3693
JOCR:-AL OF POLY:\IER SCIE:-CE, Polymer Chemistry Edition YOL. 13. 1-HI-1-156 iIQ75l
Starch Xanthate-Polyethylenimine Reaction Mechanisms
:'If. E. CARB, B. T. HOFRElTER, and C. H.. H.USSELL, Northern Re(liollal Research Laboratory, Auricultural Research Service, C.S. Department of Ayriculture. Peoria, Illinois 6'16'04-
Synopsis Thl' C'hemiC'al nature of starch xanthate (SX)-polyethylenimine (PEl) reaction produC'ts ha.~ been studied berause of their effertiveness as wet-end additives for im prllving strength properties of paper. :\lodel rompounds, in ronjunction with ultra vitllct, infrared, and chemical analyses, served to elucidate SX-PEl reaction mecha nisms. Aqueous solutions of ~X (degree:s of :sub:;titution O.l-D.;,) were titrated with PEl at pI! :.-i (2,i-:lQoC) to form SX-PEl !locrulent precipitate:s that were determined til hl' polyelectrolyte complexes. However. when :solutions of SX-PEl were kept at pH Ill-I:!. produc·ts were formed that induded dithiocarbamic acid salts in major quantities, PEl thiourea.-, and minor quantities of O-:starch PEl thionrarbamate. Acid precipita tion of thesl' ~X-PEI polymeriC' reaction products from their alkaline solutions, which ('Ilntained residual xanthate and PEl. also yielded polyelectrolyte complexe:;. :\lodel ,.'·-tems suggest th:lt PEl thiurum disulfide and starch xanthide, pos:;ible products of air lOxidal iOII, ('ould he present in minor amount:; and would react rapidly with PEl to yield thi'l\lreas and thioncarbamates, respectively. Apparently, mixtures of xanthate and alnin!' gave (1) dithioearbamic aeid salts from both xanthate groups and CS, (decom positilln from xanthate), (2) thioureas from both dithioearbamic aeid salts and thiuram eli,ulfide, and (;l) thionearbamates, principally from xanthate a:s opposed to xanthide.
INTRODUCTION Sodium : C' 19i;j hy John Wiley & :-;on~, Inc. 1-i1:2 CABB. 1I0FHEITEH. A:\D BeSSELL analyticall~' charactprizrd, InnonpolynlPric systpms. reactions of primar~' and "t'('ondar~' amilH'" \\'ith xanthut{' "alts in aqueous alkaliIlP "olution" can yidcl thioncarbamat{',.;! H{'portpdly, aqueous solutions of SX and PEl a~('cl at pH 1O-1:.! and room t{'mpprature have yielded thionearbamatp [-0('(:-;):\<, 1intPrpolyn1l'r::,,3 Howen:r, others have stated that aqueous alkalilll' mixturp;; of edlulo,.;(' xanthatp and PElon aging yielded dithio carbamic' acid salb [):\C(S)S-l and thioureas [)XC(S):,\(1of PEl but no thilllll'arhamat{' producl.' Thc' PEl dithiocarbamic groups were beIipvcd to form from CS~ of dc'composed xanthate, Reportedly, air oxidation of nOllp,,],I'IlH'ri~ dithiorarbamic aci(-alts can yield:thiuram disulfides [):\C (~)~~(:-;)(':\(l aIllI thiourc'a;;,9 TllP thiourpas may bp fornlPd readiI~' by rc'a('lion of primary and ,,('condar~' aminp;; with thiuram disulfides. Anal og'l\l" I 0 air oxidution of dithiocarhamic group;;, air oxidation of xanthatps can .\'it,ld xanthidp,.; [-OC(S)S~(S)CO-l which readily react \\'ith primary alld ,,('c'ondar~' amiIH's to yidd thioncarbamates. ~('\'('ral reaction products inrluding polyelectrolytf' complexes \\wp fornH'd in aqueous solution;; of SX \\'ith PEl at pH ranging from 5 to 12. \\'ith tIll' aid of modd system;;, tl1("se products wpre charactprized by ultra \"ioll'l. infrarc'd. and c1l<'mical analy;;ps. All reactions \\"ere at :25-:30°C. RESULTS AND DISCUSSION SX-PEI Polyelectrolyte Complex \\'llI'n a 1Sc aqu('ou" "olution of PEl GOO was slowly admixpd with a O,:!r; aqu('ou;; ;;oIution of SX havinf!; a dpgT('{' of substitution (DS) of 0.15, alld \dll'1I pH \\'a" maintailwd at 7,0, a flocculent precipitate \\'as formrd aI a dr.\'-\\'(,ight ratio of 0.1-1;) part PEI/1.0 part SX. Alternatively, wlwn "oIUlioll" of tIl<' alkalinl' rC'actant;; WPr{' combill<'d at the sanw concentra til In" and ratio". but pH wa" ;;lowly 100\'('rc,d, precipitation occurred at pH i. TIll' frc':-:h pn'C'ipitate;;. obtailwd in U;-)% yields (SX-PEI addition basis), had ;;ullllr (·L-IS;) and nitrog('n (:3.HSc) content;; that \\we about theory for a produC't c(,ntaining 0.1-1'-) part PEl 1.0 part of DS O.L':> SX (theory; 4.8% S. -!.1C;( :\). WI1('n tIll' fn'"h undri{'d prpcipitate:-; were treated with acid (pH Li) t.o deccJlnpo;;(' xantllatl' group". CS~ \\'as recovered 10 in amounts corn'"pondiug to origiual xauthat(· cout('ut;;. PEl dithiocarbamic acid salt,.;, !l0;;;;iblc' compon('ut,.; iu tIl<' SX-PEI precipitates, abo would release C~: at pH L'). Ho\\'('v('r at pH 11. thC' fn'sh undried precipitates readily "ululJiliz('d and contailll'd U:3-!l7SO of the theoretical amounts of xanthate, a;; d('(prmiIH'd by ultra\'iol('( analysis (t-~~~ = 30;'), E 17,500). These data :::ho\\'ed that tIll' [n'sh undried precipitates were SX-PEI polyclectro Iyt(, complex('s. TIl<' ('ff('cts of pH, xanthate DS, and concentration on the amount of PEl requin'd to form these complexes, and analytical data are ginn iu Table 1. STAHCII XA \TfIATE-/,OI.YETIIYLE\I\J/\E IH:l TABLE I I'rrp:lr:ltilln :lnd Analy~p." of :-'tan·h X:lnt hate (~,x )-!'olyet liyll'niminr (PEl) l'ol\'p]petrlllyte Complexe~" Amoullt of PEl rl'ljuired to pre('ipitate Analy~es of ;-;'x-PEl l'OInplpx. preeipitated eomplexh ])pgn'(' .,f Coneell part~!] 