CRYSTAL STRUCTURE OF THE METHYL 4—（N—（1—OXYPROPYL）—N—PHENYLAMINO]—1—[2—（2—THIENYL）ETHYL]—4—PIPERIDINECARBOXYLATE（R31826）HYDROCHLORIDE

<正> C22H28N2O3S.HCl, Mr = 436.9, triclinic,P1;a=8.557(3),b= 10.299(2),c= 13.894(2)A;α= 99.25(1),β=86.64(2),γ= 107.68(2)°;V= 1151.2(3)A3,Z= 2, DC = 1.27g/cm3,R=0.064. The torsion angle C(14)-C(1)-N(2)-0(19) in the title compound is 137.5 being much larger than that (106°) in R30730. The dihedral angle between mean planes of the thiophene ring and piperidine ring is about 83 .     

Preparation of 4,4a,9,9a-tetrahydrocarbazoles and 1,3a,4,8b-tetra-hydrocyclopenta[b]indoles

Halocyclization of mesylates or tosylates of 2-(cycloalk-2-en-1-yl)anilines gives N-methanesulfonyl-or N-toluenesulfonyl-1-halo-1,2,3,4,4a,9a-hexahydrocarbazoles, heating of which in DMF at 160°C or in piperidine at 110°C leads to 4,4a,9,9a-tetrahydro-3H-carbazoles. Heating N-methanesulfonyl-1-iodo-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole in DMF at 180—200°C gives 1,3a,4,9b-tetrahydrocyclopenta[b]indole, while in the presence of an ortho-methyl substituent the dehydroiodination reaction proceeds in piperidine at 110°C in high yield. The effect of the nature of the ortho substituent of N-methyl-1-iodo-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole on the conformational equilibrium of the cyclopentane ring has been established by ¹H NMR spectroscopy. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1184–1190, August, 2006.     

Formation of fluorene and anthracene derivatives in reactions of perfluorinated 1-alkyl-1-phenyl- and 1-alkyl-2-phenyl-1,2-dihydrocylobutabenzenes with antimony pentafluoride

The reaction of perfluoro(1-methyl-1-phenyl-1,2-dihydrocyclobutabenzene) with SbF₅ at 50°C, followed by hydrolysis, gave perfluoro(1-phenylindan-1-ol), while analogous reaction at 90°C afforded perfluoro[10-methylanthracen-9(10H)-one]. Perfluoro(1-methyl-2-phenyl-1,2-dihydrocyclobutabenzene) did not undergo skeletal transformations under analogous conditions, whereas at 200°C it was converted mainly into perfluoro(9-methylfluoren-9-ol). Perfluoro(1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzene) reacted with SbF5 at 200°C to form perfluoro(9-ethylfluoren-9-ol) together with perfluorinated 9,9-dimethyl- and 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorenes.     

Acyl- und Alkylidenphosphane. XII [1]. Synthese und Eigenschaften des 2,2-Dimethylpropionylphosphans und einiger Derivate

Acyl and alkylidene phosphines. XII. Syntheses and properties of 2,2-dimethylpropionylphosphine and of some derivatives At ?25°C bis(trimethylsilyl)phosphine 1b and 2,2-dimethylpropionyl chloride form (2,2-dimethylpropionyl)trimethylsilylphosphine 2b . As this compound is thermally more stable than similar acyltrimethylsilylphosphines, it might be treated at ?55°C with methyllithium to form the correspondig lithium phosphide 2d ; after the addition of chlorotrimethylsilane [2,2-dimethyl-1-(trimethylsiloxy)propylidene]-trimethylsilylphosphine 3c is obtained. At +20°C 2b rearranges to the E and Z isomer of [2,2-dimethyl-1-(trimethylsiloxy)propylidene]phosphine 3b . The NMR data of E- 3b and Z- 3b differ mostly in the coupling constants. Kept in the diffuse daylight for several days 3b dimerizes to form 2,4-di(tert.butyl)-2,4-bis(trimethylsiloxy)-1,3-diphosphetane 10 . In solution 10 is unstable and decomposes again to a mixture of the E und Z isomer of 3b . Reacting 3b or 3c with alcoholes all trimethylsilyl groups are replaced by hydrogen atoms and unstable 2,2-dimethylpropionylphosphane 4b is formed. Lithium(2,2-dimethylpropionyl)phosphide 4d , synthesized at ?60°C from 4b and methyllithium, crystallizes with one molecule 1,2-dimethoxyethane per formula unit and is dimeric in benzene. As shown by the NMR data 4d has the structure of an alkylidene-phosphine with the lithium atom bound to oxygen. At ?50°C 4d and chlorotrimethylsilane react to form 3b .     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Diazotization of Methyl 3-Amino-7-Isopropyl-2-Methoxyazulene-1-Carboxylate and its 5-Isopropyl Isomer- a Convenient Synthesis of 1,2-Azulenequinone Derivatives

