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An investigation of two component systems of cyclic hydrocarbons and liquid sulphur dioxide King, Ellis Gray 1932

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m HTVESTIGATIOII OF TWO COMPONENT SYSTEMS OF CYCLIC HYDROCARBONS AND LIQUID SULPHUR DIOXIDE. E l l i s Gray King, B.A. A T h e s i s submitted f o r the degree of Master o f A r t s i n the Department of Chemistry. The U n i v e r s i t y of B r i t i s h Columbia A p r i l 1932. Acknowledgment s The writer wishes to express his appreciation and sincere thanks for the help, guidance and adviee given him "by Dr. Seyer under whom this work was carried out. Table of Contents PART I - THE FREEZING; POINT CURVE Of CYGLOHEXENE AND LIQUID SULPHUR DIOXIDE. A - Experimental Work, a. D i f f i c u l t i e s . b. Preparation of Nitrogen. c. Preparation of Pure Cyolohexene. d. F i l l i n g the Bulbs. e. Determining the Freezing Points. C - Experimental Results. PART II - THE POLYMERIZATION OF CYOLOHEXENE AND SULPHUR DIOXIDE IN THE PRESENCE OF THE PEROXIDE OF CYOLOHEXENE. A - Preparation of Polymer. B - Purification. C - Isolated Experiments Performed. E - Determination of the Composition. F - Mechanism of Reaction. PART III - THE FREEZING POINT CURVE OF CYCLOHEXADIENE AND LIQUID SULPHUR DIOXIDE. A - Preparation of 1.3 Cyolohexadiene. a. Previous Work. b. Preparation of di-bromide. c. Preparation of 1.3 Cyolohexadiene. d. Purification. B - Reaction of Sulphur dioxide and Cyolohexadiene. SUMMARY AH INVESTIGATION OF TWO COMPONENT SYSTEMS OF CYCLIC HYDROCARBONS AND LIQUID SULPHUR DIOXIDE. PART I - THE FREEZING POINT CURVE OF CYCLOHEXENE AND SULPHUR DIOXIDE. A - PREVIOUS WORK. Ia 1918, Messrs. Moore, Morrell and Egloff based a method for the separation of paraffins and naphthenea on the solubility of paraffins, aromatios, napthenes, and olefins in liq u i d sulphur dioxide. They claimed to have obtained evidence pointing to compound formation, between cyclohexane and l i q u i d sulphur dioxide. Dr. Seyer considered the evidence rather questionable and so the sol u b i l i t y curve was redetermined by V. Dunbar, under his supervision. The resultant curve i s given on Graph III, and shows no evidence of compound formation. Sinoe then, with the assistance of Hugget (3), G i l l ( 4 ) , Peok (5) and Todd f6), Dr. Seyer has examined other hydrocarbons, from the same point of view. The paraffins were found to be miscible only above oertain temperatures. The same i s true for the saturated cyclic hydrocarbon, cyclohexane. But the aromatic compound benzene, was found to be total l y miscible under a l l conditions. The curve, however, gave no indication of compound formation. Thus Dr. Sever thought that i t would be interesting to study the other cyclic hydrocarbons, cyclohexene and eyclohexadiene. The freezing point curve, of the cyclohexene sulphur dl-oxide system, was attempted, i n 1929, by Mr. Carpenter. He was troubled by a white compound that always formed, thus preventing him from determining the freezing points. In our paper, Ap r i l 1930, we pointed out that this compound only formed i n the presence o f a i r . Also that the compound was probably formed from the peroxide of cyclohexne, and not from pure cyclohexene. The reviewers of this paper were rather sceptical of our results; one said, "It would have been more convincing i f they had given freezing point - solubility data to prove this." Thus we decided to follow this out, and the resultant curve shows definitely, that there i s no compound formed with pure cyclohexene. B - EXPERIMENTAL WORK, a . B i f f i c u l t i e s in Experimental Work. 1. Due to the white compound the CgEL^ Q must be f i r s t purified, and then kept i n an inert atmosphere. The slightest amount of a i r present seems to interfere. 