December i, 1884.] THE TROPICAL AGRICULTURIST. 



469 



I. 0-2154 gram 05820 CO., and 0-1420 H a O 

 II. 02436 gram 0-6535 CM >., and 0-1555 H 2 



III. 0-2453 gram 0-6660 00 2 and 0-1585 11 .< > 



IV. 0-2613 gram 0-7095 C( l.j and 1765 11/ I 

 Calculated for Found. 



19 H M N.O a C.. 1 ,U,,N.,0., I. H. HI. IV. 



C. .73-54" . ."7407". . 7373 73 16 71<>4 74-05 

 H. . 7(H) . . 7 41 . . 7-35 7'09 7.17 7 \50 

 From ether containing water homoquinine separates, if 

 undisturbed, partly in concentrically grouped needles, partly 

 in stout decided prisms, derived from the rhombic system, 

 terminating at the ends in a dome, the crystals being 

 sometimes isolated and sometimes a few concentrically 

 aggregated together. In a disturbed crystallization, on the 

 other hand, according to the degree of concentration of 

 the solution, either o sandy powder or a crystallization 

 consisting of delicate lamellae is obtained. In all casts it 

 contains water of crystallization, the quantity varying 

 between 2 and '_'.', molecules, a part of which is readily 

 given off at 80 °"to 100° C, and the remainder first at 

 120° to 125 °C. 



I. 0-2438 gram gave at 120 ° to 125 => C. 0"0284 H.,0 



II. 0-2784 gram gave at 120 c to 125°< '. 0031 13 H 2 



lll.i 1-2501 > gram gave at 120 c to 125 ° C. 00260 H 4 



IV. 0-2733 gram gave at 120 ° to 125 ° 0.-00273 H a O 



V. 0-2935 gram gave at 120 ° to 125 ° C. 00322 H 2 



VI . 0-6085 gram gave at 120 ° to 125 ° C. 0-0710 H.O 



Calculated for 



H,0 



CmHmNiOj + 2 H..O C sn H.. 1 N,,U, + 2.V H,0 



. ". . 10-0 ■ 12-19 



Found 



I. II. III. IV. V. VI. 



11-65 1088 10-40 1000 1097 _ 11-06 

 Crystals of homoquinine exposed to the air gradually 

 become dull through efflorescence; in the more compact 

 crystals, however, the amount of water never falls below 

 In per cent.* They can be exposed directly to a tem- 

 perature of 100 ° C. without any fear that they will fuse, 

 like, for instance, crystallized quinine trihydrate. At that 

 temperature the alkaloid loses only a portion of its water 

 of crystallization; it first melts at 170 ° C, forming, upon 

 cooling, a colourless, amorphous mass. 



Homoquinine dissolves in ether with somewhat more 

 difficulty than quinine; its solution docs not gelatinize upon 

 evaporation of the ether, but crystallizes up to the last 

 drops, if the ether be absolutely free from alcohol. In 

 chloroform it dissolves readily, but with more difficulty in 

 benzol and very slightly in light petroleum spirit. Alcohol 

 dissolves it freely and leaves it upon evaporation in the 

 amorphous form. 



The alcoholic solution of homoquinine tastes intensely 

 bitter and has a strongly basic reaction ; it neutralizes 

 hydrochloric and sulphuric 'acids perfectly. Its solution in 

 an excess of dilute sulphuric acid shows a blue fluorescence, 

 which is dispelled by sodium chloride and other haloid 

 salts. Hydrochloric acid also removes this appearance, and 

 a solution of the base in hydrochloric acid shows uo 

 fluorescence. These solutions rotate the plane of polarized 

 light to the left; they give upon the addition of chlorine 

 water or hypochlorite of lime and excess of ammonia a 

 dark green colour, like quinine. 



With acids homoquinine forms neutral and acid salts. 

 which, so far as they have up to the present been examined, 

 correspond in their behaviour towards precipitauts. such as 

 sodium hydrate and carbonate and ammonia, with the 

 corresponding quinine salts; on the other hand, they differ 

 from them in their form and partially in their greater 

 solubility. On account of insufficiency of material I have 

 only been able to deal at all exhaustively with the follow- 

 ing salts; — 



Netural Hydrochlorate of Homoquinine is obtained by 

 neutralization of an alcoholic solution of the alkaloid with 

 hydrochloric acid. Upon evaporation of this solution an 

 amorphous residue is left that dissolves readily in water. 



* The substance obtained in delicate lamellae effloresces 

 very rapidly, and frequently after a few hours the quantity 

 of water of crystallization amounts to ouly about 6 per 

 cent. This phenomenon may probably be partially clue to 

 the larger surface which the lamellae have as compared with 

 the more compact crystals. 



