UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

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

Your browser doesn't seem to have a PDF viewer, please download the PDF to view this item.

Item Metadata

Download

Media
831-UBC_1932_A8_K5_I5.pdf [ 2.1MB ]
Metadata
JSON: 831-1.0061934.json
JSON-LD: 831-1.0061934-ld.json
RDF/XML (Pretty): 831-1.0061934-rdf.xml
RDF/JSON: 831-1.0061934-rdf.json
Turtle: 831-1.0061934-turtle.txt
N-Triples: 831-1.0061934-rdf-ntriples.txt
Original Record: 831-1.0061934-source.json
Full Text
831-1.0061934-fulltext.txt
Citation
831-1.0061934.ris

Full Text

m HTVESTIGATIOII OF TWO COMPONENT SYSTEMS OF CYCLIC HYDROCARBONS AND LIQUID SULPHUR DIOXIDE.  Ellis  Gray  King, B.A.  A T h e s i s s u b m i t t e d f o r t h e degree of M a s t e r o f A r t s i n t h e Department of Chemistry.  The  University  of B r i t i s h  A p r i l 1932.  Columbia  Acknowledgment s  The w r i t e r wishes to express h i s appreciation and sincere thanks f o r the help, guidance and adviee given him "by Dr. Seyer under whom t h i s work was c a r r i e d out.  Table of Contents PART I  A  -  -  THE FREEZING; POINT CURVE Of CYGLOHEXENE AND LIQUID SULPHUR DIOXIDE.  Experimental Work, a. b. c. d. e.  C  -  Difficulties. Preparation of Nitrogen. Preparation of Pure Cyolohexene. F i l l i n g the Bulbs. Determining the Freezing Points.  Experimental Results.  PART I I -  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 I I I - THE FREEZING POINT CURVE OF CYCLOHEXADIENE AND LIQUID SULPHUR DIOXIDE. A  -  Preparation of 1.3 Cyolohexadiene. a. b. c. d.  B  -  Previous Work. Preparation of di-bromide. Preparation of 1.3 Cyolohexadiene. Purification.  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, M o r r e l l and E g l o f f based a method f o r the separation of p a r a f f i n s and naphthenea on the s o l u b i l i t y of p a r a f f i n s , aromatios, napthenes, and o l e f i n s i n l i q 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 s o l u b i l i t y curve was redetermined by V. Dunbar, under h i s supervision.  The  resultant curve i s given on Graph I I I , and shows no evidence of compound formation. Sinoe then, with the assistance of Hugget (3), G i l l ( 4 ) , Peok (5) and Todd f 6 ) , Dr. Seyer has examined other hydrocarbons, from the same point of view.  The p a r a f f i n s  were found to be miscible only above oertain The same i s true f o r the saturated c y c l i c cyclohexane.  temperatures.  hydrocarbon,  But the aromatic compound benzene, was  to be t o t a l l y miscible under a l l conditions.  found  The curve,  however, gave no i n d i c a t i o n of compound formation.  Thus  Dr. Sever thought that i t would be i n t e r e s t i n g to study the other c y c l i c hydrocarbons,  cyclohexene and  eyclohexadiene.  The f r e e z i n g point curve, o f 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, A p r i l 1930, we pointed out that t h i s 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 o f t h i s paper were rather s c e p t i c a l of our r e s u l t s ; one said, " I t would have been more convincing i f they had given freezing point - s o l u b i l i t y data to prove t h i s . " Thus we decided to follow t h i s out, and the resultant curve shows d e f i n i t e l y , 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 i n Experimental Work. 1. Due to the white compound the CgEL^Q must be f i r s t p u r i f i e d , and then kept i n an inert atmosphere.  The s l i g h t e s t  amount of a i r present seems to i n t e r f e r e . 2. The composition o f 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 t r y i n g d i f f e r e n t 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 i n e r t atmosphere tried).  (0O„ was  This was prepared as shown i n diagram (1) - N N0 &  2  s o l u t i o n was dropped into a heated solution of NH C1. The 4  nitrogen was passed thru p y r o g a l l o l , and c o l l e c t e d i n 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 f o r about one hour, then the small t i p (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 d i r e c t l y on the f i l l i n g apparatus (figure 3).  A 10 ces. portion was used i n t h i s , and thus i t  was necessary to prepare a new sample f o r 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 i n t e r n a l diameter were used.  This  i s i l l u a t r a t e d i n Diagram 3 - ( A ) . 1. Cyclohexene. The bulb and rubber stopper were f i r s t weighed, and  t h e n the  hulh  slipped  was t h o r o u g h l y allowed (D).  to  on t o  the a p p a r a t u s .  swept o u t w i t h n i t r o g e n  flow  When t h e  (this  flowed over,  (C) was c l o s e d and  removed,  rubberstopper  This  the  gave  the  amount o f  As the stop-cocks, 2.  Sulphur  section  (3)  cyclohexene d i d not  and t h e  solution  As a c h e c k , then  to  correct  this  of a transparent  the  contact with  the  grease.  the apparatus swept the of  out  shown  with  same  time.  sulphur  dioxide  gave  the  t o t a l weight  b u l b was w e i g h e d c o n t a i n i n g  obtainable for  diagram -  machine-naplha,  and of the  air.  (H) -  i n w e i g h i n g the  shown i n D i a g r a m  (F) a f r e e z i n g bath -  it  bulbs,  (4): consisted  covered with asbestos,  A very l i g h t  was u s e d i n  method made  Point.  the  and a d r y i n g s y s t e m ,  over the l i q u i d  by t h i s  bouyancy  vacuum f l a s k  h a v i n g s m a l l windows.  -  onto  cooled at  This  The a p p a r a t u s u s e d i s  container  come i n  The b u l b was t h e n s e a l e d o f f ,  D e t e r m i n i n g the F r e e z i n g  r e f e r r i n g to  The b u l b was  empty.  The a c c u r a c y  e.  had  weight.  d e s i r e d amount  w e i g h e d up w i t h t h e r u b b e r .  unnecessary  by  (b) the n i t r o g e n  condensed w i t h l i q u i d a i r .  mixture,  closing  judged)  troubled with stop-cock  ( E ) was c l o s e d a n d t h e  C^Hio SO2.  had t o be  was  dioxide.  sulphur dioxide Then  ( C ) and  (D) o p e n e d .  The b u l b was t h e n f i t t e d i n diagram  bulb  r e p l a c e d and t h e whole w e i g h e d u p .  cyclohexene  we were n o t  the  some c y c l o h e x e n e  o v e r by o p e n i n g s t o p - c o c k d e s i r e d amount  After  gasoline,  bath. for  called  (G) - l i q u i d the  a i r used to  platinum resistance  and gas air blow  thermometer.  G  -  EXPERIMENTAL R E S U L T S .  To get as pure a sample as possible, the cyclohexene was refluxed over sodium, and then fractionated,  fhe index  of r e f r a c t i o n , f o r each i s given i n fable I. We considered that the second f r a c t i o n was f a i r l y pure. 20  TABLE I. 1st Fraction  1.44619  End Fraction  1.44601  3rd Fraction  1.44636  Material standing i n Oxygen  1.48917  B e i l s t e i n and C r i t i c a l Tables  1.4451  The r e s u l t s , obtained i n determining the freezing points, are given i n Table I I .  The curves were then plotted  using both the percentage C_H_ Graph I, and the Mol. percent 6 10 Graph I I . n  These show d e f i n i t e l y that there i s no compound formed with pure  cyclohexene.  f  A  B  I  E  II  I&eatification No.  Wt.of C H 6 10  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 16  1.234 2.380  1.370  90.1  1.438  -106.7  2.599  91.6  87.7 89.5  1.403  -110.1  H14  2.776  94.9  93.5  1.435  -107.1  IS  2.079  2.924 2.151  96.6  95.7  1.441  -106.5  Ave. Wt.of 0  6 10 H  * C  Ifol.  f  6 10 H  0  Freezing Point of pure C H H * " * SO 6  1 0  6 10 E  Resistance Freezing Thermomet- Point. er Reading.  C r i t i c a l Tables -103.7 Mr. Carpenter -72.7  7  PART I I  -  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 r e s u l t s . A  -  PREPARATION. The compound was prepared by passing sulphur dioxide  through the oxidized cyclohexene, the mixture being lcept i n an i c e bath.  