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The preparation of some new floatation reagents Darrach, Marvin Don 1936

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THE PREPARATION OF SOME NEW FLOATATION REAGENTS by M a r v i n D a r r a c h A t h e s i s s u b m i t t e d i n c o n f o r m i t y w i t h t h e requirements f o r the degree o f Master o f A r t s U n i v e r s i t y o f B r i t i s h Columbia 1936 TABLE OF COMEEHTS. I , I n t r o d u c t i o n , I I . F a t t y a c i d mono-esters of G l y c o l and - &ihydroxy e t h y l - e t h e r . „ ,..«.,.?, 1. - h y d r o x y - e t h y l - s t e a r a t e , . . . . . .v. E 0 - hydro xy -e thy 1 - l a u r at e , 3, -hydroxy- - l a u r y l o x y - e t h y l - e t h e r 4 , L a u r y l o x y - e t h y l e n e hydrogen s u l p h a t e . , . . . . . . . . . . . . 5 . - l a t t r y l o x y - e t h y l - e t h e r . -dihydrogen phosphate,..,, 5, S t e a r y l o x y - e t h y l e n e - dihydrogen phosphate . 6. I I I , G l y c o l l i c a c i d d e r i v a t i v e s , P a l r a i t y l g l y c o l l i c a c i d . . 6. S t e a r y l g l y c o l l i c a c i d 8, O l e y l g l y c o l l i c a c i d . . . 8. IV. M o n o - c h l o r o - a e e t i c a c i d d e r i v a t i v e s . Hexyl-raono-chloro-aeetate ...... 9. E y r i s t y l - r n o n o - c h l o r o - a c e t a t e 9 . C e t y l mono-chloro-acetate , . 10 . Y, P y r i d i n e and Q u i n o l i n e d e r i v a t i v e s . (Carbohexoxy) methyl p y r i d i n i u r o c h l o r i d e , », „. 10. (Carbomyristoxy)' methyl p v r i & i n i u m c h l o r i d e . . . . . . . 11. (Carbocetoxy) methyl p y r i d i n i u m c h l o r i d e « 11. (Carbomyristoxy) methyl q u i n o l d i n i u m c h l o r i d e , , . . , I S . (Carbocetoxy) methyl q u i n o l d i n i n m c h l o r i d e . . . . . . . . I S . V I . C o n c l u s i o n , , , , . . . 13. INTRODUCTION. Every f l o a t a t i o n process must have a f r o t h , and every f r o t h i s the r e s u l t of the a c t i o n of some ch e m i c a l r e a g e n t . Whether the bubbles are l a r g e or s m a l l , e l a s t i c or b r i t t l e , t h i c k or t h i n , depends upon the nat u r e of the compound em-p l o y e d to produce them. I n r e c e n t years many new c o l l e c t i n g r e a g e nts have been i n t r o d u c e d to the mining i n d u s t r y , but few attempts have been made to improve upon the chemicals p r o d u c i n g the f r o t h . I n view of the f a c t t h a t we b e l i e v e the c h a r a c t e r of the f r o t h i s one of the most important f a c t o r s i n any f l o a t a t i o n p r o c e s s , we have s e t o u r s e l v e s the t a s k of p r e p a r i n g s e v e r a l new f r o t h i n g r e a g e n t s . The chem-i c a l n a t u r e of these compounds c o n f i r m on the whole w i t h the requirements of a f r o t h i n g reagent as suggested by Taggart, T a y l o r and Ince. (1) They are composed of hydrocarbon c h a i n s of v a r i o u s l e n g t h s j o i n e d through an oxygen atom to some w a t e r - a v i d group. The l e n g t h of the c h a i n , the nature of the water s o l u b l e group, and the manner i n which i t i s connected to the hydrocarbon c h a i n are a l l f a c t o r s which determine the f r o t h i n g a b i l i t y of the compound. The p r e p a r a t i o n and prop-e r t i e s of s e v e r a l nev. c h e m i c a l compounds are g i v