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A systematic study of the preparation of unsaturated hydrocarbons by elimination of halogen acid from… Bell, Alan 1934

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A Systematic Study of the P r e p a r a t i o n of Unsaturated Hydrocarbons "by E l i m i n a t i o n of Halogen Acid from Corresponding H a l i d e -by-Alan B e l l A Thesis submitted i n p a r t requirement f o r the degree of Master of A r t s i n The Department of Chemistry UNIVERSITY OP BRITISH COLUMBIA October 1934 . . V^.yJ Table of Contents In t r o d u c t i o n Page 1 Experimental Page 6 Method of A n a l y s i s Page 9 Table 1 Page 10 Table 2 Page 11 Table 3 Page 12 D i s c u s s i o n of R e s u l t s Page 13 Summary Page 17 References Page 18 ( 1 ) A Systematic Study of the Pr e p a r a t i o n of Unsaturated Hydrocarbons "by E l i m i n a t i o n of Halogen A c i d from the Corresponding H a l i d e s . The object of t h i s research has been to i n v e s t i g a t e the p o s s i b i l i t i e s of the use of c e r t a i n organic bases i n the preparation.of unsaturated hydrocarbons. The method of formation of these compounds by e l i m i n a t i o n of halogen aci d from corresponding h a l i d e has long been known. A l c o h o l i c potash i s g e n e r a l l y considered to be the best reagent f o r t h i s purpose, although i n many cases c e r t a i n organic bases can be used to b e t t e r advantage. No reference has been found i n the l i t e r a t u r e where an i n v e s t i g a t o r has q u a n t i t a t i v e l y compared the use of a l c o h o l i c potash and these organic bases. Thus the object of t h i s work, Wildermann and Aisinmann ( l ) were among the f i r s t to measure q u a n t i t a t i v e l y the a c t i o n of a l c o h o l i c potash. They measured the v e l o c i t y of the a c t i o n of t h i s reagent on halogen d e r i v a t i v e s of hydrocarbons of the a l i p h a t i c s e r i e s . B r u s s o f f (2) measured r a t e of formation of o l e f i n e during the r e a c t i o n of a l c o h o l i c potash with a l k y l h a l i d e s . There are innumerable instances i n the l i t e r a t u r e where various organic bases have been used i n preparing unsaturated compounds. A few of these deserve mention. Perkins i n h i s researches on the terpenes states i n many cases where an organic base gives a t e t t e r y i e l d than a l c o h o l i c potash (2-%) F i s c h e r and Boeder (10)'found p y r i d i n e gave a b e t t e r y i e l d ( 2 ) than c a u s t i c potash i n preparing u r a c i l . Very l i t t l e n o t i c e seems to have been taken of the a c t i o n of organic "bases on a l i p h a t i c h a l i d e s i n p r e p a r a t i o n of d e f i n e s . In an e a r l y a r t i c l e Menschutkin (12) r e p o r t s a study of the a f f i n i t y constant of A l k y l i o d i d e s and "bromides with t r i e t h y l amine. With primary h a l i d e s a quaternary ammonium "base was formed. With h a l i d e s of t e r t i a r y a l c o h o l s however no ammonium "base was formed, as above, but the unsaturated compound i s formed. Semb and McElvain (14) made a study of r a t e and course of the r e a c t i o n between d i f f e r e n t types of organic h a l i d e s and a r e p r e s e n t a t i v e secondary amine, p i p e r i d i n e . They found thsft primary and secondary bromides r e a c t to form t e r t i a r y amines; But t e r t i a r y a l k y l bromides show a decided tendency to lose hydrogen bromide to form unsaturated compounds. They d i d not r e p o r t any y i e l d s obtained i n the l a t t e r case, N o l l e r and Dinsmore (15) i n v e s t i g a t e d r a t e s of r e a c t i o n between organic h a l i d e s and a t e r t i a r y amine, p y r i d i n e . They stated: "the method