00 part~ s,x ~ul"t it ut illll tration, Yield, :-'ulfur, Xitrogell, 1):-' ,.. e c-' c-' ,I pH .i pI! i /( ,I I 0.11 O. J() i ,I O. 1,-, O.OJ 0.1.-, 0,0:; J.i ..i O. 1.-. 0.10 \1.0 14.;' \14 .0 4.0' 3.H O. 1.-, O.:?O 14 ..i o.::! O. J() l::?O W.O f).i.;i S.i 4.0 " :\qlll'OIi' PEL (I (';) wa" slowly added to aqueou" SX, with "tirring, until a prl' ,·ipitatt· wa~ fOrIUl"/. Sulfur ('ontent was determined withiu 1 hr after precipitatiou. h 1'1I1~'l'll'('trlllyte ('omplexes formed at pI! i. Yield = wt of preeipitate -;- wt (;-;X + PEli X 100. e Expl'riment wa" not made. d :'I iiik.\', uo prpl'ipitate. l'/tra\'i"lpt analyses of agp Alkaline SX-PEI Solutions :\11 aqlll'lIl1'; "(,]utioll "f SX alld PEl at pH 11 was prqlar('(] that eOIl taill!'d :-:X of DS 0.:2:2 at ,jS~ C'"l('t'lltratioll alld pntJUgh PEl noo to gin a ratill "f al1lillP to xallthatp group" of:2: 1. conditiolls that WPrP prt'\'iou"ly r('pllrt('(P to yi('ld ··"tarch polyl'thykllimino thiour,thant·." all O-stareh PEl thiolll'arhamatt·. Oil al!illg. u/tra\'ioll't ab"orptioll of t.hi" alkalillP :-:X-l'EI ""Iutio!l gradually "hift<'d from it" xallthatp maximum at :30;j IIIll tCI :mo IIIll (1-:2 da~',,). :2\1:2 11m (;j day,,). and filially :2S\lllm (:2S dny::;) \\'ith t'oIlCUrr('lIt formati"l1 of a \\'('akpr 1I01l"hifting abmrptioll at ::WO Ilnl. Tlwfl' \\'a" poorly dplillt'd ah"orpt iOIl in thc' rpgion of :2:{;-)-:24;j nn1. \Vhpn a('id-trt'atpd (pH 1..-,), till' ag('d (.-,-:2,\ day,,) mixture' exhihitpd an ab"orptioll I)('ak at :2:{!I 11m hut 1I0tH' at :2(iO :\Ild :2,\\1 11m. :\t pH i-I:!, ab"orption b~' til!' :H'id-trpatpd Illixtllfl' "hiftpd ff(l1l1 :2:{\1 Ilm to :2:37 111l1. Ultraviol(·t ~I)('('tra of tilt' fl't'"h and :2,\-da~'-old Illixtuf(' hC'fOf(' and aftt:'f acid tr<'atment art· rc'produ("('d ill Figur(' 1. .-\I>"orption at :23:>-:24.'> nm is partially ob ,,('urt·d iJ~' m'('rlappillg: ab"orption" of alkali at lower wavl'!el1gths. SX ha" a \\'('ak ah"orptioll at :.?:.?i 11m. SX-PEI prodUt"l" in alkalillt' "olutiol1 wC'rp prC'cipitatC'd in C'thanol. iso !alt·d. and rpdi".,;olv(·d at pH 1:2. The ultraviolet spectra of these redi~ sol\'('d prt·('ipitatt·" \\,pre' ~imilur to tho:-:p of tIlt' solutions from which they \n'rp prc'l·ipitatPd. Dltravioll't spl'ctra of tIlt' SX-PEI solutions in Figure 1 \\'('f(' typical of :-:p('etra that contained initial xanthate DS of 0.1-0.5, SX 1444 CARR. HOFRElTER. A:\D RUSSELL 0.0,------, ------02~ 2 .--- / ... --- r ~ 04f- I;/;/ I; ~ __ /I ' " /I ~ 4 .I' " /I 0 6f.- / , '/ '" , ,.... / ='" ~ 0 B - i .' -5 = I ' ... I II , I I I' , I I I 1 2 I I I I I I 250 300 350 Wavelength Inanometers I Fig. 1. Ultraviolet absorption spectra of DS 0.22 starch xanthate (SX)-polyethylen imine (PEI) reaction products: (1) fresh SX-PEI alkaline solution; (2) acid-treated (pH I..'i) solution of curve 1; (3) 28-day-old SX-PEI alkaline solution; (4) acid-treated solution of curve 3; (5) ethanol precipitate from solution of curve J redissolved at pH 12 and then acid-treated. cflncpntrations of 2.5-10%. and amine:xanthate ratios from 1: 1 to 10: 1 (pH 10-12). Chemical Analyses ..\mounts of CS~ rC'covC'rC'd from SX-PEI solutions and their ethanol prf' eipitatC's that \\WC' acid-treatC'd at pH 1.5 arC' listed in Table II. Yirlds. sulfur. and nitrogen contents of the prC'cipitates arC' also given. From the fn'sh SX-PEI alkaline solution (Fig. 1) containing only xanthate sulfur, CS~ recovery was 97% of theory, equal to that for an SX (DS 0.22) control. TABLE II Analyses of SX-PEI Solution~ and Corresponding Precipitates' Carbon disulfide SX-PEI precipitated product C" b recovery• .{ Sulfur, <;« From From EtOH Yield. Nitrogen, r- e- Sample solution precipitate /e Total As CS2 Ie SX control 9i fiQ !l.'i 4.i 4.i 0 Fresh SX-PEI 9i is 93 t>.7 .'i.i 2.0 5-Day-old PEl 1;0 41 92 3 ./- 2.9 2.0 28-Day-old SX-PEI 7~) 33 94 4.6 2.4 1.9 • SX-PEI precipitates were formed by addition of the SX-PEI solutions to 95% EtOH. b Trapped as CSrdiethylamine complex (>.f~fll • 13,.')00). Hecovery is based on amount of CS2 cuntained bv SX of OS 0.22. < Theoretical sulfur cont~nt for SX of DS 0.22 is i.8% and is i.2% based on SX + PEL STAHCII .