e n below; each of these i s to be t e s t e d r e g a r d i n g i t s f r o t h i n g char-a c t e r i s t i c s , and a b i l i t y to e f f e c t f r a c t i o n a l s e p a r a t i o n s of m i n e r a l s from t h e i r o r e s . F a t t y a c i d mono-esters of G l y c o l and /3-^s'-dihydroxy; e t h y l - e t h e r . A g r e a t d e a l of d i f f i c u l t y was encountered d u r i n g the p r e p a r a t i o n of these mono-esters. V a r i o u s methods were attemp-t e d , but n e a r l y always the product c o n t a i n e d the d i - e s t e r i n l a r g e e x c e s s . S t e a r i c a c i d , f o r example, was heated w i t h t w e n t y - f i v e times the e q u i v a l e n t weight of g l y c o l , and only about bfo mono-glyeeride was o b t a i n e d . T h i s i s very l i k e l y due to the f a c t t h a t the mono-glyeeride which i s f i r s t formed, passes i n t o the f a t t y a c i d phase and then produces the d i -e s t e r . I t was observed, however, t h a t at temperatures about 120°C, the f a t t y a c i d and g l y c o l appear t o be i n s i n g l e phase. S i m i l a r r e s u l t s were o b t a i n e d when the a c i d c h l o r i d e s were used; i n t h i s case, however, a s i n g l e phase c o u l d not be ob-t a i n e d u n t i l a l l the c h l o r i d e had r e a c t e d , at which p o i n t the product c o n s i s t e d almost e n t i r e l y of the d i - e s t e r . A pure p r o d u c t , but i n ve r y poor y i e l d s , was o b t a i n e d by h e a t i n g the sodium s a l t of the a c i d w i t h the mono c h l o r i d e of the a l c o h o l , i n an atmosphere of carbon d i o x i d e f o r twenty-f o u r hours at 210°C. i n a s e a l e d tube. The product was e x t r a c -t e d w i t h e t h e r , and a f t e r washing and d r y i n g , was c r y s t a l l i s e d by c o o l i n g the e t h e r e x t r a c t to 0°G. H i l d i t c h and Rigg (2) suggest the use of phenol as a s o l -vent f o r such r e a c t i o n s , A few experiments were made f o l l o w -i n g t h e i r method w i t h s u l p h o n i c a c i d c a t a l y s t s . S a t i s -f a c t o r y r e s u l t s viere not o b t a i n e d , c o n s i d e r a b l e amounts of the d i - e s t e r s t i l l b e i n g formed. The t e d i o u s r e c r y s t a l l i s -at ion's necessary t o separate the d e s i r e d p r o d u c t , j u s t i f i e d a s e a r c h f o r a "better method. A f t e r t r y i n g , s e v e r a l i n e r t s o l -vents , i t was found that, nitro-methane (CH 3E0 2) d i s s o l v e d both g l y c e r o l , / S - ^ - d i h y d r o x y - e t h y l - e t h e r , as w e l l as the c h l o r i d e s of the f a t t y a c i d s , A s u c c e s s f u l method was then worked out f o r an almost q u a n t i t a t i v e y i e l d of the mono-esters. The pro-cedure i n g e n e r a l was as f o l l o w s ; The nitro-methane wss d r i e d f o r t w e n t y - f o u r hours over an-hydrous c a l c i u m c h l o r i d e , r a p i d l y f i l t e r e d , and d i s t i l l e d . The d i b a s i c a l c o h o l " w a s : t w i c e - d i s t i l l e d , .and the c h l o r i d e p u r i f i e d by vacuum d i s t i l l a t i o n . The c h l o r i d e was d i s s o l v e d i n an equal volume of nitro-methane ond added, drop- by drop, to about t e n times the e q u i v a l e n t of d i - b a s i c a l c o h o l , d i s s o l v e d i n an equal volume of n