Chloroformates, decomposition

When the nitrogen atom of a pyridine is sufficiently nucleophilic, for example 3-cyano- (pK 1.45) but not 3-bromopyridine (pATa 0.9), attack occurs at the triple bond of the ester.238 The reaction can be very vigorous and, if carried out at - 60° in ether, pyridine itself appears to yield the zwitterion 1 which can be trapped by carbon dioxide. No direct physical evidence has been obtained for 1 and the first product detectable by low-temperature NMR measurements is the 9a//-quinolizine 5.239 Both geometrical forms of the betaine (2) have been isolated, and, at 0° in chloroform, decomposition to carbon dioxide, detected by its absorption at 2335 cm-1, and a red tar, occur rapidly. Treatment of the betaines with aqueous perchloric acid at its freezing point, however,... 

The above mechanism describes chloroform decomposition initiated by all three important radicals [Eqs. (27)-(30)]. Whether the actual break-... 

Whereas dehalogenation was initiated due to the combination of the reductive and oxidative processes in Eqs. (27)-(30), calculations [Eq. (20)] indicate that > 99% of the chloroform decomposition reactions are initiated by e aq. The pseudo-first-order rate constants [A4 in Eq. (18)] for the reaction of chloroform with e aq, H, and OH under the same conditions are shown in Table 3. 

For isopropyl chloroformate decomposition in the gas phase at 240 °C these two reactions proceed at almost equal rates . The products can be accounted for in terms of a four-centre transition state (1) for the substitution reaction, and a six-centre state (2) for the elimination reaction... 

Fit up a 1 -litre round-bottomed flask for steam distillation (Fig. II, 40,1) and place in it 22 g. of iodosobenzene (Section IV.25) made into a thin paste with water (1). Steam distil until almost all the iodobenzene has been removed (about 9 g.) cool the residue in the flask at once, filter the white solid with suction and dry in the air. Wash it with a little chloroform, filter with suction, and dry in the air upon filter paper. The yield is 10-5 g. It may be recrystallised from 800-900 ml. of water, lodoxybenzene melts with explosive decomposition at 237°,... 

Dissolve 0 01 mol of the phenohc ether in 10 ml. of warm chloroform, and also (separately) 0 01 mol of picric acid plus 5 per cent, excess (0 -241 g.) in 10 ml. of chloroform. Stir the picric acid solution and pour in the solution of the phenohc ether. Set the mixture aside in a 100 mb beaker and ahow it to crystallise. Recrystahise the picrate from the minimum volume of chloroform. In most cases equahy satisfactory results may be obtained by conducting the preparation in rectified spirit (95 per cent. CjHgOH). The m.p. should be determined immediately after recrystallisation. It must be pointed out, however, that the picrates of aromatic ethers suflFer from the disadvantage of being comparatively unstable and may undergo decomposition during recrystaUisation. 

Ben2onitri1e [100-47-0] C H CN, is a colorless Hquid with a characteristic almondlike odor. Its physical properties are Hsted in Table 10. It is miscible with acetone, ben2ene, chloroform, ethyl acetate, ethylene chloride, and other common organic solvents but is immiscible with water at ambient temperatures and soluble to ca 1 wt% at 100°C. It distills at atmospheric pressure without decomposition, but slowly discolors in the presence of light. 

Trichloroacetic acid K = 0.2159) is as strong an acid as hydrochloric acid. Esters and amides are readily formed. Trichloroacetic acid undergoes decarboxylation when heated with caustic or amines to yield chloroform. The decomposition of trichloroacetic acid in acetone with a variety of aUphatic and aromatic amines has been studied (37). As with dichloroacetic acid, trichloroacetic acid can be converted to chloroacetic acid by the action of hydrogen and palladium on carbon (17). 

Cyclizine Hydrochloride. l-(Diphenylmethyl)-4-methylpipera2ine monohydrochloride [303-25-3] (Mare2ine) (17) is a white crystalline powder, or small colorless crystals, that is odorless or nearly so and has a bitter taste. It melts indistinctly and with decomposition at ca 285°C. One gram of cycli2ine hydrochloride [303-25-3] is soluble in 115 mL water, 115 mL ethanol, and 5 mL chloroform it is insoluble in diethyl ether. It may be made by the synthesis shown in Reference 15. 

A (4-Hydroxyphenyl)glycine. This derivative (23) forms aggregate spheres or shiny leaflets from water. It turns brown at 200°C, begins to melt at 220°C, and melts completely with decomposition at 245 —247°C. The compound is soluble in alkaU and mineral acid and sparingly soluble in water, glacial acetic acid, ethyl acetate, ethanol, diethyl ether, acetone, chloroform, and benzene. 