Methyl 3-amino-2-methoxy-7-isopropylazulene-l-carboxylate( 8a ) and its 5-isopropyl isomer ( 8b ) were synthesized by reduction of the 3-nitro derivatives ( 7a,b ) with zinc/acetic acid in excellent yields. 7a and 7b were prepared by nitration and methylation of methyl 7-isopropyl-2-hydroxyazulene-l-carboxylate ( 5a ) and methyl 5-isopropyl-2-hydroxyazulene-l-carboxylate ( 5b ), respectively. Diazotization of 8a with sodium nitrite in trifluoroacetic acid at 0 °C gave methyl 5-isopropyl-1,2-azulenequinone-3-carboxylate ( 9a ) in 91% yield. Similar reaction of 8b gave the corresponding methyl 7-isopropyl-1,2-azulenequinone-3-carboxylate ( 9b ) in 93% yield. No evidence for the formation of l-diazo-1,2-azulenequinones was obtained.     

Bis(1,2-dimethoxyethan-O,O′)lithium-phosphanid, -arsanid und -chlorid – drei neue Vertreter des Bis(1,2-dimethoxyethan-O,O′)lithium-bromid-Typs

Metal Derivatives of Molecular Compounds. IX. Bis(1,2-dimethoxyethane- O,O′ )lithium Phosphanide, Arsanide, and Chloride – Three New Representatives of the Bis(1,2-dimethoxyethane- O,O′ )lithium Bromide Type Experiments to obtain thermally unstable lithium silylphosphanide at –60 °C from a 1,2-dimethoxyethane solution resulted in the isolation of its dismutation product bis(1,2-dimethoxyethane-O,O′)lithium phosphanide ( 1 ). The homologous arsanide 2 precipitated after a frozen solution of arsane in the same solvent had been treated with lithium n-butanide at –78 °C. Unexpectedly, too, the analogous chloride 3 and bromide 4 were formed in reactions of 1-chloro-2,2-bis(trimethylsilyl)-1λ³-phosphaethene with (1,2-dimethoxyethane-O,O′)lithium bis(trimethylsilyl)stibanide and of lithium 1,2,3,4,5-pentaphenyl-2,3-dihydro-1λ³-phosphol-3-ide with ω-bromostyrene, respectively. The monomeric complexes 1 {–100 ± 3 °C; a = 1391.1(4); b = 809.8(2); c = 1249.1(3) pm; β = 102.84(2)°}, 2 {–100 ± 3 °C; a = 1398.3(4); b = 819.8(3); c = 1258.5(4) pm; β = 103.35(2)°} and 3 {–100 ± 3 °C; a = 1308.4(2); b = 788.2(1); c = 1195.6(1) pm; β = 95.35(1)°} crystallize in the monoclinic space group C2/c with four solvated ion pairs in the unit cell; they are isotypic with bis(1,2-dimethoxyethane-O,O′)lithium bromide ( 4 ) {–73 ± 2 °C; a = 1319.0(2); b = 794.1(1); c = 1214.3(2) pm; β = 96.22(1)°}, already studied by Rogers et al. [13] at room temperature. The neutral complexes show a trigonal bipyramidal configuration of symmetry C₂, pnicogenanide or halide anions occupying equatorial sites {Li–P 260.4(4); Li–As 269.8(6); Li–Cl 238.6(7); Li–Br 256.3(10) pm} and the chelate ligands spanning equatorial and axial positions {Li–O_eq 205.4(4) to 207.4(4); Li–O_ax 208.9(3) to 215.5(2) pm}. The coordination within the (dme)₂Li fragment, the Li–X distances (X = P, As, Cl, Br), the structure of the chelate rings, and the packing of the neutral complexes are discussed in detail.     

