COSECHA Y BENEFICIO / Ha
3. Grandes estrategias de la Cadena del Cacao y su Agroindustria en Antioquia.
3.2. MODERNIZACIÓN PRODUCTIVA DE LA CADENA DEL CACAO Y SU AGROINDUSTRIA.
S t a r t i n g M a te r i a l s .
M ethyl r i c i n o l e a t e and m eth y l 9 -h y d ro x y o c ta d e c - c i a -12"* o n o a to w ere p re p a re d a s d e s c r ib e d p r e v io u s ly ( p p . 132 and 1 4 4 ). M ethyl l i n o l e a t e and m eth y l 1 2 - ,l3 - d ih y d r o x y o le a to fjroro a v a i l a b l e i n th e l a b o r a to r y ,
40 M ethyl 1 2 - o x o -o lo a te ,
To a s o lu t i o n o f c a s t o r e s t e r s (2 g) i n g l a c i a l a c e t i c a c id (20 m l) was added a l l a t <mce a n oaddigA ag s o lu t i o n o f sodium d ic h ro m a te d ih y d ra t© (1 ,2 0 g ) i n w a te r ( 1 ,6 m l), a c e t i c a c id (12 m l) and o o n c . s u lp h u r ic a c id ( 0 ,7 m l). A f te r s t i r r in g v ig o ro u s ly f o r 30 s e c o n d s, th e s o lu tio n was d i l u t e d w ith ic e d - w a te r (50 m l) and th e p ro d u c t i s o l a t e d by e x t r a c t i o n w ith e t h e r ,
The r e a c t i o n m ix tu re (2 g ) was ch ro m ato g rap h ed o n s i l i c a g e l ( S o r b s il M60, 100 g ) e l u t i n g w ith 200 ml P, PE5, PEIO, PE20, PB30 and PE40, M ethyl 1 2 -o x o -c le a t© (1 .1 g ) was e lu te d m a in ly by PESO and was a d ju d g ed p u re on TLC (PESO). The
e s t e r had an ECL (DEGS) o f 2 5 ,5 and showed a b s o r p tio n i n th e IR sp e c tru m a t 3010 and 1715 cm * ,
M ethyl 9 -o x Q -o c ta d e c -c is -1 2 -e n o a to ir^
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9 -h y d ro > :y o o tad ec- o i s - 12 -o n o a te (500 rag) fo llo w e d by prep.TLC (PESO) a f fo r d e d th e 9 - o x o - e s te r (294 m g). T h is e s t e r had an ECL (DEG8) o f 2 5 .7 and a ls o gave peaks i n th e IR opeotrum a t
3010 and 1715
73 M ethyl x im e n y n a te .
The m ixed a c id s o f S an talu in album seed o i l (700 mg) w ere r e c r y s t a l l i s o d s e v e r a l tim e s from p e tro le u m to y i e l d xim enynio a c id (530 Kg) m .p , 3 8 -3 9 ° l i t T ^ 3 8 ,5 -3 9 .5 ° C . M é th y la tio n
(b o ro n tr i f l u o r i d e - m e t h a n o l ) o f th e a c id (500 mg) a f f o r d e d th e e s t e r (500 mg) w hich h ad an ECL (DEGS) o f 2 2 .9 and w hich was ad ju d g e d p u re on TLC (P E 5 )#
74 M ethyl c ro p o n y n a to ,
A f z o lia q u a n z o n s ls se e d o i l ( 1 ,1 g ) was r e f lu x e d f o r
fo u r m in u te s w ith d ry m e th a n o lic sodium m eth o x id e (15 m l, 0,2% ) and th e m ixed e s t e r s (0 .9 5 g ) o b ta in e d by e x t r a c t i o n w ith
p e tro le u m .
