Oct., 1914
T H E J O r R A V A L O F I N D L-STRI.1 L A R D E A V G I N E . E R I S G C H E M I S T R Y
ha\-e found the a p p a r a t u s shown in Fig. I t o be quite satisfactory. T h e precipitate is susceptible t o oxidation a n d must be kept a w a y from air during drying. Also,'the fact t h a t high temperature will char t h e soap limits t h e drying temperature t o about 80' C. T h e precipitate m a y be dried in a desiccator connected b y a long rubber tubing t o a source of hydrogen or carbon dioxide, and t o a vacuum p u m p . After introducing t h e precipitate t o be dried, t h e desiccator m a y be placed in a low-temperature s t e a m drying oven for 3 hours. T h e results obtained b y t h e use of t h e insoluble-soap method a n d t h e d a t a from which these results were computed, are compiled in Table 11. I n calculating t h e results for this table it was decided t o accept t h e weight of t h e dried insoluble soap a s representative of t h e weight of wood oil present in t h e sample, since the FIG I error of this assumption was considered t o be within t h e limits of error 0; t h e method. Although neither of t h e above methods has proved entirely satisfactory a s a method for t h e estimation of wood oil in rosin varnishes. t h e efforts made t o apply t h e m t o t h a t end have resulted in some interesting d a t a regarding t h e conditions existing in this t y p e of varnish. TABLE 11-Ex
PRECIPITATIOV OF INSOLUBLE POTASSIUM SOAP U r 0 O D OIL 7 ADULTERANT CalReSAMPLE ADULTERANT cu- covFound c--Soap lated ered Present Xo G G Kind G G C 7 , G 7 7c 1 3.301 3 . 3 3 4 3 . 3 3 4 101.0 -0,033 -1.0 12.8140'304) 2.807 2 , 8 0 7 9 9 . 8 0.311 9.9 4:s 1 3 . 0 1 2 0 . 1 8 0 Linseed 3.021 3 . 0 2 1 1 0 0 . 3 0.171 5.5 5.6 1 2.516 0 . 5 0 6 ( 2.508 2 , 5 0 8 9 9 . 8 0.514 17.0 16.7 1 3 138 .... 3 , 1 7 0 3 , 1 7 0 1 0 1 . 0 -0.032 -1 0 1 2:859 0 : 9 5 9 Soya 2.874 2.874 100.6 0.944 24.7 2 3 : 8 1 2.6420.881)bean 2 . 6 4 5 2.645 100.1 0.878 24.9 2 5 . 0 1 3.013 . . . . .... 3.006 3 , 0 0 6 99.8 0,007 0.2 1 3 , 0 0 6 0 , 1 6 7 Soya 2 . 9 8 2 2.982 9 9 . 2 0.191 6.0 5:3 1 7 . 0 5 1 1 . 3 0 2 1 bean 2.020 2.020 98.1 1.333 39.8 38.9 1 2.461 0 . 1 2 5 , 2 . 5 3 6 2.536 1 0 3 . 0 -0.075 2.9 4.8 1 2 . 7 9 1 0 . 6 0 7 ~2.883 ~ ~2.E(83 ~ ~1 0 3~. 3 ~ 0~. 5 1 5 15.2 1 7 . 9 1 2.742 0 380 2.761 2 . 1 6 1 100.7 0.361 11.5 12.2 1 2.742 0 183; 2.741 2.741 1 0 0 . 0 0.184 6.3 6.3 1 2.528 . . . .., . 2 . 5 0 1 2.501 9 8 . 9 0,027 1.1 .. 1 2.524 ... .... 2 , 5 5 0 2 . 5 5 0 101.0 -0,026 -1.0 .. 1 2.521 . . . .... 2 . 5 1 0 2.510 9 9 . 5 0.011 0.5 1 2.510 2.514 2.514 1 0 0 . 2 -0.004 -0.2 12.3210:iOil 2.367 2.367 102.0 0.661 2 1 . 8 22:4 1 2 . 4 2 8 0 738jLinseed 2 . 5 0 8 2 . 5 0 8 103.3 0.658 20.8 23.3 1 3.019 ,... 3 . 0 1 9 3 . 0 1 9 100.0 I 3.039 o : ~ O Y Mixed 3.025 3.025 99.5 0:4i3 12:3 i i : 9 1 3.199 1.049) .3.201 3 . 2 0 1 100.3 1.038 2 4 . 5 2 4 . 7 2 3.252 . . .. .. 3.224 3.224 99.1 0.028 0.9 .. 3 3.471 . . .... 5 . 5 4 4 3 . 5 4 4 1 0 2 . 1 -0.073 -2.1 .. 4 3.1.56 . . .,, 3 , 0 1 4 3.014 95.5 0,142 4.5 ., 4 3.190 . . . . ,,. 3,092 3.092 96.9 0.098 3.1 .. NuTE-XVood oils Nos. 1 2 a n d 3 were t h e same a s those in Table I . Wood oil No. 4 was furnished'by M r . L. P. Nemzek representing t h e Educational Bureau of t h e Paint Manufacturers' Association. This oil is f r o m American-grown n u t s , %MITATION B Y
