Canadian JournaI o f Chemistry

Issued by T H E NATIONAL RESEARCH COUNCIL CANADA OF
VOL. 30

J U L Y . 1952

NUMBER 7

THE REACTIONS OF ACETALDEHYDE WITH METHANOL'

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 177.32.25.230 on 03/21/12 For personal use only.

ABSTRACT The nature of the products obtained from reactions of acetaldehyde with methanol have been investigated in neutral and acidic solutions by titration with iodine and sodium bisulphite, ultraviolet absorption, and infrared spectroscopy. I n neutral and buffered solution the hemiacetal is the only important product; in the presence of a high concentration of hydrogenions the acetal is produced nearly quantitatively. INTRODUCTION

I t is well known t h a t the reaction between many aldehydes and alcohols leads t o the formation of acetals (1,4)
R . CHO

+ 2 R'. OH -+ R . CH

/OR'

\OR!

+ Hz0

and the reaction is believed t o proceed through the formation of the corresponding hemiacetal: (1,4,6,8)
/OR1 R . C H O +R'.OH

-+ R . C H
'OH

(2)

Hemiacetals are ~lsuallyunstable compounds and are therefore difficult to isolate, but their existence, in reasonable concentration, in solutions has been postulated in a number of cases. T o interpret measurements of the rate of reaction of acetaldehyde with methanol (7), we have found it necessary to study in some detail the factors governing the formation of acetal and hemiacetal and to investigate the possible formation of other products, such as would be formed b y condensation and polymerization reactions of acetaldehyd.e.
EXPERIMENTAL

The nature of the reactions that occur when acetaldehyde and methanol are mixed under different conditioils was investigated by three methods-titration with bisulphite and iodine solutions, ultraviolet absorptioil, and infrared spectroscopy.
filanuscript received March 5 , 1952. Contribulion from tlce Division of Clbemislry, Natio?tal Research Laboratories, Ottawa, Canada. Issued as N.R.C. No. 2746. 2 National Research Council Postdoctoral ~ e l l m 1945-50;Present address: c / o E. I. ' dzrPont de Nemozrrs, Wilnzington 98, Delaware.

Some of the s a n ~ ~ l used es were distilled in an atmosphere of nitrogen and collected in small glass phials which were then sealed and used immediately after preparation. the final concentration of hydrochloric acid being about O. of the completely reacted solution of acetaldehyde in methanolic hydrochloric acid was added t o 25 cc. However.32. Reagent methanol. when 10 cc.25.092 M (excess) sodium bisulphite and allowed t o stand with occasiorlal shaking. sp.'s Research Grade n-heptane was dried with sodium before use. was used without further treatment.5%) with that calculated from the initial concentration of aldehyde. t was i found that only 6% of the original acetaldehyde added was converted t o the bisulphite compound after 30 min. for the first reaction t o be completed. I t was found that. of 0. by the addition of solid sodium bicarbonate. I n this latter case it was not feasible t o estimate the excess of bisulphite. gr.188. Under those conditiorls the concentrations of aldehyde a s measured by the two methods agreed (within f 0. and Shaffer (5). if rnethanolic hydrochloric acid were added t o the solution of acetaldehyde in methanol. The excess of bisulphite was titrated with standard iodine solution and the concentration of aldehyde calculated. Analar Grade sodium chloride was heated to l5O0C. and then estimating the Iiberated bisulphite by further titration with iodine. This was checked by decomposing the bisulphite compound.5"C.OOINl and if sufficient time were allowed for the reaction t o be comple~ed. and titrated. Can. making alkaline with sodiurll bicarbonate t o decompose the acetaldehyde-bisulphite conlpound. Chem. .80°C. since in some of it had decon~posed the strongly acid solution. 60% of the acetaldehyde could be estimated as the bisulphite compound. 1 ' 0 L . with "neutral" rnethanolic solutions. 30 iUateria1s Acetaldehyde was supplied by the Eastman Kodak Company in sealed bottles and was kept in cold storage until required. and by titrating the liberated bjsulphite with standard iodine solution. Conlnlercial hydrochloric acid. . Cotonio.O2 C B N A D l A N J O U R N A L O F CNEIIIISTRY. Downloaded from www. Ten cubic centimeters of the metha~lolicsolution of acetaldehyde was added t o 25 cc.* reproducible results were obtained orlly if the solution was left for a t least 30 min. and *These solzrtions conlained only szrch acids as were present i n the methanol and acetaldehyde. Phillips Petroleum Co. 1. but it was possible t o estimate the acetaldehyde-bisulphite compound by neutralizing t h e excess of bisulphite with iodine. On the other hand. cooled.com by 177. heated t o 60°C. J. for several hours and stored in an evacuated desiccator. was used in preparing the dilute solution employed. The bulk of the methanol was removed. supplied by the Brickman Company. Products T h e product obtained from the hydrochloric acid catalyzed reaction was isolated and purified. Bisulphite Titration T he procedure was that described by Friedemann. T h e liquid condensate in the trap was treated with sodium until no further gas was evolved and distilled twice from calcium chloride. the final product being collected between 63.nrcresearchpress.230 on 03/21/12 For personal use only. of 1 N aqueous hydrochloric acid. by shaking with excess calcium chloride and the solid mass which resulted was brolcen u p and evacuated through a trap coolecl to .

