diethyl (2-nitro-1,1-diphenylethyl)phosphonate | 131589-76-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diethyl (2-nitro-1,1-diphenylethyl)phosphonate
• 英文别名: (1-Diethoxyphosphoryl-2-nitro-1-phenylethyl)benzene
• CAS: 131589-76-9
• 化学式: C₁₈H₂₂NO₅P
• 分子量: 363.35
• InChiKey: RCZURCYZALCCBG-UHFFFAOYSA-N

物化性质

• 熔点：
  74-75 °C
• 沸点：
  507.0±50.0 °C(Predicted)
• 密度：
  1.203±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  81.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl (2-nitro-1,1-diphenylethyl)phosphonate 、 亚磷酸二乙酯 在 potassium tert-butylate 作用下， 反应 5.0h， 生成 3-(diethoxyphosphinyl)-2,2-diphenylaziridine
  参考文献：
  名称：

  Addition, substitution and deoxygenation reactions of .alpha.-phenyl-.beta.-nitrostyrenes with the anions of thiols and diethyl phosphite: formation of indoles by reaction with ethyl phosphites

  摘要：

  Reactions of excess RS- (R = Ph, t-Bu) with Ph2C = C(SPh)NO2 in Me2SO form Ph2C = CHSR via conversion of the initial Micheal-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] C = 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 Me2SO at 30-degrees-C and in > 95% yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150-degrees-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-degrees-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-degrees-C.

  DOI：

  10.1021/jo00002a032
• 作为产物：
  描述：

  1,1-diphenyl-2,2-dinitroethylene 在 potassium tert-butylate 、 亚磷酸二乙酯 作用下， 反应 1.0h， 生成 diethyl (2-nitro-1,1-diphenylethyl)phosphonate
  参考文献：
  名称：

  Addition, substitution and deoxygenation reactions of .alpha.-phenyl-.beta.-nitrostyrenes with the anions of thiols and diethyl phosphite: formation of indoles by reaction with ethyl phosphites

  摘要：

  Reactions of excess RS- (R = Ph, t-Bu) with Ph2C = C(SPh)NO2 in Me2SO form Ph2C = CHSR via conversion of the initial Micheal-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] C = 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 Me2SO at 30-degrees-C and in > 95% yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150-degrees-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-degrees-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-degrees-C.

  DOI：

  10.1021/jo00002a032

文献信息

• Nitrileoxide compound
  申请人：DAIKIN INDUSTRIES, LTD.

  公开号：US10633333B2

  公开（公告）日：2020-04-28

  The present invention provides a compound of the formula (I): wherein, A is R6(R7)s, N, O, S, or —NR5—; R6 is an s-valent organic group; R7 is each independently, —O—, —S—, —NR5— or —O—P(═O)OR4′—; R2 and R3 are each independently a hydrogen atom or a hydrocarbon group; R4′ is each independently, a hydrocarbon group; R5 is each independently, a hydrogen atom or a hydrocarbon group; and s is an integer of 1-10.

  本发明提供了一种式 (I) 的化合物： 其中，A是R6(R7)s、N、O、S或-NR5-；R6是s价有机基团；R7各自独立地是-O-、-S-、-NR5-或-O-P(═O)OR4′-；R2和R3各自独立地是氢原子或烃基团；R4′各自独立地是烃基团；R5各自独立地是氢原子或烃基团；s是1-10的整数。
• Reactions of ethyl phosphites with .beta.-nitrostyrenes. The role of nitrosoalkenes as intermediates
  作者：Glen A. Russell、Ching Fa Yao

  DOI：10.1021/jo00050a026

  日期：1992.11

  3-Phenyl-2-substituted-indoles are formed in high yields in the reaction of Ph2C=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150-degrees-C while reaction with (EtO)2PO-/(EtO)2P(O)H at room temperature forms the aziridines 1 with R = H, Me, Ph. 2,2-Diphenyl-3-substituted-2H-azirines formed by deoxygenation of the Michael-type adducts are postulated as intermediates. Reactions of PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)3P at 150-degrees-C or (EtO)2PO-/(EtO)2P(O)H at room temperature give products resulting from the addition of the phosphorus nudeophile at the benzylidene carbon atom. Evidence for the formartion of cyclic structures with pentacoordinated phosphorus atoms is presented for the reaction of Ph2C=C(Me)NO2 with (EtO)2PO-/EtO)2P(O)H and for PhCH=C(R)NO2 (R = H, Me, Ph) with (EtO)3P. The Michael-type adducts PhCH[P(O)(OEt)2]CH(R)NO2 (R = Me, Ph) undergo reaction upon treatment with aqueous base at 80-100-degrees-C followed by acidification to yield the 3-(diethoxyphosphinyl)-2-R-N-hydroxyindoles. 4-(Diethoxyphosphinyl)-3-R-4H-1,2-benzoxazines (13, R = Me, Ph) are formed by reaction with 85% H2SO4 Of the adducts of PhCH=C(R)NO2 with (EtO)2PO (R = Me) or (EtO)3P (R = Ph).
• RUSSELL, GLEN A.;YAO, CHING-FA;TASHTOUSH, HASAN I.;RUSSELL, JUNE E.;DEDOL+, J. ORG. CHEM., 56,(1991) N, C. 663-669
  作者：RUSSELL, GLEN A.、YAO, CHING-FA、TASHTOUSH, HASAN I.、RUSSELL, JUNE E.、DEDOL+

  DOI：——

  日期：——
• NITRILEOXIDE COMPOUND
  申请人：DAIKIN INDUSTRIES, LTD.

  公开号：US20180057450A1

  公开（公告）日：2018-03-01

  The present invention provides a compound of the formula (I): wherein, A is R 6 (R 7 ) s , N, O, S, or —NR 5 —; R 6 is an s-valent organic group; R 7 is each independently, —O—, —S—, —NR 5 — or —O—P(═O)OR 4′ —; R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group; R 4′ is each independently, a hydrocarbon group; R 5 is each independently, a hydrogen atom or a hydrocarbon group; and s is an integer of 1-10.
• Addition, substitution and deoxygenation reactions of .alpha.-phenyl-.beta.-nitrostyrenes with the anions of thiols and diethyl phosphite: formation of indoles by reaction with ethyl phosphites
  作者：Glen A. Russell、Ching Fa Yao、Hasan I. Tashtoush、June E. Russell、Douglas F. Dedolph

  DOI：10.1021/jo00002a032

  日期：1991.1

  Reactions of excess RS- (R = Ph, t-Bu) with Ph2C = C(SPh)NO2 in Me2SO form Ph2C = CHSR via conversion of the initial Micheal-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] C = 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 Me2SO at 30-degrees-C and in > 95% yield by the reaction of (EtO)3P with Ph2C[P(O)(OEt)2CH(NO2)2 at 150-degrees-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-degrees-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-degrees-C.