Abnormal Reactions of Fürfuryl Chloride And

Home , Furfuryl alcohol, Thionyl chloride

ABNORMAL REACTIONS OF FÜRFURYL CHLORIDE

AND RELATED COMPOUNDS

DISSERTATION

Presented in Partial Fulfillment of the

Requirements for the Degree Doctor

of Philosophy in the Graduate School

of the Ohio State University

Calvin J. Benning, B.Sc.

The Ohio State University

1953

Approved by:

' "Adviser ACKNOWLEDGEMENT

The author wishes to express his deepest thank.s to

Dr. Christopher L.Wilson for the continuous help and en couragement he has given throughout the entire course of this investigation.

The author is also indebted to the Cincinnati! Chem ical Co. for the fellowship grant which was available during the completion of the major portion of this work.

The author also wishes to thank the Quaker Oats Co. for their fellowship grant, which was essential to the final completion of this work. il TABLE OF CONTENTS

Page Introduction 1

Statement of Problem 3

Discussion of Results 3

Experimental:

Preparation of Furfuryl Chloride 8

Reaction of Furfuryl Chloride with Sodium Me- thoxide in Anhydrous Methanol 10

Attempted Separation of Furfuryl Chloride/So dium Methoxide Reaction Products 11

Preparation of W-6 Raney Nickel 12

Reduction and Separation of the Products from Furfuryl Chloride/Sodium Methoxide Reaction 13

Index of Refraction Method of Analyzing Pro ducts of W-6 Reduction and Distillation 15

Beckman Infrared Absorption Method of Analysis of Mixture 16

Reduction of Furfuryl Alcohol with W-6 Catalyst 17

Preparation of Tetrahydrofurfuryl Methyl Ether 18

Preparation of Furfuryl Methyl Ether 20

W-6 Reduction of Furfuryl Methyl Ether 21

Preparation of N-Dimethyl Levulinamide 22

LiAlH^ Reduction of N-Dimethyl Levulinamide 23

Preparation of 5-methoxy-2methyltetrahydrofuran 25

Preparation of Derivative of 5 methoxy-2 methyl- 26 tetrahydrofuran

Molecular Weight Determination of 5-methoxy-2meth- yltetrehydrofuran 26 ill TABLE OF CONTENTS(cont»d)

Page

OzonaLysis of Furfuryl Chloride/Sodium Methoxide Reaction Product Mixture 27

Iodoform Reaction of Furfuryl Chloride/Sodium Methoxide Reaction Product îUxture 29

Infrared Spectrograms of Pure Furfuryl Methyl Ether and Abnormal Product 29

Ultra-Violet Absorption Curves of Furfuryl Meth yl Ether, 2-methylfuran & Reaction Product Mixture 30

Derivatives Obtained from Methanolic HCl Solution of 2,4 dinitrophenylhydrazine 30

Attempted Synthesis of 5-methoxy-2-methylfuran gg

Reaction of Anhydrous Methanolic HCl Solution with Furfuryl Chloride/Sodium Methoxide Products 31

Summary 39

Appendix 40

Bibliography 57

Autobiography 59 1

ABNORMAL REACTIONS OF FURFURYL CHLORIDE

AND RELATED COMPOUNDS

Introduction

Furfuryl chloride is a very unstable compound and its

reactions have not been extensively stuaied. Among the first to attempt the preparation of furfuryl chloride were

Von Braun and Kohler. These authors attempted^^ the Von

Braun reaction of the benzoyl derivative of furfuryl meth yl amine with phosphorous pentachloride. This resulted in

complete résinification of the entire reaction mixture.

Later, Gilman and Vernon^l attempted to prepare furfuryl

chloride by treatment of an ethereal solution of furfuryl

alcohol with thionyl chloride at low temperature and also

by passing dry hydrogen chloride into an ethereal solution

containing calcium carbide as a dehydrating agent. The

chloride v/as never isolated. If, however, the ethereal so

lution was treated with sodium ethoxide Gilman claimed the

formation of 5-10% ether. W.R.Kirner^ was reallythe first

to isolate furfuryl chloride in fair yields (63%). His

method consisted of reacting furfuryl alcohol with thionyl

chloride in the presence of excess pyridine. All flasks

used in the distillation, were previously washed with so

dium hydroxide solution. T.Reichstein^ improved this pre

paration further by using a pentane ether mixture for the

solvent and running the reaction at the boiling point of

ether. The yield rose to about 75%. The method used in this work is a variation of the Kirner and Reichstein method.

The«abnormal» or «anomalous» reactions of furfuryl 2 chloride were first studied by Reichstein . He obtained mostly 5-methyl furoic acid and a small amount of furyl- acetic acid by hydrolysis of the reaction products ob tained by the reaction of furfuryl chloride and strong a- queous sodium cyanide. Reichstein explains the reaction according to Figure 2. Further work by hirn^^ and his co-workers confirmed this proposal but they did not es tablish the existance of Figure 2-IV, For example, 1-fur- ylethyl chloride VII under similar circumstances also gave the «abnormal acid» VIII.

k c n H-zO *CH NlTRtUE.6 \CH% 5ZEL--- 7 V lit Scott and Johnson' studied the mechanism of the re action, They reported that the hydrogen in the 5 position was essential to rearrangement because 5-methyl-2-furfuryl- chloride gave no «abnormal» product. About the same time

Reichstein^^ reported identical findings,

Scott and Johnson^^ synthesized 5-chloro-2-metiiylfuran which is isomeric with furfuryl chloride, A study of the properties showed that rearrangement prior to metathesis was impossible. 3 This reaction of furfuryl chloride appears to be an example of a bimolecular type displacement reaction with rearrangement (Winstein^^ et.al,). Only two other such cases are established. One is V/instein and Young demon

stration that cx methyl and cx ethyl-allyl chloride react with sodioraalonic ester to give 10 and 22% respectively

"abnormal" product. The other is Hughes, de la Mare, and

Vernon^® claim allylidene chloride reacts abnormally, A kinetic study (Wilson and Eland-English'^ of the furfuryl

chloride-cyanide reaction failed, owing to the non-homoge neity of the reactants.

Instead the reaction with sodium methoxide was studied.

The results showed strictly second order kinetics, first

order with respect to methoxide ion and first order in fur furyl chloride concentration. The ratio of abnormal ether

to furfuryl methyl ether, determined by precipitation of derivatives was 40;60 and nearly independent of temperature between 0°C and 40°C,

Statement of Problem

The present work v/as concerned mainly with an estab

lishment of the structure of the reaction products of the furfuryl chloride/ sodium methoxide reaction and an eluci

dation of the mechanism of the formation of levulinic acid

derivatives.

Discussion of Results (Figure 1) The reaction of furfuryl chloride with sodium meth oxide yielded a mixture of products B.P, 134-126^C.(IR 2,5j the infrared spectrograms are in the Appendix). Attempts to resolve the above mixture by distillation, crystalliza tion at lovf temperatures and formation of maleic anhydride adducts were unsuccessful. Analysis of the mixture showed the mixture to have the formula C^^EgOg, and to absorb two moles of hydrogen per mole of mixture. The reduced mix ture yielded the expected tetrahydro-furfuryl metlQ''l ether and theabnormal acetal, (IR 4,5). The reduced mixture was analysed by infrared absorption spectra and index of refraction curves. The calibration data were obtained on mixtures of the pure compounds synthesized by reliable meth ods. The methods showed there was approximately 31-36 per cent abnormal product and 64-69 percent normal.

