Synthesis and properties of a novel cyclic sulfilimine, 2-methyl-2,4,1-benzodithiazin-2-ium-1-ide

A novel cyclic sulfilimine, 2-methyl-2,4,1-benzodithiazin-2-ium-1-ide ( 4 ) was synthesized by deprotonation of the corresponding azasulfonium salt ( 3 ) with base. The compound 4 was oxidized with potassium permanganate to afford the sulfoximine 5 , exclusively. On refluxing in several solvents, compound 4 underwent a ring contraction to afford benzothiazole ( 8 ) via the 1,2-imino shift. The reaction of 4 with a variety of electrophiles, such as dialkyl acetylenedicarboxylate, acylating agents, diphenylcyclopropenone, and phenyl isocyanate, afforded ringopened adducts. Synthetic approaches to cyclic disulfonium ylides are also described.     

Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-

In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.     

Crystal and molecular structure of organosilicon titanium(iv) derivatives: (Me3Si)3SiTi(NEt2)3 and ClTi[N(SiMe3)2]3

An X-ray structural study of two titanium-containing organosilicon compounds, (Me₃Si)₃SiTi(NEt₂)₃ (1) and ClTi[N(SiMe₃)₂]₃ (2), has been performed. The conformation of molecule1 in a crystal is staggered (approximate inherentC ₃ symmetry), the Ti-Si and Ti-N bond lengths are 2.671(2) and 1.874–1.890(5) Å, respectively. A crystal of1 consists of one type of enantiomers (the space group is P4₁2₁2; the absolute configuration has been determined). The structure of2 studied previously has been refined to the value of R=0.029 on the basis of 3442 reflections (the absolute structure has been determined), the Ti-Cl and Ti-N bond lengths are 2.260(1) and 1.926(1) Å, respectively. The strong distortions in the symmetry of the valence environment of the N atoms in the molecules of1, 2, and related structures are caused by electronic effects, in which the conformation of the relevant molecular fragments plays a determining role.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1473–1476, August, 1993.     

复合阴离子稀土穴醚配合物的分子和晶体结构研究

首次合成了稀土元素镱的异硫氰酸、硝酸复合阴离子穴醚(2,2,2)配合物H2Yb(NCS)~3(NO3)~2.H2O.(2,2,2)。测定了它的晶体结构及红外光谱, 发现Yb^3+没有进入穴醚空穴, 它通过H2O桥以氢键与穴醚的O原子结合。经研究认为, 分子中2个H^+结合在穴醚中2个N原子上。与Yb^3+配位的异硫氰酸根、硝酸根及分子形成八配位的三角十二面几何构型。晶体属单斜晶系, 空间群:P2~1/n。     

Untersuchungen an Polyhalogeniden. XXII [1]. Dimethyldiphenylammoniumpolyiodide (Me2Ph2N)In mit n = 3, 13/3, 6, 8: Darstellung und strukturelle Charakterisierung eines Triiodids (Me2Ph2N)I3, Tridecaiodids (Me2Ph2N)3I13, Dodecaiodids (Me2Ph2N)2I12 und Hexadecaiodids (Me2Ph2N)2I16

Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me₂Ph₂N)I_n with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me₂Ph₂N)I₃, Tridecaiodide (Me₂Ph₂N)₃I₁₃, Dodecaiodide (Me₂Ph₂N)₂I₁₂, and Hexadecaiodide (Me₂Ph₂N)₂I₁₆ The new compounds [(CH₃)₂(C₆H₅)₂N]I₃, [(CH₃)₂(C₆H₅)₂N]₃I₁₃, [(CH₃)₂(C₆H₅)₂N]₂I₁₂ and [(CH₃)₂(C₆H₅)₂N]₂I₁₆ have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH₃)₂(C₆H₅)₂N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.     

Synthesis and molecular structure of 2,4,6‐tri[bis(diisopropylamino)boryl(methylamino)]borazine, [(NiPr2)2B(Me)N]3B3N3H3

Reaction of bis(diisopropylamino)(methylamino)borane, (NHⁱPr)₂B(NHMe), with 2,4,6‐trichloroborazine (ClBNH)₃ affords 2,4,6‐tri[bis(diisopropylamino)boryl(methylamino)]borazine, 2,4,6‐[(NⁱPr₂)₂B(Me)N]₃B₃N₃H₃, which is the first boryl‐borazine structurally characterized. According to the X‐ray single crystal structure and the chemical shifts of ¹¹B NMR resonances of boron atoms, compared with the aminoborane and borazine analogs, the borazine and boryl π‐systems are not coplanar either in the solid state or in organic solution. Copyright © 2002 John Wiley & Sons, Ltd.     