of removing hydrogen bromide from organic compounds by means of t e r t i a r y amines would not be a p p l i c a b l e to primary h a l i d e s and would be only moderately, succ e s s f u l f o r secondary h a l i d e s , with p o s s i b l e exception of a l i c y l i c compounds such as cyclohexyl bromide. For t e r t i a r y h a l i d e s i t i s q u ite s a t i s f a c t o r y " . Here again no y i e l d s were reported. Other means which have appeared i n tfce l i t e r a t u r e , f o r removal of halogen a c i d , but which are not as important are; h e a t i n g up with sodium carbonate (16,17), h e a t i n g up with 1: (18) and by the use of A l c 3 0 (19). Lime (3) I t would "be opportune at t h i s time to review a few of the other methods,. which have appeared i n , the l i t e r a t u r e , f o r the prepara t i o n of unsaturated hydrocarbons, ( l ) Removal of Water from a l c o h o l s , J. B. Sender ens (20-27) published a s e r i e s of paper on c a t a l y t i c dehydration of a l c o h o l s i n wet and dry ways, C a t a l y t i c dehydration of alco h o l s i n the wet way to give hydrocarbons may be accomplished using s e v e r a l agents, namely, aluminium sulphate, potassium a c i d sulphate, s u l p h u r i c a c i d and;.phosphoric a c i d . This method (20) has advantage of ease and r a p i d i t y as compared w i t h c a t a l y t i c dehydration i n dry way, although y i e l d s are lower and primary products l e s s pure. In the f i r s t of h i s papers on c a t a l y t i c dehydration of a l c o h o l s i n the dry way (21-23) he re p o r t s the use of animal charcoal at 350 C. to act almost q u a n t i t a t i v e l y on c e r t a i n a l c o h o l s such as e t h y l and p r o p y l . He a l s o r e p o r t s the use of phosphorus and phosphates, e s p e c i a l l y aluminium phosphate, and s i l i c a and s i l i c a t e s . H i s next paper (23) deals with c a t a l y t i c power of s i l i c a and alumina. He states that the a c t i o n of these var c a t a l y s t s i s probably due to formation of intermediate hydroxides and hydrides i n which a hydrogen atom i s replaced by an e t h y l or ethoxy group, (2) Removal of a molecule of halogen from a d i h a l i d e , Tneile (28) removed a molecule of halogen from the d i h a l i d e by means of z i n c i n a l c o h o l i c s o l u t i o n . (3) A c t i o n of Monosodium Acetylene. M. P i c o n i n a s e r i e s of papers (29-33) describes the a c t i o n of monosodium acetylene on a l i p h a t i c h a l i d e s . The r e a c t i o n takes ' 1UUS (4) place "between monosodium acetylene and a primary iodide i n l i q u i d ammonia, at - 5 0 C with, formation of acetylenes. However i case of other h a l i d e s there i s no f i x a t i o n of C E H group, but by the e l i m i n a t i o n of halogen a c i d there are formed hydrocarbons of ethylene type. H i s conclusions were as f o l l -ows: I f a side chain does not e x i s t RCH2 CH2 X gives a com-pound by f i x a t i o n of acetylene type. But i f a side chain i s e i t h e r on the halogen carbon atom or on the adjacent carbon atom there i s bbtained an ethylene hydrocarbon by e l i m i n a t i o n of hydrogen i o d i d e . Thus i s o b u t y l i odide gives 95% isobutylene and secondary h e x y l i o d i d e gives 79% hexylene. (4-) Reaction of Sodamide i n presence of l i q u i d ammonia. E. Chablay (34) i n v e s t i g a t e d a c t i o n of sodamide on a l k y l h a l i d e s . A l k y l h a l i d e s were g r a d u a l l y added to suspensions of sodamide i n l i q u i d ammonia. Methyl iodide gave methyl amine, other h a l i d e s gave corresponding d e f i n e s . Ethylene, propylene and butylene were obtained i n e x c e l l e n t y i e l d s . S t a r t i n g from e t h y l y i e l d increases up the s e r i e s and i s always