An Addition Reaction of Indane with Nitric Acid in Acetic Anhydride

1972 ◽  
Vol 50 (14) ◽  
pp. 2211-2216 ◽  
Author(s):  
A. Fischer ◽  
C. C. Greig ◽  
A. L. Wilkinson ◽  
D. R. A. Leonard
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Nitrous Acid ◽  
Addition Reaction ◽  
Cis And Trans ◽  
Cis Isomer

cis- and trans-5-Acetoxy-7a-nitro-5,7-dihydroindane are formed as well as the 4- and 5-nitroindanes when indane is reacted with nitric acid and acetic anhydride. These adducts both decompose on standing by loss of nitrous acid forming 5-acetoxyindane. The cis isomer is obtained in greater amount and it undergoes elimination less readily than the trans.

Addition Reactions in the Nitration of Some Polycyclic Aromatic Compounds

1972 ◽  
Vol 50 (20) ◽  
pp. 3367-3372 ◽  
Author(s):  
A. Fischer ◽  
D. R. A. Leonard
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Nitro Group ◽  
Aromatic Compounds ◽  
Addition Reaction ◽  
Polycyclic Aromatic Compounds ◽  
Addition Reactions ◽  
Polycyclic Aromatic ◽  
Acetyl Nitrate

Reaction of 3-oxo-1,2,3,7,8,9,10,10a-octahydrocyclohepta[de]naphthalene with nitric acid in acetic anhydride gives two stereoisomeric 4-acetoxy-6a-nitro-3-oxo-1,2,3,4,6a,7,8,9,10,10a-decahydrocyclohepta[de]-naphthalenes as well as the expected nitro substitution products. Formation of these adducts from a substrate containing a meta-directing deactivating substituent shows that the 1,4-addition reaction of acetyl nitrate is more general than previously suspected. 1,4-Acetyl nitrate adducts are also formed from tetralin, benzsuberane, 5,6,7,8-tetrahydrocyclohepta[fg]acenaphthene, and 1,2,3,4,7,8,9,10-octahydrodicyclohepta[de,ij]naphthalene. Decomposition of the last two adducts gives in each case a product with the nitro group substituted into the alicyclic ring.

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.

Nitration of 3,4-Dimethylacetophenone and 3,4-Dimethylbenzophenone. Formation and Rearomatization of Adducts

1975 ◽  
Vol 53 (11) ◽  
pp. 1570-1578 ◽  
Author(s):  
Alfred Fischer ◽  
Colin Campbell Greig ◽  
Rolf Röderer
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Nitro Group ◽  
Nitrous Acid ◽  
Main Product ◽  
Intermediate Formation ◽  
Nitro Derivatives ◽  
Acidic Conditions ◽  
Cis And Trans ◽  
Derivatives Of

Nitration of 3,4-dimethylacetophenone in acetic anhydride gives a mixture of cis-and trans-2-acetyl-4,5-dimethyl-4-nitro-1,4-dihydrophenyl acetate as the main product, together with 3,4-dimethyl-2-, 3,4-dimethyl-5-, and 3,4-dimethyl-6-nitroacetophenone. Analogous products are obtained from 3,4-dimethylbenzophenone. Rearomatization of the adducts under mildly acidic conditions occurs via 1,4-elimination of nitrous acid to form 2-acetyl- and 2-benzoyl-4,5-dimethylphenyl acetate, respectively. In strongly acidic conditions elimination of acetic acid accompanied by 1,2- and 1,3-shifts of the nitro group occurs to form the 2- and 5-nitro derivatives of the parent ketones. The rearomatization to the nitro derivatives involves the intermediate formation of an ipso-cyclohexadienyl cation which may be trapped by anisole or mesitylene to form biphenyl derivatives.

