ChemInform Abstract: Reaction of Diazoalkanes with Unsaturated Compounds. Part 8. Catalytic Cyclopropanation of Allyl Alcohol, Allylamine, and Their Derivatives with Diazomethane.

ChemInform ◽  
1990 ◽  
Vol 21 (29) ◽  
Author(s):  
YU. V. TOMILOV ◽  
A. B. KOSTITSYN ◽  
V. A. DOKICHEV ◽  
U. M. DZHEMILEV ◽  
O. M. NEFEDOV
Keyword(s):  
Allyl Alcohol ◽  
Unsaturated Compounds

STUDIES ON LIGNIN AND RELATED COMPOUNDS: VI. THE MECHANISM OF AQUEOUS HALOGENATION

1931 ◽  
Vol 4 (2) ◽  
pp. 119-133 ◽  
Author(s):  
K. Austin Taylor ◽  
O. Maass ◽  
Harold Hibbert
Keyword(s):  
Hydrochloric Acid ◽  
Allyl Alcohol ◽  
Hydrobromic Acid ◽  
Catalytic Effect ◽  
Hypochlorous Acid ◽  
The Real ◽  
Unsaturated Compounds ◽  
Acid Addition ◽  
Hypobromous Acid ◽  
Chlorine Ions

The rates of addition of hypochlorous and hypobromous acids to several unsaturated compounds, under the influence of various catalysts, have been studied.The addition of hypochlorous acid to allyl alcohol and dipropenyl glycol is catalysed by both hydrogen and chlorine ions, the catalytic effects of these ions, mole for mole, being equal. The effect of hydrogen and chlorine ions, when added together as hydrochloric acid, is not the sum of their separate effects but is proportional to their product, indicating undissociated hydrochloric acid as the real catalyst. The catalytic effect of varying amounts of added hydrochloric acid is approximately proportional to the square of the amount added, again indicating undissociated hydrochloric acid as the real catalyst.The addition of hypobromous acid to allyl alcohol is catalysed by hydrochloric and hydrobromic acids to about the same degree. This catalysis of hypobromous acid addition by hydrochloric acid provides further support for the hypothesis of undissociated hydrochloric acid as the real catalyst in the addition of hypochlorous acid.This catalytic effect of undissociated halogen acid on the addition of hypohalous acids is put forward as an explanation of the greater rates of addition of hypochlorous and hypobromous acids from chlorine and bromine water as compared with solutions of hypochlorous and hypobromous acids.The addition of hypobromous acid to fumaric acid is not catalysed by hydrobromic acid but, on the other hand, is considerably decreased. It is catalysed, however, by hydrochloric acid, although not nearly to the same degree as the addition to allyl alcohol. This difference in behavior between fumaric acid and allyl alcohol shows the necessity for studying the effect of hydrochloric and hydrobromic acids on the rate of addition of hypobromous acid to a wide variety of unsaturated compounds, before any general theory of aqueous halogenation applicable to all types of unsaturated compounds can be put forward. The possible influence of conjugation has, however, been pointed out.An attempt has been made to apply the theory of hypohalous acid addition catalysed by undissociated halogen acid to the aqueous halogenation of phenols. The reaction between hypobromous acid and m-nitrophenol has been shown to be catalysed by hydrochloric acid although not to the same extent as by hydrobromic acid. This indicates hypobromous acid addition, catalysed by undissociated hydrobromic acid, as one of the mechanisms involved in the aqueous bromination of phenols.It has been pointed out that a similar mechanism cannot be the fastest one in the aqueous chlorination of phenols, since it is in disagreement with kinetic data of Soper and Smith (21), showing chlorine to react faster than hypochlorous acid with phenols.It has been shown that resorcinol and phloroglucinol do not fall under the general classification proposed by Soper and Smith for phenols. Even here, however, the main reaction between chlorine water and the phenol seems to involve chlorine rather than hypochlorous acid.It has been suggested that several parallel mechanisms may be involved in the aqueous halogenation of phenols and the necessity for further work in this field has been emphasized.