greater using c h l o r i d e than the i o d i d e . In the r e a c t i o n sodamide resembles a l c o h o l i c potash i n i t s behavior. (5) Reaction of sodaammonium (NaEH^) to form ethylene. Chablay (35) r e p o r t s that ethylene d i c h l o r i d e r e a c t s with sodaammonium to give ethylene. S i m i l a r r e s u l t s are reported w i t h the dibromides of propylene, isobutylene or t r i methylene. However i n other cases the saturated p a r a f f i n s are formgd. (Compare the r e s u l t s of tebeau (36) j W h O j u s i n g same reagent always obtains p a r a f f i n hydrocarbons. (5) Our experimental work involved the use of the f o l l o w i n g organic "bases; q u i n o l i n e , a n i l i n e , d i methyl a n i l i n e , d i e t h y l a n i l i n e , .pyridine and p i p e r i d i n e , i n comparison w i t h a l c o h o l i c potash. (6) Experimental Work. In the pre p a r a t i o n of the hydrocarbons where the product was a gas, 5 grams of the h a l i d e were employed. In the cases where the product was a l i q u i d 10-15 grams of h a l i d e were used The f o l l o w i n g h a l i d e s were used; e t h y l bromide, e t h y l i o d i d e , n propyl bromide, sec propyl bromide, n b u t y l c h l o r i d e n b u t y l bromide;, i s o b u t y l c h l o r i d e , i s o b u t y l bromide, sec b u t y l bromide, sec b u t y l i o d i d e , ter b u t y l c h l o r i d e j t e r b u t y l bromide, ter b u t y y l c h l o r i d e , n h e x y l bromide, n h e p t y l bromide 2 brom octane, phenyl e t h y l bromide, cycle h e x y l c h l o r i d e , cyclo h e x y l bromide, 2 brom 1 methyl cyclo hexane, 3 brom 1 methyl cyclo hexane^4 brom 1 methyl c y c l o hexane, menthyl bromide, limonene hydrobromide and brom camphor„ The unsaturated hydrocarbons were prepared from a l c o h o l i c potash using 1 mol of h a l i d e to !•§- mol of potassium hydroxide, P r e l i m i n a r y i n v e s t i g a t i o n showed t h i s to be best. In the pre-p a r a t i o n of cyclohexene from cyclo h e x y l bromide the f o l l o w i n g y i e l d s were obtained; 1 m : 1 m - $$%\ . 1 m : l£ m - 8o. *>% 1 m : 2 m - 8 l . While i n pre p a r a t i o n of phenyl ethylene from phenyl e t h y l bromide, the f o l l o w i n g y i e l d s r e s u l t e d ; -1 m : l i m - 85?£ • 1 m : 2 m - 85^ Thus an excess of potassium hydroxide i s necessary but a large excess does not increase the y i e l d appreciably. The best con-c e n t r a t i o n of a l c o h o l i c potash was found to be, 25 grams of potassium hydroxide to 100 grams of e t h y l a l c o h o l . The mixture was made f r e s h f o r each determination. The absolute a l c o h o l used, was prepared from 95% a l c o h o l by r e f l u x i n g over lime f o r two days. In the preparation of the unsaturated hydrocarbons s the h a l i d e was added drop by drop to the b o i l i n g s o l u t i o n of a l c o h o l i c potash. The mixture was then r e f l u x e d on a water bath, f o r a time which v a r i e d from 1-3 hours, depending on the r a p i d i t y of a c t i o n . In cases where the product was gaseous i t was c o l l -ected over water which had been p r e v i o u s l y saturated with the gas. I f ttore product was a l i q u i d and completely i n s o l u b l e i n water, i t was separated from the a l c o h o l by a d d i t i o n of water, otherwise the mixture was f r a c t i o n a t e d . In the preparation of the hydrocarbons u s i n g organic bases the proportion employed was 1 mol of h a l i d e to 2 mol of organic base. P r e l i m i n a r y i n v e s t i g a t i o n showed the above r a t i o to be most advantageous. In preparation of c y c l o hexene from cyclo h e x y l bromide the f o l l o w i n g y i e l d s were obtained; p y r i d i n e 1 m : 1 m - 20% 1 m : 2 m - 4-6% d i e t h y l a n i l i n e 1 m : 1 m - 