Sept.. 1914
T H E J O C R N d L O F I N D C S T R I A L AJVD E N G I N E E R I J V G C H E M I S T R Y
u p a considerable q u a n t i t y of water a n d still remain clear makes i t useful for emulsion paints such as are very much in: vogue at t h e present time for t h e interior of buildings, a n d i t has been suggested t h a t t h e addition of water up t o j per cent for such a purpose is beneficial on new walls. T h e United States Bureau of Chemistry’ has developed a method for t h e determination of moisture b y t h e use of calcium carbide; TABLE11--ULTIMATE ANALYSES C H 0 1 1 ,i i 10.38 a-Terpineol (theoretical). . . . . . . . . . . . 77.85 11.9 ... French turp. (a).. . . . . . . . . . . . . . . . . . . 87.7 12.1 ... American turp.(a) . . . . . . . . . . . . . . . . . . 87. i 85.7 12.1 2.2 Wood turp.(a) . . . . . . . . . . . . . . . . . . . . . 11.8 3.9 Pine oil-first running.. . . . . . . . . . . . . 84.3 Distillate-pine oil, 345-380’ F., 17482.6 11.4 6.0 195’C . . . . . . . . . . . . . . . . . . . . . . . . . . (a)hl. Tach, “ T h e Chemistry a n d Technology of Mixed Paints,” b y D. Van S o s t r a n d Company, publishers, New York. ~~
7 23
a t t e m p t e d t o cope with t h e fire problem b y passing laws compelling either t h e “lopping” or burning of t h e tops. T h e Forest Service in leasing timber rights stipulates t h a t t h e tops must be burned or lopped a n d scattered. If only sufficient oil could be obtained t o p a y for t h e cost of handling t h e material, there would be a n economic gain t o t h e lumberman, since lopping or burning entails a n expense with no return whatever for t h e labor involved. This investigation was undertaken with a view t o determining t h e yield a n d composition of t h e leaf oils of t h e more i m p o r t a n t conifers with a view t o their utilization.
Several western species were distilled by hIr. G. LI. H u n t of t h e Forest Service. T h e yields obtained for this is being investigated a t our laboratories, b u t on these oils a n d their composition will be published later. account of being a gas-volumetric method i t is not I n most cases t h e yields from t h e western species were quite feasible for general use in technical laboratories. low. T h e odor of t h e oils from both t h e western a n d h number of commercial samples of pine oil were southern species was peculiar a n d less pleasant t h a n t h e dehydrated a n d analyzed. Tables I , I 1 a n d I11 spruce oil of commerce. This m a y be accounted for indicate t h e results obtained. b y their low alcohol a n d ester content compared with TABLE111-FRACTIONAL DISTILLATION OF COMMERCIAL PINEOIL spruce oil. From t h e yields of oil obtained from t h e Temperature Fraction in 7 15.5’ C . .’ . gr., .” _ T o t a l distillate SD. ’ southern a n d western species i t was thought t h a t a n 2 Water, 100’ 2 7 o:aa2 174-194 5 ’ approximate idea of t h e probable yield of a species 18 0.920 194-205’ 11 n.....933 205-208 i n. . _2u_ could be obtained from t h e cross section of t h e needles. . 208-210 25 53 0.939 210-213 35 88 0.941 T h e inference is logical tHat t h e yield should depend 2 13-2 16 6 94 0,942 on t h e number a n d size of t h e resin ducts per unit of 1 2 16-2 18 95 0.942 2184 99 ... cross sectional area. Cross sections of t h e needles of T h e a u t h o r is glad t o acknowledge here t h e as- several species were made a n d t h e above inference was sistance which was given him b y Mr. C. A. Lunn in verified in a striking manner, as will be noted b y reference t o Figs. I , 2 , a n d 3. furnishing t h e samples of raw materials. 320 F’IFTH.4VE., N S W YORK
OILS OF THE CONIFERAE. I-THE LEAF AND TWIG OILS OF CUBAN AND LONGLEAF PINES AND THE CONE OIL OF LONGLEAF PINE By
A.