\ A\'1'11 ATE-I'OLYETIIY LE\ I \11 \ E S r------SI--d~Se~a~ Starch xanthate ~X1:~;ion S PEl / DecompoSl"on PEl (St-OCSr;" PEI\ S II e~ "IT PEl-HNCS -~-PEI St-OC'm-PEI PEl dithiocarbamic acid salt O-starch PEl thioncarbamate ol.ldalionA" 1 S S II PEl II (PEI-HNCS+- PEl -HNCNH-PEI PEl thiuramdisulfide PEl thiourea Fig. 2. He:wti()n~ of alkaline i'X-PEI soilltioll~. Evl'n though thl' :Z~day-old SX-PEI ~olution contained no xanthate. tll<' yirld of CS.~ was still 7;jC;C o(th('()ry. showing that the' acid-un~tablc de'riva tivl' UHO. :zsn nm) \\'as a major eomponent of the' agpd mixture's. A similar conC'1u"ion wa" reaehl'd \\'it h thl' ;j-day-old SX-PEI solution. During iso lation and drying of tiw ('1 hanoI prpeipitates, including the SX control, ~ub"lanlial losse's of CS~ O('cuff('d. Howl'ver when total ~ulfur and CS~ Wl'fl' dl'tf'rminf'd simultanf'ously Oil portions of prf'cipitatl's from whieh l'lf'mf'ntal sulfur had bf'l'n rf'moVl'd, total sulfur was in excrss of the amount that could bf' removpd as CS~. This exces" re'preselltpd about 10 and :Z5% of DS 0.2:2 SX that eould bf' prf';.;('nt as thf' acid-stablf' components in thf' pff'cipitatl's of thf' ;j- and :.?S-da~·-old mixtuff', re'spectively. Thf' schl'mf' shO\\"ll in FigUfl' :.? illu~tratf''' reaction~ and reaction nwch anism" of albliIll' SX-PEI "olution" that are suggl'sted by our work and plueidatl'd in thl' ..\lodf'l Hl':!elion" "l'elion. Model Reactions Dithiocarbamic Acid Salts. \rhl'n CS2 was combinf'd with aqueous PEl 6 to give an amiIl(':CS~ ratio of 10: 1 and a pH of 12, a watrr-soluble PEl dithiocarbamir acid salt fl'''ultf'd. A ratio of 2: 1 yielded a watpr-insolublf' salt. The' fresh solubiP PEl salt f'xhibited absorption maxima at 260 and 289 nm. Thesp absorptions disappeared on acidification (pH 1.5). The aged acid-treated PEl salt solution exhibited absorption only at 237 nm. Thf'se results arl' typical of thosl' from alkaline SX-PEI solutions. Sf've'ral modd dithiocarbamie acid s<s and xanthate-a,mine aqueous solutions \\We' prf'parf'd: (a) N-e'thylammonium salt of N-f'thyldithio- IBn CARR, 1I0FHEITEH, A:\D HLSSELL i 0.6 ~ 0.8 10 I 2 1 4 200 250 300 Waveleneth Inanometersl Fi". :l. l"ltravie.let absorption spectra of fresh dithiocarbamic acid salts: (1) nOll i..;olalcd sodium salt of ethylenediamine-CS:; (2) N-ethylammonium salt of ,\'-ethyl e1it hio('nrhllmi(' acid (I): (.1) nOllisolated sodium salt of methylamine and C~2; (4) S ..\'-dicthylamnlOlliull1 salt of X,X-diethyldithiocarbamic acid (II): (5) acid-treated fresh dit hioearballlic acid salts. carbamir' acid (1) and N.N-dirthylammonium salt of N.N-diethyldithio carhamic acid (II): (b) aqul'ous. lIonisolatpd sodium salts of dithiocarbamic acid,,!! irlllll r·th~'laminl'. dipthylamim" rthylpnrdiamillP. and dil'thyIelll'tri aminl' at amilll': CS~ ratios of 1: 1; (c) O-pthyl sodium dithiocarbollatr (f'thyl xanthatc', EtX), O-butyl sodium dithiocarbonatp (butyl xanthatr, BIlX), amI D8 o.;-} SX with IlOnpolynwric aminI's; and (d) EtX with PEL '1'111' rat.ill of amine' to xanthatl' was:?: 1, I'xcrpt in thr sodium salt::- of di thiewarhamir' acids. III principJr., ultraviolrt characteristics of frr'::-h, agrd, and l\('id-tn'atf'd modc·1 ..;olutions Wl'rt· thl' same as thosp drscribf'd for SX 1'El solutions and for thl' 1'El dithiocarbamic acid salt. Doublp p('ak ubsorptions of thl' various xanthat(~aminl'solutions, which dl'vl'loped with agl'. \U'r(' idrntical to thosl' of dithioearbamie acid f3aItH that wert' prcparpd from C82 with nwthylamiIlI' (:?liO, 290 nm), f'thylaminp (2!i:3, 284 nm), l'th~'II'IH'diamil1l' (2;i;\ 288 nm), and didhyl('!lf'triamine (258, 287 nm), Dithiocarbamie aeid salts from both model xanthat(~aminl' and SX-PEl solutions formf'd morl' rapidly than could be accounted for on the basis of ('82 dl'composition ratl' of xanthatl' eontrol solutions, implying interaction of aminf' with xanthatl' groups as \n'lI as with CS2 from decomposed xan t hat c' to form dit hiorarbamie groups, Srwctral pattl'rns of thc' PEl dithiorarbamie acid f3aIt closely rcsembl('d t hosl' of thc' modl'l saIts of primar~' aminI'S. Also, the 5-day-old solutions of dif'thylaminf' with I'it!wr xanthate'!' or CS2 had no appreciable absorptions at 2:~rr-:?4;) nm whf'll acid-treatl'd. Thpse ultraviokt data suggest that PEl primary amine groups, rat hl'r than sl'condary, wpre the principal reac tivc' groups in formation of dithiocarbamic groups, Selected sppctra of frt'!'h, agc'd, and aeid-trputl'd solutions of modf'l dithiocarbamic acid salts, PEl dithiocurbamic acid suIt, and SX-diethylcnetriamine e.re reproducpd in Figurps 3 and 4, STARCH XA:\TIIATE-POLYETlIYIE\J\IJ:\E IH7 00,------=---:------, 0.2 I I I I 1.0 I I I I 1.2 \ I \./ 14 5 200 250 300 Wnelenrtb lnanomelersl Fig. 4. Ultraviolet absorption spectra of PEl dithiocarbamic acid salt and ~X (l)~ O.22!