i t r o methane. The r e a c t i o n m i x t u r e was v i g o r o u s l y s t i r r e d and kept a t a temperature of 105°C. The s t i r r i n g and h e a t i n g was c o n t i n u e d u n t i l no more fumes of HC1 were e v o l v e d , The product was.cooled, taken up i n e t h e r , and washed s e v e r a l times w i t h water, then w i t h d i l u t e sodium carbonate s o l u t i o n , and a g a i n w i t h s a t e r , I f most of the nitro-methane has been removed, by the washings, the mono-ester w i l l c r y s t a l l i s e from the e t h e r c o o l i n g to 0°C, I t may be n e c e s s a r y , however, to evaporate the e t h e r , and remove any r e m a i n i n g nitro-methane under vacuum; i n such a case, the product, was taken up i n ether a g a i n and r e c r y s t a l l i s e d , i f p o s s i b l e , at 0°C. /3 - h y dr o xy - e t hy 1 - s t e a r a t e . 20 grams of s t e a r y l c h l o r i d e were d i s s o l v e d i n 20 c«c. of dry warn nitro-methane; as d e s c r i b e d i n the g e n e r a l proc-edure mentioned above, t h i s was s l o w l y added to 50 grains o f g l y c o l d i s s o l v e d i n 50 c.c« of hot nitro-menthane, A f t e r the e b u l l i t i o n of HOI had ceased, the mi x t u r e was cooled and takien up i n e t h e r , the excess g l y c o l d i d not d i s s o l v e , The e t h e r e a l was s o l u t i o n / w a s h e d s e v e r a l times w i t h water t o remove the g l y c o l , and then w i t h sodium carbonate s o l u t i o n to remove any a c i d and a g a i n w i t h water to remove the sodium carbonate. Much o f the nitro-methane had been removed d u r i n g the washings, but there was s t i l l c o n s i d e r a b l e l e f t w i t h the p r o d u c t . .after d r y i n g the e t h e r e a l s o l u t i o n w i t h c a l c i u m c h l o r i d e , and f i l -t e r i n g , the e t h e r was evaporated away; and the n i t r o methane removed by h e a t i n g the mixture under vacuum^- 80 UC. i n a wat-er b a t h . The product was a g a i n taken up i n e t h e r , and r e -o c r y s t a l l i s e d by c o o l i n g the s o l u t i o n to 0 C. The f i r s t few c r y s t a l s s e p a r a t i n g out melted a t 65°-66°C. and were d i s c a r d e d . The remainder a f t e r a second r e e r y s t a l l i s a t i o n melted at 59°C. H i l d i t c h and Rigg (2) g i v e 56°G, as the m e l t i n g p o i n t of t h i s compound, Y i e l d BOfo. y 3 - h y d r o x y - e t h y l - l a u r a t e , This compound was prepared i n t he same manner as the one above, from 20 grams of l a u r y l c h l o r i d e i n 20 c.c. of n i t r o -methane, and 60 grams of g l y c o l i n 60 c.c, of nitro-methane. 4. The f i r s t c r y s t a l s formed, melted at 29°C-. , hence there i s no i n d i c a t i o n of any d i - e s t e r being formed, (M.P. of d i - e s t e r as g i v e n by B h a t t a c h a r y a and H i l d i t c h (3) i s 49°C.) The product melted at 28°C.-29°0. H i l d i t c h and Rigg (2) g i v e 27.5°C. as the m e l t i n g p o i n t of g l y c o l mono-laurate. Y i e l d 80$. j5 - h y d r o x y -fi -1 a u.r y 1 o x y - e t h y 1 e t h e r C„ HI3 • C - o -(CH,)J O - (c H,\ - O H T h i s compound was prepared i n a s i m i l a r manner to those above. 