W. SCHORCER
Received July 6, 1914
T h e annual consumption of leaf oils of certain native conifers a m o u n t s t o a b o u t $50,000. T h e principal species distilled for oil are t h e black spruce ( P i c e a mariavta, Mill.), white spruce ( P i c e e c a n a d m u i s , Mill.), hemlock (Tsuga c a n a d e n s i s , Linn.), red juniper ( J u n i p e r u s v i r g i n i u m , Linn.), a n d arborvitae ( T h u j a occid e n t a l i s , Linn.). N o a t t e m p t appears t o have been made t o distinguish between t h e t w o spruce oils a n d it is doubtful if much genuine hemlock oil is t o be found on t h e market, since t h e oils of t h e three species are quite similar a n d for practical purposes no distinction seems necessary. Fritzsche Brothers of hTew York City estimate t h e annual consumption of spruce oil a t .+o,ooc-~o,ooo pounds. I t is extensively employed as a perfume in greases a n d shoe-blackings a n d is quoted a t $0.4j-$0.60 per pound. T h e leaf oil of t h e red juniper is sold a t about t h e same price as spruce oil. a n d is largely used in insecticides. The annual consumption is I j , 0 0 c ~ 2 0 , 0 0 0pounds. T h e annual c u t of lumber from conifers far exceeds t h a t of t h e hardwoods. T h e tops are left i n t h e woods a n d , in addition t o being a total loss, are t h e most fruitful source of forest fires. Several states have :
U. S. Dept. Agric., Bur. Chem.. Circ. 97.
APPARATUS-The still proper was constructed in three parts (Fig. 4). T h e cylindrical body of t h e still for holding t h e needles was 3 feet 6 inches in height by 2 feet 3 inches in diameter, made of No. 16’B. W. G.’ copper. The ends were flanged out a n d attached t o iron rings inches wide. The covers of t h e still a n d of t h e heating vessel were similarly flanged a n d provided with rings. T h e t o p a n d base were clamped t o t h e cylinder b y 2 1 / 2 inch malleable iron clamps, Asbestos wire t a p e was used i n these make a n d break joints. T h e inner base of t h e cylinder was furnished with lugs upon which rested a frame covered with 2 0 mesh No. 2 j B. W. G. brass wire t o support t h e needles. T o reduce radiation a n d resultant condensation of t h e vapors t h e cylinder was covered with asbestos. T h e heating vessel was 3 feet in diameter b y z feet I inch high a n d constructed of No. 16 B. W. G. copper except t h e b o t t o m , which was No. 11 B. W. G. copper. T h e heating vessel was supplied with a 4l/2 inch funnel provided with a lever handle stop, a n d a l / ? inch water gauge. An 8 foot copper pipe, in two sections, two inches in diameter, connected t h e cover with t h e condenser. T h e latter consisted of 2 0 feet of 1 l / 4 inch copper tubing wound in a coil of 1 ’ 1 2 feet internal diameter. The coil was placed in a galvanized iron t a n k 2 feet in diameter b y 2 l / 2 feet deep. T h e receiver (Fig. j) consisted of a 2 gallon aspirator bottle furnished with a brass siphon. During distillation t h e receiver was 1
Birmingham wire gauge.
7 24
T H E IOCR.ViiL OF I N D U S T R I A L A N D E N G I S E E R l N C C H E M I S T R Y
covered with wet burlap as a protection against t h e sun’s rays. P R E P A R A T I O N O F MATERIAL-The cones Of t h e longleaf pine distilled were very green a n d pulpy, only t h e prickles being colored brown. They were mashed previous t o distillation. The twigs and needles Were run through a feed cutter driven by hand. By twigs is meant t h e woody portions of t h e limbs !/2 inch or less in diameter. One run of needles only was made for each species. They were stripped from t h e twigs by hand. This selection of material did not appear t o materially raise t h e quality of t h e oils. When t h e knives were kept sharp, t h e majority of
Fro. I I-longleas Pine ( P i n u s paiuslrir) 5 large oil ducts--average yield of oil. 0.401 per cent.
half filled with water a n d t h e fire started. By filling t h e cylinder with needles ahead of t h e rising column of steam thcy are rendered decidedly more compressible. The average content by charging t h e needles in t h e cold was 350 pounds, while by filling ahcad of t h e steam t h e charge was increased t o 400 pounds. The distillate appeared a t t h e outlet of t h c coildenser in 2 t o 3 hours after t h e fire was lighted a n d t h e distillation was continued a t t h e rate of 2. j gallons of distillate per hour. When t h c quantity of oil distilling per hour fell t o 5 t o 6 cc. per hour t h e distillation was considered coniplete. This was reached in 7 t o 8 hours. At intervals t h e distillation water from t h e receiver was returned t o t h e boiler. The exhausted needles were dumped
FIG.2
cnoss
PiO.
