67 



isomeric isobutylaldehyde, the second as metliylettij iketoii, the reaction 

 for propylene oxide proceeding as for ethylene oxide. 



Numerons are the investigations with epichloric hvdrine; Tositsch ^) 

 got on action of C^H, M^rBr a cliloric am^lah'oliol, and Klino ") 

 obtained quantitatively the chloric iodine hydrine with C^H^ iM^,! ; 

 losiTSCH '), repeating his experiments, now got botli the chloric 

 bromic hydrine and a chloric amylalcohol. Then Fournkau and 

 TiFFKNEAU *) found that with aliphatic organo magnesium bromides 

 only the chloric bromic hydrine is formed, while with aromatic 

 organo-magnesium compounds chloric propanoics with the constitution 



o 



RCH, — C T^nr— CHjCl arise for which formerly the formula 



COH -^ 



CH,ClC^CH,OH had been assumed. ') 

 R 



In conclusion we may mention that Fourneau and Tiffeneau ') 



drew the conclusion from their study on the action of oigano- 



magnesium compounds on mono substituted and asymmetrically 



di-substituted ethylene oxides that for the former the general process 



of reaction is: RC^^ CH, + R'ALBr -^ RO<^^CH,R', whereas 



for the latter a previous isomerisation to the isomeric aldehyde 

 must be assumed. 



When we take the general result of the above mentioned researches 

 into consideration, we should expect the primary formation of an 

 addition product on the action of an organo-magnesium compound 

 on cineol ; that this is really so on action of CHjiVLI was already 

 shown by Grignard '), who also observed that on heating of this 

 addition product a violent reaction sets in. This reaction, however, 

 consists in more than only in an intra-molecular conversion; the 

 reaction taking place at about 160° is very violent; the temperature 

 rises to about 260°, while during violent gas generation a liquid 

 distills over, which is coloured brown through free iodine. The 

 reaction is not always equally violent; in connection with this the 

 quantity of gas that escapes, and the quantity of liquid that distills 



Ï) losiTSCH, Journ. russ. phys. chem. Ges. 34, 96. (1902). 



2) Kling, Bull Soc. chim. (3), 31, 14 (1904) C. R. d. TAcad. des sciences 137, 

 756 (1903). 



3) losiTSCH, Journ. russ. phys. ciiira. Ges. 36, 6 (1904). 



4) Fourneau and Tiffeneau, Bull Soc. chim. (4) 1, 1227 (1907). 



5) J. D. Riedel, Akt. Ges. D. R. P. 183361 ; Gh. C. 1907 1, 1607. 



6) B'ouRNEAU et Tiffeneau, C. R. d. I'Acad. des sciences 145, 437 (1907). 



7) Griunard, Bull Soc. chim. (3) 29, 944 (1903). 



5* 