Formation of 6‐Methyl‐7,11‐diphenylheptaleno[1,2‐c]furanones

The dehydrogenation reaction of a mixture of heptalene‐1,2‐ and heptalene‐4,5‐dimethanols 4a and 4b with basic MnO₂ in AcOEt at room temperature led to the formation of the corresponding heptaleno[1,2‐c]furan‐1‐one 6a and heptaleno[1,2‐c]furan‐3‐one 7a (Scheme 2). Both products can be isolated by chromatography on silica gel. The methylenation of the furan‐3‐one 7a with 1 mol‐equiv. of Tebbe's reagent at ?25 to ?30° afforded the 2‐isopropenyl‐5‐methylheptalene‐1‐methanol 9a , instead of the expected 3,6‐dimethylheptaleno[1,2‐c]furan 8 (Scheme 3). Also, the treatment of 7a with Takai's reagent did not lead to the formation of 8 . On standing in solution at room temperature, or more rapidly on heating at 60°, heptalene 9a undergoes a reversible double‐bond shift (DBS) to 9b with an equilibrium ratio of 1 : 1.     

螯形主体分子的设计、包结性能及其在细辛挥发油 有效成分选择分离中的应用

设计了两种新的具有螯形骨架的主体分子反式-1,2-二苯基-1,2-苊二醇(1)和顺式-1,2-二(1'-萘基)-1,2-苊二醇(2),主体(1),(2)可与许多有机小分子化合物形成配位包合物。用IR和粉末XRD表征了主体分子(1)和(2)的包结物,用^1NMR测定了包结物的主客体分子摩尔比：(1)·DMF(1:2),(1)·DMSO(1:2),(1)·THF(1:2),(1)·二氧六环(1:1),(1)·吡啶(1:1),(2)·DMF(1:1)和(2)·DMSO(1:1)。单晶X射线衍射分析了包结物的晶体结构,(1)·DMF：空间群Pnaa,a=0.9377(1)nm,b=1.4351(1)nm,c=4.0463(3)nm;(1)·DMSO：空间群Pbcn,a=1.6278(1)nm,b=1.0751(1)nm,c=1.4980(1)nm;(2)·DMF：P2~1/n,a=0.9796(1)nm,b=1.2377(1)nm,c=2.2344(3)nm,β=93.02(1)°;游离主体(1)：空间群P1,a=1.0461(1)nm,b=1.1213(1)nm,c=1.5496(1)nm,α=81.74(1)°,β=75.71(1)°,γ=89.00(1)°;分析了主体分子的刚性和柔韧性对包结性能的影响。并研究了主体分子(1)选择分离细辛挥发油,将顺甲基异丁香酚从挥发油中分离出来。     

Acyl- und Alkylidenarsane. VII. Tetrakis(2,2-dimethylpropionyl)diarsan - Darstellung und struktur

Acyl- and Alkylidenearsines VII Synthesis and Structure of Tetrakis(2,2-dimethylpropionyl)diarsine Lithium dihydrogenarsenide and 2,2-dimethylpropionyl chloride in a molar ratio of 3:2 react at ?40 to ?50°C in tetrahydrofuran or 1,2-dimethoxyethane to give the corresponding etherate of lithium bis(2,2-dimethylpropionyl)arsenide ( 2a ). Treatment of these solutions with stoichiometric amounts of 85% tetrafluoroboric acid · diethylether adduct yields yelloworange tetrakis(2,2-dimethylpropionyl)diarsine ( 5 ) in 64 or 62% yield resp., but not the expected bis (2,2-dimethylpropionyl)arsine ( 4a ). The very air-sensitive compound crystallizes in the monoclinic space group P2₁/n {?100 ± 3° C; a = 1224.6(3); b = 1419.7(3); c = 1333.1(3) pm; β = 96.22(2)°; Z = 4}. According to the X-ray structure analysis (R_w = 0.036) the molecule shows synclinal conformation; the two diacylarsyl-subunits are twisted against one another by an angle of 86°. As in another acylarsine [1] the As? C distances (203 to 205 pm) were found to be significantly longer then the standard value of 196 pm. Further characteristic bond lengths and angles are: As– 242; C? O 120 to 121 pm; As? As? C 88 to 107°; As? C? O 118 to 122°     

Über Chalkogenolate. 161. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 3. Kristall- und MolekülStruktur von 1,2-Ethan-bis(methyltrithiocarbonat)

