Chemistry of Lignin VII. Distillation of Alkali Lignin in Reduced Atmosphere of Carbon Dioxide MAXPHILLIPS AKD hI. J. Goss Bureau of Chemistry and Soils, U. S. Department of a4griculture, Washington, D. C. Alkali lignin f r o m corncobs is subjected to dry distillation in a reduced atmosphere of carbon dioxide at a m a x i m u m temperature of 400' C. The following results, representing the acerage of Jive experiments (calculated on the basis of dry lignin), are obtained: aqueous dislillate, 11.7 per cent; oily distillate, 28.3; carbonized residue, 50.5; gas, 9.3 (by difference). The aqueous distillate contains acetic acid, acetone, methanol, and catechol. The yield of the first three compounds (calculated on the basis of dry lignin) amounts to 0.30, 0.10, and 0.65 per cent, respectively. The oil is successively extracted with 5 per cent sodium bicarbonate and 5 per cent sodium hydroxide
I
N THE third paper of this series (3) results were presented of a somewhat preliminary study of the products
of the dry distillation of lignin under ordinary atmospheric pressure. A review of the literature was also given in that article. The present paper contains the results of a systematic chemical examination of both the aqueous and oily distillate obtained when alkali lignin from corncobs is subjected to dry distillation. The only chemical examination of the oily distillate from the dry distillation of lignin recorded in the literature is that of Pictet and Gaulis (8) who, however, concerned themselves chiefly with thewalkali-insoluble fraction of the oil. This fraction was separated by means of liquid sulfur dioxide into saturated and uns a t u r a t e d hydrocarbons. In the fraction containing the satur a t e d hydrocarbons, l melene was identified. EXPERIMENTAL PROCEDURE The lignin used in these experiments was prepared from corncobs by the alkali method as described in a prev i o u s communication
(4)*
The apparatus used for carrying out the dry distillation experiments is illustrated in Figures 1 and 2.
It consisted of an iron retort, A , which fitted rather closely into an electrically heated shell, B, which was well insulated with an as-
solutions. I n the sodium bicarbonate extract, acelic acid and catechol are definitely identified. I n the sodium hydroxide extract the following compounds are identified: phenol, o-cresol, guaiacol, creosol, l-vinyl-3-methoxy-4-hydroxybenzene, l-n-propyl-3methoxy-4-hydroxy benzene, and a dimethoxycarboxylic acid [CSHSOZ(OCHJ~I. The fraction of the oil remaining after the PLtraction with 5 per cent sodium bicarbonate and 5 per cent sodium hydroxide solutions is steamdistilled. The steam-volatile neutral fraction upon oxidation with potassium permanganate yields anisic acid. I n the steam-nonvolatile neutral fraction, n-nonacosane is identified. bestos-magnesia mixture, C. A was provided with a tightly fitting cover 0, thermometer well D, outlet tube F , and inlet tube E for the dry carbon dioxide gas. The distillate was collected into receiver G, and the more volatile constituents were condensed by means of condenser H and flask I, which was surrounded with ice. The apparatus was so constructed that A could be readily removed from shell B . The temperature of the retort was controlled by means of the three sliding contact rheostats J. The carbon dioxide was dried by passing through SUIfuric acid in K . L served as a receiver for the sulfuric acid in the event of a back pressure developing in the system, and thus prevented the sulfuric acid from getting into the reducing valve attached t o the tank of carbon dioxide. The rate of flow of the gas was finally regulated by means of screwcock M . The temperature in the retort was read by means of the thermometer N .
For each experiment 300 grams of lignin were used. The air in the a p p a r a t u s was first replaced with dry carbon dioxide and then evacuated to 25 m m . pressure. A small s t r e a m of dry carbon dioxide at the r a t e of a b o u t o n e bubble per second was p a s s e d through t h e apparatus during the distillation experiment. The temperature was g r a d u a l l y increased until the maximum of 400" C. was attained. The distillate consisted of a n aqueous portion and a n oil. The aqueous distillate was separated from the oil by means of a separatory funnel, and the weight of each, as well as the FOR DESTRUCTIVE DISTILLATIONOF LIGNINUNDER weight of the carbonFIGURE1. APPARATUS ized residue in the reREDUCED PRESSURE 1436
I N D U S T R I A L A Pi D E N G I N E E R I N G C H E M I S T R Y
December, 1932
tort, was determined. S o attempt was made to collect the gaseous products, and the weight of the latter was obtained by difference. Figure 3 is a flow sheet of the products obtained in the distillation. The results of five experiments are given in Table I. 'rABLE
EXI'T.