M ixed e s t e r s (600 mg) w ere th e n s u b je c te d to p r e p .Ag^ TLC (d o u b le dev elo p m en t PE12§) and m eth y l c re p o n y n a te (190 mg) was i s o l a t e d a s th e band ru n n in g im m e d ia te ly above m ethyl l i n o l e a t e . The e s t e r had an ECL (DEGS) o f 2 1 .4 and was shown t o be p u re on TLC (P E 5 ),
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A ttem p ted t r a n s h y d r o x y la tio n o f m eth y l 9 -h y d ro x y -o c ta d e c -c i s - 48 1 2 - e n o a te , The h y d ro x y e s te r ( 2 ,5 g) was d is s o lv e d in fo rm ic a c id (98%; 7 ,6 m l). To th e s o lu t i o n was added h y d ro g en p e ro x id e (100 v o l . , 1 ,1 m l) and th e m ix tu re was s t i r r e d f o r 3 h o u rs a t 40°C , A d d itio n o f w a te r and e th e r e x t r a c t i o n y ie ld e d a
p ro d u c t ( 2 .5 g) w hich was th e n h e a te d f o r one h o u r a t lOO^C i n sodium h y d ro x id e s o lu t i o n (3RÎ, 30 m l). A c i d i f ic a t io n
(3M liC l) d id n o t g iv e any s o l i d and t h e r e s u l t a n t o i l was e x tr a c te d w ith e t h e r . Y ie ld = 2 ,2 g ,
A p o r tio n o f th e o i l ( 0 ,5 g) was e s t e r i f i e d (B F^-m eth a n o l) to y i e l d e s t e r s ( 0 .4 6 g) w hich had ECLs (DEGS) o f 2 1 .7 , 2 1 ,9 and 2 3 ,2 a s t h e i r t r i m e t h y l s i l y l d e r i v a t i v e s .
Prep,TLC (PESO) o f th e p ro d u c t (390 mg) gave th r e e f r a c t i o n s : A (227 mg, 69%); B (39 mg, 12%) and C (63 mg, 19% ), F r a c tio n A had ECLs o f 2 1 ,7 and 2 1 .9 w hich became 2 3 ,8 and 2 4 ,0 a f t e r tr e a tm e n t w ith m ethyl i o d i d e - s i l v e r o x id e . The meth03cy d e r i v a t iv e s h ad a m ass sp ectru m w hich was v ery
s im i l a r t o t h a t o f th e m eth y l 9 , 1 2 -e p o x y " l3 ’^ o th o x y o to a r a te s p re p a re d by c y c lo d e h y d r a tio n o f th e 9 ,1 2 ,1 3 - tr ih y d r o x y s te a r ic a c id s ( p . 1 5 4 ). Found : C -6 9 .9 , H -1 1 ,5 ; c a l c , f o r C^_H_^0.:20 ob 4 C -7 0 ,2 , H -11,1% ,
F r a c tio n B showed no p eak s on GLC and f r a c t i o n C had an ECL o f 2 3 .2 N e ith e r f r a c t i o n was i d e n tif ie d *
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A ttem p ted e p o x id a tio n o f m e th y l t h re o 1 2 ,1 3 -d ih y d r o x y o le a te , A s o lu tio n c o n ta in in g m eth y l 1 2 ,1 3 -d ih y d ro x y o le a te (500 mg; 1 .5 3 mmole) and m -c h lo ro p e rb e n s o ic a c id (350 mg, 1 .7 2 mmole) i n m eth y len e c h lo r id e (25 m l) was a llo w e d to s ta n d o v e r n ig h t a t room te m p e r a tu re . A f te r d i l u t i o n w ith e th e r
(100 m l) th e s o lu t i o n was w ashed w ith s u c c e s s iv e p o r tio n s o f sodium s u lp h i t e (10%, 30 m l), sodium b ic a r b o n a te (5%, 3 x 30 m l) and w a te r (2 x 30 m l) . A f to r d ry in g o v e r sodium s u l p h a te , th e e th e r la y e r s w ere e v a p o ra te d to y i e l d p ro d u c t (510 m g). Prep,TLC (E ) o f a p o r tio n o f th e p ro d u c t (230 mg) a f fo r d e d th r e e b a n d s: A (90 mg, 45%); B (ICO mg, 50%) and C (9 mg, 5%), F r a c tio n A h ad an ECL o f 2 2 ,0 a s i t s t r i - m e th y ls ily l d e r i v a t iv e w hich became 2 6 ,6 a f t e r tre a tm e n t w ith m eth y l i o d i d e - s i l v e r o x id e w h ils t f r a c t i o n B had ECLs o f 2 2 ,2 and 2 7 .0 b e f o r e and a f t e r m é th y la tio n . The mass s p e c tr a o f f r a c t i o n s A and B w ere n e a r ly i d e n t i c a l and o n ly th e sp e c tru m o f f r a c t i o n A i s l i s t e d b elo w , m /e m /d m /e ^ m /e I_ 341 6 170 7 119 5 94 5 340 4 169 10 113 6 93 9 309 10 168 8 111 9 07 28 * T h is p ro c e d u re w i l l be r e f e r r e d to as " e p o x id is o d i n th e u s u a l way" i n a l l s u b se q u e n t e p o x id a tio n r e a c t i o n s .
