THE PHOTOINITIATED HALOGENATION REACTIONS OF N-BROMOACETANILIDE AND N-BROMO-2,4,6-TRICHLOROACETANILIDE

1966 ◽  
Vol 44 (13) ◽  
pp. 1555-1562
Author(s):  
Dennis D. Tanner ◽  
Eugene Protz
Keyword(s):  
Carbon Tetrachloride ◽  
Bromine Atom ◽  
Benzyl Bromide ◽  
Chain Process ◽  
Chain Mechanism ◽  
Chain Component ◽  
Rearrangement Reaction ◽  
A Chain ◽  
Photoinduced Rearrangement ◽  
Long Chain

The photoinduced rearrangement reaction of N-bromoacetanilide to p-bromoacetanilide in carbon tetrachloride was found to have a quantum efficiency approaching unity, and evidence is presented to indicate a chain component to the reaction process whose product-determining species is either the mesomeric acetanilide radical or the bromine atom. It was demonstrated that small variations in the solvent composition affected the product ratio of p- to o-bromoacetanilide. The reaction of N-bromoacetanilide in carbon tetrachloride with added toluene was found to be a long-chain process producing p-bromoacetanilide as well as acetanilide and benzyl bromide. The bromination of toluene by N-bromo-2,4,6-trichloroacetanilide was shown to proceed by a chain mechanism involving the bromine radical as the chain-propagating species, and this mechanism is used as a model to explain the reaction of N-bromoacetanilide in dilute carbon tetrachloride solutions of toluene.

The Chlorine Atom Sensitized Oxidation and the Ozonolysis of C2Cl4

1974 ◽  
Vol 52 (23) ◽  
pp. 3852-3862 ◽  
Author(s):  
Eckart Mathias ◽  
Eugenio Sanhueza ◽  
I. C. Hisatsune ◽  
Julian Heicklen
Keyword(s):  
Free Radicals ◽  
Chain Length ◽  
Chlorine Atom ◽  
Chain Process ◽  
Chain Mechanism ◽  
A Chain ◽  
A Minor ◽  
Long Chain

The chlorine atom initiated oxidation of C2Cl4 was studied both in the absence and presence of O3 at 24 and 32 °C. In the absence of O3, the products are CCl3CCl(O) and CCl2O, and they are produced in a long-chain process in a ratio of 2.5 at 24 °C and 3.0 at 32 °C. The product producing step involves the decay of C2Cl5O radicals[Formula: see text]The ratio k6a/k6b is 5.0 at 24 °C and 6.0 at 32 °C since CCl3 reacts with O2 to produce another CCl2O molecule. In the presence of O3 the ratio Φ{CCl3CCl(O)}/Φ{CCl2O} drops, [Formula: see text] is produced, and the chain length is reduced. The change in Φ{CCl3CCl(O)}/Φ{CCl2O} is a function of [O3]/[O2] and is attributed to the additional reactions[Formula: see text]The epoxide yield is a function of [C2Cl4]/[O3] and is attributed to the reaction of ClO with C2Cl4. The ClO is produced by the reaction of Cl• with O3[Formula: see text]which competes with[Formula: see text]The ratio k2/kl0 = 6.7. The reduction in yield as O3 is added results from the terminating reaction[Formula: see text]The ClO2 reacts further with O3 to produce Cl2O7.The reaction of O3 with C2Cl4 at 24 °C also produces mainly CCl3CCl(O) and CCl2O with [Formula: see text] as a minor product. Other minor products detected after extended conversions included Cl2, CO, and CO2. However c-C3Cl6 was not found. The ratio [CCl3CCl(O)]/[CCl2O] is < 1. Moreover, the addition of O2 retarded the reaction, indicating a long chain mechanism in which both free radicals (species with an odd number of electrons) and CCl2 were absent. A diradical chain mechanism is presented which explains the main features. The chain step is the addition of CCl2O2 to C2Cl4[Formula: see text]The adduct then reacts with O3 in a chain regenerating step or with O2 in a chain terminating step.

scholarly journals THE REACTION OF OXYGEN ATOMS WITH CARBON TETRACHLORIDE

1962 ◽  
Vol 40 (3) ◽  
pp. 486-494 ◽  
Author(s):  
A. Y-M. Ung ◽  
H. I. Schiff
Keyword(s):  
Carbon Dioxide ◽  
Carbon Tetrachloride ◽  
Carbon Atom ◽  
Flow System ◽  
Primary Process ◽  
Chain Mechanism ◽  
Homogeneous Reaction ◽  
Secondary Reactions ◽  
Primary Reactions ◽  
A Chain