20' grams of l a u r y l c h l o r i d e were d i s s o l v e d i n 20 c .c. of nitro-methane as b e f o r e , and s l o w l y added to 90 grams of /9-/9-dihydroxy e t h y l ether d i s s o l v e d i n 90 c.c. of warm, n i t r o -methane. The r e a c t i o n m i x t u r e was v i g o r o u s l y s t i r r e d and heated to 105°C. as b e f o r e , A f t e r the washings, i t was noted t h a t n e a r l y a l l the nitro-methane had been removed, a l s o the /S-^-dihydroxy e t h y l e t h e r was more s o l u b l e i n nitro-methane than was the g l y c o l ; t h i s l a t t e r f a c t may "e x p l a i n why n e a r l y a l l the nitro-methane was removed i n t h i s procedure, whereas a c o n s i d e r a b l e amount was l e f t i n the case where g l y c o l was used. The product s e p a r a t e d from c o l d dry e t h e r i n the form of a y e l l o w o i l , t h i s o i l was a g i t a t e d w i t h a c u r r e n t of a i r w h i l e d r y i n g at 80°C. i n the oven. F u r t h e r p u r i f i c a t i o n was not attempted. The compound was a n a l y s e d by s a p o n i f y i n g i t i n standard a l c o h o l i c KOH s o l u t i o n , and t i t r a t i n g the product w i t h s t a n d a r d HC1 s o l u t i o n . Y i e l d 85$. 5 * L a u r y l o x y ~ e t h y l e n e hydrogen s u l p h a t e . _ __ _ _ C„ H23 - C - o- cri.c HL- O - S - OH o F r e s h l y d i s t i l l e d c h l o r s u l p h o n i c a c i d (HClSOg) was used here as the s u l p h a t i n g agent; s i n c e the a c i d a t t a c k s both rubber and cork, s p e c i a l p r e c a u t i o n s must be taken w h i l e con-s t r u c t i n g the d i s t i l l i n g a p p a r a t u s . I t was found t h a t c l o s e -l y packed g l a s s wool p r o v i d e s e x c e l l e n t corks f o r such a d i s -t i l l a t i o n . l b o u t 15 grams of g l y c o l ' m o n o - l a u r a t e were d i s s o l v e d i n 100 c.c. of dry e t h e r , to t h i s m i x t u r e was added, drop by drop, an e t h e r e a l s o l u t i o n of an e q u i v a l e n t of c h l o r s u l p h o n i c a c i d . The r e a c t i o n mixture was kept c o o l (20°G.) and v i g o r -o u s l y s t i r r e d . The a c i d i t s e l f i s an o i l , and i s very d i f f -i c u l t to p u r i f y ; a pure form may be o b t a i n e d , however, by sep-a r a t i n g the compound i n the form of the sodium s a l t . This s a l t may be o b t a i n e d by shaking the e t h e r e a l mixture w i t h an a l c o h o l i c s o l u t i o n of the r e q u i r e d amount of sodium. The s a l t p r e c i p i t a t e d out and was f i l t e r e d o f f and washed w i t h c o l d a l c o h o l . A s m a l l amount of the a c i d o b t a i n e d from the s a l t and a n a l y s e d f o r s u l p h u r gave 10.12$. C a l c u l a t e d 9.88$. The sodium s a l t melts above 130°0. Y i e l d 80/K / 3 - l a u r y l o x y - e t h y l - e t h e r /?-dihydrogen phosphate _ : ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ x O H 15 grams of g l y c o l mono-laurate were d i s s o l v e d i n 150 c c . of dry e t h e r , to t h i s s o l u t i o n about 20 grams of phosphoric 6 a c i d anhydride (PgOg) were added and the mixture was r e f l u x e d g e n t l y f o r 24 hours. At the end of t h i s t i m e , the e t h e r e a l s o l u t i o n was decanted from the excess phosphoric a c i d , and , then the ether was d i s t i l l e d o f f . The compound was p u r i f i e d by s e v e r a l ether e x t r a c t i o n s . F i n a l l y the product was d r i e d a t 80°C, f o r 12 hours. The m a t e r i a l o b t a