- 11T EW439 T-UFrolt (Apnls DOOM 9 usu1) ) JE~SaHO SJ&d 0 flh.llsk KH Qll C6tE# U~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
PROJECT O----19_-------- PROJECT REPORT FORM COOPERATO- ttt- - REPORT O------33--- DATE J anuary 1- a _9 OTE B00K--- 1804- Copes to: Fles p PA12., 87,_ TO Dr. Pearl (2) SGED Mr. Beyer Donad yer THE CAUSTC HYDROLYSS OF THE BARK OF VAROUS POPULUS SPECES. n Project 1932, Report umber 12, the caustc hydrolyss of Populus tremulodes bark was reported. Snce that tme, the barks of several other members of the Populus famly have been obtaned. The data derved from the hydrolyss of these barks wll be reported here, Snce the hydrolyss of the Populus tremulodes bark was run, t has been found that acetovanllone and acetosyrngone are present n these extracts. Snce the phenolc extract obtaned from the hydrolyss of Populus tremulodes was stll avalable, the fracton was dluted wth ether to a standard volume, a total solds was run to fnd how much of the extract remaned, and the quanttatve analyss of the aldehydes was rerun to nclude the acetovanllone and acetosyrngone. Ths correcton wll be ncluded n the data that wll follow. The varous bark samples were obtaned from the followng sources. Mss Barbara-Reeder brought us samples of Populus granddentata and Populus tacamahaca from northern Wsconsn (Code numbers--1 6 33-110 and 1739-17). We obtaned a sample of Populus heterophylla bark from the U.S.D.A., Forest Servce, Southern Forest Experment Staton, Delta Research Center, Stonevlle, Msssspp. Ths bark was cut so as to remove the nner bark from the outer bark. The code number for the nner bark was 1762-63-C and the number for the outer bark was 1762-63-D. FORM 7-3 2500.7-56 THE STTUTE OF PAPER CHEMSTRY
Project 1932 January 14, 1960 Page 2 Two samples of Populus deltodes were cut for us by the genetcs department from the ravne behnd the nsttute. The one sample was green smooth bark and was numbered 1804-90-B. The other sample was dark and rough and was labeled 1804-90-A. The fnal sample was Populus trchocarpa. Two samples of ths speces were receved from the Smpson Tmber Company, Everett, Washngton. The one sample was dark and rough. Ths sample was gven our number 1804-120-A. The other sample, smmoth and green, was labeled 1804-120-B. All the hydrolyss were run dentcally. A 50 gram O.D. sample of the bark sawdust was covered wth a soluton of 60 grams of sodum hydroxde n 1500 ml. of water. The mxture was strred and boled under reflux for 8 hours. When cool, the mxture was fltered, and the sold was washed wth water. The fltrate was acdfed wth dlute sulfurc acd and extracted wth ether usng a separatory funnel. The ether soluton was concentrated to a small volume, weght and volume recorded, total solds taken, and bottled. Both qualtatve and quanttatve chromatograms were run on every extract. The data obtaned from these hydrolyss wll follow n chart form. dlb/tvh
- f.- C~ -al 4,C~~~~~~~~~~Aujuas aw x - R'ausaux 9 auul LUjLUoaay x xk OS 11 U llu~ja x.--. ~7t~> x x x x x w - n~~~~~~zuu~~~~~~-j x x ~~~~x9170 PDU ajllunw3- x x x x x x x x x tvo( pdjjul~u.a~s K K K x K x K x K 90O STujas t ) x x (ou AUJl Ug(j LA K x K x K 00 0 djdc d L ;CD'f ( pq t 4 a C+ C6 C n ~dc CD~ ~l 0 4P 0, al 0 1 -o w- 0 o 0 w ow - ~~~~~~~~~~~~~ CD ~~~~~~~~~~~~~~~~~00C Sd 4 'asan L) flc~hd0aujlvuh
r C, 5- C 43 -r V - jug4yt UUQ4Q1nu - 2Kj:- (Mq anna.) UtAttflVJBGt{ -savd -3: (pwq aeuufl utlatlao.ae4om tcllod U2- C. A o - -c C o.1 co r- CD a UQOmS AL u6#tk- f (tflcolls j seojoflep aoa ct4floj * 2jJgj seploflep ao (HqfloOW" j O JJ SOW~rW4lEQlU -~ (1q4;cQWS jf uaa.50j w8-souapptt'h.t QCOj (R(tf jowb j t SBe1olms8J? 'QUOC go t 5- PC 5,. PA x x H C 0 go -j 1. f: m lll W- 11' H 1 1 1 t x ': CQ ol C t 1 1 -:-'AD C~ C~ C H H C 0<1 x '01 t 1 1 1 1 1 t -1 -C cl7 C C - x -'l -1 x cr C V *-l %4< cc C~l _' _ - - C -'--J - - -- -.
ttnote e. t d --- f tda~ P~ th C.. -- Cot. (Peak)1607-12 o. 1633-110o Go~e17. (ehercart Th42~z.J 180..9A..4 -_ 1739-17 Onc C EROL S C' lnf P, t ee& Pm ~l",,pee. delta"eu. af,7u rp e 1804D0. 18440. 1762-63-0 1762-63-D 5.7 ~rk Gn rou' A Oth ana s -- sk 4.3 ~R.ttg le~ ~ h)22. t 1804-120.1804-120 ~rk A r$.& a 0:" & emot!1804-13"- 1804-126-, 4.9 6.8 t_ (o_, f e.. (f ext. Vaall.n _ 25.4 0.5 21.0 0.5 S~rs~eyte 16.9, 0.2 15.0 0.4 9.5 7.0. 4 ot 0.2 0.2 W., 4.*1 t 16.5 0.9 12.3S' 0.7 1_bld 52 0_ 0 0 ±.5J 0.3 1 14.0 0.8 6 t. t r t. 18.5 0.9 23.0 la 0.2 : O M._ 0 ex. elj M ~, 1. 18.0 Meto'n411 13-7 0.2 12.0 0.3 5.0 8.0-0.... 4.Q0 0o7 Meto~rtoso 14.3 0.2 23 00 1.010.3 1. 10.0 0.5 5.5 0.2 0.2 A1-6 05 7.0 0.2 Teallte eel 8 6.0 $vtaa.d - 61.5, tnlle e14d 115.0- Fw..~rmflneto eat 100. m.- C.Corl ~tel 732.51 1.0 108m.8 0.7 >~232.5 1.6 ;153.8 4.0 1.2 172.3 4.4 2.8, 107.5 6.0 23.5 2.5. 62.0 1 3.4 0.6 fl.0 2.4 129.5 3.0 104.0 58.5 1 1.4 ; 71.0 8.5 :146.3 3.8-259.0 ;6.1 39.0 5.6 3.8 2.1 85.0 4.2 81.0 66.0'1 3.2 64.0 78.0.5.8 49.0 87.0 5.9 3fl.0 37.0 1.8.. 77.0 5.6 - - Te ~1111e Of Alel for theoatt. lee " edote~rl~.11o.. ttl., tsht r M D fswttf t. 1% of ex. 0.8 5.0 38.0 1 1.8 2.3 88.0 4.1 13.0 200 1. 34.0 A2. " 15C 1.2 1.2 15.0 Os4 -. [03 10.0 0.3 40 1.5 8.0 0.2 1.9 0.6 11.0 0.3 k. 3.9 m 1.0 3.3 L.7 2.9 72.0 2.1 '.4 4 4 112.0 5.3 ~.1 4.2 166.0 4.8.0 6.1 216.0 6.3
PROJECT REPORT FORM Copes to: Fles Dr. Pearl (2) Mr. Beyer PROJECT O- COOPERATOR REPORT O.- nar~ 1952 nsttute January 14, 1960 OTE BOOK1-- 84_1 PA 117 TO 19 DonaPl? 'P. CAUSTC FUSO OF KASO LG A mxture of 13 grams of sold potassum hydroxde and 2 ml. of water was strred and heated on a hot plate to 1700. At ths temperature the caustc was flud. At ths tme, 5 grams of a Klason lgnn (1410-17-A) was slowly added to the fused caustc. A reacton took place, ncreasng the temperature to 1920. The mxture was strred contnuously for fve mnutes wth the temperature held above 175. The reacton mxture was then allowed to cool and was dssolved n water. The aqueous soluton was acdfed wth dlute sulfurc acd and was extracted wth ether. The extracton contnued for a perod of 12 hours, usng the ar agtated contnuous extractor. The ether soluton was then concentrated to a small volume and was bottled. The extract amounted to 0.21 grams, 4.2% of the Klason lgnn. The sample was gven our number 1804-118-A. and quanttatvely. The ether extractves were chromatographed both qualtatvely Developed wth butanol 2% aqueous ammona. Rf 0.00 PA brown Maule 0.08 blue Syrngc acd 0.10 0.12 purple red Vanllc acd p-hydroxybenzoc acd FORM 7.3 2500-7-56 THE STTUTE OF PAPER CHEMSTRY