S B C l l O N S OI PINS3 L Z * Y B B
x
3
I50
2.-Cubm Pine ( P i n u s helcrophyllu) 10 small ail ducts-=veresc yield of oil. 0.271 Per cent.
t h e material was obtained in lcngths of onc-half t o one inch. The comminution of t h e material has three advantages as foltows: I-Oil distills from t h e needles more rapidly 2-Increased yield of oil 3-More material can be placed in t h e still The bcneficial effect of fineness of material in increasing the. yield of oil a n d speed of distillation are obvious, a n d it1 addition t o the mechanical effect of exposing t h e oil ducts, t h e finer material can be so packed a s t o prevent “channeling.” With entire needles a n d twigs uniform packing can not be secured in a small still. with t h e result t h a t channels are formed a n d 3. of t h e escapes the action the steam t o a greater or less extent. An increasc of 2 j t o 50 per cent more chopped material can he placed in the still t h a n when left i n t h e original state. DISTILLATION PRoczDr.RE---’~he boiling vessel was
Vol. 6 , No. 9
3-westerz Yellow Pine (Pinur pondnoso) 2 oil ducts-average yield of oil. n . i i 2 per cent.
from the cylinder by means of a pole furnished with a rope t h a t attachcd t o handles on t h c cylinder (Fig. 4). The oil from t h e receiver was dried, filtered, a n d weighed, a n d t h e percentage yield based on t h e weight of material in t h e charge. T h e oils discussed in this paper were distilled i n June, 1 9 1 2 , on t h e Florida National Forest. L E A F A N D T W I G OIL OF CUBAN PINE
(Pinus hetcrophylla, Ell.) TliS
PHYSICAL I N D CXBIIC*G
specific gravity s r m n i e 1 5 - c. 2797 0.8877 2798 0.8894 2799 0.8885 28W 0.8878
Re-
frrcfive index 151.4869 1.4852 1.4845 1.4845
c.
optical rotation -33.41
Acid NO. 0.65 0.75
-32.09
0.66
=DM ~~
-35.67’ -34.83
0n.s frfer NO. affer p e r c e n t Ester ~ c p t y l a - Yield
CONST*NTS OB TXE
NO.
tion
9.73
46.26
10.37
52.71
10.01
53.81 49.05
mf oil 0.269 0.268 0.278 0.268
_ - - _ 0.71
10.54
~ e s n0.69
10.16
50.46
0.271
8.75
‘43.46
0.193
Z801(0)0.8895 1.4880 -36.54 (a) Oil from needles only.
0.78
Sept., 1914 1inncr,ox*r.
T I I E J O C R S A L O F I N I ) l . ~ S Z ' R f A L_ j .YD E:\.GINEERING D*bT%LL?.TiON OF
B0iIi"i: paint. 1 c. is~~.n-~165.0 165.c~mo Ii o . (i.I 80 .o 180.0-1')7.5 197..5-250.0
on.
"B
coe*r
PiNiS
Per cent .~I.O 18.0
7.0
3.0 i6.0 18.5
m.n-.z8n.o
6.0
IleSidUe
FuRFunnLT'rhe first fraction was shaken out with watcr. T h e aqueous solution gave a n intense rose-red color characteristic of furfural whcn treated with aniline a n d hydrochloric acid. This aldehyde has been found t o be a constant constituent of leaf oils a n d is probably formed b y t h e dccomposition of ligneous material during distillation. a-PIrEaE--After repeated fractionation 19.6j grams (3.93 per cent) of oil distilled between rj6-160'. It had t h e following properties: d w , 0 . 8 6 j j ; sow, -31.39'. Fifteen grams of t h e oil gave but 1.4grams of pinene nitrosochloride b y Vv'ailach's method.'
