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Epimerization of N-acetyl-d-galactosamine to N-acetyl-d-talosamine
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Epi merixation of N - a c e t y l - ~ a | a ~ o s a r n i t . to N-acety|-D-talosamine
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~t ..~_~ r e p o r t e d r e c e n t l y t h a t N - a c e t y l - D - g l u c o s a m i n e ( z - a c e t a m i d o - z - d e o x y - D gn~cose) w a s e p i m e r i z e d in a q u e o u s a l k a l i n e s o l u t i o n t o N - a c e t y l - D - m a n n o s a m i n e ( ( 2 - a e e t a m i d o - z - d e o x y - D - m a n n o s e ) ~,'-'. T h e p r e s e n t p a p e r r e p o r t s t h a t N - a c e t y l :~-galaetosamine ( 2 - a c e t a m i d o - z - d e o x y - n - g a l a c t o s e ) is also e p i m e r i z e d u n d e r similar ¢~m~ltiations to N - a c e t y I - n - t a l o s a m i n e ( z - a c e t a m i d o - 2 - d e o x y - o - t a l o s e ) . T h i s a m i n o s u g a r Lsolated f r o m t h e h y d r o l y s a t e s of c h o n d r o i t i n - s u l f u r i c acid 3. C h e m i c a l s y n t h e s i s ~1[ ~>-talosamine w a s a c h i e v e d b y t h e c y a n o h v d r i n t e c h n i q u e f r o m n - l y x o s y l a m i n e 4, ~m,ination followed b y c o n f i g u r a t i o n a l t r a n s f o r m a t i o n of D-galactose ~. P a p e r ¢ ~ - o m a t o g r a p h i c e v i d e n c e of t h e e p i m e r i z a t i o n of N - a c e t y l - D - g a l a c t o s a m i n e w a s reW~rttedi7 while o u r w o r k w a s in progress, a n d c o n c l u s i v e e v i d e n c e h a s n o w b e e n obt~ed b y t h e i s o l a t i o n a n d c h a r a c t e r i z a t i o n of t h e c o n v e r t e d a m i n o s u g a r . I n t h e s t u d i e s on t h e e p i m e r i z a t i o n of N - a c e t y l - o - g l u c o s a m i n e s, it w a s s h o w n flialt ~'-acetyl-D-aTtannosamine f o r m e d was m ~ r e soluble in cold e t h a n o l t h a n N - a c e t y l a>-~Jt~eosamine a n d t h a t t h e f o r m e r a m i n o s u g a r f o r m e d m o r e r e a d i l y t h e p h e n y l h~-dJrazone t h a n d i d t h e l a t t e r . N - A c e t y l - D - t a l o s a m i n e w a s s i m i l a r l y s e p a r a t e d f r o m ~ ' - ~ ¢ e t y l - D - g a l a c t o s a m i n e b y u s i n g t h e d i f f e r e n t s o l u b i l i t y in alcohol, b u t it w a s ~ t a i ~ e d . o n l y as a h y g r o s c o p i c m a t e r i a l . KUHN AND FISCHER 4 also r e p o r t e d N - a c e t y l D - t a t o s a m i n e as a h y g r o s c o p i c s u b s t a n c e It w a s c h a r a c t e r i z e d as t h e c r y s t a l l i n e llenyl~ydrazone which was formed more readily than from N-acetyl-D-galacto$mmixle. H y d r o l y s i s of t h e N - a c e t y l - n - t a l o s a m i n e w i t h dil. HC1 p r o d u c e d t h e k n o w n ~ - ~ n e h y d r o c h l o r i d e *. e p i m e r i z a t i o n w a s c a r r i e d o u t at p H I O - I I . P a p e r - c h r o m a t o g r a p h i c e x a m i nadtio,n i n d i c a t e d t h a t this p H w a s t h e best for t h e f o r m a t i o n of N - a c e t y l - o - t