Synthesis and Crystal Structure of N—（1‘’‘’—Phenyl—2‘’‘’—hydroxyethyl）—2,3—naphthylenedicarboximide

IntroductionThe design and the synthesis of new chiral ox-azoline[1,2 ] and C2 symmetric bis( oxazoline) ligandsand the application of their metal complexes inasymmetric catalytic reactions have inspired manyscientists to great exertions in recent years[3— 8] .Our interest has been focussed on the studies ofenantioselective transition metal catalysis ofhetero-cyclic ligands[9— 11] . In the synthesis of our new de-signed ligands,what is crucial is to select a rigidcyclic backbone. Bis( oxazo…     

Syntheses and Crystal Structures of 4,4‘—Diformyl—diphenoxyethane and 4,4’,4‘’—Triformyl—triphenoxytriethylamine

Two title compounds, 4,4'-diformyl-diphenoxyethane (compound 1, C16H14O4)and 4,4',4'-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris2-chloroethylamine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ', = 105.823(6)o, V = 675.7(2)'3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, (MoK = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ', = 99.505(1)°, V = 2383.5(3) '3, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, (MoK = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 dialdehyde is located at the crystallographic inversion center nearby the midpoint of C8-C8A single bond. The three chains in the molecule of compound 2 trialdehyde are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.     

1,2—双（1‘—苯基—3’—甲基—5‘—氧代吡唑—4’—基）—1,2…

用萃取法合成了１５种１，２－双（１＇－苯基－３＇－甲基－５＇－氧代吡唑－４＇－基）－１，２苯二酮（ＢＰＭＯＰＰ，简作Ｈ２Ｌ）稀土配合物。元素分析确定其化学组成为ＲＥ２Ｌ３·ｎＨ２Ｏ。通过电子光谱、红外光谱、核磁共振谱、热谱、摩尔电导等进行了表征，并讨论了配合物的性质。     

六氟磷酸二（4,4‘—二甲基—2,2’—联吡啶）.（2,2‘—联吡啶—4,4’—二羧？…

用＾１Ｈ ＮＭＲ和＾１３Ｃ ＮＭＲ谱研究了新型电化学发光探针六氟磷酸二（４,４’;－二甲基－２,２‘－联吡啶）．（４．４’－二羧酸－２,２‘－联吡啶）合钌的立体结构,通过＾１Ｈ ＾１Ｈ ＣＯＳＹ,＾１３Ｃ－＾１Ｈ ＨＥＴＣＯＲ谱对其氢谱和碳谱中的各谱峰进行了归属,并给出了氢谱和碳谱峰的化学位移值。     

Formation of 1,10-disubstituted benzo

The first 1,10-heterodisubstituted benzo[c]cinnoline derivative 1 was prepared from the trinitrobiphenyl 2. Investigation of the mechanism of ring closure in 2, 5, and 8 revealed a complex reduction-oxidation-cyclization sequence. The mechanism is discussed in light of the stereoelectronic demands of the substituent functionalities. Benzo[c]cinnoline derivative 1 [C15H15N3S, monoclinic, P2(1)/c: a = 7.4063(3) A, b = 10.3739(5) A, c = 16.7642(8) A, beta = 91.816(1) degrees, Z = 4] and its 5-N-oxide 7(N5) [C18H18N3OS, triclinic, Pi: a = 8.1510(7) A, b = 8.6106(7) A, c = 12.102(1) A, alpha = 86.262(1) degrees, beta = 83.364(1) degrees, gamma = 74.711(1) degrees, Z = 4] were structurally characterized and showed a significant helical distortion of the heterocyclic ring. Oxidation of 1 with NCS or triamine 12 with PhI(OAc)2 led to a new heterocyclic ring system, ylide 13. Both benzo[c]cinnoline 1 and ylide 13 were characterized spectroscopically and the absorption spectra were correlated with the results of ZINDO calculations.     

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol(1)

The reaction of the title diketone (3) with phenyl Grignard produces (with rate constant k(1)) the conjugate base (6-M) of 10-hydroxy-10-phenylcyclooctadecanone (6), which is subsequently converted (with rate constant k(2)) to the conjugate base of the title diol, as a mixture of the cis (7, 55%) and trans (8, 45%) isomers. The ratio k(2)/k(1), 2.2 +/- 0.4, indicates that the carbonyl group in 6-M is 4.4 times as reactive as each carbonyl in 3. Competition experiments further demonstrate that the relative rates (per carbonyl) for addition of phenylmagnesium bromide to 3, 10-methylenecyclooctadecanone (11), and cyclopentadecanone (12) are 1.0:0.60:1.92. Possible reasons for this order of reactivity are discussed. Diols 7 and 8 undergo facile double dehydration to form the title diene 13, which is predicted by molecular mechanics calculations to be the most stable of the four possible symmetrical diene isomers. The structures of 7, 8, and 13 were secured by single-crystal X-ray studies.     

1,10-Phenanthrolinium ionic liquid crystals

The 1,10-phenanthrolinium cation is introduced as a new building block for the design of ionic liquid crystals. 1,10-Phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline were quaternized by reaction with 1,3-dibromopropane or 1,2-dibromoethane. The resulting cations were combined with dodecyl sulfate or dioctyl sulfosuccinate anions. The influence of both the cation and anion type on the thermal behavior was investigated. Several of the complexes exhibit mesomorphic behavior, with smectic E phases for the dodecyl sulfate salts and smectic A phases for the dioctyl sulfosuccinate salts. Structural models for the packing of the 1,10-phenanthrolinium and anionic moieties in the liquid-crystalline phases are presented. The ionic compounds show fluorescence in the solid state and in solution.     

Synthesis of 1,10-dimethylbicyclo[8.8.8]hexacosane and 1,10-dihydroxybicyclo[8.8.8]hexacosane

[structure: see text] 1,10-Dimethylbicyclo[8.8.8]hexacosane (1) and 1,10-dihydroxybicyclo[8.8.8]hexacosane (2) were prepared in 4% yield over seven steps and in 18% yield over three steps, respectively, starting from 1,10-cyclooctadecanedione. The identities and out,out conformations of these compounds were established by single-crystal X-ray analysis.     

Synthesis of Novel Substituted 1,10-Phenanthrolines

The syntheses of both 5-amino-6-nitro-1,10-phenanthroline and 5,6-diamino-1,10-phenanthroline (starting from 5-nitro-1,10-phenanthroline) are described in detail.