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.

The Nitration of 2,3,4-Tribromo-5,6-dimethylphenol and 3,4-Dibromo-2,5,6-trimethylphenol

1985 ◽  
Vol 38 (1) ◽  
pp. 133 ◽  
Author(s):  
MV Chambers ◽  
MP Hartshorn ◽  
WT Robinson ◽  
J Vaughan
Keyword(s):  
Crystal Structure ◽  
Acetic Acid ◽  
Nitric Acid ◽  
X Ray ◽  
Structure Determinations ◽  
Fuming Nitric Acid

The nitrations of 2,3,4-tribromo-5,6-dimethylphenol (9) and 3,4- dibromo-2,5,6-trimethylphenol (10) with fuming nitric acid in acetic acid give 2,5,6-trinitrocyclohex-3-enones in addition to 6-hydroxy-2,5-dinitrocyclohex-3-enones. X-ray crystal structure determinations are reported for the trinitro ketones (21) and (22), and the hydroxy dinitro ketones (23) and (24).

The nitration of 4-Nitro- and 4-Bromo-2,6-dimethylphenols; X-Ray Crystal Structures of t-6-Hydroxy-2,6-dimethyl-r-2,4,t-5-trinitrocyclohex-3-enone, r-2,t-6-Dihydroxy-2,6-dimethyl-4,t-5-dinitrocyclohex-3-enone and 4-Bromo-t-6-hydroxy-2,6-dimethyl-r-2,t-5-dinitrocyclohex-3-enone

1985 ◽  
Vol 38 (11) ◽  
pp. 1693 ◽  
Author(s):  
MP Hartshorn ◽  
JM Readman ◽  
WT Robinson ◽  
J Vaughan ◽  
AR Whyte
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Nitrogen Dioxide ◽  
Crystal Structures ◽  
X Ray ◽  
Structure Determinations ◽  
Fuming Nitric Acid

The nitration of 2,6-dimethyl-4-nitrophenol (1b), with either fuming nitric acid in acetic acid or nitrogen dioxide in dichloromethane, gives the C2-epimeric hydroxy trinitro ketones (4) and (5), the dinitro phenol (6) and the dihydroxy dinitro ketone (7). The nitration of the 4-bromo phenol (1c) is accompanied by some nitro- debromination and compounds (4), (5) and (13)-(17) are isolated. X-ray structure determinations are reported for compounds (5), (7) and (14).

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.

Nitration of 2,3,4,6-Tetramethylphenol and 1,2,3,5-Tetramethylbenzene

1985 ◽  
Vol 38 (4) ◽  
pp. 587 ◽  
Author(s):  
MP Hartshorn ◽  
JM Readman ◽  
WT Robinson ◽  
J Vaughan
Keyword(s):  
Nitric Acid ◽  
Nitrogen Dioxide ◽  
Crystal Structures ◽  
Side Chain ◽  
X Ray ◽  
Fuming Nitric Acid

Nitration of 1,2,3,5-tetramethylbenzene (2a) with fuming nitric acid gives the tetramethylnitrobenzene (22), products of side-chain modification (23)-(27), the rearranged 6,6-dimethylcyclohexenones (8), (28), (29) and (30), and 2,3,4,6-tetramethyl ketone derivatives (10)- (13), (31) and (32). Reaction of 2,3,4,6-tetramethylphenol (7) with nitrogen dioxide gives the hydroxy dinitro ketone (9) in addition to the trinitrocyclohexenones (11)-(14) and (19). X-ray crystal structures are reported for compounds (11), (19), (28), (29), (30) and (32). 1H n.m.r ./stereochemistry correlations are reported for some 2,5-dinitro- and 2,5,6-trinitro-cyclohex-3-enones.

The nitration of pentamethylphenol

1984 ◽  
Vol 37 (7) ◽  
pp. 1489 ◽  
Author(s):  
MP Hartshorn ◽  
WT Robinson ◽  
J Vaughan ◽  
JM White ◽  
AR Whyte
Keyword(s):  
Nitric Acid ◽  
Nitrogen Dioxide ◽  
Crystal Structures ◽  
X Ray ◽  
Fuming Nitric Acid

Nitration of pentamethylphenol (1) with nitrogen dioxide in benzene gives the four possible 2,5,6-trinitrocyclohex-3-enones (6), (7), (8) and (9), three 4,5,6-trinitrocyclohex-2-enones (10), (11) and [(12) or (13)], the 2-hydroxy-5,6-dinitrocyclohex-3-enone (14), quinone (17) and the 4-nitro dienone (3). The fuming nitric acid nitration of pentamethylphenol (1) for 90 h gives most of these products, except that 4-nitratomethyl-2,5,6-trinitrocyclohex-3-eones (21), (22), (23) and (24) are isolated. X-ray crystal structures are reported for compounds (6), (7), (8), (10), (11), (14) and (21).