The Structure of the Normal Ether (Figure 1,11)

The identity of furfuryl mettiyl ether was established tlirough its tetrahydro derivative. The reaction product, tetrahydro furfuryl methyl ether was identified by two inde pendent synthesis; (1) by catalytic reduction of pure fur furyl methyl ether with Yf-6 Raney nickel, (2) by converting the tetrahydro furfuryl alcohol to its ether with dimethyl sulfate. The saturated reaction product gave the same boil ing point, index of refraction, density, carbon and hydrogen analysis and identical infrared spectrograms (IR 5,6) as the authentic tetrahydrofurfuryl methyl ether.

The Structure of the Abnormal Product (Figure 1,111)

The structure of the abnormal acetal, obtained from the catalytic reduction of the original reaction mixture, was established by tv/o methods. First, the abnormal ace tal gave a yellow DWPH which gave no melting point depres sion with the DHPH of authentic ^-hydroxyvaleraldehyde thereby indicating the structure to be 5-methoxy-2-metliy 1 - tetrahydrofuran. The X-ray powder photographs of the tv/o

DNPH’s were compared and they proved to be identical. The structure of the saturated abnormal product was further es tablished by synthesizing 5-methoxy -2-me tliy It etrahy dr of ur an from authentic Y-hydroxyvaleraldehyde. The boiling point, index of refraction, dinitrophenylhydrazone derivatives, and infrared spectrograms (IR 4,7) være the same.

The abnormal ether must therefore be one of the follow ing.

H^CO

A b c Structure A is the most likely for the following reasons;

1. The infrared spectra of the reaction mixture shows absorption in the conjugated carbon double bond region (IR 2,3,8) while the ultraviolet spectra indicates a non-fur an conjugation at 2,450A (UY 1). 6

2. The reaction between 5-iodo-2-metliylfiiran and sodium methoxide at elevated temperature gave traces of

5-methoxy-2-methylfuran detected by a DNPH derivative.

The only derivative obtained was that of metiiyl levulinate which would be expected from structure B. The react ion product mixture gave three derivatives, of v/hich a small proportion was methyl levulinate. Structure B and G would be expected to give only the derivative of methyl levul- ina.te. Therefore, from the derivatives obtained, struc ture A is again favored.

5. The reaction product mixture gave an iodoform test, while pure furfuryl mettiyl ether, and 2-metliylfuran did not. This is an indication of structure A or C but not B. The mechanism of iodoform formation may be pic tured as happening according to the mechanism in Figure 4.

4. Structure A is also favored since pure furfuryl methyl ether gave the three derivatives in the same pro portion but slower than the reaction product mixture. 2,5-

Dlmethoxy-2,5-dihydro-2-methylfuran gave the same deriva tive also in the same proportions but at a slightly faster rate than the reaction mixture. This can be explained by rearrangement' of the furfuryl carbonium ion,(Figure 5).

A,rearrangement of this type was reported by Ushakov and

Kuckerov^^ in 1944. This interpretation is an indication that when furfuryl methyl ether forms these derivatives it 7 first passes through the structure A and then to the di me thoxy compound. This indicates structure A as being the abnormal ether, but not C or B.

5. Another piece of evidence favoring A is that if a mixture of abnormal and normal ethers is added to aniiy- drous metlianol containing a trace of hydrogen chloride, a small amount of 2,5-dimethoxy-2,5-dihydro-2-methylfuran is isolated plus unreacted furfuryl metliyl ether and pol ymer. Structure C would be expected to yield 2,5-dimethoxy-2,3-dihydro-2-methyli’uran or 2,5,5-trimethoxy-2-methyltetrahydrofuran, while structure B would cleave. The compounds obtained from C or B would be methyl levulinate.

No methyl levulinate or its derivatives were obtained.

6, If one considers all three structures, it be comes apparent that B and C could only arise through a hy drogen shift of structure A. The hydrogen in the five po sition, in structure A is stable to base. The two oxygen containing groups attached to the five carbon are electron releasing groups, thereby stabilizing the hydrogen against abstraction by a base. Reichstein obtained the 5-cyano-

2-metiiylfuran because the cyano group is strongly electron attracting and therefore activates the five hydrogen to basic attack.

This survey of results together with the kinetic data 9 of Wilson et. al. confirms the existence of an authentic 8

Sng» reaction,*

* The term Sn^” is used to show the displacement is tak ing place in a position two double bonds removed from the carbon bearing the active halogen.

Experimental

Preparation of Furfuryl Chloride (IR 1)

Furfuryl chloride v/as prepared by a variation of the

Kirner^, and Reichstein^ method.

In a two liter round bottomed flask, fitted with a stirrer, dropping funnel and a reflux condenser to the upper end of which a calcium chloride tube is attached, were placed 160 g, (1,65 moles) of freshly distilled fur furyl alcohol, 135 g, (1,71 moles) of pyridine dried over

BaO, and 200 ml, of anhydrous ether,

A pentane solution (200 ml.) containing 200 g, (1.68 moles) of thionyl chloride was added dropwise at the rate of 150 ml, per hour to the rapidly stirred solution main tained at 0°~ 5°C,

When all had been added the reaction mixture was stirred for an additional twenty minutes and then the dark amber liquid was decanted into an Erlenmeyer flask 9 containing 100 g, of anhydrous sodium carbonate. The ice salt bath was removed and the mixture extracted five times with 100 ml, of pentane each time precooled to O^C,

The last two extractions were conducted at room tempera ture. All extracts were combined over anhydrous sodium carbonate, (Mote, large amounts of 80g were evolved in the process of addition to anhydrous sodium carbonate but as long as sodium carbonate was in a large excess there was no danger of polymerization), The combined extracts were distilled on a water bath at 60°C, to remove all pentane and ether. At the first sign of temperature rise of the mixture above 40 vacuum was applied and furfuryl chloride distilled under vacuum into a cooled receiver.

At tne end of the distillation the product was immediate ly weighed, stoppered, and placed in a dry ice Dewar, containing enough dry ice to freeze the water vdiite fur furyl chloride and to keep it solid.

Yield 70 - 80% - 1,4898

B.P, 46 - 48°C/ 84-25 mm, n ^ - 1,4952

20 dgQ - 1,1812*

* The picnometers which were used in determining the densities of furfuryl chloride were ruined because of spontaneous decomposition of the furfuryl chloride^ Caution should be exercised at all times to eliminate all moisture and no vessel should be allowed to come in contact with any acids at any time. 10 Reaction of Furfuryl Chloride with Sodium Methoxide in

Antiydrous Methanol li— -OCM& 4------^ 1 mmm

In a one liter round bottomed flask, equipped with a mercury seal stirrer, reflux condenser and dropping funnel, was placed 850 ml. of anhydrous methanol^ which contained 190 g. of sodium (0.825 moles).

To a rapidly stirred alcohol solution was added dropwise 64.0 g, of furfuryl chloride (0.54 moles). As addi tion proceeded, the mixture turned milky yellow, from the formation of sodium chloride.

After allowing the reaction to stir overnight, an equal volume of distilled v/ater was added. The total volume v/as continually extracted by n-pentane until the original liquid gave no DNPH derivative.

The pentane was distilled off and the remaining oil distilled through a Claison flask to dryness.