Better r e s u l t s were obtained by adding a drop  or tw© of water.  A f t e r 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  a brown resinous compound formed.  The  otherwise  product i s very white,  obtained this way, but has a very high vapour pressure. B  -  PURIFICATION. In p u r i f y i n g the previous method was modified  slightly.  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 w e l l 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.  was deeanted o f f and replaced with alcohol.  This  F i n a l l y the  mixture was f i l t e r e d , the alcohol washed out with water, and the compound dryed.  8 The reason f o r t h i s method of p u r i f i c a t i o n i s that i t does not c r y s t a l l i z e from chloroform, the only l i q u i d 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 t h i s  way i s pure white, has no smell, and i s more stable to heat than the samples previously prepared. C  I.  A FEW ISOLATED EXPERIMENTS WERE PERFORMED WHICH ARE GIVEN HERE. Some sensitive tests are available f o r 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 c r y s t a l of ferrous ammonium sulphate (free of f e 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 l e s s 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. dark blue when starch was added.  This solution turned A sample of cyclohexene,  whioh had been r e d i s t i l l e d and placed i n a corked bottle about a month before, was given the same treatment. On shaking with sodium iodide, i t gave only a f a i n t  9  yellow,  this  indicated  S t a r c h gave t h i s  color  between the  reaction.  The o x i d i z e d  a  shade.  with starch gives  of p e r o x i d e s .  difference  gave  o f p e r o x i d e was p r e s e n t .  purple  sodium i o d i d e  i n the presence  cyolohexene  a trace  solution a light  Acidified  c.  that  a "blue  In t h i s  case  the  two m a t e r i a l s was t h e  rate  of  sample gave an i m m e d i a t e  a lighter  color  after  only  color.  shaking for  The  about  half  minute. This proves d e f i n i t e l y ,  w i t h the p e r o x i d e , B i r c h and  a.  and s u b s t a n t i a t e s  Stansfield.  We were  interested  cyolohexene  in  t h e h y d r o c a r b o n and t h e used as a  t h e work o f  i n knowing i f  the  compound  solution. sulphur  Benzene,  dioxide  are  into  i n which  both  soluble,  was  solvent.  b u t no d e f i n i t e  water produced  a milky  r e s u l t s were solution  w o u l d h a r d l y do a s a method o f  3.  Stephens,  a d v a n t a g e b y p a s s i n g 30^  C o n c e n t r a t i o n s v a r y i n g f r o m 10 t o used,  dealing  1 0  c o u l d be p r o d u c e d t o b e t t e r oxidized  t h a t we have b e e n  obtained.  i n the  90$ Benzene were A drop  50$ m i x t u r e ,  of but  preparation.  . The compound d i s s o l v e s  in  chloroform,  analine,  this  alcoholic  potash,  and t o a s l i g h t  insoluble  i n water,  ether,  extent  acetic  acid  i n alcohol.  and o t h e r  It i s  common  solvents. The c h l o r o f o r m s o l u t i o n t a k e s the  compound p r o b a b l y a s s o c i a t i n g  indicated by fact mass.  This fact  determination  that before and t h e  on a brown  i n solution.  shade,  This i s also  d i s s o l v i n g i t g o e s t o a gummy  small  s o l u b i l i t y prevented  o f the m o l e c u l a r weight by the  the  ordinary  methods. This  compound i s r a t h e r  r e c e n t work done b y Gonant peroxides  important  and P e t e r s o n ,  on t h e p o l y m e r i z a t i o n  9  i n view o f the  on t h e  effect of  of hydrocarbons a t high  pressures. E - DETERMINATION 03? THE COMPOSITION. A qualitative in large  quantities  quantitatively, Gatterman,  teat  showed t h a t  i n the p o l y m e r ,  s u l p h u r was p r e s e n t  f o rdetermining  this  t h e C a r i u s method was u s e d a s d e s c r i b e d i n  p . 