FIO. 4-Siilr~
AND
725
portion, h. 1;. 164-166', had t h e following constants: -zq.rzo. After oxidation of t h e 0.8joq; aDzs-, oil with alkaline permanganate solution b y Wallach's mcthod' 1 0 . 2 j grams of crystalline sodium nopinate were obtained for 33.65 grams of oil actually oxidized. .4 portion of T h e free uopinic acid melted a t r z j ' . the sodium nopinate was oxidized t o nopinone and converted t o t h e semicarhazone. This compound melted at only 1 8 j - - 1 8 6 ~ after six crystallizations from alcohol. ' DIPENTENE-After repeated fractionation 41. j grams (8.3 per cent) boiled between 1 7 ~ r 1 8 0 ~ . The portion, ---z3.10", hias examined for b. p., 17+184', phellandrene with negative results. An ether solution of this fraction on saturation with dry HCI gas yielded a dihydrochloride, m. p. 49'. T h e oil, b. p. 174-178', yielded a tetrabromide, m. p. 1 1 5 - 1 1 7 ~ . T h e dipentene tetrabromidc prohaldy contained snme of t h c active comnound.
COND)ENSBR
T h e nitrosochloride melted at 08-99'; its nitro!piperidine compound at r17-1r8". CANPIIENE-Two camphene fractions were collected as follows: ( I ) j r . 8 grams, b. p. 160--161'; dls-, 0.8666; a D Z P-30.35'; o, ( 2 ) 18.8 grams, b. p. 161-162'; These fractions were dls", 0.8676; a D t 4 o : -zX.Xr". hydrated b y t h e method of Bertram a n d WalbaumZ a n d saponified. The oi!y product obtained was distilled and t h e portion boiling below 190' rejected. T h e residue, on cooling, solidified t o a crystallinc mass. T h e crystals purified b y means of a force filter a n d crystallization from petroleum ether melted at 2092x0' in a sealed tube. Five grams of the isoborneol were oxidized with acetic and chromic acids on t h e water bath a n d z grams of camphor ohtained. T h e semicarbazone melted at 235-236O. @-PINENE---The total &pinene fractions, b. p. 1 6 2 170°, weighed 176.8 grams (3j.q per cent). The 1
CHEMISTRY
ai^^, 246 ( i m ) , 251: 25a (1880). 251. J. Droll. Chcm., 49 (1894). I .
at 2 0 1 - 2 0 2 ' . A 20.4per cent alcoholic solution showcd -2.99'. the rotation uo23T h e acids obtained from the original saponification of t h e ester fraction were converted t o their sodium salts and precipitated with AgNOi in two fractions. Analysis of t h e silver salts follows: Grams of salt
SiIYCr
0.214~ 0.1455
Grams of
follnd 0.09~4 0.0684
SilYtT
Percentage SilYEr
44.30
.no1
The silver sa!% of caprylic and caproic acids require 43.0 per cent and 48.4 per cent of Ag, respectively, and i t is probable t h a t t h e above prccipitates represent a mixture of t h e two salts. CanINENE-The oil boiling bctwecn 2 j * 2 S o o w2.s fractionally distilled over metallic sodium and 3, j.3 per cent obtained boiling between z;o-zXoo. I t has t h e following properties: dais, 0.9190; aDti", 14.76'. T h e oil was dissolved in ether, sat,urated a i t h HCI gas
+
j
Annairn, 566 (1907). 228.
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y a n d allowed t o s t a n d twelve hours in a cool place. On evaporation of t h e ether a crystalline residue remained. These crystals after washing with alcohol a n d recrystallizing from ethyl acetate melted a t 118'. An 11.3 per cent ether solution of t h e cadinene dihydrochloride h a d t h e rotation aD210, -3.51 O.
LEAF AND TWIG OIL O F LONGLEAF PIKE
, PHYSICAL
Sample
_NO _
2802 2803 2804 2805
Specific gravity, iso C. 0,8829 0,8844 0,8836 0,8849 ~
~
(Pinus palustris, Mill.) A N D CHEMICAL COXSTAXTS OF THE OILS
Refractive Optical rotation index 15O
g
~
1.4825 -29.09 1.4818 -26.38 1.4819 -29.79 1.4824 -30.49
Acid ~ No.g 0.55 0.69 0.73 0.68 -
Meau 0 . 6 6 -
.
OF FRACTIONAL DISTILLATION
Boiling point, C. 158.0-165.0 165.0-170.0 170.0-180.0 180.0-198.5 198.5-250.0 250.0-280.0 Polymerized residue
OIL O F
Ester ~
L'o.