I.
a
DRYDISTILLATIOX O F LIGXIN
(300 grams lignin used in each experiment) AQ~-EO~S CARBONIZED (3.4SEOUS OIL RESIDUE .I'ROD~CTS~ Weight Yield Weight Yield Weight Yield Weight Yield DISTILLATE
Grams
1 2 3 4
PRODUCTS O F
7;
32 10.6 34 11.3 35 11.6 39 13.0 5 36 12.0 Bli difference.
Grams
%
Grams
%
Grams
84 85 87 38 S1
28.0 28.3 29.0 29.3 27.0
160 I66 151 14i 146
63.3 51.6 50.3 49.0 48.6
24.0 26.0 27.0
% 8.0 8.6 9.0
26.0
8.6
37.0
12.3
EXALIIKATION O F AQUEOUS DIGTILLrlTE
1437
0.1804 and 0.1817 gram silver iodide, and 0.0246 and 0.0247 gram methanol (= 9.86 grams methanol-mean valuein the total aqueous distillate = 0.65 per cent calculated on the 1500 grams lignin used). A4QUEOUS RESIDUE D
The aqueous residue from the previous distillation was filtered to remove black resinous particles, and the filtrate was extracted with five successive portions of ether. The ether solution was dried over anhydrous sodium sulfate and filtered, and the solvent was removed by distillation. A brom-n sirup was obtained which appeared to have strong reducing properties. It reduced Fehling's solution and also potassium permanganate solution, and gave a dark brown coloration with ferric chloride. The sirup was distilled under reduced pressure, and an oil came over which solidified in the receiver. The product was crystallized from hot benzene, and colorless crystals were obtained melting a t 102103" C. (corrected). With ferric chloride solution a green coloration was produced which changed into red on the addition of sodium carbonate. When some of the crystals were mixed with pure catechol, the mixture melted a t 103" C. (corrected). The optical properties of the crystals were found to be identical with those of pure catechol. The presence of catechol in the aqueous distillate is therefore fairly definitely established.
The aqueous distillates from the five experiments were combined. To this norite was added, the mixture was well shaken and filtered, and the filtrate was made up to 2000 cc. in a volumetric flask; 500 cc. of this were made alkaline with sodium hydroxide and distilled until approximately 250 cc. of distillate were obtained. The distillate (,4)darkened on standing. The residue (B) remaining in the distilling flask was made acid with phosphoric acid and distilled in a current of steam until the distillate (C) coming over, no longer reacted acid. The aqueous solution (D;I remaining EXAMINATION O F OIL in the flask was set aside for subsequent examination. The total volume of distillate C amounted to 2 liters. This disThe crude oil from six distillation experiments (300 grams tillate was titrated with 0.1 N sodium hydroxide solution, lignin used in each experiment) was combined. It amounted phenolphthalein being used as the indicator, and 188.5 cc. to 506 grams. It was diluted with an equal volume of ether mere required. This corresponds to 1.1310 grams of acid and extracted exhaustively, first with a 5 per cent sodium calculated as acetic acid or 4.5240 grams of acetic acid in the bicarbonate solution and then with a 5 per cent sodium hytotal aqueous distillate (equal to 0.30 per cent yield calcu- droxide solution. There thus resulted a sodium bicarbonate lated on the 1500 grams lignin used). As distillate C con- extract (E), a sodium hydroxide extract (F), and a residual tained a small amount of reducing substances, it was ac- ether solution of the neutral fraction (G). cordingly made alkaline, an aqueous potassium permanganate EXAMINATION OF SODIUM BICARBONATE solution was added, and the mixture was allowed to remain EXTR.4CT E a t room temperature overnight. The excess potassium permanganate was destroyed with hydrogen peroxide, and the The sodium bicarbonate extract was filtered, and the filmanganese oxide was filtered off and washed with water, trate was acidified with sulfuric acid and distilled in a current the washings being added to the main filtrate. This was of steam until the distillate coming over no longer reacted acidified with phosphoric acid and distilled in a current of acid. In the distillation flask there remained an aqueous steam until all volatile acids were distilled over. The dis- solution (H) containing steam-nonvolatile compounds of tillate was neutralized with sodium hydroxide, the solu- an acid character. tion evaporated to dryness on the steam bath, arid the resiThe distillate (I) from the above-mentioned distillation due dried a t 100" C. The toluide of this