On Chalcogenolates. 161. Reaction of 1,2-Ethanedithiolates with Carbon Disulfides. 3. Crystal and Molecular Structure of 1,2-Ethane-bis(methyltrithiocarbonate) The title compound H₃CS? CS? SCH₂CH₂S? CS? SCH₃ crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 6.769(1) Å, b = 8,334(2) Å, c = 11.222(1) Å, α = 80.93(1)°, β = 72.01(1)°, γ = 78.58(2)°. The crystal structure has been determined from single crystal X-ray data measured at ?40°C and refined to a conventional R of 0.035 for 2004 independent reflections (R_w = 0.042). The structure consists of isolated molecules, which are linked together by weak interaction forces. The S? CS? S groups are plane.     

Steric carbonyl protection metalation and cleavage of highly hindered ureas. Preliminary communication

Ureas of type 3 with sterically protected carbonyl groups such as 4a-7a are prepared by successively adding 2 equivalents of a highly substituted sec. amine and an excess of dimethylamine to benzene or toluene solutions of phosgene. The piperidine derivatives 6a and 7a are metalated in high yields to 6b and 7b , respectively, with sec.-butyllithium/TMEDA in THF at 0° [see derivatives 6, 7 , ( c-i ) in Table 1]. Methods of cleaving urethanes 2 (see 8 → 9 ) and ureas 3 are described, among which the retro-Mannich reaction, removing the piperidine ring from 7 under acidic hydrolysis conditions, appears to be promising also for other applications of sterically blocked carbonyl compounds in organic synthesis.     

Synthese und Kristallstrukturen der Samarium-Komplexe [SmI2(DME)3] und [Sm2I(NPPh3)5(DME)]

Synthesis and Crystal Structures of the Samarium Complexes [SmI₂(DME)₃] and [Sm₂I(NPPh₃)₅(DME)] When treated with ultrasound, the reaction of samarium metal with N-iodine-triphenylphosphaneimine in 1,2-dimethoxyethane (DME) leads to the two samarium complexes [SmI₂(DME)₃] ( 1 ) and [Sm₂I(NPPh₃)₅(DME)] ( 2 ), which are separated from each other by fractional crystallization. 1 could be isolated in two different crystallographic forms, namely as brownish black crystals ( 1 a ) and as violet-black crystals ( 1 b ), both of them are characterized by crystal structure analyses. 1 a : Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1459.4(1), b = 1314.4(1), c = 2293.6(2) pm, β = 99.245(8)°, R = 0.0344. The structure of 1 a holds two crystallographically independent molecules [SmI₂(DME)₃], in which the samarium atoms have coordination number eight. The two individuals differ from each other particularly in their I–Sm–I bond angles, which are 157.94 and 178.45°. 1 b : Space group P2₁, Z = 2, lattice dimensions at –80 °C: a = 849.4(3), b = 1060.1(3), c = 1235.1(6) pm, b = 93.86(5)°, R = 0.0251. 1 b has a molecular structure similar to that of 1a with a bond angle I–Sm–I of 158.40°. The phosphoraneiminato complex [Sm₂I(NPPh₃)₅(DME)] ( 2 ) forms colourless, moisture sensitive crystals which contain two molecules DME per formula unit. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1405.0(4), b = 1656.5(3), c = 2208.3(7) pm, α = 89.60(3)°, β = 72.96(4)°, γ = 78.70(3)°, R = 0.0408. In 2 the two samarium atoms are linked via the μ-N atoms of two phosphoraneiminato ligands to form a planar Sm₂N₂ four-membered ring. One of the Sm atoms is terminally coordinated by the N atoms of two (NPPh₃)^– groups, thus achieving a distorted tetrahedral surrounding. The second Sm atom is coordinated by the N atom of one (NPPh₃)^– group, by the terminally bonded iodine atom, and by the O atoms of the DME chelate, thus achieving a distorted octahedral surrounding.     

