Reaction of nucleophiles with 1,1-dinitro-2,2-diphenylethylene

Russell, Glen A.; Dedolph, D. F.

doi:10.1021/jo00220a038

Cited by 19 publications

(13 citation statements)

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“…PhCH=CHN02, PhNO, o-MeC6H4N0, PhN(O)=NPh, PhN=NPh, PhN=CHPh, DABCO, and PTSA were purchased from Aldrich Chemical Co. The other /3-nitrostyrenes were prepared by literature procedures: l b [291, lc [30], 2a [30], 2b [30], 2c [31], 2d [32], and 2e [32]. t-BuHgC1 was prepared from t-BuLi and HgC1, in THF, mp (dec.) 110-1 13°C (lit.…”

Section: Reagents Arid Solveiitsmentioning

confidence: 99%

Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

Russell

Yao

1992

Heteroatom Chemistry

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Photolysis of t‐BuHgCl/KI with PhC(R2)C(R1)NO2 forms PhC(R2)C(R1)Bu‐t when R1 = R2 = H or in low yield when R1 = H, R2 = Ph. When R1 ≠ H, or when R2 = Ph, reactions with t‐BuHgI/KI/hv proceed mainly via PhC(R2)C(R1)NO2·‐, PhC(R2)C(R1)N(OBu‐t)O−HgX+, PhC(R2)C(R1)NO and PhC(R2)C(R1)N(OBu‐t)HgX to form a variety of novel products including the dimeric bisnitronic esters (6) with R1 = Me or Ph and R2 = H; PhCH(R2)C(R1) = NOBu‐t with R1 = Me or Ph and R2 = H or R1 = H and R2 = Ph; PhC(R2)(OBu‐t)C(R1)NOH with R1 = H or Me and R2 = Ph; and 3‐phenyl‐2‐R1‐indoles with R1 = H, Me, Ph, PhS or t‐BuS and R2 = Ph. Nitrosoaromatics react with t‐BuHgX in the dark to form ArN(OBu‐t)(OBu‐t)HgX+ which condenses with ArNO to form the azoxy compound. tert‐Butyl radicals will add to RNO2 [R = Ph, Ph2CCH, Ph2CC(Ph)] in the presence of t‐BuHgI2− to form products derived from RN(OBu‐t)O−HgI+.

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Section: Reagents Arid Solveiitsmentioning

confidence: 99%

Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

Russell

Yao

1992

Heteroatom Chemistry

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“…Such β ‐addition — 1,2‐shift sequence was among the first mechanisms to be considered for the nucleophilic substitution in acetylenes as early as the 1970 s . It was also proposed for the reactions of thiolates (and other soft nucleophiles) with 1,1‐diphenyl‐2,2‐dinitroethylene and α‐halovinylsulphones . Later, support for this mechanism was provided by B. Shainyan in his study of the reaction of α‐bromovinylsulphones with thiolates …”

Section: Introductionmentioning

confidence: 99%

1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

et al. 2016

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The 1,2‐shift of β‐substituent to the carbenic or carbenoid centre is one of the primary reaction pathways for these intermediates. In the present work the 1,2‐shift of various element‐centered groups in carbenoid anions [RnECF2CFCl]– (E=C, N, Si, Ge, Sn, P, As, Sb, S, Se, Te, R=Me) is for the first time examined with the help of density functional theory calculations. The calculations were performed on the models of free carbenoid anions [RnECF2CFCl]– and their Na+ and [NMe4]+ salts. In all cases the 1,2‐shift of the RnE‐groups formed by the elements of the third and subsequent periods was calculated to be much more facile than for carbon‐centred groups. Calculated ΔG≠ are as low as 4–6 kcal/mol for the 5−th period Me3Sn‐ and Me2Sb groups. An even more facile 1,2‐shift precludes the existence of the corresponding β‐element substituted carbenes. Periodicity trends, correlation analysis and NBO analysis of the transition state structures were used to discriminate between different intrinsic mechanisms. In free carbenoid anions the main mechanisms of 1,2‐shift of RnE‐groups are: a) electrophilic shift of R3E‐ (E= Si, Ge, Sn) and Ph‐groups; b) nucleophilic shift of RS‐ group c) dyotropic‐type pathway for RS‐, RSe‐, RO‐, R2N and R3C‐ groups. In carbenoid ion pairs: a) nucleophilic shift of RnE‐ (E=Si, Ge, Sn P, As, Sb) and Re(CO)5‐ groups; b) nucleophilic substitution involving the lone pair of RS‐, RSe‐ and R2N‐ groups.

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“…The stereochemical courses of the two processes are probably different also. Another possible distinction would be the intervention of a unimolecular rearrangement of R' to R'", which is possible only in the S^^l process [26].…”

Section: Rgc' > R3c-cr3mentioning

confidence: 99%

“…The reactions of 1-chloro-l-cyclopropyl-l-nitroethane ^ with various nucleophiles have been studied to determine the relative efficiency of various nucleophiles in trapping (%nitro radicals using free radical clocks [26]. However, it > "NO, + 2 Na"*" "oCH,…”

Section: Reaction Of Methoxide Ion With L-chloro~l-cyclopropyl-lnitromentioning

confidence: 99%

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Free radical chain reactions involving an electron transfer process

Baik

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Reaction of nucleophiles with 1,1-dinitro-2,2-diphenylethylene

Cited by 19 publications

References 1 publication

Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

Free radical chain reactions involving an electron transfer process

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Reaction of nucleophiles with 1,1-dinitro-2,2-diphenylethylene

Cited by 19 publications

References 1 publication

Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

1,2-Shift of Element-Centered Groups (RnE) in Carbenoid Anions [RnECF2CFCl]−and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study

Free radical chain reactions involving an electron transfer process

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1,2-Shift of Element-Centered Groups (R_nE) in Carbenoid Anions [R_nECF₂CFCl]⁻and its Relevance for Nucleophilic Vinylic Substitution: a DFT Study