Chloride distillation

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°. 

Mix 40 g. (51 ml.) of isopropyl alcohol with 460 g. (310 ml.) of constant boiling point hydrobromic acid in a 500 ml. distilling flask, attach a double surface (or long Liebig) condenser and distil slowly (1-2 drops per second) until about half of the liquid has passed over. Separate the lower alkyl bromide layer (70 g.), and redistil the aqueous layer when a further 7 g. of the crude bromide will be obtained (1). Shake the crude bromide in a separatory funnel successively with an equal volume of concentrated hydrochloric acid (2), water, 5 per cent, sodium bicarbonate solution, and water, and dry with anhydrous calcium chloride. Distil from a 100 ml. flask the isopropyl bromide passes over constantly at 59°. The yield is 66 g. 

Maleic acid may be prepared by warming malic acid with acetyl chloride, distilling the mixture under atmospheric pressure to isolate maleic anhydride, and hydrolysing the latter by boding with water. 

Beckmann rearrangement of benzophenone oxime to benz-anilide. Dissolve 2 g. of benzophenone oxime in 20 ml. of anhydrous ether in a small conical flask and add 3 g. of powdered phosphorus pentachloride (or 3 ml. of pure tbionyl chloride). Distil off the solvent and other volatile products on a water bath CAUTION ether), add 25 ml. of water, boil for several minutes and break up any lumps which may be formed. Decant the supernatant liquid, and recrystallise, in the same vessel, from boiling alcohol. The product is benzanilide, m.p. 163° confirm this by a mixed m.p. determination with an authentic specimen. 

Calcium Chloride. Distiller waste Hquor from synthetic plants can be evaporated in multiple effect evaporators, precipitating residual sodium chloride. The resulting mother Hquor is then further evaporated to a molar ratio of lCaCl2 2H20 and cooled to produce flakes that are dried in rotary or... 

Diehloromethane is dried over anhydrous calcium chloride, distilled,... 

The o-azidophenylacetyl chloride was prepared by treating o-azidophenylacetic acid with thionylchloride in portions at room temperature and then heating the solution under reflux for one hour. The a-azidophenylacetyl chloride distils at 115°C under a pressure of 10 mm Hg. 

The mandelic acid formate ester obtained as a syrup as described above Is stirred for 2 hours with 2.9 kg ( 1.75 ) of thionyl chlorideat a temperature of about 70°C. The excess thionyI chloride is removed by evaporation and the residual green solution is vacuum distilled. The product, 0-formyl mandeloyl chloride, distills over at 127°C to 130°C (15 mm) or at 108°C to 112°C (7 mm). 

Distillers solubles Sodium chloride Distilled water to 1,000 ml... 

Oi-Benrylmercaptopropionic acid (meiting point 76 C to 78 C 100 g) prepared by condensation of a-mercaptopropionic acid with benryi chioride is aiiowed to stand overnight with 80 g of thionyi chioride. After removai of excess thionyl chloride distillation in vacuo gives 70 g of a-benrylmercaptopropionic acid chloride of boiling point 138°C to l39°C/7 to 8 mm Hg. 

Seventy grams (0.25 mole) of oleic acid (Note 1) is placed in the dropping funnel H of the tangential apparatus (Fig. 2 Note 2). The thionyl chloride distillation is started and regulated (Note 2) the upper part of the column should be filled with the vapor, and reflux should be constant and steady. The acid is dropped in at the top of the column over a period of 35 minutes (120 g. per hour). The product that collects in the receiver I contains about 25-27% of thionyl chloride (Note 2) if the heated lower leg K is employed. The product in... 

The product is transferred to a modified Claisen flask (Note 4) and distilled under reduced pressure, heat being supplied by an oil bath (Note 5). Most of the thionyl chloride distils at room temperature. The yield of almost colorless product distilling at 64-66°/20 mm. (Note 6) is 122-143 g. (71-83%) 1.451. 

This Grignard reaction is particularly difficult to initiate and depends greatly on the purity of the neopentyl chloride. Commercial neopentyl chloride [Eastern] is stirred over four consecutive portions of concentrated sulfuric acid for a period of 6h each followed by 1 h for the mixture to completely settle before draining off the darkened acid layer. The fourth portion of acid is only slightly colored. The clear neopentyl chloride is washed with water followed by aqueous sodium bicarbonate solution, dried over calcium chloride, then filtered from the drying agent before use. Pure neopentyl chloride distils at 83 to 84 °C and is inert to concentrated sulfuric acid at room temperature. 

Fill the apparatus with chlorine and perform chlorination of the molybdenum, heating the place of the tube where the metal is with the flame of a burner to 200-300 °C. What colour do molybdenum pentachloride and tungsten hexachloride have If oxychlorides are produced together with the molybdenum(V) or tungsten(VI) chlorides, distil them off in a chlorine stream. Transfer the product into a weighed test tube with a stopper, weigh it, and hand it in to your instructor. Calculate the yield in per cent. 

Phosphorus dissolves in arsenic trichloride on warming without reaction and is deposited on cooling.8 If the mixture is heated in the presence of aluminium chloride at 130° to 150° C. for 40 minutes, a brownish-red compound of composition A1As3C13 results,9 from which, however, aluminium chloride can readily be removed by water or ammonia, leaving a residue of finely divided black arsenic. If the compound is heated to 190° C. in the absence of air, it turns black as arsenic trichloride and aluminium chloride distil off and a bright grey mixture of arsenic and arsenide remains. It has been suggested that the arsenic is co-ordinatively bound, and that the compound may be /Ass... 

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