Carbonyl bromides compounds

Questionable carcinogen with experimental neoplastigenic data. Mutation data reported. When heated it emits highly toxic fumes of carbonyl bromide and Br . See also ACETYLENE COMPOUNDS and BROMIDES. 

Carbonyl bromide, or bromophosgene, was prepared for the first time by Emmerling by the oxidation of bromoform with potassium dichromate and sulphuric acid. Later it was also obtained by heating boron bromide to 150° C. with phosgene, but by this method a mixture with other compounds is obtained ... 

Some carbonyl-based compounds (imines, carboxylic acids) are better electrophiles under acidic conditions than they are under basic conditions. Reactions using these compounds as electrophiles are usually executed under acidic conditions. On the other hand, enolates are always better nucleophiles than enols when carbonyl compounds are required to react with electrophiles that are not particularly reactive, such as esters or alkyl bromides, basic conditions are usually used. Carbonyl compounds that are particularly low in energy (esters, amides) have such a small proportion of enol at equilibrium that they cannot act as nucleophiles at the a-carbon under acidic conditions. Nevertheless, no matter whether acidic or basic conditions are used, carbonyl compounds are always nucleophilic at the a-carbon and electrophilic at the carbonyl carbon. 

French) or BROMOFORMO (Spanish) (75-25-2) CHBrj Noncombustible liquid. Violent reaction with chemically active metals, acetone, calcium, strong caustics, potassium, potassium hydroxide, sodium hydroxide. Increases the explosive sensitivity of nitromethane. Incompatible with crown polyethers, sodium-potassium alloys. Forms friction- and shock-sensitive compounds with lithium. Aqueous solution is a medium-strong acid. Liquid attacks some plastics, rubber, and coatings. Corrosive to most metals in the presence of moisture. Thermal decon osition products include highly toxic carbonyl bromide and hydrogen bromide fumes. On small fires, use dry chemical powder (such as Purple-K-Powder), foam, or COj extinguishers. 

There have been several reports of the preparation of MoCIsfTHFla, all based on reductive procedures starting from MoCls. " These procedures cannot be extended to the corresponding bromide and iodide compounds for lack of suitable higher-valent precursors. The alternative approach developed for these two compounds and reported here is based on the oxidative decarbonylation of lower-valent carbonyl precursors. For the preparation of the bromide compound, the commercially available Mo(CO)6 is a suitable starting compound. For the preparation of the iodide compound, on the other hand, Mo(CO)s is not sufficiently reactive to be oxidized by I2 and the more reactive (i/ -C6H5CH3)Mo(CO)3 is used instead. Because the latter compound is not commercially available and its preparation has not been previously described in Inorganic Synthesis, we also report here a detailed description of its synthesis. 

The only common synthons for alkynes are acetylide anions, which react as good nucleophiles with alkyl bromides (D.E. Ames, 1968) or carbonyl compounds (p. 52, 62f.). 

Although ethereal solutions of methyl lithium may be prepared by the reaction of lithium wire with either methyl iodide or methyl bromide in ether solution, the molar equivalent of lithium iodide or lithium bromide formed in these reactions remains in solution and forms, in part, a complex with the methyllithium. Certain of the ethereal solutions of methyl 1ithium currently marketed by several suppliers including Alfa Products, Morton/Thiokol, Inc., Aldrich Chemical Company, and Lithium Corporation of America, Inc., have been prepared from methyl bromide and contain a full molar equivalent of lithium bromide. In several applications such as the use of methyllithium to prepare lithium dimethyl cuprate or the use of methyllithium in 1,2-dimethyoxyethane to prepare lithium enolates from enol acetates or triraethyl silyl enol ethers, the presence of this lithium salt interferes with the titration and use of methyllithium. There is also evidence which indicates that the stereochemistry observed during addition of methyllithium to carbonyl compounds may be influenced significantly by the presence of a lithium salt in the reaction solution. For these reasons it is often desirable to have ethereal solutions... 

Such ylides are unstable and react with carbonyl compounds to give both the Wittig product (p. 545) as well as AsPh3 and an epoxide. However, this very reactivity is sometimes an advantage since As ylides often react with carbonyl compounds that are unresponsive to P ylides. Substituted quaternary arsonium compounds are also a useful source of heterocyclic organoarsanes, e.g. thermolysis of 4-(1,7-dibromoheptyl)trimethylarsonium bromide to l-arsabicyclo[3.3.0]octane ... 

In the preparation of the thiazides containing more highly functionalized side chains (183-185), an acetal of the aldehyde is usually used rather than the free carbonyl compound. Thus, trichlomethiazide (183) is prepared by reaction of 160 with the dimethyl acetal from dichloroacetaldehyde. In a similar vein, alkylation of the acetalthiol, 190, with allyl bromide affords 191. This yields altizide (184) on condensation with 160. Alkylation of 190 with 2,2,2-trifluoroethyl iodide gives 192. This leads to epithiazide (185) on condensation with 160. 

Muzart et al. described the coupling of aryl iodides and bromides with allylic alcohols to give the corresponding (3-arylated carbonyl compounds [87]. Calo et al... 

Ketone 13 possesses the requisite structural features for an a-chelation-controlled carbonyl addition reaction.9-11 Treatment of 13 with 3-methyl-3-butenylmagnesium bromide leads, through the intermediacy of a five-membered chelate, to the formation of intermediate 12 together with a small amount of the C-12 epimer. The degree of stereoselectivity (ca. 50 1 in favor of the desired compound 12) exhibited in this substrate-stereocontrolled addition reaction is exceptional. It is instructive to note that sequential treatment of lactone 14 with 3-methyl-3-butenylmagnesium bromide and tert-butyldimethylsilyl chloride, followed by exposure of the resultant ketone to methylmagnesium bromide, produces the C-12 epimer of intermediate 12 with the same 50 1 stereoselectivity. 

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