Methyl hypochlorite

When chlorine was put in contact with methanol, this led to a deflagration followed by a fire due to the decomposition of methyl hypochlorite. 

Several explosions involving methanol and sodium hypochlorite were attributed to formation of methyl hypochlorite, especially in presence of acids or other esterification catalyst. 

Passage of chlorine through cold recovered methanol (but not fresh methanol) led to a mild explosion and ignition, formation of methyl hypochlorite apparently being catalysed by an impurity. 

Glerup, J. et al., Acta Chem. Scand., Ser. A, 1978, A32, 673 In preparation of dichlorotetrapyridinecobalt(III) chloride by oxidation of the Co(II) salt in methanol solution with gaseous chlorine, severe explosions (formation of methyl hypochlorite) have occurred. Use of liquid chlorine at —400See Cobalt(II) chloride, Methanol, above... 

Isopropyl hypochlorite, 1247 Methyl hypochlorite, 0434 Methyl hypofluorite, 0433 Nitryl hypochlorite, 4026 Pentafluoroselenium hypofluorite, 4368 Pentafluorosulfur hypofluorite, 4367... 

Methyl Hypochlorite. CH3C10 mw 66.49 bp 12° at 726mm. Gaseous substance was prepd by Sandmeyer (Refs 2 3) by bubbling chlorine through a cold solution of NaOH in methanol. Explodes on contact with flame (Beil 1, 282 and [271])... 

Boron trifluoride and boron trifluoride-diethyl ether complex can be used as a source of fluoride ions in the presence of hypobromites and hypochlorites, e.g. methyl hypobromitc, tert-butyl hypobromite, methyl hypochlorite in carbon tetrachloride at 25 C. The addition of bromine monofluoride" and chlorine monofluoride" to various alkenes is accompanied by the formation of the corresponding alkoxybromides and alkoxychlorides which hinder the isolation of the halofluorinated products.57 jV-Bromo- and A -chloro-substiluted alkyl- and arylamines. -amides, and -imides, A -chloro-A,-methylamine, A -bromo-A -methylamine, A -chloro-A, /V-dimethylamine, A-bromo-A.A-dimethylamine, ACV-dichloro-A -methylamine, V,fV-dibromo-,V-mcthylaminc, A -bromosuccinimide, -V-chlorosuccinimide, Af-bromoacct-amide, A.A -dichlorourethane, can be used in the reaction instead of the hypohalites. The reactions with various alkenes conducted in dichloromethane at room temperature in the presence of boron trifluoride-diethyl ether complex produce bromofluoro and chlorofluoro addition products in 40-80 % yield. However, the reactions are complicated by the addition of A -halo-succinimides and Af.A-dichlorourcthane to the C = C bonds.58... 

A significant change in the fluoro halide to methoxy halide ratio does not occur with large changes in the boron trifluoride to hypohalite ratio. For example, experiments with hex-1-ene (13) and methyl hypochlorite (Table 7) have shown that variation of the boron trifluoridc methyl hypochlorite ratio from 10 1 to 1 10 does not produce large changes in the proportion of fluoride incorporation. These experiments also have shown that boron trifluoride is consumed in stoichiometric amounts in the formation of fluoro halide from methyl hypochlorite and that all three of the fluorine atoms of boron trifluoride are about equally effective. 

Table 7. Efleet of Boron Trifluoride/Methyl Hypochlorite Molar Ratio on Reaction with Hex-1-enea 50...

The calculated amount of boron trifluoride-dicthyl ether complex was added to a solution of hex-1-ene (3.2 mmol) in dichloromethanc (10mL) followed by a 1 M solution of methyl hypochlorite (1.6mL, (1.6 mmol). b Since 14 and 15 + 16 are formed in nearly equal amounts, the quantity of BF, is nearly sufficient to form products in the same ratio as in the other runs. c Unreacted methyl hypochlorite remained after several hours. 

Ethyl hypochlorite, C2H5OCl, is a substance that is decomposed with explosion when irradiated by sun-light or brought into contact with copper dust. Methyl hypochlorite, boiling at 12°C, also exhibits similar properties. 

Methylhydrazinium nitrate, 0508 Methyl hydroperoxide, 0484 Methyl hypochlorite, 0433... 

Fluorine perchlorate, 3970 Heptafluoroisopropyl hypofluorite, 1031 Heptafluoropropyl hypofluorite, 1057 Hypochlorous acid, 3989 Isopropyl hypochlorite, 1243 Methyl hypochlorite, 0433 Methyl hypofluorite, 0441 Nitryl hypochlorite, 4020 Pentafluoroselenium hypofluorite, 4362 Pentafluorosulfur hypofluorite, 4361... 

Markl has reported several valuable extensions of the dihydrostannabenzene route which have allowed the syntheses of a variety of 4-substituted arsabenzenes. 3-Substituted-3-methoxypentadiynes 30 were converted to the corresponding dihydro-stannabenzenes 31, which on treatment with arsenic trichloride gave 4-substituted arsabenzenes 2434,35). Intermediates 32 c, d, e lose the elements of methyl hypochlorite to form 24. 

Calculations have shown that the rotational barrier of the C-O bond in methanol (1.1 kcal/mol) is significantly lower than the corresponding rotational barrier of methyl hypofluorite (MeOF, 3.7 kcal/mol) or methyl hypochlorite (MeOCl, 3.5 kcal/mol), in which a strong [Pg.19]

Cobalt(II) Chloride and Methanol. Passage of chlorine into a solution of cobalt chloride, bipyridyl, and lithium chloride in methanol resulted in an explosion and ignition of the methanol, probably due to formation of methyl hypochlorite.8 9... 

It is worth noting that the adduct of CI3N with BCI3 can be obtained only at low temperature 60>. Hexachloroborazine reacts with water to boric acid and chloramine with methanol, trimethoxyborane and methyl-hypochlorite are produced and, with ethanol, triethoxyborane and acetaldehyde are obtained 59>. Substitution reactions on the B—N ring of hexachloroborazine have not yet been studied. 

On account of its low chlorine potential178 (pJ cp = 4.85 at 250)11 40 is a stronger chlorinating reagent in water than either chloramine-T or V-chlorosuccinimide.174 Methanolysis of 40 yields 1 and methyl hypochlorite.174 An earlier report122 and references179 on formation of N-methylsaccharin (8) in this reaction should be revised. 

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