains running along [100]. Those are further connected by vertices to generate a two‐dimensional layer parallel to (010). By edge‐ and vertex‐linking of [CuSe4]7— tetrahedra two crystallographically different Cu+ cations build up two‐dimensional puckered layers parallel to (010) as well. These sheet‐like structure interconnects the equation/tex2gif-stack-3.gif{[M2Se5]4—} layers to create a three‐dimensional network according to equation/tex2gif-stack-4.gif{[Cu3M2Se5]—}. Thus empty channels along [100] form, apt to take up the Cs+ cations. These are surrounded by eight plus one Se2— anions in the shape of (2+1)‐fold capped trigonal prisms with Cs—Se distances between 348 and 368 pm (8×) and 437 (for M = Sm) or 440 pm (for M = Lu), respectively, for the ninth ligand. 相似文献
Irradiation (350 nm) of 2‐alkynylcyclohex‐2‐enones 1 in benzene in the presence of an excess of 2‐methylbut‐1‐en‐3‐yne ( 2 ) affords in each case a mixture of a cis‐fused 3,4,4a,5,6,8a‐hexahydronaphthalen‐1(2H)‐one 3 and a bicyclo[4.2.0]octan‐2‐one 4 (Scheme 2), the former being formed as main product via 1,6‐cyclization of the common biradical intermediate. The (parent) cyclohex‐2‐enone and other alkylcyclohex‐2‐enones 7 also give naphthalenones 8 , albeit in lower yields, the major products being bicyclo[4.2.0]octan‐2‐ones (Scheme 4). No product derived from such a 1,6‐cyclization is observed in the irradiation of 3‐alkynylcyclohex‐2‐enone 9 in the presence of 2 (Scheme 4). Irradiation of the 2‐cyano‐substituted cyclohexenone 12 under these conditions again affords only traces of naphthalenone 13 , the main product now being the substituted bicyclo[4.2.0]oct‐7‐ene 16 (Scheme 5), resulting from [2+2] cycloaddition of the acetylenic C−C bond of 2 to excited 12 . 相似文献
1,3‐Enyne structural motifs are versatile building blocks in organic synthesis and occur widely in various natural products with many of them being highly active as cytotoxic macrolides and antitumour antibiotics. This article presents the crystal structure of three 1,1,4‐triphenyl‐substituted 1,3‐enynes, viz. 4‐(2‐methylphenyl)‐1,1‐diphenylbut‐1‐en‐3‐yne, C23H18 ( 1 ), 4‐(2‐methoxyphenyl)‐1,1‐diphenylbut‐1‐en‐3‐yne, C23H18O ( 2 ), and 4‐(4‐nitrophenyl)‐1,1‐diphenylbut‐1‐en‐3‐yne, C22H15NO2 ( 3 ). The benzene ring at position 4 of the but‐1‐en‐3‐yne group bears a weakly activating methyl group in compound 1 , a moderately activating methoxy group in 2 and a strongly deactivating nitro group in 3 . The crystal structures of 1 and 3 both have monoclinic symmetry, while that of 2 is orthorhombic, and all of them have one molecule in the asymmetric unit. All three compounds were investigated for their antibacterial and antifungal activities. Interestingly, enyne 2 is the only compound tested that inhibited the growth of Aspergillus niger. 相似文献
In the title compound, [Rh(C2H11B9)(NO3)(C18H15P)2]·2.2CH2Cl2, studied as a 2.2‐solvate of what was assumed to be dichloromethane, the nitrate ligand lies cis with respect to both cage C atoms. Accordingly, the compound displays a pronounced preferred exopolyhedral ligand orientation (ELO) which is traced to both the greater trans influence of the cage B over the cage C atoms and the greater trans influence of the triphenylphosphane ligands over the nitrate ligand. The overall molecular architecture therefore agrees with that of a number of similar 3‐L‐3,3‐L′2‐3,1,2‐closo‐MC2B9H11 species in the literature. 相似文献
The homopolymerization of the water‐insoluble N‐(isobutoxymethyl)acrylamide (IBMA) is investigated for the first time by nitroxide‐mediated polymerization. The homopolymerization is characterized by a linear increase in number average molecular weight (Mn) versus conversion (X) to X > 0.80 while maintaining dispersities of Mw/Mn < 1.30. A strong Arrhenius relationship correlates the apparent rate constants and the homopolymerization temperatures between 105 and 120 °C. All poly(IBMA) homopolymers are then successfully chain‐extended with styrene (S) to form well‐defined block copolymers of poly(IBMA)‐b‐poly(S) suggesting a high degree of livingness of the poly(IBMA) macroinitiators. Thermogravimetric analysis and differential scanning calorimetry are both used to characterize the thermal properties of the homopolymers and block copolymers and identify possible unique degradation of the poly(IBMA) block through imide formation at elevated temperatures.
