CATALYZED NITRATION OF AMINES: IV. THE ROLE OF ELECTROPOSITIVE CHLORINE IN THE NITRATION OF LYSIDINE

1948 ◽  
Vol 26b (1) ◽  
pp. 138-153 ◽  
Author(s):  
J. C. MacKenzie ◽  
George F Wright ◽  
G. S. Myers ◽  
G. N. R. Smart
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Hydrogen Chloride ◽  
Chloroacetic Acid ◽  
Decomposition Products ◽  
Linear Isomer ◽  
Chloride Catalyst

The nitration of lysidine with acetic anhydride, nitric acid, and a chloride catalyst does not yield the expected nitrolysidine. The product, instead, is 1,3-dinitroimidazolidone-2 when little or no chloride is used. A new compound is produced when a full equivalent of hydrogen chloride is included. This new compound is thought to be 1,3-dinitro-2-chloromethyl-2-acetoxylimidazolidine. Its decomposition products are ethylenedinitramine and chloroacetic acid. It is believed to be cyclic because the linear isomer, N-acetyl-N′-chloroacetylethylenedinitramine has been prepared and found not to be identical. The formation of dinitrochloromethylacetoxylimidazolidine in the nitration mixture suggests that it is formed by addition of chlorine acetate. This compound has been prepared, characterized, and found to add to allylbenzene. Since it will convert dicyclohexylamine to the chloramine it is postulated as a temporal ingredient of the catalyzed nitration mixture.

CATALYZED NITRATION OF AMINES: VIII. THE MEDIUM USED IN NITRATION OF SECONDARY ALIPHATIC AMINES

1948 ◽  
Vol 26b (3) ◽  
pp. 294-308 ◽  
Author(s):  
Thelma Connor ◽  
George F Wright ◽  
G. N. R. Smart
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Hydrogen Chloride ◽  
Zinc Chloride ◽  
Acetyl Chloride ◽  
Maximum Amount ◽  
Initial Formation ◽  
Reaction Systems ◽  
Elemental Chlorine ◽  
Rate Controlling Step

The reaction [Formula: see text] has been found to be reversible in acetic anhydride. Analysis for electropositive chlorine and for nitric acid in this reacting system indicates that consumption of NO3− and production of Cl+ passes through a maximum after which nitric acid is regenerated and electropositive chlorine disappears. This phenomenon has been interpreted as an initial formation of chlorine acetate (or other chlorine ester) which then decomposes to give elemental chlorine. The increased demand for hydrogen chloride then shifts the equilibrium toward regeneration of nitric acid. The reaction has been found to be second order in its kinetics, with an activation energy of about 8000 cal. It is probably not the rate-controlling step in the catalyzed nitration, except perhaps where such nitration is easy and efficient. When nitration is difficult the electropositive chlorine tends to accumulate. When it becomes elemental chlorine, it is ineffective for nitration catalysis and is destructive to the amine. The catalysts acetyl chloride and zinc chloride have been studied. Electropositive chlorine formation occurs at the same rate with acetyl chloride as with hydrogen chloride. Zinc chloride, on the other hand, has been found to generate the maximum amount of electropositive chlorine immediately. This indicates that zinc chloride would be a good catalyst for easily nitrated amines but less efficient for amines which react more slowly, since the chlorine acetate not consumed by chloramination would decompose to give the destructive elemental chlorine. No mono-, di-, or trichloroacetic acids, nor perchloric acid, could be detected in aged reaction systems initially hydrogen chloride – nitric acid – acetic anhydride.

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.

