1872.] 



History of the Opium Alkaloids. 



285 



precipitation with water, a yellow brittle tar not fusible at 100° when quite 

 dry ; methyl iodide is produced in quantity during the action, but only 

 traces of phosphoric acid, and this probably by atmospheric oxidation. 

 Dried at 100° the tar gave these numbers : — 



0-3660 grm. gave 0*621 C0 2 and 0-149 H 2 0. 

 0-5520 „ 0-363 Agl. 



Calculated. 



, * N Found. 



C 13C 1632 46-31 46-27 



H 15S 158 4-48 4-53 



I 10 1270 36-04 35-54 



N 8 112 3-18 



22 352 9-99 



C 130 H H0 I a N 8 O aa ,8HI 3524 100-00 



Hence this substance is formed by the reaction 

 C 1U H 168 N 8 2l5 8111 + 1 0HI= 8CH 3 1 + 2H 2 O + C 13G H 150 I 2 N 8 22 , SHI. 



N0 3 H and AgN0 3 give a blood-red coloration with this product, showing, 

 as the analytical numbers indicate, that it is derived from polymerized 

 C„ H 19 N0 3 , and not from polymerized C 17 H 20 N0 3 , or C w H 21 N0 3 . 



The foregoing results show that the methyl group in codeia is unaltered 

 during the polymerization to dicodeia and to tetracodeia, and furnishes 

 another proof of the conclusion come to in Part IV. § 2, that the addition 

 of H 2 for C 1T , when HI and P act on morphia or codeia, takes place before 

 and not after the final polymerization ; even polymerization to dicodeia 

 could not precede this addition of H 2 , as the product obtained from that 

 polymeride has only H added on for C 17 . 



The following formulae show clearly the difference in the action of hy- 

 driodic acid and phosphorus on codeia and its polymerides : — 

 Alkaloid. Temperature. Formula of product. 



Codeia .... 100° 8(C 17 H 10 N0 3 + H 9 ) + 12HI. 



.... 110°-115° 8(C 17 H 19 N0 3 + H 2 )+12HI-4H 2 O. 

 .. ..up to 130° 8(C 17 H 19 N0 3 + H 2 -0) + 12HI-4H.,0. 

 Dicodeia. . . .up to 120° 8(C 17 H 19 N0 3 + H) + 9HI-4H 2 O. 

 Tetracodeia.. up to 130° 8(C 17 H 19 N0 3 ) + 10HI-2H 2 O. 



From which it is clear that dicodeia is intermediate between tetracodeia 

 and ordinary codeia. From the fact that the basic 4 HI for 8(C 17 ) are added 

 on in the case of the first product before the elimination of 4H 2 O, as in the 

 second substance in the list, it may be inferred that the action is not 

 a true substitution of iodine for hydroxy] ; analogous facts have been 

 observed in the chlorinated substances obtained by the action of HC1 on 

 codeia and morphia, the first action being apparently a direct addition 

 of the elements of IIC1, the subtraction of the elements of H 2 O taking 

 place at a later stage. 



