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
462 Swsrmcs
.................................. ............................. .................................. ................................ ................................
Sulfur. NarS.9HzO. NaCl. NarSO4.. NaNOs.. NiClr.6HzO.. Reduced iron
............................ ............................
EFFECT ON ACTIVITY Destroyed immediately Gradually destroyed N o effect No effect No effect No effect N o effect
The three gases HzS, SO2 and Clz were also tried. I n each case t h e activity was destroyed immediately. A small amount of water vapor in t h e hydrogen was found gradually t o destroy the activity of t h e catalyzer. GENERAL SUMMARY
I-The lead-salt-ether method for separating t h e liquid f a t t y acids of oils a n d fats has been studied, a n d certain important precautions are noted. 11-The triangular diagram has been applied t o t h e study of oil hydrogenation. 111-It has been shown t h a t t h e conditions of hydrogenation, namely, pressure, temperature, per cent catalyzer a n d degree of agitation, affect t h e proportions of “saturated glycerides,” “olein,” and “linolin” in partially hydrogenated cottonseed oil. IV-By studying iodine number-time curves the effects within certain limits of pressure, temperature, per cent catalyzer and degree of agitation upon t h e velocity of hydrogenation have been determined. V-The changes undergone by melting-point and titer during hydrogenation are studied by means of curves against iodine number and time as t h e other variables. The titer is shown t o pass through a minimum before beginning its increase. VI-The degree of hydrogenation necessary t o destroy t h e response of cottonseed oil t o the Halphen test has been shown t o be a drop of about four units in iodine number. VII-A number of solid inorganic materials are shown t o have no effect on t h e activity of a catalyzer; sulfur a n d sodium sulfide, o n t h e other hand, are found t o destroy t h e activity. We wish t o acknowledge with thanks t h e many valuable suggestions made by Messrs. R. S. Pease, E . B Sebben and H. C. Fuller of this laboratory, who have in addition carried out most of t h e experimental work described in this article. RESEARCH LABORATORY BERLINMILLSCOMPANY BERLIN,NEW HAMPSHIRE
THE CHEMICAL COMPOSITION OF THE HIGHER FRACTIONS OF MAPLEWOOD CREOSOTE’ By ERNEST J. PIEPER,S. F. ACREEAND C. J. HUMPHREY Received March 7, 1917
Investigatorsz both in Europe and this country have studied t h e constituents of t h e creosote oil obtained from beechwood t a r , and in some cases from oakwood t a r , b u t no one, as far as is known t o t h e writers, has ever before attempted t h e study of maplewood creosote. The fact t h a t different species of hardwoods show a considerable difference in analysis might lead
1
1 The present paper is one of four prepared by the junior author in partial fulfilment of requirements for the degree of Doctor of Philosophy in the University of Wisconsin. ‘Hofmann. B n . , 8, 67; 11, 329; 12, 1371; Liebermann, A n n . . 169, 23; Tiemann and Koppe, Ber., 14, 2005; Behal and Choay, Compf. rend., 116, 197; 119, 166, Kebler, A m . Jour. Pharm., 1889, 409; J . SOC.Chem. 2nd.. 1894, 1087, 1187; 1891, 367. Abstracts.
Vol. 9, No. 5
one t o suppose t h a t there would possibly be a decided difference i n the composition of the wood tars obtained in destructive distillation. A commercial sample of maplewood creosote‘ was obtained by the Forest Products Laboratory. This creosote was heated in a n iron retort, a n d 1 5 liters were distilled in three separate runs, t h e fractions reported in Table I being collected and their volumes and weights determined. TABLE I-FRACTIONS OF MAPLEWOOD CREOSOTE Fraction c.
.... LOSS.. ......
TOTAL..