-diethylenetriamine: (1) fresh PEl dithiocarbamic acid ~alt: (2) acid-t reflled ~"lution of curve 1. (.1) ;-,..day-old solution of curve 1; (4) acid-treated ~olution of curve .J; (.5) J9-day-old SX (US O.22)-diethylenetriamine; (0) acid-treated solution of e\lfve 5. Thioureas. In studying thiourea formation in SX-PEI alkaline solu tions. th{' following modpl compound systems w('re pmplo;.ed. Aqurous solutions of salts I and II W('fe nitrit(,-oxidized (pH 4) to N.N'-diethyl thiuram disulfide (III) and N,N,N',N'-tctraethylthiuram disulfid(· (IV), r(·spl'cti\'('l~·. Addition of rthylamine to a solution of III in ether rapidly gan N.N '-dipthylthiourl'a (V). However, addition of dil'thylaminp to III yiPided a small amount of expectpd sid(' products (i.e.. dithiocarbamic acid salt and denwntal .:mlfur) but no appreciable N,N,N',N'-tetrapthyl t hiourl'a. Thioun'a (V) was isolatrd from crystallinp salt I that wa!S aged :2 ,,·{·{·b at :2tr-:30°C. Thl' watrr-soluble PEl dithiocarbamic acid salt, which was prepared aR previously describ<'d but at 2% concentration, was nit ritl'-oxidiZl'd to yiPid a watpr-insolublp PEl thiuram di,;ulfidp. which con currrntly rPactl'd with its unrl'actpd amine groups within I;') min to giVl' a PEl thiourra that waR RolubJ<. in both watpr and ethanol. In water, the PEl thiourpa exhibited absorption at 237 nm at pH 1.5 and 239 nm at pH 7 but at 242 mm in 9;j% ethanol, a charactpristic also of N,N'-dipthylthiourpa (t.~~~2:37, E 11,400 and t.~~~H24:3, E 11,(70) (Fig. 5). Apparrntly, an~' thiuram disulfidp in aged·SX-PEl !Solutions that might form by air oxidation would immediately react with unrpactpd primary amine groups to give PEl thioun'a. Probably, PEl thioun'a was formed principally from dithiocarbamic groups, as solutions of SX-PEI and com pound I yielded thioureas rvpn whpn storrd under nitrogrn. Thioncarbamates. Under conditions described earlier for alkaline SX PEl solutions, thioncarbamates were formed from (1) nonpolymeric xanthates with aminI'S, including PEL, and (2) SX with nonpolymeric aminI'S. However, no appreciable amount of thioncarbamate was formed in SX- PEl solutions. In all cases, dithiocarbamic acid salts also were formed. Several thioncarbamate reference compounds, including an l·HB CARR, lIOFRElTEH, A'\D HeSSELL TABLE III Aqueous Solutions of Xanthat€s with Amines Yield Thioncarbamates Concen- Amine/ tration xanthate Reaction of xanthat€ mole time, Yield, Thioncarbamates reactant, % ratio days e-Ie O-Et hyl ethylthioncarbamate 50 1.4 2 28.6 O-Butyl ethylthioncarbamate 40 2.0 4 ,'i9.0 O-Ethyl diethylthioncarbamate 10 2.0 3 0.6 O-Ethyl diethylthioncarbamate 40 2.0 4 4.0 O-Ethyl dimethylthioncarbamate ,'iO -.1') - 2 70.3 O-Starch ethylthioncarbamate (DS O. 02;i)" 10 2.0 4 i).0 O-Starch ethylthioncarbamate (l)S O.OW 10 10.0 4 12.0 O-Starch diethylthioncarbamate (!)S <0.000;;)" 10 2.0 4 L E~timated. 1.2 200 250 300 Wnelenlth lnanometers I Fig. ;;. Ultraviolet absorption ~pectra of PEl thiourea and N,N'-diethylthiourea (V): (1) PEl thiourea in 11,0, pH i; (:?) solution of curve 1 at pH 1.5; (3) PEl thiourea in !l.;';'; ethanol; (4) N,N'-diethylthiourea in H10, no pH adjustment; (5) V in 95% ethanol. interpolymeric thioncarbamate of starch and PEl (O-starch PEl thion carbamate), \\'Pre prcpan'd by reacting amines with either dithiobis(thio formates) (xanthidl's of corresponding xanthates) or methyl esters of xanthates. The convention chosen for naming thioncarbamate reaction products derived from the various polymers, from several considered, al though inadequately defines the polymeric structures precisely, does sim- STARCH XA,\TIIATE-POLYETIIYLE,\1\11 '\E U49 plify and providf' nomenclature in parallel with that of model thioncarba mat('s. Yil'ld" aT<' listed in Tablr- III of thioncarbamates from aged !'olutions of xanthatf's (EtX, BuX, and SX of DS 0.5) with nonpolymeric aminps at various amine: xanthatC' ratios and at pH 12. Thioncarbarnates of non pol~'nwrs wprl' extracted as oils and purifif'd by thin-layer chromatography (TLC) in yil'lds up to iOC;C. ThC' O-starch thioncarbamates from DS 0.5 ~X \\'ith l'th~'lamilJ(' and dif'thylamin<' werf' prf'cipitatC'd in f'thanol in ~'i('ld;< of only ;i to 12% basC'd on thioncarbamate DS of 0.02;-r-0.OG. Di l'th~'lamilj(' \\'ith l'itlwr SX or EtX gan low to nf'gligible yif'lds of thion l·arhamat(·s. Probably, thioncarbamatf's of thf' xanthatf'-amin(' mixtur('" aTl' produc·t" principally from xanthatf' groups, rathf'r than from xanthidl' that ma~' form by air oxidation, as control !'olutions of EtX and BuX gav(' onl.