Alicyclic Series Research Articles

Aliphatic and alicyclic diepoxyketones as epoxy-modifi er diluents

The effect of modifying additives of diepoxyketones of aliphatic and alicyclic series was investigated. It is shown that curing of the modifi ed ED-20 resin with the above diepoxyketones signifi cantly improves the physical and mechanical properties of the obtained compositions compared to unmodified resin.

Acid hydrolysis of amides obtained by Beckmann rearrangement of methyl ketones oximes of unsaturated γ-lactone, aromatic, and alicyclic series

Beckmann rearrangement was performed of oximes of substituted 3-acetyl-4-methyl-5,5-dimethyl(pentamethylene)-2-oxo-2,5-dihydrofuranes in the presence of boron trifluoride etherate. Aiming at establishing the spatial arrangement of the oximes the hydrolysis was carried out of acid amides obtained by Beckmann rearrangement of oximes of methyl ketones belonging to unsaturated γ-lactone series and also to aromatic and alicyclic series. The hydrolysis with 20% sulfuric acid led to the formation of the corresponding acid and amine, and the hydrolysis with acetic and hydrochloric acids resulted in retrobeckmann rearrangement giving the initial oximes.

ChemInform Abstract: Reaction of 4‐Oxocarboxylic Acids and 5‐Substituted 3H‐Furan‐2‐ones with 1,2‐Binucleophiles of Aromatic and Alicyclic Series.

Abstract5‐Substituted furan‐2‐ones and their precursors, 4‐substituted 4‐oxocarboxylic acids, readily react with the title binucleophiles furnishing tricyclic azolidine structures.

Reaction of 4-oxocarboxylic acids and 5-substituted 3H-furan-2-ones with 1,2-binucleophiles of aromatic and alicyclic series

Based on reactions of 5-substituted 3H-furan-2-ones or 4-oxocarboxylic acids with 1,2-binucleophiles of aromatic and aliphatic series methods were developed for the synthesis of tricyclic structures containing a pyrrolidine fragment fused with imidazolidine or oxazolidine ring. The pathways of the reactions are considered. It was demonstrated that the nature of the substrate did not affect the reaction direction, but changed the scheme of the interaction. The structures of compounds obtained for the first time were proved using IR and 1H NMR spectra.

Thermochemistry of N-nitro- and N -nitrosoamines of the alicyclic series

1. The thermochemical characteristics of N,N-dinitropiperazine and N,N-dinitrosopiperazine were determined. The enthalpy of sublimation of hexahydro-l,3,5-trinitrosotriazine was determined. 2. The difference in the thermochemical principles of aliphatic and alicyclic N-nitro-N-nitrosoamines is due to the interaction of the functional groups in the ring. 3. The cleavage energies of the nitrogen-oxygen bond in N-nitropiperazine, N,N-dinitropiperazine, and hexahydro-l,3,5-trinitrotriazine were calculated.

Synthesis of the tetranitrates of conduritol-E and?-epoxyconduritol-E

The general method for O-nitration of unsaturated andα-epoxidized alcohols of the aliphatic series with an equimolar mixture of concentrated HNO3 and acetic anhydride has been extended to the corresponding alcohols of the alicyclic series. The tetranitrates of conduritol-E (cyclohexene-3,4/5,6-tetraol) and ofα-epoxyconduritol-E (1,2-anhydroalloinositol) have been synthesized.

13C N.M.R. STUDIES: PART VI. CARBON-13 SPECTRA OF α,β-UNSATURATED CARBONYL COMPOUNDS

The 15.1 Mc/s 13C n.m.r. spectra of 34 α,β.-unsaturated carbonyl compounds have been obtained and the chemical shifts of the olefinic and carbonyl carbon nuclei are reported. Examples were drawn from the acyclic and five- and six-membered ring alicyclic series. A few aldehydes are included although most of the compounds are ketones. In the case of compounds assumed to be planar, variations of the olefinic shieldings with alkyl substitution parallel those observed previously for olefinic hydrocarbons. The key factor governing the chemical shifts of the carbonyl-carbon nuclei appears to be the extent of conjugation in a given system. Consequently, the 13C results provide evidence for steric interference to coplanarity in the hindered systems. This approach is compared with other methods of estimating the extent of steric inhibition of conjugation and its merits are assessed.