2. The composition of each mixture must be known. The best method i s to have the weight of each constituent, without allowing them to come i n contact with a i r . 3. The volume method of determining the amount of SOg as yet has been impossible, because the CgB^Q attacked the stop cock grease. s We were a whole year trying different methods, hut i t i s of no use going into these. Thus we w i l l only consider the method f i n a l l y used. b. Preparation of Nitrogen. Nitrogen was used as the inert atmosphere (0O„ was tried). This was prepared as shown in diagram (1) - N &N0 2 solution was dropped into a heated solution of NH4C1. The nitrogen was passed thru pyrogallol, and collected in a tank over water, previously boiled. c. Preparation of the pure CgH^Q. The CgH-^ Q (Eastman Kodak Company) was refluxed over sodium (figure 2) i n an atmosphere of Hg for about one hour, then the small tip (A) was broken, and a condenser attached. The whole was swept out with Hg, and the Q^iO d i s t i l l e d into the receiver B, wfcieh f i t s directly on the f i l l i n g apparatus (figure 3). A 10 ces. portion was used in this, and thus i t was necessary to prepare a new sample for each group of determinations. A group consisted of one to three bulbs. d. F i l l i n g the Bulbs. For the freezing point determinations, small glass bulbs about one-half fnch internal diameter were used. This i s illuatrated i n Diagram 3 - ( A ) . 1. Cyclohexene. The bulb and rubber stopper were f i r s t weighed, and then the h u l h s l i p p e d on to the a p p a r a t u s . A f t e r the bu lb was t h o r o u g h l y swept out w i t h n i t r o g e n some cyc lohexene was a l l o w e d to f l o w over by open ing s t o p - c o c k (C) and c l o s i n g ( D ) . When the d e s i r e d amount ( t h i s had to be judged) had f l o w e d o v e r , (C) was c l o s e d and (D) opened. The bu lb was removed, the r u b b e r s t o p p e r r e p l a c e d and the whole weighed u p . T h i s gave the amount o f cyc lohexene by w e i g h t . As the cyc lohexene d i d not come i n c o n t a c t w i t h the s t o p - c o c k s , we were not t r o u b l e d w i t h s t o p - c o c k g r e a s e . 2. S u l p h u r d i o x i d e . The bu lb was then f i t t e d onto the appara tus shown i n d iagram (3) s e c t i o n (b) the n i t r o g e n swept out w i t h s u l p h u r d i o x i d e and the s o l u t i o n c o o l e d a t the same t i m e . Then (E) was c l o s e d and the d e s i r e d amount o f s u l p h u r d i o x i d e condensed w i t h l i q u i d a i r . The bu lb was then s e a l e d o f f , and weighed up w i t h the r u b b e r . T h i s gave the t o t a l weight o f C^Hio SO2. As a check , the bu lb was weighed c o n t a i n i n g the m i x t u r e , then empty. The a c c u r a c y o b t a i n a b l e by t h i s method made i t u n n e c e s s a r y to c o r r e c t f o r bouyancy i n w e i g h i n g the b u l b s , e. D e t e r m i n i n g the F r e e z i n g P o i n t . The appara tus used i s shown i n Diagram (4): r e f e r r i n g to t h i s d iagram - (F) a f r e e z i n g b a t h - c o n s i s t e d o f a t r a n s p a r e n t vacuum f l a s k covered w i t h a s b e s t o s , and h a v i n g s m a l l windows. A v e r y l i g h t g a s o l i n e , c a l l e d gas m a c h i n e - n a p l h a , was used i n the b a t h . (G) - l i q u i d a i r c o n t a i n e r - and a d r y i n g sys tem, f o r the a i r used to blow over the l i q u i d a i r . (H) - p l a t i n u m r e s i s t a n c e thermometer. G - EXPERIMENTAL RESULTS. To get as pure a sample as possible, the cyclohexene was refluxed over sodium, and then fractionated, fhe index of refraction, for each is given i n fable I. We considered that the second fraction was f a i r l y pure. 20 TABLE I. 1st Fraction End Fraction 3rd Fraction 1.44619 1.44601 1.44636 Material standing i n Oxygen 