\· O.I-0.:2S( of th(' corrc'Sponding xanthidrs. :\qw-ou" "olution" of PEl with pith('r EtX or BuX, aged several days, ap!)f'am:l to ~'i('ld both thiour('a and thioncarbamatf' groups. Consqucntly, t () dl'\('rmilH' ult raviokt absorpt ion of purf' PEl thioncarbamatf's, PEl was allo\\'l'd to r('act with th(' nwthyl ('"tNS of EtX and SX to obtain (1) O-ethyl PEl thionl'arbamatl- (XII), which had O.G thioncarbamatf' group/PEl rC' l)f'ating ullit and (2) O-starch PEl thioncarbamatf', DS 0.18 (XIII). Thf' \lIt ra viokt "pl'(·tra and ('xtillction co('ffici('nts of srveral thioncarbamatrs (VI-XIII) from both polynwrs and nonpolymNI' are given in Tablr IV. (J-:-'tar('h l'\h~·lthioncarbamat(·, DB O.1:i (X), and O-starch diethylthion I·arl'amatl'. DB 0.11 (XI). Wl'r(' pT<'paT<'d from starch xanthidC' of DS 0.2;i. O-Lt h.d PEl t hioncarbamat(· (XI I) had considrrablp solubilit~· in both ,·t hall,,1 alld watl'r. ('xhibiting ab;<()rption.~ at 24:3 nm in H 20 and 24;i nm in 1'1 hall"!. Partially H,lubl(· O-stan·h PEl thioncarbamate, DS 0.18 (XIII), l'xhihitl·d a maximum at 24:)-2H nm. Th('s(' absorptions corrpspond to Ihl'; TABLE 1\' t:lt raviolpl :,ppct ral I )at:1 or Thioncurharnate" >. Ab"orption, Extinction ThilJ!warhamale :'olvent nrn ('oefficient (E) (I-Ethvl pthylthill!lmrh:lIJlatp £tOIl :24.; 11,400 (J-l\lItyl ethylthiolwarh:lIllalp EtOl! :246 10,600 (I-:"tarch ethylthioncarhamalP (1):'0.1'-'1 11 20 :24:) II. :300 (I-Et hyl diethylthinnearbamalP EtOl! :2;;0 11,000 fJ-1\1I1yl dielhylthio!lcarbamalP EtOH :2.">1 11.200 (J-:"tarch diet hylthiorwarhamate (1):' O. 11) 11 20 24!l 11 ,;iOO \H 20 24:) 12,000 ()"Ethyl PEI-thionmrhamate i EtOIl 24;; 12,000 ()-~larrh PEI-thinncarbamate (D~ O. IS) rhO 243-244 b • 0.(; lhioncarbamate p:roup/PEI repeating unit. I. Limited ""lubility. l-!50 CARll, 1I0FIlEITEIl, A:\D RUSSELL mat<'S (XI and VIII) at 249 nm (\yater) and 251 nm (ethanol). Possibly thpsp ultraviolet data indicate' that PEl primary groups as opposed to sec ondary amine g:roups we're preferentially derivatized. Although the xanthate-aminp model systems strongly suggested that SX-PEl alkaline solutions would yield O-starch PEl thioncarbamate, the reaction is so slow that xanthat~ was preferentially consumed in formation of PEl dithiocarbamic acid sal t. Infrared Spectroscopy The thiurams, thioureas, and thioncarbamates exhibited strong infrared absorptions be'tween 6.:3 and 6.6 jJ., which are attributed to C-l\' stretching vibrations of thioureides, )X-C=S and -KH-C(=S.1l·12 Spectra of sdpcted derivatives, which de'monstrate C-K absorptions in the 6.3-6.6 jJ. rpgion, art' shown in Figures 6 and i. Even with low DS, O-starch thio- cm- 1 1500 0.0 4 3 0.2 Q,) '-' =." ...c Q ...c'" c:e 2 0.4 0.6 0.8 1.0 co 6 7 Wavelength Imicrons] Fig. G. Infrared absorption spectra of model compounds: (1) N,N'-diethylthiourea (V), KBr disk; (2) X,X'-diethylthiuram disulfide (III), KBr disk; (3) D-ethyl ethyl thioncarbamate (VI), film on Irtran disk; (4) D-ethyl diethylthioncarbamate (VIII), film on Irtran disk. STAnCil \-\ \'1'1 J.-\TE-I'OL) ETIJ) LE\ 1\11 \ E I !:)1 cm- 1 2000 1500 0.0 6 ... 0.2 ...c: .c '"c; 2 .c..,'" 1 0.4 0.6 0.8 1.0 <» 5 6 7 Wavelength Imicronsl Fif.:.7. Infrared ahsorptioll spe(·tra of polymeric produ('ts: (1) PEl thiourea, film nil Irtrall disk: (;!) PEl, film nil Irtrall disk; (.1) unmodified pearl ('orn starch (suhstratc fnr xanthatioll), KEr disk; (~) pthan,,1 precipitate from ;-;X (j);-; O.;;)-PEI Ij sn!inion af.:pd Ii days, KEr disk; (.j) O-sl areh PEl thiollcarbamatp, 1>;-; O.IS (XIIIl, KEr disk; (I;) ()-st:lrt·h clhylthiollearbamatP, 1);-; 0.1.; eX), KBr disk. nearbamatps, X (Fig. 7, rurvp Ii) and XI (not shown), eharactrristie C-~ ab:,orptions arp rradily idrntificd at (j.4;,) /1- and G.5,') /1-, rpsprctivrly, The C-:\ absorption of O-starch PEl thioncarbamatp, DS 0.18 (XIII), is cent('red at G.G /1-, Thp C-:\ absorption of thr PEL thiourea, although ('pnt('rpd at (\.:3 /1-, is quite· broad pxtpnding into the lUi /1- f(·gion. Infrared analys('s alonp \\'('n' in('oJlrlu:,iv(' for charuetNizing SX-PEL products (P.g., Fig. G, run'(' 4). W('ak SX- PEl ab.sorpt ion:' at (j.;j-(i.1i /1- wpre poorly dPlilH·d b('eausr of spV<'ral int('ffpring absorptions. Thpsp inrludp absorptions on the high frpquPIl<'y sidp of 0.1/1- (moist un·) and 1i.:2 /1- (:\H2) and absorption