Analytical Methods in Rubber Chemistry. Part V. Estimation of the Oxygen of Highly Autoöxidized Rubber Contained in Carboxyl, Ester, Carbonyl, Epoxide and Hydroxyl Groups

1942 ◽  
Vol 15 (4) ◽  
pp. 965-977
Author(s):  
F. Hilton
Keyword(s):  
Functional Groups ◽  
Hydroxyl Groups ◽  
Double Bonds ◽  
Primary Products ◽  
Secondary Reactions ◽  
Methylene Groups ◽  
Products Of Reaction ◽  
Methylene Group ◽  
Alcoholic Hydroxyl ◽  
Oxidative Attack

Abstract In the course of a study of the autoöxidation of natural rubber and of low-molecular olefins of allied structure, it has been necessary to ascertain the nature and relative proportions of the functional groups to which the ingoing oxygen may give rise. Up to the present it has been established that the products of autoöxidation reactions are in general highly complex mixtures, and that even such simple olefins as dihydromyrcene and cyclohexene may give rise to molecules which bear a varied assortment of hydroperoxide, alcoholic hydroxyl, epoxide and carbonyl groups. Available evidence further indicates that the primary products of autoöxidation are hydroperoxides, formed by the reaction of oxygen at methylene groups adjacent to double bonds, and that it is the secondary reactions which these hydroperoxides undergo which are responsible, directly or indirectly, for the formation of the other oxygen-containing groups which have been observed. Molecules of rubber hydrocarbon contain, on an average, several thousand methylene groups adjacent to double bonds. Each such methylene group is at least the potential seat of oxidative attack, and it might be anticipated that if the autoöxidation of rubber proceeds in a manner analogous to that of simpler olefins, the products of reaction would be extremely complex and that they might contain any or all of the following functional groups

Studies on the Lignin of Eucalyptus regnans. II. The Nature of the Hydroxyl Groups and the Presence of the Carbonyl Group in Thiolignin

1948 ◽  
Vol 1 (2) ◽  
pp. 241
Author(s):  
JWT Merewether
Keyword(s):  
Benzoyl Chloride ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Carbonyl Groups ◽  
Eucalyptus Regnans ◽  
Trimethyl Ether ◽  
Free Hydroxyl ◽  
Active Methylene ◽  
Methylene Group ◽  
Alcoholic Hydroxyl

E. regnans thiolignin reacts with p-toluenesulphonyl chloride in pyridine to form a hexatosyl derivative ; its trimethyl ether reacts likewise to form a tritosyl derivative. Both compounds still have a free hydroxyl group which can be acetylated. Similarly they yield a hexabenzoate and tribenzoate respectively by the Schotten-Baumann reaction, but in pyridine, thiolignin reacts with benzoyl chloride to give a heptabenzoate and trimethylthiolignin a tetrabenzoate. No reaction takes place when trimethyl thiolignin is treated with triphenylchloromethane in pyridine. The above data are interpreted as evidence that of the four alcoholic hydroxyl groups three are secondary and one tertiary. With phenylhydrazine, thiolignin yields a phenylosazone ; with p-nitrophenylhydrazine it yields a p-nitrophenylhydrazone. On the other hand, trimethylthiolignin does not react with phenylhydrazine, indicating the absence of non-enolizable carbonyl groups. Thiolignin condenses with benzaldehydes indicating the presence of an active methylene group. From this evidence it is deduced that the grouping CH2-CO-CHOH- is present.

Studies on the Lignin of Eucalyptus regnans. IV. Alkali Lignin

1949 ◽  
Vol 2 (4) ◽  
pp. 600
Author(s):  
JWT Merewether
Keyword(s):  
Empirical Formula ◽  
Black Liquor ◽  
Hydroxyl Groups ◽  
Eucalyptus Regnans ◽  
Alkali Lignin ◽  
Active Methylene ◽  
Methylene Group ◽  
Alcoholic Hydroxyl ◽  
Soluble Alkali

By pulping Eucalyptus regnans using the soda process and acidifying the black liquor a crude alkali lignin has been isolated. This has been separated into two fractions, dioxan-ether insoluble alkali lignin-A and dioxan-ether soluble alkali lignin-B. A series of derivatives has been made from each. The data for alkali lignin-A are consistent with the empirical formula C68H78O27, containing nine methoxyl. groups, three acidic, and four alcoholic hydroxyl groups, one of which is tertiary, one carbonyl, and one active methylene group. Alkali lignin-B has been found to be identical with the alkali lignin previously isolated from sulphate black liquor.