The vacuum ultraviolet photolysis of hydrogen chloride. The role of the hot hydrogen atoms

1981 ◽  
Vol 55 (1-2) ◽  
pp. 9-15 ◽  
Author(s):  
A. Jówko ◽  
S. U. Pavlova ◽  
H. Baj ◽  
B. G. Dzantiev ◽  
M. Foryś
Keyword(s):  
Hydrogen Chloride ◽  
Vacuum Ultraviolet ◽  
Hydrogen Atoms ◽  
Ultraviolet Photolysis

The role of oxidizing radicals in neptunium speciation in γ-irradiated nitric acid

2012 ◽  
Vol 296 (1) ◽  
pp. 27-30 ◽  
Author(s):  
Bruce J. Mincher ◽  
Martin Precek ◽  
Stephen P. Mezyk ◽  
Leigh R. Martin ◽  
Alena Paulenova
Keyword(s):  
Nitric Acid

The Influence of Oxygen-Rich Inclusions on the Nature of Austenite Decomposition Products of Weld Metal Deposits

1983 ◽  
Vol 21 ◽  
Author(s):  
M. Ferrante ◽  
K. Akune
Keyword(s):  
Weld Metal ◽  
Catalytic Effect ◽  
Thermal Contraction ◽  
Austenite Decomposition ◽  
Decomposition Products ◽  
The Matrix

ABSTRACTRecent studies carried out on weld metal have called attention to the role of oxygen-rich inclusions on austenite decomposition. This investigation describes some evidences of the catalytic effect of dislocations upon the γ → α transformation. These defects are generated at the matrix inclusion interface and its presence has been ascertained by TEM. Estimates of the stresses arising from differences in thermal contraction between inclusion and matrix on cooling confirm microstructural observations.

scholarly journals The role and effects of glucosinolates of Brassica species – a review

2011 ◽  
Vol 48 (No. 4) ◽  
pp. 175-180 ◽  
Author(s):  
H. Zukalová ◽  
J. Vašák
Keyword(s):  
Amino Acids ◽  
Brassica Species ◽  
Development Stage ◽  
Decomposition Products ◽  
Group Iii ◽  
Indole Glucosinolates ◽  
Group I ◽  
Carcinogenic Effects ◽  
In The Beginning

  Glucosinolates are the substituted esters of thio amino acids and their synthesis is based on the corresponding amino acids. Methionine and cysteine are the natural donors in the case of the Brassica plants and L-tryptophane in the indole glucosinolates, respectively. In Brassica genus, alkenyl glucosinolates are mostly present and their content and composition differ as far as the development stage and the part of the plant are concerned. The indole glucosinolates are present in a minority level. Their role of sulphur supply is questioned by their very low content between 2% in the beginning of vegetation and 0.1% in its end. Glucosinolates are discussed mostly from the aspect of their anti-nutrition, anti-microbial, anti-fungicidal, and anti-bacterial effects and as being natural bio-fumigants. Their decomposition products have the mentioned properties. The products originate by prepared passive protection by the two-component system. From the aspect of these properties, it is useful to divide them into the following three groups according to the characters of their decomposition products. The first group (I.), whose hydrolysis in the neutral and alkaline environment creates iso-thio-cyanates. These bioactive compounds form the natural protection of the plant with bio-fumigatory effects particularly. Their anti-nutritive effects can be compensated by iodine, contrary to the second group (II.). This group is created by hydroxy-glucosinolates, whose decomposition products – iso-thio-cyanates – are not stable and they cycle while producing substituted 2-oxazolidinethione (goitrine – VTO). These glucosinolates represent a serious problem in feed industry since the VTO has a strong goitrogenic property. The third group (III.) – glucosinolates containing the indole group or the benzene ring (Sinalbin), create thio-cyanates during their hydrolysis. The role of indole glucosinolates has not been completely clarified so far. Their anti-carcinogenic effects are studied and they fulfil the role of an active protection.

Selective Nitroxylation of Adamantane Derivatives in the System Nitric Acid–Acetic Anhydride

2020 ◽  
Vol 56 (9) ◽  
pp. 1532-1539
Author(s):  
Yu. N. Klimochkin ◽  
E. A. Ivleva ◽  
I. K. Moiseev
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Adamantane Derivatives

The role of vanadium(V) in the oxidation of cyclohexanol to adipic acid by nitric acid

1985 ◽  
pp. 1677 ◽  
Author(s):  
J. R. Lindsay Smith ◽  
D. I. Richards ◽  
C. B. Thomas ◽  
M. Whittaker
Keyword(s):  
Nitric Acid ◽  
Adipic Acid

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.

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