4A;/qt[p VqD-J'4G JO %O'T Oft o~ qoearqxa so %T7Cl Oft 904a sqo~rjxq ;o %ag 02u C98s pto-r 3ozuaq~xospA~H-d pto-e o~ua~ PTO? 3TTTTuA :sflfsajgjatquqttjtrnfl? ptoe Dtozu~qAxojpR-d P~au OTTTUrA PTO-e Ot~TJuaS x ajl13'p4 Pa.1 aetd.nd aflfl an-[q unoaq umoaq um~o.tq v~ld 9900 900~0 00M (C:C:oT) J0'P - GUTpuz~d - T~Ou-enq qtmyp P96OTGAGQ 0961 '7Tf rmnuu d~6x 1DGcoacd -
s"a _c 1932 PROJECT O.--Tsttute PROJECT REPORT FORM COOPAAT.OR_- u-= REPORT O 35--- DAT Karch 29 1960 Cones to: Fles OTE O Dr. Pearl (2) pa l and C 53 Mr. Beyer Donald.eyer L. THE ETHAOL ETRACTO OF MED ASPE PULP SAMPLES n June, 1959, Mr. Clyde Faulkender of the Charmn Paper Products Company, Green Bay, arranged for us to pck up a sample of mxed aspen unbleached pulp. The wet pulp was then partally dred n the centrfuge located n the pulp lab. Ths partally dred pulp was then bagged and stored n the cold. The mosture content was taken on each of the fve bags. The average mosture was about 65%. The total.o.d. weght of pulp was about 30 pounds. Three pckle jars were flled wth pulp amountng to a total of about 5800 grams ovendry. The pulp n each jar was then covered wth absolute ethanol. After standng for two weeks, the jars were empted and the pulp was squeezed as dry as possble, returned to the jar, and covered wth fresh ethanol. After another two weeks, the pulp was agan fltered. The dry pulp was stored under our number 1804-80-B. All the ethanol used n the extractons was concentrated to a small volume usng the crculatng evaporator to a volume of 3030 ml., 2725 grams. A total solds was taken and the sold content was 1.68 g./100 g. makng the total sold content 45.8 grams, 0.8% based on the O.D. pulp. (Sample 1804-80-A) A 100-gram O.D. sample of the pulp was extracted wth absolute ethanol n a Soxhlet extractor n an attempt to determne what type of yelds mght be expected. The extracton contnued for a total of 56 hours (7 days). The ethanol was then concentrated to a volume of 275 ml., 221 grams. The extract, 1804-78-A, contaned 1.92 grams of solds, 1.92%. Ths ndcated FORM 7-3 2500.7-56 THE STTUTE OF PAPER CHEMSTRY
Project 1932 March 29, 1960 Page 2 that by merely coverng the pulp, only about half of the extractves were obtaned. n January, 1960, Mr. Faulkender brought us two more pulp samples (see letter to Dr. Pearl dated 1-18-60). The one sample was unbleached poplar pulp, the Charmn number was 1-6690, B-5155, dated 1-14-60, Pop. K # 22.0. The weght of the wet pulp was 5500 grams. The mosture was 85.9%. The O.D. pulp amounted to 775 grams. The wet pulp was fltered to remove as much water as possble, The pulp was then covered wth absolute et-anol and left to stand for one week. The pulp was then fltered and the pressed pulp was packed nto several large Soxhlet extractors. The pulp was then further extracted wth absolute ethanol for one week (40 hours). All the ethanol used was combned and concentrated to a volume of 1650 ml., 1468 grams. Ths extract was labeled 1804-151-A and was found to contan 11.3 grams of solds, 1.46%. The second sample was bleached poplar pulp. The Charmn number was 1-6690, B-5155, dated 1-14-60, Pop. K # 22.0. The wet pulp amounted to 3690 grams. The mosture was 67.8%. The O.D. weght of the pulp amounted to 1188 grams. Ths pulp was frst covered wth absolute ethanol for one week and then fltered. The pulp was then extracted for one week (40 hours) n the large Soxhlet extractors. The ethanol used was concentrated to a volume of 1345 ml., 1231 grams. The extract was labeled 1804-152-A and was found to contan 16.0 grams of solds, 1.35%. All three extracts were stored temporarly. dlb/geh
t PROJECT O. _19327 PROJECT REPORT FORM cooperator, nsttute REPORT O. 3 -- DAM-- arch 31, 1960 Copy to: Fles OTE BOOK 1 Pearl (2) PA 0 7 7 85-91 Justman Readng Copy Olver Justman STUDES O'; TRACTVES OF ASPE PULPS Analyss of Fractons of Ethyl Alcohol Extract of Unbleached Mxed Aspen Pulp A 650 g. porton of the ethyl alcohol soluton contanng the extractves (1804-151-A) was evaporated to dryness n a rotary evaporator to yeld 5.OC g. solds. The solds were taken up n tetrahydrofuran whch dssolved most of the materal, but a consderable amount of a brown flaky materal remaned nsoluble. A few grams of Celte were added to the flask and the mxture was fltered through a Buchner funnel. The fltrate was evaporated to dryness n a rotary evaporator and yelded 4.69 g. solds (1834-70-A). An nsoluble materal remaned adherng to the nsde wall of the flask. Ths nsoluble materal was treated wth bolng 95% ethanol n whch t was partally soluble. On coolng, crystals formed whch were fltered off (1834-72-A). The remanng materal nsoluble n alcohol was treated wth 2% sodum hydroxde and went readly nto soluton. Upon acdfcaton a precptate formed whch was fltered off (1834-72-B). Column Chromatography An attempt was made to separate the components n fracton 1834-70-A by column chromatography. The sample was taken up n tetrahydrofuran and the soluton was adsorbed on 15 g. of alumna whch was packed on top of 140 g. of alumna n a o. 3 glass column. The column was eluted wth 1800 ml. FORM 7.3 2500-1-57 THE STTUTE OF PAPER CHEMSTRY
l Project 1932 "arch 31. 196C Page 2 of petroleum ether, 1800 ml. of benzene, 1POC rl. of chloroform, 180C rl. of 95-3 ethanol, and 1800 ml, of 956 ethanol-l acetc acd. The followng fractons were obtaned: Sample o, Solvent Sarple Descrnton Weght 1834-71-A Petroleum Ether Clear Ol 0.56 g. (65-110 C.) 1834-71-B Benzene Yellow Wax 0.9? g. 1834-71-C Chloroform Lght Yellow Wax C.80 g. 1334-71-D 95-, Ethanol grown 'Wax 0.45 g. 1834-71-E 95$ Ethanol-l% Brown Ol 0.86 g. Acetc Acd (Ether Soluble) 1834-71-F 95$ Ethanol-l% Sold 0.41 g. Acetc Acd (Tetrahydrofuran Soluble) Total 4.06 g. Paper Chromatography of Fractons The fractons were chromatograohed on Whatman o, 1 paper mpregnated wth mneral ol (7 g. mneral ol n 100 ml. of ether). developed for 15-16 hours wth 85% acetc acd at 37 C. The papers were The ar dred papers were scanned wth ultravolet lght, odnated, agan scanned wth ultravolet lght and fnally sprayed wth phosphomolybdc acd. Duplcate papers were staned wth mercury reagent. The chromatograms were mmersed 15 mnutes n a soluton contanng 0.1% mercurc acetate and 0.05% acetc acd. Excess mercurc acetate was removed by washng n runnng tap water for forty-fve mnutes. The papers were ar dred and the spots were located by sprayng wth a 0.25 soluton of s-dphenylcarbazde n 95Z ethanol.