Adduct Intermediates in the Side-chain Nitration of 1,4-Dimethylnaphthalene

1972 ◽  
Vol 50 (24) ◽  
pp. 3988-3992 ◽  
Author(s):  
Alfred Fischer ◽  
Alan Leslie Wilkinson
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Room Temperature ◽  
Methylene Chloride ◽  
Side Chain ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
Naphthyl Acetate

cis and trans isomers of 1,4-dimethyl-4-nitro-1,4-dihydro-1-naphthyl acetate (1) have been isolated from a mixture of 1,4-dimethylnaphthalene and nitric acid in acetic anhydride by quenching at −40°. At room temperature only 1-methyl-4-nitromethylnaphthalene (4) is obtained. The conversion of 1,4-dimethylnaphthalene to 4 and of the cis (1a) and trans (1b) adducts to 4, by nitric acid in acetic anhydride, has been followed by n.m.r. 1,4-Dimethyl-4-nitro-1,4-dihydro-1-naphthyl nitrate (5) appears to be the immediate product from nitration of 1,4-dimethylnaphthalene in acetic anhydride, methylene chloride, or nitromethane. In acetic anhydride 5 is converted into 1. Decomposition of 1 in acetic acid gives 1,4-dimethyl-2-naphthyl acetate and some 4. The formation of 4 in this reaction is suppressed by urea.

Nitration of 1-chloro-2,3-dimethylbenzene in acetic anhydride. Formation and rearomatization of adducts

1978 ◽  
Vol 56 (8) ◽  
pp. 1063-1068
Author(s):  
Alfred Fischer ◽  
Colin Campbell Greig
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Nitrous Acid ◽  
Major Product ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Nitro Derivatives ◽  
Subsequent Elimination ◽  
And Migration ◽  
Cis And Trans

Nitration of l-chloro-2,3-dimethylbenzene in acetic anhydride gives the cis and trans isomers of 3-chloro-4,5-dimethyl-4-nitrocyclohexa-2,5-dienyl acetate (29%) and l-chloro-2,3-dimethyl-4-nitro- (46%), -5-nitro- (5%), and -6-nitrobenzene (20%). In formic acid and acidified methanol, exchange of acetate for formate and methoxyl, respectively, occurs and the diastereoisomers of 3-chloro-4,5-dimethyl-4-nitrocyclohexa-2,5-dienyl formate and methyl ether, respectively, are formed. Rearomatization of each isomer of 3-chloro-4,5-dimethyl-4-nitrocyclohexa-2,5-dienyl acetate in acetic acid results in initial isomerization to form the pair of diastereoisomers and subsequent elimination of nitrous acid to form 3-chloro-4,5-dimethylphenyl acetate. In 25% trifluoroacetic acid in deuteriochloroform elimination of acetic acid and migration of the nitro group to form 1-chloro-2,3-dimethyl-4-nitro-benzene and a lesser amount of its 6-nitro isomer is the dominant reaction. In the presence of mesitylene the formation of the nitro derivatives is suppressed and 3′-chloro-2,4,4′,5′,6-pentamethylbiphenyl is obtained. It is proposed that cyclohexadienyl cations are significant intermediates in ail of the reactions. Pyrolysis of the adducts gives 1-chloro-2,3-dimethylbenzene as the major product.

Nitration of p-tert-butyltoluene in acetic anhydride. 1,2 and 1,4 adducts

1976 ◽  
Vol 54 (24) ◽  
pp. 3978-3985 ◽  
Author(s):  
Alfred Fischer ◽  
Rolf Röderer
Keyword(s):  
Acetic Anhydride ◽  
Hydrogen Chloride ◽  
Nitrous Acid ◽  
Tert Butyl ◽  
Acidic Conditions ◽  
Cis And Trans

Nitration of p-tert-butyltoluene in acetic anhydride gives 5-tert-butyl-2-methyl-2-nitro-1,2-dihydrophenyl acetate (43%), cis- and trans-1-tert-butyl-4-methyl-4-nitro-1,4-dihydrophenyl acetate (16%) and 4-tert-butyl-2-nitrotoluene (41%). Reaction of either of the 1,2 or 1,4 nitroacetoxy adducts with hydrogen chloride gives a mixture of the 1,2 and 1,4 nitrochloro adducts. The 1,2 (secondary) acetate adduct eliminates nitrous acid to form 5-tert-butyl-2-methylphenyl acetate under mildly acidic conditions. Under more vigorously acidic conditions 4-tert-butyl-2-nitrotoluene is formed. The same products are formed from the 1,4 (tertiary) acetate adducts but p-tolyl acetate is also obtained. The 1,2 and 1,4 adducts couple with anisole to form 5-tert-butyl-4′-methoxy-2-methylbiphenyl.

