Sodium bisulphite

In the sodium bisulphite method [97], wool is impregnated with a solution containing 2°Tw sodium bisulphite and l Tw H,SO for 2 h. Alternatively, wool can be treated with a solution of sodium bisulphite (2 Tw) for 6 to 10 h, squeezed, and is then followed by second impregnation in H SO (l Tw) and washed thoroughly. 

---

Required Copper sulphate, 28 g. sodium chloride, 9-5 g. sodium bisulphite, 14 g. hydrochloric acid, 70 ml. aniline, 20 ml. sodium nitrite, 17 g. 

The student should note that ketones in class (1), t.c., those having the >CO group in the side chain, will form additive compounds with sodium bisulphite only if this >CO group is not directly joined to the benzene ring acetophenone therefore will not form such compounds, whereas benzyl methyl ketone, CaHsCHjCOCH, will do so. Many quinones, particularly ortho quinones such as phenanthraquinone, form additive compounds with sodium bisulphite. 

Sodium mlphanilate.—Burns with difficulty, leaving a residue of (chiefly) sodium sulphide. Add dil. HCl, and confirm without delay the evolution of HjS by means of a filter-pa per moistened with lead acetate solution. Typical of salts of the sulphonic acids. Acetone sodium bisulphite.—Almost non-inflammable, leaving a colourless residue of sodium sulphite and sulphate. Transfer residue to a test-tube, add dil. HCl, warm, and confirm the SO2 evolved. 

Sodium Bisulphite. Dissolve 600 g. of NaHS03 in water, make up to I litre and pass in SOj for a few minutes to ensure absence of NagSOg. 

Cuprous chloride. Hydrated copper sulphate (125 g.) and sodium chloride (32-5 g.) are dissolved in water (400 ml.) boiling may be necessary. An allialine solution of sodium sulphite (from 26 5 g. of sodium bisulphite and 17 -5 g. of sodium hydroxide in 200 ml. of water) or the solution of the sodium bisulphite alone is added to the resulting hot solution during about 5 minutes with constant shaking. The solution will be decolourised or nearly so. It is then cooled to room temperature (or in an ice bath), and the supernatant liquid is decanted... 

Dissolve 3 g. of copper sulphate pentahydrate and 1 g. of sodium chloride in 12 ml. of hot water, and add a solution of 1 g. of sodium bisulphite in 10 ml. of 5 per cent, sodium hydroxide solution. Shake, cool under the tap, and wash the precipitated wlute cuprous chloride with water by decantation. Dissolve the cuprous chloride in a few ml. of concentrated ammonia solution and dilute with water to 10 ml. 

If the iodide is deeply coloured, it may be decolourised with a little sodium bisulphite. A perfecUy colourless product can be obtained by distilling in the dark or in dilfusod light from a little silver powder. The iodide should be preserved in a bottle containing a short coil of copper wire made by wrapping coppor wire round a glass rod or tube. 

Trimethylene Di-iodide. Use 76 g. of trimethylene glycol, 27 - 52 g. of pmified red phosphorus and 254 g. of iodine. Lag the arm C (Fig. Ill, 40, ) with asbestos cloth. Stop the heating immediately all the iodine has been transferred to the fiask. Add water to the reaction mixture, decolourise with a httle sodium bisulphite, filter, separate the crude iodide, wash it twice with water, dry with anhydrous potassium carbonate and distU under reduced pressure. B.p. 88-89°/6 mm. Yield 218 g. (a colourless liquid). 

Reflux 1 ml. of the ether with 5 ml. of freshly distilled, constant boiling point hydriodic acid (Section 11,49,2), b.p. 126-128°, for 2-3 hours. Add 10 ml. of water, distil and collect about 7 ml. of liquid. Decolourise the distillate by the addition of a httle sodium bisulphite, and separate the two layers by means of a dropper pipette (Fig. 11,27,1). Determine the b.p. of the resulting iodide by the Siwoloboff method (Section 11,12) and prepare a crystalline derivative (Section 111,42). 

About 0-1 per cent, of hydroquinone should be added as a stabiliser since n-hexaldehyde exhibits a great tendency to polymerise. To obtain perfectly pure n-/iexaldehyde, treat the 21 g. of the product with a solution of 42 g. of sodium bisulphite in 125 ml. of water and shake much bisulphite derivative will separate. Steam distil the suspension of the bisulphite compound until about 50 ml. of distillate have been collected this will remove any non-aldehydic impurities together with a little aldehyde. Cool the residual aldehyde bisulphite solution to 40-50 , and add slowly a solution of 32 g. of sodium bicarbonate in 80 ml. of water, and remove the free aldehyde by steam distillation. Separate the upper layer of n-hexaldehyde, wash it with a little water, dry with anhydrous magnesium sulphate and distil the pure aldehyde passes over at 128-128-5°. 

