Chloride, zinc

Zinc chloride has long been known to form complexes in solution. In 1940. Robinson and Stokes (Z14) presented e.m.f. measurements for various concentrations at five degree temperature intervals from 10 to 40 C which they fit to the equation  

They then encountered difficulty in extrapolating back to Infinite dilution which led them to reject as inaccurate a number of points below. 008 m. They hypothesized that the deviation of these points from their linear extrapolation might point to incomplete dissociation  

In a similar study of zinc bromide in 1945. Stokes and Stokes (7) noted simflar behavior. They suggested the osmotic coefficient ratio plots described earlier as a method of testing for complexing behavior. With ionic radii of. 65 %. and. 74 X for the Mg and Zn ions, they felt that the osmotic coefficients should be similar. A plot of the osmotic coefficient ratios  

The NBS (1) and Russian (2) thermodynamic tables present data for the ZnCl, ZnClz (aq) and ZnClf complexes. The NBS also includes the ZnCl . There appears to be sufficient evidence of its existence that it should be included in attempts to model the zinc chloride system. It can be expected that this complex will increase in importance with an increase in concentration. 

Related Reagents. Magnesium Bromide Zinc Chloride Zinc Iodide. 

Form Supplied in white, odorless, very deliquescent granules  

Purification reflux (50 g) in dioxane (400 mL) in the presence of Zn° dust, then filter hot and allow to cool to precipitate purified ZnCh. Also, anhydrous material may be sublimed under a stream of dry HCl, followed by heating to 400 °C in a stream of dry N2. 

Handling, Storage, and Precautions very hygroscopic store under anhydrous conditions moderately irritating to skin and mucous membranes. 

Organozinc Reagents. The transmetalation of organomagne-sium, organolithium, and organocopper reagents is an important 

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It was first described in 1608 when it was sublimed out of gum benzoin. It also occurs in many other natural resins. Benzoic acid is manufactured by the air oxidation of toluene in the liquid phase at 150°C and 4-6 atm. in the presence of a cobalt catalyst by the partial decarboxylation of phthalic anhydride in either the liquid or vapour phase in the presence of water by the hydrolysis of benzotrichloride (from the chlorination of toluene) in the presence of zinc chloride at 100°C. 

C (decomp.). Prepared by reacting ketene with methanol under carefully controlled conditions in the presence of anhydrous zinc chloride. This highly reactive compound has many synthetic uses, chiefly for adding the... 

For complete acetylation of polyhydric compounds, such as glucose (p. 141) and mannitol (p. I42), even undiluted acetic anhydride is insufficient, and a catalyst must also be employed. In such cases, the addition of zinc chloride or anhydrous sodium acetate to the acetic anhydride usually induces complete acetylation. ... 

Carry out this preparation precisely as described for the a-compound, but instead of zinc chloride add 2 5 g. of anhydrous powdered sodium acetate (preparation, p. 116) to the acetic anhydride. When this mixture has been heated on the water-bath for 5 minutes, and the greater part of the acetate has dissolved, add the 5 g. of powdered glucose. After heating for I hour, pour into cold water as before. The viscous oil crystallises more readily than that obtained in the preparation of the a-compound. Filter the solid material at the pump, breaking up any lumps as before, wash thoroughly with water and drain. (Yield of crude product, io o-io 5 g.). Recrystallise from rectified spirit until the pure -pentacetylglucose is obtained as colourless crystals, m.p- 130-131° again two recrystallisations are usually sufficient for this purpose. 

Mannitol, CH,0H(CH0Hi4CH40H, is a hexahydric alcohol obtained by the reduction of mannose. Since ring formation does not occur in mannitol, the hexacetyl derivative can exist in only one form, and therefore either zinc chloride or sodium acetate can be used as a catalyst for the acetylation. 

Required Mannitol, 5 g. acetic anhydride, 30 ml. zinc chloride, ca, 0-5 g. 

Required Resorcinol, 5 g. acetonitrile, 3 5 ml. zinc chloride, 2 g., anhydrous ether, 25... 

The Fischer Indolisation Reaction occurs when the phenylhydrazone of a suitable aldehyde or ketone undergoes cyclisation with loss of ammonia, under the influence of various reagents, such as zinc chloride, ethnnolic hydrogen chloride, or acetic acid. For example, the phenylhydrazone of acetophenone (p. 257) when heated with zinc chloride gives 2 phenylindole. ... 

The mixed amines are dissolved in hydrochloric acid and zinc chloride solution added. The quinoline chlorozincate, (C H7N)2,HtZnCl, crystallises out, being almost insoluble in water, while the aniline chlorozincate remains in solution. The quinoline chlorozincate is then filtered off and decomposed by alkalis, and the liberated quinoline extracted with ether or steam-distilled. 

Required Aniline, 24 ml. nitrobenzene, 13 ml. anhydrous glycerol, 62 ml. sulphuric acid, 36 ml. zinc chloride, 23 g. 

These chlorozincates must not be confused with the non-ionic compounds which quinoline and aniline bases give with neutral zinc chloride the latter have the formulae [(C,H7N)2ZnClt] and [(C,H7N)tZnCl ] respectively, and both are only slightly soluble in water. 