RuCl2(PPh3)3 led to living radical copolymerization of N,N‐dimethylacrylamide (DMAA) and methyl methacrylate (MMA) in conjunction with a halide‐initiator (R‐X; CHCl2COPh, CCl3Br) and Al(Oi‐Pr)3 in toluene at 80°C. Both the monomers were polymerized at almost the same rate into random copolymers, where the number‐average molecular weights (Mn) increased in direct proportion to weight of the obtained polymers, and the molecular weight distributions (MWDs) were narrow throughout the reactions (Mw/Mn = 1.2‐1.6). MMA was consumed faster in the copolymerization than in the homopolymerization, which was due to the interaction of DMAA with the ruthenium complex. The Ru(II)‐based initiating system was also effective in block copolymerization of DMAA and MMA. 相似文献
In the crystal structures of both title compounds, [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]nickel(II) [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]nickel(II) chloride methanol disolvate, [Ni(C26H25.5N3O3)]2Cl·2CH4O, and [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]zinc(II) perchlorate [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]zinc(II) methanol trisolvate, [Zn(C26H25N3O3)]ClO4·[Zn(C26H26N3O3)]·3CH4O, the 3d metal ion is in an approximately octahedral environment composed of three facially coordinated imine N atoms and three phenol O atoms. The two mononuclear units are linked by three phenol–phenolate O—H...O hydrogen bonds to form a dimeric structure. In the Ni compound, the asymmetric unit consists of one mononuclear unit, one‐half of a chloride anion and a methanol solvent molecule. In the O—H...O hydrogen bonds, two H atoms are located near the centre of O...O and one H atom is disordered over two positions. The NiII compound is thus formulated as [Ni(H1.5L)]2Cl·2CH3OH [H3L is 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine]. In the analogous ZnII compound, the asymmetric unit consists of two crystallographically independent mononuclear units, one perchlorate anion and three methanol solvent molecules. The mode of hydrogen bonding connecting the two mononuclear units is slightly different, and the formula can be written as [Zn(H2L)]ClO4·[Zn(HL)]·3CH3OH. In both compounds, each mononuclear unit is chiral with either a Δ or a Λ configuration because of the screw coordination arrangement of the achiral tripodal ligand around the 3d metal ion. In the dimeric structure, molecules with Δ–Δ and Λ–Λ pairs co‐exist in the crystal structure to form a racemic crystal. A notable difference is observed between the M—O(phenol) and M—O(phenolate) bond lengths, the former being longer than the latter. In addition, as the ionic radius of the metal ion decreases, the M—O and M—N bond distances decrease. 相似文献
The absolute configuration of the title cis‐(1R,3R,4S)‐pyrrolidine–borane complex, C18H34BNO2Si, was confirmed. Together with the related trans isomers (3S,4S) and (3R,4R), it was obtained unexpectedly from the BH3·SMe2 reduction of the corresponding chiral (3R,4R)‐lactam precursor. The phenyl ring is disordered over two conformations in the ratio 0.65:0.35. The crystallographic packing is dominated by the rarely found donor–acceptor hydroxy–borane O—H...H—B hydrogen bonds. 相似文献
A number of 3‐(4,4,5,5‐tetraethoxy‐1‐hydroxy‐1‐arylpent‐2‐ynyl)quinoxalin‐2(1H)‐ones, obtained by reacting the lithium acetylide of 3,3,4,4‐tetraethoxybut‐1‐yne (TEB) with 3‐aroylquinoxalin‐2(1H)‐ones, appeared to undergo stereoselective cyclization in the 5‐exo‐Dig manner when heated at reflux in acidic, aqueous THF. In each case, the products were the corresponding (E)‐1,1‐diethoxy‐3‐(3‐hydroxy‐3‐arylfuro[2,3‐b]quinoxalin‐2(3H)‐ylidene)propan‐2‐ones and 1,1‐diethoxy‐3‐hydroxy‐3‐(3‐arylfuro[2,3‐b]quinoxalin‐2‐yl)propan‐2‐one, which were isolated in an approximate ratio of 2:1 in high total yield. Irrespective of the structure of the aryl group, both compounds were stable solids when kept in a refridgerator (3 °C), but when the latter product was dissolved in chloroform and stored at room temperature, it rearranged smoothly and quantitatively to the former compound within a few days. 相似文献