86.  RESULTS. wt. o f sample  w t . o f Barium sulphate  Percentage sulphur  (1)  .1430  grs.  .2136  grs  20.5#  (2) (3)  .1320 .1158  " "  .1996 .1731  * *  20.8g 20.5^  Average  -  20.6/&  10a  In the account copper  of the  combustion a n a l y s i s  sulphur present,  oxide by l e a d  it  was n e c e s s a r y ,  to replace  ohrornate.  A small  chrornate was a l s o u s e d i n t h e p o r c e l a i n The A b s o r p t i o n S y s t e m  two-thirds  quantity  of  on of  the  lead  boat.  -  1.  H y d r o g e n a s w a t e r - pumice m o i s t e n e d sulphuric acid.  by  2.  C a r b o n - a s c a r b o n d i o x i d e was a b s o r b e d soda l i m e ,  3.  A n o t h e r U - t u b e was u s e d o n e - t h i r d f u l l o f s o d a l i m e , t h e r e s t pumice and s u l p h u r i c .  by  RESULTS. wt. of sample  wt.  of  1.  .591  .S810  .0941  6.62$  a.  .0845  .1243  .0521  6.9$  (40.12$)  3.  .2535  .3731  .1572  6.9$  (40.14$)  4.  .0881  .1558  .0586  7.4$  48.24$  co  In the  wt.  of  Percentage Hydrogen  a  case  for  .*.  the low  48.17$  o f 2 and 3 d i f f i c u l t i e s were  t e r e d which r e s u l t e d i n the l o s s accounts  Percentage Carbon  of  carbon d i o x i d e ,  results.  Average P e r c e n t Hydrogen  -  6.95$  "  "  Carbon  -  48.2$  «  •»  Sulphur  -  20.6$  encounwhich  The oxygen was obtained by the method of differences. Percent (Sulphur  Garbon  Hydrogen) 1 75.75  Oxygen  * 2» 5 24.3  Emperical Formula,Carbon  48*2$  Sulphur  20.6$  Hydrogen  6.9  4.01  1 2  20.6 32  24.3%  Oxygen Taking  48.2  .644  6.95 1.008  6.90  24.5 16  1.52  3  approximate ratio  2  Carbon  3 2 Sulphur 3 2 Hydrogen 3 2 Oxygen 3 2  4.01  x  .644  x  6.015  12 atoms  .966  2 atoms  x  6.90  10.35  21 atoms  X  1.52  2.28  5 atoms  .*, Emperical Formula by t h i s method = C6H10SO3H+ (CgIS^oSOg)  z  For comparison we may calculate the percentages f o r various values of x. (1)  The sulphonic acid alone CgR^SOgH gives a value of 19.5$ f o r sulphur.  (2)  For x  s  1  Molecular Weight Sulphur = Carbon = Hydrogen =  20.5$ 46.45$ 7.16$  = 310.2  IS Forx s 2  (3)  Moleotaar Weight Sulphur = Garb oil = Hydrogen z  Forx = 3  (4)  = 456  21.05> 47.37$ 7.02$  Molecular  Weight  = 602  Sulphur e 21.3$ Garbon = 47.84$ H y d r o g e n = 6.!  f5)  M o l e c u l a r W e i g h t = 894  For x « 5  Experimental  Calculated S u l p h u r =21,5$ Carbon = 48.32$ H y d r o g e n = 6.96$  20.6$ 48.2$. 6.95$  Thus a s s u m i n g t h a t most s t a b l e F  -  formation,  a c h a i n o f s i x would g i v e t h e  we g e t a v e r y good  agreement.  MECHANISM OF THE REACTION.  19 Brooks  states  that  anhydrous  sulphur dioxide has  n o t b e e n shown t o r e a c t w i t h u n s a t u r a t e d h y d r o c a r b o n s t o form d e f i n i t e ,  stable  on t h e o t h e r h a n d , sulphonic in  acids.  compounds.  frequently  Aqueous s u l p h u r o u s  adds on t o f o r m v e r y  T h i s would e x p l a i n t h e n e c e s s i t y  acid,  stable of water  our r e a c t i o n . The r e a c t i o n w i t h t h e p e r o x i d e m i g h t b e c o n s i d e r e d  a s a oase o f r e c i p r o c a l separately  0  catalysis.  The two r e a o t i o n s  can be r e p r e s e n t e d a s b e l o w , -  -o  I  -0  20  taken  13  H 30 2  But i f reaction. nation  This  CT  s  t h e y a r e m i x e d t h e r e w o u l d he an indicates  the  formation  of an u n s t a b l e  w h i o h decomposes  0  H-S0 H 2  to  - SCvH 2 0  -H  The two o x y g e n atoms c o m b i n i n g w i t h two sulphurous a c i d to form s u l p h u r i c However, t h e most  stable  be w r i t t e n  or  4  H  8  HG-OH  the  i n the  Cn G  i n any r e a c t i o n  product.  