Tetrahydrofuhfuraldeh

TETRAHYDROFUHFURALDEHYDE AND RELATED COKPOUNDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By / ALBERT ANTOINE, B.S. The Ohio State Uhiverslty 1953 I'»*■•••* /••*** ,* • i'll* 1 • *I i• n i : - Approved bys i i ii i ii • • ♦ « » J * Adviser i ACKNOWLBDGBKBHT The author wishes to express his thanks and deep appreciation to Dr. Christopher L. Wilson for his con stant encouragement and guidance throughout the course of this work. K 1 3 6 6 6 ii TABLE OF CONTENTS Page I. INTRODUCTION 1 II. HISTORICAL 4 III. EXPERIMENTAL 8 A. Tetrahydrofurfuraldehyde 8 1. McFadyen-Stevena reaction 8 2. Roaennrund reaction 10 3* Oppenauer oxidation 12 If. Sodium trlmethoxyborohydride reduction * of tetrahydrofuroyl chloride 13 B. Preparation of tetrahydrofurfuraldehyde 15 C. Attempted rearrangement of tetrahydrofur furaldehyde 16 1. In ethanol, with mercuric chloride 16 2. In n-pentanol, with mercuric chloride 16 3* In ether, with phoephorua pentachloride 17 Ij.. Over acid-aaturated pumice 17 D. Preparation of a&hydroxyraleraldehyde 18 B. Preparation of glutaraldehyde 19 F. Pyrolyaia apparatua 20 1. Catalyata 20 2, Furnace 20 3« Catalyat tube 20 H i TABLE OP CONTENTS (continued) Page i|.. Constant rate addition funnel 22 5>. Control of a carrier gas 22 6. Activation of the catalyst 22 G, Behaviour of proposed intermediates in lactone formation 23 1. Tetrahydrofurfuraldehyde over 90Cu, lOPe catalyst 23 2* Dihydropyran and water over 90Cu, lOPe catalyst 26 3. c^Hy dr oxyvaloraldehyde over 90Cu, lOPe oatalyst 27 Ij.. ^Hydroxyvaleraldehyde over copper chromite catalyst 31 5. (f^Hydroxyvaleraldehyde over 80Ni, 20Cu catalyst 32 6. Glu tar aldehyde over copper chromite oatalyst 32 H. Side ohain elimination of tetrahydrofur furaldehyde 33 1« 80N1, 20Cu catalyst 33 IV. TABLES AND SPECTRA 36 iv TABLE OP CONTENTS (continued) Page V. DISCUSSION lj-7 VI. SUMMARY 55 VII. BIBLIOGRAPHY 57 VIII. AUTOBIOGRAPHY 59 I. INTRODUCTION Several attempts have been made to prepare tetrahy drofurfuraldehyde* In most instances they have been quite unsuccessful. The main difficulty encountered was apparently the result of the great susceptibility of the tetr&hydrofuran nucleus to ionic attack (25)* During the course of the present investigation, four additional methods were tried in an attempt to effect a satisfactory synthesis. cT-Valerolactone, an Isomer of tetrahydrofurfuralde hyde, has been identified as one of the products formed when tetrahydrofurfuryl alcohol is passed over metallic catalysts at high temperatures (1,2,3). The primary re action, however, was elimination of the side chain with tetrahydrofuran as the main product. It was noticed that the oatalysts of high copper content gave greater yields of the lactone. This faot suggested the intermediate formation of tetrahydrofurfuraldehyde. The lactone would then arise by the rearrangement of the aldehyde. This would be analogous to the rearrangement of cyolobutane- oarboxaldehyde to eyclopentanone (26). y-Valerolactome is also known to arise from oyclle dehydrogenation of 1,5-pentanediol under conditions simi lar to those which were present in the above reactions (1^,5) • The mechanism of its formation has not been investigated but it must proceed through one or both of the dehydrogen ation products of the diol. It has been shown (6) that e^-hydroxyvaleraldehyde exists in equilibrium with the cyc lic acetal, the latter comprising ninety-five percent of the mixture. CHOH- ■ <?ftftnl3arg=- type reaction These sequences of reactions were considered because (1) it is known that tetrahydrofurfuryl alcohol can be con verted to 1,5-pentanediol by hydrogenolysis (7*8,9), and (2) 3 ,ij--dihydro-2H-pyran is one of the products formed tvam tetrahydrofurfuryl aloohol upon dehydration and metal- catalysed pyrolysis (33*6). Addition of water and subse quent dehydrogenation would yield the lactone. <i) ♦H, 0 H _ •«qu«nee^ The purpose of this investigation was to study the behaviour of tetrahydrofurfuraldehyde as the intermedi ate in side chain elimination and lactone formation and also the behaviour of the other proposed intermediates in the formation of tf^valerolactone. II. HISTORICAL Tetrahydrofurfuraldehyde — In 192lj., Scheibler, Sots- oheck, and Frleee (10) attempted to reduce the furan ring of furfural, but found that more than two mols of hydrogen were always taken up. The diethyl acetal and the diace- tate of furfural were prepared, and reduction of the fursn ring then effected. Better success was achieved using the dlaeetate derivative, and the pure derivative of tetrahy drofurfuraldehyde was obtained. Hydrolysis of the deriva tive yielded a small amount of crude aldehyde. Mlnne and Adkins (11) also prepared the diethyl ace tal of furfural, and were able to reduce the furan ring in good yield. However, a good deal of resinification occurred during the hydrolysis of the acetal, and some difficulty was experienced in separating the aldehyde from the water-alcohol mixture. The overall yield of