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p r o d u c t i o n o f t e r p i n h y d r a t e , and i n p a r t i c u l a r ,t o improvements i n the p r o c e s s o f producingt e r p i n hydrate by the r e a c t i o n o f pinene withd i l u t e aqueous a c i d .

Terpin hydrate i s commonly produced by r ea c t i n g p i n e n e w i t h d i l u t e a c i d , u s u a l l y 25s u l f u r i c a c i d , a t temperatures o f about 3 0 t o 4 0 °C . 1 0 t o 15 o f toluene s u l f o n i c a c i d i s used t opromote t h e r a t e o f r e a c t i o n . The r e a c t i o n w h i c h ,a s c o m m o n l y c a r r i e d out r e q u i r e s s u b s t a n t i a lt i m e , f o r example, 3 0 t o 4 0 h o u r s , i s accompaniedby s i d e r e a c t i o n s r e s u l t i n g i n the formation o fdipentene and o t h e r products which d e c r e a s e t h ey i e l d .

In accordance with t h e p r e s e n t i n v e n t i o n , t h er e a c t i o n i s c a r r i e d out i n the presence o f g r e a t l yreduced q u a n t i t i e s o f t o l u e n e s u l f o n i c a c i d andadvantageously i n t h e p r e s e n c eo f r e l a t i v e l y s m a l lamoun t s o f mahogany c i d s . The use o f reducedq u a n t i t i e s o f t o l u e n e s u l f o n i c a c i d , i . e . , about2 t o 5 based on the t o t a l aqueous material g i v e sb e t t e r y i e l d s than have h e r e t o f o r e been o b t a i na b l e . The use o f a r e l a t i v e l y small proportion o fmahogany a c i d s g r e a t l y i n c r e a s e s t h e s p e e d o fthe r e a c t i o n , such that the r e a c t i o n i s a s completei n about 1 5 hours as i t i s i n 30 t o 40 hours, anda l s o r e s u l t s i n an increased y i e l d through thepromotion o f the r a t e and e f f i c i e n c y o f t h e mainr e a c t i o n Without corresponding promotion o f t h er a t e o f s i d e r e a c t i o n s . While the use o f mahogany a c i d s with the reduced proportions o f t o l u e n es u l f o n i c a c i d i s o f p a r t i c u l a r advantage, i t s usei s o f advantage where l a r g e r qu a n t i t i e s o f t h etoluene s u l f o n i c a c i d are u s e d , a s i n previousp r a c t i c e , or even where no toluene sulfonic acidi s u s e d , e . g . ,where s u l f u r i c a c i d alone i s u s e d .

The mahogany c i d s may be used a s a c i d s , ori n the fo rm o f the mahogany soaps which arethe common f o r m in which mahogany acids arehandled. I t w i l l be noted that the r e a c t i o n m i xt u r e i s a c i d , and i n view o f t h e f a c t t h a t r e l a t i v e l ys m a l l q u a n t i t i e s o f the mahogany a c i d s a r e u s e d ,i t i s p r o b a b l e t h a t the product i s p r e s e n t i n a c i df o r m whether added as s u c h or i n the f o r m o fa soap or other c o m p o u n d .

The mahogany acids which are u s e d are prod u c e d , u s u a l l y a s b y - p r o d u c t s , by t h e t r e a t m e n to f petroleum o i l swith s t r o n g s u l f u r i c a c i d . T h e ya r e the o i l - s o l u b l e p r o d u c t s , a s d i s t i n g u i s h e df rom green a c i d s , which are water-soluble produ c t s produced i n such t r e a t m e n t . T h e greena c i d s a r e not e f f e c t i v e in promoting the reactiono f p i n e n e t o t e r p i n h y d r a t e .

The high r e a c t i o n r a t e s and high y i e l d s o b

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2t a i n a b l e through the use o f reduced q u a n t i t i e sof toluene s u l f o n i c acid and the u s e o f a smalla m o u n t o f m a h o g a n y a c i d s i n the reaction areshown i n the f o l l o w i n g t a b l e , which g i v e s ther e s u l t s o f s e v e r a l runs f o r the production o ft e r p i n h y d r a t e from p i n e n e . The p r o d u c t t r e a t e dwas steam d i s t i l l e d t u r p e n t i n e , which i s 8 0 t o90 p i n e n e . Y i e l d s are based on the turpentineused. In the ?rst run, s u l f u r i c acid alone w asu s e d . I t w i l l be noted that a t the end o f 1 5 hourso n l y 8 .7 o f t e r p i n hydrate had been producedand i n 3 0 hours only 33 . When 2 5 p a r t s o fthe s u l f u r i c a c i d were replaced by 2 5 p a r t s o f2 5 t o l u e n e s u l f o n i c a c i d , the y i e l d i n 1 5 hourswas 3 4 and i n 3 0 hours 59.2 . When, i n addit i o n , 2 o f m a h o g a n y soap was included i n ther e a c t i o n m i x t u r e , the y i e l d i n 1 5 hours was 45.3a n d i n 30 hours 67.4 . Similar r e s u l t s wereobtained using s u l f u r i c a c i d and other lowproportions o f toluene s u l f u r i c a c i d , a s shown i nthe t a b l e . Q u a n t i t i e s shown a r e p a r t s by w e i g h t .

