The Formation of Monomeric and Dimeric Nitro Nitrates in the Reaction of Phenanthrene With Nitrogen Dioxide: X-Ray Crystal Structure of trans-10-Nitro-9,10-dihydrophenanthren-9-yl Nitrate

1990 ◽  
Vol 43 (1) ◽  
pp. 125 ◽  
Author(s):  
MC Judd ◽  
MP Hartshorn ◽  
RJ Martyn ◽  
WT Robinson ◽  
GJ Wright ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Liquid Chromatography ◽  
Nitrogen Dioxide ◽  
Benzene Solution ◽  
Gas Liquid Chromatography ◽  
X Ray ◽  
Product Yields

Reaction of phenanthrene (1) with nitrogen dioxide in benzene solution gives the dimeric nitro nitrate (3), trans and cis nitro nitrates (7) and (8), and 9-nitro- (4), 3-nitro- (5) and 1-nitro-phenanthrene (6). The X-ray crystal structure of the trans nitro nitrate (7) is reported. The effect of the phenanthrene (1) concentration on product yields is reported. Gas-liquid chromatography results for the nitro nitrates (3) and (7) point to difficulties in using this technique for product analyses in reactions of phenanthrene (1) with nitrogen dioxide.

Reactions of 4-Methyl-2,6-diphenylphenol and 4-Nitro-2,6-diphenylphenol with Nitrogen Dioxide

1985 ◽  
Vol 38 (11) ◽  
pp. 1613 ◽  
Author(s):  
MP Hartshorn ◽  
RJ Martyn ◽  
WT Robinson ◽  
KH Sutton ◽  
J Vaughan ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Nitrogen Dioxide ◽  
Benzene Solution ◽  
Reaction Conditions ◽  
X Ray

Reaction of 4-methyl-2,6-diphenylphenol (11a) with nitrogen dioxide in benzene solution gives the polysubstituted cyclohex-2-enones (14), (15), (16), (17) and (18) via the 4-nitro dienone (13). The reversibility of the 4-nitro dienone (13)/4-hydroxy dienone (19) conversion under these reaction conditions is demonstrated. Reaction of 4-nitro-2,6-diphenylphenol (11b) with nitrogen dioxide in benzene solution gives the C2-epimeric 2,6-dihydroxy-4,5-dinitrocyclohex-3- enones (32) and (33) via the 6-nitro-6-phenyl dienone (12b). X-ray crystal structure analyses are reported for compounds (14), (15), (16), (17), (18) and (33).

The Nitration of 4,6-Disubstituted 2-Phenylphenols. Some Structural Studies

1985 ◽  
Vol 38 (4) ◽  
pp. 575 ◽  
Author(s):  
MP Hartshorn ◽  
WT Robinson ◽  
J Vaughan ◽  
JM White
Keyword(s):  
Crystal Structure ◽  
Nitrogen Dioxide ◽  
Structural Studies ◽  
X Ray ◽  
Structure Determinations

Nitration of the bromophenols (4a) and (5a) give products of nitro-debromination . Reaction of 6-methyl-4-nitro-2-phenylphenol (5c) with nitrogen dioxide gives 2-hydroxy-2-phenylcyclohex-3-enones (8) and (9), and probably stereoisomers (10), (20), (21) and (22). The mode of ormation of these compounds is discussed. X-ray crystal structure determinations are reported for compounds (8) and (9).

The X-ray crystal structure of 4-t-Butyl-r-2-(4'-t-butyl-2',6'-dimethyl-phenoxy)-t-6-hydroxy-2,6-dimethyl-t-5-nitrocyclohex-3-enone

1984 ◽  
Vol 37 (6) ◽  
pp. 1369
Author(s):  
MP Hartshorn ◽  
KH Sutton ◽  
J Vaughan
Keyword(s):  
Crystal Structure ◽  
Nitrogen Dioxide ◽  
Structure Determination ◽  
Crystal Structure Determination ◽  
Reduced Pressure ◽  
X Ray

The X-ray crystal structure determination of 4-t-butyl-r-2-(4'-t-butyl-2',6'-dimethylphenoxy)-t-6- hydroxy-2,6-dimethyl-t-5-nitrocyclohex-3-enone (3) is reported. This compound is formed by reaction of 4-t-butyl-2,6-dimethylphenol(1) with nitrogen dioxide (1 mol) in benzene, followed by removal of the benzene under reduced pressure.