Synthesis of Cyclic Nitramines From Products of the Cyclocondensation Reaction of Guanidine With 2,3,5,6-Tetrahydroxypiperazine-1,4-dicarbaldehyde

1994 ◽  
Vol 47 (11) ◽  
pp. 2033 ◽  
Author(s):  
IJ Dagley ◽  
JL Flippenanderson
Keyword(s):  
Nitric Acid ◽  
Hydrochloric Acid ◽  
Acetic Anhydride ◽  
Formic Acid ◽  
Guanidine Hydrochloride ◽  
Chloride Ion ◽  
Trifluoroacetic Anhydride ◽  
Cyclocondensation Reaction ◽  
Cyclic Nitramines ◽  
Cis Isomer

The reaction of 2,3,5,6-tetrahydroxypiperazine-1,4-dicarbaldehyde (1) with guanidine hydrochloride in hydrochloric acid can be controlled to give 2,6-diiminododecahydrodiimidazo[4,5-b:4′,5′-e] pyrazine (2a) or the cis isomer of 4,5-diamino-2-iminoimidazolidine (4). Compound (4) reacts with formaldehyde, or formic acid followed by reduction, to give 2-iminooctahydroimidazo[4,5-d] imidazole (7). Treatment of (2a) or (7) with nitric acid gives dinitro derivatives that were isolated as nitric acid salts of the cyclic guanidines. Reaction of the dinitro derivatives with nitric acid/acetic anhydride in the presence of chloride ion gives 4,8-dinitro-2,6-bis( nitroimino ) dodecahydrodiimidazo -[4,5-b:4′,5′-e] pyrazine (3a) and 1,3-dinitro-5-( nitroimino ) octahydroimidazo [4,5-d] imidazole (9). The reaction of (7) with nitric acid/ trifluoroacetic anhydride was controlled to give either the tetranitro or a dinitro bis ( trifluoroacetyl ) derivative of the corresponding bicyclic urea.

CATALYZED NITRATION OF AMINES: III. THE EASE OF NITRATION AMONG ALIPHATIC SECONDARY AMINES

1948 ◽  
Vol 26b (1) ◽  
pp. 114-137 ◽  
Author(s):  
G. E. Dunn ◽  
J. C. MacKenzie ◽  
J. W. Suggitt ◽  
George F Wright ◽  
W. J. Chute ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Nitrous Acid ◽  
Active Form ◽  
Secondary Amines ◽  
Side Reactions ◽  
Aqua Regia ◽  
Nitryl Chloride ◽  
Alkyl Groups ◽  
Chloride Catalyst

A series of secondary amines, the proton-attracting ability of which had previously been determined, have been converted to their nitramines with nitric acid and acetic anhydride. The gradation in ease of nitration has been found to vary inversely with the proton-attracting ability of the amine. Nitration becomes so difficult at an amine strength corresponding to that of diethanolamine that nitric acid and acetic anhydride alone are ineffective; a chloride catalyst must be used. The amount of this catalyst must be increased as the proton-attracting ability of the amine becomes greater until a full equivalent is required for adequate yield from the strongest amine in the series, diisopropylamine. As the nitration in the series becomes more difficult, side reactions become apparent such as nitrosation, acetylation, and fission of the secondary amine to primary amine and aldehyde. The extent of nitrosation is dependent on the concentration of catalyst, although nitrosation is not catalyzed by presence of chloride. This implies that hydrogen chloride generates nitrous acid in the reaction mixture. Acetylation is independent of presence or concentration of catalyst, but it does not occur during the formation of dicyclohexylnitramine or diisopropylnitramine. This is thought to be owing to steric hindrance from the secondary alkyl groups in these amines. Since nitracidium perchlorate has been found to be ineffective as a catalyst for this nitration, it is doubtful that nitryl chloride is the active form of the catalyst except in so far as it exists in the form of chlorine nitrite. Evidence has accumulated to show that electropositive chlorine is the effective catalyst, and that it is formed by a modification of the aqua regia reaction.

scholarly journals IX. The electric conductivity of nitric acid

1898 ◽  
Vol 191 ◽  
pp. 365-398 ◽  
Keyword(s):  
Nitric Acid ◽  
Physical Properties ◽  
Nitrous Acid ◽  
Internal Resistance ◽  
The Other ◽  
Reasonable Degree ◽  
Mineral Acids ◽  
Artificial Illumination ◽  
The Subject ◽  
Deep Green

