N o v . , 1914
T H E JOURLVAL OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
of pressure is t o decrease rather t h a n increase t h e yield of alcohol. This was also substantiated b y a . number of preliminary distillations. cHeRcoaL-LAt 60 lbs. pressure, 8 per cent more charcoal mas obtained t h a n a t o lb., a n d a t I Z O lbs. there was a n increase of 1 1 per cent over atmospheric distillations. DISTILLATE-The clear pyroligneous acid, independent of moisture content of wood! was decreased a b o u t 20 per cent under 60 Ibs. pressure b u t h a d only small further decrease a t I Z O lbs. or I j o lbs. cAs--There \\-as a similar b u t rei-erse effect on t h e gas (determined b y difference). At 6 0 lbs. pressure there was about 2 j per cent more gas t h a n :it o lb., b u t I Z O or 150 Ibs. only gave very little more gas or even less t h a n 6 0 lbs. (maple sawdust a t I j o lbs. gave z per cent less t h a n a t 6 0 lbs.). . TAR-The most decided effect of distilling under pressures greater t h a n o lb. was on t h e t a r . At 60 Ibs. t h e yield of t o t a l t a r ( t a r which settled o u t of t h e distillate plus t a r dissolved in t h e crude pyroligneous acid) was 60 t o 6 j per cent less t h a n a t o lb. a n d a t 1 2 0 lbs. a n d I j o lbs. pressure a b o u t 68 per cent less. This same effect was even more apparent on t h e dissolved t a r alone. A decrease of as much as 7 j per cent a t 1j0 lbs. over o lb. being obtained for maple sawdust. T h e high yield of t a r from birch chips a s compared t o sawdust was probably due t o t h e fact t h a t t h e chips were very d r y . Other work on a much larger scale has given t h e same effect using very d r y wood. R E L A T I O N B E T W E E N GAS, TAR, A N D C H A R C O A L
It seemed probable t h a t some relation might be established between gas, t a r , a n d charcoal, a n d this has been indicated in Table 11. A n y such relation is not very marked, however, although t h e s u m of t h e three products is fairly constant. It is of interest t o compare these results with some recent work of Klasonl who has studied t h e effects of distilling birch under pressures lower t h a n atmospheric, a pressure of 0.01 mm. being maintained even during t h e gas stage b y immersing t h e receiver in liquid air. I n brief, t h e same tendencies were obtained, v k . , t h e higher t h e pressure (in t h i s case atmospheric compared t o pressures of 0.01 m m . ) t h e more alcohol a n d charcoal were obtained a n d less t a r , b u t Klason reported practically no effect on t h e acetic acid. S U 31 M A R Y
I-Destructive distillations of birch a n d maple were made on a small scale t o s t u d y t h e effect of pressures greater t h a n atmospheric on t h e yields of products. 11-In general, t h e effect of destructively distilling wood under increasing pressure is t o increase t h e alcohol slightly when moderate pressures are used a n d t o increase t h e charcoal a n d gas. Further effects were t o decrease t h e acetic acid, t h e pyroligneous liquor, and tar. 111-The effects of 60 lbs. pressure over o lb. are much more decided on all products t h a n t h e effects of increasing t h e pressure beyond 6 0 lbs. 1 “Experiments on the Dry Distillation of Wood,” Peter Klason, Arch. f . Kemie M i n . and Geol., Vol. 5, KO.7.
893
IV-The most decided effect of pressure was on t h e t a r . At 60 lbs. pressure this product v,-as decreased 60 t o 6 j per cent. T--From a practical standpoint. t h e most interesting effect of pressure is in connection with t h e yield of soluble t a r . Distillations were made a t pressures as high a s I j O lbs.. b u t t h e exothermic reaction w2.s so violcnt t h a t it was not advisable t o continue t h e experiments. X t this pressure, t h e concentration of t k e clissolred t a r in t h e pyroligneous acid w a s so low t h h t redistillation was not necessary in order t o t i t r a t e t h e distillate -or in practical operation t h e f r s t distillation of the primary liquor would not be necessery in order t o make gray acetate of lime. It is possible t h a t pyroligneous acid free from soluble t a r might be obtained by subjecting t h e distillate to a high pressure during t h e x-apor stage b u t t h e application of this result is not yet ZIPparent. FORESTPRODCCTS LABORATORY XIADISOX,WISCOSSIN
OILS OF THE CONIFERAE: 111. THE LEAF AND TWIG AND THE CONE OILS OF WESTERN YELLOW PINE AND SUGAR PINE B y A.
