Cleavage of tert-Butyl Benzoates with NaH in DMF: Comments on the Mechanism and a Simple and Safe Alternative Procedure

被引：11

作者：

Filali, Emane ^{[1
]}

Lloyd-Jones, Guy C. ^{[1
]}

Sale, David A. ^{[1
]}

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

来源：

SYNLETT | 2009年 / 02期

关键词：

tert-butyl esters; cleavage; hydrides; DMF; hazard; SODIUM HYDRIDE; ESTERS; HYDROLYSIS;

D O I：

10.1055/s-0028-1087668

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The hazardous and inconvenient Schmidt procedure for tert-butyl benzoate ester cleavage by NaH in DMF has been reinvestigated. The reaction is suggested to involve B(AC)2 ester cleavage, facilitated by adventitious, NaH-derived NaOH, rather than the proposed E2 elimination of isobutylene by DMF-derived NaNMe2. Powdered KOH in THF is a significantly safer and simpler alternative that effects cleavage of tert-butyl benozoates, at ambient temperature, in excellent yield (94-99%).

引用

页码：205 / 208

页数：4

共 17 条

[1]

BENNETT H, 1947, CONCISE CHEM TECHNIC, P107

[2]

BRETHERICK L, 1990, HDB REACTIVE CHEM HA, P1181

[3]

Furniss B.S., 1989, VOGELS TXB PRACTICAL, V4th

[4] GENERAL PROCEDURE FOR BASE-PROMOTED HYDROLYSIS OF HINDERED ESTERS AT AMBIENT-TEMPERATURES [J].

GASSMAN, PG ;

SCHENK, WN .

JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (05) :918-920

[5] SUBSTITUTED TRIARYL PHOSPHINES [J].

HOOTS, JE ;

RAUCHFUSS, TB ;

WROBLESKI, DA .

INORGANIC SYNTHESES, 1982, 21 :175-179

[6] COBALT CARBONYL-CATALYZED POLYCARBONYLATION OF ARYL HALIDES IN NAOME/MEOH UNDER PHOTOSTIMULATION [J].

KASHIMURA, T ;

KUDO, K ;

MORI, S ;

SUGITA, N .

CHEMISTRY LETTERS, 1986, (06) :851-854

[7]

Kocienski P.J., 2003, PROTECTING GROUPS, V3rd

[8] A new, one-step, effective protocol for the iodination of aromatic and heterocyclic compounds via aprotic diazotization of amines [J].

Krasnokutskaya, Elena A. ;

Semenischeva, Nadya I. ;

Filimonov, Victor D. ;

Knochel, Paul .

SYNTHESIS-STUTTGART, 2007, (01) :81-84

[9]

LOWRY TH, 1987, MECH THEORY ORGANIC, P718

[10] NOVEL AROMATISATION REACTION OF CYCLOHEXENONE DERIVATIVES WITH SODIUM HYDRIDE AND DIMETHYLFORMAMIDE [J].

NASIPURI, D ;

BHATTACHARYYA, A ;

HAZRA, BG .

JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS, 1971, (13) :660-+

← 1 2 →