tend t o p o l y m e r i z e , might  combi-  such as  f03l  of  immediate  acid.  the r e a c t a n t a  As these u n s a t u r a t e d intermediate following  molecules  product  tend to  compounds  and  0- ^ 2  E  \  °4  H  8  HG-CH  G  4  H  8  HG-OH  \_  all  decomposition  manner,-  SO H O  form  14 The problem of the terminal valencies i n similar chains l i k e aldehydes and rubber i s s t i l l unsolved.  Stand-  inger has shown that i n the case of the polymers of formaldehyde, 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 b e l i e f that i n t h i s case we have sulphurous acid attached to these free bonds. The polymer i s insoluble i n most solvents including strong acids.  I t i s reasonably stable at room temperatures, a  property predicted for the product of sulphurous acid and unsaturated hydrocarbons. potash.  F i n a l l y i t i s soluble i n alcoholic  Thus as a tentative formula,-  °4 ^8  G  HO-CH  4  CS H  *8  4  HO-GH  8  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,^4 ^8  ®a  i i HG-OH  r r HG-OH > _ /  \ _ o _  ^4 ^8  i I HG-OH  '  This polymerization was carried out to advantage i n the presence of Benzoyl peroxide.  As yet we have not found any reference to an oxide of cyolohexene  i n the l i t e r a t u r e ,  Thus we might explain the  reaction by auto-oxidation,-  >— o  O  +  AO  Then an intermediate compound forms and i s decomposed,-  n  rv : L /  0  1  >f  8  HG-OH  _ /  >fH  c  HG-G  \ _ o _ /  \ . o -  However, the benzoyl peroxide does not aot as a c a t a l y s t , since i t oxidizes i n proportion to i t s own mass, and since i t does not emerge unchanged from the reaction. Thus t h i s would hardly explain why 2 $ of the peroxide was sufficient. Therefore we suggest that the peroxide of cyolohexene was present, either due to natural causes or to activation 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,-o I "°  °4 ?8 r i  ^ * '  » ^  HC-CH - /  G  4 ?8 Ii HC-GH  \ - o - /  \ - o  As they say that i t polymerized with great d i f f i c u l t y t h i s probably gives the reason. El  In 1915 Mathews and Elders  prepared similar com-  pounds with sjf butylene, propylene, amylene, ethylene and  sulphur dioxide. lj)  Their method was to treat a mixture of say  butylene and sulphur dioxide i n a sealed tube, to the  action of sunlight.  They evaporated o f f the excess liquor,  and got a horny, or glassy clear white s o l i d , soluble i n OHCig and GgHgCl^; (G H S0 ) 4  Q  to which they gave the simple formula  .  2  These are exactly the conditions necessary f o r the formation of peroxides with these unsaturated hydrocarbons. As no e f f o r t was made to exclude oxygen, i t seems that these compounds are f i r s t converted to peroxides, which then decompose and polymerize.  This product might, i n the l i g h t of  recent f a c t s be,-  H  Q 3,  GH  %{  3  , 3  3  HC  ^3  3,  02  , 3  HC - CH  HG - CH  HC - CH  CH  0, c  PART I I I -  THE FREEZING POINT CURVE OF CYOLOHEXADIENE AND L I Q U I D SULPHUR D I O X I D E .  The o b j e c t been t o bility bon.  see i f in  system,  A  some r e l a t i o n b e t w e e n t h e  and the  completion  o f the  structure  and l i q u i d  o f the  cyolohexene  sulphur  hydrocar-  sulphur  systems are  solu-  dioxide  complete.  Hexane  fa) (3) (4) f5)  C y c l o h e x a n e and l i q u i d s u l p h u r d i o x i d e Cyolohexene » » « « Benzene ™ . 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 n  required  given in  the  structure,  the  t h e 1-3  oyolohexadiene  n  to  following  complete  the  series.  pages,  CYOLOHEXADIENE.  Cyolohexadiene quinone  dioxide  n  only cyolohexadiene  PREPARATION OF 1-3  may e x i s t  in  two f o r m s ,  o t h e r a conjugated double is  t h e most s t a b l e  t h e method o f p r e p a r a t i o n , more l i k e l y to use  has  (1)  system i s  -  dioxide  s e r i e s of i n v e s t i g a t i o n s  t h e f o l l o w i n g two oomponent  Thus i t That  t h e r e was n o t  sulphur  With the  of t h i s  and,  one h a v i n g bond.  