; “ 
}. ai 
- 1 
aa ‘ethyl bromide, idepirtion ester CoFlta : CH-CH: CH (m. p. 181°) and cam- 
ae _ phene carboxylic acid CoHis: CH:-COOH (m. p. 124 to 125°) were obtained. The last- 
: _ named: yielded camphenilone on oxidation (m. ‘p. 223 to 224°). 
Ske _ In a similar manner to bromocamphene Langlois prepared the -chlorocamphene ; 
(bp. 95;to 98° [15 mm.]; ‘diso 1.016 to 1.017; «, + 37°), which with hydrobromic acid 
x gas yielded 2-bromo- -«-chlorocamphane (VII) CioHisBrCl (m. p. 103°), but which did not 
ef _add on any hydrochloric acid gas. The camphene dichloride of literature is hence 
Be c according to Langlois to be crossed out. Trichlorocamphene Ci H;,;Cls (m. p. 104°) 
and _ chlorodibromocamphene CioHisCl- Bro (m. p. 64 to 65°) were also prepared.. From 
ae camphene, trioxymethylene, and glacial acetic acid Langlois obtained the acetate of 
aa c-methylol camphene. The alcohol itself (CoHis: CH-CH2OH) had the constants: — 
x y ‘neutral solution and formed the. above-mentioned camphene dibromide. The semi-- 
carbazone. of the c-methylolcamphene - pyroracemic acid ester melted at 167°. On con- 
gt _ tinually heating o-methylol ‘camphene with alcoholic potash bis-8,8'-camphenilidene- 
; - 6-diethy! ether CoHy,: CH-CH2-O-CH2CH: CoHis (b. p. 235 to 240° [25 mm.], deoo 0.983) 
a - was produced. Whilst on shaking the alcohol with alkaline (Na2CO;) and permanganate, 
ay | camphenilone, hydroxycamphenilanic acid CsHis-OH-COOH a p. 184°) and oxalic acid 
“ean were. produced; an intramolecular rearrangement partly ‘resulted on treating with 
es : pac was chief product accompanied by camphenilone and oxalic acid. 
-——s w-Chloromethyl camphene CyHis: CH- CHCl (b. p. 100 to 102° at 6 mm.; diso 1.020; 
4 [elp + 27.38°) was obtained together with the corresponding oxide rani methylol 
ard 
re cacid mixture and by autoxidation, camphene carboxylic acid Cofig: CH-COOH and 
a little camphenilidene-6-acetaldehyde CoHi,: CH-CHO. Under the same conditions, 
ae er under which here only the side-chains were attacked, methyl camphene underwent no 
oe change, whilst on the contrary, camphene suffered a radical alteration. On attempting 
x to reduce with sodium and alcohol, #-chloromethyl camphene exchanged its chlorine ~ 
P atom for the OC.H; group and formed camphenilidene- 6-ethoxyethane CoHi4: CH.0-C.Hs 
3 (b. p. 230°; 150 0.917). After keeping for 4 years the substance had changed into 
-camphene carboxylic acid and camphenilidene-6-acetaldehyde by autoxidation. 
On the other hand chloromethylcamphene, when treated with zinc and hydrochloric 
acid, was able to exchange its chlorine atom for hydrogen. The 6-methylcamphene 
had the constants: — dio 0.880, [a] + 4.28°. Further, the chlorine atom was exchanged 
~ 
by ie 
VAS 
H: : 
Ee for CN with the formation of a nitrile CyHis:CH-CHCN (b. p. 140° [12 mm.]). ‘One 
j zo yielded a mixture of two isomeric acids to which the formule CyHis: CH- CH: COOH, 
and. C,Hi;-CH: CH- COOH may probably be assigned. By the action of ee or 
- magnesium on an ether-solution of -chlormethylcamphene (Wurtz Reaction), - 
_ dicamphenilidene butane CeAs : CH: CHe- CH.:-CH:C,His, was obtained after 4 to 5 dae 
phy _- asa thick oil (b. p. 210°, diso 0.952, [@]p -- 67.39), which in chloroform added bromine. 
2 From «-chloromethylcamphene and sodium camphene methylate CyHis: CH: CH,ONa the 
ae symmetrical ether CyHiz-O-CisHiz (b. p. 235° at 25 mm.; diso 0.93) was obtained. 
E. - Oxidation of camphenilidene-6-ethanol with chromic and mixture yielded, in addition 
2 
BA saponification, ‘the nitrile, in consequence of partial migration of the double bond, 
Fs 
eS 
re z 
Pet Kat Ns oe, Pere pee Le ohn ae OP es Mee 
RM Aditi fas! ~ (> 2! <9) in taele Cae Th ab St 
; i . PRON aN ec 125 
b.p. 234 to 238°, diso 0.987 to 0.988, Oy + 45°; it added on two atoms of bromine in ~ 
potassium “permanganate rendered alkaline with caustic alkali. Camphenecamphoric . 
E camphene; it yielded camphenilone with potassium permanganate; and with chromic ~ 