substance was pre- was made up to a volume of 2250 cc., and 20 cc. of this pared according to the method described by Mulliken ( 2 ) . solution when titrated with 0.1 A' sodium hydroxide soluIt melted a t 146-147" C. (corrected) and, when mixed with tion required 4.6 cc., which corresponds to 3.10 grams acid a pure specimen of aceto-p-toluide, no depression in the melt- calculated as acetic acid. ing point was observed. The optical properties of the crysA portion (150 cc. 2 34.5 cc. 0.1 N sodium hydroxide) tals of the toluide prepared from the acid of distillate C were of the distillate was distilled, and the following Duclaux found to be identical with those of a known and pure speci- values were determined: men of aceto-p-toluide. The volatile acid present, consisted, 0.1 N NaOH DUCLAUX VALUE therefore, chiefly of acetic acid. Cr
DISTILLATE A To distillate A some norite was added, amd the mixture was well shaken and allowed to stand for one-half hour. This was filtered and the filtrate was made up to 500 cc. and analyzed for acetone and methanol by methods referred to in a previous communication ( 5 ) . ACETONE DETERI\IINATION. Three 10-cc. samples consumed, respectively, 7.95, 7.85, and 8.05 cc. 0.l A' iodine solution (mean = 7.95 cc. 0.1 N iodine solution = 1.5380 grams acetone in the original aqueous distillate or 0.10 per cent of the weight of lignin used). METHANOL DETERMINATION. Two 5-cc. saniples gave
First 10 cc. Second 10 ccl Third 10 cc.
2.3 2.1
2.05
6.6 6.1 5.9
This corresponds approximately to the Duclaux value for acetic acid (1). The remainder of distillate I was neutralized with a solution of sodium hydroxide and evaporated to dryness on the steam bath. The residue was dried a t 105" C., and the toluide of the acid was prepared according to the method of Mulliken ( 2 ) . The toluide obtained was identified as the aceto-p-toluide by its melting point, mixed melting point, and the optical properties of the crystals. A nitrogen determination of toluide obtained gave the following results:
Il3K
1 N D U S T H I h I . A N D I S N G 1 iY i?: E I{ 1 N (;
c H i?: >I 1 S T H Y
Vul. 24, No. 12
A m l y s z s (modified Kjeidehl). C n l d a t e d i w : ~ ~ : ~ t ~ j - ~ilrous ~ - ~ ether. ~ ~ l ~ The ~ i ~filtrate i ~ ~ (L) was examined separately as (Cdf,,OX): nitrogen, 9.39. Found: 9.44, described elsewhere in this papcr. The solid phenolates obtained as above described were The volatile acid present i ~ sodiuni i liicarboiinte cxtraot 1.: dissolved in water and acidified with dilute sulfuric acid, consisted therefore principally of acetic acid. The residual aqueous solution (11) remainiiig after the dis- and this solution was extracted with ether. The ether solutillation of the steam-volatile acids of the sodium bicarbonate tion of the phenols was dried over anhydrous sodium sulextract, v a s filtered, and the filtrate was extracted rvith five fate. After removal of the solvent the residual oil amounted successive portions of ether. The ether solution was dried to 19 grams. It was fractionally distilled under ordinary over anhydrous sodinui sulfate and filtered, and the solvent pressure, a three-bulb fractionating column being used. was removed by distillation. A light brown sirup was ob- The followiiig fractions were obtained:
tained which amounted to 11.5 grams. This was distilled under reduced pressure (25 mm.),and the following two fractions were obtained: (1) 160-175' C., 3.5 grams; (2) 210230" C., 3.0 g r a m .
Fxncmoi 0
e.
Below 205
205-210 210-215 215-220
Wrioa~ CIam* 0.6
2.1 3.0 3.5
Flnrrloa 0
c.
224-225
wsroav Cmma 2.5
225-230
230-235,, Above234
2.3 2.1 1.7
Tlre identification of the phenols present in each fraction was accomplished by the method described in a previous communication (6). I n all cases one gram of phenol was used for the preparation of the 3,5-dinitrobenzoyl ester. The 3,5-dinitrobenzoyI derivatives were identified by their me16 ing points and by the optical properties of the crystals. Nitrogen was determined by the modified Kjeldahl method (7). FRACTION DISTILLING BELOW 205' C. The 3,5-dinitrobenzoyl ester of this fraction was identified optically as that of 0-crmol. The melting point of tlie ester, however, was not sharp (125-130' C.), and it was evidently not pure, but because of the small amount of material available it was not possible to purify it further. Analysis. Calculated for dinitrobenaoylcresol (CMHXOO&): nitrogen, 9.27. Found: 9.03.
