对羟基苯乙酸 → 3-[((4-Chloroanilino)carbonyl)methyl]phenol

HRID 6442

反应方程式

HRID 6442 反应方程式
[CH3:1][C:2]([CH3:4])=[O:3].[OH:5][C:6]1C=[CH:10][C:9](CC(O)=O)=[CH:8][CH:7]=1.[Cl:16][C:17]1[CH:23]=[CH:22][C:20]([NH2:21])=[CH:19][CH:18]=1.P(Cl)(Cl)(Cl)(Cl)Cl>C1(C)C=C(C)C=C(C)C=1.C(C(CC)=O)C>[Cl:16][C:17]1[CH:23]=[CH:22][C:20]([NH:21][C:6]([CH2:7][C:8]2[CH:1]=[C:2]([OH:3])[CH:4]=[CH:10][CH:9]=2)=[O:5])=[CH:19][CH:18]=1

参与物

7

反应物 4

HCID 127对羟基苯乙酸HCID 180丙酮HCID 78124-氯苯胺HCID 24819五氯化磷

产物 1

HCID 234407563-[((4-Chloroanilino)carbonyl)methyl]phenol收率 90%

试剂、催化剂与溶剂 2

HCID 72883-戊酮溶剂HCID 7947均三甲苯溶剂

实验过程

FIG. 6b presents a similar reaction scheme to FIG. 6a, except that 3- rather than 4-hydroxyphenylacetic acid (HPAA) is used as the precursor material so that the final compound has a meta rather than a para substitution. In addition, rather than reacting with acetone (dimethyl ketone) a diethyl ketone is used to position ethyl, rather than methyl, moieties in the group substituted on one of the phenyl rings. By example, 1.5 g (10 mmol) 3-HPAA and 2.6 g (20 mmol) 4-chloroaniline in 20 ml of mesitylene was heated to reflux. Then 0.33 g (2.55 mmol) PCl5 solution was then slowly added to the above refluxing solution and the refluxing was continued for two hours. The reaction mixture was then cooled and then worked up as described above to yield 2.2 g (90% yield) of 3-[((4-chloroanilino) carbonyl)methyl]phenol. As described above, chloroform (0.8 ml) was added to a stirred and ice-cooled mixture of 1.23 grams of 3-[ ((4-chloroanilino)carbonyl)methyl]phenol and 1.6 g NaOH in 15 ml of acetone. The reaction mixture was allowed to warm to room temperature and stirring continued for an additional 10 hours. The usual work-up yielded 2-[3-(((4-chloroanalino)carbonyl) methyl)]phenoxy]-2-methylpropionic acid as a low temperature melting sticky solid (C,H,Cl,N analysis yielded (C18H18ClNO4); NMR δPPM: 1.42 (6H, s, CH3), 61 (2H, s, benzylic CH2), and 6.6-7.75 (8H, m, aromatic H)). However, rather than using acetone as the reaction solvent, diethylketone can be used in the same manner as described above to yield the butanoic acid (as opposed to propanoic acid) structure shown in FIG. 6b.

后处理

  1. temperatureThe reaction mixture was then cooled

来源与证据

ORD记录
ord-70204c4fc8114c65865ea0d378637a4f
来源数据集
uspto-grants-1993_09
专利号
US05248785

关联笔记

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