1.48917 Beilstein and C r i t i c a l Tables 1.4451 The results, obtained i n determining the freezing points, are given i n Table II. The curves were then plotted using both the percentage C_H_n Graph I, and the Mol. percent 6 10 Graph II. These show definitely that there i s no compound formed with pure cyclohexene. f A B I E II I&eat-i f i c a -tion No. Wt.of C H 6 10 Ave. Wt.of 06 H10 * C6 H10 Ifol. f 06 E10 Resistance Thermomet-er Reading. Freezing Point. H# • 0580 2.537 2.29 1.80 1.753 -75.9 Carp. 3.25 31.69 10.3 8.22 - -77.5 H7 .1849 1.169 15.8 12.8 1.732 -77.8 H3 .7348 3.393 21.4 17.5 1.728 -78.2 E5 .2277 .8615 24.3 20.0 1.725 -78.5 112 .6291 1.533 41.4 35.5 1.720 -79.0 IB .4511 .9237 48.8 42.7 (1.733) q. -79.6 2F .8935 1.759 50.8 44.6 (1.730) -79.9 Al .5146 .8623 59.7 53.62 mm -81.7 HI 1.263 1.982 63.8 57.9 1.688 —82.2 111 2.026 £.812 72a 66.9 1.666 -84.3 H13 1.502 1.860 80.8 76.7 1.612 -89.7 21 . 8834 1.095 80.7 76.6 1.623 -90.3 G6 .8653 1.029 84.1 80.5 1.569 -93.9 G5 1.823 2.137 85.3 81.5 1.535 -97.2 11 1.732 1.932 89.6 87.3 1.473 -103.4 G3 1.234 1.370 90.1 87.7 1.438 -106.7 16 2.380 2.599 91.6 89.5 1.403 -110.1 H14 2.776 2.924 94.9 93.5 1.435 -107.1 IS 2.079 2.151 96.6 95.7 1.441 -106.5 Freezing Point of pure C 6H 1 0 C r i t i c a l Tables -103.7 H * " * SO Mr. Carpenter -72.7 7 PART II - THE POLYMERIZATION OF CYCLOHEXENE AND SULPHUR DIOXIDE IN THE PRESENCE OF THE PEROXIDE OF CYCLOHEXENE. This polymer was described by us i n our paper of 1930. This i s merely to add a few more experimental details and to summarize the results. A - PREPARATION. The compound was prepared by passing sulphur dioxide through the oxidized cyclohexene, the mixture being lcept i n an ice bath. Better results were obtained by adding a drop or tw© of water. After the mixture seemed to be f a i r l y well saturated with sulphur dioxide, about 50 e.cs. of water were adfted. This water was found to be very neeessary otherwise a brown resinous compound formed. The product i s very white, obtained this way, but has a very high vapour pressure. B - PURIFICATION. In purifying the previous method was modified sli g h t l y . The mixture was immediately f i l t e r e d through a Gooch erueible, i n which was placed a f i l t e r paper. The compound was well washed with alcohol and water, and then placet i n a tessieator to dry. After a few days the material was placed i n a beaker and digested with hot ether. This was deeanted off and replaced with alcohol. Finally the mixture was f i l t e r e d , the alcohol washed out with water, and the compound dryed. 8 The reason for this method of purification i s that i t does not crystallize from chloroform, the only liquid i n which i t i s soluble to any extent. In using the above procedure we have no method of t e l l i n g whether the product Is a pure substance. However, the material prepared i n this way i s pure white, has no smell, and i s more stable to heat than the samples previously prepared. C - A FEW ISOLATED EXPERIMENTS WERE PERFORMED WHICH ARE GIVEN HERE. I. Some sensitive tests are available for the detection 9 of peroxides. J. B. Conant and W. R. Peterson give the following as tests that may be applied. a. Add a 10$ solution of ammonium thiocyanate, to which a crystal of ferrous ammonium sulphate (free of fe r r i c salt) has been added, to the material (a peroxide develops a red color). This test i s very delicate and was considered too sensitive, as the cyclohexene would probably have a trace of peroxide present. b. A less sensitive test i s to shake the material with neutral aqueous iodide solution, the peroxide, i f present, causing a yellow to red-brown color. On adding one drop of the oxidized cyclohexene to a solution of sodium iodide, a brown color developed immediately. This solution turned dark blue when starch was added. A sample of cyclohexene, whioh