The Meisenheimer Rearrangement in Heterocyclic Synthesis. IV. Derivatives of the 2H,6H-1,5,4-Benzodioxazocine and 7H-1,6,5-Benzodioxazonine Ring Systems: X-Ray Crystal Structure of 10-Methoxy-5-methyl-7-phenyl-2,3,4,5-tetrahydro-7H-1,6,5-benzodioxazonine

1988 ◽  
Vol 41 (3) ◽  
pp. 293 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
LM Engelhardt ◽  
IWK Gunawardana ◽  
AH White
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Ring System ◽  
Heterocyclic Synthesis ◽  
Rearrangement Product ◽  
Ring Systems ◽  
X Ray ◽  
Derivatives Of ◽  
Moderate Yield

Meisenheimer rearrangement of the N-oxides (4) derived from a series of 5-aryl-4-methyl-2,3,4,5-tetrahydro-1,4-benzoxazepines (3) gave rise to eight derivatives (5) of the new 2H,6H-1,5,4-benzodioxazocine ring system. Reaction of 9-methoxy-5-methyl-6-phenyl-3,4,5,6- tetrahydro-2H-1,5-benzoxazocine (6) with 3-chloroperoxybenzoic acid gave an unstable N-oxide (7). A Meisenheimer rearrangement product from (7), 10-methoxy-5-methyl-7-phenyl-2,3,4,5-tetrahydro-7 H-1,6,5- benzodioxazonine (8), the first example of this ring system, was isolated directly in moderate yield on oxidation of (6) with cooling. The crystal and molecular structure of (8) has been determined by X-ray crystallographic methods.

The Meisenheimer rearrangement in heterocyclic synthesis. II. Synthesis and X-ray crystal structure of a tetrahydro-1H-2,3-benzoxazocine and preparation of a hexahydro-2,3-benzoxazonine

1980 ◽  
Vol 33 (6) ◽  
pp. 1323 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
PE Davies ◽  
CLWAH Raston
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Acetic Acid ◽  
Crystal And Molecular Structure ◽  
Phosphorus Oxychloride ◽  
Crystallographic Analysis ◽  
Heterocyclic Synthesis ◽  
Reaction Conditions ◽  
X Ray ◽  
Heterocyclic Derivatives

The heterocyclic derivatives, 8,9-dimethoxy-3-methyl-1-phenyl-3,4,5,6- tetrahydro-1H-2,3-benzoxazocine(3a) and 9,10-dimethoxy-3-methyl-1- phenyl-1,3,4,5,6,7-hexahydro-2,3-benzoxazonine (3b),examples of two new ring systems, have been prepared by Meisenheimer rearrangement of the corresponding 2-benzazepine and 2-benzazocine N-oxide derivatives (2a) and (2b). The Bischler-Napieralski-type cyclization reaction was used in the preparation of the tertiary amine precursors of these N-oxides reaction conditions for the cyclization were critical and phosphorus oxychloride in refluxing butanenitrile was found to give the best yields of the seven- or eight-membered cyclic imine intermediates. Reductive cleavage of the benzoxazocine derivative (3a) with zinc in acetic acid followed by N-methylation gave the expected product, [2-{3- (dimethylamino)propyl}-4,5-di-methoxyphenyl]phenylmethanol (12). The crystal and molecular structure of (3a) has been determined by X-ray crystallographic analysis.

Derivatives of the Benzo[5,6]cyclohepta[1,2,3-Cd]thieno[3,2-C]pyridine System. X-Ray Crystal Structure of 8,9-Dimethoxy-1,2,3,6,11,11a-hexahydrobenzo[5,6]cyclohepta[1,2,3-Cd]thieno[3,2-C]pyridine-1-carbonitrile

1988 ◽  
Vol 41 (4) ◽  
pp. 575 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
LM Engelhardt ◽  
BA Hyland ◽  
GS James ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Cyanogen Bromide ◽  
Heterocyclic System ◽  
Crystal And Molecular Structure ◽  
Ring Cleavage ◽  
Methyl Derivative ◽  
X Ray ◽  
Derivatives Of ◽  
By Products

During attempts to prepare 9,10-dimethoxy-4,7,12,12a-tetrahydro-5H- benzo [g] thieno [3,2-a] quinolizine (1), and subsequent cyanogen bromide- induced ring cleavage of this tetracyclic base, two by-products were isolated. The preparations of these two compounds are described, and their structures elucidated as 8,9-dimethoxy-1,2,3,6,11,11a-hexahydrobenzo [5,6] cyclohepta [1,2,3-cd] thieno [3,2-c]pyridine (5a), and its 1-carbonitrile derivative (5b). An N-methyl derivative (5c) has been prepared from (5a). These products (5) are the first examples of a new heterocyclic system. The crystal and molecular structure of the cyanamide (5b) has been determined by X-ray crystallographic methods.

