The Thermal Decomposition of 2-Phenoxybenzoyl Peroxide

DeTar, DeLos F.; Hlynsky, Alex

doi:10.1021/ja01621a070

Cited by 25 publications

(11 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The regioselectivity of these reactions has been attributed to entropy factors (163). 102 103 104 0· Ö 105 Photolysis of 5-hexenyl nitrite (106) affords no cyclic product (163,265). Unfortunately, no accurate rate constants are available, but ESR data (268) and product studies (265) suggest that cyclization of 103 is very fast (k > 10 8 sec -1 ) and competes effectively with intramolecu lar hydrogen transfer from an unactivated CH 2 group.…”

Section: E Alkenoxy Alken Aminyi and Other Heteroatom-centered Radimentioning

confidence: 99%

Free-Radical Rearrangements

Beckwith¹,

Ingold²

1980

Organic Chemistry: A Series of Monographs

114

View full text Add to dashboard Cite

Section: E Alkenoxy Alken Aminyi and Other Heteroatom-centered Radimentioning

confidence: 99%

Free-Radical Rearrangements

Beckwith¹,

Ingold²

1980

Organic Chemistry: A Series of Monographs

114

View full text Add to dashboard Cite

“…[1] Notably,a ryl migration from an aryl ether to form an ester is rare.In1955, this migration was first observed upon the thermal decomposition of 2-phenoxybenzoyl peroxide in 25 %y ield by DeTar and Hlynsky. [2] Recently,t he migration was promoted by silver catalysis at 130 8 8CbyHossian and Jana, who used acarboxylic acid as the starting material. [3] However,t he stoichiometric strong oxidant K 2 S 2 O 8 and ab ase were required.…”

mentioning

confidence: 99%

Efficient Aryl Migration from an Aryl Ether to a Carboxylic Acid Group To Form an Ester by Visible‐Light Photoredox Catalysis

Wang

Cao

2017

Angewandte Chemie

View full text Add to dashboard Cite

We have developed ahighly efficient aryl migration from an aryl ether to ac arboxylic acid group through retro-Smiles rearrangement by visible-light photoredoxc atalysis at ambient temperature.T ransition metals and as toichiometric oxidant and base are avoided in the transformation. Inspired by the high efficiency of this transformation and the fundamental importance of C À Ob ond cleavage,w ed eveloped anovel approachtothe C À Ocleavage of abiaryl ether to form two phenolic compounds,a sd emonstrated by ao ne-pot, twostep gram-scale reaction under mild conditions.T he aryl migration exhibits broad scope and can be applied to the synthesis of pharmaceutical compounds,s uch as guacetisal. Primary mechanistic studies indicate that the catalytic cycle occurs by ar eductive quenchingpathway.Various aryl-migration reactions have been developed and display broad application. [1] Notably,a ryl migration from an aryl ether to form an ester is rare.In1955, this migration was first observed upon the thermal decomposition of 2-phenoxybenzoyl peroxide in 25 %y ield by DeTar and Hlynsky. [2] Recently,t he migration was promoted by silver catalysis at 130 8 8CbyHossian and Jana, who used acarboxylic acid as the starting material. [3] However,t he stoichiometric strong oxidant K 2 S 2 O 8 and ab ase were required. Furthermore,t he transformation only resulted in up to 64 %y ield. No clear electronic effects on this aryl migration were observed. Thus, the transformation was identified as aSmiles rearrangement. Herein, we demonstrate ahighly efficient aryl migration from an aryl ether to form the ester of acarboxylic acid by visiblelight photoredox catalysis at ambient temperature without an oxidant [Scheme 1, Eq. (1)].O nly 1mol %o faphotosensitizer (PDI or Acr + -Mes ClO 4 À )a nd 10 mol %o fabase (K 2 HPO 4 )w ere required. Notably,e lectron-donating groups on the migrating aryl ring generally induced higher yields in this transformation, which differs from the typical Smiles rearrangement [4] and can be understood as ar etro-Smiles rearrangement. [4a,5] As this developed aryl migration is the retro-reaction of the reported Smiles rearrangement involving aryl migration from an ester to form an aryl ether. [6] And the Smiles rearrangement always requires ah eteroatom as the nucleophilic component and an electrophilic arene activated by strong electron-withdrawing groups,acarbonbased nucleophile,orfree-radical attack on the ipso-position of sulfonates or sulfonamides. [4] By taking advantage of visible-light photoredox catalysis,transition metals and astoichiometric amount of an oxidant and abase are avoided, thus leading to an environmentally benign and highly atom economical transformation. Moreover,i nspired by the high efficiency of this aryl migration and the fundamental importance of CÀOb ond cleavage, [4i, 7] we demonstrate an ovel approach to CÀOb ond cleavage in biaryl ethers to give two phenolic compounds in ao ne-pot, two-step reaction under mild conditions as as ubsequent transformation [Scheme 1, Eq. (2)].Visible...

show abstract

“…Acetyl chloride, 4-benzoyl chloride, 2-naphthoyl chloride, 4-phenylbenzoyl chloride, 4-nitrobenzoyl chloride, 2-phenoxybenzoic acid, N -phenylmaleimide, and hydroquinone (Aldrich) were used as received. 2-Phenoxybenzoyl chloride was prepared following a known procedure …”

Section: Methodsmentioning

confidence: 99%

Preparation of Polyimides Utilizing the Diels−Alder Reaction. 1,4-[N,N‘-Bis(butadienyl-2-methyl)diamido]-2,3,5,6- tetramethylbenzenes with Bismaleimides

1996

View full text Add to dashboard Cite

Bis(amide-1,3-diene) monomers were prepared from 1,4-[N,N‘- bis(butadienyl-2-methyl)diamino]-2,3,5,6-tetramethylbenzene and several alkyl and aryl acid chlorides. The corresponding poly(amide imide)s were prepared by the Diels−Alder reaction involving these bis(amide-1,3-diene)s with bismaleimides. The polymers exhibited inherent viscosities of 0.21−0.81 dL/g and glass transition temperatures ranging from 202 to 269 °C. Moderate thermal stability was observed by dynamic thermogravimetric analysis, with 10% weight loss occurring between 318 and 350 °C in helium. The polymers were soluble in N,N-dimethylacetamide and chlorinated solvents. Creasable films were obtained by solution casting from chloroform. The chemistry and physical properties of the monomers and polymers are discussed.

show abstract

The Thermal Decomposition of 2-Phenoxybenzoyl Peroxide

Cited by 25 publications

References 1 publication

Free-Radical Rearrangements

Free-Radical Rearrangements

Efficient Aryl Migration from an Aryl Ether to a Carboxylic Acid Group To Form an Ester by Visible‐Light Photoredox Catalysis

Preparation of Polyimides Utilizing the Diels−Alder Reaction. 1,4-[N,N‘-Bis(butadienyl-2-methyl)diamido]-2,3,5,6- tetramethylbenzenes with Bismaleimides

Contact Info

Product

Resources

About