Photochemical Nitration by Tetranitromethane. XXXII. Adduct Formation in the Photochemical Reaction of Phenanthrene and Tetranitromethane

1996 ◽  
Vol 49 (4) ◽  
pp. 469
Author(s):  
CP Butts ◽  
L Eberson ◽  
KL Fulton ◽  
MP Hartshorn ◽  
WT Robinson
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Nitrogen Dioxide ◽  
Photochemical Reaction ◽  
Charge Transfer Complex ◽  
Major Product ◽  
Adduct Formation ◽  
X Ray ◽  
Structure Determinations ◽  
Ion Recombination

Photolysis of the phenanthrene/tetranitromethane charge-transfer complex yields the triad of phenanthrene radical cation, nitrogen dioxide, and trinitromethanide ion. Recombination of this triad in dichloromethane at 20° gives 9-nitrophenanthrene (1), trans-10-trinitromethyl-9,10-dihydrophenanthren-9-yl nitrate (2a), trans-9-nitro-10-trinitromethyl-9,10-dihydrophenanthrene (2b), and trans-10-trinitromethyl-9,10-dihydrophenanthren-9-ol (2c). Adduct formation is partially suppressed when trifluoroacetic acid (0.7 M) is added to the dichloromethane solvent at 20°, the major product identified being 9-nitrophenanthrene (1). At -20° in dichloromethane, or in acetonitrile at 20°, 10'-nitro-9,9',10,10'-tetrahydro-9,9'-biphenanthren-10-yl nitrate (3) is formed, apparently by reaction of nitrogen dioxide with phenanthrene. X-Ray crystal structure determinations are reported for adducts (2a,b).

Assigning structures to diastereomeric aliphatic α,α'-dibromo ketones

2002 ◽  
Vol 80 (4) ◽  
pp. 413-417 ◽  
Author(s):  
Masood Parvez ◽  
SM Humayan Kabir ◽  
Ted S Sorensen ◽  
Fang Sun ◽  
Brian Watson
Keyword(s):  
Liquid Chromatography ◽  
Key Words ◽  
Crystal Structures ◽  
Chemical Shifts ◽  
Gas Liquid Chromatography ◽  
X Ray ◽  
Nmr Chemical Shifts ◽  
H Nmr ◽  
Dibromo Ketones

X-ray crystal structures are reported for two symmetrical aliphatic α,α'-dibromo ketones: a meso diastereomer of 3,5-dibromo–2,2,6,6-tetramethylheptan-4-one, and a rac isomer of 4,6-dibromo–2,2,3,3,7,7,8,8-octamethylnonan-5-one. Using these secure assignments and a previously confirmed structure for the diastereomers of 2,4-dibromopentan-3-one, we show in this study that gas-liquid chromatography (GLC) retention times (meso > rac) can be used to confidently assign the diastereomers for a range of symmetrical and unsymmetrical aliphatic α,α'-dibromo ketones. 1H NMR chemical shifts for the >CHBr hydrogen(s) can also be corroboratively used for assignment purposes (δracH > δmesoH).Key words: α,α'-dibromo ketones, X-ray crystal structures, GLC retention times, isomer assignment

Eine pentagonal pyramidale Koordination des Bismuts. Kristallstruktur von Methylbismutbis( diethyldithiocarbamat) / A Pentagonal Pyramidal Coordination of Bismut. Crystal Structure of Methylbismuthbis( diethyldithiocarbamate)

1979 ◽  
Vol 34 (7) ◽  
pp. 1037-1039 ◽  
Author(s):  
Christian Burschka ◽  
Markus Wieber
Keyword(s):  
Crystal Structure ◽  
Free Electron ◽  
Title Compound ◽  
Crystalline State ◽  
Electron Pair ◽  
Benzene Solution ◽  
X Ray Diffraction ◽  
X Ray ◽  
Free Electron Pair

Abstract Methylbismuth-bis(diethyldithiocarbamate), X-ray The crystal structure of the title compound, recrystallized from ethanol, was solved by means of X-ray diffraction methods and could be refined to an i?-value of 0.050 with 2126 reflections observed. In contrast to its behaviour in benzene solution, where the compound is monomeric, in the crystalline state dimeric units are formed by intermolecular Bi-S-interactions. The bismuth atoms are coordinated in form of a slightly distorted pentagonal pyramid with the free electron pair presumably directed opposite the apical C-atom.

The solid-state structure of bis(pentafluorophenyl)zinc

1998 ◽  
Vol 76 (5) ◽  
pp. 513-517 ◽  
Author(s):  
Yimin Sun ◽  
Warren E Piers ◽  
Masood Parvez
Keyword(s):  
Crystal Structure ◽  
Diethyl Ether ◽  
Benzene Solution ◽  
Close Contact ◽  
Monoclinic Space Group ◽  
State Structure ◽  
X Ray ◽  
Anhydrous Zncl ◽  
Ring Centroid ◽  
Linear Geometry