Yield 95^ n^^ - 1.4520

B.P. 132.5 - 153 C. d^g - 1.0149

Theoretical 7.15 64.2

Observed 7.20 64.26 11 Attempted Separation of the Furfuryl Chloride/Sodium

Methoxide Reaction Mixture Products (IR 2)

Various columns have been employed to separate the reaction products in the furfuryl chloride/sodium meth oxide reaction. The first attempt was using a 40 x 1.4 cm. helice packed column. The temperature of the distillate varied from 134-136^0. over the entire distillation.

Eight fractions were taken and successive infrared spec trograms ran superimposed on one sheet. The spectrograms showed a continuous gradation with fractions collected uniformly over that two degree range. The index of re fraction were all within the range 1.4507 and 1.4523.

Other attempts were tried on a distillation column

80 X 1.0 cm, with a rotating band. The principle is one of total take off from partial reflux brought about by an au>:iliary air condenser and a secondary water condenser.

Only partial separation was obtained, a similar result to that mentioned above v/as encountered.

The second method was through the preparation of maleic anhydride adducts. The melting point of the adduct obtained from pure furfuryl methyl ether, and from the re action mixture were different. M.P, of adduct from pure furfuryl methyl ether 193°C. M.P. of adduct from mixture

185^to 195*C. Attempts to recover the original compounds

only led to tar formation. 12 The third method was through chromatographic separ ation. Using bbfo silicic acid, 45^ celite, as an absorb ant, nitro-benzene as solvent and various ether-benzene- ligroin mixtures as developers. No separation was accom plished.

The fourth method was lev/ temperature fractional crystallization; but only glassy plastic materials were obtained at -80*C.

Preparation of W-6 Raney Nickel

The catalyst used in the reductions was prepared according to the procedure of Adkins and Billica^,

In a tv/o liter Erlenmeyer flask equipped with a ther mometer and a stirrer, was placed 160 g. of sodium hy droxide in 600 ml. of distilled water. To the rapidly stirred solution was added 125 g. of Raney nickel allu- minum alloy while maintaining the temperature of the mix ture at 48-52^0. This was done by regulating the addition of the alloy. At the completion of the addition, the sus pension was digested at 50°C. for fifty minutes with gen tle stirring. It was sometimes necessary to change from an ice bath to a steam bath to maintain the desired tem perature. After digestion, the catalyst was washed three times by décantation and then transferred immediately to the washing tube for further washing.

The washing was done under a half atmosphere of hy drogen with twenty five gallons of distilled water, in an 13 apparatus similar to the one used by Adkins'^. The rest of the procedure was simply to remove the Raney nickel and wash it several times with anhydrous methanol, fol lowed by décantation. The metal was stored in the deep freeze under methanol.-Jî-

The W-6 Raney nickel can be used effectively for ten days following the preparation without loss of activity.

Reduction and Separation of the Products from Sodium

Methoxide Reaction with Furfuryl Chloride (Figure 9) DL CH -t* ►" 4- 3 Haco

Into a 250 ml. citrate bottle was placed 47.0 g, of reaction products from reaction of furfuryl chloride and sodium methoxide, 50 ml, of anhydrous methanol and 3 scoops (approx. 3 g.) of freshly prepared W-6 catalyst.

The bottle was placed on a shaker and the hydrogen commenced to be absorbed immediately. The compound ab sorbed 1,86 moles of hydrogen for every mole of reaction mixture, and stopped absorbing. The reduction mixture was filtered, and catalyst washed vfith anhydrous methanol

(20 ml.). The alcohol was distilled through 1.4 x 25 cm. helice packed column. The resulting residue was taken up in ether and dried over anhydrous calcium chloride. The ether was removed through the same column and the result- 14 ing oil fractionated,-::-

RUN A

Fraction Weight DNPH (M.P.) 1. 116-118 1.4110 6.8 g. 124.6-126.0 2. 118-138 1.4215 9.5 g. 125.0-126.0 3. 139-141 1.4238 7.0 g. None

RUN B

Fraction Weight DNPH (M.P.) 1. 109-119 1.4088 3.5 g. 124.8-125.4 2. 120-137 1.4190 2.8 g. 124.6-125.6 3. 139-141 1.4240 8.0 g. None

* All yields of DNPH precipitates not significant because of not being able to get 100^ yields from 5-methoxy-2- methyIfuran.

Reduction Data

Hydrogen absorption of furfuryl chloride sodium meth oxide reaction mixture with W-6 Raney Nickel. (See Figure 9)

Time Amount of Hp absorbed (min. ) (Ibs/iu

0 0 5 3.5 For 0.42 moles of mix- 10 7.5 ture 68.7 lbs/in'^ is 15 11.0 the theoretical Ho up 20 14.0 take (for 2 double bonds). 30 20.5 35 25.0 64.5 = 93.6^ 45 32.0 68.7 55 37.5 65 43.0 75 48.0 85 52.0 95 55.5 105 58.5 115 60.0 142 63.0 160 63.5 178 64.3 208 64.5 15 Index of Refraction Method of Analysing Products of

Y/-6 Raney Nickel Reduction and Distillation (Figure 7)

The pure components of the irdxture were synthesized by independent means. (Ref.5,6,8) The samples were all weighed on an analytical balance.

1. Pure 5-methoxy-2-raetl:]yltetrahydrofuran n ^ - 1.4093

2. 0.50 g. of 5-methoxy“2-metbyltetrahydrcfuran added to 1.00 g. of tetrahydrofurfuryl methyl ether

n ^ - 1.4195 25 3. 0.50 g. of each component n ^ - 1.4167

4. 1.00 g. of 5-methoxy-2-methyltetrahydrofuran added to 0.50 g. of tetrahydrofurfuryl methyl ether 25 n^ - 1.4150 25 5. Pure tetrahydrofurfuryl inetiiyl ether n ^ - 1.4240

Figure 7 illustrates how closely the refractive index of the mixtures of the two compounds follow a linear rela tionship.

The application of this method to the mixtures de scribed in the previous section gave the fo3lowing results, by extrapolation on Figure 7.

RUN A - Contains 6.8 g. plus 1.7 g. = 8.5 g. abnormal

7.0 g. plus 7.8 g. =14.8 g. THFONiE

Therefore Run A contains 56.5^ abnormal product 16

RUN B - Contains 3.5 g. plus 1.0 g. = 4.5 g. abnormal

8.0 g. plus 1.8 g. = 8.8 g. TïïFOm

Therefore Run B contains 51.5^ abnormal product

Beckman Infrared Absorption Method of imalysis of Mixture (Figure 6) Q Redistilled 5-methoxy-2-methyltetrahydrofuran and tetrab^mrofurfuryl metljyl ether^'^ were used in the in frared absorption method of analysis.

Two standard solutions were made up and then various percentage compositions made up from the standard solu tions, using graduated pipettes.

Solution A contains 0.9146 g. of tetrahydrofurfuryl-

methyl ether in 11.2362 g. of carbon disulfide solu

tion, 8.15^.

Solution B contains 0,9227 g. of 5-methoxy 2-methyl

tetrahydrofuran in 11.3747 g. of carbon disulfide

solution, 8.17#.

From the two solutions mentioned above five standard solutions were made up.

Solution 1 contains pure A

Solution 2 contains 1 part A to 2 parts B

Solution 3 contains 2 parts A to 2 parts B

Solution 4 contains 2 parts A to 1 part B

Solution 5 contains pure B

The infrared absorption spectra of the pure compounds 17 was noted and the largest difference in absorption being at approximately B.72 microns.