a l o s a m i n e . .At p i t 8 - 9 , t h e r e w a s little f o r m a t i o n of N - a c e t y l - D - t a l o s a m i n e , a n d N - a c e t y l t ~ L ~ e t o s . a m i n e r e m a i n e d l a r g e l y t m c h a n g e d , while a t p H 1 2 - 1 4 a n a d d i t i o n a l subwas formed. It migrated more rapidly than the two N-acetylhexosamines. ,~'-Acetyl-r~-galactosamine 9 (I 5 g) w a s t r e a t e d w i t h 4 ° m l of dil. N a O H ( p H IX) ffo~ 3; d a y s a t r o o m t e m p e r a t u r e . A f t e r p a s s i n g t h r o u g h a c o l u m n of A m b e r l i t e I R - I Z O ((H ÷ i~rm~ a n d a c o l u m n of A m b e r l i t e I R - 4 B ( O H - form), t h e r e a c t i o n s o l u t i o n w a s ¢¢meet~trated t o a s y r u p w h i c h w a s d i s s o l v e d in a m i x t u r e of 15 ml e a c h of m e t h a n o l ~mt e~ol. Additi, n of e t h y l - c e t a t e to a slight t u r b i d i t y a n d keeph~g t h e m i x t u r e in ~ r e f r i g e r a t o r s e p a r a t e d 12 g of t h e u n c h a n g e d N - a c e t y l - D - g a l a c t o s a m i n e . A f t e r ¢~neetI~ration of t h e filtrate a s y r u p r e m a i n e d w h i c h c o n t a i n e d a l m o s t p u r e N - a c e t y l D - t a l o s a m i n e a c c o r d i n g to p a p e r c h r o m a t o g r a p h y ; it w a s p r e c i p i t a t e d as a h y g r o s c o p i c $~mrder f r o m e t h a n o l w i t h e t h e r . ~ . o ~--- - - 4 '~ (c, I.O % / i n w a t e r ) . T i m s y r u p y N - a c e t y l - D - t a l o s a m J n e (I g) w a s d i s s o l v e d in I m l of w a t e r a n d to l t ~ w e r e a d d e d 0.5 g of p h e n y ! h y d r a z i n e a n d o.25 g of a c e t i c acid. A f t e r k e e p i n g t h e mLx-tttre a t r o o m t e m p e r a t u r e for 6 tt a c r y s t a l l i n e m a t t e r s e p a r a t e d w h i c h w a s ~e¢t, a f t e r s t a n d i n g o v e r n i g h t , b v filtration" t h e y.,eld w a s 1.5 g. I t w a s d i s s o l v e d 26~ m I of w a t e r , d e c o l o r i z e d ~ i t h c h a r c o a l , c o n c e n t r a t e d t o a b o u t 5 m l a n d k e p t a r e f r i g e r a t o r for c r y s t a l l i z a t i o n . T h e r e c r y s t a l l i z a t i o n wan r e p e a t e d o n c e m o r e a n d fmaI crsy-stals w e r e w a s h e d w i t h a little cold m e t h a n o l a n d d r i e d ; t h e 3deld w a s ~mg; m . p . I96°, [~]D = ~ I 6 ° --> + 5 °0 (c, Z.O% in w a t e r ) . [Calc. for C ~ , H , x N z O ~" C~ 54.o,x ; H, 6.8o; N, z3.5o. F o u n d : C, 53.9 o ; H, 7.oz ; N, z3.48 %.] Biochim. Biophys. Acta, 69 (x963) 572-573
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Under similar reaction conditions, N-acetyl-D-galactosamine [tthm~_.tl~.5~ne was n o t o b t a i n e d , b u t r e f l u x i n g ;'~,2 g of N - a c e t y l - D - g a l a c t o s a n f i n e , rr.~5..~¢/lL-ii~n~th y d r a z i n e a n d I g of acetic a c i d in 2o a~xl of m e t h a n o l for z h, exm~p~fi,r,~. ,~f( r.,he s o l v e n t , t r e a t m e n t w i t h e t h e r a n d r e c r y s t a l l i z a t i o n f r o m h o t ethancil~m~er~eW_,',,m'.:, i. _ ~--- + 5 9 " (c, :x.o %,.in~a~:m~,~. (,_~t~ti h y d r a z o n e in a yield of i. 5 g; m. p. I 6 O - 1 6 2 °, [c,~r) - " ' .