N-(2-Hydroxy-2-phenylethyl)-N-methyl-triphenylessigsaeure-amid | 66415-39-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: N-(2-Hydroxy-2-phenylethyl)-N-methyl-triphenylessigsaeure-amid
• 英文别名: N-(2-Hydroxy-2-phenylethyl)-N-methyl-2,2,2-triphenylacetamide
• CAS: 66415-39-2
• 化学式: C₂₉H₂₇NO₂
• 分子量: 421.539
• InChiKey: SNBVEZMTDGCVIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三苯基乙酸 生成 N-(2-Hydroxy-2-phenylethyl)-N-methyl-triphenylessigsaeure-amid
  参考文献：
  名称：

  CH-Acidit�t in ?-Stellung zum N-Atom inN,N-dialkylamiden mitsterisch gesch�tzter Carbonylgruppe zur nucleophilen minoalkylierung

  摘要：

  CH‐Acidity in α‐position to the N‐Atom of N, N‐Dialkylamides with Sterically Protected Carbonyl Groups Contribution to the Nucleophilic Amino AlkylationSterically protected amides 1 such as the 2,4,6‐triisopropyl‐benzoic acid derivatives 3, 8b and 10 undergo readily H/Li‐exchange with s‐butyllithium at the CH3N‐ or CH2N‐groups. The resulting organolithium compounds (cf. 9, 11) are alkylated and hydroxyalkylated with primary haloalkanes, aldehydes, and ketones under chain elongation in the amine position of the amides. The (E/Z)‐rotamers of the dialkylamides 7 and 8are separated by chromatography; the amides 4–6, 12, and 13 formally derived from β‐hydroxyamines are obtained in the (Z)‐form only. The configurational (E/Z)‐assignments follow from NMR. and IR. data. The erythro and threo configuration of the two diastereomeric amides 12a and 12b are tentatively concluded from Eu(fod)3‐1H‐NMR.‐shift experiments. The results strongly suggest that the H/Li‐exchange takes place regioselectively at the CHN group which is in cis‐position to the CO double bond (→14). The methyl 2,4,6‐tri(t‐butyl)benzoate (18) can also be deprotonated to the lithium acyloxymethanide 19 which is trapped by alkylation with 1‐iodooctane (→20). – The steric protection of the carbonyl groups in the products 4–8, 10, 12, 13, and 20 prevents their ready hydrolysis to amines and alcohols, respectively. Therefore, triphenylacetic acid derivatives 21 rather than 2,4,6‐triisopropylbenzoic acid derivatives for use in the electrophilic substitution of equation (1) are recommended. The trityl group in 21 may be considered a C‐leaving‐group (CC protective group, cf. 22, 23). The acetamide 25 reacts readily (→26) and then with electrophiles to give products 27a–c. As shown in the Table, the amides 27 are cleaved under a variety of conditions with formation of triphenylmethane. LiAlH4 produces a tertiary amine, CH3Li a secondary amine, and dissolving alkali metals/naphthalene under aprotic conditions mixtures of secondary amine and its formamide (hydrolysed by acid treatment). Thus the overall process (2) is feasible.

  DOI：

  10.1002/hlca.19780610144

文献信息

• CH-Acidit�t in ?-Stellung zum N-Atom inN,N-dialkylamiden mitsterisch gesch�tzter Carbonylgruppe zur nucleophilen minoalkylierung
  作者：Rainer Schlecker、Dieter Seebach、Winfried Lubosch

  DOI：10.1002/hlca.19780610144

  日期：1978.1.25

  CH‐Acidity in α‐position to the N‐Atom of N, N‐Dialkylamides with Sterically Protected Carbonyl Groups Contribution to the Nucleophilic Amino AlkylationSterically protected amides 1 such as the 2,4,6‐triisopropyl‐benzoic acid derivatives 3, 8b and 10 undergo readily H/Li‐exchange with s‐butyllithium at the CH3N‐ or CH2N‐groups. The resulting organolithium compounds (cf. 9, 11) are alkylated and hydroxyalkylated with primary haloalkanes, aldehydes, and ketones under chain elongation in the amine position of the amides. The (E/Z)‐rotamers of the dialkylamides 7 and 8are separated by chromatography; the amides 4–6, 12, and 13 formally derived from β‐hydroxyamines are obtained in the (Z)‐form only. The configurational (E/Z)‐assignments follow from NMR. and IR. data. The erythro and threo configuration of the two diastereomeric amides 12a and 12b are tentatively concluded from Eu(fod)3‐1H‐NMR.‐shift experiments. The results strongly suggest that the H/Li‐exchange takes place regioselectively at the CHN group which is in cis‐position to the CO double bond (→14). The methyl 2,4,6‐tri(t‐butyl)benzoate (18) can also be deprotonated to the lithium acyloxymethanide 19 which is trapped by alkylation with 1‐iodooctane (→20). – The steric protection of the carbonyl groups in the products 4–8, 10, 12, 13, and 20 prevents their ready hydrolysis to amines and alcohols, respectively. Therefore, triphenylacetic acid derivatives 21 rather than 2,4,6‐triisopropylbenzoic acid derivatives for use in the electrophilic substitution of equation (1) are recommended. The trityl group in 21 may be considered a C‐leaving‐group (CC protective group, cf. 22, 23). The acetamide 25 reacts readily (→26) and then with electrophiles to give products 27a–c. As shown in the Table, the amides 27 are cleaved under a variety of conditions with formation of triphenylmethane. LiAlH4 produces a tertiary amine, CH3Li a secondary amine, and dissolving alkali metals/naphthalene under aprotic conditions mixtures of secondary amine and its formamide (hydrolysed by acid treatment). Thus the overall process (2) is feasible.