7.22 6.64 6.05 7.08 -
6.75
Ester No. after Per cent acetyia- yield tion of oil 36.53 0.429 42.77 0.381 46.37 0.412 43.18 0.382 _
_
42.2 1
Vol. 6, NO.9
sylvestrene. By brominating it portion of t h e oil a tetrabromide melting a t I 24 O was obtained. BORNEOL-The fraction b. p. 198.j-2 j o ' was saponified a n d t h e oil recovered by steam distillation. T h e portion boiling i n t h e neighborhood of borneol h a d a By means of i t s phthalic rotatian a ~ 2 8 O-37.1;'. ester borneol, m . p. 2 0 1 - 2 0 2 ' , was obtainid. T h e borneol was t h e n oxidized t o camphor whose semicarbazone melted a t 231-233' after two crystallizations from alcohol. .Lack of material prevented further recrystallization. T h e acids obtained b y saponification of t h e esters were accidentally lost b u t there is no reason t o expect a difference from t h e acids of t h e leaf oil of this species, t h e analysis of which will be found below. CADINENE-The sesquiterpene fraction b. p. 2 j O 280' a n d weighing j3.6 grams ( 1 0 . 7 per cent) distilled mainly between 260-270'. T h e portion with t h e latter boiling point h a d t h e specific gravity d: 0.918j a n d optical rotation aD2?0+6.82'. On t r e a t ment with HCl gas a dihydrochloride, m. p. I I 7-1 18', was obtained in large quantity. An 8.37 per cent ether solution of t h e crystalline dihydrochloride h a d a rotation -2.8 j '.
A
0,401
LONGLEAF PINE Per cent 38.0 25.0
5.0
2.0 16.0 10. i 3.0
FURFURAL-The aqueous extract of t h e first fraction gave a good color reaction for furfural with aniline a n d hydrochloric acid. a-PINENE-After nine fractional distillations 42.8 grams (8.6 per cent) distilled between I j6-160'. T h e fraction tested for a-pinene h a d t h e following constants: B. p., 156-1 j8'; d150, 0.8661; a D ? l O , -13.47'. Ten grams of this fraction yie1de.d 2 . 2 1 grams of pinene nitrosochloride. The latter body was transformed t o t h e nitrolpiperidine melting at I 19 '. CAMPHENE-The following fractions were examined for camphene: ( I ) b. p., 160-162'; dlbo, 0.8686; a 0 1 7 ° , -I j.28'; weight, 5 1 . 3 grams; (2) b. p., 162-163'; weight, 16.2 grams. T h e fractions treated b y t h e method of Bertram a n d Walbaum yielded about I O per cent of their weight of solid iwborneol. After repeated crystallizations from petroleum ether t h e product melted a t 207-210'. The low melting point m a y be explained b y t h e fact t h a t b y this method of identification some borneol is usually formed along with t h e isoborneol. (3-PINENE-TWO hundred grams (44.0 per cent) of oil were finally obtained boiling between 163-170', t h e major portion boiling between 164-166'. The fraction with t h e latter boiling point h a d t h e constants: d150, 0.8724; a o Z l o , -17.96'. One hundred grams of oil were oxidized b y Wallach's method. By steam distillation 53.3 grams of oil were recovered. T h e oxidation liquors yielded 13.1j grams of crystalline sodium nopinate. The free nopinic acid melted a t 126-127'. On oxidizing 8.85 grams of sodium nopinate with 3 grams of potassium permanganate a n d 2 grams of sulfuric aicd, 2.24 grams of nopinone were obtained. T h e nopinone semicarbazone melted a t 187 '. DIPENTENE-The oil boiling finally between I 7 0 180' weighed 24.8 grams. T h e optical rotation of t h e fractions b. p . 170-174' a n d 174-180" were: a D 1 7 0 , -z1.85' a n d -22.9; ', respectively. Phellandrene was not detected a n d t h e crystalline dihydrochloride obtained melted a t so', indicating t h e absence of
( Y D ~ ~ O
LEAF OIL O F LONGLEAF PINE
One charge of needles t h a t h a d been separated from t h e twigs by h a n d yielded, on distillation, 0.417 per cent of oil having the following properties: dlSo, 0.8841; nD15o, 1.4834; ( ~ ~ 2 8 -32.50; 0 , acid No., 0.67; ester No., 5-91; ester No. after acetylation, 40.46. T h e ester numbers a r e equivalent t o 2 . 0 7 per cent ester calculated as bornyl acetate, C10H17.00C.CH3, a n d 9.7 j per cent. of free alcohol, C1OH17.0H, calculated a s borneol. Chemical analysis showed t h e same constituents t o be present as i n t h e leaf a n d twig oil above. I t was anticipated t h a t t h e leaf oil would show at greater alcohol a n d ester content t h a n t h e leaf a n d twig oil a n d a correspondingly less terpene content. I n fact, however, as calculated from t h e ester numbers after acetylation, t h e leaf oil showed a total alcohol content, as borneol, of 11.38 per cent, while t h e average total alcohol content of t h e leaf a n d twig oils was 11.88 per cent. As is well known, t h e oil from t h e wood of this species consists largely of a-pinene. The leaf oil should accordingly contain less a-pinene t h a n t h e leaf a n d twig oil. I n so far as fractionation is of value i n quantitative determination this assumption was true. T h e acids obtained b y saponification of t h e esters were recovered in t h e usual way a n d precipitated in two fractions with A g N 0 3 . T h e silver salts were analyzed as follows: No.