The following readings were taken,

Slit 0.4 Cell 0.1 mm

EXTINCTION VALUES Wave Length Soln.l Soln.2 Soln.5 Soln.4 Soln.5 Pure CS^

9.66 .220 .398 .485 .580 .739 .055 9.68 .225 .420 .510 .610 .795 9.70 .225 .445 .555 ,665 .875 9.72 .230 .465 .578 .695 .900 9.74 .242 .470 .572 .693 .890 9.76 .462 .562 .665 —

The reduced mixture from the furfuryl ciiloride re action was completely distilled into one flask from a

Claison flask. The mixture is used directly in a carbon disulfide solution.

0.7527 G, of the unknovm in 9.2975 g. of carbon di sulfide solution (8.12J^) was examined.

Wave length Extinction Slit 0.4

9.72 0.468 Cell 0.1 mm

Therefore the percentage composition of the mixture according to Figure 6 was 56.0%

Reduction of Furfuryl Alcohol with W-6 Raney Nickel

S C H g O H 18

In a pressure bottle v/as placed 100 g. (1.02 moles) of redistilled furfuryl alcohol (B.P, 62/7 mm) in 60 ml. of O.P. methanol. To this v/as added approximately 5 to

10 g, of W-6. The bottle was attached to the shaker and hydrogen pressure increased to 40 Ibs./in^, The reduc tion v/as continued until hydrogen ceased to be absorbed.

Absorption stopped after furfuryl alcohol absorbed 156

Ibs./in^, (8.2 Ibs./in^ per 0.1 mole of double bonds).

Therefore 1.91 moles of ïiydrogen was absorbed or 95.5^.

The methanol was distilled through a 25 x 1.4. cm. column, followed by the fractional distillation of the tetra hydrofurfuryl alcohol.

B.P. 174-175^0 Yield 85 g. (81^)

%C %E Theoretical 58.9 9.8

Observed 58.89 9.89

Preparation of Tetrahydrofurfurylmetliylether^^^ (IR 6)

Into a 500 ml. round bottom f jask equipped with con

denser, stirrer, and stopper, was placed 98 g. (1.0 mole)

of freshly distilled tetrahydrofurfuryl alcohoj., and 156 g.

(1.1 mole) of mettiyl iodide. To this rapioly stirred so

lution was gradually added 70 g. of finely powdered po 19 tassium hydroxide. The temperature of the reaction was maintained below the boiling point of metiiyl iodide by using an ice bath. After the reaction had subsided, the reaction was refluxed on a steam bath for thirty min utes, Upon cooling, the reaction mixture was placed in a separatory funnel and the oily layer removed and dried over calcium chloride and later was distilled,

B.P. 159-141°C Yield 75 g. (66^)

n ^ = 1.4255 = 0.9650

Theoretical 62.04 10.41

Observed 62.08 10.22

In a round bottomed flask fitted v/ith a stirrer, and two dropping funnels was placed a 100^ excess of 40^ sodium hydroxide solution. The tetraliydrofurfuryl al cohol and a 50^ excess of dimethyl sulfate were simul taneously added from the dropping funnels into the rap idly stirred caustic solution at 0 - 5°C. After addi tion, the reaction v/as allowed to stand several hours.

The mixture was placed in a separatory funnel, and the oily layer was removed and the aqueous solutions ex tracted with ether several times. The oil was combined with the ethereal extracts. The combined extracts were dried over calcium chloride, and fractionated. 2 0

B.P. 140-141 °C Yield 50%

- 1.4250 - 0,9660

%E Theoretical 62.057 10.41

Observed 62.02 10,48

Preparation of Furfuryl Methyl Ether^^*^ (IR 3) QL,

To 400 g, of 40^ caustic potash solution was added

90 g. (0.9 moles) of freshly distilled furfuryl alcohol and 210 g. (1.61 moles) of dimethyl sulfate simultane

ously with stirring and cooling. The reaction mixture was allowed to stand overnight with slight stirring (10 hours). The resulting solution was put in a separatory funnel and the oily layer removed and dried over calcium

chloride, and distilled.

B.P. 154-136°C Yield 48-49#

n ^ - 1.4518

%R Theoretical 7.15 64.2

Observed 7.29 64.33 2 1

To a mixture of 15 g. (0,3.53 moles) of freshly dis tilled furfuryl alcohol and 24 g. (0,169 moles) methyl iodide v/as added 10 g. (0,178 moles) of finely divided potassium hydroxide. The reaction mixture v/as kept at 0 0-5 C, while addition v/as taking place. Upon completion of the addition, the mixture was refluxed on a steam bath for 5 hours. The solution was placed in a separatory funnel and the oily layer removed and dried over calcium chloride and distilled,

B.P, 133-156*0. Yield 50-55^

- 1,4511

Theoretical 64.2 7.15

Observed 64.29 7,19

W-6 Reduction of Furfuryl Methyl Ether (Figure 8)

CH^OCWa,

To a solution of furfuryl methyl ether (9 g.)G/7 in 3 100 ml. of anhydrous methyl alcohol was added three scoops of W-6 Raney nickel‘d. The mixture v/as placed in a pres sure bottle and hydrogenated at 49 lbs,/in^ (Hg pressure) at 30'c, 22 The hydrogen uptake:

12.0 lbs./in.^ Observed

15.2 lbs./in.^ Theoretical

91^ absorption or 1.82 double bonds

The above mixture was fractionated, yielding a pro duct.

B.P. 159-141®C. Yield 08%

n|^ - 1.4245 d|0 - 0.9645

%C Theoretical 62.18 10.26

Observed 62.04 10.41

Preparation of M-dimethyl Levulinamide 0 0 0 0 II II II II CHi;?—C—CHq—GHo “ C. CH%—C—CHr,—CH;-,—C\. . CHr, ^ ^ ^OH UJsOCTg-'^’ ^ ^ ^ ^

(2) (CHg)gNH

To 105 g. (0.905 moles) of levulinic acid was added dropwise 108 g. (0.885 moles) of thionyl chloride and the reaction mixture v/as heated on a steam bath to drive the hydrogen chloride from the mixture.

The greenish reaction mixture v/as cooled and diluted with 200 ml. of anl'iydrous ether. This acid chloride solu tion was added dropwise to a well stirred second ether solution containing 100 g. (2.22 moles) of dime thy lamine.

The temperature was maintained between 0-5°C. until the 23 addition was complete. The mixture was allovæd to grad ually come to room temperature by allowing to stand over night.

Upon completion of the reaction, the mixture was filtered and dried over calcium chloride. The ether so lution was distilled through a 20 x 1.4 cm, he lice packed column,

B.P, 97-102°C./I mm. Yield 80.0 g, 60-65^ (approx.)