on th(·Iow frpquPllcy sidp of ti.8/1- (CH2). EXPERIMENTAL General Adjustment,; of pH wen~ made with pither HCI, ac(·tic acid, or XaOH. Those with aeptie aeid an' noted in thp following sections. Ultraviolet sppctra wprp T<'corded with a Perkin-Elmer l\lodel 202 spectrometpr, In- CAHH, 1I0FHEITER, A:\D BUSSELL fraf('d sprC'tra wrrr drtrrmined with a Perkin-Elmrr ::\Iodcl 137 spC'ctrom rl('f from film;.: cast on rithC'r Irtran disks, AgCI plates, or I\:B: disks (sl'r Fig", Gand 7), :\!l'ltinp; points werr obtain·_'d with a Fishrr-Johns appara tu". Tit- wa" u;.:rd for componrnt srparations of nonpolymC'ric modds on !lb.,,;.: platrs filnwd with Silica Ge,1 G. Hl'xan('-C'thyl acetatl' (4: 1, v/v) was t h(' <'!ul'nt. Hhndaminl' 6-G fluorC'scent spray was used to dC'trct tic com pOIH'nts. Carbon, hydrogrn, and nitrogen of nonpolymC'ric dC'rivatives W('f(' drtrrmin('d with a PC'rkin-Elmrr 240 rkmf'I1tal analyzC'r. KitrogC'I1 of polynwri(' dl'ri\'ativp;.: was drterminrd by thl' Ejeldahl mrthod, Sulfur was d('1 ('rmin('d by the' method of \VhitC',13 Sodium Salts of Xanthates ('omnwrrial p('arl corn starch wa;.: convC'rtrd to SX (DS O,2;j and 0,5) ill a :\Iod(,! ;-)0 !\o-Ene:lder,14 dilutl'd to lOS'c solid;.:, and stored at 1°C, Et X alld BuX \\'l'r(' prC'parC'd C's:,elltially by the method of Ingram and 1'0111:'.1:, Et X alld BuX \\'C're dis"oln'd ill acetone and rC'crystallizC'd in (,t lI<'r h('fof(' U"l'. Xanthides .\qu<~'u" "olutioll;': of SX (0.1 c;[ concf'ntration, pH 12) with KaKO~ (2 m, >II'" mole' xantha1l') \\'erf' rapidly stirrC'd whik pH was slowly 10werC'd to 4-4,;-, wit h g!ae'ial acC'tic acid t·o obtain starch xanthidl's as bulky prC'cipi tat,·", TII<' xallthidl';': wC'rC' filtC'rC'd and thrn wa"hC'd with watC'r (pH 2), !I.-)r; EtOH, ah"olutr £lOH, Ill'xam" and dll<'r ill that ordC'r. ThC'dC'greC' "Ill )"t i1 u t iOIl (DS) of f'ach starch xanthide i" basrd on onC'-half xanthidC' l!rlIIlJ' h\'dn ,x~'1 gr, )UP of ;.:tarc'h and \\·a;.: about !l0c;[ t hr drgrrf' of substitu t illllllf t II<' origilla! SX. Yidd;.: W('f(' about U;jS'e, starch basis. I-:t X :lIld BuX at lOSe aquC'ou;.: cOllcentration WC'f(' oxidizC'd with KaKOz a" dl'"rrih('d for SX. ThrsC' liquid xanthidl';': \\'C'f(' f'xtractC'd with f'thN, wa"lwd with \\'atf'r. and vacuum dril'd (;jO°C). Yirlds wC'rr about 80%. TII<' x:lIlthidr" C'xhibitl'd strong, broad doubk"pl'ak infrarf'd absorptions at I.!I and !I.I p. for tlI<' nonpolynwric xanthide;; alld at 1".1 and 9.7 p. for starch xant hidr". Methyl Esters of Xanthates SX of DS 0,2, at ;jc;[ roncPlltratioll in watrr-D?\ISO (l: 1, v/v), and CH3I (:2 moll''' moll' xallthate') Wl'f(' allo\\'l'd to mix 1 hr. Ultravio!C't analysC's of til<' mixturl' aftrr 1 hr ;;hO\\'(,d ollly xanthate' l';.:tpr ab;.:orption (maximum at :2,'\0 nm). TIl<' prodw·t \\'a;.: prl'C'ipitatpd ill ?\!e{)H and wasIl<'d with EtOH, IH'xall<', alld dhrr, 01: til<' ba~i;.: of ultraviolrt analysis, DS wa;; approxi ma1 ('!~' 0.:2; yie·ld. UOS~ "tarch basis: ;\ Kllr :-U, !l.4 p. (xallthatr rstC'r). :\ :20S e rthl'r solution of EtX with CH31 (Lj molC';.:/mok xanthatr) was ;.:tirrpd ovC'rnight. CHJSH, a fe'action product, and excrss CH3I were re mo\'('d by vacuum (-tQ°C) to lC'avC' thC' methyl C'stC'r of EtX, which was vola tiiP und fumrd wh('JJ C'xpo;;C'd to air. EstimatC'd yield, 75%; X~~~H :277 nm; ;\Irtran 8.20 and 9.-1;j p. (xanthatC' C'ster). Slight carbonyl (C-O) ab"orption at 5.i-5.9 p. indicated soml' oxidation of C=S to C=O. STAHCII XA ,\TIIATE-POLYETIIYI.E'\! \1 I '\ E PEl PEl Ii (nsSc solids. mo!0cular wpight GOO) and PEl GOO (:~:~s:( ,.;olid". mol('('ular wpight 40.000 to GO.OOO) wprp supplipd by Do\\' CI1Pmical Com pany. :\Iidland. :\lichigan. lnfrarpd s!wctra haY<' bp<'ll rpportpd. 4 SX-PEI Products SX-I'EI alkalinp :-:olution,.;. prpparpd as dpscribpd abo\'<'. wprp agpd in scn'\\'-capppe! yials and ppriodically mixpd b~' invprting thp ,·ial:-:. Thp SX-I'EI ,.;olutions wprp stirrpd into EtOH to gi\'<' prpcipitatps \\'hich wprp IiIt ('n'd :1Ilc! \\'a:-:hpd succpssiypl~' wi th watPI'. pthanoi. hpX:1lH" and pt hpr. \·olatill''': \\'prl' dptrrminpd on pthpr-dripd :-:amplP:-: simultaJH'ously with clwl11i('al al\[lI~·sP":. CS~ Determinations SX-I'EI ,.:olution,.: and prpcipitatps (and SX control:-:) wpr<' tr<'atpd at pH Li for -I-Hi hI' at :30-50°C in a clospd s~'stpm swppt wit.h nitrogPll. Thp libpra1('c! CS~ was Happpd in a chillPd solution of dipthylamiJl(' (0.41j( in EtOH) having 100 amilH' group,.:(original xanthatp group. Salts of Dithiocarbamic Acids N-Ethylammonium Salt of N-Etbyldithiocarbamic Acid (I). A solution of iOr eaqul'ou:-: Pth~'lamilH' \\'ith CS~ (:2 molp/molp of amiJl('). wlH'n slowly mix{'c! amI maintainpd at :2;i-:Wo(' for I;i min. gayp a light yC'11ow solid OJl imnH'r,.:ing tIlt' rpaction f1a:-:k ill all icp bath. Thp !'olid \\'a:-: furtlH'r cooke! ;11 a Dry 1(·t~arptolH' bath. filtprl'd. and \\'ashpd with ('old ptl1('1' to obtaiJl a pun' w}lit {. ,.;olid: yidd. iSSe; A~~~ :2S4 (E II.SiO). N,N-Diethylammonium Salt of N,N-Diethyldithiocarbamic Acid (II). Salt II wa:-: prpparpc! from dipthylamiJl(' and CS2 as dp:-:cribpd for 1. Yidd. iOSe; mp. sl-S:2°C: A~~~ :2."4 (E I:2AGO). A:'\.