As  a s shown  in  t o be p u r e , we  a  decided  It, We f o u n d i t  none was fa)  a pure  sample,  as  obtainable. Previous The 1-3  Work: 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  number o f d i f f e r e n t 1.  necessary to prepare  a  ways:  The method u s e d b y B a e y e r  11  and C r o s s l e y ,  IS  was  to  12 distill  the dibromide  of  cyolohexene w i t h q u i n o l e n e .  Fortey  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 , b u t s a y s t h a t i t c a n a l s o be , p r e p a r e d by t r e a t i n g the d i b r o m i d e w i t h a l c o h o l i c p o t a s h .  2.  14 The method used by Harries. He treated the dibromide  with trimethylamine, i n a sealed tube. obtained was  The ammonium s a l t  changed to the base with Ag Q. 9  the hydrocarbon was obtained free from  Then on heating  cyclohexene.  The physical properties of the samples prepared by 15 £ Harries, W l l l s t a t t e r and Hatt , Zelinsky and Gorsky, Bruhl IS and Perkins  are given i n Table I I I .  The samples prepared  by d i f f e r e n t methods do not vary any more than the samples prepared by d i f f e r e n t men but by the same method.  This  v a r i a t i o n 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 C r o s s l e y ^ Method.  Physical Properties Refractive Index  Harries  o  #  t  Zelinsky Gorsky  Bruhl  Perkins  ^£'.4700  1.4699  1.47254  5  *j) 1.475O6 D  Density  0  Willsttter ait  20 20 3421  .47429  D|°.8404  .83 76  l|° 8406 Boiling Point  80-80.5  at 727 m. m. 78.378.8  80.5  D|?84 79  19 Harries  1  method was t r i e d , 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 s i l v e r oxide, t r i methylamine, and absol u t e 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 i n any quantity.  Also on opening the tube, contrary to statements  of Harries, there was never any l i q u o r unless the temperature was about f i f t y degrees centigrade.  Therefore t h i s method  was discarded and the Grossley method used. b.  Preparation of dibromide: This has been prepared by a number of people (17),  ( I ) . (18) Baeyer's method was used by us. 3  For a t r i a l run, 20 grs. of cyolohexene and 39 grs. of bromine were used.  These were dissolved i n chloroform,  the former 50$, the l a t t e r 10$ s o l u t i o n .  The oyclohex^ene  was cooled i n an i c e bath, and the bromine dropped i n 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 product dryed over C a C l . g  o.  The CHClg was then d i s t i l l e d o f f .  Preparation of 1-3 Gyclohexadiene: We used Grossley"s method.  F u l l d e t a i l s are given  on page 1416 of the Journal of the Chemical S ooiety, 1904. These were followed out and a y i e l d of 2 1 j grams obtained. About 47 grams of the material were made i n t h i s manner. d.  Purification: In view of the f a c t s , that we had only a small  quantity of the hydrocarbon and that i t i s r e l a t i v e l y unstable, we decided that f r a c t i o n a l d i s t i l l a t i o n would be  the hest method of p u r i f i c a t i o n .  Provided that the eolumn  has a good r e f l u x , t h i s should e f f e c t a good separation from any dihromide or cyclohexene present. at 145-146 C at 100 m.m.,  The dibromide b o i l s  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 f l a s k .  The column  was lagged with a layer of asbestos and about twenty turns of niehrome wire were wound on uniformly. with another layer of asbestos.  This was conversed  The column was then f i l l e d  with glass beads, and was ready f o r use. The material was d i s t i l l e d slowly, various fractions taken o f f .  The r e f r a c t i v e index of each sample was then  taken, the r e s u l t s are shown i n the Table I?.  The material  was then again fractionated, t h i s time from sodium, more care being taken with the f r a c t i o n s .  The index of r e f r a c t i o n 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 D i s 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 f r a c t i o n would be pure enough f o r  our purpose.  