Volume cc. 7 60 840 815 445 840 590 805 1000 1000 480 740 515 1375 950
Weight Grams 709.46 844.20 811.84 443.22 867.72 605.34 821.50 1,029.60 1,029.50 496.80 771.82 532.51 1,442.38 979.93
-
Per cent b y volume of entire distillate 6.23 7.40 7.10 3.89 7.72 5.40 7.20 9.06 9.04 4.36 6.77 4.67 12.66 8.60
__
-
11,155 11,385.62 100.00 95 11,250 cc. = Tot‘ai’ijistillate 75’per cent of Wood Creosote 3,750 cc. = Pitch = 25 per cent of Wood Creosote 15,000 cc. Total Wood Creosote
-
The percentages of total distillate contained in t h e three fractions 93-195’ C., 195-230’ C., a n d 230280’ C. are shown in Table 11. The first fraction consists principally of water and some pyroligneous acid; t h e second principally of the mono- and dihydroxy phenols, especially guaiacol and creosol; and t h e third mainly of t h e tri-hydroxy phenols, especially pyrogallol-dimethyl-ether a n d its homologues. The pitch residue is being thoroughly investigated. TABLE11-FRACTIONS OF MAPLEWOOD CREOSOTE Fraction Volume Per cent of Total Distillate 0 c. cc. 1600 13.63 93-195 3495 31.21 195-230 6060 55.16 230-280
Just as in t h e case of other wood creosotes, t h e relation shown in Table I1 is not absolutely constant, b u t depends upon a number of factors, such as t h e method of distilling t h e raw material, etc. A liter of the crude wood creosote was then distilled from t h e iron retort, and t h e distillate fractionated from a glass vessel connected with a Hempel column. The fraction above 195’ C., which we will term the creosote oil, was a light yellow oil with a specific gravity of 1.04 a t 2 0 ’ C. When well shaken in a separatory funnel with an equal volume of 1 5 per cent NaOH solution t o dissolve and separate t h e acid oil from t h e neutral oil, t h e latter floated t o t h e t o p of t h e mixture and was removed and shaken with more alkali t o dissolve any remaining acid oil. One treatment of t h e refined creosote with a n equal volume of 1 5 per cent NaOH solution is usually sufficient t o dissolve practically all t h e acid oil. The neutral oil obtained was washed with water until free from alkali, and distilled from a glass vessel connected with a Hempel column. The alkali extract was then treated with dilute sulfuric acid until slightly acid. The acid oil which 1 After standing several months the sample showed a gradual and partial change into pitch.
Mayl 1 9 1 7
THE J O U R N A L O F I N D U S T R I A L A N D El?-GIYEERING C H E M I S T R Y
separated was washed with water until free of sulfuric acid a n d was then distilled in t h e same manner as t h e neutral oil. The entire creosote oil (above 195' C.) gave 24 per cent neutral oil, a n d 68 per cent acid oil. Evidently 8 per cent was lost in t h e process of separation. Table I11 shows t h e percentage of acid and neutral oils found in the fractions above 230' C. TABLE 111-ACID OIL AND NEUTRAL OIL IN MAPLEWOOD CREOSOTE Fraction c. 230-240 24 0-2 5 0 250-255 255-265 265-280
Per cent Acid Oil 70 86 79 84 85
Per cent Neutral Oil 23 8 13 8 6
Per cent
Loss 7 6 8 8 9
I n the separation of t h e neutral oil from t h e acid oil in t h e fractions boiling above 230' C. a crystalline sodium salt was precipitated in t h e presence of a n excess of a 1 5 per cent NaOH solution. Hofmann,' Liebermann, and other investigators also obtained a sodium salt in t h e same manner in their investigation of t h e oils of beechwood creosote. The identification of this sodium salt from maplewood creosote was, therefore, undertaken and t h e results compared with those obtained from beechwood creosote. FRACTION 23-240' C. This fraction was redistilled and 1 7 0 0 cc. ( 1 7 8 5 grams) were treated with a n equal volume of I 5 per cent NaOH whereupon t h e neutral oil immediately separated. A white crystalline sodium salt precipitated from t h e alkaline solution and was filtered by suction and washed with a mixture of alcohol and ether: 2 0 g. of an apparently pure white substance were obtained in this way. The material is easily soluble in water, less soluble in ethyl alcohol and methyl alcohol, and insoluble in ether, benzene, acetone or chloroform. On standing in the air, or more quickly on heating, t h e sodium salt turned blue. This color change was due to an oxidation and will be explained later in detail. The salt was treated with dilute sulfuric: acid until t h e solution was slightly acid: 1 5 g. of a heavy oil were precipitated out and were washed with water in a separatory funnel until free of sulfuric acid. I t was taken up in ether, separated from the aqueous solution, and after evaporation of t h e ether was distilled under reduced pressure. I n this manner a very pale yellow, almost colorless oil was obtained which boiled between 2 j 3 - 2 7 j o C. The oil had a spicy peppermint odor and gave a brownish-red coloration with ferric chloride. Treating 2 g. of' t h e oil with benzoyl chloride in a strongly alkaline solution gave 2 . 9 g. of t h e benzoyl derivative after t h e first crystallization from alcohol. I t was very difficult t o obtain a substance which melted sharply. I t was found t h a t part of t h e benzoyl derivative was soluble in petroleum ether a t room temperature. The solution was filtered by suction from t h e insoluble portion, and from t h e filtrate a fraction was obtained which on six crystallizations from alcohol had the melting point gc-91' C. The portion insoluble in cold petroleum ether was treated Ber., 3, 67; 11, 329; 12, 1371; Ann., 169, 231.
