Nakashima, Ruka

Shigemasa, Yoshihiro

Suetoki, Yoshinori

Waki, Eiichi

Tottori University Research Result Repository

Formose Reactions.XII. Formose Reactionin the Presence of BenzoinbyYoshihiro SIIGEMASA*, Yoshinori SuETOKI*,Eiichi WAKI*,and Ruka NAKASHIMA*(Received June,30,1979)Effects of various co‐catalysts on the formose reaction and its product dist―ribution vere studied. Benzoin was found to give a simple gas chromatogramof trimethyl silylated(TMS)der?atives of products. The main productwas separated and assigned to l,2-diphenyl glyceroユ. The scheme of th  for―mation of l,2 diphenyユ glycerol in the Formose reaction in the presence ofbenzoin 、vas also proPosed。1, Introductio■Formose is composed of over thirty products which are obtained by condellsationof forttaldehyde in the presence of a baseo As monosaccharides are obtained in ahigh yield by this silnple procedure, formose has been noted as a solution for thefood problem in the future, furthermore, the reaction has dra、vn the in erest ofresearchers、vho think that it lnay provide an explanation for the pri:nordial originof monosaccharides.Sillce Butlero、71) fOund the reaction in 1861 and the product=nixture, C6】・ 1206'was termed formose by Loew,2)many investigations have been caried out. Howe―ver, formose has not yet been utilized in spite of such efforis. The ilnportantfactors involved in solving the problem are the selectivity of products and the isol―ation of the desired product.Recently,、ve3,4)haVe reported that 2-C―hydroxymethyl glycerin, 3-C―h droxyme―thyl pentitol, and 2,4-C―dihydroxymethyl pentitol could be synthesized selectivelyby using the ORP method,5.6)which is very effective in finding out the formosereaction step.It is already kno、vn that the formose reaction consists of three steps, namely, theinduction period,the sugar‐formation step,and the sugar―decompo ition period, andthe induction period is shortened by the addition of enediol compounds, such asglyceraldehyde, glucose, acetoin etc.7)However,there are few papers which have described the effect of enediol comp―*DepArtment of lndustrial chemistry, Faculty of Engineering, Tottori University,「Fottori 680|   ゝReports of the Faャulty of Engineering,Tottori University,Vol. 10113ound on the products distribution. In this paper, vヽe、vish to report about the pro―duct of the fofmose reaction, which is carried out in the presence of enediol comp―ounds,especially,bexlzoin and acetoin.2. Experil■ntalMttο″ゲ,た。 A formaldehyde solution was prepared as follows i 200g of paraforma―ldeLyde(A/1erck)was Suspended in 400■1l of distilled water, refluxed forユ と andfiltered through a sintered glass disk. The filtrate containing ca. 30 wt―身歩 Offormaldchyde、vas stored in a brown bottle in a dark place, and、vas used for exp―eriments within a fe、7 days, in order that no substances accelerating the formosereaction could be produced,Phenacyl alcohol was prepared by refluxing 4 g of phenacyl broH?d  and 4 g ofBaC03 in 50 ml of distilled water and recrystalユzation from thanol.8) Reductonewas prepared from glucose according to the general procedure.9) Chromotropic acidused for the deterHlination of formaldehyde、vas of ah extra pure reagent. A/1onos―accharides, ascorbic acid, bellzoin,acetoin, and other reagents were of an analyticalgrade.P″οθιブク″θ.  The apparatus and the experilnental procedures 、vere virtually thesame as those described previously.6) The reaction ■lixture was k pt to pH 12.0during the reaction by adding a saturated KOII solution. The formaldehyde collsu―mption, the sugar yield, and the oxidation―reduction potential(ORP)of the reacti―on■1lxture were measured by the methods described in the previous papers.