Reactions of Alkoxy Radicals. I. The Reactions of Di-tert.-butyl Peroxide with n-Butyric Acid and Ethyl n-Butyrate

1960 ◽  
Vol 13 (2) ◽  
pp. 244 ◽  
Author(s):  
ALJ Beckwith
Keyword(s):  
Butyric Acid ◽  
Electron Acceptor ◽  
Dicarboxylic Acids ◽  
Cupric Chloride ◽  
Hydrogen Atoms ◽  
Alkoxy Radicals ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Butoxy Radical

The relative yields of meso- and racernic-2,3-diethylsucoinic and 2-ethyl-3-methyl-glutaric acids from the reaction of di-tert.-butyl peroxide with n-butyric acid indicate that abstraction of hydrogen atoms from the acid by tert.-butoxy radicals occurs preferentially at the α-position. A similar directive effect has been noted in the reaction of ethyl n-butyrate with di-tert.-butyl peroxide. These results suggest that the tert.-butoxy radical has negligible electron-acceptor properties and that polar effects do not influence the course of its reactions. Catalytic amounts of cupric chloride profoundly modify the reaction of di-tert.-butyl peroxide with n-butyric acid. New analytical methods for the separation and determination of hydroxy- and dicarboxylic acids are described.

Photolysis of Di-tert-butyl Peroxide at High Pressure

1972 ◽  
Vol 50 (10) ◽  
pp. 1531-1534 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Gaseous Phase ◽  
Chemical Reactivity ◽  
Hydrocarbon Concentration ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Butoxy Radical ◽  
Peroxide Molecule

Di-tert-butyl peroxide has been photolyzed at 2537 Å in the gaseous phase in the presence of up to 47 amagats (2.10 mol/l) of propane and of cyclopropane. It was confirmed that no acetone is formed in the limit of infinite hydrocarbon concentration and therefore that the primary chemical act leading to the eventual formation of acetone is the formation of two tert-butoxy radicals from the excited peroxide molecule; in addition, some crude information was obtained concerning relative rates of photochemical vs. deactivation processes. It was also found that at these densities the tert-butoxy radical formed in the photolysis of di-tert-butyl peroxide did not appear to differ in chemical reactivity from the tert-butoxy radical formed in the thermal decomposition of di-tert-butyl peroxide.

REACTIONS OF ALKOXY RADICALS: V. PHOTOLYSIS OF DI-t-BUTYL PEROXIDE

1958 ◽  
Vol 36 (9) ◽  
pp. 1227-1232 ◽  
Author(s):  
Garnett McMillan ◽  
M. H. J. Wijnen
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Energy Difference ◽  
Butyl Alcohol ◽  
Reaction Products ◽  
Butyl Ether ◽  
Alkoxy Radicals ◽  
Temperature Range ◽  
Butyl Peroxide ◽  
Butoxy Radical

The photolysis of di-t-butyl peroxide has been investigated over the temperature range 25 ° to 79 °C. As reaction products were observed: acetone, t-butyl alcohol, methyl t-butyl ether, i-butylene oxide, ethane, methane, and carbon monoxide. The following reactions, involving the t-butoxy radical, have been studied:[Formula: see text]An activation energy difference of E2 − E6 = 3 kcal has been obtained.

Studies on allylic peroxides. II. Allyl-t-butyl peroxide

1980 ◽  
Vol 58 (5) ◽  
pp. 450-453 ◽  
Author(s):  
R. Hiatt ◽  
V. G. K. Nair
Keyword(s):  
Computer Modelling ◽  
Hydrogen Abstraction ◽  
Radical Addition ◽  
Experimental Results ◽  
Alkoxy Radicals ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Induced Decomposition ◽  
Good Agreement

Allyl-tert-butyl peroxide decomposes thermally in toluene with kd = 1013.8 exp (−33200/θ) (s−1). Product studies show the reaction to be a mixture of homolysis and radical-induced decomposition, the latter involving both radical addition to C=C and allyl hydrogen abstraction by alkoxy radicals. Computer modelling of the system gives good agreement with the experimental results and suggests that the overall decomposition is about 50% homolysis.

INFLUENCE OF DICARBOXYLIC ACIDS ON SOWING QUALITY OF SPRING BARLEY

1970 ◽  
pp. 22-25
Author(s):  
N. N. Loy ◽  
S. N. Gulina
Keyword(s):  
Organic Acids ◽  
Spring Barley ◽  
Dose Range ◽  
Dicarboxylic Acids ◽  
Rotary Machine ◽  
Working Solution ◽  
Negative Effect ◽  
Sprouted Seeds