W.SCHORGER
Received October 1, 19 14
T h e leaf oil of western yellow pine (Pipius $ o n derosa,. Laws.) has apparently never been examined chemically. Brown’ in 1901 briefly described a plant i n Ore-gon operating on t h e needles of Piiius p o n d e r o s a , t h e products obtained being oil a n d fiber. A t o n of t h e needles produced t e n pounds of oil, equivalent t o a , yield of 0 .j o per cent of ,oil, which is considerably larger t h a n t h e yield obtained from t h e California trees. L E A F A K D T W I G O I L S O F XVESTERN Y E L L O T V P I S E
T h e oils varied in color from bright yellow t o green. When exposed t o t h e light for t w o or three days t h e yellow oils also acquired a green color. Some oils showed a green fluorescence. FRACTIONAL DISTILLATION OF
THE
LEAFOIL O F
Boiling point, C. 16 1-1 65 165-170 170-185 385-250 155-185 (35 m m . )
~ ’ E S T E R N Y E L L O ~PVI K E
Per cent 10
64 9
12.5 3
PHYSICAL A N D CHEMICAL COXSTANTS OF THE OILS OF TVESTERXYELLOW PIXE S o s . 2 173-2443 distilled from needles only; 2497-2560, from needles and twigs Ester Percentage T7.0
SamSp. gr. pie So. 15O C.
Ref. index 15“ C.
2173 2174 2384 2385 2386 2387 2403 2404 2442 2443 2497 2498 2499 2560
1.4815 1.4812 1.4794 1 ,4793 1.4789 1.4797 1.4807 1.4832 1 .4802 1 ,4808 1 ,4805 1.4837 1.4838 1.4812
0 8762 0.8718 0.8729 0.8750 0.8739 0 8747 0 8784
0,8849 0 8722
0.8765 0 8793 0,8838 0 8844 0.8755
a-PIsEsE-The 1
c
~
-15.73 -17.30 -18.72 -1i.62 -11.47 -18.62 -18 72 -16 81 -17.82 -19.59 -17.26 -17.02 -16.77 -15.94
after Acid Ester acetyl~No. ~ 90. ~ o ation 2.36 1.87 1.15 1.58 1.73 1.58 2.11 1.28 0.88 0.85 0.87 0.84 0.67 0.73
4.02 5.70 5.15 6.71 7.11 3.88 5.94 5.15 7.65 7.83 6.32 8.10 5.89 6.73
oil contains
Scientific ilmerican, 84 (1901), 344.
27.58 24.11 34.18 34.15 32.52 26.19 35.10 28.81 28.79 31.97 35.68 30.59 31 . 5 8 25.14
.
-h__
.4ce-
tate 1.41 2.00
1 .so
2.35 2.49 1.36 2.08 1.80
2.68 2.74 2.21 2.84 2.06 2.35
Free alco-
hol
Yield of oil
6 . 6 0 0.040 5 . 1 3 0 . 040 0 057 0 072 7 , 12 0 . 0 6 6 6.24 0.097 8.20 0.058 6 . 6 2 0 . I15 5.91 0.095 6.76 0,074 8.08 0.126 6.29 0.122 7.20 0.124 5.14 0.084
::;g
b u t a small a m o u n t
894
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
of a-pinene, since after repeated fractionation only 7 . 2 5 g. ( I . 5 per cent) were obtained between I jj a n d 160'. T h e oil h a d a specific gravity of 0.8660 a t 15' a n d t h e optical rotation ~ 1 ~ 2 -32 0j O . o . A small yield of pinene nitrosochloride melting a t I O Z . 5 ' was obtained. Camphene was not detected in t h e portion b. p . 16163'. 6-PINEN.E-The oil consists largely of &pinene, 37 j g . ( j j per cent) boiling between 160-170°, mainly T h e fraction boiling a t 166' between 164-167'. h a d t h e specific rotation CYD -19.87'. After oxidizing I jo g. of t h e oil with alkaline potassium permanganate, 76 g. of oil were recovered b y steam distillation, while t h e oxidation liquor yielded 2 7 . 5 g . of sodium nopinate, equal t o a yield of 3 j . 2 per cent based on 74 g r a m s of oxidized oil. T h e free nopinic acid melted at 126'. By further oxidation t h e ketone nopinone was obtained, t h e semicarbazone of which melted a t 188". DIPEKTENE-The oil boiling betm-een 17c-180' a m o u n t e d t o 33 g . (6.6 per cent). T h e fraction b. p . I 7 0 - 1 7 5 O , cYD200 -I I . 