\I.. Cakd for C,I1..,X,:',: :'. 4S.()r;: H, n.!l";: N, I:!,G~;; :', :!8.8':;;. Found: C, 41'.8(';; II. 10.0(';; X. I:!)·W;; :', :2K()(";. Tbiuram Disulfides N,N'-Diethylthiuram Disulfide (III). To a :2;j A:'\.\L. Calrd for C,H"X,~.: C, 30.0S"(; H, .'i.0':;;; X, 11.i';O; [-I, ;i3.3':;~. Found: C, 30.017;; II, .i.O':';; :K, 11.4 (;;: :', .i2.;)':;( . CAlm. IIOFREITEB. A:\D BUSSELL N,N,N',N'-Tetraethylthiuram Disulfide (IV). Compound I\' was obtaim'd by nitritl' oxidation of II as dpseribpd for preparation of III from 1. Hpcry"tallization in hpxanc' gavp purp whitp crystals: yidd. ,;jS(: mp. -0I .;)- 00\. (. S harp ) : "max,Kllr"U. G'))_ IJ.. "max,EtOH ')')0__ ( f ')0_ .u"1-);J , ",EtOH .).y__il ( f 1-;).,)"-0)I• and "EtOIl :2,';7 (f l4,4G.')). A:-u1.. Cakd for CIOH20!\2~': C, 40.i>':(; H, B.8e;(; N, 9.;')<;[; S,43.2e;(. Found: C. 40.7 c ;: H, 7.2';;: !\, 9..')';(; S,42.9':(. Thioureas N,N'-Diethylthiourea (V). To a 4<;( solution of thiuram disulfidr (III) in l'tlll'r was admixrd 70S~ aqupous rthylamine (2 mok/mok of disulfidr). ;\ft('r I hr. tIll' mixturp was \\'a~l1Pd in a spparatory funnC'1 with \\'ater. and ('t lll'r was r('mo\'('d by vacuum (:30°C) to Irave a light ydlow solid. Thp solid was n'cr~'stalliz('d twic(' in h('xanr as dpscribed for III and IV to get purr whitf' cry.~tal:-:: yidd. 70se; mp. 77.5-7SoC; A~~l; G.32 IJ. (strong EtOH EtOll absorption abo at G.;j:2 IJ.); A :214 (f S200), A 243 (f 11,400), AU,O 21:3 (f 11.,,00). and A11,0 :237 (f 1I.700) . .h.\L. Cakd for C:.H I1!\,:-;: C, 4;').0':(; H, 9.1'7(; N, 2I.2e;(; S,24.2<;(. Found: C. 4.',.(J';: Il, !U";: !\, 21.1 ,.;; :-;,24.2:';. Thioncarbamates from Xanthides and Xanthate Esters O-Ethyl Ethylthioncarbamate (VI). To a solution of 200/0 pthyl xanthid(' in /'tlll'r was admixpd aqu('ou" 70S-~ pthylamine (:2 mok/mok xanthidp.) ;\ft('r 10 min. tIl(' mixtun' was waslH'd \\ith water, and the ether was re nll,\'('<1 h~' \'3euum (:30°(') to !('uV(' a dark yellow liquid. Preparativp thin IaYl'r ('hromatograph~' (TLC) ga\'(' VI. a light ypllow liquid and a trace ('arhon~'1 compolll'nt; yi('ld of VI, SOse; A~~~an G.;j IJ.; ultraviokt, sec Tabl(· 1\'. A:\\L. Cakd forC:.Ilo!\O~: C, 4;'•. Jf;;; H, 8.3'7(; N, 10.0':(; S,24.1'/c. Found: C. 44.!1(';: Il, /0\.2';: !\, 10.2";: :-;, 24.2'/~' O-Butyl Ethylthioncarbamate (VII). Compound VII, a Iwarly colorlpss liquid, \\'as pn'pan'd from butyl xunthidp and pthylamine as described for \'I; yi(·ld. 70se: ,,~~~~un (i.;j:2 IJ.: ultraviolpt se(' Table IV. A:\\L. Cakd for CJII1!\O~: C, .,2.1'7;; II, U::3'7;; N, 8.7'7(; S,1U.U'7(. Found: C,i>2.1~;; Il,!J.2',;: !\,k.3";;~, HI,;)";. O-Ethyl Diethylthioncarbamate (VIII) and O-Butyl Diethylthioncar hamate (IX). Compounds \'II I and IX \\'('fp prpparpd by rpaeting ethyl and butyl xanthidps with dipthylamilH' as described for preparation of VI and VII. Pn'pnratiw TLC showpd that the corresponding monoethyl thioncarbamatps (\'I and \'II) "up also obtained with VIII and IX in an approximatp ratio of 1 : 10 ('ven with freshly rC'f1uxed, distilled diethylamine to remo\'(' any eth~·lumine. Ir showed absorptions of carbonyl components at ;j.7-.').: IJ. remo\'('d by tIc. Compound VIII fumed on exposure to air. STARCH XA\TIIATE-POLYETIIYLE\IML\E liS5 Yield of YIIl (estimated). 7;"iC;C; A~;~an 6.65 jJ. (film bet\\'f>ell Irtrall di,;k:<) ultraviolet. St'P Table IY; yidd of IX, 65%; A~;~an 6.6:2 }J.; ultraviolpt. ,;pc' Tab!P IY. Dup to volatility of YIlI. CH:\"S wa,; not reliablP in detprmining thc· ,;trurturc' of YIlI. Thp struct.Uf(' of YIlI was &upportpd by l\.:\IR in frarc·d. and ultravio]Pt data. A:\.