~. for C14H21NaOs" C, 5 4 . o i ; H, 6.80; N, I3.5o. F o u n d " C, 5 4 . i 6 ; H , , 6 ~ O ~ ; ~ , ~,-~:'*~:. : The sirupy N-acetyl-D-talosamine prepared from N-acet#~~mmline (I5 g) w a s h y d r o l y z e d in o. 5 N HC1 for 6 h on a b o i l i n g - w a t e r ba~h~antltflimti~. 0[taoL~,~ s a t e e v a p o r a t e d to a s m a l l v o l u m e . I t w a s a p p l i e d to a c o l m n n :(2o .~ ~m0 n m 0 ) o f D o w e x s o w X 8 (H + form) a n d e l u t c d w i t h o.33 N HCI. T h e f r a c t i o n s ~ t t i i ~ w~r,e p o s i t i v e to t h e ELSON--MORGAN r e a c t i o n ~° w e r e c o m b i n e d a n d e v a p o r a t ~ t ~ v d t r 3 m ~ s s ~ T h e r e s i d u e w a s d i s s o l v e d in IO ml of w a t e r a n d a g a i n applietl ~to ~ , ~ d l m l m ((m, < 400 m m ) of D o w e x 5 o W X 8 (H + form) a n d e l u t e d similarly. T h e ~-a~lii~m~ l ~ ~ e to t h e ELSON--MORGAN r e a c t i o n w e r e a g a i n c o m b i n e d , concentrated~mI{t~ttttm~]]and~ e t h y l a c e t a t e w e r e a d d e d to t h e r e s i d u e u n t i l a t u r b i d i t y w a s o b t a i n e t l . ~ ~ n ~ in a r e f r i g e r a t o r , D - t a l o s a m i n e h y d r o c h l o r i d e w a s o b t a i n e d in c r 3 ~ l ! ! i ~ e ~ r m i~, a, yield of 460 m g . I t w a s r e p e a t e d l y r e c r y s t a l l i z e d f r o m a mix'tu~e ,~ff ~ttttxm~|l andl m e t h a n o l b y c a r e f u l a d d i t i o n ot' e t h y l a c e t a t e . T h e final p r o d u c t ((,3kiellfl ,-,~ m ~ ) ~ e a single s p o t in p a p e r - c h r o m a t o g r a p h i c a s s a y n. I t h a d m . p . x - S x - ~ ° (0tim~rrrL~)),~ad~ l a i d = - - 5 . 0 ° (c, ~.O % in w a t e r ) . [Calc. for C ~ H I s N O ~. HCI" C, 33~t.~:;lIB~,0B.~g~:~-'~K,8,5o: F o u n d " C, 33.84; H , 6.62; N, 6 . I 3 %. ] KUHN ~,~D FISCHER 4 r e p o r t e d for t h i s c o m p o u n d m . p . x-~d~x~x-~~ ~ (0[h~uath~))and~ l a i d = ~* 3.4 ° --~ - - 5 . 7 °. T h e i n f r a r e d s p e c t r u m of o u r p r o d u c t . w a s i i t t e m ~ r ~ ] ~ t ~ a ~ of D - t a l o s a m i n e h y d r o c h l o r i d e s y n t h e s i z e d a n d s u p p l i e d b y ~ . [ K ~ . IM~tmtL~ t h a t an a b s o r p t i o n at 1485 c m -1 in t h e s p e c t r u m of D - t a l o s a m i n e i l ~ y & - m ~ i m i i ~ a ~ c h a r a c t e r i s t i c of t h i s a m i n o s u g a r , b e i n g a b s e n t f r o m t h a t of *.he ~ . , ~ , ; l , , , ; i r , ~ o~ ,-galactosamine, D-glucosamine and D-mannosamine. W e are g r e a t l y i n d e b t e d t o Dr. KUHN for his g e n e r o u s g i f t c f f ! ~ , M l ~ t t ~ l ~ - c h l o r i d e , a n d we w i s h to t h a n k Dr. K. ONODERA a n d Dr. S. K I ~ A o K ~ t f f tK~ritt~ ~Tniv v e r s i t y for t h e i r a d v i c e a n d e n c o u r a g e m e n t . R e s c a r c h L a b o r a t o r y , K a k e n - y a k u - k a k o Co. L t d . , Kyoto (Japan) I p . ~I. CARROLLAND J. ~,V. CORNFORTH, Biochim. Biophys. Acta, 39 (I06o) .~f~l. -~C. T. SPIVAK AND S. ROSEMAN,J. A m . Chem. Sot., 8x (i959) 2403. 3 M. J. CRUMPTON, Nature, i8o (I9.57) 605.