had been r e d i s t i l l e d and placed in a corked bottle about a month before, was given the same treatment. On shaking with sodium iodide, i t gave only a faint 9 y e l l o w , t h i s i n d i c a t e d t h a t a t r a c e o f p e r o x i d e was p r e s e n t . S t a r c h gave t h i s s o l u t i o n a l i g h t p u r p l e shade . c. A c i d i f i e d sodium i o d i d e w i t h s t a r c h g i v e s a "blue c o l o r i n the p r e s e n c e o f p e r o x i d e s . In t h i s case the o n l y d i f f e r e n c e between the two m a t e r i a l s was the r a t e of r e a c t i o n . The o x i d i z e d sample gave an immediate c o l o r . The cyo lohexene gave a l i g h t e r c o l o r a f t e r shak ing f o r about h a l f a m i n u t e . T h i s p r o v e s d e f i n i t e l y , t h a t we have been d e a l i n g w i t h the p e r o x i d e , and s u b s t a n t i a t e s the work o f Stephens , B i r c h and S t a n s f i e l d . 1 0 a . We were i n t e r e s t e d i n knowing i f the compound c o u l d be produced t o b e t t e r advantage by p a s s i n g 30^ i n t o o x i d i z e d cyo lohexene i n s o l u t i o n . Benzene, i n which bo th the hy d roc a r bon and the su lphur d i o x i d e are s o l u b l e , was used as a s o l v e n t . C o n c e n t r a t i o n s v a r y i n g from 10 to 90$ Benzene were u s e d , but no d e f i n i t e r e s u l t s were o b t a i n e d . A drop o f water produced a m i l k y s o l u t i o n i n the 50$ m i x t u r e , but t h i s would h a r d l y do as a method o f p r e p a r a t i o n . 3 . . The compound d i s s o l v e s i n c h l o r o f o r m , a n a l i n e , a l c o h o l i c p o t a s h , and t o a s l i g h t e x t e n t i n a l c o h o l . I t i s i n s o l u b l e i n w a t e r , e t h e r , a c e t i c a c i d and o ther common s o l v e n t s . The c h l o r o f o r m s o l u t i o n t a k e s on a brown shade, the compound p r o b a b l y a s s o c i a t i n g i n s o l u t i o n . T h i s i s a l s o i n d i c a t e d by f a c t t h a t b e f o r e d i s s o l v i n g i t goes t o a gummy mass. T h i s f a c t and the s m a l l s o l u b i l i t y p r e v e n t e d the d e t e r m i n a t i o n o f the m o l e c u l a r we ight by the o r d i n a r y methods . T h i s compound i s r a t h e r impor tant i n v iew o f the r e c e n t work done by Gonant and P e t e r s o n , 9 on the e f f e c t o f p e r o x i d e s on the p o l y m e r i z a t i o n of hydrocarbons a t h i g h p r e s s u r e s . E - DETERMINATION 03? THE COMPOSITION. A q u a l i t a t i v e t e a t showed t h a t s u l p h u r was p r e s e n t i n l a r g e q u a n t i t i e s i n the p o l y m e r , f o r d e t e r m i n i n g t h i s q u a n t i t a t i v e l y , the C a r i u s method was used as d e s c r i b e d i n Gat terman, p . 86. RESULTS. w t . o f w t . o f Bar ium Percentage sample su lpha te s u l p h u r (1) .1430 g r s . .2136 g r s 20.5# (2) .1320 " .1996 * 20.8g (3) .1158 " .1731 * 20.5^ Average - 20.6/& 10a In the combust ion a n a l y s i s i t was n e c e s s a r y , on account o f the s u l p h u r p r e s e n t , t o r e p l a c e t w o - t h i r d s o f the copper ox ide by l e a d ohrornate. A s m a l l q u a n t i t y o f l e a d chrornate was a l s o used i n the p o r c e l a i n b o a t . The A b s o r p t i o n System -1. Hydrogen as water - pumice mois tened by s u l p h u r i c a c i d . 2 . Carbon - as carbon d i o x i d e was absorbed by soda l i m e , 3 . Another U-tube was used o n e - t h i r d f u l l o f soda l i m e , the r e s t pumice and s u l p h u r i c . RESULTS. w t . of sample w t . o f c o a w t . o f Percentage Hydrogen Percentage Carbon 1. .591 .S810 .0941 6.62$ 48.17$ a . .0845 .1243 .0521 6.9$ (40.12$) 3 . .2535 .3731 .1572 6.9$ (40.14$) 4 . .0881 .1558 .0586 7.4$ 48.24$ In the case o f 2 and 3 d i f f i c u l t i e s were encoun-t e r e d wh ich r e s u l t e d i n the l o s s o f carbon d i o x i d e , which a c c o u n t s f o r the low r e s u l t s . .