Fuc'rioN ilT 20.5210" C. This was found to consist of guaiacol. F ~ o u m2. I'HOTOUHAIW
OF
APP.~ATUS
Fraction 1 solidified in the receiver, and after two recrystallizations from benzene the crystals melted at 101" C. (corrected). The crystals were very soluble in water, and the aqueous solution of this product gave a precipitaw with lead acetate solution, and a green coloration with ferric chloride solution which became red on the addition of sodium carbonate. The crystals were identified as catecliol by their melting point, mixed melting point (lOl-lOZo C., corrected), and the optical properties of the crystals. Fraction at 210-230" C. wits a viscid brown oil. With ferric chloride solution its aqueous solution gave a green coloration which on standing became brown. Nothing definite vas isolated from this oil.
EXAXINATION OF SoniuM HYDIWXIDE EXTRACTF The sodium hydroxide extract wa,s inade acid with SUIfuric acid and distilled in a current of steam until no more oil came over. The oil was separated from tlie aqueous distillate, the latter was extracted with ether, and after removal of the solvent the residue waa added to the main oily distillate (J). There remained in the distillation flask a steamnonvolatile phenolic fraction (K).
EXAMIN.ATION OF STEAM-VOLATILE PHENOLS J The oil was distilled under ordinary pressure, and 76 grams of oil were obtained. This was dissolved in an equal volume of anhydrous ether, and two volumes of a saturated solution of potassium hydroxide in absolute alcohol were added. After standing for a few minutes, the entire solution became nearly solid, owing to the separation of the potassium phenolates. These were filtered off and wilshed with anhy-
Analysia. Calculated for dinitrobenanylguaincol(C,,&,O,N,) nitrogen, 8.80. Found: 8.73, 8.80. FEAcTIOKS AT 210-215', 215-220°, 220-225", 230O C. Creosol (l-methyl;i-metiioxy-4-hydroxy was identified in these fractions.
:
226benzene)
AND
Analysis of Fraction af e10-$16' C. Calculated for dinitrobenmyloreosol (C16K207N*): nitrogen, 8.43. Found: 8.53,8.44. Analysis of Fraction at Bl6-$80" C. Calculated for dinitrobenzoylcreosol (C,,€I,,O,N,): nitrogen, 8.43. Found: 8.64,8.59. FRAcTroiv AT 220-225" C. The dinitrobcnzoyl ester of this fraction after repeated crystalliaatioiis from ethyl alcohol, methanol, ligroin, and dilute acetone was resolved into two fractions. The first fraction, which was by far the largest, was identified as the 3,5-dinitrobenzoyl ester of creosol. Analysis. Calculated for rlinit,robensoyloreosol (CWHUOJV~ : nitrogen, 8.43. Found: 8.47, 8.52.
The dinitrobenzoyl ester of the second fraction melted a t 108" C. (corrected). When mixed with some pure 3,5diiiitrohenzoyl ester of l-vinyl-3-methoxy-4-hydroxy benzene, the mixture also melted a t 108" C. (corrected). The identity of these substances was further confirmed by the determination of the optical properties of the crystals. The pure 3,5-dinitrobenzoyl ester used in the abovementioned identification was prepared from 1-vinyl-3-methoxy4-hydroxy benzene which was synthesized iron! vanillin as fol1ou.s:
heatid over"&Ismxll flame &til tlk evolution of carl& dioxide ceased. More heat was then applicd, and the oil that distilled over wag collected. It was dissolved in ether, and the ether
INDUSTR IAL AN D EN GIN EER IN G CHEMISTR Y
December, 1932
1439
solution was dried over anhydrous sodium sulfate, and filtered. After removal of the ether by evaporation, the residual oil was distilled. It distilled over a t 230-40' C., yielding 1.1 grams.
Analysis. Calculated for dinitrobensoylphenol (C13HSOBNZ) : nitrogen, 9.72. Found: 9.46, 9.44.
The 3,5-dinitrobenzoyl ester of this substance was prepared by the general method previously described ( 7 ) . It was crystallized successively from 95 per cent ethyl alcohol, and from ligroin and ethyl alcohol (melting point, 109" C., corrected),
guaiacol.
Analysis. Calculated for dinitrobenzoyl ester (:if l-vinyl-3msthoxy-4-hydroxy benzene (Cl~Hls07N~) : nitrogen, 8.13. Found: 8.05, 8.09.
