Of bromoform

Methylene bromide (CHjBfj) and methylene iodide (CHjIj) are easily prepared by the reduction of bromoform or iodoform respectively with sodium arsenite in alkaline solution ... 

In a 1-litre three-necked flask, mounted on a steam bath and provided respectively with a separatory funnel, mechanical stirrer and double surface condenser, place 165 g. of bromoform (96 per cent.). Add 10 ml. of a solution of sodium arsenite made by dissolving 77 g. of A.R. arsenious oxide and 148 g. of A.R. sodium hydroxide in 475 ml. of water. Warm the mixture gently to start the reaction, and introduce the remainder of the sodium arsenite solution during 30-45 minutes at such a rate that the mixture refluxes gently. Subsequently heat the flask on the steam bath for 3-4 hours. Steam distil the reaction mixture (Fig. 11, 41, 1) and separate the lower layer of methylene bromide (79 g.). Extract the aqueous layer with about 100 ml. of ether a further 3 g. of methylene bromide is obtained. Dry with 3-4 g. of anhydrous calcium chloride, and distil from a Claisen flask with fractionating side arm. The methylene bromide boils constantly at 96-97° and is almost colourless. 

In the known absence of bromoform, iodoform, chloral, and other halogenated methanes, the formation of phenyhsonitrile with aniline provides a simple and faidy sensitive but nonspecific test for the presence of chloroform, the carbylamine test. Phenyhsonitrile formation is the identification test given in the British Pharmacopoeia. A small quantity of resorcinol and caustic soda solution (10% concentration) added to chloroform results in the appearance of a yellowish red color, fluorescing yeUow-green. When 0.5 mL of a 5% thymol solution is boiled with a drop of chloroform and a small quantity of potassium hydroxide solution, a yellow color with a reddish sheen develops the addition of sulfuric acid causes a change to brilliant violet, which, diluted with water, finally changes to blue (33). 

The use of sodium tribromoacetate as the dibromocarbene precursor has been investigated and found to provide the Ciamician-Dennstedt product in higher yield than the traditional alkoxide/alcohol reaction conditions. Deprotonation of bromoform with sodium ethoxide in ethanol and reaction of the resultant carbene with 6 provides quinoline 9 in 9% yield thermolysis of sodium tribromoacetate in the presence of 6 furnishes 9 in 20% yield (Scheme 8.3.3). 

The authors (ref. 19) managed to perform this reaction selectively as telomerization at the C-Br bond of bromoform using initiating system Fe(CO)5 + DMF, which facilitates a bromine transfer at a step of a chain transfer (ref. 19). In this case only one row of telomers is formed which contain three bromine atoms in molecules ... 

The use of metal-complex initiating systems proved to be especially promising in carrying out the reactions with acrylic monomers which can be easily polymerized, when the common initiators of radical reactions are excepted. The use of Fe(CO)s -I- DMFA system allows us to perform homolytical addition of bromoform to acrylic monomers selectively at C-Br bond with no essential polymerization (ref. 10). 

The radical addition of bromoform to ketensilylacetals has been described, initiated with AIBN or Et3B (ref. 12). The reaction yields polyfunctional silicon-containing compounds of CHBr2C(R)CBr(OR )OSiR type or products of their conversions (hydrolysis, fragmentation of R etc.). 

Irradiation of chloroform yields a -CC13 radical, whereas irradiation of bromoform yields -CHBra radicals(122) ... 

Cyclic polyethylene oxides) ( Crown ethers ), Potassium hydroxide Le Goaller, R. etal., Synth. Comm., 1982, 12, 1163-1169 Crown ethers promote dihalocarbene formation from chloroform or bromoform and potassium hydroxide. However, in absence of diluent dichloromethane, dropwise addition of bromoform to the base in cyclohexane led to explosions. 

Ohsawa N, Ogata Y, Okada N, Itoh N (2001) Physiological function of bromoperoxidase in the red marine alga, Corallina pilulifera production of bromoform as an allelochemical and the simultaneous elimination of hydrogen peroxide. Phytochemistry 58 683-692... 