The experimental procedure to be followed depends upon the products of hydrolysis. If the alcohol and aldehyde are both soluble in water, the reaction product is divided into two parts. One portion is used for the characterisation of the aldehyde by the preparation of a suitable derivative e.g., the 2 4-dinitrophenylhydrazone, semicarbazone or di-medone compound—see Sections 111,70 and 111,74). The other portion is employed for the preparation of a 3 5-dinitrobenzoate, etc. (see Section 111,27) it is advisable first to concentrate the alcohol by dis tillation or to attempt to salt out the alcohol by the addition of solid potassium carbonate. If one of the hydrolysis products is insoluble in the reaction mixture, it is separated and characterised. If both the aldehyde and the alcohol are insoluble, they are removed from the aqueous layer separation is generally most simply effected with sodium bisulphite solution (compare Section Ill,74),but fractional distillation may sometimes be employed. 

The most satisfactory reagent is a saturated solution of sodium bisulphite containing some alcohol it must be prepared aa required since it oxidises and decomposes on keeping. Frequently, a saturated aqueous solution is used without the addition of alcohol. 

Prepare 10 ml. of saturated sodium bisulphite solution and add 4 ml. of the aldehyde shake thoroughly and observe the rise in temperature. Filter the crystalline precipitate at the pump, wash it with a little alcohol, followed by ether, and allow it to dry. 

This sodium bisulphite reagent Is prepared by treating a saturated aqueous solution of sodium bisulphite with 70 per cent, of its volume (if rectified (or methylated) spirit, and then adding just sufiScient water to produce a clear solution. 

Prepare a saturated solution of sodium bisulphite at the laboratory temperature from 40 g. of finely powdered sodium bisulphite about 70 ml. of water are required. Measure the volume of the resulting solution and treat it with 70 per cent, of its volume of rectified spirit (or methylated spirit) add sufficient water (about 45 ml.) to just dissolve the precipitate which separates. Introduce 20 g. of commercial cycZohexanone into the aqueous-alcoholic bisulphite solution with stirring and allow the mixture to stand for 30 minutes stir or shake occasionally. FUter off the crystalline bisulphite compound at the pump, and wash it with a little methylated spirit. 

Preparation of the sulphones. Dissolve the 2 4-dinitrophenyl-sulphide in the minimum volume of warm glacial acetic acid and add 3 per cent, potassium permanganate solution with shaking as fast as decolourisation occurs. Use a 50 per cent, excess of potassium permanganate if the sulphide tends to precipitate, add more acetic acid. Just decolourise the solution with sulphur dioxide (or with sodium bisulphite or alcohol) and add 2-3 volumes of crushed ice. Filter off the sulphone, dry, and recrystaUise from alcohol. 

Suspend in a round-bottomed flask 1 g. of the substance in 75-80 ml. of boihng water to which about 0 -5 g. of sodium carbonate crystals have been added, and introduce slowly 4 g. of finely-powdered potassium permanganate. Heat under reflux until the purple colour of the permanganate has disappeared (1-4 hours). Allow the mixture to cool and carefully acidify with dilute sulphuric acid. Heat the mixture under reflux for a further 30 minutes and then cool. Remove any excess of manganese dioxide by the addition of a little sodium bisulphite. Filter the precipitated acid and recrystallise it from a suitable solvent (e.g., benzene, alcohol, dilute alcohol or water). If the acid does not separate from the solution, extract it with ether, benzene or carbon tetrachloride. 

Pour the resulting dark reddish-brown liquid into 500 ml. of water to which 17 ml. of saturated sodium bisulphite solution has been added (the latter to remove the excess of bromine). Steam distil the resulting mixture (Fig. II, 41,1) , collect the first portion of the distillate, which contains a little unchanged nitrobenzene, separately. Collect about 4 litres of distillate. Filter the yellow crystalline solid at the pump, and press well to remove the adhering liquid. The resulting crude m-bromonitrobenzene, m.p. 51-52°, weighs 110 g. If required pure, distil under reduced pressure (Fig. II, 19, 1) and collect the fraction of b.p. 117-118°/9 mm. it then melts at 56° and the recovery is about 85 per cent. 

The amlnation reaction is reversible thus P-naphthylamine can be reconverted into p-naphthol by heating with aqueous sodium bisulphite solution, then adding alkali and boiling until all the ammonia is expelled. 

Method 1. Prepare a solution of cuprous bromide by refluxing 31-5 g. of erystallised eopper sulphate, 10 g. of elean eopper turnings, 77 g. of crystallised sodium bromide, 15 g. (8-2 ml.) of concentrated sulphuric acid and 500 ml. of water contained in a 2 5 litre round-bottomed flask over a flame for 3-4 hours until the solution acquires a yellowish colour if the blue colour is not discharged, add a few grams of sodium bisulphite to complete the reduction. 

Warm the copper sulphate solution to 50-60°, and add dilute sulphuric acid until it is acid to Congo red. Add the sodium bisulphite solution. 

Benzonitrile (phenyl cyanide). Prepare a cuprous cyanide solution in a 500 ml. round-bottomed flask as above, but use the following quantities 65 g. of crystallised copper sulphate in 205 ml. of water, 18 g. of sodium bisulphite in 52 ml. of water, and 18 g. of potassium cyanide in... 

---