4-1% 1 m : 2 m - 75% d i methyl a n i l i n e 1 m ; 1 m - 67% 1 m : 2 m - 70% A f u r t h e r increase i n the .quantity of base used d i d not i n -crease the y i e l d . The organic bases were always r e d i s t i l l e d be-f o r e u s i n g . The h a l i d e here again was added gradually to the b o i l i n g organic base and the mixture r e f l u x e d . A f t e r the ac-t i o n was complete the mixture was f r a c t i o n a t e d i f a l i q u i d or (8) c o l l e c t e d o v e r w a t e r i f a g a s . (9) Methods of A n a l y s i s . ( 1 ) I f product i s a l i q u i d . This i s the method of t i t r a t i n g a double bond with bromiQe i n carbon t e t r a c h l o r i d e , At the same time as a n a l y z i n g the un-known, analyze a known amount of the pure product and compare r e s u l t s . A A-f? s o l u t i o n of bromide i n carbon t e t r a c h l o r i d e was used. In a n a l y z i n g the product the f o l l o w i n g procedure was f o l l o w e d ; One cubic centimeter of the unknown was d i l u t e d to ten cubic centimeters w i t h carbon t e t r a c h l o r i d e . Two ccs. of t h i s stock s o l u t i o n were taken and d i l u t e d w i t h f i v e ccs. of carbon t e t r a c h l o r i d e . A s i m i l a r amount of the pure product was used. Bromine was added simultaneously to both, 1/20 cc. at a time. The end p o i n t was reached when the orange color p e r s i s t e d f or 30 seconds. (2) I f product i s a gas. A sample of the gas was analyzed f o r unsaturated hydro-carbon by passing i n t o a Hempel p i p e t t e , which contained a saturated s o l u t i o n of bromine water. (10) © c -H •ti • •H o O O O r n ^ c O O! \ f \ t s -<0 P i •rH ft •H •H rH ^  rH [>- I>-£ r rH 5>» © -t-» -H •rH r—J G O - O N CM O -10 ® •rt 'S '"'CO ON ON © c •H rH O O O f O O O c O O N ' t l A a l ' d - O O N ' ^ O * <H rH CO t>- CM © a -H r-i ' O - O O ^ " * 0 * A l t \ W A O J - U v l A n M D nl ftl n •3 • G ? O -H rH O O 5 ^ ^ V r x r o ^ o C^tH IfAcM ^ ^ l r \ 0 OJ CM i r v H r i c o rH ^ c o o N ^ i s ^ H S a j a ) i H <5 <r> <i> TJ © <D 13 "H © • H O © TJ Q) -H Q> d) <D g •H O -H M -H g - H O -H - H T j -H ® O S M J H - ' H O « O t J H fi*Ci-Hrt £ pn 3) fl> O f q o g H o ^ o ^ o o g o i d •CS 0> h r H O ^ ^ p q M O h r - l O f - i + ' . H pq ;, O ^" rH S-rH WOW- , rH rH rH rH   &o pA - P : - P 3 3 pq pq pq 2 pq K ft H rH rH r-i U 3 pq Pq PQ <L> V P4 >> >> >> ft -rpq pq , . . . -WW c j^jxl S M ; S & K H CQ C Q - E H - E H EH j2}-^i CM K ( 1 1 ) © •H U © P i •H ft O CM tS-O CO CM © E •H •H M ft O c o rH >» v ,E E +> -rt CD r-f •ri • H E !>> E CO -H S rH •H -H E lCN t S O IN-CM CO tS- CM (S- m co CM ON ON O N CO c •H iH •H E UN CO ts-vO CO r-J ON C O co CD E •ri rH a c o CO o (S-rH CO 'ts- r n O N o 3 a? o £D -ri >CS rH rH O •H O O rH CO o ON IS- CO IS- CO ON ON a) CD c c © c8 c8 K K "a •H CD CO •ri a rH O H-| <-i-i o rH rH ft 6 CD o rH O o rH M © o rH O >* o © rH S o CM © • ^ s o J-I r n © c X © .'W rH © o pq © •cs -H" a o ft .E E © © o u m o © E © E O a •H •o a o ft (12) Table 3 c o h o l i c Potash and Quinoline on A l i p h a t i c Bromid A l c o h o l i c KOH Quino.line E t h y l Br omide 4 10 N. P r o p y l Bromide 15 45 N. B u t y l Bromide 10 55 Iso. B u t y l Bromide 6l 62 N. Hexyl Bromide 10 36 N. H e p t y l Bromide 12 42 Sec. P r o p y l Bromide 83 84 Sec. B u t y l Bromide 85 76 Ter. B u t y l Br omide 74 85 2 Brom Octane 82 74 (13) D i s c u s s i o n of R e s u l t s . A l c o h o l i c potash i s widely recommended by most text books and l a b o r a t o r y manuals f o r the removal of halogen a c i d from h a l i d e s . The r e a c t i o n i s as f o l l o w s : KOH -+- C^ H Br > C-^H g + K Br + HgO However, at the same time, a side r e a c t i o n takes place wi th formation of an ether, C2H^0K + Cy^Br ^ C - ^ O C ^ + K Br Sometimes t h i s side r