5,12-Diacylated-5,6,11,12-tetrahydrodibenzo[b,f][1,4]-diazocines and related compounds

Both N,N′ -(o-phenylene)diformamide (1) and N,N′ -(4-chloro-1,2-phenylene)diformamide (30) reacted with α,α-dibromo-o-xylene (2) in DMF at 95–100° to give 5,6,11,12-tetrahydrodibenzo-[b,f][1,4]diazocine-5,12-dicarboxaldehyde (3a) and the corresponding 2-chloro derivative (3b). With potassium hydroxide in ethylene glycol at 110°, 3a and 3b were selectively saponified to the 5-carboxaldehyde derivatives (4) and either 21a or 22a. Reacylation of the latter led to a series of 5,12-unsymmetrically diacylated derivatives, 5–18. Additionally, 4 was subjected (a) to a basecatalyzed addition to acrylonitrile to give the 12-cyanoethyl derivative (19) and (b) alkylation with α-bromotoluene to give the 12-benzyl compound (20). Saponification of both carboxaldehyde groups in 3a,b required potassium hydroxide in ethylene glycol at 135° and gave the N,N′ -unsubstituted heterocycles (23 and 24) ; these were subsequently reacted with several aldehydes to yield the 5,12-methano derivatives (25–29) .     

The hydroxyacetylpiperidines and their N-benzyl derivatives. The 2-hydroxymethyl-2-piperidyl- and 2-hydroxymethyl-2-pyridyl-1,3-dioxolanes

The hydroxyacetylpiperidines, their ethylene ketals, and the N-benzyl derivatives of these new piperidines have been synthesized. Methylolation of 2-(2- and 4-pyridyl)-1,3-dioxolanes by heating with paraformaldehyde at 185° led to 2-hydroxymethyl-2-(2- and 4-pyridyl)-i,3-dioxolanes ( 7,8 , respectively). 2-Hydroxymethyl-2-(3-pyridyl)-1,3-dioxolane ( 13 ) was obtained by reaction of 2-bromomethyl-2-(3-pyridyl)-1,3-dioxolane with aqueous sodium hydroxide at 190°. Hydrogenation of these pyridine ketals with rhodium-charcoal catalyst produced the corresponding piperidine ketals (16,17,18). Acid hydrolysis of the piperidine ketals and their N-benzyl derivatives led to the hydroxyacetylpiperidines (1,2,3) and their N-benzyl derivatives (25,26,27). The N-benzylhydroxyacetylpiperidines undergo rapid hydrogenolysis with palladium-charcoal catalyst to produce the hydroxyacetylpiperidines. Further hydrogenation produces the piperidyl-1,2-ethanediols. The hydroxyacetylpiperidines are somewhat unstable, hygroscopic substances which polymerize with dehydration on standing; in solution they are relatively stable. Their N-benzyl, ketal, and hydrochloride salt derivatives, on the other hand, represent stable, synthetically useful intermediates from which the reactive trifunctional hydroxyacetylpiperidines may readily be prepared.     

Cycloadditionsreaktionen von Isocyaniden an Bis[tris(trimethylsilyl)methyl]diphosphen

Cycloaddition Reactions of Isocyanides with Bis[tris(trimethylsilyl)methyl]diphosphene The [2 + 1] cycloaddition reactions of isocyanoacetonitrile ( 1 a ), pentacarbonyl(diisocyanomethane)chromium ( 1 b ), and 2,2,2-trifluoroethylisocyanide ( 1 c ) with the diphosphene R–P=P–R (R = C[Si(CH₃)₃]) ( 2 ) yield the expected diphosphirane imines 3 a – c . All compounds are thermally very stable and show no evidence for a [2 + 1] cycloreversion reaction. The structures of 3 a : triclinic, P 1, a = 918.0(2), b = 1174.7(4), c = 1821.9(5) pm, α = 93.83(2), β = 97.22(2)°, γ = 97.08(2)°, Z = 2, R₁ = 0.069; 3 c : monoclinic, P2₁, a = 928.6(2), b = 1659.8(3), c = 1261.2(3) pm, β = 107.65(2)°, Z = 2, R₁ = 0.073, and 1,2-Bis[tris(trimethylsilyl)]methyl-N-trifluormethyl-3-diphosphiranimin: monoclinic, P2₁/n, a = 1374.6(3), b = 1685.9(1), c = 1658.6(5) pm, β = 108.99(9)°, Z = 4, R₁ = 0.092, were elucidated by X-ray crystallography. All three compounds possess a similar three membered PCP ring system with an exocyclic C–N double bond.     