Project 1932 March 31, 196C Page 3 Fracton 1834-71-A Rf Fl. 12 PmA Vg Corronent O.00 Dsrk 0.25 0.32 0.76 Fl. 12 WPA Hg = Fluorescence under ultravolet lght = Appearance of spot under ultravolet lght after odnaton = Phosphomolybdc acd spray = Mercury stan Fracton 1834-71-B Rf Fl. 12 Hg Component 0.00 Unsaturated Acds? Streak 0,00-0.05 x Unsaturated Acds? 0.15 ' Unsaturated Acd- 0.20 ' Unsaturated Acd 0.27 '? 0.30 ' Unsaturated Acd 0.36 ' Unsaturated Acd 0.45 ' Olec Acd 0.65 0.76 x
Project 1532' March 31, 1960 Page 4 Fracton 1834-71-C Fl. 12 PlA Hg Component 0.C0 Unsaturated Acds? o.oc-o.05 Unsaturated Acds? 0.20 0.25 Unsaturated Acd 0.31 Unsaturated Acd 0.36 x? 0.40 Unsaturated Acd 0.49 Olec Acd 0.65 x 0.76 x Fracton 1834-71-D Fl. 12 PMA Hg Conmonent 0.00 0.00-0.12 0+75 0.84 Pos.? Very Heavy Spot 0.89
Project 1932 "arch 31, 1960 Page 5 Fracton 1834-?1-E Fl. 12 PYA Hg Co-rponent 0.00 0.00-0.14 x 'C x 'C 0 *13 'C Unsaturated Acd 0.25 'C Unsaturated Acd 0.3 'C 0.38 'C Unsaturated Acd 0. 46 'C Stearc Acd 0.50 0.55 'C Olec Acd 0. 64 'C Lnolec Acd 0.75 0.*82 0.90 'C 'C Fracton 1834-71-F Fl. 2 PYA Hg Corrponent 0.*00 0.*00-0.*12 'C 'C 0.*72 0.*82 0.*8? 0.93 0.72-0.93 'C Very Heavy Spot
Project 1932 'arch 31, 1960 Page 6 The fractons were also chromatogranhed by the peracd method for the detecton of saturated fatty acds. The samples were spotted on Whatman Yo. 1 paper mpregnated wth mneral ol. The papers were developed 15-16 hours at 37 C. wth 6:1:1 acetc acd-formc acd-301 hydrogen peroxde. The spots were located by stanng wth mercury reagent. Fractons A, B, C, and D dd not show any spots, ndcatng the absence of saturated acds. Fractons E and F showed a number of spots. The spots appearng on the chromatogram of fracton F dd not appear on the other chromatogram developed wth 35% acetc acd. Perhaps the sample was not spotted n large enough concentraton. Fracton 1834-71-E Rf Component 0.38 Stearc Acd 0.,45 Palmtc Acd 0.59 Myrstc Acd 0.80? Fracton 1834-71-F Rf Component 0.00 Hgh Acds 0.00-0.15 Behenc Acd and Hgher? 0.27 Arachdc Acd 0.38 Stearc Acd 0.45 Palmtc Acd 0,54 7 0.59 Myrstc Acd 0.74 Laurc Acd 7
Project 1932 March?1, 196C Page 7 Fractons 1834-71-B, C, and E should be chromatorraphed agan wth 85% acetc acd along wth known samples of hgh unsaturated acds n order to dentfy the unsaturated acds whch apparently are present. Paper Chromatography of 1834-72-A and 1834-72-B for Phenolcs The nsoluble materal remanng n the flask after dssolvng the extractves wth tetrahydrofuran was chromatographed to determne whether the materal was phenolc. The samples were dssolved n 2% sodum hydroxde and spotted on Whatman o. 1 paper. The paper was exposed to the vapors of bolng acetc acd for several mnutes, allowed to dry, and developed for 22 hours n 3:10:3 pyrdne-butanol-water. A duplcate paper was developed n butanol-2% aqueous ammona. The ar dred papers were sprayed wth dazotzed p-ntroanlne. Both samples showed a graysh-whte spot at Rf 0.07 on the paper developed wth pyrdne developer. The same type of spots appeared at Rf 0.03 on the paper developed wth the butanol-ammona developer. The appearance of the spots suggests the composton of the materal to be ether norganc or more lkely alphatc n nature. o other spots appeared on the papers. Analyss of Ethyl Alcohol Extract of Bleached Aspen Pulp A 426 g. porton of the ethyl alcohol soluton of the extractves (1804-152-A) was evaporated to dryness n a rotary evaporator to yeld 5.5 g. solds The dry solds were extracted wth tetrahydrofuran whch yelded 4.69 g. materal (1834-85-D). An nsoluble materal remanng n the flask was treated wth bolng 95% ethanol. On coolng a precptate appeared whch
Project 1932 March 31, 1960 Page 8 was fltered off (1834-85-A). The materal remanng soluble n the cooled soluton amounted to 0.60 g. (1834-85-B). Column Chromatography The solds obtaned by extracton wth tetrahydrofuran were redssolved n the same solvent. A small amount of materal remaned nsoluble and was fltered off (1834-85-C). The soluton was adsorbed on 15 g. of alumna whch was packed on top of 140 g. of alumna n a o. 3 glass column. The alumna column was eluted wth 1800 ml. of each of the followng solvents: petroleum ether (65-110 C.), benzene, chloroform, 95% ethanol, 95% ethanol- 1% acetc acd. The fracton obtaned by eluton wth alcohol-acd was extracted wth ether and tetrahydrofuran to separate the organc from norganc materal from the alumna. Solvent Sample o. Descrpton Weght Petroleum Ether 1834-86-A Clear Heavy Ol 0.31 g. (65-110C.) Benzene 1834-86-B Yellow Ol 0.82 g. Chloroform 1834-86-C Yellow Ol 0.92 g. 95% Ethanol 1834-86-D Brown Sold 0.78 g. 95% Ethanol-l% Acetc Acd 1834-86-E Brown 0.42 g. (Ether Soluble) 95% Ethanol-l% Acetc Acd (Tetrahydrofuran 1834-86-F Brown 0.53 g. Soluble) Total 3.78 g. The fractons were chromatographed reverse phase on mneral ol mpregnated paper wth 85% acetc acd developer for 15-16 hours at 37 C. The papers were scanned wth ultravolet lght, odnated, agan scanned wth