Oxidative Decomposition of the Ozonide of Butadiene Rubber

1959 ◽  
Vol 32 (1) ◽  
pp. 288-294 ◽  
Author(s):  
A. I. Yakubchik ◽  
N. G. Kasatkina ◽  
G. I. Demidova ◽  
G. B. Fedorova
Keyword(s):  
Hydrogen Peroxide ◽  
Acetic Acid ◽  
Levulinic Acid ◽  
Butadiene Rubber ◽  
Double Bonds ◽  
Oxidative Decomposition ◽  
Mild Conditions ◽  
Oxidative Breakdown ◽  
Secondary Reactions ◽  
Methylene Group

Abstract 1. Among the products of oxidative decomposition with acetyl hydroperoxide of the ozonide of butadiene rubber (prepared at 5°) are levulinic, formic, succinic, 1,2,4-butanetricarboxylic, 1,2,3-propanetricarboxylic and l,x,y,6-hexanetetracarboxylic acids. Levulinic acid could be formed by isomerization of 1,4-1)2-1,4-chains of the rubber macromolecule and by partial decarboxylation of β-ketoadipic acid, as well as by the peroxy-formate rearrangement in presence of acetyl hydroperoxide. 1,2,3-Propanetricarboxylic acid is more likely to be formed from 1,4-1,4-chains branched at the α -methylene group, or from 1,4-1,2-1,4-chains in which the double bonds had undergone suitable rearrangement, rather than as a result of secondary reactions during oxidative breakdown of the ozonide. 1,2,3-Propanetricarboxylic acid was also detected among the products of ozonolysis obtained under mild conditions of breakdown. 2. Products of oxidative breakdown of the ozonide of the rubber in question with hydrogen peroxide were acetic, formic, succinic, 1,2,4-butanetricarboxylic, 1,2,3-propanetricarboxylic and 1,x,y,6-hexanetetracarboxylic acids. Acetic acid could have been formed from 1,4-1,4-portions of the rubber molecule branched at the α -methylene group, as well as from isomerized 1,4-1,2-1,4-portions.

ATISINE: THE HETEROCYCLIC RING AND FUNCTIONAL GROUPS

1954 ◽  
Vol 32 (5) ◽  
pp. 465-473 ◽  
Author(s):  
O. E. Edwards ◽  
Tara Singh
Keyword(s):  
Functional Groups ◽  
Heterocyclic Ring ◽  
Double Bonds ◽  
Secondary Hydroxyl ◽  
Exocyclic Methylene ◽  
Methylene Group ◽  
Hydroxyethyl Group

Evidence is presented which confirms the presence in atisine and isoatisine of vinylamine double bonds, an N-(β-hydroxyethyl) group, an exocyclic methylene group, and a secondary hydroxyl in an allylic relation to the latter. The size and substitution of the heterocyclic ring is discussed. The pyrolysis of atisine and isoatisine hydrochlorides to give a C20H29ON base is described.

scholarly journals Mechanical Properties of Graphene Oxide Coupled by Multi-Physical Field: Grain Boundaries and Functional Groups

Crystals ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 62
Author(s):  
Xu Xu ◽  
Zeping Zhang ◽  
Wenjuan Yao
Keyword(s):  
Mechanical Properties ◽  
Graphene Oxide ◽  
Grain Boundaries ◽  
Functional Groups ◽  
Oxygen Content ◽  
Tensile Fracture ◽  
Hydroxyl Groups ◽  
Molecular Configuration ◽  
Spatial Design ◽  
Out Of Plane

Graphene and graphene oxide (GO) usually have grain boundaries (GBs) in the process of synthesis and preparation. Here, we “attach” GBs into GO, a new molecular configuration i.e., polycrystalline graphene oxide (PGO) is proposed. This paper aims to provide an insight into the stability and mechanical properties of PGO by using the molecular dynamics method. For this purpose, the “bottom-up” multi-structure-spatial design performance of PGO and the physical mechanism associated with the spatial structure in mixed dimensions (combination of sp2 and sp3) were studied. Also, the effect of defect coupling (GBs and functional groups) on the mechanical properties was revealed. Our results demonstrate that the existence of the GBs reduces the mechanical properties of PGO and show an “induction” role during the tensile fracture process. The presence of functional groups converts in-plane sp2 carbon atoms into out-of-plane sp3 hybrid carbons, causing uneven stress distribution. Moreover, the mechanical characteristics of PGO are very sensitive to the oxygen content of functional groups, which decrease with the increase of oxygen content. The weakening degree of epoxy groups is slightly greater than that of hydroxyl groups. Finally, we find that the mechanical properties of PGO will fall to the lowest values due to the defect coupling amplification mechanism when the functional groups are distributed at GBs.