Crystal Structure of (NH4)2[Mo3S(S2)6] Containing the Novel Isolated Cluster [MO3S13]2-

1979 ◽  
Vol 34 (3) ◽  
pp. 434-436 ◽  
Author(s):  
A. Müller ◽  
S. Pohl ◽  
M. Dartmann ◽  
J. P. Cohen ◽  
J. M. Bennett ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Aqueous Solutions ◽  
Single Crystal ◽  
Ammonium Salt ◽  
Crystal And Molecular Structure ◽  
Monoclinic Space Group ◽  
The Novel ◽  
Mean Values ◽  
X Ray

Abstract The novel tri-nuclear metal-sulfur cluster [Mo3S(S2)6]2- can be obtained as its ammonium salt by the reaction of a Moiv containing aqueous solutions with polysulfide. Its crystal and molecular structure has been determined by a single crystal X-ray study. The crystals are monoclinic (space group Cm, with a = 11.577(6) Å, b = 16.448(7) Å, c = 5.716(2) Å, β = 117.30(3)°, V = 967.2 Å3 , Z = 2, dexptl. = 2.54(2) g/cm3 , dcal = 2.54 g/cm3). The structure consists of isolated [Mo3S(S2)6]2- units, with three Mo atoms at the vertices of a triangle. There are bridging as well as terminal S22--ligands lying above and below the Mo3-plane (bond distances: Mo-Mo = 2.722 Å, Mo-S(terminal) = 2.435, Mo-S(bridging) = 2.452, Mo3-S = 2.353(4) Å and S-S = 2.04 Å (mean values)).

The crystal structure of dibutyl-bis(pentamethylenedithiocarbamato)tin(IV)

1986 ◽  
Vol 51 (11) ◽  
pp. 2521-2527 ◽  
Author(s):  
Jan Lokaj ◽  
Eleonóra Kellö ◽  
Viktor Kettmann ◽  
Viktor Vrábel ◽  
Vladimír Rattay
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Coordination Polyhedron ◽  
Crystal And Molecular Structure ◽  
Distorted Octahedron ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray

The crystal and molecular structure of SnBu2(pmdtc)2 has been solved by X-ray diffraction methods and refined by a block-diagonal least-squares procedure to R = 0.083 for 895 observed reflections. Monoclinic, space group C2, a = 19.893(6), b = 7.773(8), c = 12.947(8) . 10-10 m, β = 129.07(5)°, Z = 2, C20H38N2S4Sn. Measured and calculated densities are Dm = 1.38(2), Dc = 1.36 Mg m-3. Sn atom, placed on the twofold axes, is coordinated with four S atoms in the distances Sn-S 2.966(6) and 2.476(3) . 10-10 m. Coordination polyhedron is a strongly distorted octahedron. Ligand S2CN is planar.

Crystal and Molecular Structure of 3-Iodo-2-propynyl-N-butylcarbamate

1997 ◽  
Vol 52 (2) ◽  
pp. 256-258 ◽  
Author(s):  
Evgeni V. Avtomonov ◽  
Rainer Grüning ◽  
Jörg Lorberth
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Title Compound ◽  
Crystal And Molecular Structure ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Dimensional Network ◽  
Carbamate Group ◽  
Oxygen Atoms

Abstract The crystal structure of the title compound has been determined by X-ray diffraction methods. Due to the Lewis acidic character of the iodine substituent a “zig-zag” chain is formed via intermolecular interactions (2.933(4) A) between iodine and oxygen atoms of theocarbamate moiety. A three-dimensional network is formed through hydrogen-bridging (2.04 A) between NH-groups and the oxygen atoms of the neighbouring carbamate group of the next molecule.

The Crystal Structure of the Tetrameric Adduct of Antimony Trichloride and Phosphoryl Isothiocyanate, [SbCl3·OP(NCS)3]4

1994 ◽  
Vol 49 (4) ◽  
pp. 441-444 ◽  
Author(s):  
Alexander V. Sienkiewicz ◽  
Anatoliy A. Kapshuk
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Antimony Trichloride ◽  
Cage Structure ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cubic System ◽  
Tetrameric Complex

The crystal and molecular structure of the tetrameric complex of the composition [SbCl3·OP(NCS)3]4 synthesized from SbCl3 and OP(NCS)3 in CCl4 waso determined by X-ray crystallography [143 m space group, cubic system with a = 13.927(4) Å]. The complex exhibits a tetranuclear "cage" structure with a [Sb4O4] core which consists of μ3-bridging oxygen and six coordinate antimony(III) atoms; the Sb-O distance, 3.060 Å, is exceptionally long.