H Theoretical 58,74 9,09 9,79

Observed 58.72 9.06 9,70

Lithium Aluminum Hydride Reduction of U-dimethvllevulin- amide 0 0 , . 0 0 II II fcH,) U A I H 4 II II CHg-C-CHg-CHg-C^ ^ CHg-C-CHg-CHg-C\ N H

Into a 500 ml, round bottom flask equipped with thermometer, mercury seal stirrer, condenser, and drop ping funnel was placed 150 ml, of anhydrous ether con taining 55 g, (0,382 moles) of N-dimethyllevulinamide,

While the rapidly stirred solution was cooled to -20*to 0 -30 C., 200 ml, of anhydrous ether containing 7,23 g,

(0,191 moles) of lithium aluminum hydride was added dropwise very slov/ly, so as to keep the temperature be tween -10°and -20*C. After approximately 25^ of the 24 of the ethereal solution of the hydride was added, the whole reaction mixture became gummy and slowly thinned

out toward the end of the reaction. The reaction mix

ture was refluxed an additional hour. To the reaction mixture v/as added 20 ml. of water, followed by 150 ml.

of 6^ sulfuric acid solution, to decompose the complex

formed by the hydride and the starting material. The mixture v/as stirred an additional hour and. v/as placed

in a continuous ether extractor for three days. The

reaction mixture was extracted for this time until the mother liquor gave no test with dinitrophenylhydrazine

solution. The ether extracts were dried over magnesium

sulfate, and fractionated through a 25 x 1.4 cm. helice

packed column.

B.P. 70 C./11-12 mm. Yield 30-40^

n'Y - 1.4515 The 11 -hydroxy valeraldehyde gave a bright yellow

dinitrophenylhydrazone, M.P. 123-124.8 C, 0.3.10 G. of

the aldehyde yielded 0.300 g. of dinitrophenylhydrazone,

99.6% yield.

M.P, of pure DNPH of ^-hydroxyvaleraldehyde 123-

124.6 C.

M.P. of DNPH from fraction B.P. 116-118 C.

from reduction of fur fury 1 chloride sodium meth-

oxide reaction 124.6-126.0 C.

Mixed M.P. of the above 123-124.8 C; 25

Theoretical 46.8 4.96 19,85

Observed 46.81 4.86 19.89

X-ray powder photographs-Jf- were taken of the two above samples and they proved to be identical.

^ The X-ray powder photographs were taken by Clayton Olson and results and interpretation done by same.

Preparation of 5-methoxy-g-methyltetrahydrofuran (IR 7)

//O »‘7b

Into a 250 ml. round bottom flask was placed 50 ml, of 1% hydrochloric acid in O.P. methanol containing

9.0 g. (0,088 moles) of ^-hydroxyvaleraldehyde. The mixture was heated to 60 C. for several minutes and v/as allowed to stand at room temperature for approximately

40 hours.

At the completion of this time, the alcohol was dis tilled through a 20 X 1.4 cm. helice packed column. The distilJ.ation was stopped after the methanol ceased being distilled from a steam bath. 200 Ml. of anhydrous ether was added and the ethereal solution was dried over anhy drous calcium chloride to remove any water or hydroxy compounds. After 24 hours, the solution was fraction ated.

B.P. 113-114 0. Yield 43^

n^l - 1.4090 26

%E foOCÏL % Terminal Methyl

Theoretical 62.04 10.4 26.7 12.9

Observed 61.9 10.5 26.4 12.8

Preparation of DMPH Derivative of 2-methyl-5-methoxytet- rahydrof-gran

To 0.18 g. of 2-methyl-5-methoxytetra]riydrofuran was added 100 ml. of boiling DNPH in 2N HCl solution. 0.2658 G. of the derivative was obtained (57^ yield) M.P. 124.5 -

125.2 0. M.P. of DNPH obtained from reduction product of fur fury 1 chloride/sodium methoxide reaction M.P. 124.6 -

126 C. Mixed M.P. 124.5-126 C.^

* 57^ Is the highest yield obtained from the 5-methoxy compound. TAhether using DNPH in either alcohol or water solutions, or in boiling or solutions at room temperature. Only at boiling temperatures was 57^ attained. At room temperature the yields usually average around 30^.

Determination of the Molecular Weight of 2-methyl-5-meth-

oxytetrahvdrofuran (Figure 3) In 14.8469 g, of t-Bu OH was placed 0.2575 g. of

2-methyl-5-methoxytetrahydrofuran and the cooling curve

taken on the homogeneous solution.

The freezing point data of pure t-BuOH is given on

the left, while the freezing point data for the above so

lution is given on the right. 27 Time Time Temp.. Temp.

0.0 4.1 0.0 4.0 0.5 3.64 0.5 3.47 1.0 3.20 1.0 2.92 1.5 2.74 1.5 2.38 2.0 2.45 2.0 1.83 2.5 2.45 2.5 1.33 3.5 — 3.5 1.34 4.0 — 4.0 1.57 4.5 2.93 4.5 1.33 5.0 2.96 5.0 5.5 2.94 5.5 1.21 6.0 2.92 6.0 1.15 6.5 2.89 6.5 — 7.0 2.87 7.0 1.00 7.5 2.85 7.5 0.0925 8.0 2.82 8.5 2.79

Calculation of Molecular Weight

Kf = 8.36 C.

t = 3.24-1.96 = 1.28 0.

Observed - Mol. V/t. = 8.37 x .2575 x 1000 = nn, ilsB X i 2.846'9 113.5

Theoretical - 116,1

Ozonolysis of Mixture from the Reaction of Furfuryl

Chloride/Sodium Methoxide

To insure the best possible results of ozonolysis reactions, several "blanlcs" were run first.

The first blank; 150 Ml. of redistilled dimethyl formamidei^ was ozonized for six hours in a stream of

■5:- The reason for using dimethylformamide is that the ozonide formed in the ozonolysis is insoluble in CCl^, CH^Cl^, CHCl^, etc. In the reagents mentioned above, the ozonide is a bullty crystalline mass which is very explosive. 28 oxygen containing 5-6^ ozone. The ozonized solution was added to distilled water and heated to boiling tempera ture, while a stream of air was being passed through the solution, condenser, and out into a dinitrophenylhydra zine chain (consisting of four receivers with bubblers attached in series, so that all air was scrubbed in DNPH solution) to determine the presence of any volatile alde hydes, This experiment was repeated with Zn in acetic acid replacing the distilled water, and also a dimedon^ chain replacing the DNPH c'nain, thereby making four sets of each blank run. No precipitate was obtained in any of the traps during any of the aforementioned runs. The time of decomposition was 6 hours for all runs.

The second blank; 150 H'll. of dimethyl formamide containing pure redistilled furfuryl methyl ether (5.0 g.) was subjected to the identical procedure outlined above, with no precipitates forming in any of the reactions. But in this latter case the mother liquor, after decomposition was finished, yielded between 20 and 30^ of the theoreti cal amount of dinitrophenylhydrazones of glyoxal.

The third experiment; 150 Ml. of dimethyl formamide containing pure reaction products from furfuryl chloride reaction was also subjected to identical procedures, with only result being between 20^ and 30^ glyoxal derivative being isolated. Also, tests were conducted to attempt 29 detection of the presence of acetic acid or acetate ion in basic solution, but all attempts to detect ace tic acid or acetate ion were either negative or in conclusive.

Iodoform Reaction on Furfuryl Chloride/Sodium Methoxide

Reaction Product Mixture^^ (Figure 4)

The procedure followed was that of Shriner and Pus on,

"Identification of Organic Compounds". The tests were run on identical samples and with identical procedures, ex cepting that one test contained six drops of reaction mix ture, while the second one contained six drops of furfuryl methyl ether. The reaction mixture gave a precipitate in

10 minutes, yellow crystals that became plastic and sub limed between 115-120°C. (iodoform sublimes at 118^0.)