Project 1932 r'arch 31, 196C Page 9 ultravolet lght, and fnally sprayed wth nhosphomolybdc acd. Duplcate papers were staned wth mercury reagent. Duplcate papers of Fractons 1834-86-A, B, and C were also sprayed wth slcotungstc acd spray and antmony pentachlorde spray. These sprays have been used for the detecton of sterods. Known samples of fatty alcohols (Adol 22 and Adol 60) showed whte to tan colors when sprayed wth these reagents. A known sample of /-stosterol gave reddsh colored spots. Fracton 1834-86-A Rf Fl. 1 PMA Hg S SbC19 Component 0.00 Blue Red Tan 0.OO-0.07 Blue 0.87 Blue S = 25% SbCl 5 = 205 Alcoholc soluton of slcotungstc acd Antmony pentachlorde n chloroform Fracton 1834-86-B Rf Fl. 12 PMA Hg S SbCl 5 Component 0.00 x Blue Brown Tan 0.00-0.14 Blue 0.17 0.30 0.37 Blue Acd? 0.42 0.79
Project 1932 March 31, 1960 Page 1C Fracton 1834-86-C Rf Fl. 12 PMA Hg S SbCl 5 Component 0.00 Tan Tan 0.00-0.10 0.00-0.21 Blue 0.39 Blue 0.45 0.95 Blue Fracton 1834-86-D Rf Fl. 12 PMA Hg Component 0.00 Blue 0.82 Blue 0.92 0.970 Blue Fracton 1834-86-E R Fl. 12 PMA Hg Component 0.00 Blue 0.34 Stearc Acd and Unsaturated Acd 0.46 Palmtc Acd and Olec Acd 0.57 Blue Myrstc Acd and Lnolec Acd 0.71 0.90 Blue Acd? The fractons were also chromatogranhed by the peracd method for the detecton of saturated fatty acds. Fractons A, B, and C dd not show the presence of saturated acds.
Project 1932 Yarch 31, 196C Page 11 Fracton 1834-86-D Rf Component 0.90 Acd? Fracton 1834-86-E Rf Component 0.00 Hgh Acds 0.08 Behenc Acd? 0.22 Arachdc Acd 0.34 Stearc Acd 0.46 Palmtc Acd 0.57 Myrstc Acd 0.90 Paper Chromatogranhy of Fradtons for Phenolc Components The materal nsoluble n tetrahydrofuran (1834-85-C) and the materal crystallzng from the alcohol (1834-85-A) were chromatographed wth 3:10:3 pyrdne-butanol-water. Sample 1834-85-B was also chromatographed. Duplcate papers were developed wth butanol-2% aqueous ammona. The papers were sprayed wth dazotzed p-ntroanlne. o phenolc components were detected. Fractons 1834-86-A, B, and C obtaned by eluton of the column wth petroleum ether, benzene, and chloroform were also chromatographed as above. The chromatograms dd not yeld any evdence to ndcate the presence of phenolcs. Fractonaton of 1834-86-C The fracton obtaned by eluton of the alumna column wth chloroform was taken up n bolng 9 5? ethanol. On coolng and standng
Project 1932 March 31, 1960 Page 12 several days an ol separated out. The alcohol was decanted from the ol whch gradually hardened on standng (1834-91-A). varous sprays. Sample 1834-91-A was spotted on Whatman o. 1 paper and sprayed wth Spray Antmony Pentachlorde Slcotungstc Acd Phosphomolybdc Acd Color Red Brown Tan (Reddsh) Blue The colors obtaned wth sprays ndcate the possblty that the materal may consst of a sterol and further examnaton should be made for dentfcaton. oj/geh
PROJECT REPORT FORM ~ PROJECT O. 1--9--_--?... COOPERATORnsttute REPORT O.-------3--- DATE_ porl 5, 1960[ Copes to: -les OTEO 1804 Dr. Pearl (?) PAGE 4 0-149C an4 53-155 r, Beyer GED - Dona L. er THE CAUSTC HYDLCLYSLS CF S..L b'-gl. P.D -KS L3SO SC n project 1932, report number 33, the caustc hydrolyses of the barks of varous Populus speces were descrbed. Snce the wllows belong to the same famly, t was decded to hydrolyze the wllow harks also. At the present tme, only one bark s avalable; that beng Salx nlra. The sample of Salx ngra that we have was cut n the ravne behnd the nsttute. The lower porton of the trunk was dark and rough. Ths bark was peeled, chpped, ar dred, and fnally '.ley mlled. The dry ground sawdust was bagged and labelled 1804-90-D. Ths tree contaned very lttle smooth green bark. Ths bark s usually found on the upper secton of the truck as well as on the smaller branches. Ths tree, however, was covered wth clmbng vnes whch were apparently stranglng the tree, therefore, there were very few branches. A lttle smooth green bark was obtaned from some very small branches. Ths bark was ar dred, and W'ley mlled. The dry sawdust was bagged and labelled 1804-90-E. Both of the bark samples were hydroyzed n the same manner. A ffty gram sample of oven dred sawdust was treated wth 60 grams of sodum hydroxde dssolved n 1500 ml. of water. The mxture was strred and boled under reflux for 8 hours. Then cool, the mxture was fltered, and the sawdust was washed wth water. The fltrate was acdfed wth dlute sulfurc acd and was extracted manually wth ether. The ether soluton was concentrated to a small volume, weghed, and a total solds determnaton was run to fnd the yeld of extractves. The ether solutons were FORM 7.3 2500-1 57 THE STTUTE OF PAPER CHEMSTRY
Project 1932.prl 5, 3]96 Page 2 then chronatographed, both qualtatvely and quanttatvely. The qualtatve chromato:;rams for the two bark extracts were dentcal. Developed wth butanol-2. aqunous ammona. Rf PA 1'B: 2,l _. t-rule Fluor. FeC1 0.00 yellow 0.02 0.0o yellow blue A Syrngc acd 0.10 purple :; Vanllc acd 0.12 0.14 pnk blue-gr. p-hydroxybenzoc and ferulc acds p-coumarc acd 0.18 blue 0.38 green x Syrngaldehyde 0.44 volet.- Vanlln 0.50 yellow x x( Acetosyrngone 0.60 volet Acetovanllone 0.88 pnk Lt. blue* Developed wth butanol-pyrdne-water (10:3:3) 0.00 0.04 0.18 yellow yellow yellow * Ths spot lght blue wth ferrc chlorde only for sample 1804-145-A (green bark). The spot - BuOH Rf 0.88 and Py. Rf 0.B4 s much larger for sample 1804-145-A than for sarple 1804-140-A. The spot s estmated as beng at least ten tmes as large.