* . Average P e r c e n t Hydrogen - 6 .95$ " " Carbon - 4 8 . 2 $ « •» Su lphur - 20 .6$ The oxygen was obtained by the method of differences. Percent (Sulphur Garbon Hydrogen) 1 75.75 Oxygen Emperical Formula,-Carbon 48*2$ Sulphur 20.6$ Hydrogen 6.9 Oxygen 24.3% Taking 3 2 Carbon 3 2 Sulphur 3 2 Hydrogen 3 2 Oxygen 3 2 x x x X 4.01 .644 6.90 1.52 48.2 1 2 20.6 32 6.95 1.008 24.5 16 6.015 .966 10.35 2.28 * 2» 5 24.3 4.01 .644 6.90 1.52 approximate ratio 12 atoms 2 atoms 21 atoms 5 atoms .*, Emperical Formula by this method = C6H10SO3H+ (CgIS^oSOg)z For comparison we may calculate the percentages for various values of x. (1) The sulphonic acid alone CgR^SOgH gives a value of 19.5$ for sulphur. (2) For x s 1 Molecular Weight = 310.2 Sulphur = 20.5$ Carbon = 46.45$ Hydrogen = 7.16$ IS (3) F o r x s 2 Moleotaar Weight = 456 Su lphur = 21.05> Garb oil = 47.37$ Hydrogen z 7.02$ (4) F o r x = 3 M o l e c u l a r Weight = 602 Su lphur e 21.3$ Garbon = 47.84$ Hydrogen = 6.! f5) For x « 5 C a l c u l a t e d Su lphur =21,5$ Carbon = 48.32$ Hydrogen = 6.96$ M o l e c u l a r Weight = 894 E x p e r i m e n t a l 20.6$ 48.2$. 6.95$ Thus assuming t h a t a c h a i n o f s i x would g i v e the most s t a b l e f o r m a t i o n , we get a v e r y good agreement. F - MECHANISM OF THE REACTION. 19 Brooks s t a t e s t h a t anhydrous s u l p h u r d i o x i d e has n o t been shown to r e a c t w i t h u n s a t u r a t e d hydrocarbons t o form d e f i n i t e , s t a b l e compounds. Aqueous su lphurous a c i d , on the o t h e r h a n d , f r e q u e n t l y adds on t o form v e r y s t a b l e s u l p h o n i c a c i d s . T h i s would e x p l a i n the n e c e s s i t y of water i n our r e a c t i o n . The r e a c t i o n w i t h the p e r o x i d e might be c o n s i d e r e d as a oase o f r e c i p r o c a l c a t a l y s i s . The two r e a o t i o n s taken s e p a r a t e l y can be r e p r e s e n t e d as b e l o w , -0 -o I -0 20 13 H 2 3 0 s CT But i f t h e y are mixed t h e r e would he an immediate r e a c t i o n . T h i s i n d i c a t e s the f o r m a t i o n of an u n s t a b l e combi-n a t i o n such as f03l H-S0 2 H whioh decomposes t o 0 - SCvH - H 2 0 The two oxygen atoms combin ing w i t h two mo lecu les o f s u l p h u r o u s a c i d t o fo rm s u l p h u r i c a c i d . However, i n any r e a c t i o n the r e a c t a n t a tend t o form the most s t a b l e p r o d u c t . As these u n s a t u r a t e d compounds a l l tend t o p o l y m e r i z e , the i n t e r m e d i a t e p r o d u c t and decompos i t ion might be w r i t t e n i n the f o l l o w i n g manner , -Cn SO2HEO 0- ^ \ or G4 H 8 HG-OH °4 H 8 G4 H 8 HG-CH HG-OH \_ 14 The problem of the terminal valencies in similar chains like aldehydes and rubber i s s t i l l unsolved. Stand-inger has shown that in the case of the polymers of formalde-hyde, water, methyl alcohol and sulphuric acid have been added to the ends of the molecule depending on the method of polymerization. The following facts lead to the belief that in this case we have sulphurous acid attached to these free bonds. The polymer i s insoluble in most solvents including strong acids. It i s reasonably stable at room temperatures, a property predicted for the product of sulphurous acid and unsaturated hydrocarbons. Finally i t i s soluble in alcoholic potash. Thus as a tentative formula,-°4 ^ 8 G4 *8 CS4 H 8 HO-CH HO-GH HG-OH -3— A recent paper of J. B, Gonant and W. H. Peterson gives a similar formula for the polymerization product of cyclohexene oxide,-®a ^4 ^ 8 ^4 ^ 8 i i r r i I HG-OH HG-OH HG-OH > _ / \ _ o _ ' This polymerization was carried out to advantage in the presence of