①The preparation of trilnethyl silylated (rrWIs)deriVatives of products and its gaschromatography were carried out in the same manner as described prevlously,10)Quantitative estilnation of products was made by measuring the areas under thepeaks given by the separated componentsH)and using pentaerythritol as an internalstandard. This measurement could be accomplished by tracing the peaks onto paperof uniform dellsity from which they were cut and weighed.S2形″α′どοη翻′ Iじ3ηチ′/ゲθαチゲο% げ P/0′"θん.  Formaldehyde (5.7g), bellZOin (2。12 g),and CaC12(0・l g)in 200 ml of water were added to the reactor and the formosereaction was started by adiusting iHHnediately the pF[of the reaction Hlixture to 12.0with an aqueous K()H at 60°C, The13, at the yellowing point, the reaction wasstopped by shghtly acidifying the reaction lnixture with 9N―HCl. The GLC patternof Fig. l thus obtained indicates a very selective formation of products correspon―ding to peaks 22 and 23(above 90ラろ)。 At first, unreacted bellzoin (0,08g), whiChwas suspended in the reaction lnixture, was recovered by filtering in a sinteredglass disk.  The aqueous mixture was extracted with fifteen 50 ml portions ofbenzene, The eluate、vas dri d with anhydrous sodiuln sulfate and concentrated in114 Yoshihiro SHIGEMASA,Yoshinoi SUETOKI,E?chi wKAI,and Ruka NAKASHIMA:Formose Reactions, xll Formose Reaction in the Presence of Benzoin???????」????vacuo to give l。95 g of a product corr―esponding to peaks 22 and 23 as a ye―1low sirup(83.1%baSed On the startingbellzoin)。 0・86 g of the yellow sirupcould be purified by distillation(41nm―Hg,200°C)uSilag a“Kugelrohr'' disti一1lation oven, and amounted to O.84g.IR (KBr):3400(OH Stretth), 3050(CH Stretch;aromatics),2890(CH St―retch; branched hydrocarbons), 2C100-1667, 1600, 1480, 1060, and 710 cm~1 ,NMR δ(CDC13):7.12(10H,m), 4.68(lH,S,CH),3,91(lH,d,geminal non―equivalent a, b type CF正2)' and 3.52(lH, d,geminal nonequivalent a,b typeCH2)'JfrFr=18 Hz,J/zν=0・5 MS iacetate derivative (yel10ヽT syrup),In/e(relatiVe intensity),311(ヽ1-CH3 COO'3),180(84),and 138(100);UV:え″,.,214 nm(solVent,MeOH).i0     20     30Retention time t min)Fig. 1. Gas chromatogram of TMs derivativesof products.〔HCHO〕=1.OM,〔CaC12〕=0,005M,〔BenZOin〕=0,01M,PH=12.0(adjustedby KOH),temp.=60°C,total volume=200ml.:― ibon o■Structure (1)[と,2-diphenyl glycerol] waS assigned for the product of peaks 22 and23,based on the above data. FurthermOre, this product was identical with an aut―hentic sample by the comparison of the NA/1R and IR spectra.dノ競ЙθSλりrヱ,2-詭o力ιηダ′gttει″ο′・ 1,2-Diphenyl glycerol was synthesized in orderto ascertain that l,2、diphenyl glycerol corresponded、vith a product of GLC peaks22 and 23 in the formose reaction,5,82 g Of benzoin,2.7 mlof 37ラ疹aqueOus formaldehyde, and 10.5 ml of triethylamine、vere refluxed in 7.6 ml of ethanol for 3と, diluted with、vater (50 ml), andthen extracted、vith four 50 ml portioコs of bellzelle.12) The beコzene extract 、vasdried(Na2 S04),and COncentrated in vacuo, giving a、vhite residue,RecrystallizationfrOFl ethanol gave 6.57 g of α―m thyk)l benzoin, white crystal l yield, 98,9% mp,85°C;IR(KBr):3500,3360, 3050, 2890,1660,16C10,1480,1070 and 710 cm~1,NMR δ(CDC13):7.3(10■,m),4.46(1■,d,Jrr=18 Hz,Jんν=0,2,geminalとЮnequivalentRePortS Of the Faculty of Engineeirng,Tottori University,Vol, 10a, b type CF12),3.40(lH, d, 」frr = 18 Hz, J/zレ= 0°2, ge“linal nonequivalent a, btype CH2)'4.00(lH,bri s,OH,disappeared by D2 0),3.30(lH,S,OH,disappearedby D2 0)・1.82 g of α―methylol bellzoin and O。85 g Of NaBH4 WaS allo、ved to stand for 8 hin 30 ml of ethanol at room temperature, then diluted with water(100 ml)。 