J. the instrument being set a t A2925 A.AlEADOlVS AAlD DARII'ENT: .) for experiment 299 was approximately linear during the early stages but later a slight curvature occurred.07 1. using Becklnan Model D. and it is likely that this was responsible for the increased rate in the latter part of the experiment.42 X 10-%nd 6. Can.-L Extrapolation of the initial linear portion t o zero time showed the initial density t o be 3. quartz cell was filled and the optical density measured at frequent intervals.d.. during the course of the reaction. at 758 mnl.208.15 M) were measured over the range X 2200 A t o 2300 A.8. quartz cells..15 M) and of acetaldehyde distilled under nitrogen (0.66 X n1in.79 1.25. = 1. The rate of the reaction of acetaldehyde with methanol was measured spectrometrically.nrcresearchpress.The plot of log (dl . The temperature of the solution was foul~d o have increased from 25" t o 31. ( 3 . experinlent No.5"C.228 M soltltion. The absorption spectra of n-heptane solutions of untreated.23 The lower values obtained for log em. and 65°C.32. 299 and 301. indicating a small accelerat tion in rate. 299 represents the disappearance of the carbonyl band in neutral solution and No.230 on 03/21/12 For personal use only. probably owing t o the heating effect of the adjacent lamp housing. 9 ) . The absorption maxima and extinction coefficients are recorded in Table I together with values previously reported in the literature.com by 177. This value.22 0. which corresponds to log k.8"C. a t 761 nlm. The boiling point of dimethyl acetal has been reported as being between 63°C. a sample supplied by the Eastman Kodak Company was found t o have a boiling point of 63. I t is interesting to note . The rate constants a t the start and end of the reaction were 5. in conjunction with the final density value of 0. acetaldehyde (0. After the solution was stirred for one minute a 1 cln. T h e results of two experiments. are show11 in Fig.. spectrophotometer with 1 cm.19 1. TABLE I ARSORPTION COEFFlClENT OF ACETALDEHYDE I 1 N 1Z-HEPTANE I Untreated acetaldehyde Distilled acetaldehyde Bielecki and Heilri (2) Schou (10) Herold and Wolf (6) (unpurified) Herold and Wolf (6) (purified) 2900 2900 2900 2950 2900 2900 1.22 ior the 0. Downloaded from www. Chem. The solution was prepared by breaking a glass phial containing a known weight of acetaldehyde under a known volume of methanol.4CETtlLUEHYDE-2TIETHA1VOL E A C T I O N S R 503 63. showed that 95y0 of the original material had reacted. 1 . We have examined the acetaldehyde ~nethanol system by this method.. 301 the subsequent reaction on addition of acid.U.07 1...4"C. are probably caused by the presence of polymer in the untreated acetaldehyde and the agreement obtained with Herold and Wolf's figure suggests that the nitrogen distilled acetaldehyde useci in our experiments was reasonably pure. Ultraviolet Absorption Herold and Wolf (6) studied the reaction between various aldehydes and alcohols spectrometrically.

114 N hydrochloric acid to 25 cc. 1. of 0. The reaction which occurs when 1 cc. A . 2 9 S n e u t r a l solution. I t was found to correspond to the complete disappearance of the carbonyl group remaining in solution and t o proceed in a first order manner. FOL. OF L'HEAflSTRY.* using methanol as .C A N A L > I A N JOCKNAIL. j 0 Can. T h e stro~ig absorption of methanol made it necessary to use a very * W e are i7zdebted to D r .nrcresearchpress.228 A Expt. Cole a7rd Mr. 301-reaction induced by adding 1 cc. K.230 on 03/21/12 For personal use only. T h e velocity constant for this reaction was 2.-' Infrared Spectroscopy The products o the uncatalyzed and hydrochloric acid catalyzed reactions f were characterized b y infrared absorption measurements. N. L Expt. of the completely reacted'neutral solution from Expt. Latczon for the n~easurements. of a reacted solution of acetaldehyde i11 neutral methanol has also bee11 followed spectro~netrically(Fig.of asolutiol~ of acetaldehyde in methanol a t room temperature". acetaldehyde concentration (initial) = 0. R. the solvent. J. Jones for the zcse of the spectrometer and to Dr. 301).25. . R. H. The effect of time onLhe intensityof the carbonyl absorption a t 2925 A. Expt.114 N hydrochloric acid is added t o 25 cc. Downloaded from www. of 0.com by 177.32. 299. 1. Chem.70 X lop2 ~nin. that the initial molar extinction coefficient of acetaldehyde was the same in methanol as in n-heptane. 10 20 MINUTES 30 40 FIG.

