Monomer Reactivity Factors for Methyl Vinyl Sulfide and Sulfone. Some Comments on Covalent Sulfur Bonding

Price, Charles C.; Zomlefer, Jack

doi:10.1021/ja01157a004

Cited by 88 publications

(36 citation statements)

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“…The low reactivity of dimethyl sulfoxide is consistent with its low radical stabilization factor (Q=0.1) as determined from copolymerization experiments by Price and Zomlefer (21).…”

Section: Resultssupporting

confidence: 79%

Reactivities of organic compounds toward phenyl radicals

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Signature was redacted for privacy.Signature was redacted for privacy.Signature was redacted for privacy. Table 1. Reactivities of compounds toward phenyl radicals at 600C Table 2. Effects of functional groups on reactivities of carbon-hydrogen bonds on conqjounds of the type Z-CH^ toward the phenyl radical at 60°C Table 3. Effects of functional groups on reactivities of carbon-hydrogen bonds on confounds of the type Z-CH2-CH3 toward the phenyl radical at 60°C l^le k. Effects of functional groups on reactivities of carbon-hydrogen bonds on compounds of the type Z-CHfCHjig toward the phenyl radical at 60°C Effects of functional groups on reactivities of carbonhydrogen bonds toward the phenyl radical at 60°C ^0Effects of functional groups on reactivities of carbon-jhydrogen bonds on compounds which contain a five-membered ring toward the phenyl radical at ÔO^C Effects of functional groups on reactivities of carbon-hydrogen bonds on compounds containing a six-membered ring toward the phenyl radical at 60°CProducts of the complete decomposition of PAT in cyclohexane and carbon tetrachloride in the presence of oxygen at 60°C INTRODUCTIONThe primary objective of this work was to establish a conqarehensive scale of the reactivities of hydrogen atoms °C to common functional groups toward the phenyl radical. Because of the experimental difficulties involved in measuring absolute rates of radicals in solution, the method of competitive reactions is generally used in solving such problems (l).In the competitive method two compounds are allowed to compete for some reactive intermediate. The necessary experimental data are similar to those required in a kinetic study except that the time variable has been eliminated. Experimentally all that is required is the measurement of either the disappearance of reactants or the appearance of products. In this work the appearance of products was measured by gas liquid chromatography (g .1 ,c.).The data obtained have the form of relative rates or relative reactivities. By determining the relative rates of reaction of appropiate model compounds it is possible to arrive at conclusions regarding the influence of molecular structure on the reactivities of individual bonds.Comparisons can also be made with similar data for other radicals and conclusions drawn concerning the reactivities and selectivities of the radicals.In the present work phenyl radicals were generated by the thermal decoDçiosition of phenylazotriphenylraethane. The relative reactivities of more than II4.O compounds toward the phenyl radical were investigated hy the method of competitive reactions using carbon tetrachloride as the reference solvent. All reactions were conducted at 60°C. The compounds Bipheryl resulting from the coupling of two phenyl radicals is seldom isolated as a product.In the case of phenylazotriphenylmethane as a phenyl radical source, Eliel and coworkers (9) suggest that removal of the hydrogen atom from the phenylcyclohexadieryl radical is accomplished by the triphenylmethyl radical so that t...

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“…The low reactivity of dimethyl sulfoxide is consistent with its low radical stabilization factor (Q=0.1) as determined from copolymerization experiments by Price and Zomlefer (21).…”

Section: Resultssupporting

confidence: 79%

Reactivities of organic compounds toward phenyl radicals

Hunt

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“…16 Therefore the observed Q value of sulfonium salts in radical copolymerization emphasizes that some of the resonance structures shown below contribute to the propagating species:…”

Section: Radical Copolymerization Of (1) and (2) With Styrenementioning

confidence: 97%

Preparation and free radical polymerization of dimethyl‐p‐vinylphenylsulfonium tetrafluoroborate

Ogura

Kondo

Tsuda

1981

J. Polym. Sci. Polym. Chem. Ed.

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“…The ability of organic compounds of elements PhT + (CH,),COCl -+ PhI / of the third period to expand their valence shell \ to accommodate nine electrons forming a re-OC(CHd3 (IBBC) active radical intermediate has been in the cases of phosphorus (1)(2)(3)(4) and sulfur (5)(6)(7)(8)(9). The formation of radical intermediates of compounds of elements of higher atomic number having energetically low-lying d orbitals would also be predicted favorable.…”

Section: C1mentioning

confidence: 99%

“…Reaction schemes involving a sequence of reactions The rapid reaction of IBBC with hydrogen chloride yielded iodobenzene dichloride and t-butyl alcohol (reactions [3] and [5]). Sinceiodobenzene dichloride has been shown to undergo photo-initiated radical chain halogenation where phenyl iodonyl chloride is the abstracting species (1 1) the sequence of reactions [1 1, [2], [3], [5], [6], [7], and [8] must be considered in any evaluation of the halogenation reactions of IBBC. The primary :secondary:tertia.ry selectivities for hydrogen abstraction by PhICl radicals has been reported as 1 :2 1 :368 (12).…”

Section: /1vmentioning

confidence: 99%

On the chemistry of iodonyl radicals. The oxidation of iodobenzene by t-butyl hypochlorite

Tanner¹,

Gidley²

1968

Can. J. Chem.

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The reaction of iodobenzene with t-butyl hypochlorite proceeds by a free radical chain mechanism, forming as the sole product iodobenzene t-butoxy chloride (IBBC). The photoinduced or tl~er~nally induced reactions of IBBC with hydrocarbon substrates yield chlorinated hydrocarbons by a radical chain halogenation sequence involving t-butoxyiodonyl benzene as the principal chain-carrying species. The photolysis or thermolysis of IBBC in the absence of molecular oxygen yields products resulting from a variety of free radical chain reactions, while thermolysis in the presence of oxygen yields only iodobenzene and t-butyl hypochlorite.

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Monomer Reactivity Factors for Methyl Vinyl Sulfide and Sulfone. Some Comments on Covalent Sulfur Bonding

Cited by 88 publications

References 0 publications

Reactivities of organic compounds toward phenyl radicals

Reactivities of organic compounds toward phenyl radicals

Preparation and free radical polymerization of dimethyl‐p‐vinylphenylsulfonium tetrafluoroborate

On the chemistry of iodonyl radicals. The oxidation of iodobenzene by t-butyl hypochlorite

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