i n e d d i d not have a d e f i n i t e m e l t i n g p o i n t , bu.t was s o f t at room temperature. An a n a l y s i s f o r phosphorous gave £.20$; c a l c u l a t e d 8.05$, Yield 85 S t e a r y l o x y - e t h y l e n e dihydrogen phosphate. iO ,oH. ' "OH 10 grams of /9-hydroxy-ethyl s t e a r a t e were. d i s s o l v e d i n 150 c.e. of dry e t h e r , 15 grams of pho s p h o r i c a c i d anhydride were added, and the m i x t u r e was re f l u x e d g e n t l y f o r 48 hours. At the end of t h i s time, the m i x t u r e was c o o l e d , and the e t h e r e a l s o l u t i o n decanted from the phosphoric a c i d r e s i d u e . The e t h e r was evaporated away, and the compound p u r i f i e d by. s e v e r a l e t h e r e x t r a c t i o n s . The product thus o b t a i n e d melted a t 65°C., and was s o l u b l e i n most common o r g a n i c s o l v e n t s . A n a l y s i s for- phosphorous gave 7.18$; c a l c u l a t e d 7 .60$. P a l m i t y l g l y c o l l i e a c i d . C,s- H 3^ - C . o C H» C -OH T h i s compound was prepared by a l l o w i n g the sodium s a l t of p a l m i t i c a c i d to r e a c t upon the m o n o - e h l o r o - d e r i v a t i v e of a c e t i c a c i d , sodium c h l o r i d e was s p l i t o f f , and p a l m i t y l g l y -c o l l i c a c i d formed. Seventeen grams of sodium pain: i t ate were i n t i m a t e l y mixed w i t h s i x grams of mono-ehloro-aeetic a c i d , I'he mixture was p l a c e d i n a s m a l l f l a s k , and the a i r i n the f l a s k r e p l a c e d by , carbon d i o x i d e . The m i x t u r e was then heated to 1Q0°--11G°C. f or 5 hours t d u r i n g which time i t was g e n t l y a g i t a t e d by means of a s t i r r e r . At the end of t h i s time,the product was i n a l i q u i d s t a t e , and a w h i t e p r e c i p i t a t e c o n t a i n i n g the sodium c h l o r i d e had separated o u t . '%e product was taken up i n e t h e r and washed s e v e r a l times w i t h water; a f t e r d r y i n g , the e t h e r was evaporated away l e a v i n g a white waxy m a t e r i a l , t h i s was r e c r y s t a l l i s e d from 75$ e t h y l a l c o h o l , l e a f y waxy c r y s t a l s b e i n g o b t a i n e d . These c r y s t a l s a f t e r d r y i n g melted a t 50°G., and were analysed by t i t r a t i n g w i t h s t a n d a r d a l c o h o l i c sodium hydroxide s o l u t i o n . As a check, the product was s a p o n i f i e d w i t h s t a n d a r d base s o l u t i o n , and t i t r a t e d w i t h s t a n d a r d HC1. The s o l i d m a t e r i a l l e f t i n the r e a c t i o n f l a s k was d i s s o l v e d i n w a t e r , and the s o l u t i o n f i l t e r e d , upon e v a p o r a t i o n a quan-t i t a t i v e y i e l d of sodium c h l o r i d e was obtained,'showing t h a t the r e a c t i o n goes almost to c o m p l e t i o n , '^'he p a l m i t y l g l y c o l l i c a c i d i s s o l u b l e i n a l l common o r g a n i c s o l v e n t s . Y i e l d 95$. The sodium s a l t of t h i s a c i d was prepared by s l o w l y adding to a warm a l c o h o l i c s o l u t i o n of the a c i d , a s o l u t i o n of the-quant i t a t i ve amount of sodium necessary f o r n e u t r a l i s a t i o n , d i s s o l v e d i n a l c o h o l , I1 he a l c o h o l was c a r e f u l l y evaporated away, l e a v i n g the s a l t as a r e s i d u e , "Lhe s a l t begins to s o f -t e n at about 100°C. 8, S t e a r y l g l y c o l l i c a c i d . C,7 H 3 S - C - o - c t - L ' C - o H This compound was prepared from sodium s t e a r a t e and mono-c h l o r o - a c e t i c a c i d i n e x a c t l y the same manner as p a l m i t y l g l y c o l l i c a c i d . 