Aqueous sodium thiosulfate solutions ate neutral. Under neutral or slightly acidic conditions, decomposition produces sulfite and sulfur. In the presence of air, alkaline solutions decompose to sulfate and sulfide. Dilute solutions can be stabilized by small amounts of sodium sulfite, sodium carbonate, or caustic, and by storage at low temperatures away from air and light. Oxidation is inhibited by Hgl2 (10 Ppm) amyl alcohol (1%), chloroform (0.1%), borax (0.05%), or sodium benzoate (0.1%). 

Riboflavin forms fine yellow to orange-yeUow needles with a bitter taste from 2 N acetic acid, alcohol, water, or pyridine. It melts with decomposition at 278—279°C (darkens at ca 240°C). The solubihty of riboflavin in water is 10—13 mg/100 mL at 25—27.5°C, and in absolute ethanol 4.5 mg/100 mL at 27.5°C it is slightly soluble in amyl alcohol, cyclohexanol, benzyl alcohol, amyl acetate, and phenol, but insoluble in ether, chloroform, acetone, and benzene. It is very soluble in dilute alkah, but these solutions are unstable. Various polymorphic crystalline forms of riboflavin exhibit variations in physical properties. In aqueous nicotinamide solution at pH 5, solubihty increases from 0.1 to 2.5% as the nicotinamide concentration increases from 5 to 50% (9). 

The heavy metal salts, ia contrast to the alkah metal salts, have lower melting points and are more soluble ia organic solvents, eg, methylene chloride, chloroform, tetrahydrofiiran, and benzene. They are slightly soluble ia water, alcohol, ahphatic hydrocarbons, and ethyl ether (18). Their thermal decompositions have been extensively studied by dta and tga (thermal gravimetric analysis) methods. They decompose to the metal sulfides and gaseous products, which are primarily carbonyl sulfide and carbon disulfide ia varying ratios. In some cases, the dialkyl xanthate forms. Solvent extraction studies of a large number of elements as their xanthate salts have been reported (19). 

Unreacted phosgene is removed from the cmde chloroformates by vacuum stripping or gas purging. Chloroformates of lower primary alcohols are distillable however, heavy-metal contamination should be avoided. As stated earlier, chloroformates generating a stable carbonium ion on decomposition, ie, secondary or tertiary chloroformates or henzylic chloroformates, are especially unstable in the presence of heavy metals and more specifically Lewis acids and, hence, should be distilled at as low a temperature and high vacuum as possible. 

Chemical initiation generates organic radicals, usually by decomposition of a2o (11) or peroxide compounds (12), to form radicals which then react with chlorine to initiate the radical-chain chlorination reaction (see Initiators). Chlorination of methane yields all four possible chlorinated derivatives methyl chloride, methylene chloride, chloroform, and carbon tetrachloride (13). The reaction proceeds by a radical-chain mechanism, as shown in equations 1 through. Chain initiation... 

Chloroform and water at 0°C form six-sided crystals of a hydrate, CHCl I8H2O [67922-19-41which decompose at 1.6°C. Chloroform does not decompose appreciably when in prolonged contact with water at ordinary temperature and in the absence of air. However, on prolonged heating with water at 225°C, decomposition to formic acid, carbon monoxide, and hydrogen chloride occurs. A similar hydrolysis takes place when chloroform is decomposed at elevated temperature by potassium hydroxide. 

Aminocyclopropanes were prepared from enamines by the addition of Simmons-Smith reagent (688) or best through the cuprous-chloride-promoted decomposition of diazomethane (689). The reaction of an enamine with chloroform and base and opening of the resultant aminocyclopropane to an ynamine was reported (690). 

During the next fifty years the interest in derivatives of divalent carbon was mainly confined to methylene (CHg) and substituted methylenes obtained by decomposition of the corresponding diazo compounds this phase has been fully reviewed by Huisgen. The first convincing evidence for the formation of dichlorocarbene from chloroform was presented by Hine in 1950. Kinetic studies of the basic hydrolysis of chloroform in aqueous dioxane led to the suggestion that the rate-determining step was loss of chloride ion from the tri-chloromethyl anion which is formed in a rapid pre-equilibrium with hydroxide ions ... 

Carbon tetrachloride was also found to react with pyrryl potassium to give 3-chloropyridine, however the mechanism is obscure and would justify further investigation. In a preparatively useful reaction, pyrrole and chloroform in the vapor phase at 500-550° gave 3-chloro-pyridine (33%) and a little 2-chloropyridine (2-5%). No interconversion of the isomers occurred under these conditions, though pyrolytic rearrangement of N-alkylpyrrole to 3-substituted pyridines is considered to involve 2-alkylpyrroles as intermediates. There is some independent evidence that dichlorocarbene is formed in the vapor phase decomposition of chloroform. ... 

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