1869.] 



Hydrochloric Acid on Codeia. 



87 



204 



67-22 



67 04 



18 



5-93 



6-25 



14 



4-61 





32 



10-54 





35-5 



11-70 





303*5 



100 00 





Calculated. Found. 



I. II. 



c„ 



H„ 

 N 



O, . 



CI 35-5 11-70 



C 17 H 17 NO a ,H 

 Hence the reaction which takes place is 



C 18 H 20 CI N0 2 =CH 3 Cl + C„ H 17 NO,. 

 It is worthy of notice that this reaction probably takes place gradually, 

 while that whereby apomorphia and chloride of methyl are formed direct 

 from codeia appears to occur suddenly, thereby bursting the large majority 

 of sealed tubes used : this never occurred with chlorocodide. 



§ 3. Action of Water on the Hydrochlorate of Chlorocodide. 



When the hydrochlorate (obtained by dissolving the base freed from 

 codeia &c. by the process previously described in as small an excess of hy- 

 drochloric acid as possible) is sealed up with ten to fifteen times its weight 

 of water and heated for three hours to 130°-140°, it splits up into hydro- 

 chloric acid and hydrochlorate of codeia, no gas whatever being formed 

 during the reaction. 



C 18 H 20 ClNO 2 , HC1+H 2 0 = HC1 + C 18 H 21 N0 3 , HC1. 



In two experiments the amount of free hydrochloric acid thus formed 

 was estimated by titration with a solution of carbonate of sodium, and after 

 subtraction of the small amount due to the excess of hydrochloric acid in 

 the original liquid (estimated in the same way), was found to amount re- 

 spectively to 9 and 10 per cent, of the hydrochlorate employed, the theo- 

 retical amount according to the above equation being 10*3; the amount of 

 undecomposed chlorocodide was found to be very small, the liquid result- 

 ing from the digestion giving but a minute precipitate with carbonate of 

 sodium. The nitrate from the carbonate-of-sodium precipitate was extracted 

 with ether, and the ethereal solution obtained shaken with a few drops of 

 hydrochloric acid ; an oily liquid was thus obtained, which on standing 

 several hours deposited crystals ; these, when drained from the mother 

 liquors and recrystallized, had the character of hydrochlorate of codeia, and 

 gave the following numbers after drying in an ordinary water-bath till con- 

 stant in weight. 



As crystallized hydrochlorate of codeia is stated to lose one-fourth of its 

 water of crystallization at 100°, a sample was prepared by dissolving codeia 

 in hydrochloric acid and recrystallizing the product; after drying in the 

 same water-bath it was also burnt as a comparison (III.). 



(I.) 0'3110 gramme of hydrochlorate of codeia from chlorocodide gave 

 0*6595 carbonic acid and 0-2015 water. 



(II.) 0*2790 gramme of the same, burnt with lime, gave 0*1090 silver 

 chloride. 