Preparation of Thieno[3,2-e][1,2]oxazepine, Thieno and [1]Benzothieno-[3,2-g][1,4]oxazonine, and 5H-Thieno and 1H-[1]Benzothieno-[3,2-h][1,5]oxazecine Derivatives by Ring Expansion Methods. X-Ray Crystal Structure of 1-Phenyl-1,3,4,5,6,7-hexahydro[1]benzothieno-[3,2-g][1,4]oxazonine-5-carbonitrile

1988 ◽  
Vol 41 (12) ◽  
pp. 1815 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
LM Engelhardt ◽  
CS Greenwood ◽  
AH White
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Tertiary Amine ◽  
Cyanogen Bromide ◽  
Crystal And Molecular Structure ◽  
Ring Expansion ◽  
Standard Methods ◽  
X Ray ◽  
Medium Ring

10-Phenyl-4,5,6,7,8,10-hexahydrothieno[3,2-g][1,4]oxazonine-6-carbonitrile (6a) and 11-phenyl-4,6,7,8,9,11-hexahydro-5H-thieno[3,2-h][1,5]oxazecine-6-carbonitrile (7a) were prepared in moderate yields by cyanogen bromide-induced ring expansion of tetrahydrothieno [2,3- c] pyridinylalkanol precursors (4a) and (5a), respectively. 1-Phenyl-1,3,4,5,6,7-hexahydro[1]- benzothieno [3,2-g][1,4]oxazonine-5-carbonitrile (6b) and 1-phenyl-3,4,5,6,7,8-hexahydro-1H- [1] benzothieno [3,2-h][1,5]oxazecine-6-carbonitrie (7b) were similarly prepared from the [1] benzothieno [2,3-c] pyridinylalkanol precursors (4b) and (5b). The medium-ring cyanamides (6b) and (7b) were converted by standard methods into their N-methyl analogues (8b) and (9b). 6-Methyl-8-phenyl-4,5,6,8-tetrahydrothieno[3,2-e][1,2] oxazepine (13) was prepared by thermal Meisenheimer rearrangement of the corresponding tertiary amine N-oxide (12). The compounds (6a, b), (7a, b) and (13) are each the first reported examples of new heterocyclic systems. The crystal and molecular structure of (6b) has been determined by X-ray crystallographic methods.

The coordination of the dimethylthallium ion in the crystal and molecular structure of 1,10-phenanthroline-dimethylthallium (III) perchlorate

1972 ◽  
Vol 331 (1585) ◽  
pp. 161-169 ◽  
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Single Crystal ◽  
Crystal And Molecular Structure ◽  
Pentagonal Bipyramid ◽  
Equatorial Position ◽  
Polymeric Structure ◽  
X Ray

A single crystal X-ray analysis of the crystal structure of [TlMe 2 1,10-phen]ClO 4 confirms the presence of a bent dimethylthallium group with a C-Tl-C angle of 168.3 (1.5)°. The thallium coordination is best described as a distorted pentagonal bipyramid with one equatorial position vacant. The equatorial bonds are predominantly electrostatic, and the perchlorate ions are bidentate giving rise to a polymeric structure in the crystal.

The Crystal and Molecular Structure of catena-{Aquabis[2-methyl-2-(phenylthio)-propanoato]cadmium(II) monohydrate}

1988 ◽  
Vol 41 (11) ◽  
pp. 1769 ◽  
Author(s):  
G Smith ◽  
EJ Oreilly ◽  
CHL Kennard ◽  
TCW Mak ◽  
WH Yip ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Chelate Ring ◽  
Propanoic Acid ◽  
Cadmium Complex ◽  
Carboxylate Group ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Carboxylate Groups

The crystal structure of the cadmium complex of 2-methyl-2-(phenylthio) propanoic acid, [ Cd (C6H5SC(CH3)2CO2)2(H2O)]. H2O has been determined by X-ray diffration and refined to a residual R 0.051 for 2725 observed reflections. Crystals are orthorhombic, space group Pbca with a 10.819(2), b 9.030(1), c 47.24(2) A and Z 8. The stereochemistry about cadmium is distorted MO6S seven-coordinate with Cd -S 2.747(2)Ǻ and a Cd -O range 2.277-2.491(5)Ǻ. Bonds are from cadmium to a water, and to four oxygens from two bidentate carboxylate groups, one of which also forms a polymer link. The same carboxylate group is also involved in a five- membered (S,O) chelate ring.

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