30 grams of sodium s t e a r a t e and 10 grams of mono-chloro-a c e t i c a c i d were i n t i m a t e l y mixed and t r e a t e d as above. The pr o d u c t was r e c r y s t a l l i s e d from 80$ e t h y l a l c o h o l , and the dry c r y s t a l s were found t o melt at 63°C. The q u a n t i t a t i v e amount of sodixim c h l o r i d e was o b t a i n e d from the r e s i d u e , showing t h a t the r e a c t i o n had gone almost to c o m p l e t i o n . • The a n a l y s i s was made by h y d r o l y s i s i n stan d a r d a l k a l i , and by t i t r a t i o n as b e f o r e , and was found to s o f t e n around 125°C. O l e y l g l y c o l l i c a c i d . i s above., t h i s compound was prepared from the sodium s a l t of o l e i c a c i d , and m o n o - c h l o r o - a c e t i c a c i d , 20 grams of sodium o l e a t e , and 6,5 grams of m o n o - c h l o r o - a c e t i c a c i d were i n t i m -a t e l y mixed and t r e a t e d as b e f o r e . The product was taken up i n e t h e r , and washed s e v e r a l times, w i t h water, a f t e r d r y i n g and e v a p o r a t i n g away the e t h e r , the product remained as a y e l l o w o i l which was a n a l y s e d by t i t r a t i n g w i t h standard bro-mine s o l u t i o n , and by t i t r a t i o n w i t h standard a l c o h o l i c base, and by s a p o n i f i c a t i o n i n s t a n d a r d base and subsequent t i t r a t i o n w i t h standard a c i d . The Q u a n t i t a t i v e amount of sodium c h l o r i d e was o b t a i n e d from the r e s i d u e i n the r e a c t i o n f l a s k . Y i e l d 9.0jfc; He xy 1 -rao no - ch l o r o - ac e t a t e . C6 ri l 3 - o - c - c H . a . T h i s compound was prepared by s l o w l y adding 50 c.e. of c h l o r o - a c e t y l c h l o r i d e to 50 grams of h e x y l a l c o h o l , A v i g o r -ous e b u l l i t i o n of HC1 ensues, and the r e a c t i o n mixture becomes q u i t e warm. A f t e r the r e a c t i o n was a p p a r e n t l y over, the f l a s k was warmed f o r one hour a t 50°C. , w h i l e i t s c o n t e n t s were v i g -o r o u s l y s t i r r e d . The m ixture was then s u b j e c t e d to d i s t i l l -a t i o n , the m a t e r i a l coming over between. 210° — 220°C. was saved and d i s t i l l e d a g a i n ; n e a r l y a l l t h i s f r a c t i o n b o i l e d at 215°--216°C» The product was a c o l o r l e s s o i l , s o l u b l e i n most com-mon o r g a n i c solvents', An a n a l y s i s f o r c h l o r i n e gave 20,07$; c a l c u l a t e d 19,87$, Y i e l d 85$, My r i s t y1-mo n o - c h i o r o - a c e t a t e . C M H - O - C - C rttQJL To 50 grams of molten m y r i s t y l a l c o h o l , 25 c . c. of c h l o r o -a c e t y l c h l o r i d e were- s l o w l y added* HG1 was evolved i n l a r g e q u a n t i t i e s and the r e a c t i o n mixture became q u i t e warm, As be-f o r e , the s o l u t i o n was s t i r r r e d and heated f o r one hour. The p r o d u c t was p u r i f i e d by vacuum d i s t i l l a t i o n , corning over under a p r e s s u r e of 25 mm, at 215°C» • This product was a c o l o r l e