The reaction of cis- and trans-1,2-dianisyl-2-phenylvinyl-2-13C bromides with acetic acid and silver acetate

Lee, Choi Chuck; Oka, M.

doi:10.1139/v76-086

Cited by 6 publications

(4 citation statements)

References 8 publications

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“…The synthesis of (E)-and (Z)-3-Br-2-14C was carried out via a series of reactions analogous to those utilized in previous preparations of (E,Z)-1,2-diani~yl-2-phen~:1[2-~~C]vin~l (7), (E,Z)-2-phenyl-1,2-ditolyl[2-13C]vinyl (8), and (E,Z)-1,2-dianisyl-2-tolyl[2-14C]vinyl (9) bromides. Starting with [I4C]-BaC03, 1,2-dipheny'l[l-14C]ethanone (carbonyl labeled desoxybenzoin) was prepared as previously described (10).…”

Section: (E)-and (2)-3-br-2-14c or (E)-and (2)-3-br-2-i3cmentioning

confidence: 99%

Solvolytic rearrangement studies with ¹⁴C or ¹³C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Lee¹,

Wanigasekera²

1986

Can. J. Chem.

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The reaction of (E)-, (Z)-, or a 2:3 mixture of (E)- and (Z)-1,2-diphenyl-2-tolyl[2-14C]vinyl bromide ((E)-, (Z)-, or (E,Z)-3-Br-2-14C) in HOAc–AgOAc gave a 1:1 mixture of the structurally unrearranged but isotopically scrambled (E)- and (Z)-1,2-diphenyl-2-tolyl[1,2-14C]vinyl acetates ((E,Z)-3-OAc-1,2-14C), with an average of 18.3% scrambling of the 14C label from C-2 to C-1 arising from 1,2-tolyl shifts in the 1,2-diphenyl-2-tolylvinyl cation (3). No detectable amount of the structurally rearranged 2,2-diphenyl-1-tolylvinyl acetate (4-OAc) was formed. Solvolysis of (E,Z)-3-Br-2-14C in TFE-2,6-lutidine gave as products 62% 4-OTFE-1,2-14C and 38% of a 1:1 mixture of (E)- and (Z)-3-OTFE-1,214C. Only (Z)-3-OTFE-1,2-14C could be isolated as a pure product and it showed an average of 44.7% scrambling of the label from C-2 to C-1. Similar trifluoroethanolyses of (E,Z)-3-Br-2-13C coupled with gas chromatographic - mass spectral analyses of the diphenyl and phenyl tolyl ketones from ozonolysis of the product mixture showed 44.6% scrambling in the (E,Z)-3-OTFE-1,2-13C, confirming the 14C results for the (Z) isomer. Nondegenerate rearrangements from 1,2-phenyl shifts before and after the degenerate 1,2-tolyl shifts to give 4-OTFE-1-13C and 4-OTFE-2-13C were also observed, demonstrating the occurrence of successive 1,2-aryl shifts in these triarylvinyl cations.

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Section: (E)-and (2)-3-br-2-14c or (E)-and (2)-3-br-2-i3cmentioning

confidence: 99%

Solvolytic rearrangement studies with ¹⁴C or ¹³C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Lee¹,

Wanigasekera²

1986

Can. J. Chem.

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“…[3] (13), from which k;/kr(~,) can be obtained for the mean scrambling of 38.1% as given in eq. [4]. By dividing [2] by [4], one would obtain kpkr(An)lkAkr(ph).…”

Section: Cmentioning

confidence: 99%

“…[4]. By dividing [2] by [4], one would obtain kpkr(An)lkAkr(ph). If one were to assume that in the triazene decomposition in HOAc, k, and k; for the product formation from the 1,2-dianisyl-2-phenylvinyl and trianisylvinyl cations are about equal, then kr(An)/kr(Ph) would be 30.811.25 = 25.…”

Section: Cmentioning

confidence: 99%

“…The 1: 1 mixture of cis and trans acetate products was treated twice (7) with LiAIH, to give a mixture of erythro-and threo-l,2-dianisyl-2-phenyl[l ,2-14C]ethanol (3-1 ,2-I4C) as previously described (4 For personal use only. experiment with alkaline KMNO, (7) gave the anisyl phenyl [L4C]ketone (4I4C) which melted alone or in admixture with an authentic sample at 61-63OC.…”

Section: Degradation Proceduresmentioning

confidence: 99%

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Rearrangement studies with ¹⁴C. XLV. The decomposition of cis- and trans-1,2-dianisyl-2-phenyl[2-¹⁴C]vinylphenyltriazenes in acetic acid

Lee¹,

Obafemi²

1981

Can. J. Chem.