Synthesis and Characterization of Cobalt(II), Nickel(II), and Zinc(II) Complexes with N,N ′-bis( Trans- Cinnamaldehyde)-1,2-Diiminoethane Ligand, (ca 2 en): Crystal and Molecular Structures of Co(ca 2 en)Cl 2 , Co(ca 2 en)Br 2 and Ni(ca 2 en)Br 2

A series of new complexes of the Schiff base obtained from trans- cinnamaldehyde and 1,2-diaminoethane (en) with the general formula of M(ca 2 en)X 2 (M = Co(II), Ni(II), Zn(II); X = Cl, Br, I, NCS, N 3 ; (ca 2 en) = N,N '-bis( trans- cinnamaldehyde)-1,2-diiminoethane) have been synthesized and characterized. The crystal structures of three pseudo -tetrahedral complexes, Co(ca 2 en)Cl 2 ( 1 ), Co(ca 2 en)Br 2 ( 2 ), and Ni(ca 2 en)Br 2 ( 5 ), were determined by X-ray diffraction. Crystal data for 1 , Co(ca 2 en)Cl 2 : monoclinic; space group P 2 1 / c ; a = 7.1925(14) Å, b = 20.327(4) Å, c = 14.029(3) Å; g =95.06(3)°; V = 2043.1(7) Å 3 ; Z = 4; and final R 1 = 0.0381 ( wR 2 = 0.0718) for 4653 independent reflections with I > 2 σ ( I ) and 226 parameters; 2 , Co(ca 2 en)Br 2 ; monoclinic, space group P 2 1 / c ; a = 7.3780(6) Å, b = 20.4372(17) Å, c = 14.1649(12) Å; g = 94.902(2)°; V = 2128.1(3) Å 3 ; Z = 4; and final R 1 = 0.0491 ( wR 2 = 0.1052) for 5858 independent reflections with I > 2 σ ( I ) and 227 parameters; 5 , Ni(ca 2 en)Br 2 : monoclinic, space group P 2 1 / c ; a = 7.2388(6) Å, b = 20.4651(16) Å, c = 14.2782(12) Å; g = 94.160(2)°; V = 2109.6(3) Å 3 ; Z = 4; R 1 = 0.0481 ( wR 2 = 0.0907) for 5914 independent reflections with I > 2 σ ( I ) and 227 parameters. The structures consist of discrete molecules in which the coordination polyhedra about the central metal ion are highly distorted tetrahedra with Cl(1)-Co-Cl(2), 115.51(3)°; N(1)-Co-N(2), 83.71(7)°; Br(1)-Co-Br(2), 114.58(4)°; N(1)-Co-N(2), 84.92(19)°; and Br(1)-Ni-Br(2), 125.23(3)°; N(1)-Ni-N(2), 85.11(15)° in 1 , 2 , and 5 , respectively. The stiryl groups are cis -endo with respect to the metal atom and the chelate ring is puckered. Utilization is made of electronic and vibrational spectra in structural diagnosis of other complexes.     

N,O‐chelate aluminum and zinc complexes: synthesis and catalysis in the ring‐opening polymerization of ε‐caprolactone

Reaction between 2‐(1H‐pyrrol‐1‐yl)benzenamine and 2‐hydroxybenzaldehyde or 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde afforded 2‐(4,5‐dihydropyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL¹NH, 1a) or 2,4‐di‐tert‐butyl‐6‐(4,5‐dihydropyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL²NH, 1b). Both 1a and 1b can be converted to 2‐(H‐pyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL³N, 2a) and 2,4‐di‐tert‐butyl‐6‐(H‐pyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL⁴N, 2b), respectively, by heating 1a and 1b in toluene. Treatment of 1b with an equivalent of AlEt₃ afforded [Al(Et₂)(OL²NH)] (3). Reaction of 1b with two equivalents of AlR₃ (R = Me, Et) gave dinuclear aluminum complexes [(AlR₂)₂(OL²N)] (R = Me, 4a; R = Et, 4b). Refluxing the toluene solution of 4a and 4b, respectively, generated [Al(R₂)(OL⁴N)] (R = Me, 5a; R = Et, 5b). Complexes 5a and 5b were also obtained either by refluxing a mixture of 1b and two equivalents of AlR₃ (R = Me, Et) in toluene or by treatment of 2b with an equivalent of AlR₃ (R = Me, Et). Reaction of 2a with an equivalent of AlMe₃ afforded [Al(Me₂)(OL³N)] (5c). Treatment of 1b with an equivalent of ZnEt₂ at room temperature gave [Zn(Et)(OL²NH)] (6), while reaction of 1b with 0.5 equivalent of ZnEt₂ at 40 °C afforded [Zn(OL²NH)₂] (7). Reaction of 1b with two equivalents of ZnEt₂ from room temperature to 60 °C yielded [Zn(Et)(OL⁴N)] (8). Compound 8 was also obtained either by reaction between 6 and an equivalent of ZnEt₂ from room temperature to 60 °C or by treatment of 2b with an equivalent of ZnEt₂ at room temperature. Reaction of 2b with 0.5 equivalent of ZnEt₂ at room temperature gave [Zn(OL⁴N)₂] (9), which was also formed by heating the toluene solution of 6. All novel compounds were characterized by NMR spectroscopy and elemental analyses. The structures of complexes 3, 5c and 6 were additionally characterized by single‐crystal X‐ray diffraction techniques. The catalysis of complexes 3, 4a, 5a–c, 6 and 8 toward the ring‐opening polymerization of ε‐caprolactone was evaluated. Copyright © 2008 John Wiley & Sons, Ltd.     