tetrahydrofurfural was if. percent based on furfural. Hins, Meyer, and Schuoking (12) made several attempts to prepare tetrahydrofurfuraldehyde. They tried to re duce furfural diaoetate by hydrogenation in ether with Raney nickel but obtained only furfuryl acetate and aeet- io add. Reduction of the cyclic ethylene glycol acetal of furfural in ether solution with Raney nickel was accom plished in 96 percent yield. However, the hydrolysis of -5- of the tetrahydrofurfural derivative resulted in a 9 per cent yield of aldehyde• The bulk of the acetal was re covered unchanged. These workers also oxidized tetrahydrofurfuryl alco hol with chromium trioxide, but obtained poor (less than 10 percent) yields of the aldehyde, unchanged alcohol and tetrahydropyromucic acid* Attempted dehydrogenation of the alcohol with a copper catalyst yielded only a slight trace of tetrahydrofurfuraldehyde, A very small yield of this aldehyde was obtained by Wilson (13) from the passage of tetrahydrofurfuryl alco hol over nickel and nickel alloy catalysts, but only at low pressure. In attempting a synthesis, he pyrolyzed a mixture of barium tetrahydrofuroate and barium formate, but tetrahydrofurfuryl alcohol was formed. Also attempted was a Stephens reduction of tetrahydrofurfuronitrile, but this reaction yielded ^hydroxyvaleraldehyde. Two more approaches were investigated in which cases the 2,4-dl- nitrophenylhydrazone was identified but no aldehyde was Isolated, In the first instance furoin was formed, re duced to the plnaool, then oxidized In glacial acetic acid with lead tetraacetate. Secondly, tetrahydrofurfuryl al cohol over copper chromite at 300-35>0° gave a fraction boiling 11*0-160° from which the derivative was obtained. The most successful method reported to date is that -6- of Brenner and Coata (Uj.)* They claimed a 60 percent yield of tetrahydrofurfuraldehyde by the oxidation of tetrahydrofurfuryl alcohol. The reaction was carried out in the vapor phase by passing a mixture of alcohol, water and air over a silver-gauze catalyst. Formation of ^valerolactone — Wilson (13) investi gated the behaviour of tetrahydrofurfuryl alcohol over a variety of nickel and nickel alloy catalysts. Removal of the side chain was the main reaction observed, with tetrahydrofuran as the chief product. Among the gaseous prod ucts was carbon monoxide. Other catalysts (2) 80 Co, 20 Cu; cupronickel (19.7 Ni, 80.3 Cu); ferry alloy (1^3.9 Ni, #4-3 Cu); 80 Ni, 20 Cu; 20 Co, 80 Cu gave similar results, but also small amounts of VWalerolactone. Possible lactone formation by direct re action of carbon monoxide and tetrahydrofuran in the vapor phase was investigated by Ballantlne (5>), but no reaction was observed. Thomas (3) also found ^valerolactone when tetrahydrofurfuryl alcohol was passed over iron-copper catalysts; the amount of laotone in the product Increased with the copper content of the catalyst. Accompanying products were valeric acid and tetrahydrofurfuryl valerate. The presence of valeric a d d was not unexpected since it was shown to arise from reductive fission of ^valerolactone (2). -7 Several investigators have reported </-valerolactone from 1,5-pcntanediol. A 78 percent yield of crude lactone (1$) was obtained by refluxing the diol over copper chromite at 210-245° for thirty minutes. Similarly, Bremner and Jones (ij.) obtained the lactone by refluxing the pentanediol at 180-230° over copper chromite. They also re ported a vapor phase reaction yieldings^valerolactone. This product was formed in 65 percent yield when the diol was passed over a copper-zinc oxide catalyst which had been reduced at 300° with hydrogen. Further vapor phase reactions were carried out by Ballantine (5). He inves tigated the behaviour 1,5-pcntandiol over copper chromite, a 50Fe, 50Cu catalyst and a 50Ni, 50Cu catalyst, and ob tained the lactone in all cases; the lactone was the main product when the chromite catalyst was used. (f-Valerolaotone was also formed by air oxidation of ^hydroxyvaleraldehyde (16). The yield without a catalyst, at 100°, was 65 percent, and with a cobalt acetate catal yst >vat ?6 percent at 80-90°. -8 III. EXPERIMENTAL A. Totrahydrofurf uraldehyde 1. McPadyen-Stevens Reaction (27) CH?— CHP CHjj— CHp \c | * 0 + HpNNH^HpO | I / + MeOH CHo C-C-OMe -=--- — QH-, C-C-NHNH? " V > i o ' 2 /<^rCH3 CHo— CEU C C CHp— CH0 C C-CHi | 2 \J/ ♦ |l 1 — » I Li //* H I CHg /c-c-nhnh2 cy^ ^ ch^ ^c-c-nhnhso2cn £ CHo—CHp C^-CHo CHp—CHp C^CH3 1 2 L V 11 I j KpCO, w I 2 |.20 4. II t +N* CH^ ^fT-C-NHNHS02q ^ glycefoT Ji-CH <yj Methyl tetrahydrofuroate was prepared by reduction of methyl furoate under fifteen atmospheres pressure at 130°, using Raney niokel as the oatalyst. In a typical reduction, four raols of the ester were reduced in eight hours. The average yield was seventy percent, Tetrahvdrofuroylhvdraslde — Methyl tetrahydro furoate, 65 g.(0.5 mol), and 1 mol of 100 percent hydra zine hydrate were placed in a 250-ml, Erlenmeyer flask.

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