s s o i l which s o l i d i f i e s on long s t a n d i n g , A s m a l l q u a n t i t y r e -c r y s t a l l i s e d from d i l u t e a l c o h o l melts at ZS °C,, and analysed f o r c h l o r i n e g i v i n g 12,49$; c a l c u l a t e d 12,21$, Y i e l d 80$„ 1 0 . C e t y l mono-ehlo r o-ac e t at e. Thi s compound was prepared i n the same manner as m y r i s t y l mono-chloro a c e t a t e , from 50 grams of molten c e t y l a l c o h o l and 25 c.c. of c h l o r o - a c e t y l c h l o r i d e . The product was a c o l o r -l e s s o i l , which s o l i d i f i e d on s t a n d i n g ; i t d i s t i l l e d under a pr e s s u r e of 21 mm, a t 242°C. A sample r e c r y s t a l l i s e d from d i l -ute a l c o h o l melted at 35°G., and ana l y s e d f o r c h l o r i n e g i v i n g •11.80$; c a l c u l a t e d 1 1 . 1 4 $ . T h i s compound was prepared by the a c t i o n of h e x y l rnono-c h l o r o - a c e t a t e on p y r i d i n e a t a temperature of 100°C. Two p a r t s of he x y l . ' c h l o r o - a c e t a t e were mixed w i t h one p a r t of p y r i d i n e i n a s m a l l round-bottomed f l a s k connected w i t h an up-r i g h t a i r condenser, the mix t u r e was heated i n a b o i l i n g water b a t h f o r 2-| hours, a t the end of which time a dark v i s -cous mass had formed. The product was p u r i f i e d by d i s s o l v i n g i t i n as l i t t l e a l c o h o l as p o s s i b l e , and r e p r e c i p i t a t i n g by the a d d i t i o n of e t h e r . A f t e r s e v e r a l washings w i t h e t h e r , the product was obtain e d i n the form Of a y e l l o w o i l . I f t e r d r y -ing a t 80°C. i n a c u r r e n t of a i r , i t analysed f o r c h l o r i n e g i v -(Cai-bohexoxy) methyl p y r l d i n i u m c h l o r i d e , <0 . Cl/==r\ i n g 13.02$; c a l c u l a t e d 13.7 8$. Y i e l d 80$. 11. (Carbomyristoxy) methyl p y r i d i n i u m c h l o r i d e . This compound was prepared i n a s i m i l a r manner as the analogous h e x y l d e r i v a t i v e . Seven p a r t s of m y r i s t y l c h l o r o -a c e t a t e were mixed w i t h two p a r t s of p y r i d i n e , and heated f o r 5 hours i n a b o i l i n g water b a t h under an a i r condenser. Upon c o o l i n g , the v i s c i d mass e r y s t a l i z e s ; t h i s product was p u r i f -i e d by d i s s o l v i n g i t i n as l i t t l e acetone a s ' p o s s i b l e , and r e -p r e c i p i t a t i n g a g a i n by the a d d i t i o n of about o n e - t h i r d the volume of e t h e r . The c r y s t a l s were f i l t e r e d , and, d r i e d by warming f o r 12 hours at 80°C. They melt at 96°C., and gave on a n a l y s i s f o r c h l o r i n e 9,32$; c a l c u l a t e d 9.60$, Y i e l d 85$. Four p a r t s of c e t y l c h l o r o - a c e t a t e were mixed w i t h one p a r t of p y r i d i n e as b e f o r e , and heated under an a i r condenser f o r 5 hours i n a b o i l i n g water b a t h . The p r o d u c t , i n a s o l i d c r y s t a l l i n e form, was p u r i f i e d by d i s s o l v i n g i n acetone, and r e p r e c i p i t a t i n g w i t h e t h e r . A f t e r d r y i n g at 80°C. f o r 12 hours, the product melted at 108°C, and gave on a n a l y s i s f o r c h l o r i n e 8.07$; c a l c u l a t e d 8,92$. Y i e l d 85$. (Carboc etoxy) methyl p y r i d i u m c h l o r i d e . 