Bisquaternary ammonium salts derived from 3α,12α-Diamino-5β-cholane and 3α,12α-Diamino-24-nor-5β-cholane

1971 ◽  
Vol 24 (3) ◽  
pp. 521 ◽  
Author(s):  
S Ahmed ◽  
M Alauddin ◽  
B Caddy ◽  
M Martin-Smith ◽  
WTL Sidwell ◽  
...  
Keyword(s):  
Deoxycholic Acid ◽  
Ammonium Salts ◽  
Hydroxyl Group ◽  
Amino Compound ◽  
Hydroxyl Groups ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Polyhydric Alcohols ◽  
Methane Sulphonate ◽  
Methylene Group

The preparation of 3α,12α-bisdimethylamino-5β-cholane dimethiodide, 3α,12α-bisdimethylamino-5β-cholane dimethiodide, 3α,12α- bisdimethylamino-24-nor-5β-cholanedimethiodide, and 3α,12α- bisdimethylamino-24-nor-5β-cholanediethiodide, from deoxycholic acid are described. During this work it was found that attempted copper- quinoline decarboxylation of dehydrocholic acid gives rise to lactol formation, and that what had previously been considered to be 3α,12α- dihydroxy-5β-cholane is a mixture of this compound and 12α,24- dihydroxy-5β-cholane. Comparable selectivity of attack by methanesulphonyl chloride and toluene-p-sulphonyl chloride occurs with various polyhydric alcohols derived from bile acids, as evidenced from the products of reduction of the sulphonates with lithium aluminium hydride. With both 5α- and 5β-cholane derivatives, a C 3 equatorial hydroxyl group exhibits comparable reactivity to the terminal primary hydroxyl group, generated from the bile acid carboxylic group, towards both sulphonyl chlorides. With axial hydroxyl groups at C 7 and C 12, toluene-p-sulphonate formation is much more difficult than methane- sulphonate formation. Reduction by means of lithium aluminium hydride of equatorial sulphonate esters at C 7 and C 12 gives rise to a methylene group, but the axial sulphonates under the same conditions give the axial alcohol. The same clear distinction between equatorial and axial sulphonate esters is not observed at C 3 and C 6, but 17α- methanesulphonyloxy-5α-androstane gives 5α-androstane and the 17β- ester gives 17β-hydroxy-5α-androstane. Reduction of 12-oximino groups in both 5α- and 5β-cholanes with sodium and ethanol, hydrogen in the presence of a catalyst, or lithium aluminium hydride gives solely the 12α-amino compound.

scholarly journals Titanium Dioxide Modified with Alcoholic Hydroxyl Groups

1994 ◽  
Vol 67 (8) ◽  
pp. 489-495 ◽  
Author(s):  
Tsuneo SUHARA ◽  
Hiroshi HUKUI ◽  
Michihiro YAMAGUCHI
Keyword(s):  
Titanium Dioxide ◽  
Hydroxyl Groups ◽  
Alcoholic Hydroxyl

Diffusion coefficients and viscosities of organic aerosol components through equilibrium and non-equilibrium molecular dynamics simulations

2021 ◽  
Author(s):  
Katerina S. Karadima ◽  
Vlasis G. Mavrantzas ◽  
Spyros N. Pandis
Keyword(s):  
Molecular Dynamics ◽  
Functional Groups ◽  
Organic Compounds ◽  
Diffusion Coefficients ◽  
Amorphous Solid ◽  
Good Effect ◽  
Hydroxyl Groups ◽  
Chemical Structures ◽  
Organic Particles ◽  
Non Equilibrium

<p>Organic aerosols have been typically considered to be liquid, with equilibration between gas and aerosol phase assumed to be reached within seconds. However, Virtanen et al. (Nature, 2010) suggested that particles in amorphous solid state may also occur in the atmosphere implying that mass transfer between the atmospheric particulate and gas phases may be much slower than initially thought. Experimentally, the direct measurement of the diffusion coefficients of different compounds inside atmospheric organic particles is challenging. Thus, an indirect approach is usually employed, involving viscosity measurements and then estimation of diffusion coefficients via the Stokes-Einstein equation, according to which the diffusion coefficient is inversely proportional to the medium viscosity. However, the corresponding diffusion estimates are highly uncertain, especially for highly viscous aerosols which is the most important case. Molecular simulation methods, such as molecular dynamics (MD), can be an alternative method to determine directly the diffusion rates and the viscosity of the constituents of atmospheric organic particles. MD also provides detailed information of the exact dynamics and motion of the molecules, thus offering a deeper understanding on the underlying mechanisms and interactions.</p><p>In the present work, we use equilibrium and non-equilibrium MD simulations to estimate the viscosity and diffusion coefficients of bulk systems of representative organic compounds with different chemical structures and physicochemical characteristics. Hydrophilic and hydrophobic compounds representative of primary and secondary oxidized organic products and of primary organic compounds emitted by various sources are considered. The viscosity and self-diffusion coefficients calculated by our simulations are in good agreement with available experimentally measured values. Our results confirm that the presence of carboxyl and hydroxyl groups in the molecule increases the viscosity. The number of carboxyl and hydroxyl groups, in particular, seems to have a good effect on diffusivity (the diffusivity decreases as the number of these functional groups increase), and to a lesser extent on the viscosity. We also discuss the role of the hydrogen bonds formed between these functional groups.</p>

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