e a c t i o n a t t a i n s such proportions that i t i s i n r e a l i t y the main r e a c t i o n . In the case of normal h e p t y l bromide, a 12% y i e l d of normal heptene i s obtained and a 70^ y i e l d of n h e p t y l e t h y l ether. Where the h a l i d e i s a s t r a i g h t chasm compound, the main r e a c t i o n i s formation of an ether. I f a side chain e x i s t s the unsaturated compound pre-dominates. Normal b u t y l bromide y i e l d s 10% butylene while, i s o b u t y l bromide gives a 6l% y i e l d of butylene. In the case of secondary and t e r t i a r y h a l i d e s almost g u a n t i t a t i v e y i e l d s of unsaturated hydrocarbons are obtained. Thus, t h i s method of preparing d e f i n e s from a l k y l h a l i d e s with a l c o h o l i c potash i s i n a p p l i c a b l e i n case of the s t r a i g h t chain hydrocarbons, but ex-c e l l e n t when a side chain e x i s t s . With c y c l i c compounds there i s very l i t t l e tendency to form ethers. Here the c y c l i c compounds behave as secondary h a l i d e s and e x c e l l e n t y i e l d s of unsaturated compounds are ob-tained , In the preparation of the alkylene compounds from organic bases, the primary r e a c t i o n i s the formation of an a d d i t i o n (14) product. P 0 r example, t e r t i a r y b u t y l bromide and p y r i d i n e y i e p r i m a r i l y a quaternary Ammonium base. + ( C H 3 ) CEr-(CH.) C-N-Br 5 3 i s being unstable breaks down when heated. (CHo) C-N-Br • 3 -f (CR%) C - CH H-H-Br \ That such compounds as these quaternary ammonium bases do e x i s t j has been shown by many i n v e s t i g a t o r s . Recently Semb and McElvain (14) studied the r a t e s of r e a c t i o n of organic h a l i d e s and piper i d ine. They found that primary and secondary bromides r e a c t to form quaternary ammonium bases, while the t e r t i a r y bromides showed a decided tendency to lose hydrogen bromide with formation of unsaturated compounds. N o l l e r and Dinsmore (15) u s i n g p y r i d i n e as the base reported s i m i l a r r e -s u l t s . Tnus the f a c t , that quaternary ammonium bases are p r i -m a r i l y formed., i s e s t a b l i s h e d . Therefore i t depends on the s t a b i l i t y of these compounds whether an unsaturated product i s obtained. Accordingly, owing to s t e r i c hindrance, an open chain h a l i d e with the base would be most s t a b l e . The more side chains and the longer the chains the l e s s s t a b l e the compound would be. Thus f o r normal h a l i d e s and lower secondary h a l i d e s the y i e l d of unsaturated compound should be poor. . The higher secondary and t e r t i a r y h a l i d e s should give e x c e l l e n t y i e l d s . d 5 ) The c y c l i c compounds, "being secondary h a l i d e s , should a l s o give good y i e l d s . As can he seen from t a b l e s 1 & 2 these con-c l u s i o n s are c o r r e c t , except i n the case of q u i n o l i n e . Quinoline gives good y i e l d s w i t h almost a l l h a l i d e s , even with the primary h a l i d e s . P r o p y l bromide gives a y i e l d and b u t y l bromide a 55^ y i e l d . Other examples can be seen by con-s u l t i n g t a b l e 3• The p o s s i b l e explanation f o r t h i s i s , that a quaternary ammonium base w i t h q u i n o l i n e i s l e s s stable than with the other organic bases. This probably i s due to the f a c t that q u i n o l i n e has an e x t r a benzene r i n g i n i t s s t r u c t u r e . Thus, owing to s t e r i c hindrance, a compound such as N-Br ^-CHgCIIgCH^ i s l e s s s t a b l e than the f o l l o w i n g one, H-BT 0-CH2CH2CH3. Quinoline i s thus recommended f or the preparation of the d e f i n e s from primary h a l i d e s . As a study of ta b l e s 1 & 2 w i l l i l l u s t r a t e , bromides and iodides