Pro Ce:t 1932 -prl 5, 1960 Page 2 :f P.: BaP?,L-_:.!aule Fluor. FeCld - 0.27 yellow 0.38 blue : Syrrnc acd 0.44 purple Vanllc and ferulc acds 0.56 pnk p-;!ydroxvbenzoc and p-coumarc 0.78 blue-gr. '. Syrngaldehyde and acetosyrngo 0.84 pnk -th Lt. blue* Vanlln and acetovanllone yellow * Ths spot lght blue wth ferrc chlor-!e only for sample 1804-145-A (green bark). The spot - BuO! :lf 0.88 and Py..f 0.P4 s much larger for sample 1804-1,15-A than for sample 1801-140-A. The spot s ostrtted as beng at least ten tmes as large. The data obtaned from the two hydrolyses follows: Zsther extract: Code no. Yeld, grams Yeld, percent rough bark 1804-140-A 2.17 4.34 Green smooth bark 1804-145-A 2.79 5.58 Quanttatve determnatons: mg. % of ext. mg.. of ext. Vanlln 5.0 0.2 9.0 0.3 Syrngaldehyde 9.0 0.4 12.0 0.4 p-hydroxybenzaldehyde none none Acetovanllone 15.0 0.7 14.0 0.5 Acetosyrngone 6.0 0.3 7.0 0.2 Vanllc acd 74.0 3.4 62.0 2.2 Syrngc acd 78.0 3.5 76.0 2.7
ProTect 1972.-prl 5, 1960 P.ge 4 mg. % of ext. mg. < of ext. Ferulc acd 96.0 4.4 44.0 1.6 p-hydroxybenzoc acd 50.0 2.3 60.0 2.1 p-counarc acd 28.0 1.3 28.0 1.0 The Hydrolyss of Salcn A mxture of 5 grams of salcn, 60 grams of sodum hydroxde and 1500 ml. of water was strred and boled under reflux for 8 hours. The soluton was clear. The soluton was acdfed wth dlute sulfurc acd and extracted manually wth ether. The other soluton was concentrated to a small volume and a total solds determnaton was run. of solds. The extract, labelled 1804-153-A, was found to contan 1.29 grams 25.8)' ;' The ether extract was chromatographed together wth authentc samples of salcyl alcohol and gentsyl alcohol. The papers developed wth butanol-2% aqueous ammona showed only a sngle spot at Rf 0.88. The spot was blue to ferrc chlorde. The spot was yellow to PA changng to pnk after the sodum carbonate spray. Ths spot matched dentcally wth the authentc salcyl alcohol. The authentc gentsyl alcohol was located at Rtf 0.05 and showed a lght greensh color to PA. When developed wth butanol, pyrdne, and water (10:3:3), the only spot found had an Rf value of 0.86. Agan ths matched wth authentc salcyl alcohol. The gentsyl alcohol was located at Rf 0.82 streakng from 0.50 to 0.80. From ths data t also becomes apparent that salcyl alcohol could very probably be present n the bark hydrolyses of wllow. The spot located at Rf 0.88
Project 1932 Aprl 5, 1960 Page 5 on the butanol developed papers and at :f 0.F4 on the pyrdne developed papers showed blue to ferrc chlorde ard also pnk to FfA. Addtonal barks of the Salx famly wll probably be obtaned n the sprng of the year and addtonal data wll then be accumulated. dlb/lc
PROJECT REPORT FORM ROJECT O..1932 ------ _ cooperatorlnstte_- REPORT O.- 38 -- --- Pages: 1304: DATE-unee3o,1960_ Copes to: Fle- 155-160 OTE BOOK 1Q_&4andl_1121 - Dr. Pearl (2) 1121: PAE -TO Yr. Beyer 102-121 WsED 125, 135 'dnald L. Beye A COLD CAUSTC YTRACTO AD CAUSTC HYDROLYSS OF ASPE SAT-UST. Several years ago, a sample of authentc Populus tremulodes sawdust was hydrolyzed wth caustc. The data obtaned from that hydrolyss was reported n project 809-13 report number 29. The saw dust used n that hydrolyss carred our number 1093-115-C. n ths report, we wanted to determng what compounds, f any, could be obtaned from Aspen sawdust by a cold caustc extracton. Also, we could learn f sawdust after standng for several years would yeld the same results as when freshly cut. A 100 gram sample of sawdust (1093-115-C) was covered wth 3000 ml. of water and 120 grams of sodum hydroxde were added. The mxture was strred for 8 hours, then allowed to stand over nght. The mxture was fltered and the fltrate was acdfed wth dlute sulfurc acd and extracted manually wth ether. The ether soluton was concentrated to a small volume and a total solds was taken. The extractve yeld amounted to 0.86 grams. Ths frst extracton was labeled 1804-155-A. The sawdust was agan covered wth 3000 ml. of water and 120 grams of caustc were added. The mxture was agan strred for 8 hours and then allowed to stand over nght. The mxture was fltered, the fltrate was acdfed and extracted wth ether. The ether contaned 0.27 grams of extract and was labeled 1804-156-A. The sawdust was covered wth water and caustc for the thrd tme. After 8 hours of strrng, the mxture was allowed to FORM 7-3 2500.1 57 THE SnTTUT OF PAPER CHEMSTRY
Project 1932 June 30, 1960 Page 2 stand over the week-end. Agan the mxture was fltered and the fltrate was worked up. Ths thrd extracton yelded 0.13 grams of solds and was labeled 1804-156-B. The sawdust was treated for the fourth tme wth caustc and water, strred for 8 hours and allowed to stand overnght. Ths fourth extracton yelded 0.13 grams of solds (1804-157-A). The sawdust was once more covered wth 3000 ml. of water and 120 grams of sodum hydroxde were added. Ths tme, however, the mxture was strred and boled under reflux for hours. 'hen cool, the mxture was fltered and the fltrate was acdfed wth dlute sulfurc acd. The acdfed soluton was manually extracted wth ether. The ether soluton yelded an extract amountng to 0.40 grams (1121-102-A). Another sample of the Populus tremulodes sawdust (1093-115-C) was taken and hydrolyzed wth caustc. A 50 gram o.d. sawdust sample, 60 grams of sodum hydroxde, and 1500 ml. of water was strred and boled under reflux for 8 hours. The mxture was fltered and the fltrate was acdfed and extracted wth ether. The yeld amounted to 1.33 grams, 2.66% and the extract was labeled 1121-107-A. results: The sx extracts were chromatographed wth the followng 1st extracton (1804-155-A) - p-hydroxybenzoc acd, vanllc acd, p-coumarc acd. 2nd extracton (1804-156-A) - 3rd extracton (1O04-156-B) - p-hydroxybenzoc acd and vanllc acd. p-hydroxybenzoc acd only.