Mix 1 g. of quinaldine and 1 g. of powdered />-dimethylaminobenzab dehyde, add 2 -3 drops of 10% etl nolic zinc chloride solution, and heat under reflux in an oil-bath at 150 for 1 hour. Cool the product in ice-water, and reciystallise it from ethanol. p-Dimethylaminostyryl-quinoline (I) separates as bright yellow crystals, m.p. 177-178°. 

Deliquescence and efflorescence. A substance is said to deliquesce (Latin to become liquid) when it forms a solution or liquid phase upon standing in the air. The essential condition is that the vapour pressure of the saturated solution of the highest hydrate at the ordinary temperature should be less than the partial pressure of the aqueous vapour in the atmosphere. Water will be absorbed by the substance, which gradually liquefies to a saturated solution water vapour will continue to be absorbed by the latter until an unsaturated solution, having the same vapour pressure as the partial pressure of water vapour in the air, is formed. In order that the vapour pressure of the saturated solution may be sufficiently low, the substance must be extremely soluble in water, and it is only such substances (e.g., calcium chloride, zinc chloride and potassium hydroxide) that deliquesce. 

Pure pyridine may be prepared from technical coal-tar pyridine in the following manner. The technical pyridine is first dried over solid sodium hydroxide, distilled through an efficient fractionating column, and the fraction, b.p. 114 116° collected. Four hundred ml. of the redistilled p)rridine are added to a reagent prepared by dissolving 340 g. of anhydrous zinc chloride in a mixture of 210 ml. of concentrated hydrochloric acid and 1 litre of absolute ethyl alcohol. A crystalline precipitate of an addition compound (probable composition 2C5H5N,ZnCl2,HCl ) separates and some heat is evolved. When cold, this is collected by suction filtration and washed with a little absolute ethyl alcohol. The yield is about 680 g. It is recrystaUised from absolute ethyl alcohol to a constant m.p. (151-8°). The base is liberated by the addition of excess of concentrated... 

There appear to be at least two zinc chloride complexes of pyridine, one of m.p. 207 and composition 2CsH,N,ZnCh, sind the other of m.p. 152° and probable composition 2C,H,N,ZnClt,HCl. The former is slightly soluble in water and in hot ethyl alcohol the latter passes into the former in aqueous solution, is readily soluble in hot absolute ethanol and can therefore be readily recrystaUised from this solvent. 

Zinc cyanide. Solutions of the reactants are prepared by dis solving 100 g. of technical sodium cyanide (97-98 per cent. NaCN) in 125 ml. of water and 150 g. of anhydrous zinc chloride in the minimum volume of 50 per cent, alcohol (1). The sodium cyanide solution is added rapidly, with agitation, to the zinc chloride solution. The precipitated zinc cyanide is filtered off at the pump, drained well, washed with alcohol and then with ether. It is dried in a desiccator or in an air bath at 50°, and preserved in a tightly stoppered bottle. The yield is almost quantitative and the zinc cyanide has a purity of 95-98 per cent. (2). It has been stated that highly purified zinc cyanide does not react in the Adams modification of the Gattermann reaction (compare Section IV,12l). The product, prepared by the above method is, however, highly satisfactory. Commercial zinc cyanide may also be used. 

The only important precaution in this preparation is to ensure an excess of zinc chloride over sodium cyanide. If the latter is in excess, the zinc cyanide generally precipitates as a sticky mass, which is difficult to filter and unsatisfactory for the preparation of hydroxy-aldehydes. 

Lucas reageut is prepared by dissolving 68 g. (0-5 mole) of anhydrous zinc chloride (fused sticks, powder, etc.) in 62 6 g. (0 6 mole) of concentrated hydrochloric acid with cooling to avoid loss of hydrogen chloride. 

By refluxing the alcohol with a mixture of concentrated hydrochloric acid and anhydrous zinc chloride, for example ... 

After the butyl chloride fraction has been collected, change the receiver and continue the distillation untU the zinc chloride commences to crystallise. Allow to cool and stopper the flask. The anhydrous zinc chloride thus obtained may be used in another preparation and recovered repeatedly. This results in considerable economy when the preparation is conducted by a large number of students. 

Reflux a mixture of 68 g. of anhydrous zinc chloride (e.g., sticks), 40 ml. (47 -5 g.) of concentrated hydrochloric acid and 18-5 g. (23 ml.) of sec.-butyl alcohol (b.p. 99-100°) in the apparatus of Fig. 777, 25, 1 for 2 hours. Distil oflF the crude chloride untU the temperature rises to 100°. Separate the upper layer of the distillate, wash it successively with water, 5 per cent, sodium hydroxide solution and water dry with anhydrous calcium chloride. Distil through a short column or from a Claisen flask with fractionating side arm, and collect the fraction of b.p. 67-70° some high boiling point material remains in the flask. Redistil and collect the pure cc. butyl chloride at 67-69°. The yield is 15 g. 

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

Reaction with 3 5-dinitrobenzoyl chloride. Ethers undergo cleavage with 3 5 dinitrobenzoyl chloride in the presence of zinc chloride ... 

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). 

CH3)3COH+CH3COCl+C H5N(CH3), CH3COOC(CH3)3+C.H5i (CH3)jHCl or from the alcohol and acetic anhj dride in the presence of a little anhydrous zinc chloride ... 

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