Of the commoner mineral acids the chemical changes of Nitric Acid, from their evident complexity, have formed the subject of numerous memoirs, while those of sulphuric acid, from their assumed simplicity, have been to some degree neglected; on the other hand, the physical properties of the latter have been studied with considerable elaboration, while those of the former have been passed over, doubtless on account of the corrosive nature of the acid and the difficulty of preparing and preserving it in a reasonable degree of purity. Further, with certain exceptions, the alterations in physical properties induced by the products of reduction, be they nitrogen peroxide or nitrous acid, either singly or conjointly, have attracted but little attention, though it is a common matter of observation that the current intensity of a Grove’s or other cell containing nitric acid remains constant, even though the fuming acid, originally colourless or red, has become of a deep green tint. It is more than probable that of the factors of Ohm’s law, both the E. M. F. and internal resistance are continually varying. At the earliest stages of the enquiry it was found that the passage of a few bubbles of nitric oxide gas into a considerable volume of nitric acid produced an alteration of one percent, in the resistance, and the same result could be effected to a less degree by exposure to sunlight, and to a still less degree by exposure to artificial illumination. Therefore, we determined to investigate the alterations of conductivity produced by changes of concentration and temperature in samples of acid purified with necessary precautions, more especially as former workers upon the subject have either used samples of acid confessedly impure, or have been silent as to any method of purification, or have adopted no special care in dealing with a substance so susceptible of polarisation.

scholarly journals Increases in plasma trans-EETs and blood pressure reduction in spontaneously hypertensive rats

2011 ◽  
Vol 300 (6) ◽  
pp. H1990-H1996 ◽  
Author(s):  
Houli Jiang ◽  
John Quilley ◽  
Anabel B. Doumad ◽  
Angela G. Zhu ◽  
John R. Falck ◽  
...  
Keyword(s):  
Blood Pressure ◽  
Spontaneously Hypertensive Rat ◽  
Blood Pressure Reduction ◽  
Maximal Velocity ◽  
Spontaneously Hypertensive ◽  
Cis And Trans Isomers ◽  
Wistar Kyoto Rat ◽  
Wistar Kyoto ◽  
Cis And Trans ◽  
Cis Isomer

Epoxyeicosatrienoic acids (EETs) are vasodilator, natriuretic, and antiinflammatory lipid mediators. Both cis- and trans-EETs are stored in phospholipids and in red blood cells (RBCs) in the circulation; the maximal velocity ( Vmax) of trans-EET hydrolysis by soluble epoxide hydrolase (sEH) is threefold that of cis-EETs. Because RBCs of the spontaneously hypertensive rat (SHR) exhibit increased sEH activity, a deficiency of trans-EETs in the SHR was hypothesized to increase blood pressure (BP). This prediction was fulfilled, since sEH inhibition with cis-4-[4-(3-adamantan-1-ylureido)cyclohexyloxy]benzoic acid (AUCB; 2 mg·kg−1·day−1 for 7 days) in the SHR reduced mean BP from 176 ± 8 to 153 ± 5 mmHg ( P < 0.05), whereas BP in the control Wistar-Kyoto rat (WKY) was unaffected. Plasma levels of EETs in the SHR were lower than in the age-matched control WKY (16.4 ± 1.6 vs. 26.1 ± 1.8 ng/ml; P < 0.05). The decrease in BP in the SHR treated with AUCB was associated with an increase in plasma EETs, which was mostly accounted for by increasing trans-EET from 4.1 ± 0.2 to 7.9 ± 1.5 ng/ml ( P < 0.05). Consistent with the effect of increased plasma trans-EETs and reduced BP in the SHR, the 14,15- trans-EET was more potent (ED50 10−10 M; maximum dilation 59 ± 15 μm) than the cis-isomer (ED50 10−9 M; maximum dilation 30 ± 11 μm) in relaxing rat preconstricted arcuate arteries. The 11,12-EET cis- and trans-isomers were equipotent dilators as were the 8,9-EET isomers. In summary, inhibition of sEH resulted in a twofold increase in plasma trans-EETs and reduced mean BP in the SHR. The greater vasodilator potency of trans- vs. cis-EETs may contribute to the antihypertensive effects of sEH inhibitors.

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