Project 1-3~2 June 33, 1pc Eydrolyss ex:tracts-: Develooedw h butanol 2;; aqueous armona. Page 2a 112 1-102-A Rf PA 2,4-D. rbule Fl. PA 1121-107-A, 2,4-D. Maule Fl. 0.00 Brown Brown' 0.08 Blue x Blue K yrng a acd O.10 Fur pe Purple Vanllc acd 0. 12 0. 14 Pnk Green K Pnk Green p-bydroxybenzoc acd (fl1. ferulc acd) p-coumarc acd 0.18 Blue 0.33 Green x x Green AC K Syrngaldehyde 0. 44.Volet K Volet K Van ll n 0.50 Ye flow x K Yellow K K Acetosyrngone o. 6o Volet K Volet K Acetovanllone 0.88 Pnk P nk Developed wth butanol, pyrdne, water (10:3:3) 0.00 Brown Brown 0.02 Brown 0.16 Yellow Q.27 Yellow 0.38 Blue K Blue K Syrngc acd 0. 44 0.56 0.73 0.84 Purple Pnk Green Volet K K K K Purple Pnk Green Volet K K K Vanllc acd (17l. ferulc acd) p-hydroxybenzoc & p-cou~marc acds Syrngaldehyde & Acetosyrngone Vanlln & Acetovanllone
O p~oe oujewwo~d ptoe e OVL~Oj plow o-mujwas plot 01ltrueA *uo2uja"sflaoy *pt4apr ezuoc~xaopxh-d opxqap~er2uaas Ur nwea ~-'OA (;4Snpnes 'S 001 uo poses) ;:4oezxo Jaq'4 3 H H 4' - co Q) (~ -L 0 0 c.~ -ape Gem S!SA~vue ou.ztfqqo n o ;uasead Sen ppeu ottujoj Ou.10j4401 usnjuy OU G; Ct-6Eas ;oafoad '6Z Ou w40do UT flv, teurwo O * 5 911 Z' 9 0'6 Q1 Vt O-CrC ('at WUT a- 's. 917 ('at o saz emuc~ C '9c - -lou cra 019 pou9.uoqop ;0u poutwqoop OU *1*1 90T -ou 9'0 a-s 6Z a9 0'6 C' 01 Cez 9'1 9*0 9.0 l Cr o'6 5 9 Ole - macu - Qmuo - wzou - QUOta - QUOU - em0u - QUou ' n 01 0t - GUOUa - -lou CZ Oc175 l a ' 17 : ZVT 9.Z ;4xa Jo % 2wo 9'T La.- 5xeO 0 Z11 VO 09c CVT 01?qT 0 T1 '2u ;4 JO % G'tZ 9Lt 47' 47 'xg Jo % Vt s-az, LT * 3m - emau - -lou - suot ;G JO % '2w - Gna - 0muc -.xo Jo % Sz~.,4Q - QUOUa Jo % 'Sm '2 99C 2 W '2 &4-0.2 elcc.2 95 v-gqtt-c6o 0 T v-ta1t-t v-ear-trtt 0l95-1t47og Y-99a--1 1 91r.STSTOpCB '2Wa l40e;g SGst'EWPSq Plau noa, l43eflzo GSSLT PLH uonoe0nxs Pa( U0Cf1.40WQ Puz UWflOeZO Sl Jsf.l-S r-u0'fafu -SMEMld AO SSDO?1t11 ZSOY CY OJDflV~f OJSOYDO MOD MU1 01 SZUS2H aanvalvlt
Project 1932 June 30, 1'60 Page 3 4th extracton (1804-157-A)- showed nothng. The presence of ferulc acd n the ether extract of the hydrolyzed sawdust after havng been extracted wth cold caustc (1121-102-A) was hghly unusual, snce ferulc acd has never been found n any hydrolss of Populus tremulodes. t was decded that more defnte proof was needed to verty the presence of ferulc acd. A complete rerun of the experment was made. Another 100 grams of the same Populus tremulodes sawdust was strred n caustc for 8 hours as before, fltered and fresh caustc was added. n all, the same four extractons were made, after whch the sawdust was boled n caustc. The resultng ether extract (1121-113-A) showed the dentcal chromatographc results as dd extract 1121-102-A. A sample of the extract, 1121-113-A, was streaked on several papers and developed wth benzene saturated wth formc acd. The area contanng both the ferulc acd and vanllc acd was cut from each paper. The paper strps were extracted wth 95% ethanol n the mcro-soxhlet extractors. The extracts were combned and streaked agan on paper and developed wth 0.31 sulfurous acd. The strongly fluorescent band was cut from the paper and treated wth 0.2% alcoholc potassum hydroxde. The UV curve of the soluton was then read on the recordng DK-2 spectrophotometer. The resultng curve was nothng lke the ferulc acd curve, Fg., wth peaks at 263, 257, 251. All chromatographc data so closely matched that of ferulc acd that t was decded to work up the entre sample, ether provng
.t-s nf fl1w Vt ~&A.. //A na--t -7. *, flt OSTY L - F- BE1 (R MRh 2 flltcwmwaw - 7lT. p : : m.. : p.1.. 1 l-.,.1 wmto ~ vat. ~ /,a ea ;- ' a j a Mo a a Fl s. Z - fl O 520 5 Mo
Project 1932 June 30, 1960 Page 4 the presence of ferulc acd or possbly obtanng suffcent matter to determne what-t mght be. The entre sample, 1121-113-A, was streaked on several papers and developed for 40 hours n n-heptanebutyl ether-water (6:1:1). When dry, the same papers were developed for 7 hours n benzene saturated wth formc acd. When dry the papers were cut nto four sectons. 1. Baselne down to 3 cm. 2. 3 cms. to 10 cm. 3. 10 cms. to 22 cm. 4. 22 cms. to solvent front, 45 cms. All four samples were extracted wth 95,' ethanol n Soxhlet extractors. The ethanol solutons were then concentrated and chromatographed. On the followng chart showng the chromatographc results, - normal amount, H - heavy amount, and T - trace of materal. Developed wth butanol 2% aqueous ammona.- Rf 1 2 3 4 0.00 0.08 H T Syrngc acd 0.10 T H Vanllc acd 0.12 p-hydroxybenzoc acd, underlned ferulc acd. 0.38 T T T T Syrngaldehyde 0.44 T T T T Vanlln 0.50 T T T T Acetosyrngone o.60 T T T T Acetovanllone 0.83
Project 1932 June 30, 1l60 Page 5 Rf Developed 1 2 wth butanol - pyrdne - water (10:3:3) 3 4 0.38 T Syrngc acd 0.44 Vanllc acd, underlned fluorescent 0.56 p-hydroxybenzoc acd 0.78 Syrngaldehyde and acetosyrngone 0.84. Vanlln and acetovanllone Rf Developed 1 2 wth 0.3 sulfurous acd. 3 4 0.00 0.07 0.27 Underlned fluorescent (ferulc acd) 0.40 Syrngc acd 0.45 Vanllc acd 0.54 T p-hydroxybenzoc acd 0.66 T T Syrngaldehyde 0.73 T T T Vanlln Samples 2 and 3 were combned and spotted agan on several sheets of paper and developed wth 0.3 J sulfurous acd for 20 hours. Agan the papers were cut, ths tme nto fve sectons. 1. Baselne to 6 cms. down 2. 6 cms. to 11 cms. fluorescentt) 3. 11 cms. to 18 cms. 4. 18 cms. to 25 cms. (brghtly fluorescent) 5. 25 cms to bottom of paper