90°, yielded a dihydrochloride T h e fraction b. p . 1 7 5 - I ~ o ' , CYD220 melting at 50'. -I I . 83 ', gave a tetrabromide melting at I 24'. B O R N E O I -T h e oil boiling between 20 5-2 jo' was saponified a n d t h e portion b . p . 20j-217', CYD250 -17. 68', heated with phthalic anhydride. The phthalic ester was purified in t h e usual way. On saponification a n d s t e a m distillation a small a m o u n t of oil was recovered. On oxidizing t h e oil with Beckmann's reagent solid camphor was obtained. T h e a m o u n t of camphor was too small for recrystallization. After sublimation i t melted a t a b o u t 160'. T h e material h a d t h e appearance a n d odor of camphor a n d showed t h e property of t h e latter substance of rotating when dropped on water. " G R E E K oIL."-On distillation at 3 5 m m . pressure I j,j g . ( 3 . I per cent) of oil distilled between 1 5 j18j'. T h e oil was greenish yellow in color a n d h a d : d150 0 . 9 2 7 0 ; a D 2 6 0 -8.39' for a 56 per cent solution i n ether. K O solid derivations were obtained. It gave t h e usual color reactions for "green oil." ACIDS-The oil previous t o distillation was extracted with sodium carbonate. Acetic a n d formic acids were found t o be present in t h e extract by means of their silver salts. These acids were also obtained by hydrolysis of t h e esters. COKE OIL O F WESTERIi YELLOW P I K E
T h e oil h a d t h e following properties: Color, light 2 0 0 green: dljo 0 . 8 5 3 7 , nD150 1.4j89, ~ ~ ~ -11.48', acid S o . I . 2 7 , ester No. j . 20, ester IYo. after acetylation 2 2 4 1 yield ~ of oil 0.063 per cent. FRACTIOXAL DISTILLATION O F C O N E OIL Boiling point, C
164-170
170-195 195-250 250-290
OF WESTERN YELLOW P I N E
Per cent 57 29 3.5
3.5
FURFURAL-The aqueous extract from t h e first fraction gave a strong color reaction for furfural when treated with aniline a n d hydrochloric acid. cY-PIxENE-The a-pinene fraction b. p . I j9-164',
Vol. 6, N o .
II
a'D250 -zj.33', amounted t o 7 . 8 g . (6.3 per cent). Pinene was identified b y means of t h e nitrosochloride melting at 103'. @-PINEKiE-On oxidation of t h e fraction b. p . 164-170', d150 0.86j9, a D 2 2 0 -18.62', with alkaline K M n 0 4 sodium nopinate was obtained. T h e free nopinic acid melted a t 126-127'. T h e total P-pinene fractions amounted t o 7 4 . 2 g. (60 per cent). DIPENTEKE-TWOfractions, amounting t o I j.8 g . (12.8per c e n t ) , were collected between 17-1 76". T h e fraction b. p. 17~-1j3', fxD200 -6.40, was examined for phellandrene with negative results. Dissolved in d r y ether a n d saturated Tvith d r y HC1 gas, t h e oil gave a good yield of dihydrochloride melting a t jo'. BORSEOL-The ester fraction was too small for examination. T h e free alcohol a n d ester content have been calculated a s borneol a n d bornyl acetate. " G R E E N oIL"-The oil boiling between 2 jc-290' was d a r k green in color a n d weighed 4.08 g . ( 3 . 3 per cent). A crystalline hydrochloride was not obtained.
L E A F Ah-D T R ' I G O I L S O F S U G A R P I S E
T h e color of t h e oils of t h e sugar pine ( P i n u s l a m h e r t i a n a , Dougl.) ranged from pale lemon-yellow t o dark reddish yellow a n d light green t o greenish yellow. FRACTIONAL DISTILLATION OF OIL OF SUGAR PINE Boiling point, C. Per cent 158-165
40
170-186 186-210 210-250
1 9
_29 _ 18
I 6.5-1 . .. .. 713 .