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Can. J. Chem. 59, 1636 (1981). The decomposition of cis-or trans-l,2-dianisyl-2-phenyl[2-'4C]vinylphenyltriazene (cis-or trans-1-NNNHPh-2-I4C) in HOAc gave a 1: 1 mixture of cis and trans products which showed about 3% scrambling of the label from C-2 to C-1 due to 1,2-phenyl shifts in the 1,2-dianisyl-2-phenylvinyl cation. The presence of the more nucleophilic acetate ion from the addition of different amounts of NaOAc was found to decrease or even completely suppress the extent of isotopic scrambling. Comparisons with earlier data such as those obtained from the decomposition of triani~y1[2-~~C]vinylphenyltriazene (2-NNNHPh-2-I4C) led to a calculated k,,,,/kNPh) of about 25 for the relative anisyl to phenyl migration ratio. A kOAc/kHOAC ratio of about 1.5 x lo3 for the product forming capture reactions in the 1,2-dianisyl-2-phenylvinyl cation from the decomposition of 1-NNNHPh-2-I4C was also obtained.CHOI CHUCK LEE et CRAIG A. OBAFEMI. Can. J. Chem. 59, 1636 (1981). La decomposition des dianisyl-1,2 pher1yl-2['~C-2] vinylphenyltriaz2nes cis ou trans (NNNHPh-1 I4C-2 cis ou trans) dans du AcOH donne un melange I: 1 de produits cis et trans dont le marquage est echangk d'environ 3% entre C-2 et C-1 par suite des deplacements 1,2 du ~h e n~l e du cation dianisyl-1,2 phenyl-2 vinyle. On a trouve que la presence d'un ion acetate plus nuclCophile, provenant de I'addition de differentes quantites de AcONa, diminue ou mime supprime completement le degre d'echange isotopique. Une comparaison avec des donnees anterieures, comme celles obtenues a partir de la decomposition du triani~yl[~~C-2]vinyIphenyltriaztne (NNNHPh-2 14C-2), a conduit a une valeur calculee de k,o,)/k,ph, d'environ 25 pour le rapport de migration de I'anisyle vers le phenyle. On a egalement obtenu un rapport kAcO/kAeOH d'environ 1,5 x lo3 pour le produit engendrant les reactions de capture dans le cation dianisyl-1,2 phenyl-2 vinyle partir de la decomposition du NNNHPh-1 14C-2.[Traduit par le journal]The isomeric cis-and trans-1,2-dianisyl-2-solvolysis in HOAc-NaOAc of a 5: 1 mixture of phenylvinyl bromides and chlorides (cis-and cis-and trans-1-anisyl-2-p-[2H,]methoxyphenyltrans-1-Br and 1-C1) were prepared and their 2-phenylvinyl bromides (cis-and trans-l-Br-2-stereochemistry determined in 1969 by Rappoport methoxy-d,), but some scrambling was observed and Apeloig (1). Solvolytic studies in various sol-in the solvolysis of this D-labeled substrate in vents, with or without added nucleophiles, gave a 1: 1 aqueous ethanol or in 2,2,2-trifluoroethanol. In the mixture of the cis and trans products and it was present work, a study was made on the possible concluded that S,l reactions took place via the degenerate rearrangement from 1,2-phenyl shifts dissociated 1,2-dianisyl-2-phenylvinyl cation. Fur-in the 1,2-dianisyl-2-phenylvinyl cation generated ther work with cis-and trans-1-Br, cis-1-C1, and from the decomposition in HOAc of 1,2-dianisylthe methanesulfonates cis-and trans-1-OMS, in-2-phenyl[2-14C]vinylphenyltriazene (1-NNNHPhcluding kinetic studies ...

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ChemInform Abstract: THE REACTION OF CIS‐ AND TRANS‐1,2‐DIANISYL‐2‐PHENYLVINYL‐2‐13C BROMIDES WITH ACETIC ACID AND SILVER ACETATE

Lee¹,

Oka²

1976

Chemischer Informationsdienst

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The reaction of cis- and trans-1,2-dianisyl-2-phenylvinyl-2-¹³C bromides with acetic acid and silver acetate

Cited by 6 publications

References 8 publications

Solvolytic rearrangement studies with ¹⁴C or ¹³C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Solvolytic rearrangement studies with ¹⁴C or ¹³C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Rearrangement studies with ¹⁴C. XLV. The decomposition of cis- and trans-1,2-dianisyl-2-phenyl[2-¹⁴C]vinylphenyltriazenes in acetic acid

ChemInform Abstract: THE REACTION OF CIS‐ AND TRANS‐1,2‐DIANISYL‐2‐PHENYLVINYL‐2‐13C BROMIDES WITH ACETIC ACID AND SILVER ACETATE

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The reaction of cis- and trans-1,2-dianisyl-2-phenylvinyl-2-13C bromides with acetic acid and silver acetate

Cited by 6 publications

References 8 publications

Solvolytic rearrangement studies with 14C or 13C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Solvolytic rearrangement studies with 14C or 13C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Rearrangement studies with 14C. XLV. The decomposition of cis- and trans-1,2-dianisyl-2-phenyl[2-14C]vinylphenyltriazenes in acetic acid

ChemInform Abstract: THE REACTION OF CIS‐ AND TRANS‐1,2‐DIANISYL‐2‐PHENYLVINYL‐2‐13C BROMIDES WITH ACETIC ACID AND SILVER ACETATE

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The reaction of cis- and trans-1,2-dianisyl-2-phenylvinyl-2-¹³C bromides with acetic acid and silver acetate

Solvolytic rearrangement studies with ¹⁴C or ¹³C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Solvolytic rearrangement studies with ¹⁴C or ¹³C labeled (E)- and (Z)-1,2-diphenyl-2-tolylvinyl bromides

Rearrangement studies with ¹⁴C. XLV. The decomposition of cis- and trans-1,2-dianisyl-2-phenyl[2-¹⁴C]vinylphenyltriazenes in acetic acid