Sila-, bora-, thio-, and phosphono-carboxylation of unsaturated compounds with carbon dioxide: An overview

2021 ◽  
Vol 48 ◽  
pp. 101522
Author(s):  
Shi Nan ◽  
Wang Hai-Bin ◽  
Gao Li ◽  
Zhang Jing-Yao ◽  
Guo Jian-Feng ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Unsaturated Compounds

scholarly journals THE CATALYTIC EFFECT OF FERRICYANIDE IN THE OXIDATION OF UNSATURATED COMPOUNDS BY OXYGEN

1931 ◽  
Vol 94 (2) ◽  
pp. 411-413
Author(s):  
G. Payling Wright ◽  
James B. Conant ◽  
S.E. Kamerling
Keyword(s):  
Catalytic Effect ◽  
Unsaturated Compounds

scholarly journals Positive Selection of Novel Peroxisome Biogenesis-Defective Mutants of the Yeast Pichia pastoris

Genetics ◽  
1999 ◽  
Vol 151 (4) ◽  
pp. 1379-1391
Author(s):  
Monique A Johnson ◽  
Hans R Waterham ◽  
Galyna P Ksheminska ◽  
Liubov R Fayura ◽  
Joan Lin Cereghino ◽  
...  
Keyword(s):  
Pichia Pastoris ◽  
Allyl Alcohol ◽  
Alcohol Oxidase ◽  
Methylotrophic Yeast ◽  
Direct Selection ◽  
Toxic Exposure ◽  
Peroxisome Biogenesis ◽  
Yeast Pichia Pastoris ◽  
Methylotrophic Yeast Pichia Pastoris ◽  
Selection Of

Abstract We have developed two novel schemes for the direct selection of peroxisome-biogenesis-defective (pex) mutants of the methylotrophic yeast Pichia pastoris. Both schemes take advantage of our observation that methanol-induced pex mutants contain little or no alcohol oxidase (AOX) activity. AOX is a peroxisomal matrix enzyme that catalyzes the first step in the methanol-utilization pathway. One scheme utilizes allyl alcohol, a compound that is not toxic to cells but is oxidized by AOX to acrolein, a compound that is toxic. Exposure of mutagenized populations of AOX-induced cells to allyl alcohol selectively kills AOX-containing cells. However, pex mutants without AOX are able to grow. The second scheme utilizes a P. pastoris strain that is defective in formaldehyde dehydrogenase (FLD), a methanol pathway enzyme required to metabolize formaldehyde, the product of AOX. AOX-induced cells of fld1 strains are sensitive to methanol because of the accumulation of formaldehyde. However, fld1 pex mutants, with little active AOX, do not efficiently oxidize methanol to formaldehyde and therefore are not sensitive to methanol. Using these selections, new pex mutant alleles in previously identified PEX genes have been isolated along with mutants in three previously unidentified PEX groups.

Toxicity of Glycols and Allyl Alcohol Evaluated by Means of Co-cultures of Microcarrier-attached Rat Hepatocytes and BALB/C 3T3 Mouse Fibroblasts

1992 ◽  
Vol 20 (2) ◽  
pp. 266-270
Author(s):  
Jens-Uwe Voss ◽  
Hasso Seibert
Keyword(s):  
Lactate Dehydrogenase ◽  
Ethylene Glycol ◽  
Allyl Alcohol ◽  
Rat Hepatocytes ◽  
3T3 Cells ◽  
Active Metabolites ◽  
Mediated Effects ◽  
Cells Cultured

The toxicity of allyl alcohol and several glycols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, methoxyethanol, and the glycol ether dioxane) was studied in cultures of 3T3 cells and in co-cultures of 3T3 cells with microcarrier-attached hepatocytes. Metabolism-mediated effects on the cytotoxicity to 3T3 cells were recorded by differences in the growth of the cultures exposed in the presence or absence of hepatocytes. Hepatocyte viability was determined by depletion of intracellular lactate dehydrogenase and effects on the biotransformation ability of hepatocytes were assessed by determination of O-deethylation of 7-ethoxycoumarin (EOD activity). Allyl alcohol was the only substance more toxic to the hepatocytes than to 3T3 cells cultured in the absence of hepatocytes. Toxicity to 3T3 cells of allyl alcohol, ethylene glycol, and 1,3-propanediol, but not of 1,2-propanediol, methoxyethanol and dioxane, was markedly enhanced when the cells were co-cultured with hepatocytes. The results indicate that the toxicity of allyl alcohol, ethylene glycol, and 1,3-propanediol, to 3T3 cells depends on the formation of active metabolites. For ethylene glycol and 1,3-propanediol, growth of 3T3 cells in co-cultures was reduced at concentrations without effects on hepatocyte viability. Co-culture of 3T3 cells with microcarrier-attached rat hepatocytes represents a suitable approach for the in vitro evaluation of metabolism-mediated cytotoxicity.

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