Using the published method of Wiedenbruch, bis(pentafluorophenyl)zinc, 1, was prepared from anhydrous ZnCl2 and 2 equiv. of LiC6F5 in diethyl ether. Base-free 1 was obtained in 60-65% yield by repeated distillation of the initially formed bis(diethyl) ether adduct of 1. The X-ray quality crystals of 1 were obtained from benzene solution. The molecular structure of 1 revealed a near linear geometry for the two-coordinate zinc center (C(1)-Zn-C(7) = 172.6(2)°), typical of monomeric ZnR2 derivatives. In the crystal structure, stacking interactions between C6F5 rings on adjacent molecules is a dominant motif, with ring centroid to ring centroid distances of 3.503 and 3.563 Å observed. A weak intermolecular C-F ...Zn interaction between F(2) and an adjacent zinc center, as judged by the close contact of 2.849(2) Å, also appears to be an important aspect of the crystal structure. Compound 1 is an effective but nonselective C6F5 transfer agent to BCl3; 1: monoclinic, space group P21/n, a = 11.902(2) Å, b = 7.732(2) Å, c = 13.735(2) Å, β = 110.58(1)°, V = 1183.4(4) Å3, Z = 4, R = 0.048, Rw = 0.069.Key words: organozinc complex, pentafluorophenyl transfer agent.

1,1,3,5,5,7,9,9,11-Nonachlor-1,5,9-triphospha-2,4,6,8,10,12-hexaazacyclododecahexaen: [Cl2PN2CCl]3, Synthese, Spektren und Kristallstruktur/ 1,1,3,5,5,7,9,9,11-Nonachloro-1,5,9-triphospha-2,4,6,8,10,12-hexaazacyclododecahexaene: [Cl2PN2CCl]3, Preparation, Spectra and Crystal Structure

1986 ◽  
Vol 41 (7) ◽  
pp. 839-844 ◽  
Author(s):  
H .-D. Hausen ◽  
G. Rajca ◽  
J. Weidlein
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Structure Determination ◽  
Title Compound ◽  
Benzene Solution ◽  
Molar Ratio ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Low Symmetry

AbstractThe title compound, Cl2PN2CCl, has been synthesized by the reaction of PCl5 with Me3Si -N = C = N - SiMe3 (Me - CH3) in a 1:1 molar ratio. The colourless com pound is trimericin benzene solution and in the solid state and has a structure with a highly puckered 12-membered P3N6C3-ring skeleton of low symmetry. The X-ray structure determination shows a monoclinic space group P 21/a with 4 trimeric units per cell.

The nitration of 2,4-dibromo-3,5,6-trimethylphenol and some reactions of polysubstituted phenols with nitrogen dioxide; X-ray crystal structure of 4-Acetyl-1-bromo-r-3,c-4-epoxy-2,t-5-dimethyl-3,5-dinitrocyclopentene

1983 ◽  
Vol 36 (8) ◽  
pp. 1589 ◽  
Author(s):  
MP Hartshorn ◽  
RJ Martyn ◽  
WT Robinson ◽  
KH Sutton ◽  
J Vaughan ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Acetic Acid ◽  
Nitric Acid ◽  
Nitrogen Dioxide ◽  
Reaction Conditions ◽  
X Ray ◽  
Fuming Nitric Acid

Nitrations of phenols (3a), (3b), (7) and (8) with nitrogen dioxide in cyclohexane give similar patterns of reaction to those with fuming nitric acid in acetic acid. Nitration of 2,4-dibromo-3,5,6-trimethyl- phenol (19) with nitrogen dioxide gives isomeric trinitrocyclohex-3-enones (24), while fuming nitric acid reactions yield either the trinitro ketone (24a) and the cis-dinitro ketone (25) or the C2-epimeric ketones (25) and (26) depending upon the reaction conditions. Some reactions of these products are described, and the X-ray crystal structure of the epoxycyclopentene derivative (30) is reported.

A Proton-Catalyzed Dimerization of a 2-Amino-1,3-diene which Ultimately Yields a 3-Aminobicyclo[4.2.0]octa-2,4-diene

2005 ◽  
Vol 60 (6) ◽  
pp. 673-676 ◽  
Author(s):  
Gerhard Maas ◽  
Rainer Rahm
Keyword(s):  
Crystal Structure ◽  
Structure Analysis ◽  
Benzene Solution ◽  
Chloroform Solution ◽  
Crystal Structure Analysis ◽  
X Ray ◽  
Iminium Salt

The 2-pyrrolidino-1,3-dienes (E)-5 and (Z)-5 are obtained by the reaction of lithium di(tertbutyl) cuprate with propyne iminium salt 3. Quantitative Z→E isomerization of 5 takes place within 4 hours at 20 °C. In benzene solution, (E)-5 slowly equilibrates with a [1,5]-H shift to form the 1-amino-1,3-diene derivative 6. In concentrated chloroform solution, however, (E)-5 is transformed into the 3-pyrrolidino-bicyclo[4.2.0]octa-2,4-diene 7 which is identified by X-ray crystal structure analysis. A mechanism for this transformation is proposed.

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