Thereaction mixture was passed through the 40 ml cation exchange resin Amberlite IR120(H)cOlllmn and extracted with t、velve 50 ml portions of benzene. The beJjlZeneextract、vas dried、vith anhydrous sodiu■l ulfate and concentrated in vacuo, givingl.2 g of a yellow syrttp,1,2-diphenyl glycerol i yield,61.4%,IR, NMR, and theretention tilne of l,2-diphenyl glycerol TWIS derivatives agreed those of the productof the formose reaction corresponding tO the GLC peaks of 22 and 23.IR and NMR spectra Of commercial benzoin are as follows.IR(KBr):3400,3050,2930,166Cl, 1600, 1480, 1070,and 710 cm~1,NMR δ(CDC13):7.18( 011,S)and 6.10(lH,S,CH).9"ガ″″ケυι,紘7'ysゲりr bιηzοゲη, α―筋ιチカノ乃′ι¢″zOゲ″, ,%, 1,2-01っ力をηノ′ど妙θじ″0′・An aliquot of the reaction mixture which contained about 100 mg of benzoin, α―methylol benzoin,and l,2-diphenyl glycerol was lleutraiZed with 9N HCと, xtractedwith five 10 ml portions of CIIC13, and Colxcentrated in vacuo tO a pale yellowsirup. ユH NⅢlR spectrum of the sirup was taken on a Varian T-60A spectrometer.The relative amounts of these three compounds were calculated by measuring thepeaks of 5,90,4.46d,and 3,91d ppttl corresponding to benzoin, α―methylol benZoin,andと,2-diphenyl glycerol,respectively. Table l shows the results in which theseauthentic samplesヽvere deterttlined by this method. On the other hand, the GLCTable l. Quantitative analysis of products by NMRBenz01n(mg)α―methylolbenzoin(mg)1,2 diphenylglycerol(mg)Integral ratio in l H NMRa)Benzdn αLttrd1,2-diphenylg ycerol??????152530302515252815821―-          16--           17--           1728           -―a) Integrating the peaks ot 5,90, 4,46d, and 3,91d ppm corresPonding to benzOin,α―methylolbenzoin, and l,2-diphenyl glycerol, resPectiVely,analysis using pentaerythritol as an internal standard gave only qualitative data,but it could llot be applied to these compounds quantitatively (Table 3)。Yoshihiro SHIGEMASA,Yoshinori SUETOKI,E?chi VAKI,and RukA NAKASHIMA:Formose Reactions, xll Formose Reaction in the Presence of Benzoin3. Results and Discussion近Ittοθチ9ズ フ物″ゲο″s Cοιαサt7.」§サdO%′力θFケθプ%θサDλサπゲう"サ′οη. It is reported that cocatal―ysts、vhich have an ellediol structure, such as fructose,glucose, and xylose, shortenthe induction period in the formOse reaction.7)Fujino θチα′13)prOposed that the com―olex (2)of enediOl compound and alkaline earth metal is effective on the formosereaction and the catalytic activity of the complex (2) dependS upon the kind ofalkaline ear倒ュm tal or of enediOl cOmpound.Hc ｀ち^_0■???、?玉と＼。`′や玉弓岳 ??However, no relationship bet、veen t e cocatalyst and the product distribution hasbeen discussed. Table 2 shows the effects of various cocatalysts on the productTable 2. Effects oF cocatalystsa)Cocatalyst T″,″(min)Sugar yield(%)Products(glC―%)2   13   14   18    19   22    23   26FructoseAscorbic acRdClucoseXylosePhenacyl alcoholTriose reductoneAcetoュnBenzoュn27.053.025.031.523.532.019214332.5251031.036.037.029,07.010,010108104102b)2    b)     2    23    b)2    2    2   28   b)2    2    2   23    2b)   b)   b)   21    2b)   b)    5   23    22    b)     2    23     210    37     9     3     2b)   b)   b)   b)   502   312  394  272  406   393  315  836  b)b)ReactiOn conditions:〔HCHO〕=1・OM,〔CaC12〕=0'005M,〔CoCatalyst〕=0・01M,PH=12.0(adiusted by KOH),Temp.=60°C,Total volume=200 ml.Glc―%waS below l%.distributiont The addition of monosaccharides, triose reductone, ascorbic acid, andphenacyl alcoLol was found to give a selective formose reaction which is similar tothose described ittl a previous paper3),4)and Of which the main products are 2-C―hydroxymethyl glycerol, 3-C―h droxymethyl pentitol corresponding to the GLC pe―aks of 2, 19, and 26, respectively.The addition of benzoin, however, resulted in a different selective reaction givingthe peaks of 22 and 23(about 90 glc―%). In he case of acetoin, a GlC peak of 14was a main procuct and amounted to 36 glc―身チ. BenZoin and acetoin are supposedReports of the Faculty of Engineering,Tottori University,Vol. 10117to have different effects on the formose reaction compared with monosaccharides。