THE EXTENT OF THE ABNORMAL RECOMBINATION OF CYANISOPROPYL FREE RADICALS FROM 2,2<sup>′</sup>-AZO-BIS-ISOBUTYRONITRILE

Talât-Erben, M.; Isfendiyaroğlu, A. N.

doi:10.1139/v58-169

Cited by 12 publications

(5 citation statements)

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“…The abnormal recombination of the two resonating forms of the cyanoisopropyl radicals (structures IIa and IIb ) to yield dimethyl‐ N ‐(2‐cyano‐2‐propyl)‐ketenimine ( VII ) has also been reported21 [eq. (3)]: The ketenimine ( VII ) is an unstable substance and at higher temperatures (i.e., ≥60°C) it rearranges to tetramethylsuccinodinitrile ( III ) 22.…”

Section: Resultsmentioning

confidence: 99%

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Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

Zahran

Morsy

Mahmoud

2003

J of Applied Polymer Sci

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ABSTRACT:The feasibility of a cellulose thiocarbonateazobisisobutyronitrile (AIBN) initiation system to induce graft copolymerization of methyl methacrylate (MMA) and other acrylic monomers onto cotton fabric was investigated. Other acrylic monomers were acrylic acid, acrylonitrile, and methyl acrylate. The initiation system under investigation was highly activated in the presence of a metal-ion reductant or a metal-ion oxidant in the polymerization medium. A number of variables in the grafting reaction were studied, including AIBN concentration, pH of the polymerization medium, nature of substrate, monomer concentration, duration and temperature of polymerization, and composition of the solvent/water polymerization medium. The solvents used were methanol, isopropanol, 1,4-dioxane, cyclohexane, benzene, dimethyl formamide, and dimethyl sulfoxide. There were optimal concentrations of AIBN (5 mmol (2 mmol/L). A polymerization medium of pH 2 and temperature of 70°C constituted the optimal conditions for grafting. The methanol/water mixture constituted the most favorable reaction medium for grafting MMA onto cotton fabric by using the Fe 2ϩ -cellulose thiocarbonate-AIBN redox system. MMA was superior to other monomers for grafting. The unmodified cotton cellulose showed very little tendency to be grafted with MMA compared with the chemically modified cellulosic substrate. A tentative mechanism for the grafting reaction was proposed.

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Section: Resultsmentioning

confidence: 99%

“…The abnormal recombination of the two resonating forms of the cyanoisopropyl radicals (structures IIa and IIb) to yield dimethyl-N-(2-cyano-2-propyl)ketenimine (VII) has also been reported 21…”

Section: Tentative Mechanismsmentioning

confidence: 94%

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

Zahran

Morsy

Mahmoud

2003

J of Applied Polymer Sci

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“…Qualitatively, the rate of formation of IV decreased in the order of greater substitution of the amine group•-i.e., 3°< 2°< Io. These results suggest that III is being catalytically decomposed to IV and hydrogen.8 9 Ar-N H2…”

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confidence: 87%

“…(9) We wish to express our gratitude to Drs. 7 van der Kerk, Noltes, and Luijten give evidence for the stoichiometry.…”

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confidence: 99%

Attempted Hydrogenolysis of Amines with Triphenyltin Hydride¹

Stern¹,

Becker²

1962

J. Org. Chem.

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2Rk3nN(C2H5)2 + Con + H 2 0 + (Rdh)?COs + 2(C2H6),NH (3) ( R = GH6, n-CaH7, or n-GHg) Infrared absorptions characteristic to the diethylaminotin grouping, Sn--N (C2H&, were observed a t 1290 (m), 1173 (vs), 1010 (s), 880 (s), and 780 (s) cm.-l, all being common to the three trialkyl(diethylamin0) tins herein described. These bands completely disappeared on exposure of the sample to air for several minutes on a sodium chloride plate, when characteristic bands of organotin carbonate appeared at 1560-1520 (vs), 1370 (vs), 1070 (m), and 840 (m) cm.-' instead.These results show that the organotin-nitrogen bonding is rather stable to heating, as indicated by no change upon distillation, but is highly reactive toward proton-containing reagents. ExperimentalAnalyses .-A microelementary analysis for carbon and hydrogen waa given up because of the too high sensitivity of the sample to air (equation 3). As soon as a sealed ampoule was cut, diethylamine which was recognized by the strong odor vaporized.Nitrogen was analyzed by titration according to equation 2: an exactly weighed sealed ampoule containing about 2.0 g. of the sample waa crushed with a glass rod in 30 ml. of standardized 0.5 N hydrochloric acid, and the excess acid was back-titrated with 0.5 N sodium carbonate with methyl orange as an indicator.Tin analyses were carried out according to Farnsworth and Pekola.9 In this case the vaporization of diethylamine has no effect on the analytical values of tin. Triethyl(diethy1amino)tin.-A tetrahydrofuran solutionof diethylaminomagnesium bromide prepared from 2.9 g. (0.12 g.-atom) of magnesium, 10.9 g. (0.1 mole) of ethyl bromide, and 7.3 g. (0.1 mo!e) of diethylamine in 50 ml. of tetrahydrofuran was added dropwise to a solution of 14.5 g. (0.06 mole) of triethyltin chloride10 (b.p. 86-88'/9 mm.) dissolved in 50 ml. of tetrahydrofuran. An exothermic reaction was observed during this procedure. After refluxing for 4 hr. the solvent was distilled and the reaction product, was fractionated under reduced pressure. A fraction boiling a t 72-88'/11 mm. was collected; yield, 10.5 g. (6370). Redistillation gave 9.5 g. of an analytically pure fraction boiling a t 114-117'/23 mm. All procedures were carried out in a nitrogen atmosphere. This sample gave a negative Beilstein test for halogen. The product was stored in sealed ampoules under nitrogen.Anal. Calcd. for CloH~5KSn: Sn, 42.69; N, 5.04. Found: Sn,42.64,42.98,42.45; N,4.92. Tri-n-propyl(diethy1amino)tin and tri-n-butyl(diethy1amino)tin were also obtained in about 707, yields by an analogous way from tri-n-propyltin chloride10 (b.p. 122-123"/10 mm.) and tri-n-butyltin chloride10 (b.p. 130-132'/4 mm. ), respectively.Tri-n-propyl(diethy1amino)tin had b .p. 11&120°/13 mm .Anal. Calcd. for C13HslNSn: Sn, 36.97; ?;, 4.36.Found: Sn, 37.41; N, 3.96.Tri-%-butyl( diethy1amino)tin distilled a t 124-1 34 O / 8 mm.