Metallderivate von Molekülverbindungen. III. Molekül- und Kristallstruktur des Lithium-bis (trimethylsilyl)-phosphids · DME und des Lithium-dihydrogenphosphids · DME

Metal Derivatives of Molecular Compounds. III. Molecular and Crystal Structure of Lithium bis(trimethylsilyl)phosphide · DME and of Lithium dihydrogenphosphide · DME Lithium bis(trimethylsilyl)phosphide · DME 1 prepared from tris(trimethylsilyl)-phosphine and lithium methanide [2, 4] in 1,2-dimethoxyethane

1 1,2-Dimethoxyethan (DME); Tetrahydrofuran (THF); Bis[2-(dimethylamino)ethyl]methyl-amin (PMDETA).

, crystallizes in the orthorhombic space group Pnnn {a = 881.1(9); b = 1308.5(9); c = 1563.4(9) pm at ?120 ± 3°C; Z = 4 formula units}, lithium dihydrogenphosphide · DME 2 [10] prepared from phosphine and lithium- n -butanide in the same solvent, in P2 ₁ 2 ₁ 2 ₁ {a = 671.8(1); b = 878.6(1); c = 1332.2(2) pm at ?120 ± 3°C; Z = 4 formula units}. X-ray structure determinations (R _w = 0.036/0.045) show the bis(trimethylsilyl) derivative 1 to be dimeric with a planar P? Li? P? Li ring (P? Li 256 pm; Li? P? Li 76°; P? Li? P 104°), and the dihydrogenphosphide 2 to be polymeric with a linear Li? P? Li fragment (P? Li 254 to 260 pm; Li? P? Li 177°; P? Li? P 118°). The shortened P? Si distance (221 pm) of compound 1 and the structure of the PH ₂ group in 2 are discussed in detail. Lithium obtains its preferred coordination number 4 by a chelation with one molecule of 1,2-dimethoxyethane (Li? O 202 to 204 pm).     

螯形二羟基主体分子的包结性能与其结构关系的研究

报道了螯形主体分子，反式－9，10－二－1'－萘基－9，10－菲二醇（1）， 能与多种含氮有机化合物，诸如喹啉、异喹啉、哌啶、二环已胺等形成包化合物； 而反式－9，10－二苄基－9，10－菲二醇（2）则不具有包结性能。还报道了这些 包结化合物的IR，粉末XRD的表征，用~1H NMR谱测定了它们的分子摩尔比，分别为 （1）／喹啉(1:2), (1)/异喹啉(1:2)，（1）／哌啶（1:2）和（1）／二环忆胺 (1:2)。用单晶X射线衍射法测定了（1）与二环忆胺包结物以及（2）的结构，结果 表明前者属正交晶系，空间群为Pnca(标准型Pbca)，晶胞参数: a = 1.6714(3) nm, b = 1.6875(3) nm, c = 1.7224(3) nm, V = 4.858 nm~3, Z = 8，形成了隧 道型配位笼状包合物。后者属三斜晶系，空间群为P1-bar，晶胞参数: a = 0. 8058(2) nm , b = 0.9715 (2) nm, c = 1.4437(3) nm, α = 109.59(3)°, β = 95.96(3)°, γ = 96.03(2)°, V = 1.0471 nm~3, Z = 2, 还比较了(1)和(2) 的结构差异，分析了(1)的结构和包结性能的关系。