The homogeneous reaction between O atoms and CCl4 was studied in a flow system under conditions of complete consumption of atoms, in the presence and in the absence of molecular oxygen. The only products of the reaction are Cl2, CO, CO2, and COCl2. No compounds containing more than one carbon atom were detected. The dependence of the products on CCl4 concentration suggests that the primary reactions are[Formula: see text]which are too slow to consume all the atoms. Carbon dioxide is produced by secondary reactions which are fast enough to consume all the atoms, the most important of which is[Formula: see text]However, the dependence of the ratio (CO2 + COCl2/CO on CCl4 concentration in the presence of O2 indicates other reactions also produce CO2. The rapid disappearance of O atoms in the systems containing O2 suggests a chain mechanism in which Cl2 is mainly converted to the atomic form. Carbon dioxide can then be produced by the sequence[Formula: see text]The rate constant for the primary process was found to be independent of O, O2, and CCl4 concentration and could be represented by the equation[Formula: see text]

scholarly journals Integrated lipidomics and proteomics reveal cardiolipin alterations, upregulation of HADHA and long chain fatty acids in pancreatic cancer stem cells

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Claudia Di Carlo ◽  
Bebiana C. Sousa ◽  
Marcello Manfredi ◽  
Jessica Brandi ◽  
Elisa Dalla Pozza ◽  
...  
Keyword(s):  
Pancreatic Cancer ◽  
Stem Cells ◽  
Fatty Acid ◽  
Cancer Stem Cells ◽  
Acyl Chain ◽  
Fatty Acid Elongase ◽  
Acyl Chains ◽  
A Chain ◽  
Pancreatic Cancer Stem Cells ◽  
Long Chain

AbstractPancreatic cancer stem cells (PCSCs) play a key role in the aggressiveness of pancreatic ductal adenocarcinomas (PDAC); however, little is known about their signaling and metabolic pathways. Here we show that PCSCs have specific and common proteome and lipidome modulations. PCSCs displayed downregulation of lactate dehydrogenase A chain, and upregulation of trifunctional enzyme subunit alpha. The upregulated proteins of PCSCs are mainly involved in fatty acid (FA) elongation and biosynthesis of unsaturated FAs. Accordingly, lipidomics reveals an increase in long and very long-chain unsaturated FAs, which are products of fatty acid elongase-5 predicted as a key gene. Moreover, lipidomics showed the induction in PCSCs of molecular species of cardiolipin with mixed incorporation of 16:0, 18:1, and 18:2 acyl chains. Our data indicate a crucial role of FA elongation and alteration in cardiolipin acyl chain composition in PCSCs, representing attractive therapeutic targets in PDAC.

THE KINETICS OF THE OXIDATION OF GASEOUS ACETALDEHYDE

1932 ◽  
Vol 7 (2) ◽  
pp. 149-161 ◽  
Author(s):  
W. H. Hatcher ◽  
E. W. R. Steacie ◽  
Frances Howland
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Induction Period ◽  
Reaction Vessel ◽  
Oxidation Products ◽  
Main Reaction ◽  
Chain Mechanism ◽  
Subsequent Reaction ◽  
A Chain ◽  
Kinetics Of

The kinetics of the oxidation of gaseous acetaldehyde have been investigated from 60° to 120 °C. by observing the rate of pressure decrease in a system at constant volume. A considerable induction period exists, during which the main products of the reaction are carbon dioxide, water, and formic acid. The main reaction in the subsequent stages involves the formation of peroxides and their oxidation products. The heat of activation of the reaction is 8700 calories per gram molecule. The indications are that the reactions occurring during the induction period are heterogeneous. The subsequent reaction occurs by a chain mechanism. The chains are initiated at the walls of the reaction vessel, and are also largely broken at the walls.

Réactions ion–molécule dans les méthylbutènes: radiolyse du méthane

1976 ◽  
Vol 54 (4) ◽  
pp. 555-559
Author(s):  
Guy J. Collin
Keyword(s):  
Tertiary Structure ◽  
Ionic Mechanism ◽  
Chain Mechanism ◽  
A Chain

The radiolysis of gaseous methane has been studied in the presence of one of the three methylbutenes. We have observed an important isomerization of the added olefin. An ionic mechanism initiated by the CH5+ and C2H5+ ions seems to be compatible with the observations reported. Isomerization proceeds through a chain mechanism where the chain carrier may be the tert-C5H11+ ion. In the presence of 3-methyl-1-butene, the initially formed (CH3)2CHCHCH3+ ion isomerizes to the tertiary structure before producing the observed isomerization.

scholarly journals Bacterial precursors and unsaturated long-chain fatty acids are biomarkers of North-Atlantic demosponges