The effect of presowing seed treatment on various concentrations of dicarboxylic (organic) acids on the sowing characteristics of spring barley has been studied. Seeds were treated with organic acids obtained by exposing cuttings to the radiation with a dose of 100 kGy and consequent hydrolysis, in concentrations: 1•10-7 %; 1•10-9; 1•10-11; 1•10-13 and 1•10-15 % on a laboratory rotary machine RVO-64 for one day before laying for germination. Distilled water was used for the control case. The rate of application of the working solution calculated as 10 liters / ton of seeds. Seeds were germinated in filter paper rolls in accordance with GOST 12038-84 requirements. The temperature was maintained at +24 ° C in the thermostat where the glasses with rolls were placed. For determination of germinative power and laboratory germination the sprouted seeds were evaluated after three and seven days, respectively. In laboratory experiments it was established that the treatment of barley seeds of varieties Zazersky 85, Nur and Vladimir with organic acids (OK) in different concentrations had both a stimulating and a negative effect. On the Zazersky 85 variety, in variants with acid concentrations of 1•10-9 and 1•10-11, an increase in germination energy (EP) by 2-4% and a significant decrease (by 3-4%) of laboratory germination (LV) of barley seeds were noted. On the Nur variety, the increase in EP was observed at 4% (concentration 1•10-11), LV and seed growth force (CPC) by 2-7% at a concentration of 1•10-7 and in the dose range 1•10-11 - 1•10-14 compared to the control values. On the grade of Vladimir, an increase in EP, LV, and CPC was found to increase by 1-6% at concentrations OK 1•10-7 and 1•10-13. It was shown that the treatment of seeds with acids led to an increase in the length of the germ in all studied varieties (by 3-9%) and dry biomass of 7-day-old seedlings - by 3-6%. Consequently, the treatment of seeds with a mixture of dicarboxylic acids has a stimulating effect on the sowing quality of spring barley.

Fundamental Thermal Hazard Investigation for Tert-Butyl Peroxide Reactor Using DSC and TGA Techniques

2011 ◽  
Vol 21 (1) ◽  
pp. 53-63 ◽  
Author(s):  
Chien-Jung Chen ◽  
Jen-Hao Chi ◽  
Sheng-Hung Wu ◽  
Cheng-Tung Chen ◽  
Hsiu-Fen Tsai
Keyword(s):  
Thermal Hazard ◽  
Tert Butyl ◽  
Butyl Peroxide

Determination of diethylene glycol in oligomeric ethylene glycol esters of some aromatic dicarboxylic acids

1974 ◽  
Vol 39 (11) ◽  
pp. 3272-3277 ◽  
Author(s):  
R. Komers ◽  
M. Řeřichová ◽  
Z. Šír
Keyword(s):  
Ethylene Glycol ◽  
Diethylene Glycol ◽  
Dicarboxylic Acids ◽  
Aromatic Dicarboxylic Acids

Tunable electrochemical behavior of dicarboxylic acids anchored Co-MOF: Sensitive determination of rutin in pharmaceutical samples

2021 ◽  
Vol 622 ◽  
pp. 126667
Author(s):  
Thushatharcchini Sivam ◽  
N.S.K. Gowthaman ◽  
H.N. Lim ◽  
Yoshito Andou ◽  
P. Arul ◽  
...  
Keyword(s):  
Electrochemical Behavior ◽  
Dicarboxylic Acids ◽  
Pharmaceutical Samples ◽  
Sensitive Determination

Energy partitioning on photolysis of di-tert-butyl peroxide

1971 ◽  
Vol 75 (24) ◽  
pp. 3651-3655 ◽  
Author(s):  
F. H. Dorer ◽  
S. N. Johnson
Keyword(s):  
Energy Partitioning ◽  
Tert Butyl ◽  
Butyl Peroxide

Ab Initio Determination of a New Complex Structure (55 Non-Hydrogen Atoms) from Synchrotron Powder Data: An Uncommon Nickel Succinate, Ni7(C4H4O4)4(OH)6(H2O)3•7H2O

2004 ◽  
Vol 443-444 ◽  
pp. 333-336
Author(s):  
N. Guillou ◽  
C. Livage ◽  
W. van Beek ◽  
G. Férey
Keyword(s):  
Ab Initio ◽  
Complex Structure ◽  
Three Dimensional ◽  
Free Water ◽  
Hydrogen Atoms ◽  
Monoclinic System ◽  
Synchrotron Powder Diffraction ◽  
Chloride Hexahydrate ◽  
Autogenous Pressure

Ni7(C4H4O4)4(OH)6(H2O)3. 7H2O, a new layered nickel(II) succinate, was prepared hydrothermally (180°C, 48 h, autogenous pressure) from a 1:1.5:4.1:120 mixture of nickel (II) chloride hexahydrate, succinic acid, potassium hydroxide and water. It crystallizes in the monoclinic system (space group P21/c, Z = 4) with the following parameters a = 7.8597(1) Å, b = 18.8154(3)Å, c = 23.4377(4) Å,ϐ = 92.0288(9)°, and V = 3463.9(2) Å3. Its structure, which contains 55 non-hydrogen atoms, was solved ab initio from synchrotron powder diffraction data. It can be described from hybrid organic-inorganic layers, constructed from nickel oxide corrugated chains. These chains are built up from NiO6hexameric units connected via a seventh octahedron. Half of the succinates decorate the chains, and the others connect them to form the layers. The three dimensional arrangement is ensured by hydrogen bonds directly between two adjacent layers and via free water molecules.

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