463
with fresh petroleum ether and heated on a steam bath for a few minutes and quickly filtered. This operation was repeated several times and from t h e filtrates a benzoyl derivative was obtained which on I O crystallizations from alcohol had t h e melting point I I O III' C. The residue insoluble in warm petroleum ether was recrystallized from alcohol and after 6 crystallizations showed a melting point of I I 7-1 18 ' C. It is evident, therefore, t h a t t h e oil consists of a mixture of substances which gave three definite benzoyl derivatives. On oxidation with potassium bichromate a n d dilute acetic acid t h e oil gave a mixture of coerulignone and dimethoxyquinone, whose constitutions are discussed below. On heating t h e mixture with warm glacial acetic acid t h e dimethoxyquinone was dissolved while t h e coerulignone was unaffected. On recrystallizing t h e dimethoxyquinone from glacial acetic acid a sharp melting point of 249' C. was obtained. Hof mannl obtained dimethoxyquinone by oxidizing propyl-pyrogallol-dimethyl-ether. Later, Will2 obtained dimethoxyquinone, together with mononitropyrogallol-trimethyl-ether by oxidizing t h e trimethylether of pyrogallol with concentrated nitric acid. A t the same time he obtained dimethoxyquinone by oxidizing t h e trimethyl-ether of propyl-pyrogallol which he obtained by treating t h e propyl-pyrogalloldimethyl-ether with methyl iodide a n d potassium hydroxide. Will considered t h a t there are two possible structures (I and 11) for this dimethoxyquinone. Ciamician and SilberS obtained t h e same dimethoxyquinone by 0
0
II
It
C H C ~ - O C H (
C cH~o-cf)c--ocfi
HC()C-OCHI
I/
C
CH80-c&-oCHI
H C w C H
C
C
0 I
0
II
0
I1 I1
I/ I HCvCH C II
0 I11
oxidizing t h e trimethyl-ether of phloroglucin and considered t h e structure t o be as shown in 111. The coerulignone obtained is insoluble in the ordinary solvents. It can be obtained very pure by dissolving it in phenol a t 30' C. and treating t h e solution with alcohol or ether. I n this way deep violet-blue needles are formed. Hofmann4 obtained coerulignone by the oxidation of the dimethyl-ether of pyrogallol obtained from beechwood tar. Alkalies and acids decompose coerulignone, giving a violet-blue color with acids. Coerulignone is easily reduced t o hydrocoerulignone. Liebermann and Flataub showed t h a t coerulignone condenses with primary amines t o give blue dyes containing only two methoxy groups. Hofmann believed coerulignone t o have the constitution I (shown above) while Liebermann and Flatau showed t h a t there were in addition the possibilities I1 and 111. Ber., 11, (1S78), 329. 607. 2 I b i d . . 26 (1893), 786. I b i d . , 11 (1878). 329. 6 I b i d . , 30 (1897), 324. 1
* Zbid., 2 1 (1888),
.