2020 ◽  
Author(s):  
Anna de Kluijver ◽  
Klaas G.J. Nierop ◽  
Teresa M. Morganti ◽  
Martijn C. Bart ◽  
Beate M. Slaby ◽  
...  
Keyword(s):  
Fatty Acids ◽  
North Atlantic ◽  
Deep Sea ◽  
North Atlantic Ocean ◽  
Carbon Isotopic Composition ◽  
Building Blocks ◽  
Functional Ecology ◽  
The North ◽  
A Chain ◽  
Long Chain

AbstractSponges produce distinct fatty acids (FAs) that (potentially) can be used as chemotaxonomic and ecological biomarkers to study endosymbiont-host interactions and the functional ecology of sponges. Here, we present FA profiles of five common habitat-building deep-sea sponges (class Demospongiae, order Tetractinellida), which are classified as high microbial abundance (HMA) species. Geodia hentscheli, G. parva, G. atlantica, G. barretti, and Stelletta rhaphidiophora were collected from boreal and Arctic sponge grounds in the North-Atlantic Ocean. Bacterial FAs dominated in all five species and particularly isomeric mixtures of mid-chain branched FAs (MBFAs, 8- and 9-Me-C16:0 and 10 and 11-Me-C18:0) were found in high abundance (together ≥ 20% of total FAs) aside more common bacterial markers. In addition, the sponges produced long-chain linear, mid- and a(i)-branched unsaturated FAs (LCFAs) with a chain length of 24‒28 C atoms and had predominantly the typical Δ5,9 unsaturation, although also Δ9,19 and (yet undescribed) Δ11,21 unsaturations were identified. G. parva and S. rhaphidiophora each produced distinct LCFAs, while G. atlantica, G. barretti, and G. hentscheli produced similar LCFAs, but in different ratios. The different bacterial precursors varied in carbon isotopic composition (δ13C), with MBFAs being more enriched compared to other bacterial (linear and a(i)-branched) FAs. We propose biosynthetic pathways for different LCFAs from their bacterial precursors, that are consistent with small isotopic differences found in LCFAs. Indeed, FA profiles of deep-sea sponges can serve as chemotaxonomic markers and support the conception that sponges acquire building blocks from their endosymbiotic bacteria.

Rheology of Thermoplastic Polyurethanes

2007 ◽  
Author(s):  
Chang Dae Han
Keyword(s):  
Rheological Behavior ◽  
Thermoplastic Polyurethane ◽  
Complete Characterization ◽  
Chain Extender ◽  
Reaction Sequence ◽  
Molecular Weights ◽  
Soft Segments ◽  
Hard Segments ◽  
A Chain ◽  
Long Chain

Thermoplastic polyurethane (TPU) has received considerable attention from both the scientific and industrial communities (Hepburn 1982; Oertel 1985; Saunders and Frish 1962). Applications for TPUs include automotive exterior body panels, medical implants such as the artificial heart, membranes, ski boots, and flexible tubing. Figure 10.1 gives a schematic that shows the architecture of TPU, consisting of hard and soft segments. Hard segments, which form a crystalline phase at service temperature, are composed of diisocyanate and short-chain diols as a chain extender, while soft segments, which control low-temperature properties, are composed of difunctional long-chain polydiols with molecular weights ranging from 500 to 5000. The soft segments form a flexible matrix between the hard domains. TPUs are synthesized by reacting difunctional long-chain diol with diisocyanate to form a prepolymer, which is then extended by a chain extender via one of two routes: (1) by a dihydric glycol chain extender or (2) by a diamine chain extender. The most commonly used diisocyanate is 4,4’-diphenylmethane diisocyanate (MDI), which reacts with a difunctional polyol forming soft segments, such as poly(tetramethylene adipate) (PTMA) or poly(oxytetramethylene) (POTM), to produce TPU, in which 1,4-butanediol (BDO) is used as a chain extender. There are two methods widely used to produce TPU: (1) one-shot reaction sequence and (2) two-stage reaction sequence. The reaction sequences for both methods are well documented in the literature (Hepburn 1982). It should be mentioned that MDI/BDO/PTMA produces ester-based TPU. One can also produce ether-based TPU when MDI reacts with POTM using BDO as a chain extender. TPUs are often referred to as “multiblock copolymers.” In order to have a better understanding of the rheological behavior of TPUs, one must first understand the relationships between the chemical structure and the morphology; thus, a complete characterization of the materials must be conducted. The rheological behavior of TPU depends, among many factors, on (1) the composition of the soft and hard segments, (2) the lengths of the soft and hard segments and the sequence length distribution, (3) anomalous linkages (branching, cross-linking), and (4) molecular weight.

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