Bromomethyl ethyl ketone

This is a colourless liquid with a boiling point of 94 5° C. at a pressure of 5 mm. of mercury. Its specific gravity is 1584 at 13° C., and it is soluble in water, alcohol and ether. 

The bromine atom of bromoacetone is easily separated from the molecule and substituted by other atoms or radicles. Thus on treating bromoacetone with alcoholic potash, hydroxyacetone and potassium bromide are obtained with sodium iodide iodoacetone is formed, this being a substance with strongly lachrymatory properties, but of little importance as a war gas because of its high cost. 

Bromoacetone reacts with iron, but does not attack lead, so it is essential to store it in lead-lined containers. 

The animal fibres absorb more bromoacetone than do the vegetable fibres. The absorption capacity is fairly high and textiles are discoloured. It is found that textiles which are merely air-dried absorb more bromoacetone than those which have been completely freed from all water.  

For the purification of places contaminated with bromoacetone, spraying with a solution of 240 gm. liver of sulphur in 140 ml. of a soap solution diluted with 10 litres of water is recommended. 

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Includes Chloroacetone Bromoacetone Bromomethyl ethyl ketone Chloroacetophenone Ethyl chloroacetate Phosgene Acrolein... 

During the war of 1914-18, bromoacetone and bromomethyl ethyl ketone were especially used. Chloroacetone was employed only for a short time, being soon superseded by other substances having a more powerful aggressive action. 

Bromomethyl ethyl ketone is a colourless or pale yellowish liquid which boils at ordinary pressure at 145° to 146° C. with decomposition. Its specific gravity is 143. It is insoluble in water alteration on exposure to light is rapid. It is not decomposed by the action of water, and in general its chemical behaviour is very similar to that of bromoacetone. It is easily absorbed by active carbon. Places contaminated with bromomethyl ethyl ketone can be decontaminated by spraying with a soapy solution of liver of sulphur. ... 

Bromomethyl ethyl ketone is an irritant especially to the eyes. The minimum concentration capable of causing irritation of the eyes is i 6 mgm. per cu. m., according to Muller. The limit of insupportability is ii mgm. per cu. m. of air (Fries), and the mortality-product is 6,000. 

Ethyl bromoacetate Chloroacetone Xylyl bromide Benzyl bromide Bromomethyl ethyl ketone Bromoacetone Iodoacetone Ethyl iodoacetate Benzyl iodide Acrolein... 

Reaction of 9-bromomethyl-4-oxo-4//-pyrido[ 1,2-a]pyrimidine-3-carboxylates 505 and their homologs with 2,4-dihydroxy-3-propyl-and -3-allyl-acetophenone 506 in boiling methyl ethyl ketone in the presence of potassium carbonate afforded 9-(4-acetyl-3-hydroxy-2-substituted phenoxymethyl) derivatives (507) [87EUP242230 88JAP(K)88/246375]. 

Diorgano tellurium compounds have been reacted with methyl iodide (Vol. IX, p 1076), ethyl iodide ethyl iodoacetate, cyclohexyl iodide , methyl bromide, allyl bromide , benzyl bromide , bromoacetone , bromomethyl phenyl ketone , a-bromocarboxylic acids , a-bromocarboxylic acid esters , methyl chloride, and benzyl chloride . 

In 1991, Li and Chan reported the use of indium to mediate Barbier-Grignard-type reactions in water (Eq. 8.49).108 When the allylation was mediated by indium in water, the reaction went smoothly at room temperature without any promoter, whereas the use of zinc and tin usually requires acid catalysis, heat, or sonication. The mildness of the reaction conditions makes it possible to use the indium method to allylate a methyl ketone in the presence of an acid-sensitive acetal functional group (Eq. 8.50). Furthermore, the coupling of ethyl 2-(bromomethyl)acrylate with carbonyl compounds proceeds equally well under the same reaction conditions, giving ready access to various hydroxyl acids including, for example, sialic acids. 

Bicyclic keto esters can easily be prepared by a process called a,a -annulation.29 Thus, treatment of the enamine of cyclopentanone (64) with ethyl a-(bromomethyl)acrylate (98) affords, after work-up, the bicyclic keto ester (99) in 80% yield (equation IS).2911 The mechanism probably involves an initial Michael addition and elimination (or a simple Sn2 or Sn2 alkylation) followed by an intramolecular Michael addition of the less-substituted enamine on the acrylate unit. The use of the enamine of 4,4-bis(ethoxycarbonyl)cyclohexanone (100 equation 26) with (98) gives a 45% yield of the adaman-tanedione diester (101) (yield based on 100 70% when based on 98) via a,a -annulation followed by Dieckmann condensation.29 Enamines of heterocyclic ketones can also serve as the initial nucleophiles, e.g. (102) and (103) give (105) via (104), formed in situ, in 70% yield (Scheme 11 ).29>... 

Yields are high (70-80%) except in the case of sterically hindered ketones (f-BuCOCH3). In all cases, the branched versus linear alcohol ratio is at least 95 5. a-methylen-y-lactones are prepared from ethyl 2-(bromomethyl)acrylate and carbonyl compounds using the same procedure (Protocol 4) with yields depending on the steric environment of the carbonyl compound.11... 

Ethyl a-(bromomethyl)acrylate has proved to be an excellent reagent for conversion of aldehydes and ketones, both acyclic and cyclic, into the corresponding a-methylene-y-butyrolactone derivatives4"9 in a Re-formatsky type reaction. The yield was excellent in the case of several spiro a-methylene-y-butyrolactones.10 Synthetic a-methylene-y-butyrolactone derivatives have been shown to possess antitumor activity.5 6,7 1112 Ethyl a-(bromomethyl)acrylate has also proven of value in the synthesis of alkylated products of enol ethers of cyclohexane-1,3-dione.13... 

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