Agarwal AK, Mehendale HM. 1983a. Absence of potentiation of bromoform hepatotoxicity and lethality by chlordecone. Toxicol Lett 15(2-3) 251-257. 

A. 1,1-Dibromo-2,2-bis(chloromethyl)cyclopropane (1). Into a 1-L, threenecked, round-bottomed flask, equipped with an efficient mechanical stirrer, a thermometer, and a condenser equipped with a potassium hydroxide drying tube, are placed 54.1 g (0.403 mol) of 3-chloro-2-(chloromethyl)propene (Note 1), 212 g (0.805 mol) of bromoform (Note 2), 1.70-2.00 g (14.4-16.9 mmol) of pinacol (Note 3), and 1.45 g (3.94 mmol) of dibenzo-18-crown-6 (Note 4). With very vigorous stirring (Note 5), 312 g of an aqueous 50% sodium hydroxide solution that has been cooled to 15°C is added in one portion. The reaction mixture turns orange, then brown, then black within 5 min, and the temperature of the reaction mixture begins to rise. Within 20 min, the internal reaction temperature is 49-50°C at which point the reaction flask is cooled with a room-temperature water bath, and the reaction temperature decreases to ca. 

Their study of bromoform was extended to include thirty organic solvents with a wide variety of function groups. For the aliphatic solvents AJ from cyclohexane to the solvent in question gave the following order of magnitudes ... 

Similar interpretation can be used in explaining the results of Skell and Maxwell (86) who dehydrated 2-methyl-1-butanol in the presence of bromoform and aqueous potassium hydroxide in solution. 

Surface Water. Kaczmar et al. (1984) estimated the volatilization half-life of bromoform from rivers and streams to be 65.6 d. 

A. Dibromoearbene addition to (IR)-nopadiene. A 250-raL, three-necked flask is equipped with a mechanical stirrer, nitrogen Inlet, and serum cap. The flask is charged with 26.2 mL (0.30 mol) of bromoform (Note 1), 29.5 g (0.20 mol) of (IR)-nopadlene (Notes 2 and 3), 1.0 g (4.4 mmol) of benzyltriethylammonium chloride (TEBA), 0.8 mL of ethanol, and 20 mL of dichloromethane (Note 4). The suspension Is stirred and cooled In an Ice bath while 100 mL of 50t sodium hydroxide solution Is added over 10 min from a dropping funnel. The reaction mixture Is stirred at room temperature for 24 hr and poured into 250 mL of water. The lower layer Is separated and the... 

The submitters used a purified grade of bromoform purchased from the Fisher Chemical Company. 

However, what remains unknown is the source of the original bromine that initiates the chemistry. There have been a number of hypotheses, including the photolysis of bromoform which is generated by biological processes in the ocean (Barrie et al., 1988) or reactions of sea salt, either suspended in the air or deposited on, or associated with, the snowpack. These include photolysis of BrN02 formed from the reaction of sea salt particles with N2Os (Finlayson-Pitts et al., 1990), the... 

The 6,7-dihydro-5/f -1,4-dioxepin (266) has been prepared (54CR(38)982). and more recently it has been shown that the 2,3-dihydro-5jF/-l,4-dioxepins (263) and (265) can be produced from 1,4-dioxine-halocarbene adducts (264), either by heating under reflux in xylene or by treatment with bases. The allylic chlorine atom in (263) is readily substituted by alkoxide or cyanide ions (77ZC331, 76UKZ968). Saturated rings of type (267) have been prepared by the treatment of cyclic acetals of ethane-1,2-diol with vinyl ethers in the presence of boron trifluoride, and l,4-dioxepan-5-one (268) has been prepared by the reaction of bromoform and silver nitrate with aqueous dioxane (60AG415). 

No epidemiological data relevant to the carcinogenicity of bromoform were available. 

There is limited evidence in experimental animals for the carcinogenicity of bromoform. 

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