The aqueous solution leaves again upon spontaneous evapor. 

 ation an amorphous residue. 



Acid Hydrocldorate of Homoquinineis obtained upon adding 

 some hydrochloric acid to a concentrated aqueous solution 

 of the neutral hydrochlorate ; the acid hydroclilorate sepa rates 

 at once in stout colourless prisms, which dissolve pretty 

 freely in water, but less readily in hydrochloric acid. 



Acid i 'hloroplatinate of Homoquinine. — Upon mixing an 

 aqueous solution of the previous salt with platinum solution 

 a pale yellow flocculent precipitate results, which almost 

 immediately is re-arranged in small orange-red prisms. The 

 salt contains water of crystallization that is first given off 

 at 120 = 0. 



Hydrosulphocyanide of Homoquiniiu is obtained upou mix- 

 ing a solution of the neutral hydrochlorate with potassium 

 cyanide. It is amorphous, dissolves slightly in cold water, 

 but more freely in hot water and in alcohol. 



Neutral Sulphate of 'Homoquinine is obtained upon satur- 

 ation of hot dilute sulphuric acid with the base. Upon coi -line 

 of the solution the sulphate crystallizes in short six-sided 

 colourless prisms, which being very brittle are broken more 

 or less in collection. The salt dissolves iu about thirty 

 parts of boiling water, very slightly in cold water, freely 

 in boiling alcohol, and is nearly insoluble iu chloroform and 

 ether. 



Samples prepared on different occasions gave upon analysis 

 the following results: : — 



1. 02190 gram gave at 120° C. 0-0333 H a O. 

 II. 0-4848 gram gave at 120 ° O. 0-0608 H..O. 



III. 0-3300 gram gave at 120°O. 00420 HJO. 



IV. 



and 00925 

 S(> 4 Ba. 



IV. 

 13-01 



ii 124 :; gram gave at 120 ° O. 0'0293 H a O. 

 Calculated for Found. 



(0„,H»,N.,0 ; ,),S0 1 tf., + ( H,0. I. II. III. 



K.o . . . 12-64 .... 13-37 12-50 1285 

 S0 3 . . . 9-37 .... — — 9-62 



The crystals of this salt effloresce superficially in air, 

 and become consequently dull; the loss of water is, how- 

 ever, not worth notice. Even after a considerable time 

 the water of crystallization amounts still to 12-50 per cent. 

 On the other hand, quinine sulphate exposed to exactly 

 the same conditions would at the end of a couple of hours 

 have fallen to a powder, and would then contain only 4 2 

 to in percentof water. If the two sulphates, dehydrated 

 at 120°0., be etpo .1 to moist air, the quinine sulphate 

 rapidly takes up 1 per cent of water, but the homoquinine 

 almost three times as much, namely, 11 to 12 per cent. 



It was if especial interest to ascertain the behaviour of 

 homoquinine to polarized light, since the alkaloid on account 

 of tins behaviour received from Whiffen the name "ultra- 

 quinine." According to Whiffen this sulphate in acid 

 solution showed (n) ° --= — 221 ° , whilst quinine sul] hate, only 

 showed («)°=— 196°. Of the water of crystallization of 

 the two sulphates, in which they certainly differ from 

 each other. Whiffen makes no mention, so that it is quite 

 possible that the difference iu question was purely dependent 

 upon the different quantities of water of crystallization 

 which they contain. 



In my experiments the amount of water of crystallization 

 rst exactly estimated, and then a quantity of each 

 of the hydrated sulphates corresponding to 1-25 gram of 

 anhydrous salt was dissolved in 10 e.c. of normal hydrochloric 

 acid. These solutions were then each diluted with water 

 up to 25 c.c, and finally examined at i=50 ° and /— 220, 

 the deviation being sometimes determined first by means 

 of the quinine solution, and then this solution changed 

 for the homoquinine solution, ami sometimes the order 

 being reversed. In this way it was ascertained that the 

 '.utions did not differ from <>,ie another in respect to 

 their opt\cal be/iaviour. In an average of thirty determin- 

 ations (or)=25-92°, which gives for the anhydrous sulphate 

 (a)°=— 235-6°. 



Neutral Tartrate of Homoquinine is obtained by mixing 

 a hot aqueous solution of the sulphate with solution of 

 rochelle salt. It forms delicate white concentrically grouped 

 needles, which dissolve with some difficulty in hot water 

 and are very slightly soluble in cold. The composition of 

 the salt is represented by the formula: — 

 i<:;,„II 2J N,')j,.( , ,H li O„ + 21l,M 



0-3305 gram of air-dried substance gave at 120° C null 

 H,0. 