The optical properties of the crystals were determined, and the following results were obtained: Crystallizes in colorless rods. I n parallel polarized light (crossed nicols), the extinction is straight and the sign of elongation *. The refractive indices are n, = 1.550 and n, = 1.663 (both * 0.003). (Solutions of potassium-mercuric iodide in glycerol and water were found to be most satisfactory in studying this substance microscopically.) FRACTIOK . 4 ~225-230 " C. The 3,5-dinitrobenzoyl ester of this fraction was identified as that of creosol.
FRACTION AT 200-205" C. This consisted principally of Analysis. Calculated for dinitrohenzoylguaincol (ClaEL007NP) : nitrogen, 8.80. Found: 8.81, 8.80.
FRACTIONS AT 205-210" sisted principally of creosol.
AXD
210-215" C. These con-
Analysis. Calculated for dinitrobenzoylcreosol (ClaH1,07N2): nitrogen, 8.43. Found: fraction at 205-210' C.. 8.48, 8.52; fraction at 210-215' C., 8.42, 8.47.
FRACTION Kr 215220" C. This fraction consisted principally of creosol together wit'h a small proportion of l-npropyl-3-methoxy-4-hydroxy benzene. The 3,5-dinitrobenzoyl derivative of the latter was identified by its melting point and by optical methods, The quantity of material obtained was insufficient for a nitrogen determination I
Analysis (First Fraction). Calculated for dinitrobenzoyl8.43. Found: 8.66, 8.69. creosol ( C I I H I ~ O ~:Nnitrogen, ~)
FRACTION AT 220-225" C. In this fraction creosol was
Analysis. Calculated for dinitrobenzoylcreosol ((&H1*0;N2): identified.
nitrogen, 8.43. Found: 8.34, 8.31.
FRACTION AT 230-235
C. The dinitrobenzoyi derivative of this fraction was resolved by successive fractional crystallization from 95 per cent ethyl alcohol, from dilute ethyl alcohol, and from ligroin and 95 per cent ethyl alcohol into two fractions. The first fraction was identified as the 3,5-dinitrobenzoyl ester of l-n-propyl-3-methoxy-4-hydroxybenzene and the second as the 3,5-dinitrobenzoyl ester of l-vinyl-3methoxy-4-hydroxy benzene. O
Analysis of Fraction 1. Calculated for dinitrobenzoyl ester of l-n-propyl-3-methoxy-4-hydroxy benzene (C,,HlsO; N2): nitro-
gen, 7.77. Found: 7.94.
Analysis of Fraction 8. Calculated for dinitrobenzoyl ester of l-vinyl-3-methoxy-4-hydroxy benzene (C16H110PN1) : nitrogen,
8.13. Found: 8.07, 8.07.
The fraction boiling above 235" C. was a dark viscid oil. No crystalline dinitrobenzoyl derivative of this could be obtained.
EXAMINATION OF PHENOLS IN FILTRATE: L The filtrate (L) obtained from the filtration of the solid potassium phenolates was acidified with dilute sulfuric acid, and the oil obtained was distilled in a current of steam. The oil was separated from the aqueous distillate, and the latter was extracted with ether; the ether solution was dried over anhydrous sodium sulfate, and, after removal of the solvent by distillation, the residue was added to the main oily distillate. The weight of the latter amounted to 38 grams, It was fractionally distilled under ordinary pressure with a three-bulb fractionating column. The following fractions were obtained: FRACTION
c.
Below 200 200-205 205-210 210-215
WEIQHT Grama
1.0 6.3 7.5 3.5
FRACTION
c.
215-220 220-225 225-235
WEIGHT Grams
5.2 2.8 2.0
A small amount of tarry residue remained in the distilling flask. The 3,5-dinitrobenzoyl derivative of each fraction was prepared and fractionally crystallized using the method previously indicated. FRACTION DISTILLING BELOW 200" C. In this fraction phenol was identified.
Analysis. Calculated for dinitrobenzoylcreosol (Ci&~07Nd : nitrogen, 8.43. Found: 8.50, 8.53.