\L. Cakd for C,H 19 NOS (IX): C, 57.1~.; H, 1O.0~.; N, iAC;;; S, IG.9~. Found: C. ;;7AC;-;; H, 1O.1 ~; N, 7.2~; S, lG.;j~. O·Starch Ethylthioncarbamate, DS 0.15 (X), and O·Diethylthioncar. bamate, DS 0.11 (XI). To aqU('ous suspensions of DS 0.25 starch xanthide "tirrc'd at 1c;{ conC'pntratioll \\'f'n' addpd (a) ethylamine and (b) diethyl aminc' for pn'paration of dpriyatiyt':< X and XI, respectively. After 16 hr. pach mixturc' wa" dilutrd with an pqual volume of pyridine and treated with IU' 10 rOllvC'rt any u!lfeactpd xanthide to xanthatr. The drcompositioll of X:lIlt hidc· with H~S i" an extpnsion of a preyiously reported 16 method of dp ('ompo"ing xanthide with p-chlorothiophenol in pyridine. After the mix tun'." had !Jppn treated with H 2S, xanthate was decomposed at pH 2. In a "pparalory fUllIlC'] the mixtures \\'eT(' \\'ashpd several times with chloroform, "0 that grayi: ;\'\ \L. Calc-d for slar('h-OC(:,)NIIC,IL of I):' 0.147 based on nitrogen analysis: N. 1.1;';";: ~. :2.W";. Found: N, 1.1l';";: ~,2.G2C;-;. ('"It'd for slur('h-{)C(:'lN(C,H·.), (If I):' O.ll I ba.sed on nitrogen analysis: N, 0.8S~; :-. :2.lJ I';. Found: N, O.S8~·;: :-, 2.0n r ;. O.Ethyl PEl Thioncarbamate (XII). To a 10% ethanol solution of EtX m('thyl ('st('r wa,; admixPd PEl Ii at USc;{ solids to givt' a mixture containing OIl(' c·"t ('f grouP! amilH' group. Aftpr Ili hr, the product (soluble in eithpr f'th:lII A=--.\L. Calcd for C,ILOC(:,)~-PEI containing O.G thioncarbamate group/PEl repealing IInit ba."ed on nitrogen analysis: N,8.S'7"0; S, 20.0~.. Found: N, 8.8%; ~. I"->.Sr:;. O·Starch PEl Thioncarbamate, DS 0.18 (XIII). To a 1% aqueous slurry of aDS 0.:2 nwthyl ('ster of SX \\'Us admixed PEl (j to give an amine-: ('ster ratio of :!: 1. t·" monitoring of th£> mixture showed an absorption maximum. initially at :2S0 nm (xanthatC' ester), that gradually disappeared \\ith coneurrC'llt formation of a nC'w maximum at 243 nm within 1 hr. After 1456 CARR. HOFREITER. A:'\D RUSSELL 4 hr thp partially watpr-solublp product (XIII) was prpcipitatpd ill DOH and washpd \\'ith EtOR. hpxall(·. and pthpr; yipld. UO~ both starrh basis and DS basis; AKllr G..jO J.L. :\:-':.\L. Caleulated for starch-()C(:-,)X-PEI of ]):-, 0.11' based on sulfur analysis and ('{lntainin~ L:, unre:H·ted amine ~roups/thioncarbamategroup based on nitro!,en anal ysis: X,:~.;)('~; ~,3.0';(. Found: ~,3.3(/~; S,3.0';(,. Thioncarbamates from Xanthates Hpartiolls of EtX. BuX. and SX in aqupous solutions \\'ith dhylamille. dicthylamiIH'. alld dinwth:\'Iaminp to ~'idd thioncarbamaH's an' Jlarliall~' c!('scrilH'd ill HpstJlts and Di.~cusf'ioll. Structurps of thiollcarbamat(-s from tl]('sp amilH's. with xallthatps wPr<' charactprizpd h.\· comparill~ tlwir ill fran-d. ult raviolpt. and chpmical analysps data wit h thiollcarbamatp rP[pr Pllrp compounds (VI-XIII) that wprp prpparpd from xallthidps and xall thatr pstprs. Thr O-ethyl- and O-starch dinwt.hylthioncarbamates (Tablp III) wprr prpparpd from xanthatf'1' only. Except for ReS tn-atnwnts. tIl<' stareh thioncarbamatps from SX (Tab!f' III) Wf'rP acid-trpatpd. isolat(,d. and ullalyzrd as df'scribrd for dprivativps X-XII. Th('n' \\'as only a trap(' of O-starch dif'th~'lthioncarbamatpfrom a f'olutioll of dipth.\'IamiIH' \\'ith DPo (J.;'j SX a~pd ;) days. Thl' mention of firm names or trade products does not constitute nn endorsement by the r.:-'. Department of Agriculture over other products or firm names not mentioned. References 1. (i. E. IIllmerstrand,:'II. E. Carr, 13. T. !Iofreiter, and C. E. Hisl. TClppi, 50, XO. S, !l'\.-\ (I9G7). 2. :'II. E. Carr. W. :'II. Doane, (;. T·:. !Iamerstrand, and 13. T. lIofreiter, J. .-Ippl. !'ol'/m. Sci., ]7,721 (l9i:n :\. (;. G. :'Ilaher, A. J. Ernst, JI. D. Heath, 13. T. Jlofreiter, and C. E. Hist, Tappi, 55, ~o. 9, I:m, (l9i2). 4. PEl-The ]'er8C1lile PolJlma. ])ow Chemical Co., ])esi~ned Products. Department of Hesellrch and Development, :'Ilidland :'Ili('hi~nn, 1!16S . .i. A.:--. :'Ilichnels, IlIcI. Ell(I. Chem., 57. ~o. 10, :l2 (l96.i). G. H. E. Win~, C. L. :--wanson, and W. :'II. J)oane, J. WaleI' 1'011111. COlliI'. Feci., in i. C. X. \'. Xamhury, l'ikram, 2. ~o. 1, 101 (I!l.iS). 1'. B. Philipp and II. Lan~. TClppi, 52. No.6, lli9 (1969). 9. H. E. Heid, Org. Chem. nil'C1lelll S/llf/lr. 4. 21:{ (1962). 10. B. S. :--ha.~ha, W. :'II. Doane, C. H. Hu';"ell. and C. E. Hist, Carbohyd. Res., 5. ;H6 (l96i). l!. L. J. Bellamy, The Illfrared Speclra of Com pie]' .1foleel/les, :'Ilethuen and Co.• London, Wiley, ::-;ew York. 2nd ed., 1!).iS, p. a.ii. 12. H. l\IeC'ke, Jr.. and H. :'IleC'ke. :--r.. Chem. Ner., 89. !\o. 6, :H;~ (I!l;iG). l:l. D. C. White, .1fikroehim. Acla. ]962.1'07. 14. C. L. :--wanson, T. 11. NatTzip:er, C. H. Hu,;.~ell, B. T. Hofreilcr, and C. E. Hist, Illd. EII(I. Chem., Prod. Nes. Develop., 3, !\o. 1,22 (19M). I:,. <..:. Ingram and B. A. Toms, J. Chelll. Soc., ]96]. III'. 16. D. Trimnell, B. :--. Sha.'iha, W. :'II. Doane, and C. H. Hussell, J. Appl. Poillm. Sci., 17. 160i 09i3). Received December G. 1U74 Revised January 15. 197.5 Purch.aserl by U. S. Dept. of Agriculture for Official Use.