m /e - 162 m /e m/e
m/e
277 / 10 p. %5 153 11 110 7 85 11 202 5 140 6 109 13 84 5 201 41 139 46 101 6 03 13 200 6 137 17 98 0 02 6 185 30 133 10 97 4 01 16 172 11 127 32 96 8 79 8 171 100 121 26 95 67 75 55F r a c tio n C showed no p eak s on GLC and was n o t I n v e s tig a te d f u r t h e r .
M ethyl 9 ,1 0 ,1 2 ,1 3 - d i- e p o x y s t e a r a t e .
M ethyl l i n o l e a t e (300 mg, 1 mmole) was e p o x id is o d w ith p e r a c id (450 mg, 2 ,2 mmole) i n m e th y le n e c h lo r id e (25 m l) i n th e u s u a l w ay. The p ro d u c t (310 mg) was shown to b e p u re on TLC (P E 4 0 ).
The d i-e p o x id e (310 mg, 0 ,9 0 mmole) was s t i r r e d o v e r n ig h t I n d io x a n c o n ta in in g B F g*-etherate ( 0 ,1 3 m l, 1*05 mmole) A f te r e x t r a c t i o n w ith e t h e r , th e p ro d u c t was exam ined on TLC and GLC,
The r e a c t i o n m ix tu re had ECLs o f 2 1 ,6 (DEGS) and 1 0 ,0 and 2 0 ,6 on ApL. Prep,TLC a f f o r d e d f iv e b a n d s; A (53 mg, 21%); B (11 mg, 4%); C (44 mg, 17%); D (51 mg, 20%) and E (100 mg, 39%).
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F r a c tio n A*
T hese e s t e r s had ECLs o f 2 1 ,6 (DEGS) and 1 8 .0 (A pL), The N.M .R. sp e c tru m showed a b s o r p tio n a t 4 .3t (2tl) and some d e t a i l s o f th e m ass sp e c tru m a r e g iv e n b elo w .
m A L m /e L m /e k 300 10 103 0 107 11 877 7 152 10 105 0 251 10 237 9 151 79 95 100 179 7 135 15 94 9 177 5 131 7 93 13 166 10 109 13 91 20 165 67 100 15 F r a c tio n B .
A n a ly tic a l TLC (PE40) showed t h i s band to be a m ix tu re o f s e v e r a l m inor b an d s and i t was n o t exam ined f u r t h e r .
F r a c tio n C,
T h is f r a c t i o n had an ECL o f 8 7 ,5 (DEGS) and 2 0 ,6 (ApL) and had a p o l a r i t y b etw een s y n th e t i c 9 ,1 2 -e p o x y and m ono- h y d r o x y e s te r s on TLC (JPE30), The IB sp ectru m showed peaks a t 3000 and 950 cm w h ils t N.M.U, sp ectru m gave a s ig n a l a t 5 ,9 5t (1H) and showed th e a b se n c e o f o l e f i n i c p r o to n s . Pound: C, 6 9 .4 ; H, 1 0 .1 ; c a l c , f o r C^gH^^O^; C, 6 9 ,9 ; H, 10,4% ,
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