12, (C-arb omy r i s t oxy) _rne t hy 1 qu ino I d i n ium _chlor ide . CHHk, -O- C c H, - ^ ^ ^ The r e a c t i o n of m y r i s t y l c h l o r o - a c e t a t e w i t h q u i n o l i n e , was not n e a r l y as smooth as w i t h p y r i d i n e , c o n s i d e r a b l e decom-p o s i t i o n took p l a c e j and a f t e r 5 hours h e a t i n g only a 55$ y i e l d was o b t a i n e d , Two p a r t s of m y r i s t y l - c h l o r o - a c e t a t e , and one p a r t of q u i n o l i n e were mixed, and the ssrae procedure f o l l -owed as f o r the p y r i d i n e d e r i v a t i v e . The product was o b t a i n e d i n the form of y e l l o w c r y s t a l s , by p r e c i p i t a t i n g i t from a s a t u r a t e d acetone s o l u t i o n w i t h e t h e r , The c r y s t a l s so ob~-t p i n e d were s o l u b l e i n Benzene, E t h y l A l c o h o l , C h l o r o f o r m , and Acetone, The compounds began to s o f t e n at 85°C. and a t 90°C. i t was l i q u i d , A n a l y s i s f o r c h l o r i n e gave $ ,K?fo; c a l c u l a t e d 8.4-5$. (Carbocetoxy) methyl q u i n o l d i n i u m chloride,, C ,6 H 3 3 - ° - C - C H , - iv This compound was prepared from 2,5 p a r t s of c e t y l c h l o r o -a c e t a t e and one p a r t of q u i n o l i n e , i n e x a c t l y the same manner as the analogous, m y r i s t y l compound. The product was obtai n e d i n the form of y e l l o w c r y s t a l s by p r e c i p i t a t i n g i t w i t h ether from a s a t u r a t e d acetone s o l u t i o n . These c r y s t a l s were s o l -uble i n C h l o r o f o r m , Acetone, E t h y l a l c o h o l and Benzene. They d i d not have-a d e f i n i t e m e l t i n g p o i n t , but began to s o f t e n about 90°.C. and were l i q u i d at 95°G. A n a l y s i s f o r c h l o r i n e gave 7 .18%; c a l c u l a t e d 7.92$. CONCLUSION. In c o n c l u s i o n , a few words should be w r i t t e n r e g a r d i n g the p r a c t i c a l a p p l i c a t i o n of these.compounds as f r o t h i n g r e a g e n t s . At the time of w r i t i n g these l i n e s , p r a c t i c a l t e s t s are bei n g mode on ore from-the B. C. N i c k e l Mine; a t a f u t u r e date the r e s u l t s o b t a i n e d may be made known, i t the p r e s e n t time, how-eve r , i t i s s u f f i c i e n t t o say that these compounds are a l l e x c e l l e n t f r o t h e r s , the v a r i o u s reagents y i e l d i n g d i f f e r e n t types of f r o t h s which are q u i t e p e r s i s t e n t over a wide range of pH v a l u e s , I f not a l r e a d y i n l i q u i d form, the compounds must be d i s s o l v e d i n a very s m a l l amount of s o l v e n t f o r p r a c -t i c a l use. The p y r i d i n e and q u i n o l i n e d e r i v a t i v e s , f o r ex-ample, d i s s o l v e d i n very l i t t l e acetone, i f a few drops of a l c o h o l were added. The phosphate d e r i v a t i v e s d i s s o l v e d q u i t e w e l l i n s m a l l amounts of c h l o r o f o r m . Whether the work r e p o r t e d here w i l l prove of b e n e f i t to the mining i n d u s t r y or not, only time and e x p e r i m e n t a l r e s u l t s can t e l l . I t i s hoped, however, t h a t t h i s ' s m a l l c o n t r i b u t i o n w i l l a i d the e f f o r t s of those s e e k i n g a more fundamental and s c i e n -t i f i c under s t a n d i n g of the f l o a t a t i o n p r o c e s s . 

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