Benzoyl peroxide. As yet we have not found of cyolohexene in the literature, reaction by auto-oxidation,-any reference to an oxide Thus we might explain the O > — o + AO Then an intermediate compound forms and i s decomposed,-Hc r v 0 : n >f8 >f L / 1 HG-OH HG-G _ / \ _ o _ / \ . o -However, the benzoyl peroxide does not aot as a catalyst, since i t oxidizes in proportion to i t s own mass, and since i t does not emerge unchanged from the reaction. Thus this would hardly explain why 2 $ of the peroxide was sufficient. Therefore we suggest that the peroxide of cyolo-hexene was present, either due to natural causes or to acti-vation by the benzoyl peroxide. As no attempt was made to exclude the oxygen, the former was probably the case. Thus the reaction could be represented as below,-°4 ?8 G4 ?8 -o ^ r i I i I * » HC-CH HC-GH " ° ' ^ - / \ - o - / \ - o As they say that i t polymerized with great d i f f i -culty this probably gives the reason. E l In 1915 Mathews and Elders prepared similar com-pounds with sjf butylene, propylene, amylene, ethylene and sulphur dioxide. Their method was to treat a mixture of say lj) butylene and sulphur dioxide i n a sealed tube, to the action of sunlight. They evaporated off the excess liquor, and got a horny, or glassy clear white solid, soluble i n OHCig and GgHgCl^; to which they gave the simple formula (G 4H QS0 2) . These are exactly the conditions necessary for the formation of peroxides with these unsaturated hydrocarbons. As no effort was made to exclude oxygen, i t seems that these compounds are f i r s t converted to peroxides, which then de-compose and polymerize. This product might, in the light of recent facts be,-H Q GH3 3, , 3 HC - CH 02 % { 3 ^ 3 HG - CH 0, c HC CH 3, , 3 HC - CH PART I I I - THE FREEZING POINT CURVE OF CYOLOHEXADIENE AND LIQUID SULPHUR DIOXIDE. The o b j e c t o f t h i s s e r i e s o f i n v e s t i g a t i o n s has been t o see i f t h e r e was n o t some r e l a t i o n between the s o l u -b i l i t y i n s u l p h u r d i o x i d e and the s t r u c t u r e o f the h y d r o c a r -b o n . W i t h the c o m p l e t i o n o f the cyo lohexene s u l p h u r d i o x i d e sys tem, the f o l l o w i n g two oomponent systems are complete . (1) Hexane and l i q u i d s u l p h u r d i o x i d e fa) Cyc lohexane and l i q u i d s u l p h u r d i o x i d e (3) Cyolohexene » » « « (4) Benzene n ™ n. n f5) The t h r e e t o l u e n e s and l i q u i d s u l p h u r d i o x i d e Thus i t r e q u i r e d o n l y cyo lohexad iene to complete the s e r i e s . That system i s g i v e n i n the f o l l o w i n g p a g e s , A - PREPARATION OF 1-3 CYOLOHEXADIENE. Cyo lohexad iene may e x i s t i n two fo rms , one h a v i n g a quinone s t r u c t u r e , the o t h e r a con juga ted double bond . As the 1-3 oyo lohexad iene i s the most s t a b l e and, as shown i n the method o f p r e p a r a t i o n , more l i k e l y to be p u r e , we dec ided t o use I t , We found i t n e c e s s a r y t o p repare a pure sample, as none was o b t a i n a b l e . fa) P r e v i o u s Work: The 1-3 c y o l o h e x a d i e n e has been p r e p a r e d i n a number o f d i f f e r e n t ways: 11 IS 1. The method used by Baeyer and C r o s s l e y , was to 12 d i s t i l l the d ib romide o f cyo lohexene w i t h q u i n o l e n e . F o r t e y u s e d d i o h l o r o h e x a m e t h y l e n e , but says t h a t i t can a l s o be , p r e p a r e d by t r e a t i n g the d ibromide w i t h a l c o h o l i c p o t a s h . 