809
A comparison of t h e molecular weights of t h e f a t t y acids from raw wood oil a n d t h e light breaks seems t o show t h a t this light break is a n isomer rather t h a n a polymer, a n d t h a t there is practically no difference between t h e light break formed slowly b y sunlight alone a n d t h a t catalyzed b y iodine. USIVERSITY OF ICZICHIGAW ANN ARBOR ~
OILS OF THE CONIFERAE. 11-THE LEAF AND TWIG, AND BARK OILS OF WHITE FIR By A . \V. SCHORGER
Received August 15. 1914
T h e white fir [ A b i e s concolor (Gord.) P a r r y J is found on t h e mountain slopes from southern Oregon t o Lower California and from Nevada, U t a h , a n d southern Colorado through Arizona and New Mexico. T h e dense crown consists of short, heavily foliaged branches. T h e leaves a t t h e t o p of t h e tree are usually I t o I l i g inches in length, while those of t h e lower branches are somewhat longer-1 ljg t o 3 inches. L E A F A X D TTVIG O I L S
T h e oils were greenish yellow in color with a green fluorescence with t h e exception of samples Nos. 2439 a n d 2487, which were lemon-yellow in color and showed no fluorescence. The residue left after removal of t h e terpenes b y distillation was fluorescent t o a marked degree, b u t this property was n o t noted in t h e "green oil" fraction obtained, though the oil owes its green color t o this fraction. T h e properties of t h e oils and the yields are given in Table I. TABLEI-PROPERTIES
7 m
7
Sample No. dijo
n
2176 2180 2181 2183 2439 2440 2487
1.4788 1.4786 1.4786 1.4796 1.4787 1.4790 1.4781
~
" "
0 8758 0.8738 0.8732 0.8737 0.8720 0.8745 0.8777
OF OILS Ester No. AcePer cent Yield of oil aftet t a t e alcohol Acid Ester acetyl- Per -APer --~e~~~~ ~ o KO. S o . ation cent Free Total cent LEAF A N D TWIGOILS -27.94 1.13 12.52 48.88 4.38 10.28 13.73 0.140 -20.18 1.81 27.34 54.58 9.57 7.65 15.17 0.029 -21.65 1.43 24.03 52.45 $41 7.99 14.60 0.050 -26.87 1.07 20.55 54.22 t.19 9.50 15.15 0.150 -26.59 1.01 14.48 51.83 5.07 10.57 14.55 0.163 -24.08 1.32 14.80 47.84 5.18 9.32 13.39 0.095 -20.11 1.06 18.79 55.51 6.58 10.39 15.56 0.272
_______
Mean, 6.63 9.39
14.59 0.128
BARK OILS OLDiOo
2209 0.8i67 1.4833 -20.95 2423 0.8702 1.4809 -20.15
1.22 0.87
6.88 23.34 2.41 6.43 20.45 2.25 ~
Mean, 2.33
4.58 3.90
6.48 0.07 5.67 0.12
4.24
6.08 0.095
-
-
" "
An examination of t h e separated constituents of a Chinese-wood-oil rosin varnish seems t o show t h a t t h e polymerization of wood oil in t h e presence of rosin is practically a s complete as in t h e oil, subject t o t h e same heat t r e a t m e n t in t h e absence of rosin. T h e f a t t y acid in each case shows a molecular weight double t h a t of t h e f a t t y acid of r a w wood oil. T h e difference in characteristics between these t w o polymerized products h a s not a s yet been satisfactorily accounted for.