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 CHEMISTRY
464 OCHa
c O z{!):CHa
OCH:
I
0
o HCfiC=O
€IC f i C - O C H a
HC,/C-OCHa
HCdC-OCHa
C
C
C
OCHs I
OCHa I1
0 I11
I
I
1I
It should also be noted t h a t there is a possibility of having t h e methoxy groups in t h e following positions with respect t o t h e C=O group: (I) ortho-ortho-orthoortho; (2) ortho-ortho-meta-meta; and (3) meta-metameta- meta. F R A C T I O K 240-250' C. F r o m 1189 g. of this fraction 106 g. of a sodium salt were obtained as in t h e previous fraction. The oil obtained, 52.7 g., boiled between 253'-269' C. On benzoylation two derivatives were obtained with t h e melting points 1 1 0 - 1 1 2 ' C. and 116-117' C. On oxidation the oil gave a mixture of coerulignone a n d dimethoxyquinone. On treating a chloroform solution of t h e oil with bromine a crystalline derivative was obtained after t h e solution had stood for a week. After 3 crystallizations from alcohol t h e derivative showed a melting point of 125-126' C. On treating t h e oil with methyl alcohol saturated with HC1 gas and heating in a sealed t u b e a t 1 2 5130' C. for 5 hours, a charred residue was obtained which was dissolved in absolute alcohol. A few crystals which h a d t h e melting point 127-128' C. separated on standing. The amount was too small for purification. FRACTIOK 2 jo-2 j 5 O c. The sodium salt, 34 g., obtained from j o g. ~ of this fraction was treated as in t h e previous fractions, a n d 17 g. of a n oil were obtained which distilled between 249-258' C. On oxidation t h e oil gave only coerulignone. On benzoylation a derivative was obtained which gave a melting point of I I I - I I Z O C. after 8 crystallizations. No crystalline derivative was obtained on treating t h e oil with a saturated alcoholic solution of hydrochloric acid. FRACTION 2 j j-265 ' c. T h e sodium salt, 2 2 1 g., secured from 1123 g. of this fraction was treated as in t h e previous fractions a n d 92.5 g. of a n oil1 distilling between 251-269' C. was obtained. On benzoylation a derivative was obtained which had t h e melting point 1 1 0 - I I I ' C. On oxidation coerulignone was obtained. When treated with alcohol saturated with HC1 gas, as in t h e previous fractions, a pronounced odor of methyl chloride was observed, b u t no crystalline compound was obtained. Five grams of oil were then treated in a methyl alcoholic solution with a n excess of 2 5 per cent N a O H 1 It is advisable t o centrifuge the oil in the higher fractions when suspended in water. This will separate any paraffin!that'is present.
V O ~9, . XO. j
solution a n d dimethyl sulfate was added drop by drop until a n excess was present. T h e solution was t h e n heated on t h e steam b a t h until t h e excess of dimethyl sulfate was decomposed. The sodium sulfate was removed by treating t h e solution with alcohol, a n d t h e filtrate was shaken with ether. On evaporation a n oily residue was obtained which from alcohol gave a few crystals with the melting point 43-46' C.' The mother liquor obtained from t h e crystals above gave dimethoxyquinone on oxidation with cold concentrated nitric acid, and therefore contained pyrogallol-trimethyl-ether but no appreciable amount of pyrogalloldimethyl-ether. The remaining methylated oil was boiled with a concentrated solution of potassium permanganate until all t h e oil h a d been decomposed. The excess of permanganate was decomposed with warm alcohol, t h e solution filtered a n d t h e filtrate acidified with dilute sulfuric acid. The solution was treated with ether a n d a n oily residue was obtained from t h e extract. When this oil was kept i n a refrigerator for several days a few crystals were formed which, without crystallization, melted a t 92-96' C. Will2 obtained a trimethyl-ether of pyrogallol carboxylic acid which melted a t 99' C. By t h e use of potassium permanganate he first oxidized t h e methyl pyrogallol t o t h e pyrogallol carboxylic acid a n d t h e n methylated t h e methyl ester with potassium hydroxide a n d methyl iodide. The ester was afterwards converted into t h e free acid melting a t 99' C. FRACTION 265-280' C. The sodium salt, 1 3 j g., from 642 g. of this fraction gave 7 8 g. of oil which distilled between 256-271' C. On benzoylation a derivative was obtained which had t h e melting point I I 1-1 I 2 C. On oxidation, coerulignone, together with a possible trace of dimethoxyquinone, were obtained. On methylation with dimethyl-sulfate a n oily residue was secured which gave dimethoxyquinone on oxidation with concentrated nitric acid. T h e oily residue was oxidized with potassium permanganate b u t no crystalline product was obtained. Equal parts of t h e oil from this fraction a n d phenyl mustard oil, together with a trace of solid sodium hydroxide, were heated in a sealed tube immersed in a steam b a t h for three days. The crystals t h a t separated on cooling were filtered by suction a n d recrystallized several times from alcohol. Crystalline leaflets were obtained with a melting point 1j6-157' C. I n a similar manner a compound with t h e same melting point was obtained from t h e oil of the sodium salt of fraction 255-265' c. The sulfur was determined according t o t h e Carius method: 0.1493 g. gave 0.1283 g. BaSOc, or S, 11.61 per cent. Calculated for CsHs(0CHa)rOSCNCsHo: S, 10.99 per cent.
