Penn) ihe h ce Wh ane oe a4 "hes Nd | 
niet oF PLM aR Rod Otley 
em 1h * ‘ : ' 
RI Ripe sh Cr rae 121 
- oe by ( 
ie 5 ip \ @ ott : j 
ket ies: Bhetholansy| “ketone, ethylbuty! Reine! “add aapol ketone, ee fitter pre- 
dominating. Thid ketone, when | prepared from calcium butyrate, yielded a semi- 
car bazone of the m. p. 1250; the’ corresponding fraction from the heavy oil, however, 
F. ve no semicarbazone on treatment with | semicarbazide. | A further examination of. 
ris fraction will be youmaae io aan, it as rercry ketone. 
ees 5 andrews)! reports. on cee aeration of p- cymene tO, mononitrocymene-t, 2 4, .The 
m. atter being only of minor importance for our branch of chemistry, we content our- 
selves: with a short abstract. The yields of the ‘methods described hitherto in the 
li i erature are very low. 7. yield of 85 per cent. is obtained by the following method: — 
Or 1e-half ‘mol. of p-cymene was added to. an equal weight of sulphuric acid (d 1.84) 
vith stirring, the temperature being kept constantly below 0°. A well- cooled mixture’ . 
fot 50 g. of nitric acid: (d 1.42) and 105g sulphuric acid (d 1.84) was then added drop 
by drop to the sulphuric acid solution of the hydrocarbon, keeping the temperature 
1t O° or below and stirring the mixture efficiently. After the acid mixture is added 
(in 5 hours) the reaction was. allowed to proceed for from 15 to 30 min., the mixture 
ti en. poured into cold water, the oily product washed well and distilled: with steam — 
im vacuo; b. p. 115 to 116° (3 to 5. mm. pressure). ott consisted inthe main of 
Be searativély. pure mononitrocymene. Small amounts of p-toluic acid and of p-tolyl- 
n nethylketone are produced as by-products, but no isomeric mononitrocymene. Reduction 
of the mononitrocymene by means of tin and ‘hydrochloric ee resulted in the: quan- 
; titative formation of the corresponding. amine. SiG ies ervane ‘ 
+ 
3 Conceming the ‘identification of p- Cymer see. p: 56 of the present Report. 
: On the transformation of p-cymene from spruce turpentine spirits an to. carvacrol see 
p. a! of this ak he | ! 
S or ‘ : Mat ot ; hes : att isan ; * 
Saeeactin of terpenes with diethyl oxonium sulphate. = Amongst the oxonium compounds, 
oO. ). Aschan®) counts the mixture of ‘stoechiometrical ‘amounts of absolute ether and 
existance of diethyloxonium sulphate: — 
a a eee ot Biase os = abt! o. Ce : es Se 
3 Re ee vr Gi O-SO.-OM oN le Or 
This ‘mixture was allowed ‘to act on- several terpenes whereby alcohols as well as 
nydrocarbons were obtained. Apparently, it is here the case of. ‘hydration reactions 
which pass off with catalytic action of diethyloxonium sulphate. 
~The experiments proceeded best with camphene, _by adding a little ‘more than 
| molecule of sulphuric acid monohydrate, drop by drop, with strong cooling by 
means of ice and salt, to 1 molecule of absolute ether, then by adding, in three 
po tions, about 10 per cent. less than the molecular quantity of camphene. Ajiter 
adding each portion the temperature of the mixture: Was allowed to rise slightly by 
noving the flask from the cooling mixture, but. not above 20°; before adding the 
1ext portion of camphene, the mixture was cooled down again. After all the camphene 
was added, the mixture was allowed to stand some time at room temperature, then 
giv en drop by drop to a saturated solution of sodium carbonate. in excess containing 
«< 
rr. 
- 
a a 
PS 
Lae 
5 Bilas | Seat ee eng. Chemistry 10 cist 8), 463) = Big Meddelemnden fran. K. Yotonshaakeatemiens Nobelinstitut 5 
19), No.8 ; < he Vi ; Ws 3 eee A 
s sulphuric acid monohydrate, in which be “Picoumes == eeeny couse: aa the ee 