FRACTION AT 225-235" C. The 3,s-dinitrobensoy1 ester of this fraction was identified optically as that of l-n-propyl3-methoxy-4-hydroxy benzene. It was, however, not possible to isolate the pure 3,5-dinitrobenzoyl ester of this phenol. The product even after several crystallizat'ions did not melt sharply, and the melting point was always below that recorded for the 3,5-dinitrobenzoyl ester of l-n-propyl-3methoxy-4-hydroxy benzene. EXAMINATIOS OF PHENOLIC FRACTIOX K, NOT VOLATILEWITH STEAM The residue remaining in the flask after the steam distillation of the phenols was a black viscid mass. It was dissolved in ether, the ether solution was dried over anhydrous sodium sulfate, and filtered, and the ether was distilled off. The residue amounted to 196 grams. This product was distilled twice under reduced pressure (7 mm.) in order to remove tarry substances, and the distillate was then fractionally distilled under reduced pressure (7 mm.). The following fractions were obtained: FRACTION WEIGHT
c.
105-110 110-125 125-135 135-155 155-170 170-225 225-2 40
APPEARANCE OF PRODUCT
Grams
7.0 3.5 8.5 20.0 5.5 28.0 26.5
Brown viscid oil Brown viscid oil Brown viscid oil Brown viscid oil Viscid oil containing some crystale Viscid oil containing some crystal8 Glassy mass
FRACTION AT 170-225" C. This was redistilled under reduced pressure (25 mm.) and resolyed into two fractions: 205-220 O; 220-270 " C. The fraction a t 205-220' C. on standing deposited crystals, which were filtered off and recrystallized first from a mixture of benzene and ligroin, and finally from benzene. It was obtained as colorless plates; the yield was 0.4 gram (melting point 122" C. corrected). A carbon, hydrogen, and methoxyl determination gave the following results: Carbon and Hydrogen. Subs., 0.0790, 0.0637. Carbon dioxide: 0.1769, 0.1427; water, 0.0432, 0.0360. Methozy2. Subs., 0.0656, 0.0564; Ag I, 0.1582, 0.1359. Calculated for CsHsOl-OCH~: carbon, 61.20; hydrogen, 6.16; -0CHa
1440
INDUSTRIAL AND ENGINEERING CHEMISTRY
,
Made rteamdislilld m d and ACETONE
Made m d w l h H SO, and Iteani-dAst,hd
Vol. 24, No. 12
,
+ 11) H) l RESIDUE(D) I I I. I I I
VOLATILE ACIDS (C) Made alkalinetKMnO+ and rleamdtit!llco
STEAM-VOLATILE ACIDS ACETIC ACID (as TOl"Id,)
E d r r c l e d with dher
VOLATILE ACIDS
CATTECHOL
CATECHOL
I
(RESIDUE
E d m k a x l h ether
,
E x l r a ~ l ~w d~ j h5%
,
NIOH
NEUTRAL
,
STEAM-MLATILE WENOLS (J) T r e a l d with KOH
jirohDlls
,
I
FkACTION (G) I
NEUTRAL Fi U t T l O N Stiamdi$ttlllrd
1
STEAM NON-VOLATILE PHENOLS (K)
I
DlMETHOXYCARBOXYLlC ACID
~ c g ~ 6 0 2 ( o cI ~3i
STEAM VOLATILE e N Fnrltonrted and O I i d n U w8lh KMnO,
I
v
o
I
t Ai,,,
A N I S I C ACID
I PHENOLS IDENTlfIED
THROUGH T H E 3.5-DINIlROBENZOYL ESTERS
I
GUAIACOL n-PROPY L GdA~ACOl CREOSOL
ORTWCRESOL GUAIACOL CREOSOL I-VINYL-3-METHOXY-4-H~DROXY BENZENE n-PROPYL GUAIACOL
FIGURE3. PRODUCTS OBTAINED IN DRYDISTILLATIOX OF LIGNININ REDUCED ATMOSPHEREOF CARBON DIOXIDE OCHa, 31.63. Found: carbon, 61.06, 61.09; hydrogen, 6.12, 6.31; OCHs, 31.86, 31.83.