The pure furfuryl methyl ether gave no Iodoform test under the same conditions. Pure redistilled 2-methylfuran gave no Iodoform test.

Infrared Spectrograms of Abnormal Product and Pure Furfuryl

Methyl Ether The infrared absorption curve of pure furfuryl methyl ether (IR 5) was compared with the infrared absorption curve of the last fraction from the distillation of the furfuryl chloride/sodium methoxide reaction mixture (iR 9).

There is a noticeable difference in the double-bond con jugated region. The main difference in the spectra is at 30

6.05 and 6.1 micron region. In this region there appears

a double peak, not in the pure furfuryl metïiyl ether.

Ultra-violet Absorption Curves of Furfurylmethvlether.

2-methvlfuran. and Mxture from Methoxide Reaction with

Furfuryl Chloride (Figure UVl)

Ultra-violet absorption spectra were made on pure furfuryl metliyl ether, 2-methylfuran and the mixture of

products from the furfuryl chloride reaction. The pro-

duct mixture shov/ed strong absorption at 2.45 x 10

Angstroms while the pure furfuryl methyl ether and meth yl fur an showed no such peak.

2.4 Dinitrophenylhydrazone Derivatives (Figure 5)

The standard dinitrophenylhydrazine solution used,

was made up in the following manner. Twenty grams of

dinitrophenylhydrazine was mixed with 80 ml. of concen

trated hydrochloric acid and diluted to two liters with

O.P.. methanol. Water solutions of the reagent v/ere not

used because of extensive polymerization taking place in

water solution. To 200 ml. of DNPH solution was added

0.20 g . of the reaction products from the furfuryl chlor

ide/sodium methoxide reaction. The first derivative to

precipitate was a red dinitrophenylhydrazone, M.P. 270-

275°G. The second precipitate, yellow in color, proved

to contain two derivatives, (a) M.P. 135-136 C, and

(b) M.P. 223-225*0. 31

The above procedure v/as repeated v/ith pure furfuryl methyl ether. The same derivatives were isolated in the same proportion but the time of reaction was much slower.

The same derivatives were also isolated in the same proportion at a rate equivalent with that of the mixture, by S,5-diraethoxy-g,5-dihydro~2-methylfuran.

The red derivative was identified by synthesis;

Red' derivative M.P. 270-275°C.

Derivative of dehydrolevulinic aldehyde M.P. 271-27S°C.

Mixed M.P. 270.6-273°C.

The lovf melting yellow derivative was soluble in methanol.

Yellow derivative M.P. 135-136°C.

Derivative of methyl levulinate M.P. 156-137*0.

Mixed M.P. 135-136.5°C.

The high melting yellow derivative was insoluble in methanol.

Yellow derivative M.P. 223-225°C.

The 2,4-dinitrophenylhydrazide-2,4-di- M.P. 222-224°0. nitrophenyIhydrazone of levulinic acid

Mixed M.P. 223-225°C.

Reaction of Anhydrous Methanolic Hydrogen Chloride with

Reaction Mixture (IR 10)

To 150 ml. of anhydrous ether v/as added 20 g. of reaction products. Several drops of thionyl chloride was 52 added and the mixture allowed to stand fifteen minutes.

The mixture turned dark green. To the mixture was added

15 g. of anhydrous sodium carbonate to neutralize the

HCl after the reaction has proceeded for about 20 to SO minutes. To this mixture was added 150 ml. of water and the mixture extracted 3 times (50 ml, each) with pentane.

The combined extracts were fractionated, yielding 10 g, of recovered furfuryl methyl ether, B.P. 49-50°C./SO mm.,

- 1.4518 and 2,0 g, of 2,5-dimethoxy-2,5-dihydro-2- methylfuran, B.P, 60°C./20 ram,, n ^ - 1,4290. The infra red absorption curves of the latter compound and an authen tic 2,5-dimethoxy-2,5-dihydro-2-methylfuran proved iden tical. The rest of the material was non-distillable poly mer.

Attempted Synthesis of 5-methoxy-2-methylfuran

4- NAOCH^ ►► NR.

Method 1

The 5-bromo-2-methylfuran v/as synthesized by direct bromination of 2-methylfuran.^^ Equimolar amounts of

5-bromo-2-methylfuran and sodium methoxide in methanol were inserted in a Carius tube, sealed, and heated in an oven at 200^0. for 48 hours. The runs were made at vary ing times of 48 hours to 7 days. The tube was opened at ù ù the completion of the desired time and the solvent dis tilled off through 25 x 1,4 cm. helice packed column.

The resulting liquid is diluted to 150 ml. with anhy drous ether and 20 g. of anhydrous calcium chloride add ed, The resulting solution was fractionated, after drying for 24 hours. All fractions were tested with DNPH solu tion hut no derivatives were obtained. The only product obtained was that of the starting material. Spectra taken of various cuts were the same, indicating no change in composition of the distillate.

Method 2 \^o + >4a O C H ^ ----->-

The 5-iodo-2-methylfuran was prepared from the iodine- potassium iodide titration with the 5-cliloromercuri-2-methylfuran.^ Equimolar amounts of the iodo compound and so dium methoxide in anhydrous methanol were placed in a Car ius tube, sealed, and put in an oven at 165 C. for a per iod of 48 hours. At the end of this time, the tube v;as opened and the solvent distilled through a 25 x 1.4 cm. helice packed column. The resulting oil was diluted to

150 ml. and 25 g. of calcium chloride (anliydrous) was add

ed as the drying agent. The resulting ethereal solution was fractionated, all fractions being tested with dinitro- 34 phenylhydrazine solution and giving a derivative M.P. 135-

136*^0. At no time did the vfeight of the dinitrophenyl hydrazone exceed 2.0% of the theoretical. The middle fraction was sent in for analysis, the results are below. foC iE %1 _gOCHg 28.93 2.45 61.01 0.75

From the above data, it can be seen that the com pound was 99^ of tlie recovered 5-iodo compound, which did not give a dinitrophenylhydrazone.

Identification of Derivative

M.P. of unknown 135-136*0.

M.P. of DNPH of pure methyl levulinate 136-138*0.

M.P. of mixture 135-138*0.

Analysis for Iodo Compound

iO %E

Theoretical 28.90 2,4 61.1

Observed 28.95 2,45 61.01

Method 5 0 s o » "

The pyridine sulfur trioxide, prepared according to I *7 the procedure of Sisler and Audith v/as reacted with methylfuran^^. The 5-sulfo compound, isolated as the bar ium salt, was heated with an equimolar concentration of 35 sodium methoxide in methanol in a constant temperature bath at 200 C., contained in a Carius tube. The temper

ature was varied for three separate runs, 110 C., 150 C.

and 200 C, The only product obtained was a dark oily

polymeric material, which gave no dinitrophenylhydrazone

derivative, and was uneffected by concentrated hydro

chloric acid. No 5-methoxy-2-raetlrjylfuran was obtained in any runs.

Method 4 .LjL ri +<.Cl

Equimolar concentrations of 5-chloromercuri-2-methylfuran and sodium methoxide in anhydrous methanol are

placed in a Carius tube, sealed, and put in an oven from

100 to 200 C, The resulting mixture was distilled after

being heated for 48 hours. The low boiling fraction, a

yellow oil, gave a dinitrophenylhydrazone M.P. 128-150 C.,

authentic DNPH from levulinaldehyde 129-132 C., mixed

M.P. 129-130 C. No other products were isolated. Methyl-

fur an v/as therefore obtained as the product instead of

the desired methoxy compound.