The reaction of tosylhydrazones with lithium aluminium hydride

The reaction of tosylhydrazones or aromatic aldehydes and steroidal ketones has been studied. In the case of aromatic aldehydes, the aldehyde group be means of the tosylhydrazone is reduced to a methyl group. In the alicyclic series, the reaction seems to follow the same course, but some exceptions are reported.

Studies in the Alicyclic Series. Part II.1 Synthesis and Reactions of 2-Phenylcyclopent-2-enone

Studies in the Alicyclic Series. Part II.¹ Synthesis and Reactions of 2-Phenylcyclopent-2-enone

Studies in the alicyclic series. Part I. 1-Benzoylcycloalkenes as acceptors in the Michael condensation

Studies in the alicyclic series. Part I. 1-Benzoylcycloalkenes as acceptors in the Michael condensation

Studies in the alicyclic series. Part III. Michael condensation of 1-acetylcycloalkenes with cycloalkanones

The first page of this article is displayed as the abstract.

Synthesis of?-amino-?-cyclohexylpropionic acid and CF some of its derivatives

1. Rodionov's method for synthesis ofβ-amino acids has been extended to aldehydes of the alicyclic series. 2. A simple method of preparation of hexahydrobenzaldehyde or cyclopentylmaldehyde from cyclohexyl-or cyclopemyl-glycidic ester, respectivelu, is described. 3. Condensation of hexahydrobenzaldehyde with malonic acid leads to formation ofβ-amino-β-cyclohexylpropionic acid, in 50% yield. 4. The yield ofβ-amino acid is raised to 66% when the aldimine is taken for the condensation instead of the free sidehyde. 5. The N-benzoyl, N-acetyl-, and N-carbomethoxy-derivatives ofβ-amino-β-cyclohexylpropionic acid and its amide are described, as well asβ-ureodi-β-cyclohexylpropionic acid and cyclohexyldihydrouracil. 6. The Hoffmannreaction is carried out with the acylated derivative of the aminopropiomanides, and it is shown that the N-benzoyl- and N-carbomethoxy-derivatives give 5-cyclohexylglyoxalidone and its N-benzoyl-or N-carbpmethoxy-derivatives. β-Acetamide-β-cyclohexylpropionamide gives only cyclohexylglyoxalidone when treated with hypobromite. 7. The formation of acylated cyclohexylglyoxalidones confirms the correctness of mechanism propored by Rodionoc and Zvorykina [4] for the Hoffmann reaction ofβ-amino acids.

The combustion of aromatic and alicyclic hydrocarbons. III. Ignition and cool-flame characteristics

In a previous communication (Burgoyne 1937), attention was drawn to certain apparently anomalous features of the slow combustion of n -butyl benzene, and it was shown, inter alia , that the observed irregularities in the temperature coefficient of the reaction could be accounted for by the occurrence of cool-flame ignitions of the same type as those exhibited by the higher aliphatic hydrocarbons (Townend and Chamberlain 1936). These circumstances suggested that a general survey of the ignition characteristics of the aromatic hydrocarbons would be desirable as an aid to elucidating the mechanism of their combustion; and the present paper embodies the results for the series previously studied, together with two members of the alicyclic series which have been included to serve as a connecting link with the paraffins and olefines. Owing to the wide variations in reactivity towards oxygen of the compounds in question, it was found impracticable to employ the same experimental technique throughout the series; for whilst the ignitions of the more reactive members could safely be studied in silica and glass vessels, the remainder involved high pressures and required the use of steel apparatus. Comparative experiments, however, showed that no essential alteration in the ignition characteristics resulted from the substitution of one material for the other.