14 2. The method used by Harries. He treated the dibromide with trimethylamine, i n a sealed tube. The ammonium salt obtained was changed to the base with Ag9Q. Then on heating the hydrocarbon was obtained free from cyclohexene. The physical properties of the samples prepared by 15 £ Harries, Wlllstatter and Hatt , Zelinsky and Gorsky, Bruhl IS and Perkins are given i n Table III. The samples prepared by different methods do not vary any more than the samples prepared by different men but by the same method. This variation shows that i t i s doubtful whether any of the samples are s t r i e t l y pure. T A B L E III Crossley^ Method. Physical Harries Properties Willst-ttter ait Zelinsky Gorsky Bruhl Perkins Refractive o 0 # 5 Index *j) 1.475O6 .47429 ^£'.4700 1.4699 1.47254 D e n s i t y D20 20 3421 l|° 8406 D|°.8404 .83 76 D|?84 79 Boiling Point 80-80.5 at 727 m. 80.5 m. 78.3-78.8 19 Harries 1 method was tried, hut i t was found that i t involved a great many d i f f i c u l t i e s . The method required large quantities of silver oxide, t r i methylamine, and abso-lute alcohol, and also the use of a sealed tube. Thus i t would have been d i f f i c u l t to obtain the cyolohexadiene in any quantity. Also on opening the tube, contrary to statements of Harries, there was never any liquor unless the temperature was about f i f t y degrees centigrade. Therefore this method was discarded and the Grossley method used. b. Preparation of dibromide: This has been prepared by a number of people (17), ( I 3 ) . (18) Baeyer's method was used by us. For a t r i a l run, 20 grs. of cyolohexene and 39 grs. of bromine were used. These were dissolved in chloroform, the former 50$, the l a t t e r 10$ solution. The oyclohex^ene was cooled in an ice bath, and the bromine dropped in slowly. (A mechanical s t i r r e r was used). The product was treated with a small quantity of KgGOg solution to remove any exoess bromine. The two layers were separated by means of a separating funnel and the pro-duct dryed over CaCl g. The CHClg was then d i s t i l l e d off. o. Preparation of 1-3 Gyclohexadiene: We used Grossley"s method. Full details are given on page 1416 of the Journal of the Chemical S ooiety, 1904. These were followed out and a yield of 21j grams obtained. About 47 grams of the material were made in this manner. d. Purification: In view of the facts, that we had only a small quantity of the hydrocarbon and that i t i s relatively un-stable, we decided that fractional d i s t i l l a t i o n would be the hest method of purification. Provided that the eolumn has a good reflux, this should effect a good separation from any dihromide or cyclohexene present. The dibromide boils at 145-146 C at 100 m.m., the cyclohexene at 83°C, and the eyelohexadiene at 80-80.5°e. A column was made i n the following manner. A tube about two feet i n length and one-half inch i n diameter was sealed to a seventy-five ce. round bottom flask. The column was lagged with a layer of asbestos and about twenty turns of niehrome wire were wound on uniformly. This was conversed with another layer of asbestos. The column was then f i l l e d with glass beads, and was ready for use. The material was d i s t i l l e d slowly, various fractions taken off. The refractive index of each sample was then taken, the results are shown i n the Table I?. The material was then again fractionated, this time from sodium, more care being taken with the fractions. The index of refraction of each of these samples i s also given i n Table 17. T A B L E IV. Refractive Index D 1st D i s t i l l a t i o n 2nd Dis t i l l a t i o n , 1st Fraction 1.46847 1.46972 2nd Fraction 1.46775 1.46858 3rd Fraetion 1.46616 1.46780 ' We considered that the f i r s t fraction would be pure enough for our purpose. E l B - THE REACTION OF SULPHUR DIOXIDE AND GYGLOHEXADIENE. We s t a r t e d to determine the f r e e z i n g - p o i n t curve by the method used f o r c y o l o h e x e n e . However, immedia te ly on a d d i n g s u l p h u r d i o x i d e the cyo lohexad iene tu rned a y e l l o w i s h -g r e e n , and a s m a l l amount o f a whi te compound formed. Even w i t h the e x c l u s i o n o