......
1 . . .. Z............
. . . .. .. ,
Grams of silver salt 0.0638 0.0871
Grams of silver found 0.0274 0,0406
Percentage silver 42 95 46.61
The silver salts of caprylic, heptoic, a n d caproic acids require 43.0, 4 5 . j , a n d 48.4 per cent Ag, respectively. T h e first fraction agrees with silver caprylate a n d t h e second fraction probably consists of a mixture of t h e silver salts of caprylic or heptoic acid with caproic acid.
Sert.. 19-14
T H E JO17R9-4L OF INDC'STRIA L A N D E S G I S E E R I N G CHEHISTRY
COKE OIL OF LONGLEAF PIKE
The green cones yielded 0 . 3 6 3 per cent of oil having the following properties: dlso, 0.87 j 6 ; % ~ 1 5 ~ ,1 . 4 7 6 0 ; f f ~ 2 8 O , -9.22'; acid No., 0.42; ester No., 3 . 9 3 ; ester No. after acetylation, 3 1 . 0 7 . The oil h a d a disagreeable odor t h a t was especially pronounced in t h e first fraction on fractionation. This odor resembled t h e higher aldehydes of t h e aliphatic series. FRACTIONAL DISTILLATION OF CONE OIL OF LONGLEAF PINE Boiling point, C . Per cent 11.0 61.0 11.0 3.5 1.5 8.3 1.4 Residue 2.3
727
The rotation of the cadinene as given above must be accepted with certain reservations. While t h e sesquiterpene fractions were d-rotatory, their dihydroPERCENTAGE COMPOSITIONS OF PINE OILS
LONGLEAF
CUBAN I Leaf and twig Leaf and twig Leaf Furfural.. . . . . . . . . . . . . . . . . . . . . Trace Trace Trace 4 8-9 2 1-a-Pinene . . . . . . . . . . . . . . . . . . . . 1-Camphene. . . . . . . . . . . . . . . . . . 10 13-14 12-13 .................... &@-Pinene 35-36 44 50 Dipentene . . . . . . . . . . . . . . . . . . . . 8 5.0 5 3.5 2.4 2 Bornyl ester (as acetate) . . . . . . . Free alcohol (as 1-borneol) . . . . . 11.4 10.0 9.8 d-Cadinene. . . . . . . . . . . . . . . . . . . 18-19 10-11 11 9 6.0 7..5 Losses b y polymerization, etc. , (a) d-a-pinene.
Cone Trace 39-400 12 25 6-7 1.4 7.6 1-2 6.5.
chlorides were all I-rotatory. The only oil containing d-rotatory cadinene whose dihydrochloride was likewise d-rotatory, as recorded in t h e literature, is t h a t of Atlas cedar and possibly also West Indian sandalwood oil .'