On the other hand, in the absence of cocatalystS no formose reaction could proceedunder the reaction cOnditions described in Table 2.Ttt Яο/2ηθsι ttθ,,ゲοηゲ″チカιP/ι∫ι″θθ ιデBι%Zοケ″. It is worth lloting that the additionof benzoin resulted in a selective formation of products corresponding to the GLCpeaks of 22 and 23. The effects of the concentration of benzoin was investigated(lrable 3). The results qualitatively show that increasing the concentration of ben―Table 3. Effects of the benzoin concentration3)〔HCHO〕(M)〔BenZOin〕(M)Tヵ,″(min)Sugar yicld(%)Productsb)   (glc―%)22           231,01,01.00.0101050,194.084.082.011.013.015.061(3.6)  28(1.6)73( 9,7)      15(1.9)80(16.2)     11(2.2)2)Reaction conditions:〔CaC12〕=0・005M,PH =12,0(adjusted by KOH),Temp.=60°C,Total volume = 200 ml.b) Parentheses indicate the product concentration (mg/ml), IVhiCh Was determined in gaschromatogram of TMS derivatives by pentaerythritol as an internal standard.zoin ttnded to increase the GLC peaks of 22 and 23. The products corresponding tothe GLC peaks of 22 and 23、vere extracted 、vith benzcne, purified by distillation,and identified as l,2-diphenyl glycerol. Perhaps, they ■light be diastereomers ofl,2-diphenyl glycerol.In order to kno、v this reaction pathway, the tiinecourse of products was measured.The reaction was carried out in a higher concentration of benzoin because, undersuch reaction condition, intermediatts such as α―me hyk)とb nzoin would be securedeasily. In these cases, the total amount of the products which vere extracted withchlorofor■l was nearly equivalent to the initial amount of beazoin, In Table 4, itseems reasonable to assume that α―methylol benzoin would be an intermediate ofl,2-diphenyl glycerol.Table 4. Tittne coutse of the productsa)Reactlon time(min)HCHO consumption(%)BenzOin i α―methylol : 1,2 diphenyユb)benzoin       glycerol103011540,062,095,0261646.5           043             41             7Reaction conditions:〔HCHO〕(adjuSted by KOH),Temp.=The ratios were calculated by=1.OM,〔BenzOin〕=0・5M,〔CaClク〕=0・005M,PH=12.060°C,Total volume=200mユ.integr ing the peaks of 5,90,4.46d,and 3.91d PPmYoshihiro SHIGEMASA,Yoshino? SUETOKI,E?c i WAKI,and Ruka NAKASHIMA:Formose Reactions, xll Formose Reaction in the Presence ct BenzoinThe above results led us to propose the reaction mechanlsms of the formosereaction in the presette of benzoin as foコow I At first,the methylollation of benzoinwith formaldehyde proceeds selectively to for■l α―methyk)l benzoin, folloved by across‐Cannizzaro reaction of α―me hylol benzoin with formaldehyde to yield,finally,1,2-diphenyl glycerol.  Of course, the Cannizzaro reaction of formaldehyde takesplace silnultaneously、vith the above reactiolls。OH OH                     H OHripttrΩtip⑥「l③繹粋 ③We authors thattk Mr.Toshio Hamada for his assistaltlce in our investigation.Referencesl)A.Butlerow,Ca里チ´・買¢″ど ,53,145(1861),4物・,120,295(1861).2) O.Loew,デ.PT歳チ. C″,″.,33,321(1886),Dar・,22 471(1889),30,1592(1906),3)Y.Shigemasa,0.Nagae,R.Nakashima, and T, Matsuura, ユ 4解。 C力♂防, Sο♂., 100, 1309(1978).4)Y.Shigemasa,R.Nakashima,C.Sakazawa,and T.M4tsuur2, 0/を力 ■′Lすノ杉,211(1978).5)T.MatSuura,Y.Shigemasa,and C.Sakazawa,C物″″.Lガチ.,1974,713.6)Y.Shigemasa,Mo Shimao,T.Matsuura,and C,Sakazawa, B″〃, C物♂′″。Sοθ.ヵ)″., 48, 2099(1975);Y.Shigemasa,T.Fujitani,C.Sakazawa,and T.Matsuura, β″″ C ヮ々筋。 Sο♂. 力″.,50,1527(1977).7)A.Kusin,β″.,68,619,1495,2169(1927).3)R.B.Wagner and H.D.Zook,“働″テルrゲσO/g,ガθC力劣″ゲd√ゅ",JOhn Wiley 8c Sons,Inc.,NewYork(1965),P.170.9)H.Euler and H.Hasselquist,4″″ク.る″″ゲ.,26B,Nr.5(1948).10)Y.Shigemasa,Y.Matsuda,C.Sakazawa,and T. Matsuura, B″〃.Cみ勢 . 助σ. 力″., 50, 222(1977),11)A.Matsuguma,“G,s(ン狗″,チ昭物少わ 却♭'SS,ゲ,'Tokyo Kagaku Dojin,Tokyo(1967),P,60.12) A,Wilttam,Cカヮ脇。4ι.81,170273(1974).13) K.Fu ino,J.Kobayashi,and I.IIiguchi,,V´ο´″FFg,そ″K″ゲs力が,1972,2297.

Formose Reactions.XII. Formose Reactions in the Presence of Benzoin

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Formose Reactions.?. Formose Reactions in the Presence of Benzoin

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