trans-2,2'-Bi(1-phenyladamantylidene): the most twisted biadamantylidene

The Grignard coupling of 2,2-dibromo-1-phenyladamantane gave trans-2,2'-bi(1-phenyladamantylidene) (1-Ph). Single-crystal X-ray analysis indicated that 1-Ph has a 23.2 degrees twisted double bond, which is much more distorted than that of parent 2,2'-biadamantylidene (1-H) and that of the ethyl-substituted derivative (1-Et). A cyclic voltammogram showed a reversible electron oxidation wave at 0.87 V vs Fc/Fc(+), which is 0.19 V lower than 1-H, indicating a significant increase in the HOMO energy level due to the distortion. The reaction of 1-Ph with 0.9 equiv of bromine gave an intramolecular Friedel-Crafts alkylation product, while bromination of 1-H and 1-Me has been reported to give a bridged bromonium ion and a rearranged product, 2-(1-methyl-2-adamantylidene)-4-bromotricyclo[5,3,1,0(3.9)]undec-4-ene, respectively.     

Atropisomeric (R,R)-2,2'-Bi([2]paracyclo[2](5,8)quinolinophane) and (R,R)-1,1'-Bi([2]paracyclo[2](5,8)isoquinolinophane): synthesis, structural analysis, and chiroptical properties

Atropisomeric (R,R)-2,2'-bi([2]paracyclo[2](5,8)quinolinophane) [(R,R)-1] and (R,R)-1,1'-bi([2]paracyclo[2](5,8)isoquinolinophane) [(R,R)-2] have been prepared in moderate overall yield (17 and 9%, respectively) by a four-step sequence starting from (R)-(-)-4-amino[2.2]paracyclophane and (R)-(-)-4-carboxy[2.2]paracyclophane, respectively. The structures have been determined on the basis of NOE (1)H NMR analysis and molecular mechanics (MM) calculations performed with a Spartan02 program, using the MMF94s force field. A preliminary, qualitative analysis of the chiroptical properties of these two compounds has also been attempted. The main spectral data can be interpreted in terms of an almost planar 2,2'-bisquinoline chromophore inserted in a paracyclophane structure in the case of (R,R)-1, while in the case of (R,R)-2, the main role is played by a distorted 1,1'-bisisoquinoline chromophore. On the basis of the above structural results, a hypothesis about the enantioselection capability of these two molecules has also been formulated.     

六元瓜环与二氯化-1,8-二(2-苯并咪唑基)辛烷的自组装模式

采用¹H NMR、 荧光光谱和紫外吸收光谱法考察了主体六元瓜环与合成客体二氯化-1,8-二(2-苯并咪唑基)辛烷的自组装模式. 结果表明, 六元瓜环能与二氯化-1,8-二(2-苯并咪唑基)辛烷发生相互作用, 瓜环包结客体分子的苯并咪唑基团, 烷基链置于瓜环端口外侧. 自组装模式与主客体的摩尔比密切相关. 当主客体的摩尔比为1:1时, 1个瓜环包结客体分子的一端苯并咪唑基团形成棒槌形的包结配合物; 当主客体的摩尔比为2:1时, 2个瓜环分别包结客体分子的两端苯并咪唑基团形成哑铃型的主客体包结配合物.     

2,2-diphenyl-1-(trifluoromethanesulphonyl)-hydrazyl

2,2-diphenyl-1-(trifluoromethanesulphonyl)-hydrazyl was prepared by oxidation of the corresponding hydrazine, and is stable in solution. Its ESR spectrum is interpreted in terms of a larger coupling constant for the tricoordinated than for the dicoordinated nitrogen, and of proton coupling constants indicating non-equivalent phenyl groups.     

Synthesis of Dialkyl 1-Methyl-2,2-dichlorocyclopropylcarbonylphosphonates and Alkyl (1-Methyl-2,2-dichlorocyclopropylcarbonyl)arylphosphinates

Russian Journal of General Chemistry -     

2-Chloro-3-(Tetrachlorophosphoranyloxy)succinyl Dichloride

Russian Journal of Organic Chemistry -     

(烷基环戊二烯基)环戊二烯基二氯化钛的合成与反应

Richard在1959年合成了第一个环戊二烯基(取代环戊二烯基)钛衍生物,(CH₃C₅H₄)(C₅H₅)T1Cl₂^[1].我们曾报道了环戊二烯基(烯烃基环戊二烯基)二卤化钛的合成和反应^[2]。     

Optically active 1-Alkoxy-2,2-bis(trifluoromethyl)aziridines

1-Alkoxy-2,2-bis(trifluoromethyl)aziridines containing an ester group in the position of the alkoxy substituent undergo nucleophilic substitution (ammonolysis and hydrolysis) with retention of the aziridine ring. The corresponding carboxylic acids, which were separated to give the antipodes with an optical purity of 95% through the diastereomeric salts with R- and S--phenylethylamine, were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1495–1500, November, 1980.     

Hexahydroxybenzene–2,2′-bipyridine (1/2)

2,2′-Bi­pyridine (2BPY) and hexa­hydroxy­benzene (HHB) crystallize in a 2:1 ratio as a neutral molecular adduct, C₆H₆O₆·2C₁₀H₈N₂, in space group P with Z = 1 and with the HHB molecule lying on an inversion centre. HHB, of which this is the first single-crystal X-ray structure determination, forms O—H⃛O hydrogen-bonded chains parallel to the a axis, with O⃛O distances of 2.761 (1) and 2.782 (1) Å. O—H⃛N hydrogen bonds to the 2BPY molecules crosslink these chains, with O⃛N distances of 2.707 (1) and 2.735 (1) Å.     

Synthesis and Structure of Tri(p-tolyl)antimony Dichloride

Tri(p-tolyl)antimony dichloride was prepared by oxidation of tri(p-tolyl)stibine with chlorine or copper(II) chloride. As found by X-ray diffraction analysis, the antimony atom in tri(p-tolyl)antimony dichloride has the configuration of trigonal bipyramid with axially located chlorine atoms. The Sb-Cl and Sb-C distances are 2.476(2) and 2.104(7) Å, and the CSbC and ClSbCl angles are 120 and 180°, respectively.