CATALYZED NITRATION OF AMINES: VI. THE NITRATION OF DI-n-OCTYLAMINE

1948 ◽  
Vol 26b (3) ◽  
pp. 271-283 ◽  
Author(s):  
K. K. Carroll ◽  
George F Wright
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Hydrogen Chloride ◽  
Nitro Compound ◽  
Acetyl Chloride ◽  
Nitration Product ◽  
By Products

The yield of purified dioctylnitramine from di-n-octylammonium chloride is low and the crude nitration product is badly contaminated with by-products which contain halogen. Since dioctylamine can be nitrosated, acetylated, chlorinated, and p-toluenesulphonated with ease it is considered that the low yield of nitro compound is owing to decomposition of the dioctylchloramine which is intermediate during the nitration process. A mechanism for this decomposition is suggested on the basis of the products isolated from treatment of the chloramine with hydrogen chloride, acetyl chloride, acetic acid, or acetic anhydride.

Acetylation and Formylation of 3-Ferrocenylpyrroles

1999 ◽  
Vol 64 (1) ◽  
pp. 99-106
Author(s):  
Battsengel Gotov ◽  
Štefan Toma ◽  
Eva Solčániová
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Aluminum Chloride ◽  
Acetyl Chloride ◽  
Trifluoroacetic Anhydride ◽  
Acid Mixture ◽  
Chloride Method

Acetylations of 3-ferrocenyl-1-methylpyrrole as well as 3-cyano-4-ferrocenylpyrrole and 3-cyano-4-ferrocenyl-1-methylpyrrole were performed. The course of the acylation is highly dependent on the acylation agent, that is acetyl chloride/aluminum chloride (method A), trifluoroacetic anhydride-acetic acid mixture (method B) or acetic anhydride/Sc(OTf)3 (method C). Method A gives the acetylation on ferrocene moiety, method B affords the trifluoroacetylation on pyrrole moiety and method C affords pyrrole moiety acetylation. Vielsmeier-Haack formylation gives the products of substitution on pyrrole moiety.

The Nitration of α- and β-Acylnaphthalenes

1995 ◽  
Vol 48 (12) ◽  
pp. 1969 ◽  
Author(s):  
SD Barker ◽  
K Wilson ◽  
RK Norris
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Nitro Compound ◽  
Nitro Compounds ◽  
The Other ◽  
Coupling Constant ◽  
Significant Extent ◽  
Nitro Derivatives ◽  
High Yields

The nitration of α- and β- acylnaphthalenes with copper(II) nitrate in acetic anhydride or nitric acid/acetic acid mixtures gives high yields of the corresponding mononitro compounds. The assignment of constitution to these products is made on the basis of extensive 1H n.m.r. chemicl shift and coupling constant data. In the case of α- acylnaphthalenes, with the notable exception of α- pivalonaphthone, nitration occurs in the α-positions of the unsubstituted ring to give mixtures of 5- and 8-nitro compounds. α- Pivalonaphthone gives appreciable amounts of the 4-nitro compound and also of the 8-nitro compound. This result indicates that the pivaloyl group does not shield the 8-position sterically to any significant extent and is effectively electronically neutral, unlike the other acyl substituents , in allowing attack at the α-position (position 4) of the acylated ring. This result is ascribable to the lack of coplanarity of the pivaloyl group with the naphthalene system. All of the β- acylnaphthalenes gave mixtures of 4-, 5- and 8-nitro derivatives in proportions that did not vary significantly with the nature of the acyl group.

Hot-Tube Reactions of Dehydroabietic Acid with Ketene-Producing Reagents. Pyrolysis of the Acid Chloride and Symmetrical and Mixed Anhydride Derivatives of Dehydroabietic Acid

1973 ◽  
Vol 51 (19) ◽  
pp. 3236-3241 ◽  
Author(s):  
Ray F. Severson ◽  
Walter H. Schuller
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Acid Chloride ◽  
Acetyl Chloride ◽  
Dehydroabietic Acid ◽  
Mixed Anhydride ◽  
Temperature Range ◽  
Acid Isomerization ◽  
Derivatives Of ◽  
Isopropenyl Acetate

Dehydroabietic acid (1a) was reacted with diketene, acetic acid, acetic anhydride, isopropenyl acetate, acetyl chloride, and acetone on Vycor rod at 450 °C in a hot tube. Dehydroabietic anhydride (1b) and acetyl dehydroabietate (1c) were pyrolyzed at 450 °C and dehydroabietyl chloride (1d) was pyrolyzed over a temperature range of 290–500 °C. The major olefin products resulting from decarboxylation of the various derivatives were 19-norabieta-4,8,11,13-tetraene (2), 19-norabieta-4(18),8,11,13-tetraene (3), 19-norabieta-3,8,11,13-tetraene (4), and cis-1,10a-dimethyl-7-isopropyl-1,2,3,9,10,10a-hexahydrophenanthrene (5). High conversions to these compounds were obtained. In the presence of the ketene-producing reagents the olefins were oxidized to yield substantial amounts of retene (6), compounds 2 and 5 being the most readily dehydrogenated. The acid isomerization of 2, 3, 4, and 5 was studied using p-toluenesulfonic acid in toluene at 110 °C.

