The Reaction of Trialkyl Phosphites with Thiyl and Alkoxy Radicals<sup>1</sup>

Walling, Cheves; Rabinowitz, Robert

doi:10.1021/ja01514a057

Cited by 136 publications

(44 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The radical chain nature of the photo-initiated formation reaction was substantiated by its initiation by light, the inhibition of the reaction by small amounts of added p-cresol and galvinoxyl, and by the induced halogenation of added cyclohexane. The intermediacy of (1) by analogy to the radical addition intermediates proposed for phosphorus (1)(2)(3)(4) and sulfur (1, 6-8) compounds with t-butoxy radicals and because of the precedented involvement of iodonyl radicals in the halogenation reactions of IBBC (see discussion on chlorination reactions), iodobenzene dichloride (12,13), and the polymeric t-butyl hypoiodite reagent (14).…”

Section: Discussionmentioning

confidence: 99%

“…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%

See 1 more Smart Citation

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

Tanner¹,

Gidley²

1968

Can. J. Chem.

View full text Add to dashboard Cite

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.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: C1mentioning

confidence: 99%

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

Tanner¹,

Gidley²

1968

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…This oxidized form then can decompose hydroperoxides catalytically. The decomposition of hydroperoxides by organic phosphites, however, appears to be stoichiometric [18,8].…”

Section: Mechanism Of Oxidationmentioning

confidence: 97%

“…As seen in Figure 4, the decomposition of tertbutylhydroperoxide (TBHP) by DLTDP is quite temperaturedependent, whereas, Walling and Robinowitz [18] .07 More recent advances in the light stabilization of polypropylene fibers have evolved around the use of nickel stabilizers, such as Cyanamid's UV 1084 1 _ [2,2'-thiobis (4-t-octylphenolato) ]-n-butylamine Nickel (II) and Ferro's Al\1:-101 2 -2-2'-thiobis( 4-t-octylphenol) Nickel complex. The nickel complexes generally have low absorption in the ultraviolet, which suggests that they stabilize polymers in a different manner than conventional uv screeners.…”

Section: Mechanism Of Oxidationmentioning

confidence: 99%

Practical Approaches to the Light Stabilization of Polypropylene Multifilaments

Bonkowski

1969

Textile Research Journal

View full text Add to dashboard Cite

The stabilization of polypropylene against the effects of ultraviolet light has been the subject of considerable research. Stabilizing polypropylene multifilament yarns is understandably more difficult than stabilizing monofilaments or molded articles. Due to the small diameters of fiber « 50 microns), conventional uv screeners (such as the benzophenones and benzotriazoles) offer little protection from ultraviolet light. Peroxide decomposers of the dialkylthiodipropionate variety have been found to be virtually ineffective in increasing fiber lifetimes, whereas certain phosphites are quite useful. Supporting laboratory data have shown that at low temperatures phosphites decompose hydroperoxides more rapidly and more efficiently than the dialkylthiodipropionates. Nickel stabilizers appear to be considerably more effective for multifilaments than the uv screeners. Our findings indicate that the Ni compounds function as quenchers of electronically excited carbonyl groups which arise from the photolysis of carbonyl impurities in the polymer. Combinations of the various types of stabilizers can lead to increased fiber lifetimes.

show abstract

“…The yields of the desulfurization reactions of NmocFCG, NmocÀLeuÀpenicillamine, NmocÀPheÀpenicilla-mine, and (NmocLC) 2 are listed in Ta ble 1. The desulfurization reactions converted Cys and penicillamine functionalities into Ala and Valm oietiesr espectively.T he thiol group formed at hiyl radical at 80 8C, [69] which underwent ad irect attack on TECP and formed as ulfurÀphosphoranyl radicalwith nine electrons in the outer valence shell. Moreover,h omolytic cleavage of the CÀSb ondl ed to the formation of an alkyl radical at the b-carbon atom.…”

mentioning

confidence: 99%

Controlling Peptide Self‐Assembly through a Native Chemical Ligation/Desulfurization Strategy

Rasale

Konda

Biswas

et al. 2016

Chemistry An Asian Journal

View full text Add to dashboard Cite

Self-assembled peptides were synthesized by using a native chemical ligation (NCL)/desulfurization strategy that maintained the chemical diversity of the self-assembled peptides. Herein, we employed oxo-ester-mediated NCL reactions to incorporate cysteine, a cysteine-based dipeptide, and a sterically hindered unnatural amino acid (penicillamine) into peptides. Self-assembly of the peptides resulted in the formation of self-supporting gels. Microscopy analysis indicated the formation of helical nanofibers, which were responsible for the formation of gel matrices. The self-assembly of the ligated peptides was governed by covalent and non-covalent interactions, as confirmed by FTIR, CD, fluorescence spectroscopy, and MS (ESI) analyses. Peptide disassembly was induced by desulfurization reactions with tris(2-carboxyethyl)phosphine (TCEP) and glutathione at 80 °C. Desulfurization reactions of the ligated peptides converted the Cys and penicillamine functionalities into Ala and Val moieties, respectively. The self-supporting gels showed significant shear-thinning and thixotropic properties.

show abstract

The Reaction of Trialkyl Phosphites with Thiyl and Alkoxy Radicals¹

Cited by 136 publications

References 1 publication

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

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

Practical Approaches to the Light Stabilization of Polypropylene Multifilaments

Controlling Peptide Self‐Assembly through a Native Chemical Ligation/Desulfurization Strategy

Contact Info

Product

Resources

About

The Reaction of Trialkyl Phosphites with Thiyl and Alkoxy Radicals1

Cited by 136 publications

References 1 publication

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

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

Practical Approaches to the Light Stabilization of Polypropylene Multifilaments

Controlling Peptide Self‐Assembly through a Native Chemical Ligation/Desulfurization Strategy

Contact Info

Product

Resources

About

The Reaction of Trialkyl Phosphites with Thiyl and Alkoxy Radicals¹