4CET. were found t o be identical (Curve A .285. for two solutions of the same concentrations.85 A f and the measurements made with a Perkin-Elmer 12 C Infrared Spectrometer with a rock salt prism and a 0.867 J6 solution of dimethyl acetal in methanol the optical density a t 869 cm. A 0. was found the t o be identical with that observed for the two solutions previously examined. one containing the purified product of the hydrochloric acid catalyzed reaction of acetaldehyde and methanol and the other Eastinan Kodak dimethyl acetal in methanol.32. which further supports the conclusion that the acetal formation reaction goes nearly to coinpletion in the presence of excess methanol.2. A -- DIMETHYL ACETAL (AND PRODUCT OF COMPLETE REACTION OF CH3CHO) I N M e D H Can.nrcresearchpress. The solutions were between 0.847 M. The optical density of the reacted acetaldehyde solution at. J.com by 177.lLDEIIYDE-J~IETHA O L KEACTIOlVS N 505 thin cell and.230 on 03/21/12 For personal use only. Fig.? was found t o be 0.-l and 1240 c m .80 M solution of acetaldehyde in neutral methanol was prepared and . infrared absorption. corresponding t o concentrations of 0.-l was 0.853 M solution of acetaldehyde was prepared in 0. Infrared absorption spectra of the products of the reaction of acetaldehyde with methanol.- PRODUCT O r "INCOMPLETE" REACTION OF CH3CH0 IN NEUTRAL MsOH F R E Q U E N C Y ( CM.111E:JDOTI'S A X D DARIVEIVT: .' ) FIG. Chem.25. For a 0. measured over the same range.80 M and 0. somewhat higher concentrations of acetaldehyde than in the dilatonleter experiments. 2). Downloaded from www.292. A 0.0016 N methanolic hydrochloric acid. 8.869 cm. 7 . After sufficient time was allowed for the reaction t o be con~pleted. therefore. cell.025 inm. The absorption curves between 880 cnl.

CLAUS. chim. G. This latter evidence rules out the possibility of the production of paraldehyde. 2. 5. Z. E.. Hence the two reactions ( I ) and (2) leading t o the hemiacetal and the acetal may be readily separated and studied individually b y controlling the hydrogen ion concentration. which is characteristic of the ether linkage. 8. 220: 104. 26: 77. J.W. J. 50: 178. Chem. a n d t h e bisulphite titration showed t h a t the cornpound produced did not react readily to form the bisulphite add. and TRAINER.) 7. C.230 on 03/21/12 For personal use only.and HENRI. B. MEADOWS. Am. 46: 3627. ADKINS. 1927. FRIEDEMANN. 17. B. 12: 165. 1911. 1931. Biol Chem. J .. Downloaded from www. I<. as expected if the hemiacetal were produced. 77: 284. AD.IISTRY. A. Ann. P. T h e observecl d. CONCLUSIONS T h e results give11 above indicate strongly t h a t the hydrochloric acid catalyzed reactio~lof acetaldehyde with ~nethanolresults i11 the formation of acetaldehyde dimethyl acetal and t h a t no other products such a s aldol or polymers are produced. A. physik. M. A. and SHAFFER. ( I n press.. N. 1928. SCHIFF. J.'.com by 177. 71: 3651. and DARWENT. and BRODERICK. 1913. Soc. S. Chem. Fig. 73: 342.-l.icating an ether linkage.ition compound. Chem. and b y the fact that the compound forked had an infrared spectrum quite different from that of the dimethylacetal and showed a strong absorption a t 1140 cm.-I.ifference between the t\vo curves shows t h a t unique products are formed a t each stage of the reaction between methanol and acetaldehycle. and WOLF. H. Soc. This was shown by the fact t h a t all of the acetaldehyde could be compoirnd. Chem. 1886. MELCHOIR. T h e spectrunl was nleasured in the region 880 cln. BIELECKI. also the system is not complicated by the occurrence of other reactions such as the formation of aldols o r polynlers. E. R. the spectrum of the intermediate product showed strong absorption a t 1140 cnl.32. SCHOU. H. 19: 3004. 1929. COTONIO. 6. I-Iowever. ind. infrared spectroscopy showed t h a t the only detectable product had a spectrum indistinguishable from that of dimethylacetal. 30 allowed to react completely.-I and the resulting curve (Curve B. since this substance cannot be obtained in the form of a pure stable compound. 10.-' t o 1240 c~n. I t is 11ot possible t o correlate the observed spectrum with t h a t of methyl hemiacetal. HEROLD. Ber. DE LEEUW.506 C A N A D I A N JOURNAL OF CFIE. Z.ifferent from that obtained for the acetal solutions. Chem. Am. VOL.25. J. T. L. 1949. t h a t the intensity of the carbonyl accounted for a s the bis~rlphite band a t 2900 was greatly diminished. 4. E. in significant arnounts. phys. J. W. IJltraviolet spectroscopy showed t h a t the carbonyl group completely disappears. 3. 499. 2) was found to be quite d. a REFERENCES 1. Can. Ber. .DEB.nrcresearchpress. I n "neutral methanol" it is probable t h a t acetaldehyde forms only the hemiacetal.I. 9. physik. 1883. L.

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