The nitration of 1,2,3,4-tetramethyl-5,6-dinitrobenzene; X-ray crystal structure of cis-2,5,6,6-Tetramethyl-2,3,4,5-tetranitrocyclohex-3-enone

1982 ◽  
Vol 35 (6) ◽  
pp. 1237 ◽  
Author(s):  
MJ Gray ◽  
MP Hartshorn ◽  
KE Richards ◽  
WT Robinson ◽  
KH Sutton ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Nitric Acid ◽  
Structure Analysis ◽  
Crystal Structure Analysis ◽  
Mechanism Of Formation ◽  
X Ray ◽  
Fuming Nitric Acid ◽  
Cis And Trans ◽  
Cis Isomer

Nitration of 1,2,3,4-tetramethyl-5,6-dinitrobenzene (1) with fuming nitric acid in dichloromethane gives cis-and trans-2,5,6,6-tetramethyl-2,3,4,5-tetranitrocyclohex-3-enones (9) and (10), the structure of the cis isomer being confirmed by X-ray crystal structure analysis. The mechanism of formation of tetranitro ketones (9) and (10) is discussed.

The nitration of 3,4,5-tribromo-2,6-dimethylphenol; X-ray crystal structures of C 2-epimeric 3,4,5-tribromo-6-hydroxy-2,6-dimethyl-2,5-dinitrocyclohex-3-enones ;an unusual isomerization reaction

1982 ◽  
Vol 35 (11) ◽  
pp. 2229 ◽  
Author(s):  
AM Chittenden ◽  
MP Hartshorn ◽  
KE Richards ◽  
WT Robinson ◽  
KH Sutton ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Single Crystal ◽  
Crystal Structures ◽  
Structural Data ◽  
Isomerization Reaction ◽  
X Ray ◽  
Fuming Nitric Acid

Nitration of 3,4,5-tribromo-2,6-dimethylphenol (10) with fuming nitric acid in acetic acid gives the C2-epimeric 2,5-dinitrocyclohex-3-enones (11) and (12), the structures of which were determined by single-crystal X-ray analyses. Some implications of these structural data are discussed.

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).

Synthesis and properties of 1,3-bis(4-nitrophenyl)-1-butene

1980 ◽  
Vol 45 (7) ◽  
pp. 2120-2124 ◽  
Author(s):  
Gabriel Čík ◽  
Anton Blažej ◽  
Kamil Antoš ◽  
Igor Hrušovský
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Double Bond ◽  
Fuming Nitric Acid

1,3-Bis(4-nitrophenyl)-1-butene was prepared by nitration of 1,3-diphenyl-1-butene (I) with fuming nitric acid in acetic acid. The double bond in I was protected by addition of bromine which was eliminated after the nitration. The UV, IR and 1H- spectra of the synthesized compounds are interpreted.

scholarly journals Nitration of Jharia basin coals, India: a study of structural modifications by XRD and FTIR techniques

2021 ◽  
Author(s):  
Prabal Boral ◽  
Atul K. Varma ◽  
Sudip Maity
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Linear Relationship ◽  
Glacial Acetic Acid ◽  
Vitrinite Reflectance ◽  
Aqueous Media ◽  
Interlayer Spacing ◽  
Acetic Acid Medium ◽  
X Ray ◽  
The Media

AbstractFour coal samples from Jharia basin, India are treated with nitric acid in glacial acetic acid and aqueous media to find out the chemical, petrographic and spatial structure of the organic mass by X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) techniques. X-ray parameters of coal like interlayer spacing (d002), crystallite size (Lc), aroamticity (fa), average number of aromatic layers (Nc), and coal rank (I26/I20) have been determined using profile-fitting software. Considerable variation is observed in treated coals in comparison to the demineralized coals. The d002 values of treated coals have increased in both the media showing increase in disordering of organic moieties. A linear relationship has been observed between d002 values with the volatile matter of the coals. Similarly, the d002 values show linear relationship with Cdmf contents for demineralized as well as for the treated coals in both the media. The Lc and Nc values have decreased in treated coals corresponding to demineralized coals. The present study shows that nitration in both the media is capable of removing the aliphatic side chains from the coals and aromaticity (fa) increases with increase in rank and shows a linear relationship with the vitrinite reflectance. The corresponding I26/I20 values are least for treated coals in glacial acetic acid medium followed by raw and then to treated coals in aqueous medium. FTIR studies show that coal arenes of the raw coals are converted into nitro-arenes in structurally modified coals (SMCs) in both the media, the corresponding bands at 1550–1490 and 1355–1315 cm−1 respectively. FTIR study confirms that nitration is the predominant phenomenon, though, oxidation and nitration phenomena takes place simultaneously during treatment with nitric acid to form SMCs. In comparison to raw coals, the SMCs show higher aromaticity and may be easily converted to coal derived products like activated carbon and specialty carbon materials.

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