FURFURAL-A qualitative test showed furfural t o be present in t h e first fraction. FORESTPRODUCTS LABORATORY a-PIKENE-The total a-pinene fractions, b. p . I j6FORESTSERVICE,U. S . DEPARTMENT OP AGRICULTURE 160'. weighed 1 9 3 grams ( 3 9 . 6 per cent). The fraction (In codperation with the University of Wisconsin) b. p. I j 6 - I j 8 ' , dlso 0 . 8 6 3 7 , f f ~ 2 4 ' + 6 . 8 2 ' . gave an exMADISOX cellent yield of pinene nitrosochloride. I t s nitrolTHE SPECIFIC HEAT OF CALIFORNIA PETROLEUMS It will be piperidine compound melted a t 118-119'. B y HAROLDE. WALES noted t h a t t h e a-pinene fraction from t h e cone oil is Received May 1 1 , 1914 d-rotatory, while t h a t from t h e needle oil was I-rotatory. The following work was carried out a t t h e University CAMPHEKE-The fractions examined for camphene of California under t h e direction of Prof. E. O'Neill. were as follows: ( I ) 3 0 . 8 j grams, b. p. 1 6 0 - 1 6 1 ' , I t was intended t o furnish those interested with d a t a dlso 0 . 8 6 7 1 , a~?6'--o.31'; ( 2 ) 2 8 . 6 grams, b . p. 161on t h e available oils and their specific heats. By treatment with 162', dljo 0 . 8 6 8 j , a ' ~ 2 6 ' -3.41 '. METHODS-TWO methods were employed: ( I ) T h e glacial acetic and. sulfuric acids isoborneol, m . p. use of a n electric method; ( 2 ) t h e application of a modi2 08- 2 I 0 O , was obtained. P-PIXENE-.~ total of 1 2 j grams ( 2 j per cent) boiled fied form of Regnault's calorimeter. The electric method consisted in using t h e ordinary between 1 6 2 - 1 j 0 ' . The major portion, b. p. 164166".h a d : d16O1 0 . S i 1 . l ; a D 2 6 0 , -11.80'. E y oxidation form of a n electric lamp as a source of heat. The with alkaline permanganate a yield of 26.8 per cent of lamp was immersed in t h e oil which was placed in a crystalline sodium nopinate was obtained. The free calorimeter cup a n d t h e current turned o n ; t h e rate of rise in temperature was measured a n d by comparison nopinic acid melted a t I 2 j-I 26 '. with t h e rate of rise of a similar weight of water t h e DIPEZjTESE-In t h e oil h. p. I j 0 - 1 8 0 " phellandrene could not be detected. By treatment with d r y HCl specific heats were calculated. The apparatus used in t h e modified Regnault method gas t h e dihydrochloride obtained melted a t 49- jo'. The fraction b. p. 1 j 4 - 1 8 0 ° , a n d having a rotation consisted of a Dewar flask which was surrounded by an insulated container and in which t h e oil was placed. ~ ~ --I 2 8 . 2~4 ', yielded 0 dipentene tetrabromide melting A brass or metal weight was heated in a condenser at 123-124'. BORNEOL-The fraction b. p. 1 9 j . j-250' was saponi- by means of steam a n d then dropped in t h e oil, the fied a n d t h e recovered oil heated with phthalic a n - 'rise in temperature of t h e oil being measured. By hydride. By t h e customary procedure borneol, m. p . means of t h e formula below t h e specific heats were calculated : 202-203 ', was obtained. An alcoholic solution of M ( T - t )_ _ W the borneol was I-rotatory. c = CADINEKE-The highest boiling fraction contained Cm(f- to) m the sesquiterpene cadinene. The crystalline dihydro- where W = water equivalent of the apparatus A 3 . 3 4 per cent of t h e chloride melted a t 116-117'. m = mass of oil hydrochloride in ether gave a rotation ( Y ~ 2 8 ' - I . 18". c = specific heat of t h e oil SUMMARY C = specific heat of t h e brass or metal weight M = weight of t h e brass or metal weight The several oils of t h e t w o species examined are T = initial temperature of t h e weight practically identical in composition. The same conto = initial temperature of t h e oil stituents, in varying percentages, were found in each. f = final temperature of t h e oil. The compositions of t h e oils a n d t h e approximate percentages of t h e constituents are shown i n t h e folThe electric method was found t o be t h e least sensilowing table. tive of t h e two, results checking within about z to The combined borneol in t h e leaf a n d twig oil of t h e j per cent. I n t h e case of t h e modified Regnault Cuban pine probably occurs as t h e esters of caproic method t h e accuracy very often approached 1.j per a n d caprylic acids; t h a t in t h e leaf oil of longleaf pine cent. a s t h e esters of caprylic, heptoic, a n d caproic acids. Gildemeister and HoRman, "The X'olatile Oils," 1 (1913), 330. 1