Color Reactions of Rubber and Gutta-Percha

1929 ◽  
Vol 2 (2) ◽  
pp. 193-196
Author(s):  
F. Kirchhof
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Zinc Chloride ◽  
Trichloroacetic Acid ◽  
Acetyl Chloride ◽  
Oxidation Products ◽  
Arsenic Trichloride ◽  
Gutta Percha ◽  
Long Time ◽  
Color Reactions

Abstract THE present paper was suggested by a recent publication of Pauly on the same subject, who applied the well known sterol reactions of Hesse, Liebermann, Tschugajeff, etc., to the hydrocarbons of rubber and gutta-percha. These reactions depend either upon the action of concentrated H2SO4 on chloroform solutions of the substances in the presence or absence of acetic anhydride (Liebermann, Burchard and Hesse reactions) or other solvents, or condensation reagents are used, such as acetyl chloride and zinc chloride by Tschugajeff, and acetic acid with arsenic trichloride by Kahlenberg, and trichloroacetic acid with a trace of formaldehyde by Godoletz. All the known sterol reactions take place also with rubber or gutta-percha, with the appearance of intense red or violet colorations of varying stability, the color depending in part upon the quality and in part upon the purity of the samples. The Burchard reaction in particular is very sensitive in these respects. Thus with rubber purified with alkali by the Pummerer method, the color is a Bordeaux red which does not change for a long time, whereas solutions of unpurified rubber change rapidly, a change which is rightly ascribed by Pauly to relatively rapid oxidation in the presence of oxidation products in the case of the unpurified rubber.

NITROLYSIS OF HEXAMETHYLENETETRAMINE: VI. RECOMBINATION OF FRAGMENTS DURING HEXAMETHYLENETETRAMINE NITROLYSIS IN ACETIC ANHYDRIDE

1949 ◽  
Vol 27b (6) ◽  
pp. 520-544 ◽  
Author(s):  
E. Aristoff ◽  
J. A. Graham ◽  
R. H. Meen ◽  
G. S. Myers ◽  
G. F Wright
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Ammonium Nitrate ◽  
Degradation Products ◽  
Stepwise Synthesis ◽  
Alternative Hypotheses ◽  
Enhanced Yield ◽  
By Products

Alternative hypotheses can account for the yield of more than one equivalent of Cyclonite from hexamine when the Bachmann reagents, ammonium nitrate, nitric acid, and acetic anhydride are used. In the nitrolysis, evidence for a stepwise synthesis from unit fragments is presented as the enhanced yield when methylenedinitramine is added with paraform to ammonium nitrate and acetic anhydride according to the Schiessler–Ross method for Cyclonite synthesis. However, this evidence is discounted because the expected by-product, 1,5-diacetoxy-2,4-dinitro-2,4-diazapentane is not found. Alternatively it is believed that the Bachmann reaction is actually a combination of the direct nitrolysis of hexamine with nitric acid, concurrent with a resynthesis of hexamine from the fragments produced by the nitrolysis. On this basis all by-products from the hexamethylenetetramine nitrolysis must be accounted as degradation products of hexamethylenetetramine and not capable of synthesis from unit fragments like formaldehyde, ammonia, and acetic acid. No exception has been found; the addition of acylamides to the Bachmann reaction mixture increases the yield of two by-products, 1-acyl-3,5-dinitro-1,3,5-triazacyclohexane and 1-acyl-3,5,7-trinitro-1,3,5,7-tetrazacycloöctane. It has been shown that these can be formed only from degradation products of hexamethylenetetramine such as 1,5-diaceto-3,7-endomethylene-1,3,5,7-tetrazacycloöctane and acetaminomethylhexamethylenetetramine nitrate.

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.

Photochemical reactions of azo compounds. VII. Studies of the photochemical reactions of azobenzene under various acidic conditions

1966 ◽  
Vol 19 (8) ◽  
pp. 1445 ◽  
Author(s):  
GE Lewis ◽  
RJ Mayfield
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Sulphuric Acid ◽  
Photochemical Reaction ◽  
Acetyl Chloride ◽  
Photochemical Reactions ◽  
Aluminium Chloride ◽  
Azo Compounds ◽  
High Yield ◽  
Acidic Conditions

An investigation has been made of the photochemical and dark reactions of azobenzene in acetic acid-ferric chloride and acetic acid-aluminium chloride mixtures for comparison with the corresponding reactions of azobenzene in sulphuric acid. The photochemical reactions resulted in cyclodehydrogenation of azobenzene to benzo[c]cinnoline, and small quantities of reduction products of azobenzene were also isolated. The formation of reduction products was again observed in the dark reactions, but there was no sign of cyclodehydrogenation. The significance of these observations is now discussed. Irradiation of azobenzene in acetyl chloride, or in acetic anhydride containing hydrogen chloride, resulted in a novel photochemical reaction in which NN?-diacetyl-4-chlorohydrazobenzene was formed in high yield.

An unusual reaction of a bridged triterpenoid α-diketone with acetic anhydride

1991 ◽  
Vol 56 (12) ◽  
pp. 2917-2935 ◽  
Author(s):  
Eva Klinotová ◽  
Václav Křeček ◽  
Jiří Klinot ◽  
Miloš Buděšínský ◽  
Jaroslav Podlaha ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Nmr Spectroscopy ◽  
Acetic Anhydride ◽  
Spectral Methods ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mild Conditions ◽  
Condensation Products ◽  
Unsaturated Lactones ◽  
C Nmr

3β-Acetoxy-21,22-dioxo-18α,19βH-ursan-28,20β-olide (IIIa) reacts with acetic anhydride in pyridine under very mild conditions affording β-lactone IVa and γ-lactones Va and VIIa as condensation products. On reaction with pyridine, lactones Va and VIIa undergo elimination of acetic acid to give unsaturated lactones VIIIa and IXa, respectively. Similarly, the condensation of 20β,28-epoxy-21,22-dioxo-18α,19βH-ursan-3β-yl acetate (IIIb) with acetic anhydride leads to β-lactone IVb and γ-lactone Vb; the latter on heating with pyridine affords unsaturated lactone VIIIb and 21-methylene-22-ketone Xb. The structure of the obtained compounds was derived using spectral methods, particularly 1H and 13C NMR spectroscopy; structure of lactone IVa was confirmed by X-ray diffraction.

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