was heated in a boiling water bath, and potassium permanganate solution added from time to time until no further decoloraThe substance was rather insoluble in cold water but tion of the permanganate solution took place. The excess readily soluble in hot. An aqueous solution of this material of potassium permanganate was destroyed with hydrogen gave no coloration with ferric chloride solution. It appeared peroxide, the manganese dioxide was filtered off, the alkaline to be an acid and judging by its composition it would seem filtrate was concentrated to a volume of about 250 cc. and to be a dimethoxyphenylacetic acid. By means of mixed filtered, and the filtrate was acidified with hydrochloric acid. melting point determinations it was, however, definitely A colorless precipitate was obtained. This was crystallized proved not to be identical with the following four of the six successively from dilute aIcohol and ligroin and was obtained theoretically possible dimethoxyphenylacetic acids: Homo- as colorless needles (melting point 184" C., corrected). veratric acid, 2,3-, 2,4-, and 2,5-dimethoxyphenylaceticacids. When mixed with pure anisic acid, the mixture also melted The crystals which separated out from the fraction a t a t 184' C. The optical properties of the crystals of this 155-170" C. were identical with those isolated from the frac- acid were found to be identical with those of pure anisic acid. The acid filtrate from the crude anisic acid was extracted tion a t 170-225" C. Nothing definite was obtained from with ether, and after removal of the solvent the residue was the other fractions. crystallized from dilute alcohol and from ligroin. The crysEXAMINATION OF NEUTRAL FRACTION G tals obtained were identified as anisic acid. FRACTIONS 220-230°, 230-240", ASD 24Cb-250" C. These The ether solution of the oil which had been successively extracted with sodium carbonate and sodium hydroxide fractions were similarly oxidized with potassium pennansolutions was dried over anhydrous sodium sulfate. After ganate solution, and in all cases anisic acid was obtained. removal of the solvent by distillation, the residual oil FRACTIONS AT 250-260" AND 260-280' C. The concenamounted to 73 grams. This was distilled in a current of trated solutions from the permanganate oxidation when steam and thus resolved into a steam-volatile neutral frac- acidified with hydrochloric acid gave no precipitate. The tion (M) and a steam-nonvolatile neutral fraction (N). solutions were extracted with ether, and after removal of the ether the residues were dissolved in alcohol and allowed EXAMINATION OF STEAM-VOLATILE NEUTRAL to crystallize. However, nothing definite was obtained. FRACTION M STEAM-NONVOLATILE NEUTRALFRACTION N. The black Fraction M was taken up in ether, and the ether solution tarry mass remaining in the flask after the steam distillawas dried over anhydrous sodium sulfate and filtered. After tion of neutral fraction G was dissolved in ether, the ether removal of the ether by distillation, the oily residue amounted solution was dried over anhydrous sodium sulfate, and after to 28 grams. This was fractionally distilled under ordinary removal of the ether by distillation the residue was distilled under reduced pressure (25 mm.). Most of the material pressure, and the following fractions were obtained: distilled over a t 205-230' C. The distillate, which amounted FRACTION WEIQHT FRACTION WEIQHT to 16 grams, solidified in the receiver to a butter-like mass. c. Grams c. Grams The product Tas dissolved in acetone, and, on standing, 205-220 1.5 250-260 3.0 colorless crystals separated out. These were filtered off 220-230 3.5 260-280 3.0 230-240 6.0 Residue 2.5 and recrystallized from hot acetone (melting point 67-68" C., 240-230 4.0 corrected). When this substance was mixed with pure 12nonacosane, no depression in the melting point was observed. OXIDATION OF FRACTION AT 205-220' C. WITH POTASSIUM The original acetone filtrate from the above-mentioned The oil was placed in a flask provided PERMANQANATE. with a mechanical stirrer and reflux condenser. The flask crystals was placed on the steam bath, and the acetone evapoO
1)eceeihcr. 1932
I iv D US T R I A L A N D E N C I N E E R I N G C H E M I S T R Y
rated off. The residue was found to be resistaiit to oxidation with potassium permanganate and appeared to be a mixture of saturated compounds from which nothing definite could be isolated
ACKNOWLEDGMENT The apparatus used for the dry distillation experiments was coustructed by It. Hellbaeh of the mechanical staff of this laboratory. All identifications of conipounds by optical methods were made 1)y G . L. Keenan of the Mieronnalytic.al Laboratory of the Food and Drug Administration of t h i s department.
1441
LITERATURE Crmn (1) Duolaur, Ann. inst. Pa8tezLI.9.2fi‘J(1895j.
for Identification of Pure Organic (.omp&da.”~ol. 1, g . 81. Wiley. 1906. Pliillips, J . Am. C h m . Soc., 51. 2420 (1929) Pliilliys. lbid., 51, 2421 (1929). I’lAlips, lbid.. 51, 2423 (lW29). Phillim and Koensn, Ibid.. 53, 1924 (1931).
12) , , Mullikcn. S. P.. “Method
(3) (4) (5)
(6)
R r o r w m July 8. 19:12. ContribuLion 203 irom the Color m d P n i m Waste Divirion. I?ureau oi Chemistry and Soils.