There is a considerable variation in t h e ester a n d free alcohol content in t h e various samples b u t t h e t o t a l alcohol content is fairly uniform. Samples Nos. 2439 a n d 2440 were distilled from material taken from t h e top a n d base, respectively, of t h e same tree. T h e needles from t h e t o p of t h e tree show a slightly greater total alcohol content. Six hundred grams of oil distilled as follows: 1611 6 j o , 1 j . j per cent: 16j-1joo1 4 2 per cent; 1 7 0 - 1 8 0 ° , 1 8 . j per c e n t ; 18*19j", 3 per cent; 1 g j - - 2 4 0 ~ , 1 3 per c e n t ; z40-310", 3 per cent. IDENTIPICATIOS O F CONSTITUEKTS
FURFURAL-The first fraction was shaken out with water. On treating t h e aqueous extract with aniline and hydrochloric acid a deep crimson color characteristic of furfural was obtained. a-PISEh?z-The fraction examined for a-pinene h a d
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
810
Vol. 6, KO. I O
t h e following properties: B. p . 156.5'-I j 9 . o o , d160 in ether. T h e oil was emerald-green i n color a n d 0.8671, aD220 -24.29'. T h e nitrosochloride separated showed no fluorescence. N o solid derivatives were very slowly from t h e mother liquor. T h e purified obtained. This oil appears t o be similar t o t h e "green compound melted at 103' a n d i t s nitrolpiperidine at oil" obtained b y t h e author from t h e leaf oil of Douglas 118.5'. T h e t o t a l fractions boiling below 160' fir1 a n d showed t h e same color reactions. a m o u n t e d t o 75 g. (12.5 per c e n t ) . BARK OIL CAMPHENE-The camphene fraction b. p. 160-164' T h e b a r k distilled was a b o u t one-quarter of a n inch a m o u n t e d t o 8 per cent. T h e fraction b . p . 160-162', thick a n d h a d been peeled from small trees cut for poles. dlSo 0.8695, aD230-27.390, was tested according t o t h e T h e properties of t h e oils a n d t h e yields are given i n m e t h o d of B e t r a m a n d Walbaum.' On treating t h e Table I. T h e following results were obtained on distillation saponified product with water t h e isoborneol separated 65 per cent; b. p . a s a viscous oil. On s t e a m distillation oil first passed of I I O g. of oil: b. p. 162.5-170', 170-180', 14 per c e n t ; b . p . 180-192', 8 per c e n t ; over, followed b y isoborneol t h a t solidified i n t h e con192-2joo, 4 per c e n t ; 2j0-3oo0, 5 per cent. denser. T h e purified isoborneol melted a t 209-210' i n a sealed t u b e . T h e fraction b. p. 1 6 ~ - 1 6 4 ~ . y i e l d e d IDENTIFICATION O F COKSTITUENTS smaller a m o u n t s of isoborneol. FURFURAL-This aldehyde was detected i n t h e first P-PINENE-This terpene is t h e major constituent fraction b y t h e color method. F r o m t h e intensity of of t h e leaf oil, since 254 g. (42.3 per cent) were finally color produced a larger q u a n t i t y of furfural is present obtained boiling between 164-170'. On oxidation of i n t h e bark oil t h a n i n t h e leaf a n d twig oil. -23.66', CX-PINENE-BY repeated fractionation I O g. (9.1 per a fraction, b. p. 164-166.5', dl50 0 . 8 7 1 5 , aD230 cent) of oil were obtained of b. p. 160-163', cyD2o9 with alkaline potassium permanganate, large quantities of sodium nopinate were obtained. T h e free nopinic -16.43'. This oil yielded 2.1 g. (21 per cent) of pinene acid melted at 126.6-127'. nitrosochloride. I t s nitrolpiperidine melted a t I 18 '. PHELLASDRENE-The fractions b . p . 170-180 ', P-PINENE_The &pinene fractions distilled a s folweighing 90 g., gave large a m o u n t s of phellandrene lows: ( I ) b. p . 163-16j0, 14.9 g . ; ( 2 ) b . p . 16j-17oo, nitrite. T h e fraction b . p. 174-177'~ d150 0.8572, j 1 . 