7
FURFCRAL-This aldehyde was qualitatively detected i n t h e first fractions. a-PIKENE-The fraction examined for a-pinene h a d : b. p. 1j6-158', d150 o 864j, O(D240 -10.16'. A good yield of pinene nitrosochloride, m . p. 103', was obtained. T h e nitrolpiperidine melted at 119'. T h e t o t a l a-pinene fractions, b . p . 156-160'. weighed 89.j g. ( 2 0 . 7 per cent). P-PIxErJE-The P-pinene fractions a m o u n t e d t o j~ per cent a n d distilled largely between 164 a n d 167". Oxidation of L O O g . of oil having a b . p. of 164-16j0, d150 0.8680, a D 2 5 0 -I j. 73, with alkaline K h l n 0 4 PHYSICAL A N D CHEMICAL CONSTANTS OF THE OILS OF SUGAR PINE Ester Percentage No
Sample Sp. gr. No. 15OC. 2175 0.8738 2405 0.8703 2406 0.8710 2409 0.8676 2413 0.8686 2469 0.8705 2470 0.8695
Ref. index
15OC. aD200 1.4794 -11.07 1.4777 -16.50 1.4779 -16.18 1.4794 -15.52 1.4795 -15.49 1.4790 -11.83 1.4785 -12.70
after
.----Free
No.
Ester acetyl- AceNo. ation tate
2.38 1.34 1.44 0.68 0.97 1.06 1.02
28.46 1 . 4 1 6.84 29.68 0 . 7 8 7 . 7 1 0 045 3.55 32.04 1 . 2 4 8.01 0.052 4 . 5 1 24.35 1.58 5 . 5 4 0.098 5 . 9 1 23.25 2.07 4 . 8 4 0.097 5 . 4 2 2 9 . 2 7 1 . 9 0 6.68 0.110 4 . 1 9 28.49 1 . 4 7 6.81 0.120
Acid
alco- Yield hol of oil
4.04 2.22
gave 1 2 g . of sodium nopinate, 64 g. of oil being recovered b y s t e a m disiillation. T h e free nopinic acid melted at 126' a n d t h e nopinone semicarbazone at 188.5'. D I P E N T E N E - Bromination of a fraction b. p . 174-178', d150 0.8j81, ~ ~ ~ - 2 2 .91 70' , gave a t e t r a bromide melting a t 124'. T h e dihydrochloride of t h e fraction b. p . 17-1j4' melted a t joo,indicating t h e absence of sylvestrene. T h e total dipentene fractions amounted t o 52.4 g. ( 1 2 per cent).
Nov., 1914
T H E J O U R N A L OF I N D C T S T R I A L A N D ENGINEERIJVG C H E M I S T R Y
BORNEOL-The fraction b. p. 2 0 5-23 j o was saponified, distilled with s t e a m , a n d heated with phthalic anhydride. On saponification of t h e phthalic ester a n d distillation with steam a n oil first passed over followed by a ver.y small a m o u n t of solid borneol. On oxidizing, t h e oil camphor melting a t 167-170' was obtained. An alcoholic solution of t h e camphor was I-rotatory. C O M B I N E D ACIDS-The acids obtained by saponification of t h e esters were precipitated in three fractions containing 3 j . 2 7 per cent, 40.80 per cent a n d 64 86 per cent silver. T h e silver content of t h e fractions shows t h a t acetic acid is present along with a higher f a t t y acid or acids. ' * G R E E N om"-About I per cent of "green oil" was obtained from t h e residue after removal of t h e esters, a n d appeared t o be identical with t h e highboiling fraction occurring in other needle oils.
895
solving t h e oil in ether a n d saturating with HC1 gas t h e solution turned purple. A crystalline hydrochloride was not obtained. SUMMARY
T h e percentage composition of t h e leaf a n d twig a n d cone oils is approximately as follows: WESTERNYELLOWPINE SUGAR PIKE Leaf Leaf and twig oil
Furfural.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-a-Pinene. . . . . . . . . . . . . . . . . . . . . . . . . 1-Camphene.. . . . . . . . . . . . . . . . . . . . . . . . .
...............
Cone oil Trace 6
2
75 6
..
60 12-13
?
"Green oil". . . . . . . . . . . . . . . . . 3 Sesquiterpene(?) . . . . . . . . . . . . . . . . . . . . . Losses.. . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.5 4
and twig oil Trace 21
10
Trace 22
..
21
P
3.5
51 39-40 12 4-5 1.5 1.5 1
3-4
..
Cone oil
, .
..
1
7
FOREST PRODVCTS LABORATORY FOREST S E R V I C E , DEPARTMENT O F AGRICULTURE (In Cooperation with the University of Wisconsin) MADISON
CONE OIL O F SUGAR PINE
The oil a n d t h e following properties: Color, light green; d15. 0.8692, f l ~ 1 5 0 1.4771, ck'D200 -23.18', acid No. 0.63,ester No. 3.75, ester No. after acetylation I 7.04, yield of oil 0.318 per cent.
