Amdt-Eistert reaction

An ethereal solution of diazomethane free from alcohol may be prepared as follows such a solution is required, for example, in the Amdt-Eistert reaction with acid chlorides (compare Section VI,17). In a 100 ml. longnecked distilling flask provided with a dropping funnel and an efficient downward condenser, place a solution of 6 g. of potassium hydroxide in... 

Acetoacetic ester condensation Amdt-Eistert reaction Bart reaction. ... 

IsothiazoIe-5-carboxyIic acid, 3-methyI-bromination, S, 58 Isothiazolecarboxylic acid chlorides Amdt-Eistert reaction, 6, 157 Reissert reactions, 6, 157 Isothiazolecarboxylic acids esters... 

At the laboratory scale, the a-bromoketone was prepared by an Amdt-Eistert reaction which gives the good isomer in a univocal way (eqn. 2). 

The use of copper as a catalyst in carbenoid transfer has its roots in the Amdt-Eistert reaction, Eq. 1 (3). Although the original 1935 paper describes the Wolff rearrangement of a-diazo ketones to homologous carboxylic acids using silver, the authors mention that copper may be substituted in this reaction. In 1952, Yates (4) demonstrated that copper bronze induces insertion of diazo compounds into the X-H bond of alcohols, amines, and phenols without rearrangement, Eq. 2. Yates proposal of a distinct metal carbenoid intermediate formed the basis of the currently accepted mechanistic construct for the cyclopropanation reaction using diazo compounds. 

ANDROSTAN-nU-OL, 52,122 Anthracene, cyanation, 50, 55 Amdt-Eistert reaction, modified, 50, 77 7-Aryl-0-diketones, general synthesis, 51, 131... 

A number of examples to show that this method is more mild than the Amdt-Eistert reaction... 

Method 3. An ethereal solution of diazomethane free from ethanol may be prepared by this method such a solution is required, for example, in the Amdt-Eistert reaction with acid chlorides (compare Expt 5.130). In a 100-ml distilling flask provided with a dropping funnel and an efficient downward condenser, place a solution of 6 g of potassium hydroxide in 10 ml of water, 35 ml of carbitol (diethyleneglycol monoethyl ether) and 10 ml of water connect the condenser to two conical flasks in series containing 10 and 35 ml of ether respectively and cooled in an ice-salt bath (see Method 1). Heat the mixture on a water bath at 70-75 °C in a beaker of water placed upon a hot-plate incorporating a magnetic... 

One important application of this reaction is the chain extension of acyl chlorides to their homologous esters, known as the Amdt-Eistert reaction. Notice that the starting material for the Wolff rearrangement is easily made from RCO2H by reaction of the acyl chloride with diazomethane the product is RCH2CO2H—the carboxylic acid with one more carbon atom in the chain. A CH2 group, marked in black, comes from diazomethane and is inserted into the C-C bond between R and the carbonyl group. 

Anhydrides—Continued reduction to alcohols, 155 reduction to lactones, 535 Arenes, see Hydrocarbons, aromatic Amdt-Eistert reaction, 433, 487, 573 Aryl esters. Fries rearrangement, 344 hydrolysis, 169 preparation, 169 Aryl halides, see Halides Atyloxy acids, preparation, by aceto-acetic ester synthesis, 430 by malonic ester synthesis, 429 from atyloxy alcohols, 419 from atyloxy cyanides, 414 preparations listed in table 48, 460 Aryloxy acyl halides, preparation, 547 preparations listed in table 61, 553 Aryloxy esters, preparations listed in table 55, 516... 

The 3-amino acid homoproline can be synthesized via an Amdt-Eistert reaction from (S)-proline. ... 

WofS rearrangement (Amdt-Eistert reaction. The reagent has been used in acetonitrile-methanol to effect homogeneous rearrangement, for example of a-diazoacetophenone. After standing for several hours at room temperature, methyl phenylacetate is obtained in good yield. 

Amdt-Eistert reaction [1, 194, after citation of ref. 29]. The procedure here described for the preparation of ethyl l-naphthylacetate29a represents a modified Arndt-Eistert reaction as developed by Newman and Beal.29b The use of triethyl-amine in the formation of the diazoketone makes possible the use of only one equivalent of diazomethane.29b... 

Amdt-Eistert reaction (2,102-103, ref. 29a). The procedure for preparation of ethyl 1 -naphthylacetate has been published.2... 

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