Method 5

The 2,5-dimethoxy-2,5-dihydrofuran was prepared ac

cording to the electrolytic méthoxylation of furan by 36 Clauson-KaasInto a 500 ml. flask was introduced

0,5 moles of dimethoxy compound, to vdiich was added 0,6 moles of methyl magnesium bromide in anhydrous ether.

The reaction mixture was allowed to stir at room temper ature for five hours and the solvent gradually removed by heating on a steam bath. Toward the end of the ether removal, a reaction took place with large evolution of heat and the compounds turned into a brown oily mass.

The procedure was varied so as to distill off the ether and replaced it with various solvents, like tetrahydrofuran and benzene. In either of the variations, although the reaction v/as controlled better, the only product iso lated was the starting material and some traces of dimethoxy acetal of the unsaturated straight chain compound.

(Analogous reactions have been reported in the liter- 17 ature). '

Method 6

In a pentane solution containing 2,5-dimethoxy-2,5- 15 dihydro-2-methylfuran, was added bromine dropwise with vigorous agitation at 0 C., until the dark amber color of bromine ceased to disappear (89-94fo theoretical uptake).

The resulting mixture was poured into a methanol solu tion containing equimolar concentration of potassium hy droxide. Potassium chloride was formed immediately. The resulting mixture was refluxed for one hour, filtered and 37 powdered zinc in a 3 to 1 excess in n-propyl alcohol, v/as added and refluxed an additional 4 hours. The resulting mixture was fractionated, the only product being isolated was that of the starting material; the only other product v/as a thick black polymeric material.

Method 7

CW 3 a C H o ^ 0 CH 3

The tertiary butyl hypochlorite v/as synthesized ac cording to the method of Hennion and Irwin.To a 6 mole excess of methanol containing 2 me thyIfuran (1 mole) and

1 mole of KOH, was added 1 mole of tertiary butyl hypo chlorite with rapid stirring. The temperature was kept at O-b'^C. After addition was completed, the reaction mix ture was allowed to stand overnight. The next morning, the solution was diluted to twice its volume with dis tilled water and continuously extracted with pentane for

5 days. The pentane extracts were dried and distilled through a 25 X 1.4 cm, helice packed column, yielding a product, B.P. 54*C./15 mm., n ^ - 1.4290, yield 40 g. (30^),

^OCHg

Theoretical 43.1

Observed 43.0

The infrared absorption of 2,5-dimethoxy-2,5-dihy- 38 dro-2-metliylfuran^^ was identical with the compound ob tained (IR 9, 10). The physical constants were similar.

Both compounds gave the same DNPH derivatives.

Method 8

To 500 ml. of O.P. methanol containing 2.2 moles of sodium and 1 mole of redistilled 2-methylfuran, was bub bled in one mole of chlorine. The reaction temperature v/as kept between 7-14 C. The solution was allowed to stand overnight and diluted to tv/ice its volume with dis tilled water. The remaining solution was extracted for five days with pentane in a continuous extractor. The pen tane extract v/as fractionated through a 25 x 1.4 cm, helice packed column.

B.P. 60-61 C./20-21 mm. Yield 40-50#

n ^ - 1.4271

#OCH,

Theoretical 43.1

Observed 42.9

The compound has same IR as 2,5-dimethoxy-2,5-dihy- dr 0-2 , me thy If uran. 39

s m m m Y

Furfuryl chloride v/as synthesized in good yields and reacted with sodium methoxide. The reaction mix ture was reduced with W-6 Raney nickel and hydrogen to two products. The mixture of reduced products showed to he 35^ h-metho^y-S-metliyltetrahydrofuran, and 65^ of tetrahydrofurfuryl methyl ether. The original compounds were identified by spectra, various diagnostic reactions, and the normal ether by synthesis. This work, together with the kinetic data prove the existence of a bimolecular displacement reaction Srig”. 40

APPENDIX

Figure 1 - Diagram of Reaction Covered in This Work

Figure 2 - Diagram of Reichstein Reaction^

Figure 3 - Molecular Weight Determination of 5-methoxy-2-

methyltetrahydrofuran

Figure 4 - Iodoform Reaction and Accepted Mechanism

Figure 5 - Reaction of 2,4-dinitrophenyIhydrazine with

Reaction Products

Figure 6 - Infrared Absorption Curves of Reduced Products

Figure 7 - Index of Refraction Curve of Reduced Products

Figure 8 - W -6 Reduction of Furfuryl Methyl Ether

Figure 9 - W -6 Reduction of Reaction Products

IR 1 - Furfuryl Chloride, Pure Compound, 0.025 ram. NaCl

Sample Cell, Solid NaCl Comparison Cell

IR 2 - Reaction Product Mixture, 0.025 mm. NaCl Sample

Cell, Solid NaCl Comparison Cell

IR 5 - Furfuryl Methyl Ether, Pure Compound, 0.025 mm,

NaCl Sample Cell, Solid NaCl Comparison Cell

IR 4 - 5-methoxy-2,methyltetrahydrofuran (W-6 Reduction

of Reaction Mixture) 0.025 ram. NaCl Sample Cell

Solid NaCl Comparison Cell

IR 5 - Tetrahydrofurfuryl Metliyl Ether (W-6 Reduction

of Reaction Mixture) 0.025 ram. NaCl Sample Cell

Solid NaCl Comparison Cell 41

APPENDIX

IR 6 - Tetrahydrofurfuryl Methyl Ether, Authentic 0.025 ram.

NaCl Sample Cell, Solid NaCl Comparison Cell

IR 7 - 5-methoxy-2-methyltetrahydr of uran. Authentic

0.025 mm. NaCl Sample Cell, Solid NaCl Comparison

Cell

IR 8 - Last Fraction of Abnormal and Normal Ether Distil

lation, 0.025 mm. NaCl Sample Cell, Solid NaCl Com

parison Cell

IR 9 - 2,5-dimethoxy-2,5-dihydro-2-methylfuran, Authentic^

Sandwich Cell NaCl (Sample) Solid NaCl Comparison

Cell

IR 10- 2,5-dimethoxy-2,5-dihydro-2-methylfuran, (Reaction

Mixture Plus Anhydrous HCl and Methanol), Sandwich

Cell NaCl (Sample) Solid NaCl Comparison Cell

UV 1 - Comparative Ultraviolet Spectra CHgOH O'" ' CHgOCHg

I 0 ^ CHgCL ^^CHgOCH^ f CH3O 3L H

CHp-CHp ' \ w H 0 - ^ q ^ C H 3 CH30 CH3 O CH: •Q A

Qy CHg-CHg CHg-CHg I I N-C,^ ,C-CH3 0 HO " 0

FIGURE C H g C N CHgCOOH O' \ ^ C H X I n 3E 0 ^

‘=C H CH- NC NC HOC- - 0 -

° m

FIGURE 2 44 Molecular Weight Determination of

4.0 CH,0 CH

FIGURE 3 3.6

Pure t-Bu-OH

2.8

2.4

C l.96°C. 2.0

T- Bu OH + solute

0.6 0 2 3 4 5 6 7 Time (rnin.) 45

l2 H . C O ^ NaOH H3GO CH. GHgl 0 H

H3GO. H i

I etc. li'GHI:

B. N. R. GH3 N q OH 0 "

I2 N.R. GH2OGH3 NaOH 0

FIGURE 4 46

^QX^CHgOCHg CH; 'O'

CH3OH

H+-/ HOCH3 CHgO H > X

R -CH, '0 R' CH H R

NH “ N = R =

FIGURE 5 nfroRed Absorption Curve for Analysis of Mixture of

^ 0' ’ ■ 2 3

FIGURE 6

0 .5 0 Unknown 36.0%

X = 9.72 0.30 — Slit = 0.4 Cell = 0.1 mm 0.20 Conc.= 8.15-8.17% in CSg

0.10

0.00 ± ± 0 10 20 30 40 50 60 70 80 90 IOOcH.O-C^CH, 100 90 80 70 60 50 40 30 20 10 0 % Composition ndex of Refraction for Mixtures of

1.4250 and CH,0 CH 1.4230 FIGURE 7 1.4210 25

.4 Î 9 0 -

1.4170

25 N 1.4150

1.4130

I.4II0

1.4090

.4 0 5 0 . 50 6 0 7 0 8 0 9 0 100 THFOMe 50 40 30 20 10 0 5-CH,0-

0 0 % Composition 49

W “ 6 Reduction of

FIGURE 8

«M . C

ui jD

40 80 120 160 200 Minutes 50

W “ 6 Reduction of and O-O ^ C H g O C H a ,CL ^ CH 2 ^ C H 3O ^ FIGURE 9

0 50 100 150 200 Minutes WAVE NUMBERS W CM-' WAVE NUMKitS IN CM-' 5000 4000 MOO 2500 1500 1400 I MO 1200 9 0 0 ( 0 0

5 6 7 12 13 14 WAVE 1B4GTH M MK3LONS WAVE LENGTH IN MICRONS

W#v# Nwmbef* in cm

nil 1 U i\! i 1 i CT i i ! 1 i i 1 M ..n rr III ! i M \\ I ! i 1 j i I ! M f 1 i ■ i V r 1 ! ! t i i ! 1 j i t 1 ' !% ! 1 : i ‘! I 1 in 1 1 1 l,j_J I- i il k j ! i i -'7 i 11 A 1 i i : ! : ! r TT

Wave LnngHi in Mitrons WAVE WAVE HUMKU IN CM-' 3M0 2*00 2000 ispe 1400 I wo 1100 1000 WO US

oi _

4 0

WAVE imGTH IN MORONS WAVE LENGTH IN MICRONS

WAVE NUMBERS IN CM-' WAVE NUMBERS IN CM-' 5 0 0 0 4 0 0 0 0 0 2 5 0 030 2000 1500 1400 1200 1200 1100 1000 WO too 7 0 0 6 2 5 100 100

1 “ 6 0 = IW u t

WAVE LENGTH IN MICRONS WAVE LENGTH IN MICftONS cn PERCENT TRANSMITTANCE PERCENT TRANSMITTANCE

âSï »

PERCENT TRANSMITTANCE PERCENT TRANSMITTANCE WAVE NUMKJtS IN CM-' WAVE NUMEAS IN CU' 1100 7 0 0 #100 100

- r

r : 20

2 I 4 S * 7 I » 10 II 12 14 ISI* WAVE WAVE

WAVE NUMfitS M CM-i WAVE NUMKRS IN CM-< <000 MW 1 4 0 0 i m im 1100 1000 9 0 0 4 2 5 100

4 -

4 0

20 mm

WAVE IB46TH M MCK9NS WAVE im eiH M MCltONS PERCENT TRANSMITTANCE PERCENT TRANSMITTANCE

PER C EN T transmittance PERCENT TRANSMITTANCE gg 56

Ultraviolet Absorption Curve .001 M furfuryl mettiyl ether in ethanol .001 M reaction mixture ■...... 001 M of 2 - methylfuron

U.V.

20 32 36 A° X 10^ 57

BIBLIOGRAPHY

1. Kirner, W, R., J, Am. Chem. Soc,, 50 (1928), p. 1955.

2. Reichstein, Ber., 63 (1930), p. 750.

3. Limd & Bjerrum, Ber., ^ (1931), p. 210.

4. Adkins, J. Am. Chem. Soc., _70 (1948), p. 695.

5. Kirner, W. R., J. Am. Chem. Soc., ^ (1930), p. 3251-56.

6 . Pummerer & Gump, Ber., 56 (1923), p. 999.

7. Von Wissell & Tollens, A 272 (1893), p. 297.

8 . Helferich, B., Ber., 52 (1919), p. 1123.

9. Horning & Horning, J. Org. Chem., 11 (1946), p. 95.

10. Shriner & Fuson, «Identification of Organic Compounds”.

11. Kolb, K. E., Doctoral Dissertation, Ohio State Univer

sity, (1953).

12. Gilman & Wright, J. Am. Chem. Soc., ^ (1933), p. 3302

13. Inorganic Synthesis, Vol. 2 Me Graw & Hill, (1946), p.175

14. Kazitayna, L. A., Vetnik Moscow University, No. 3 (1947),

pp. 109-111

15. Clauson-Kaas, Belgium 500,356, (Jan. 15, 1951).

16. Clauson-Kaas, Act. Chem. Scand,, AFH #1, #3, #4.

17. Compte Rendu, ^ (1949), pp. 1301-03

226 (1948), p. 184

18. Irwin, C. F., & Hennion, G. F., J. Am. Chem.: Soc., 63

(1941), p. 858. 58 19. Ushakov and Kucherov, V. F., J. Gen. Chem. (U. S. S. R.)

14 (1944) p. 1080; C.A. 40 (1946), p. 7185. 20. Berichte ^ (1918), p. 87.

21. Gilman and Vernon, J. Am. Chem. Soc. ^ (1924) p. 2576.

22. Kirner, W. R., J. Am. Chem. Soc. 50 (1928) p. 1955.

22. Reichstein, T., Helv. Chem. Acta. (1932) pp 1124-7.

24. Reichstein, T., Helv, Chem. Acta. (1932) pp 249-53.

25. Scott and Johnson, J. Am. Chem. Soc. M (1932) pp. 2549-6.

26. Kepner, R.E., V/instein, S., And Young,. W.G,, J. Am.

Chem. Soc. 71 (1949) p. 115.

27. Kland-english, M. J., and Y/ilson, C.L., Priv. Comm.

28. "Structure and Mechanism in Organic Chemistry" by

C, K. Ingold pp. 594-5. 59 Autobiograpliy

I, Calvin J. Berming, was born on August 6 , 1925, in Chicago, Illinois. In June 1939 I was graduated from

St Mathias Grammar School, and in June 1943 I was grad uated from St Gregory High School. Three Days later I enlisted in the United States Navy. After spending seven weeks at boot camp, I was sent to the University of Wisconsin Radio Operators School. In February, 1944

I vfas sent overseas as radio operator to Commander

Carrier Division 3. After two years in the Pacific

Theater, I was sent home and discharged on March 3, 1946,

In September 1946 I entered the University of Notre Dame and was graduated with honors from Notre Dame in June

1950 with a B. Sc. in chemistry. I entered Ol'ilo State

University Graduate School in September 1950, as an

Assistant on the Junior Staff for two years. I was appointed a Cincinnati Chemical fellow in June 1951. I married Miss Genevieve H. Hunstiger on June 21, 1952.

I was appointed a Quaked Oats Fellow in March 1953.