This reaction with phenyl mustard oil will be further investigated t o see if i t offers a method of isolating crystalline derivatives of t h e different phenolic compounds present in t h e wood creosotes. 1 Will obtained a trimethyl-ether of pyrogallol, which melted a t 47' C.. by treating pyrogallol with methyl iodide and potassium hydroxide in methyl alcohol. 2 Ber., 4 1 (1888), 607.
May-, 1 9 1 7
T €IE J O G R S A L O F I N D GS T RI A L A N D ENGI A'EE RI iVG C H E M I S T R Y
T h e percentage of methoxyl groups in t h e oil of this fraction was determined according t o the Zeisel' method. I n t h e apparatus (Fig. I) all connections were made by means of ground-glass joints, a n d specially modified washing bottles containing t h e red phosphorus a n d silver nitrate, respectively, were used: 0.1063 g . oil gave 0.2839 g. AgI or CHaO. 35.25 per cent. Calculated for C6Hs(OCHs)z(OH) : CHaO, 40.26 per cent.
T h e difference arises because t h e oil is probably a mixture. This will be further studied. I n t h e same manner methoxyl determinations were made on t h e benzoyl derivatives melting a t 11-
C.n.*Ejoints m o s t be ground 3 h in. /on9 and obou'r Us in. diameter a t narrow and h in. diameter of wdest po(nt. A*Bjoinh musr be round q+I V . /on9 and about / / = i n .d?oinomefer of narrow and i n . diameter Qf widest p oinf.
FIG.I-ZEISEL
APPARATUSFOR DETERMININGCHsO GROVP
111' C.,a n d 116-117' C., respectively, b u t not enough of t h e derivative melting a t 90-91' C. was obtained t o determine t h e percentage of methoxyl group. BENZOYL DERIVATIVE11. P. 110-1 11 C. 0.1347 g. gave 0.2377 g. AgI, 0.03137 g. CHsO = 23.29 per cent. Calculated lor CsHa(0CHa)zOCOCsHs: 24.02 per cent.
BENZOYLDERIVATIVEM. P. 1 1 6 - l l i o C . 0.0918 g. gave 0.1531 g. AgI, 0.02021 g. CHaO = 22.01 per cent Calculated for CHaCsHz(0CHa)zOCOCsHs: 22.79 per cent.
T h e following methoxyl determinations were also made: Crude tar, 6.81 per cent CHaO; acid oil (195-255' C.). 11.06 per cent; neutral oil (195-260' C . ) , 5.14 per cent; pitch, 5.10 per cent.
T h e results secured from t h e s t u d y of t h e sodium salt obtained from t h e higher boiling fractions of maplewood creosote are summarized in Table IV. I n t h e first a n d second columns are given t h e names of t h e compound or compounds identified a n d t h e corresponding characteristic oxidation product which was obtained. I n t h e third column is given t h e melting point of t h e characteristic benzoyl derivatire. F r o m these results i t is evident t h a t t h e oil obtained from t h e sodium salts of t h e fractions above 230' C. consists primarily of a mixture of pyrogallol-dimethylether a n d methyl-pyrogallol-dimethyl-ether, together with a trace of propyl-pyrogallol-dimethyl-ether. It was previously mentioned t h a t t h e sodium salt Monalsh.. 6 (1885), 989; 7 (1886). 406.