give much better y i e l d s than c h l o r i d e s . In f a c t the chlor ides are almost useless i n preparing unsaturated com-pounds. While i o d i d e s and broraides give e q u a l l y good y i e l d s , the bromides are recommended. The iodides are d i f f i c u l t to obtain i n the pure state and q u i c k l y decompose. As we have stated q u i n o l i n e i s bes£ f o r preparation of d e f i n e s from normal h a l i d e s and lower secondary h a l i d e s . In other cases a l c o h o l i c potash i s equally good, as are the other organic bases. Where the product was gaseous the y i e l d s i n a l l cases were pure. If the product was a l i q u i d i t was (16) easier to obtain i t i n the pure s t a t e when a l c o h o l i c potash was used. ( 1 ? ) SUMMARY •1. Unsaturated hydrocarbons of 25 h a l i d e s have been prepared by the use of the f o l l o w i n g : a l c o h o l i c potash, q u i n o l i n e , a n i l i n e , d i methyl a n i l i n e , d i elfchyl a n i l i n e , p y r i d i n e and p i p e r i d i n e . 2. A q u a n t i t a t i v e comparison of the above methods i s presented. 3. A l c o h o l i c potash gives poor y i e l d s with the normal h a l i d e s owing to formation of ethers. 4. Q,uinoline i s recommended f o r p r e p a r a t i o n of unsaturated hydrocarbons from normal h a l i d e s . 5. A l c o h o l i c potash and a l l the organic bases give e x c e l l e n t y i e l d s from higher secondary, t e r t i a r y and c y c l i c h a l i d e s . 6. Bromides and iodides g i * e b e t t e r y i e l d s than c h l o r i d e s . (13) References 1. Wildermann and Aisinmann, Z e i t . f u r Fny. Chem. , 8, 66l, (l89ir-2. Br u s s o f f , i b i d 34, 129, (1900) 3. W. H. Perki n s Jun., Chem. Soc. T. , 85, 654, (1904) 4. W. H. P e r l i n s Jun. and S. S. P i c k l e s , i b i d 545, (1905) 5. W. H. Perkins Jun. and T u t t e r s a l , i b i d 1091, (1905) 6. W. H. Pe r k i n s Jun. and Tutter s a l , i b i d 49 0, (I907) 7 K. P i s h e r and W. H. Perki n s Jun. i b i d 1877, (1908) 8. W. H. Pe r k i n s Jun. and 0. Wallach, i b i d 1443, (1910) 9. Haworth, Perkins and Wallach, i b i d 124, (1911) 10. F i s c h e r and Roeder, Ber. , 34, 3751, (1901) 11. Wallach, Ann. Chim. Phy., 23©, 233, (1885) 12. Menschutkin, Z e i t . f u r Phy. Chem. , 5, 589 (1890) 13. Long, J . Chem. Soc. , 99, 2164, (1911) 14. Semb and McElvain, J . A. C. S., 53, 690, (1931) 15. H o l l e r and Dinsmore, i b i d 54, 1025, (1932) 16. W. H. Perkins Jun. , Chem. Soc. T. , 85, (190^ 17. W. H. Pe r k i n s Jun. , and J . P. Thorpe, i b i d 85, 128, 142 (190 6) 18. J . Klimont, Ch. Z e i t . , 4 6, 521, (1922) 19. Mouneyrat, B u l l . Soc. Chim., (3), 19, 182. 20. J . B. Senderens, Ann. Chim., 18, 117,(1922) 21. J. B. Sender ens, Cbmpt.iRendljC144, 381. 2§. J. B. Senderens, i b i d 144, 1109• 23. J. B. Senderens, i b i d 14 6, 125. 24. J , B. Senderens, i b i d 14 6, 1211. ( 1 9 ) 2 5 . J . B. Sender ens, B u l l . Soc. Chira. , ( 4 ) , 1 , 637 • 2 6 . J . B. Sender e n s , Ann . Chim. Play. , 2 5 , 44Q. 2 7 . J . B. Sender ens, B u l l . Soc. Chim., (4) 3 , 6 3 3 2 8 . T h i e l e , L i e b i g Ann., 3 0 8 , 3 3 9 , ( 1 8 9 9 ) 2 9 . Legeau and P i c o n , Compt. Bend. 1 5 6 , 1 0 7 7 -3 0 . M. Picon, i b i d 1 5 8 , 1 1 8 4 . 3 1 . M. Picon, i b i d 1 6 8 , 8 2 5 , ( 1 9 1 9 ) 3 2 . M. Picon, i b i d 1 6 8 , 8 9 4 , ( 1 9 1 9 ) 3 3 - M. Picon, i b i d 1 6 9 , 3 2 , ( 1 9 1 9 ) 3 4 . E. Chablay, i b i d 1 5 6 , 3 2 7 . 3 5 . E. Chablay, i b i d 142, 9 3 , ( 1 9 0 6 ) 3 6 . P a u l Lebeau, i b i d 140, 1042, ( 1 9 0 5 ) The author takes t h i s opportunity to express h i s sin c e r e indebtedness to Dr. R. H. Clark f o r h i s encouragement and co-operation without which th research would not have been p o s s i b l e . 

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