f a lmost a l l the a i r t h i s r e a c t i o n took p l a o e . T h i s w h i t e compound was found to a c t v e r y s i m i l a r l y to t h a t o f the c y o l o h e x e n e . I t c o u l d he p r e p a r e d , w i t h a b e t -t e r y i e l d f rom an o x i d i z e d sample i n the p resence o f w a t e r . It was a l s o s o l u b l e i n c h l o r o f o r m , but t o a l e s s e r e x t e n t . On e v a p o r a t i n g o f f the c h l o r o f o r m , t h i s compound c r y s t a l -l i z e d , i n t h i s i t d i f f e r s f rom the o t h e r compound. A p p a r e n t l y cyo lohexad iene i s s t i l l more s e n s i t i v e to the p r e s e n c e o f a i r than c y o l o h e x e n e . Thus i t has no t been p o s s i b l e so f a r to determine the f r e e z i n g p o i n t c u r v e , due t o the v i g o u r o u s r e a c t i o n which t a k e s p l a o e when the two compounds are brought t o g e t h e r . I t was to be expec ted t h a t t h i s r e a c t i o n would take p l a o e because a compound w i t h i s o p r e n e and s u l p h u r d i -ox ide has a l r e a d y been observed by de B r u i n a 0 . He g i v e s the f o r m u l a 0 &H 8SO g. T h i s work on oyc lohexad iene and s u l p h u r d i o x i d e comple tes the s e r i e s o f s u l p h u r d i o x i d e and hydrocarbon systems Of benzene . SIfMMART (1) The freezing-point solubility curve of cyclohexene and li q u i d sulphur dioxide has been determined. (2) Oyolohexene and li q u i d sulphur dioxide are misoible in a l l proportions above 75.43 Centigrade. (3) No compound i s formed between pure oyolohexene and liqu i d sulphur dioxide. (4) It has been shown that oyolohexene and sulphur d i -oxide polymerize in the presence of air, due to the formation of a peroxide. (5) A tentative formula and a chain mechanism have been suggested that seem to account for a l l the observed fact. This not only applies to this polymer, but also explains the SI results observed by Mathews and Elders. It has also been pointed out that the same process may take place in the polymer-ization of isoprene. (6) Certain suggestions have been made as to the mechan-ism of Conant and Peterson, that seem to give a better expla-nation of their results. (7) It has been shown that oyclohexadiene i s s t i l l more sensitive to air than cyclohexene. (8) With sulphur dioxide i t forms at least two products. A white polymer similar to that of cyclohexene, and a greenish-yellow l i q u i d . Bibliography 1. Metallurgical and Chemical Engineering Journal, Vol.1, 1918 - p.396. 2. Trans. Royal Society of Canada, Third Series, Vol.XVI, 1922. -3. Trans. Royal Society of Canada, Third Series, Vol.XVIII, 1924 - p.213. 4. Trans. Royal Society of Canada, Third Series, Vol.XVIII, 1924 - p.209. 5. Journal of the American Chemical Society, 52 - 14, 1930. 7. Journal of Industrial and Engineering Chemistry, Vol.23, 1931 - p.325. 8. King, E.G., - B.A. Thesis, 1930. 9. Journal of the American Chemical Society, February 1932 - p.628. 10. Stephens, H.H., J.A.C.S. 50, 1928 - p.568. 10. Birch, S.F., and Stanfield, R., Hature, 123, 1929, p.491. II 11. Baeyer, Mebig's Anna!en, Vol. 278 - p . 94. 12. Grossley, J. 0, S., 1904 - p. 1416. 13. lortey, Trans. Chem. Soo., 1898 - p. 946. 14. Harries, Ber. Vol. I, 1912 - p. 809. 15. Willstatter and Hott, Ber. Vol. II, 1912 - 1464. 16. 2elinaky and Corsky, Ber. Vol. II, 1911 - p. 2312. 17. Baeyer, Mebig's Annalen, Vol. 278 - p. 108. 18. Markownikoff, Liebig's Annalen, Vol. 302 - p. 29. 19. Brooks, The Hbn-Benzenoid Hydrocarbons, The Chemical Catalog Co. Inc., p. 144, 20. de Bruin, Chemical Abstracts 9, 623 (1915). I l l 2 1 . Mathews and E l d e r s , E n g . P a t . 11635 (1914); J . Soe . Chem. I n d u s t r y , 34 , 670 (1915); Chemica l A b s t r a c t s , 9, 2971 (1915) . 

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