107 A-109.] 



METHYL-N-AMYL KETONE 



201 



ketone (Konowaloff, Journ. Russ. Soc. 

 25,487; Ber. 26, Ref. 881). 



[B.] Heptoic aldehyde or cenant/tol 

 [97] by the action of phosphorus penta- 

 chloride gives I : i -dichlorheptane = 

 oenanthylidene chloride (Limpricht, Ann. 

 103, 81), which by the extreme action 

 of alcoholic potash is converted into 

 6-(a)-heptine = O3nanthine or oananthyl- 

 idene (Ibid. 84 ; Rubien, Ann. 142, 294 ; 

 Welt, Ber. 30, 1496). The latter, on 

 dissolving- in sulphuric acid and dis- 

 tillation with water, yields 2-heptanone 

 (Be"hal, Ann. Chim. [6] 15, 270). 



The ketone is formed also by heating 

 the hep tine with acetic acid to 280 

 and decomposing the product with water 

 (Behal and Desgrez, Comp. Rend. 114, 

 1074: see also Desgrez^ Ann. Chim. 

 [7] 3, 228, and Moureu and Delange, 

 Comp. Rend. 131, 710; 800). 



Or the sodium derivative of heptine 

 interacts with chlorocarbonic ester (from 

 carbon oxychloride and the alcohol) to 

 form amylpropiolic ester, the free acid 

 of which, on heating with alcoholic 

 potash, gives hexoylacetic acid. The 

 latter decomposes readily at 60 into 

 carbon dioxide and methyl-n-amyl ke- 

 tone (Moureu and Delange, loc. cit. 

 132, 1121). 



Or the free acid on esterification with 

 hydrogen chloride and an alcohol gives 

 amyl-/3-chloraerylie ester, and this also 

 yields methyl-n-amyl ketone on treat- 

 ment with alcoholic potash (Ibid.]. 



Or the sodium derivative of heptine 

 interacts with ethylformate to form amyl- 

 propiolic aldehyde, CH 3 [CH 2 ] 4 . C : 

 C. CHO, and this gives methyl-n-amyl 

 ketone among the products of its de- 

 composition by boiling aqueous alkali 

 (Ibid. 133, 96). 



[C.] From n-heptyl alcohol [26] and 

 palmitic acid [Vol. II]. Heptyl palmi- 

 tate gives n^heptylene on heating to 

 350 in an atmosphere of carbon dioxide, 

 and the heptylene combines with brom- 

 ine to form a dibrOmide (i : 2-dibrom- 

 heptane), which, by the action of alco- 

 holic potash, yields heptine = n-amyl- 

 acetylene (Welt, loc. tit. 1493). From 

 heptine as above under B. 



108. Methyl-n-heptyl Ketone ; 

 2-Nonanone. 



CH 3 .CO.[CH 2 ] a .CH 3 



NATURAL SOURCES. 



Occurs to the extent of about 5 per 

 cent, in oil of rue from Ruta graveolens 

 (Thorns, Ch. Centr. 1901, 1, 524; Ber. 

 deut. pharm. Gesell. 11, 3; Houben, 

 Ber. 35, 3587). This ketone is the 

 chief constituent of Algerian oil of rue 

 (v. Soden and Henle, Pharm. Zeit. 

 46, 277; 1026; Pharm. Journ. 67, 

 1619; Ch. Drug. 6O, 304; Power 

 and Lees, Trans. Ch. Soc. 81, 1588). 

 Has been found also in oil of cloves 

 (SchimmeFs Ber. April, 1903; Ch. 

 Centr. 1903, 1, 1086). 



SYNTHETICAL PROCESSES. 



[A.] From acetic and n-octoic acids 

 [Vol. II] by distilling a mixture of the 

 barium salts (Thorns, loc. oil.). 



[B.] From n-heptyl [26] and n-propyl 

 alcohol [15], a mixture of which on heat- 

 ing with sodium to 230 gives a decanol 

 = 8-methyl-9-nonanol. The latter, on 

 fusion with alkali, yields a decoic acid, 

 CH 3 . [CHJ 6 . CH(CH 3 ) . COOH, 

 which on oxidation with chromic acid 

 gives the above ketone among other 

 products (Guerbet, Comp. Rend. 135, 

 172; Ann. Chim. [7] 27, 67). 



1O9. Methyl-u-iioiiyl Ketone ; 

 2-TJiidecanone. 



CH 3 .CO.[CH 2 ] 8 .CH 3 



NATURAL SOURCES. 



Occurs as the principal constituent 

 of oil of rue from Ruta graveolens (Gre- 

 ville Williams, Phil. Trans. 1858, 1, 99 ; 

 Hallwachs, Ann. 113, 109 ; Harbordt, 

 Ann. 123, 293 ; Giesecke, Zeit. [2] 6, 

 429 ; Carette, Journ. Pharm. [6] 1O, 

 255 ; Thorns, Ch. Centr. 1901, 1, 524; 

 Houben, Ber. 35, 3590) ; in Algerian 

 oil of rue (v. Soden and Henle, Ch. 

 Centr. 1901, 1, 1006; Pharm. Zeit. 46, 