urpentine _ _ _ _ _ _ _ 150 150 150 150 150 150 15025 s u l f u r i c a c i d _ _ _ _ 5 0 0 4 7 5 4 7 6 4 6 0 4 6 0 4 4 0 4 4 025 t o l u e n es u l f o n i c

a c id _ _ _ _ _ _ _ _ _ _ _ _ ._ 25 25 4o 40 6 0 6 0Mahoganysoap____ ___ ___ 2 0 4 0 4Temperature, °0___ 3 5 - 3 8 34 e 3 7 3 4 - 3 7 3 4 - 3 7 3 4 - 3 7 3 4 — 3 7 3 4 - 3 71 5 h r . y i e l d

percent__ 8 . 7 3 4 . 0 4 5 . 3 4 9 . 0 5 7 . 4 1 7 . 0 6 4 . 3iggny ie lgmdauu 3 3 . 0 5 9 . 2 6 7 . 4 6 8 . 7 7 5 . 4 4 7 . 0 7 3 . 3

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p e r c e n t _ _ _ _ _ 2 6 . 4 5 7 . 7 6 7 . 3 6 2 . 2 7 6 . 2 3 6 . 2 8 7 . 6

T h e a m o u n t o f m a h o g a n y soap which i s usedi n carrying out the process may be varied overa r e l a t i v e l y wide range f rom a fraction o f 1 ,based on the quantity o f pinene treated t o a smuch as 10 or even more . There s e e m s t o bel i t t l e advantage i n u s i n g more than about 5 .but increased q u a n t i t i e s do not seem t o i n t e r f e r ewith the production o f t h e d e s i r e d p r o d u c t .

I c l a i m :1 . In t h e p r o d u c t i o n o f t e r p i n hydrate by t h e

treatment o f p i n e n e w i t hd i l u t e a c i d a t temperat u r e s o f about 3 0 ° t o 4 0 ° C . , t h e s t e p o f i n c l u d i n gi n the reaction mixture a small quanti ty o fmahogany acids as a reaction promoter.

2 . In t h e p r o d u c t i o n o f t e r p i n h y d r a t e by t h etreatment o f pinene with s u l f u r i c a c i d andt o l u e n e s u l f o n i c a c i d a t temperatures o f about3 0 ° t o 4 0 ° C . , the s t e p o f i n c l u d i n g i n the r e a c t i o nmixture a small quanti ty o f mahogany a c i d s a sa r e a c t i o n promoter.

3 . In t h e p r o d u c t i o n o f t e r p i n h y d r a t e by t h etreatment o f pinene with d i l u t e a c i d a t temperat u r e s o f about 3 0 ° t o 4 0 ° C . , t h e s t e p o f i n c l u d i n gi n the r e a c t i o n mixture 2 t o 5 o f t o l u e n e s u l »

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f o n i c a c i d a s a . r e a c t i o n promoter, based on thet o t a l aqueous m a t e r i a l .

4 . In t h e p r o d u c t i o n o f t e r p i n hydrate by t h etreatment o f pinene with s u l f u r i c a c i d andt o l u e n e s u l f o n i c a c i d a t temperatures o f about3 0 °t o 4 0 f }C r ,t h e s t e p o f i n c l u d i n j g y i nt h e r e a c t i o nm i x t u r é7 2 t o o f i t ‘ o l i i e n es i i l f o n i e a c i i i‘ b a s e don the o t a l aqueous m a t e r i a l .

5 . In t h e p r o d u c t i o n o f t e r p i n hydrate by t h et r e a t m e n t o f p i n e n e w i t h d i l u t e s u l f u r i c a c i d a tt e m p e r a t u r e s o f a b o u t 3 0 ° t o ‘ i ? h { 3 . 3t h e ’ s t e p o f ’i n c l u d i n g i n the r e a c t i o n mixture a q u a n t i t y o fmahogany a c i d s u p t o about 5 o f theamounto f p i n e n e and from 2 t o 5 o f t o l u e n e s u i t o r - l i ea c i d based on the t o t a l a q u e o u s T r Y n ‘ a t e ‘ r - i a l . ~

6 . The p r o c e s s i n c l a i m 1 i n which t h e q u a n t i t yof mahogany a c i d s i s o f t h e a p p r o x i m a t e‘ c r e e po f 1 t o 10 o f t h e amount o f p i n e n e t r e a t e d .

7 . The p r o c e s s o f c l a i m 2 i n which t h e q u a n t i t yo f mahogany a c i d s i s o f t h e approximate o r d e ro f 1 t o 10 o f t h e amount o f p i n e n e t r e a t e d .

ROBERT GARDNER K I N G .

R E F E R F Z W EQ I E QThe ‘ f o l l o w i n g rereréneesa? o r r e c o r d i n t h e

? l e o f t h i s p a t e n t :

1 0 STATES PATENTS

Number ‘Name Date2,178,349 S h e ? i g l d _ _ _ _ _ _ _ _ __ Oct . 3 1 , 19392 , 2 9 5 , 1 0 5 Weisjsenbom _ _ _ _ _ S e p t . 1 5 , 1 9 4 2 .

‘ ? a s f s i e l s t r o m _ _ _ _ _ __ Sept. 2 8 , 1 9 4 3

y _ REFEREN ES 7

K i i n u r a , JounSoc . Chem. Ind, J a p a n , v o l .4 0 ,J u l y 1 e 3 7 , . p a g e2 3 7 B .