Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite: Formation of Indoles by Reaction with Ethyl Phosphites

Glen A. Russell, Ching-Fa Yao, June E. Russell, Douglas F. Dedolph, Hasan I. Tashtoush

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Reactions of excess RS- (R = Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2. In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and PH2C[P(O)(OEt)2]CH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2C[P(O)(OEt)2]CHO. The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2C[P(O)(OEt)2]Cs≡N via a Perkow-type reaction of the Michael adduct to yield Ph2C[P(O)(OEt)2]CH=N(O)OP(O)(OEt)2 as an intermediate. The nitrile is also formed from Ph2C[P(O)(OEt)2]CH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2O at 30 °C and in >95% yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150 °C. Reaction of Ph2C=CHNO2 or Ph2C-[P(O)(OEt)2]CH2NO2 with excess (EtO)2PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2; and 2, 2-diphenyl-2H-azirine. Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution. Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 °C in (EtO)3P with X = H, PhS, or t-BuS while 2-nitro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 °C.

Original languageEnglish
Pages (from-to)663-669
Number of pages7
JournalJournal of Organic Chemistry
Volume56
Issue number2
DOIs
Publication statusPublished - 1991 Jan 1

Fingerprint

Phosphites
Indoles
Sulfhydryl Compounds
Anions
Substitution reactions
Nitriles
Reaction products
3-phenylindole
diphenyl

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite : Formation of Indoles by Reaction with Ethyl Phosphites. / Russell, Glen A.; Yao, Ching-Fa; Russell, June E.; Dedolph, Douglas F.; Tashtoush, Hasan I.

In: Journal of Organic Chemistry, Vol. 56, No. 2, 01.01.1991, p. 663-669.

Research output: Contribution to journalArticle

@article{417b901ee4804b9a9307495448dc424d,
title = "Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite: Formation of Indoles by Reaction with Ethyl Phosphites",
abstract = "Reactions of excess RS- (R = Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2. In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and PH2C[P(O)(OEt)2]CH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2C[P(O)(OEt)2]CHO. The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2C[P(O)(OEt)2]Cs≡N via a Perkow-type reaction of the Michael adduct to yield Ph2C[P(O)(OEt)2]CH=N(O)OP(O)(OEt)2 as an intermediate. The nitrile is also formed from Ph2C[P(O)(OEt)2]CH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2O at 30 °C and in >95{\%} yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150 °C. Reaction of Ph2C=CHNO2 or Ph2C-[P(O)(OEt)2]CH2NO2 with excess (EtO)2PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2; and 2, 2-diphenyl-2H-azirine. Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution. Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 °C in (EtO)3P with X = H, PhS, or t-BuS while 2-nitro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 °C.",
author = "Russell, {Glen A.} and Ching-Fa Yao and Russell, {June E.} and Dedolph, {Douglas F.} and Tashtoush, {Hasan I.}",
year = "1991",
month = "1",
day = "1",
doi = "10.1021/jo00002a032",
language = "English",
volume = "56",
pages = "663--669",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite

T2 - Formation of Indoles by Reaction with Ethyl Phosphites

AU - Russell, Glen A.

AU - Yao, Ching-Fa

AU - Russell, June E.

AU - Dedolph, Douglas F.

AU - Tashtoush, Hasan I.

PY - 1991/1/1

Y1 - 1991/1/1

N2 - Reactions of excess RS- (R = Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2. In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and PH2C[P(O)(OEt)2]CH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2C[P(O)(OEt)2]CHO. The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2C[P(O)(OEt)2]Cs≡N via a Perkow-type reaction of the Michael adduct to yield Ph2C[P(O)(OEt)2]CH=N(O)OP(O)(OEt)2 as an intermediate. The nitrile is also formed from Ph2C[P(O)(OEt)2]CH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2O at 30 °C and in >95% yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150 °C. Reaction of Ph2C=CHNO2 or Ph2C-[P(O)(OEt)2]CH2NO2 with excess (EtO)2PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2; and 2, 2-diphenyl-2H-azirine. Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution. Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 °C in (EtO)3P with X = H, PhS, or t-BuS while 2-nitro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 °C.

AB - Reactions of excess RS- (R = Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2. In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and PH2C[P(O)(OEt)2]CH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2C[P(O)(OEt)2]CHO. The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2C[P(O)(OEt)2]Cs≡N via a Perkow-type reaction of the Michael adduct to yield Ph2C[P(O)(OEt)2]CH=N(O)OP(O)(OEt)2 as an intermediate. The nitrile is also formed from Ph2C[P(O)(OEt)2]CH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2O at 30 °C and in >95% yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150 °C. Reaction of Ph2C=CHNO2 or Ph2C-[P(O)(OEt)2]CH2NO2 with excess (EtO)2PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2; and 2, 2-diphenyl-2H-azirine. Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution. Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 °C in (EtO)3P with X = H, PhS, or t-BuS while 2-nitro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 °C.

UR - http://www.scopus.com/inward/record.url?scp=0009950509&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0009950509&partnerID=8YFLogxK

U2 - 10.1021/jo00002a032

DO - 10.1021/jo00002a032

M3 - Article

AN - SCOPUS:0009950509

VL - 56

SP - 663

EP - 669

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -