Of chloroform

CH2C1 CH2C1. Colourless liquid with an odour like that of chloroform b.p. 84 C. It is an excellent solvent for fats and waxes. Was first known as oil of Dutch chemists . Manufactured by the vapour- or liquid-phase reaction of ethene and chlorine in the presence of a catalyst. It reacts with anhydrous ethano-ales to give ethylene glycol diethanoate and with ammonia to give elhylenediamine, these reactions being employed for the manufacture of these chemicals. It burns only with difficulty and is not decomposed by boiling water. 

C7H6O2 Oily liquid of aromatic odour b.p. 196°C. (t is prepared by the action of chloroform and caustic potash on phenol (the Reimer-Tiemann reaction) or by the oxidation of the glucoside salicin. It is easily reduced to salicyl alcohol or oxidized to salicylic acid. 

Ulness D J, Stimson M J, Kirkwood J C and Albrecht A C 1997 Interferometric downconversion of high frequency molecular vibrations with time-frequency-resolved coherent Raman scattering using quasi-cw noisy laser light C-H stretching modes of chloroform and benzene J. Rhys. Chem. A 101 4587-91... 

A) Extract the mixture with about 40 ml. of chloroform, in which the free base is very soluble. Run off the lower chloroform layer, dry it with potassium carbonate as in (a), and then add carbon tetrachloride slowly with stirring to the filtered chloroform solution until the base starts to crystallise out. Allow to stand for a short time (t.e., until the deposition of crystals ceases) and then filter at the pump as the crystals lose the last trace of solvent, they tend as before to break up into a fine powder, the deep green colour becoming paler in consequence. 

Fehling s solution. Reduces Fehling s solution on warming an excess of the latter should be used. The odour of chloroform is also noticeable, due to the action of the alkali in Fehling s solution. 

Isocyanide reaction. Add a few drops of chloroform to about 0 2 g. of the substance, and then 2 3 ml. of ethanolic NaOH solution. Mix well and warm gently the foul odour of isocyanide (carbylamine) is produced. Immediately the odour of isocyanide is detected, cool the tube and add carefully an excess of cone. HCl the isocyanide is thus hydrolysed to the odourless amine. 

Isocyanide reaction. Heat together gently 0 2 g. of the anilide, 3 ml. of ethanolic NaOH solution and i ml. of chloroform hydrolysis of the anilide occurs, and the odour of the isocyanide can be detected after about i minute s heating. [This test clearly differentiates an anilide of type R CONHC Hj from one of type R CO N(CH3)CeH5.]... 

Physical Properties. All heavier than, and insoluble in water. All liquids, except iodoform, CHI3, which is a yellow crystalline solid with a characteristic odour. The remainder are colourless liquids when pure ethyl iodide, CjHjI, and iodobenzene, CjHgl, are, however, usually yellow or even brown in colour. Methyl iodide, CH3I, ethyl bromide, CgH Br, ethyl iodide, chloroform, CHCI3, and carbon tetrachloride, CCI4, have sweetish odours, that of chloroform being particularly characteristic. 

Hydrolysis with alcoholic NaOH solution. Boil together in a small conical flask, fitted with a reflux water-condenser, 1 ml. of chloroform and 10 ml. of alcoholic NaOH solution for 10 minutes. Then dilute with water to dissolve any NaCl which may have separated, add dil. HNO3 until acid and then AgN03 solution. A copious precipitate of AgCl is produced. 

Colorations with resorcinol and naphthol. Dissolve about 0-2 g. of resorcinol in I ml. of 30% aqueous NaOH solution, add i ml. of chloroform and warm gently the aqueous layer turns red and shows a slight fluorescence. 

Reduction of Fehling s solution. Boil i ml. of chloroform gently with 3 ml. of Fehling s solution with constant shaking for 3-4 minutes. Reduction occurs and reddish cuprous oxide slowly separates. 

Isocyanide reaction. Repeat Test i for chloroform (above) using 0 5 g. of iodoform instead of i ml. of chloroform the foul odour of isocyanide is produced as before. 

Solid carbon dioxide (Dry Ice, Drikold) is employed when very low temperatures are required. If it is suspended in solvents, such as alcohol or a mixture of equal volumes of chloroform and carbon tetrachloride, temperatures down to — 50° can be easily attained. Lower temperatures still are reached if intimate mixtures of solid carbon dioxide and organic solvents are employed with ethyl alcohol, — 72° with... 

Methylene chloride CHjCl, b.p. 41°, is obtained as a by product in the com mercial preparation of chloroform by the reduction of carbon tetrachloride with moist iron and also as one of the products in the chlorination of methane it is a useful extraction solvent completely immiscible with water. 

Add 1 ml. of the alcohol-free ether to 0-1-0-15 g. of finely-powdered anhydrous zinc chloride and 0 5 g. of pure 3 5-dinitrobenzoyl chloride (Section 111,27,1) contained in a test-tube attach a small water condenser and reflux gently for 1 hour. Treat the reaction product with 10 ml. of 1-5N sodium carbonate solution, heat and stir the mixture for 1 minute upon a boiling water bath, allow to cool, and filter at the pump. Wash the precipitate with 5 ml. of 1 5N sodium carbonate solution and twice with 6 ml. of ether. Dry on a porous tile or upon a pad of filter paper. Transfer the crude ester to a test-tube and boil it with 10 ml. of chloroform or carbon tetrachloride filter the hot solution, if necessary. If the ester does not separate on cooling, evaporate to dryness on a water bath, and recrystallise the residue from 2-3 ml. of either of the above solvents. Determine the melting point of the resulting 3 5 dinitro benzoate (Section 111,27). 

The ethyl orthoformate required in this preparation may be prepared by the action of sodium upon a mixture of chloroform and dry alcohol ... 

Carry out a second run with the recovered chloroform-alcohol mixture (A) add 100 g. of dry chloroform and sufficient super-dry ethyl alcohol (200-250 ml.) to give a total volume of 750 ml. Add 52 g. of sodium as before. Remove the excess of chloroform and attohol as before on a water bath through a fractionating column, add the intermediate fraction (B) from the first run, and fractionate again. The yield of product b.p. 144-146°, is 45 g. 

Procedure 1. Dissolve 1 g. of the compound in 5 ml. of chloroform in a test-tube and cool in ice. Add 5 ml. of chlorosulphonic acid CA UTION in handhng) dropwise and with shaking. When the initial evolution of hydrogen chloride subsides, remove the reaction mixture from the ice and, after 20 minutes, pour it into a 50 ml. beaker filled with crushed ice. Separate the chloroform layer, wash it well with water, and evaporate the solvent. Recrystallise the residual aryl sulphonyl chloride from light petroleum (b.p. 40-60°), chloroform or benzene this is not essential for conversion into the sulphonamide. 

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. 

P-Hydroxy-a-naphthaldehyde, Equip a 1 litre three-necked flask with a separatory funnel, a mercury-sealed mechanical stirrer, and a long (double surface) reflux condenser. Place 50 g. of p-naphthol and 150 ml. of rectified spirit in the flask, start the stirrer, and rapidly add a solution of 100 g. of sodium hydroxide in 210 ml. of water. Heat the resulting solution to 70-80° on a water bath, and place 62 g. (42 ml.) of pure chloroform in the separatory funnel. Introduce the chloroform dropwise until reaction commences (indicated by the formation of a deep blue colour), remove the water bath, and continue the addition of the chloroform at such a rate that the mixture refluxes gently (about 1 5 hours). The sodium salt of the phenolic aldehyde separates near the end of the addition. Continue the stirring for a further 1 hour. Distil off the excess of chloroform and alcohol on a water bath use the apparatus shown in Fig. II, 41, 1, but retain the stirrer in the central aperture. Treat the residue, with stirring, dropwise with concentrated hydrochloric acid until... 

When polymers or other water-soluble substances are present in the sample, it is advantageous to add a small amount of chloroform to the initial reaction mixture after the subsequent addition of water, a two-phase system results which may be titrated in the usual way to a starch end point or by observing the disappearance of the iodine colour in the chloroform layer. 

To determine the exact perbenzoic acid content of the solution, proceed as follows. Dissolve 1 -5 g. of sodium iodide in 50 ml. of water in a 250 ml. reagent bottle and add about 5 ml. of glacial acetic acid and 5 ml. of chloroform. Introduce a known weight or volume of the chloroform solution of perbenzoic acid and shake vigorously. Titrate the liberated iodine with standard O lA sodium thiosulphate solution in the usual manner. 

The m.p. is not always a safe criterion of purity. Benzoyl peroxide may be analysed as follows -. Dissolve about 0-6 g., accurately weighed, of benzoyl peroxide in Is ml. of chloroform in a 350 ml. conical flask. Cool to — 5°, and add 25 ml. of 0- IN sodium methoxide solution at once with cooling and shaking. After 5 minutes at — 5°, add 100 ml. of iced water, 5 ml. of 10 per cent, sulphuric acid, and 2 g. of potassium iodide in 20 ml. of 10 per cent, sulphuric acid in the order mentioned with vigorous stirring. Titrate the liberated iodine with standard 0-lN sodium thiosulphate solution. 

Neutralise the cold contents of the flask with 500-600 ml. of 40 per cent, aqueous sodium hydroxide solution, equip the flask for steam distillation and steam distil until about 1 litre of distillate is collected. The steam distillate separates into two layers. Add solid sodium hydroxide (< 100 g.) to complete the separation of the two layers as far as possible. Remove the upper (organic) layer and extract the aqueous layer with three 50 ml. portions of chloroform. Dry the combined organic layer and chloroform extracts with anhydrous potassium carbonate and distil the mixture through a short fractionating column (e.g., an 8 Dufton column) after a fore run of chloroform, followed by pyridine, collect the crude 4-ethylpyridine at 150-166° (49 g.). Redistil through a Fenske-... 

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