84 REPORT 1871. 



diclironiate, one of sulphuric acid, aud thirty of water, an inverted condenser being 

 attached, a slow evolution of CO^ is noticed. After six or eight hours but little 

 action has appareutlj^ taken place ; but on distilling the product there is obtained, 

 besides unaltered hesperidene, an acid liquid, which yields by neutralization a 

 barium salt, giving all the qualitative reactions of acetate, and containing the cal- 

 culated percentage of barium ; a little formiate is possibly also produced, as the 

 barium salt reduces silver nitrate slightlj^ on boiling. The silver salt got by 

 precipitation with strong silver nitrate and recrystallization from boiling water is 

 pure acetate. 



The action of potassium chlorate and sulphuric acid on hesperidene is very 

 energetic, a viscid tany 'substance, not yet examined, being produced. 



The production of acetic acid fi'om hesperidene renders a grouping of carbon 

 atoms of the following nature probable : — 



CH3 

 CH(C,H,,)". 



We hope to be able to gain some further insight into the stmcture of the gi-oup 

 C^ H,2, and propose to submit to examination several other essential oils, hoping 

 that the results may throw some light on the causes of the "physical isomerism " 

 of the turpentine group of hydrocarbons. 



On certain new Derivatives from Codeia. By C. R. A. Wrigitt, D.Sc, 

 Lecturer on Chemisfri/ in St. Mari/'s Hospital Medical Scliool. 



When codeia is heated to 100° C. for two or three hours with from three to six 

 parts of aqueous hj-drobromic acid containing 48 per cent. IIBr, there are formed, 

 without appreciable evolution of methyl bromide, three new bases, of which the 

 two last are produced by a further action on the first. These are — 



Bromocodick C,, H^oBrNO^ 



Deoxycodeia ^'ie^^2i NOj 



Bromotetracodeia C^^ H^j Br N^ Oj,. 



The two first are soluble in ether, and may thus be separated (after precipitation 

 by sodium carbonate) from the last, which is almost insoluble in this medium. By 

 agitation of the etherial extract with hydrobromic acid there is obtained a viscid 

 liquid, which contains little but bromocodide hydrobromate, if the digestion of the 

 codeia have been carried on for a short time only, but contains also much deoxy- 

 codeia hj'drobromate if the digestion have been continued somewhat longer. This 

 latter salt separates in crystals from the viscid liquid on standing, the bromocodide 

 hydrobromate furnishing a gummy mass only on standing and evaporation. 



By dissolving the portion insoluble in ether in dilute hydrobromic acid, and 

 fractionally precipitating the coloured solution thus got with strong hydrobromic 

 acid several times successively, bromotetracodeia hydrobromate is ultimately 

 obtained in white amorphous flakes, that become tarry if warmed while moist, 

 and colour more or less on drying. When once dry, a temperature of lOO^C. does 

 not soften the amorphous salt. 



The following reactions explain the productions of these three bases from codeia 

 hydrobromate — 



Codeia hydrobromalc. Broiuoeodide hydrobromate. 



0,, H,, NO3, IIBr + HBr = H, + C„ II,, Br NO,, IIBr 



Codeia liydro- Bromocodide liydro- Deoxycodeia hydro- Bromotetracodeia 



bromate bromate. bromate. hydrobromate. 



4(Ci,Il,iN03,IIBr) + C,JI,„BrNO„IIBr=C,3H,jNO„IIBr+G-,II,,BrN,0,„4IlBr. 



By the further action of hydrobromic acid on each of the above bases methyl 

 bromide is copiously evolved, and the following series of products formed : — 

 (A) From bromotetracodeia : hromotetrcnnorphia, probably by the reaction — 



Bromotetracodeia. Bromotctramorphia. 



C,, H,3 BrN, O,, + 4HBr = 4CH3 Br + C,, H,, BrN, O,,. 