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“…decreased in the order of greater substitution of the amine group•-i.e., 3°< 2°< Io. These results suggest that III is being catalytically decomposed to IV and hydrogen.8 9 Ar-N H2 PhgSnH->-Ph3SnSnPh3 + H2 Experimental Allylamine and III.-To a round bottom flask equipped with a stirrer, reflux condenser, gas inlet tube, and gas exit tube leading from the top of the condenser to a trap containing 95% ethanol kept at -78°were added 32.2 g. (0.092 mole) of triphenyltin hydride and 2.6 g. (0.046 mole) of allylamine. Evolution of a gas was observed on mixing.…”

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confidence: 90%

The Photochemical Preparation of Dimethyl-N-(2-cyano-2-propyl)ketenimine from 2,2'-Azobisisobutyronitrile¹

Smith¹,

Sheats²,

Miller³

1962

J. Org. Chem.

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decreased in the order of greater substitution of the amine group--i.e., 3" < 2' < 1". These results suggest that 111 is being catalytically deconiposed to IV and hydrogen.8 Ph3SnH -Ph3SnSnPhs + HP Experimental Allylamine and 111.-To a round bottom flask equipped with a stirrer, reflux condenser, gas inlet tube, and gas exit tube leading from the top of the condenser to a trap containing 95y0 ethanol kept a t -78" were added 32.2 g. (0.092 mole) of triphenyltin hydride and 2.6 g. (0.046 mole) of allylamine. Evolution of a gas was observed on mixing. The reaction mixture was stirred under a nitrogen atmosphere til solidification was complete. The contents of the trap gave a negative test with Nessler's reagent for ammonia, no characteristic brown-red color being observed. The solid in the flask was recrystallized from benzene, m.p. 230-232'. It did not depress the melting point on admixture with an authentic sample of 117.In a second experiment, using the same procedure as described above, 20 g. (0.057 mole) of I11 and 1.62 g. (0.029 mole) of I were used. Any possible propylene being evolved was led from the top of the condenser into a trap containing I-hexene kept at -78", but no propylene was detected upon running the trap contents into a vapor phme chromatograph.Benzylamine and 111.-The procedure of Kupchik and Connolly was followed. The first few drops of distillate collected showed bands in the infrared (cm.-l) a t 3077,

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THE EXTENT OF THE ABNORMAL RECOMBINATION OF CYANISOPROPYL FREE RADICALS FROM 2,2^′-AZO-BIS-ISOBUTYRONITRILE

Cited by 12 publications

References 0 publications

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

Attempted Hydrogenolysis of Amines with Triphenyltin Hydride¹

The Photochemical Preparation of Dimethyl-N-(2-cyano-2-propyl)ketenimine from 2,2'-Azobisisobutyronitrile¹

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THE EXTENT OF THE ABNORMAL RECOMBINATION OF CYANISOPROPYL FREE RADICALS FROM 2,2′-AZO-BIS-ISOBUTYRONITRILE

Cited by 12 publications

References 0 publications

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

Attempted Hydrogenolysis of Amines with Triphenyltin Hydride1

The Photochemical Preparation of Dimethyl-N-(2-cyano-2-propyl)ketenimine from 2,2'-Azobisisobutyronitrile1

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THE EXTENT OF THE ABNORMAL RECOMBINATION OF CYANISOPROPYL FREE RADICALS FROM 2,2^′-AZO-BIS-ISOBUTYRONITRILE

Attempted Hydrogenolysis of Amines with Triphenyltin Hydride¹

The Photochemical Preparation of Dimethyl-N-(2-cyano-2-propyl)ketenimine from 2,2'-Azobisisobutyronitrile¹