El B -  THE REACTION OF SULPHUR DIOXIDE AND We s t a r t e d t o  determine  the f r e e z i n g - p o i n t  b y t h e method u s e d f o r  cyolohexene.  adding sulphur dioxide  the  green,  and a s m a l l amount  w i t h the  exclusion  GYGLOHEXADIENE.  However,  cyolohexadiene of a white  o f almost a l l  the  curve  immediately  on  turned a y e l l o w i s h -  compound f o r m e d .  Even  air  took  this  reaction  plaoe. This white to  that  o f the  ter yield  cyolohexene.  f r o m an o x i d i z e d  I t was a l s o  soluble  On e v a p o r a t i n g o f f lized,  compound was f o u n d t o a c t v e r y  in this  it  in  to the presence been p o s s i b l e  sample i n t h e p r e s e n c e  chloroform,  differs  this  from the  is  to determine  the  water.  extent.  crystal-  more  Thus i t  sensitive has not  freezing point  curve,  due t o t h e v i g o u r o u s r e a c t i o n w h i c h t a k e s p l a o e when t h e compounds a r e b r o u g h t  two  together.  I t was t o be e x p e c t e d t h a t take p l a o e because  this reaction  a compound w i t h i s o p r e n e  o x i d e h a s a l r e a d y b e e n o b s e r v e d b y de B r u i n  would  and s u l p h u r a 0  .  di-  He g i v e s  formula 0 H SO . &  8  g  T h i s work on o y c l o h e x a d i e n e completes the s y s t e m s Of  series of  benzene.  bet-  compound.  still  than cyolohexene.  of  a lesser  compound  other  cyolohexadiene  of a i r  so f a r  c o u l d he p r e p a r e d , w i t h a  c h l o r o f o r m , but t o  the  Apparently  It  similarly  and s u l p h u r  sulphur dioxide  dioxide  and h y d r o c a r b o n  the  SIfMMART  (1)  The freezing-point s o l u b i l i t y curve of cyclohexene  and l i q u i d sulphur dioxide has been determined. (2)  Oyolohexene and l i q u i d sulphur dioxide are misoible  i n a l l proportions above (3)  75.43  Centigrade.  No compound i s formed between pure oyolohexene and  l i q u i d sulphur dioxide. (4)  I t has been shown that oyolohexene and sulphur d i -  oxide polymerize i n the presence of a i r , due to the formation of a peroxide. (5)  A tentative formula and a chain mechanism have been  suggested that seem to account f o r a l l the observed f a c t . This not only applies to t h i s polymer, but also explains the SI r e s u l t s observed by Mathews and Elders.  I t has also been  pointed out that the same process may take place i n the polymeri z a t i o n of isoprene. (6)  Certain suggestions have been made as to the mechan-  ism of Conant and Peterson, that seem to give a better explanation of t h e i r r e s u l t s . (7)  I t has been shown that oyclohexadiene i s s t i l l more  sensitive to a i r than (8)  cyclohexene.  With sulphur dioxide i t forms at l e a s t two products.  A white polymer similar to that of cyclohexene, and a greenishyellow l i q u i d .  Bibliography  1.  M e t a l l u r g i c a l 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 I n d u s t r i a l 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, M e b i g ' s Anna!en, V o l . 278 - p . 94.  12.  Grossley, J . 0, S., 1904 - p. 1416.  13.  lortey, Trans. Chem. Soo., 1898 - p. 946.  14.  Harries, Ber. V o l . I, 1912 - p. 809.  15.  W i l l s t a t t e r and Hott, Ber. V o l . I I , 1912 - 1464.  16.  2elinaky and Corsky, Ber. V o l . I I , 1911 - p. 2312.  17.  Baeyer, Mebig's Annalen, V o l . 278 - p. 108.  18.  Markownikoff, Liebig's Annalen, V o l . 302 - p. 29.  19.  Brooks, The Hbn-Benzenoid Hydrocarbons, The Chemical Catalog Co. Inc., p. 144,  20.  de Bruin, Chemical Abstracts  9, 623 (1915).  Ill  21.  Mathews and  Elders,  E n g . P a t . 11635 ( 1 9 1 4 ) ; J . S o e . Chem. I n d u s t r y , 3 4 , 670 ( 1 9 1 5 ) ; C h e m i c a l A b s t r a c t s , 9 , 2971 ( 1 9 1 5 ) .  

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0061934/manifest

Comment

Related Items