Project 1932 June 3C, 1'60 Page 6 All the sectons were extracted and chromatographed. Developed wth butanol - pyrdne - water (10:3:3) Rf 1 2 3 4 5 0.38 Syrngc acd 0.44 Vanllc acd, underlned fluorescent 0.56 p-hydroxybenzoc acd 0.78 T Underlned fluorescent 0.84 Developed wth 0.3 sulfurous acd. Rf 1 2 3 4 5 C.00 0.07 T 0.27 Underlned fluorescent (ferulc acd) 0.40 Syrngc acd 0.45 Vanllc acd 0.54 p-hydroxybenzoc acd 0.66 T 0.73 T From the chromatographc data, sample o. 4 appears to be almost pure ferulc acd. Ths sample was agan streaked on several papers and developed agan n 0.3 sulfurous acd, ths tme for 15 hours. Each paper showed a brghtly fluorescent area. The brghtly fluorescent foward porton was cut as sample o. 1 whle the tralng fluorescent porton was cut as sample o. 2. Both were extracted wth 955' ethanol. A sample of o. 1 was treated wth 0.24 alcoholc potassum
- Project 1932 June 30, 1960 Page 7 hydroxde and was mmedately run on the DK-2 recordng spectrophotometer. The sample was then stood for about fve hours n the lght and another curve was run. As reported n project 809-13 report number 39, the ferulc acd curve shfts n poston wth a change n the peak untl the soluton becomes stable, Fg.. The two curves run for the sample obtaned from the hydrolyss also shfts upon standng. The curve for the stable soluton have the peak at 332 x whch s the peak assocated wth ferulc acd, Fg.. Snce no ferulc acd was found n the extract from a regular hydrolyss of Populus tremulodes. and snce ferulc acd has now been found n the extract of a hydrolyss whch has been subjected to a caustc soluton for a perod of days, two more sawdust samples were set up to be hydrolyzed. The frst sample was boled under reflux for 8 hours as a regular hydrolyss would be; however, before workng up the hydrolyss t was allowed to stand for 7 days. The second hydrolyss frst stood for 7 days and was then strred and boled for 8 hours. The ether extract of the frst hydrolyss yelded 1.0 grams sold and the yeld of the second hydrolyss was 1.2 grams. Both showed the same chromatographc data whch was also the same as sample 1121-102-A and both showed fluorescent evdence of ferulc acd. dlbl/ak
L L t p ±.. a -J C C W-t -1. l- - = - * 9p 3 on.x...n Te 4- -J -< t s ~ - --- - Pt1. - n.-- ---. --- -1 -- -4-.-- - t-- --- - -. -l..... 1 $. t F tf r - r ~! ~~.~ 4. - 7*0 -- 001--- r - - 7/ m -a LL. = 4 a.: 7 4-2\ T --f, - a- VA Fw-p.7l3d31f bnt -,.najv A7L7 OE-3m 17V VMVJ CSa V ' TYTLS.. r+th+ f4- - 1 CQfl 31Jwd&1S -4 -, -blnf J fl fla s n asn L.! 4-4- t;ra--, - r h 7 T fln m r 7 - -- - -. - U W J J3 - - -1
Oct! : _ -4-- v 7!.xY7F t On ly r r-!-.. - ~ alt ----- ~,-e j- Lw tktt - Ak> ~ Tt 4 Ma " o =1- L. - +.. 6 +-H.'! 1; 4- trth±hh1 F-4-r.,!. f. -. ::,.1'. 1 14 W.tOc Ma e -7747= OA_-_'- * 4 ' 1r * - 2 F, ': : : :! Wd 111 t,- 1- --- --- - - -- - 1_ To'-, 4 : r-,-- ;-: 4. --t-,, rr. -. T - H4 00 On -* 1-0 0/ 03d -a uqxs a Ff 4 V K! - A1 F 7. r M. Y-7-.P - \ - Y.,G;;; s~ 1 5w/A~ r '.af. pm _E7OW_/VS -- H-- H+.,. r r tsr- A.,L.%en..~ no.at at HH, _+, r - PF, L ; 1 :- ½'M M..~!4t, 144-.-. rk rhtrr 4-- --,'4t4 -'-w -W- - :-l~- 4 T- -1 T4 44V. L T'T,-1 mrr~~anrm1 6.-l f 1- P _H R :- ±-l -- ~t-# r+- - -~h H-lP- f-._:4 -. j_._l hr11- V - _Ww - WYUW) MJ93 t
PROJECT REPORT FORM PROJECT O._193 COOPERAToR--nsttutl REPORT O. -39 DATr July 1. 1960 Copes to: Fles Pages: 122-124 OTE n 1121 Pearl (2) 126-129 PAGE - - - Beyer 136-150 MS Readn4 -Ca y Donald L. eer A COLD CAUSTC ETRACTO AD CAUSTC HYDROLYSS OF ASPE SAWDUST.. n Project 1932, Report umber 38, t was found that when Populus tremulodes was allowed to stand n a cold caustc soluton for a perod of tme and then hydrolyzed wth caustc, ferulc acd was found n the ether extract. The followng experments were run wth a dual purpose n mnd, frst to see f a new sample of sawdust would produce the same results, and secondly, to see how long a perod of caustc treatment was necessary to produce whatever change that takes place. The only Populus tremulodes sample avalable at ths tme were chps obtaned from the pulp lab and carred ther number 1800-T-23-59 (notebook 1816-48). The tree sample had been cut by the Genetcs Department on Aprl 14, 1960, the tree was labeled T-23-59. Ths tree was dentfed as a trplod aspen. The chps, when ar dred, were Wley mlled and labeled as 1121-122-A. The wood used n the experments reported n Report umber 38 was beleved to have been a dplod aspen. Ths was merely the opnon of the Genetcs Department, snce no postve dentfcaton was made at the tme the tree was cut. Sx separate hydrolyses were run on a trplod aspen sample. The frst hydrolyss was done n the normal manner--the sawdust was covered wth the caustc soluton and boled under reflux wth strrng for eght hours. The next day, when cool, the reacton mxture was fltered, acdfed, and extracted wth ether. FORM 7-3 25007.56 THE STTUTE OF PAPER CHEMSTRY