46 5
TABLE IV-PRODUCTS OBTAINEDFROM THE OIL PRODUCED FROM SODIUM SALT Fraction
c.
230-240
Compound identified I. Pyrogallol dimethylether. .. , . . . . . . . . . . . . . . . 11. Methyl pyrogallol-dimethyl-ether., , . . , , . , 111. Propyl - pyrogallol-dimethyl-ether.. . . . . . . . . . , I. 11. I. I. (b) 11. I.(b) 11. or 111.
-
-
..
.
Oxidation Product
THE
M. P. Benzoyl Derivative
c.
Coerulignone
110-1110
Dimethoxyquinone
117-1 18' C.
Dimethoxyquinone 90-91' C. Coerulignone 110-1120 c. Dimethoxyquinone 117-1 18' C. Coerulignone 111-1120 c. Coerulignone , 11O-I1lo C. Dimethoxyquinone (c) 111-1120 c. 265-280 Coerulignone Dimethoxyquinone (trace) (a) This oil gave a brom derivative m. p. 125-6'. A compound melting a t 127-8' was obtained b y treatment with alcoholic hydrochloric acid. ( b ) We also obtained a phenyl mustard oil addition product melting a t 156-157' C. ( 6 ) T h e pyrogallol-dimethyl-ether in this fraction was converted into t h e 43-6O m. p. trimethyl-ether and the 92-96' m. p. trimethyl-ether carboxylic acid was obtained from the methyl-pyrogallol-dimethyl-ether.
240-250 (a) 250-2.55 255-265
turned blue in t h e air or more quickly on heating. Hofmann' also found t h a t t h e sodium salt obtained from t h e higher fractions of beechwood creosote turned blue, a n d showed t h a t t h e color was due t o t h e formation of eupithonic acid or hexamethoxyaurine [C19H~03(OCH3)6], from t h e oxidation of two molecules of pyrogallol-dimethyl-ether a n d one molecule of methyl-pyrogallol-dimethyl-ether in t h e presence of a n alkali. We have isolated this dye a n d find t h a t t h e aqueous solutions of its alkali salts are deep indigoblue. Acids change it t o a carmine-red solution. The sodium salt obtained from t h e higher fractions of maplewood creosote was in general about t h e same as was found b y Hofmann in beechwood creosote. One decided difference is apparent in t h e amounts of these constituents present. T h e higher boiling fractions of beechwood creosote contained a considerable quantity of propyl-pyrogallol-dimethyl-ether, while in maplewood creosote there was only a small quantity of this substance present, t h e principal constituents being pyrogallol-dimethyl-ether and methyl-pyrogallol-dimethyl-ether. S U N MARY
I--A commercial sample of maplewood creosote gave per cent of wood creosote a n d 2 j per cent pitch. a b o u t 14 per cent of t h e creosote boiled a t g3-195', a n d 5 5 per cent a t 230-280'. 3 1 per cent a t 195-230', 11-When t h e different fractions of creosote were extracted with alkalies, from io t o 85 per cent was found t o be phenolic compounds. 111-The sodium salts of some of t h e phenols were isolated and found t o consist chiefly of pyrogalloldimethyl-ether, methyl-pyrogallol-dimethyl-ether, a n d propyl-pyrogallol-dimethyl-ether. These substances were identified b y their oxidation products a n d benzoyl derivatives. These sodium salts are therefore identical with those found by others in beechwood creosote, b u t differ in t h e amount present. These and t h e other substances present in a number of commercial hardwood tars are being further investigated in this laboratory. j j
INVESTIGATIONS IN
FOREST P A T H O L O G Y . BUREAUOF P L A N T INDUSTRY LABORATORY
IN COOPERATION WITH THE FOREST PRODUCTS
MADISON,WISCONSIN 1
Bey., 12 (1879). 1371.