2 g. T h e l a t t e r fraction h a d dlso 0.8654, ~i~~~~ aD220 -28.74', formed a solid mass of crystals on t r e a t - - 2 2 . j 2 O . On oxidation of t h e oil a yield of 2 1 . 7 per m e n t with KNOz a n d acetic acid. T h e nitrite melted cent of sodium nopinate was obtained. T h e free at 1 0 2 ' . Limonene was not detected a s either t h e nopinic acid melted a t 126-127'. Five grams of dihydrochloride or tetrabromide. sodium nopinate yielded 24 per cent of nopinone, BORNEOL-The oil obtained b y saponification of t h e whose semicarbazone melted a t 188'. fraction b. p . 200-240' distilled i n a b o u t equal proDIPENTENE-The oil boiling between I 70-180' h a d portions between 2 0 j - 2 1 j o a n d 2 1 5-220'. T h e first t h e rotation -29.37'. On treating t h e d r y oil portion h a d t h e rotation cyD24o -29.16'. Both frac- with d r y HC1 gas a dihydrochloride m. p. 49-jo' was tions were t r e a t e d with phthalic anhydride. Sapon- obtained, b u t no solid derivative was obtained on ification of t h e phthalic esters yielded oils. On bromination. oxidizing t h e l a t t e r with chromic acid mixture camphor A L C O H O L FRACTIOP-The a m o u n t of oil obtained by was obtained melting a t I 7 1-1 7 2 '. Considerably saponification of t h e fraction b. p. 192-2j0° was too larger yields of camphor were obtained b y oxidizing small for identification of t h e alcohol present. T h e t h e borneol fraction directly with s a t u r a t e d potassium ester a n d free alcohol h a v e been calculated as bornyl permanganate solution without a t t e m p t i n g i t s puri- acetate a n d borneol as i t is most probable t h a t these are fication through t h e phthalic ester. T h e camphor was t h e constituents present. converted t o i t s semicarbazone melting at 236-237'. ' ( G R E E NoIL"-The fraction b . p. 2 j0-3oo0, weighing A C E T I C ACID-The acids recovered from t h e ester 5.4 g., was bright green i n color a n d from i t s color saponification liquors were precipitated as their silver reactions appeared identical with t h e "green oil" from salts in five fractions. Analysis of portions of t h e t h e leaf a n d twig oil. I t is possible t h a t t h e "green various precipitates without further purification gave a oil" i n t h e leaf a n d twig oil is n o t derived from t h e silver content of 63.04-63.72 per cent, showing t h a t needles themselves, b u t from t h e b a r k of t h e twigs. acetic acid must be practically t h e only acid present, SUMMARY since *silver propionate theoretically requires 59.91 T h e oils of white fir have approximately t h e following per cent Ag, silver acetate 64.64 per cent Ag, a n d silver composition. formate 70.59 per cent Ag. T h e combined precipitates Leaf a n d TxIig oil Bark oil Percentages Trace Trace Furfural were recrystallized from water several times. T h e fine 9 12 l - ~ - P i n e n e. . . . . . . . . . . needles obtained were analyzed as follows: 8 I-Camphene . . . . . . . . . . 60 42 1-0-Pinene.. . . . . . . . . . . 0.1140 g. silver salt gave 0.0736 g. Ag = 64.56 per Dipentene 12-13 15 l-Phellandrene . . . . . . . . 2.5 6.5 Ester as bornyl acetate cent Ag. 4.5 9.5 +e borneol.. . . . . . . . 5 3 Green oil". . . . . . . . . . . " G R E E K oIL"-The residue remaining after removal 7 4 Losses,. . . . . . . . . . . . . . of t h e ester fraction h a d a strong green fluorescence. FOREST PRODUCTS LABORATORY T h e fraction b. p . 240-31oO on redistillation distilled FOREST SERVICE, U. S. DEPARTMENT OF AGRICULTURE mainly between 265-285'. I t h a d d19.50 0.925, (In Cooperation with the University of Wisconsin) &1.4DISON nDIs01.4936, an200-o.490, for a 37.83 per cent solution 1
Jour. frlr prakt. Chem., [Z] 49 (1894), 1.
1
J o u r . A m . Chem. Soc., 95 (1913), 1895-7.