2-Imidazolines. III (1). 1-Aryl- and 1-acyl-2-amino-(ormethoxy)-4,5-diamino-4,5-dihydroimidazoles. Synthesis and properties

Diimmonium salt (5) reacts with guanidines (6) and o-methylisoureas (7) affording 2-amino-4,5-dimorpholinoimidazolines (9) . 1-Aryl-2-amino-4,5-dimorpholinoimidazolines lose the amino functionality under mild acidic conditions with formation of 2-amino-5-morpholinoimidazole derivatives (10) whereas 1-acyl derivatives undergo under the same conditions a ring expansion process leading to pyrimidine derivatives (13) .     

Coordination compounds of ethylhydrazine and 2,2,2-Trifluoroethylhydrazine; crystal and molecular structure of dichlorotetrakis(2,2,2-Trifluoroethylhydrazine) nickel(II)

Ethylhydrazine (EH) forms the complexes MX₂(EH)₂ (M = Co, Ni; X = Cl; M = Co, X = Br), NiBr₂(EH)₂(H₂O) and MX₂(EH) (M = Zn, Cd; X = Cl; M = Zn, X = Br). Spectroscopic evidence suggests that these all contain bridging hydrazine ligands, the cobalt and nickel complexes containing six coordinated metal atoms while the zinc and cadmium complexes are tetrahedral. 2,2,2-Trifluoroethylhydrazine (TFEH) in contrast, forms six coordinate complexes of the type MX₂(TFEH)₄ (M = Co, Zn, X = Br; M = Co, Ni, X = NCS; M = Ni, X = Cl) for which spectroscopic evidence points to unidentate coordination by the hydrazine. An X-ray crystal structure determination on NiCl₂(TFEH)₄ confirms that the hydrazine bonds to nickel through the NH₂ nitrogen only, in a tetragonal structure with axial chlorine atoms. One bis(TFEH) complex ZnBr₂(TFEH)₂ and one hexakis (TFEH) complex, NiBr₂(TFEH)₆, have also been isolated.     

Preparation and Structure of [Me3N(CF3)2BCCB(CF3)2NMe3]

Bis‐trimethylamine‐ethynyl‐di‐bis(trifluoromethyl)borane [Me₃N(CF₃)₂BCCB(CF₃)₂NMe₃] ( 1 ) has been prepared from trimethylamine‐ethynyl‐bis(trifluoromethyl)borane, [HCCB(CF₃)₂NMe₃], and dimethylamino‐bis(trifluoromethyl)borane, (CF₃)₂BNMe₂. The structure of 1 has been determined by x‐ray crystallography. In the solid state the molecule possesses crystallographic C_i symmetry. The acetylenic attachment to the boron atom is characterized by a short B–C bond length of 1.565(4) Å and an essentially linear B–C–C′ bond angle of 178.1(4)°.     

Design and synthesis of 3-acyl-2(3H)-benzoxazolone and 3-acyl-2(3H)-benzothiazolone derivatives

Abstract  

A simpler and efficient “green” method using solid sodium hydroxide in a solvent mixture of acetone/water was found to catalyze N-acylation of 2(3H)-benzoxazolones and 2(3H)-benzothiazolones for facile and rapid synthesis of N-acyl derivatives in excellent yields. This method was applied to the synthesis of a series of 132 compounds employing a variety of acyl chlorides.     

1,1,3,3-Tetramethylguanidine-gallane, (Me2N)2CN(H).GaH3: an unusually strongly bound gallane adduct

The novel adduct 1,1,3,3-tetramethylguanidine-gallane, (Me2N)2CN(H).GaH3, has been prepared by the reaction of [(Me2N)2CNH2]+Cl- with LiGaH4 in Et2O solution. Its spectroscopic properties indicate a monomeric species with an unusually strong coordinate link between the imido function and GaH3, an inference confirmed by the crystal structure at 150 K which also reveals significant secondary interactions through non-classical N-H...H-Ga bridges. Despite the intrinsic strength of the Ga-N bond, however, vaporisation at ca. 310 K occurs with partial dissociation, and decomposition via more than one pathway proceeds at temperatures >330-350 K to give a variety of products, including the free base, Me2NH, H2, and a novel gallium-nitrogen compound composed of a Ga4N4 cubane-like core bridged on three edges by -N{C(NMe2)2}GaH2- units.     

Pentacarbonylmanganato-Mn)1,3-bis(2-chlorophenyl)-1-triazenato-N 1,N 3-mercury. Preparation,properties, crystal and molecular structure

Summary Mixed mercury complexes of the type (2-XC₆H₄)₂-N₃HgMn(CO)₅ (X = F, Cl, Br or I) have been prepared by synproportionation of the respective symmetric compounds. The new air-stable complexes were characterized by i.r., u.V., n.m.r. and mass spectroscopy. The molecular structure of the title compound shows bidendate bonding of the triazenato ligand to mercury: Hg-N(1), 231 pm; Hg-N(3), 243 pm; Mn-Hg-N(1), 161 deg; Mn-Hg-N(3), 146 deg. The smallest Hg...Cl intramolecular nonbonding distance is 334 pm.