AM E R I C AN C 0 N T E M P 0 H A R I E S Charles Holmes Herty IND words for the living are viewed asknnee. But omdor will say that Charles IIolmer Ilertp loves his fellaw man and is in turn beloved. Hia life has been marked by tireless d e v o t i o n to onc worthy cause after another. In the day of great need he led in bringing chemistry to t,he service of thr nation. A personal lradrr among chemists, be became a statesman of vision and achievement, unofficial and unmindful of political expediency. This career of service began half a cent.ury ago. Charles in his early teem, arphaned and living with his mstrmd p a n h o t h e r and aunt, w m not doing re11 at school. Thereupon his aunt. B woman of character and resnurrefulness, led him to his mother’s maw and earnestly unfolded to him the possihilitics that Iny ahead if only he would devote his life to worthwhile ohjrrtives. Then and there thm Saul hecame Paul. apostle ol worthy causes. He made himself the man of the household and munred responsibility for his little &er two years his junior. Devotion grew with the boy and the man until it emhraced the whole Southland, the whole nation, in the furtherance of objectives of far-reaching importnnre. It w m at Milledgeville, Gs., on December 4,1807, that Charles’s eventful life bcgan. His father, Bernard R. Flerty, who way of Irish Iinm~e,served in the ConJedrm1.e nrmy and was by vocation a druggist. His mother, Louisa T. Holmes, came u i old Georgia stork. Both parents died before he was nine yeam old.
Following prepmation a t Georgia Military and Agricultural College, Charles attended tire University of Groraia. I k r e r a r d there sarriLnt8 us in assuming that he continued t,o “keep hi6 eye an the ball.” Those who have matched their skill against his at tho game of billiard-, may misundemtand the figure of specch. Purely his adept,ness with the cue almost tielies blip fact that he was graduated a t the ape of Piahtern and at the head of his cIas8. He had the advantage o i not being spoiled by riches, hut poverty had its drawbarks. As honor man it hecame his duty to officiate, spade in band, at. tire planting of the elas- tree. The ceremonial day dawned hot, and the overcmt he felt constrained to wear brnughl bends of perspiration to his tiruw. But the dignity of the occasion rnlght not have h n
preserved had he exposed the seat of his trousers. Follou,ing his graduation Charles received a legacy of a few thousand dollars. Thk made rasier his further pursuit, o i an e d u c a t i o n . The next lour years were spent with Remsen a t J o h n s I l o p k i n s University. There he studied hml, entcred actively into athletics, and “supered” in the chorus a t the theatre. He received his doctorate at the age of twenty-two. Cdlcd to t a c h chemistry a t his Alma Mater, the University of Georgia, young Doctor IIerty brought mth him thc spirit of research, and n l m Pop Vl’nmcr and the game of football, [,hen new to t h e colleges of t.he S o u t h . While a t floplrins, Remen had hken him to task lor soendine so much time in extracurricular activities. But Berty coiitended that lie II’RS prepurin8 himself to be a teacher and wanted to bo B porsonwl leader of his pupils. A pict,ure of Georgia’s baseball team of 1891 reveals in uniform Doctor Charles 11. Herty, first faculty director of rzthlctics at Georgia. I2o~ouryeam later we find him denominated I’liyaieni Director and Adjunct Profrssar of Chemistry. In this dual til.le the order af mention may have been significant. It --as at, least prophetic. “Doc“ Ilerty v’m a boy among the boys ha sought to lend to a knowledge of chemistry. Charley Iierty, B chemist among chemists, was fimt of all a man among men. It remained for vision, dovotion, and initiative t o provide tho strong persons1 leadership that came to mean so much in bringing oitr nation’s lawmakers and citizen8 in general to a knowledge of the importance of ch-mintry t o nationti1 nelfare. IIerty has always enjoyed sporb, hut he finds in them lessons for life’s more important pursuits. Baseball to him inculcate the principles that make for success in all organized effort--coneentrution, aeemacy, c o o i d ~ ~ d e d n t a squi& , deeision, rand, above all, t,rurnwork. 13ecuming adjunct professor must have suggeatcd to young Doetor Herty the p o d i i i t y of assuming a d d 4 responsibilit,iq for the itme year ho took RS his bride Miss Sophie Sehnller, t,lie belle of Athens. Thus began a life-long devotion that was later shared by two sons, Charles fiolmes, Jr., and 1“mnk Bernard, and a daughter, Sophie Dorothea. Herty’s first paper hefore the AMERICAN CHEMICAL SOCIETY was presented in 1894. It was a seared boy who addressed his.
