October 15, 1870 .] THE PHARMACEUTICAL JOURNAL AND TRANSACTIONS. 
303 
alcohol in beautiful acicular prisms, which sometimes 
attain some magnitude. Heated, it melts and sublimes 
I with a partial loss of the elements of water. The crys¬ 
tals which first sublime lose water, but nearly resemble 
those obtained from a solution, both as regards their 
appearance and composition. Those which afterwards rise 
(or, if the first, are resublimed) lose more water and form 
hexagonal plates, or fern-like fronds, of great beauty. 
It was found impossible to accurately measure the large 
crystals already mentioned, the twelve months’ immer¬ 
sion having rounded and worn the faces, from the rise 
and fall of temperature in the medium in which they 
I were formed. They seem to belong to the dimetric 
system, and are the result of the combination of the two 
prisms of that system. 
The hydrated crystals, when placed over sulphuric 
acid, or in vacuo , gradually lose water and effloresce, 
but as the substance is itself volatile, the loss could not 
be measured under such circumstances. When placed 
under a bell-glass over sulphuric acid, the surface of the 
acid becomes covered with green film, produced, as will 
afterwards be explained, by the mutual action of the 
water, sulphuric acid and colophonic hydrate. Some 
difficulty was experienced in procuring the anhydrous 
compound. From the above results it was supposed 
that, on submitting the hydrate to sublimation, the water 
of hydration would be dissociated. Such, however, was 
not the case, and a combustion of the sublimed crystals 
pointed to no formula. The sublimate was, in fact, a 
mixture of the anhydrous and hydrated compounds. 
The first of these substances I obtained in the follow¬ 
ing manner:—I gently fused in a test-tube for some 
time the crystals obtained from an aqueous solution, oc¬ 
casionally drying out the moisture which condensed at 
the top of the tube with bibulous paper. The sublimated 
crystals were repeatedly broken down and mixed with 
the fused mass. This process was continued as long as 
moisture was given off. I retained the crystalline mass 
for analysis. It seemed to have suffered no decomposi¬ 
tion exclusive of dehydration, and formed a friable and 
nearly perfectly white substance. 
On making a combustion of the above, O'218 gramme 
gave 0*505 gramme C0 2 and 0*218 gramme H s O. 
In a second experiment 0*307 gramme of the fused 
mass gave 0*7076 gramme of C0 2 , and 0*324 gramme of 
H 2 0. 
These experiments point to the empirical formula 
O 10 H 22 O 3 . 
1 2 Theory. 
Carbon . . 
63*16 
62*86 
63*15 
120 
Hydrogen . 
11*10 
11*72 
11*58 
22 
Oxygen . . 
25*27 
48 
100*00 
190 
The crystals obtained from an aqueous solution gave 
when burnt the following results: 0*265 gramme of 
■crystals produced 0*557 gramme of C0 2 , and 0*270 
gramme of H 2 0. 
Theory. 
/"- A >» 
Carbon . . . 57*35 57*70 120 
Hydrogen . . 11*32 11*53 24 
Oxygen . . . 30*77 64 
100*00 208 
Colophonic hydrate . C 10 H 22 O 3 : H 2 0. 
Colophonine .... C 10 H 22 O 3 . 
Products formed therefrom 
Hydroearbides. by the occult molecule H 2 0 Hydrates. 
(“Turpentine Camphors.’’) 
C, 0 H 1S , C, 0 H 16 . C,„H 16 , C 10 H lt ; H,0.* 
(“Diterebene.”) (“ Terpinole.”) 
C 10 H 16 . (a) C 10 H 16 ; H 2 0. C 10 H lfi ; H 2 0: H 2 0. 
(Turpentine, or (“Liq. Turpentine (Hypothetical hy- 
“terebin- Camphor.”) drate, supposed 
thene.”) transition pro- 
c 10 h 16 . (B) 
^io^Ti6 5 2H 2 0 
(“ Terpine.”) 
C 10 H 16 ; 3H>0 
(“ Terebene.”) (Colophonine.) 
n tr a! C 
-2(C 2 H 4 0 2 )-%|30 
‘ Principles,* p. 396. 
H 
transition 
ducts.) 
C 10 H 16 ; 2H 2 0: IRO. 
(Terpine hydrate.) 
C 10 Hj 6 ; 3H 2 0 : H 2 0. 
(Colophonic hydrate.) 
H 34 0. 
—Vide Naquet’s 
(Terpinole.) 
20 - 
In the above table I have endeavoured to convey, by 
the punctuation, the accretion of the series, and the dif¬ 
ferent degrees of molecular integration. 
It will be observed that each hydrate would be isomeric 
with the next higher homologue in the camphor series. 
The hydrates to the first two in the series are wanting, 
but it is probable that they exist, as the compound called 
liquid, turpentine camphor is, in the presence of water, 
converted into terpine, the isomer of its hydrate. If we 
do not suppose that the hydrate is first formed, we could 
hardly account for the formation of terpine. 
Colophonic hydrate was violently acted on by bromine, 
accompanied by a copious separation of carbon and hy- 
drobromic acid. In water the action was more manage¬ 
able, and the ultimate product was a brominated oil, 
which, after washing first with a diluted solution of car¬ 
bonate of sodium and then with water, was dried over 
sulphuric acid. *471 gramme of this oil, after being de¬ 
composed in a sealed tube with pure soda, was treated 
with an excess of nitric acid and nitrate of silver. It 
gave *766 gramme of bromide of silver, agreeing very 
nearly with the formula of a tetrabrominated compound. 
Professor Jellett, who kindly examined this substance 
for me, as regards its optical properties, finds that it is 
perfectly inert when in solution, and possesses neither 
right nor left-handed rotation, f 
As previously stated, the light oils from resin, when 
treated with sulphuric acid and then with water, produce 
a green substance. This coloration is, however, due to 
the presence of colophonic hydrate. On treating that 
compound with acids, a series of striking phenomena is 
exhibited, conjugated acids being formed, which exhibit 
a fine display of colours. The generality of these are 
green. Sulphuric, phosphoric (monobasic and tribasic), 
arsenious, citric and tartaric acids give these reactions. 
On treating the crystals with an excess of the acid, 
and then adding spirit, the colour is developed. It is 
necessary to use heat in most cases. The sulphuric acid 
reaction is capable of rendering evident a milligramme 
of the new substance, if properly applied. It is not 
necessary to use heat in this case. Under certain cir¬ 
cumstances, hydrochloric acid is capable of producing 
this green reaction; but when colophonic hydrate is 
treated with an excess of strong hydrochloric acid, after 
the expiration of half an hour, a brilliant rose colour is 
developed on pouring it into alcohol. If the experiment 
is pushed further, different shades of violets are produced, 
until the ultimate result of the maceration is a magnifi¬ 
cent indigo blue. 
Terpine does not give any of these reactions. 
As regards the origin of colophonic hydrate, it is pro- 
Colophonine is, therefore, isomeric with terpine hydrate, 
or is more properly a homologue of terpine. It is 
another instalment towards filling up an interesting 
series. This compound is probably derived from tere¬ 
bene. 
* Formed by the action of dibromhydrate of citrene on 
acetateof silver, 2 (C l0 H 18 Br 2 ) =4(C 2 H 3 Ag0 2 ) —4(AgBr). 
f It does not differ in this respect from its congeners the 
terpine hydrates and similar products, in which, although 
the hydrocarbide preserves its integrity, its gyratory power 
is suspended. 