THE EFFECT OF RESENE ON THE LATHERING OF SOAP SOLUTIONS By
CHAS
H. HERTYAND
c. W.
WILLIARD
The total annual production of rosin on a conservative estimate is not less t h a n 2,j00,000 barrels of 500 FRACTIONAL DISTILLATION O F C O N E OIL OF S U G A R P I K E lbs. each. Not less t h a n half of this rosin is used in Per cent Boiling point, C. t h e manufacture of soap. The reason for its use in 159 5-165 64 165 -170 19 this industry lies in t h e fact t h a t t h e acids of t h e rosin 170 -194 11 194 -230 2 5 readily form alkali salts which are very soluble in water, 230 -255 1 2 5 5 -290 1 hydrolyze readily and form solutions which lather FURFURAL-FUrfUral was qualitatively detected freely when agitated. B u t rosin contains on a n average, approximately in t h e first fraction. CY-PINEKE - T h e fraction b. p . I jj-I j9", dI50 7 per cent of "resene" or unsaponiijable matter. As 0.8646, ~ ~ ~ -30.62', 1 7 0 gave a nitrosochloride melt- this resene possesses none of t h e properties which make ing a t 98-99 '. T h e pinene nitrolpiperidine melted rosin valuable for soap-making it must be considered a t 116' after three crystallizations from alcohol a n d as a filler. According t o t h e above figures therefore, a fourth crystallization did not raise t h e melting point. from 40,000,000t o 4 j,ooo,ooo lbs. of this filler, resene, go into soap annually. The t o t a l a-pinene fractions amounted t o j7. j g. I s it t r u e t h a t resene is t o be regarded simply as a CAMPHENE-The camphene fractions distilled as follows: ( I ) b. p . 160-I~I', weight 2 1 . j g . , (2) b. p. filler in soaps? M a y i t not have some positive action, 161-163', weight 33.9 g., d150 0.8683, 0 ~ 1 7 0 -26.42 '. either prejudicial or beneficial? A search of t h e literaFifty grams of t h e oil were treated with glacial acetic t u r e failed t o show a n y recorded experiments on this acid-sulfuric acid mixture. From t h e reaction product subject a n d conversations with chemists of soap works 6 . j g. of crystalline isoborneol were recovered. After failed t o elicit a n y very definite convictions on t h e subject. I n view of t h e large a m o u n t of this material repeated crystallization t h e isoborneol melted a t 2 1 Iannually used i t seemed desirable, therefore, t o carry 2 1 2 o in a sealed tube. o u t some experiments t o determine this point. The @-PIixEsE-The (3-pinene fractions amounted t o 104. j g. (39.43 per c e n t ) . I t boiled between 163- line selected was t h e effect of resene on t h e lathering 170' a n d h a d : d150 0.8688, ( ~ ~ 1 7-22.6jO. 0 On of soap solutions. oxidation a yield of 35 per cent of sodium nopinate PREPARATION O F RESENE was obtained. T h e free nopinic acid melted a t 126'. T h e resene used in these experiments was prepared Five grams of sodium nopinate on further oxidation as follows: 1200 g. of t h e oleoresin of P i n u s heteroyielded I . 6 g. of nopinone whose semicarbazone melted phylla ( C u b a n or slash pine) were dissolved in 9 liters a t 188-188.5'. of N/2 alcoholic potash a n d t h e solution allowed t o DIPENTENE-The fraction b. p. 170-180', ck'D17o s t a n d 18 hrs. After filtering, water was added almost -I j.IO', amounting t o 4 4 per cent gave a dihydro- t o precipitation a n d t h e solution extracted three times chloride melting a t 49- jo'. by shaking out thoroughly with petroleum ether, E S T E R FRACTION-The portion b. p . I94-23o0, boiling below 70' C. Eight liters of t h e petroleum a f t e r saponification, was t o o small for further examina- ether were used in each extraction. The three extion. T h e free alcohol a n d ester content have been t r a c t s were combined a n d shaken out with I O liters of calculated as borneol a n d bornyl acetate. jo per cent alcohol, in order t o remove dissolved poBetween 2 j5-29Oo,I per cent of a yellow oil was ob1 Presented a t t h e 48th Meeting of the American Chemical Society, tained t h a t appeared t o be a sesquiterpene. On dis- Rochester, September 8-12, 1913. O