project 1932 July 15, 1960 Page 2 The next four hydrolyses were done after the sawdust had been allowed to stand for a perod of tme n the caustc soluton. The sawdust samples were left to stand for 3 days, 7 days, 10 days, and 14 days before the mxture was boled. All the experments were worked up the day followng the eght hour bolng perod. The fnal hydrolyss was boled under reflux wth strrng for a perod of 37 hours. n ths experment, as n the frst, the heatng began as soon as the caustc was added to the sawdust. All sx hydrolyses were worked up wth the followng results: Ether Code o. Extract Yeld, grams % Based on Sawdust Weght 1. Hydrolyzed at once 2. After standng 1/2 week 3. After standng 1 week 4. After 1 and 1/2 weeks 5. After standng 2 weeks 6. Boled 37 hours 1121-126-A 1121-123-A 1121124-B 1121-136-A 1121-136-B 1121-124-A 1.18 2.36 0.99 1.98 1.14 2.28 1.08 2.16 0.95 1.90 1.61 3.22 From the above data t becomes apparent that there s essentally no change n the yeld of ether extractves due to any cold caustc treatment. However, an ncrease s noted when the sawdust s hydrolyzed for a longer perod of tme. The sx extracts were then chromatographed. All the extracts showed dentcally the same materals. Ferulc acd was found n every sample. Ths s the frst sample of Populus tremulodes sawdust that yelded ferulc acd on
PTZ~l Z) TREJTass x an~q AOfl3x AOfl9 ge~ 0 Le, o 9t 0 av0. 00*0 (E:e:or) :awtv - upttd- TOulflfq 1fTA paddy~a(ja 99 0 c9.0 GUODUTax sospow C AOTTQ UT PTDL' :)Ta- urnoo-d Ua2Jfl SpToR DTra PUfl otozuaqqxo PTDR OT TTTu'RA C 49TOTA 2UTxCs x x ua~ S.rpAR-d PT3v OTRUTxRs C an~q UT amnaw.cl-11 V~c BTuoawm snoanbv %P{Tou9nq mn4ra P~dOTQAaG og 0o 11' 0 ge, 0 lr0 FT' 0 OT* 0 9000 00* s ;nsaj 3Thdvj~oqWWoxflD 'P2ZCOJ:PTl aq 4S11W otdmffs st; Put UaCsB PTOTdVp GT44 JO admesaoafts~od P u~vwvqo a; 1 C12s033au samooaq ;-p sapto-hu3j sn~dog onmaq,.~nn sfla yr qut" 4daoxa paz~oxpa~j A-rsncTA~ad poo,4 at;.jo n~qnmxrnq atfl a; s s s;5xa.joosd 9AT;TSqd ou ao~ 'flaqaafl -o q art; uaaa~aq RouRJ2JJTp 9t14 a4on a; RU 4a~ W ATSuTsnOOuT sao3q 14 'SPTOTdTp Tn 3.r3A ;svd ~l'n 11 T 9P~ Glq4 4q4q SUTunssV STSTbOPcq ot.srnn c96t 'gy ~Tnp a~e6t 43oCaJal
Project 1932 July 15, 1960 Page 4 Rf PA 2,4-D Maule Fl. 0.44 Purple Vanllc and ferulc acds 0.56 Pnk p-hydroxybenzoc & p-coumarc acds 0.78 Green Syrngaldehyde and acetosyrngone 0.84 Volet Vanlln and acetovanllone All sx extracts were then chromatographed quanttatvely. The results follow. From the results, t becomes apparent that no change occurred by the cold caustc treatment. The prolonged bolng showed an effect only on the syrngyl materals. Syrngaldehyde and acetosyrngone show an ncrease of about three- tmes as much as n the other extracts, whle syrngc acd showed better than twce the amount. The other materals o*wed essentally no change.
1rO gt 9'91 Eco' PT 9a1 aoo 6,o o.01 eo~o 6Ec o'o O'O 9'T 41T o'o T 941T eo o 6'o fl17tw 0O9 1.) Oo T.0 99q zmo 6,o 001 CCo' 90o < COo S.C g'6 90'0 9'3 PE~1 ~'0 6T 9'gx o'o T YET To'o L'T ggt 10*o oma g%1t t?0 91T P6T 'O 0T '991?00 mlt 96 3O'O 0T 90OT SO OT 911T ayoo 90 Qq'.?O0 0 Wo coo o'o 9'0 9gaT T0-0 90 0' 900oo,0 fo 0 'O Tr 6omo, 10.0 91yt 4om'o eoo 9aE amoo s0 % 100O o P17!oco' <.0 9 E!oo~o 0 9 e go mo' t o 0¼7 7oco' F c maf 4o0 o atro 6 E P39 oo 91T tl O'~oo L T 0 9 13 1y00 Q 6 cra FF O' L af Oeta 4O'o a ~ a E 99a Vlya1aTF Er-9 11aflT V-9ET-aTl ff-je-t3tt V-eaT-TM v-9a1t-at 2cO PF 1 4~L( * (SMe2-xS o~) ptz-cjp~q atdmrrs ;snp'tns GT44 JO 4WS2Tam atq; no pas eq st Eq-, 0p 4 3-\ ;w~'mx aqq JO 4qSaA a~qq ua paasq st B-, Leo 9 TT 9 991TKVo Trgx o'f)t1 1Vo g'~ 'OLT 9 L 91 01T6T E0 t<lx 9 L ~ *0 9'1yT 9'FLT 70.0 a1, 9,6T E 'c 1(1 P F ct O'O aut T o'o FC 0½' Y OO L T 9'9T1 fj 1 0 9T 9'LT O'0 T1T PLT EO00 ac q-%4 '- 'Sm q-% ec 911T ama ot nt ooo 6 o *Stn q- ~ e- q-% BO-% g0o acre 11T- 9 01T ao-o 6 901O 'Sw q-% ~-% doqm sacu0'alt sflfmldod Cl0'Mu go0 STSYTOHG 3RZ H0J smrmsah aavlvflbh
(suresd 04) PazA~oWpJtq a-plums ;snptves alq4 jo ;rjq?;ax at4;. uo paseq 9T q$% qomqpxa atfl jo!~{9am at{; uoc pp 9T v- )9T ~e'o T'9T oab)t t 1 7P g9'rt PoLE qpo L,91 0,T6T 4Po glt g9eur gvo Tt?T 9BFLT.PTOB otozuaqb-opaeg-d FT Eo'o PT 9BFT aoa 6,o 001o e00 &t 6 0 lot e0'o0 9T - 94T E0'O PT 941T plon otavmnoo-d PWB' OTtns;;a PTO9 OT9UTSA3 T FoO 0 OT 96 F0o' o1t 9c a F' OT ' 9-TT ao o g0o g1 BYO' g' o ot PTO8 OTTTTU73A apxqaprgbut-ss UTTTTU'UA (T TWO 9.0 PA To, 9 To 9q ao o 6' o 0.01 TUC 90 P4g Fo00 g0 g'6!1 7o 1 T 00 61t L'gl oo PT 9Et tly00 LT 9 9T 1?00 o~e g'6t 1 1 oy0 9 T P6 :T TW0 g'a o*4 g Loom go, qfo 0 Le Loomo w'o o,~ 6ocoo Pa 4'E g90cm ra ff0 4'1y OO'O o'o g4? Too 9-0 P6 O. 1T.000 g o O'F oo'o FB C PB auo2upx.tso4aoz GuOTTTU'BAOqWOV 1 cyo ~'T PET LamO CT PET LaO CT 01y1T L0'0 LT 9 91 *fo*0 LT 441T ap,~qep~zueq~xoapg-d :9 E0ra 9-T LLT WOo LT o'rt ~0mo 6'T o,0 go 4ro A',-6, ~o?, c;g 99e 1T Oam FT gtt Fama 0'T PTT B00o 6La gmt BO TT 9'0T Fam 6,o 90oT.2m q-% e-%.2wu B -.% U-% E-9ET1BFTT v-9et-tgtt E-17FT-tFTT V-ECT-TFTT V-981-1T1T ClooM SawCa 1TgjUL Snraoa Q102d8n JO SS'O&C ML Hod SnnSaU MlLMD~h~ b