4 R . K U H N AND H . F I S C H E R , A n n . Chem,, 6 1 2 (I9.57) 6 5 . I~[. K U H N AND J . c . J o c H I , M S , A n n . Chem., 6 4 x ( I 9 6 I ) x43. ¢ R. "~V. JEANLOZ, Z. T. GLAZER AND D. A. JEANLOZ, J. Org. Chem., 26 (I061)~32-. R . HEYXVORTtl, H. R. P E R K I N S AND P . G . "~VALKER, Nature, I 9 o ( I 9 6 I ) ~ G x . s I-]. K U S H I D A , S. F U J I I AND T . O F U j I , S e i k a g a k u , 3 3 ( I 9 6 I ) 2 3 7 , S, ROSEMAN AND J , LUDO~VIEG, J. A m . Chem, Sot., 7 6 ( 1 9 5 4 ) 3 o x . 10 L . A. EL-~ON AND VV. T . J . MORGAN, Biochem. J . , 27 ( 1 9 3 3 ) i 8 2 4 . it R . K U H N , Vv'. B i t T E R AND H . F I S C H E R , A n n . Chem., 6 1 7 (T958) IO9.
R e c e i v e d O c t o b e r I o t h , 1962 Biochim. Biophys. ,B eta, ~69 ( ~ )
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SHORT COMMUNICATIONS SC 2205
Epi merixation of N - a c e t y l - ~ a | a ~ o s a r n i t . to N-acety|-D-talosamine
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~t ..~_~ r e p o r t e d r e c e n t l y t h a t N - a c e t y l - D - g l u c o s a m i n e ( z - a c e t a m i d o - z - d e o x y - D gn~cose) w a s e p i m e r i z e d in a q u e o u s a l k a l i n e s o l u t i o n t o N - a c e t y l - D - m a n n o s a m i n e ( ( 2 - a e e t a m i d o - z - d e o x y - D - m a n n o s e ) ~,'-'. T h e p r e s e n t p a p e r r e p o r t s t h a t N - a c e t y l :~-galaetosamine ( 2 - a c e t a m i d o - z - d e o x y - n - g a l a c t o s e ) is also e p i m e r i z e d u n d e r similar ¢~m~ltiations to N - a c e t y I - n - t a l o s a m i n e ( z - a c e t a m i d o - 2 - d e o x y - o - t a l o s e ) . T h i s a m i n o s u g a r Lsolated f r o m t h e h y d r o l y s a t e s of c h o n d r o i t i n - s u l f u r i c acid 3. C h e m i c a l s y n t h e s i s ~1[ ~>-talosamine w a s a c h i e v e d b y t h e c y a n o h v d r i n t e c h n i q u e f r o m n - l y x o s y l a m i n e 4, ~m,ination followed b y c o n f i g u r a t i o n a l t r a n s f o r m a t i o n of D-galactose ~. P a p e r ¢ ~ - o m a t o g r a p h i c e v i d e n c e of t h e e p i m e r i z a t i o n of N - a c e t y l - D - g a l a c t o s a m i n e w a s reW~rttedi7 while o u r w o r k w a s in progress, a n d c o n c l u s i v e e v i d e n c e h a s n o w b e e n obt~ed b y t h e i s o l a t i o n a n d c h a r a c t e r i z a t i o n of t h e c o n v e r t e d a m i n o s u g a r . I n t h e s t u d i e s on t h e e p i m e r i z a t i o n of N - a c e t y l - o - g l u c o s a m i n e s, it w a s s h o w n flialt ~'-acetyl-D-aTtannosamine f o r m e d was m ~ r e soluble in cold e t h a n o l t h a n N - a c e t y l a>-~Jt~eosamine a n d t h a t t h e f o r m e r a m i n o s u g a r f o r m e d m o r e r e a d i l y t h e p h e n y l h~-dJrazone t h a n d i d t h e l a t t e r . N - A c e t y l - D - t a l o s a m i n e w a s s i m i l a r l y s e p a r a t e d f r o m ~ ' - ~ ¢ e t y l - D - g a l a c t o s a m i n e b y u s i n g t h e d i f f e r e n t s o l u b i l i t y in alcohol, b u t it w a s ~ t a i ~ e d . o n l y as a h y g r o s c o p i c m a t e r i a l . KUHN AND FISCHER 4 also r e p o r t e d N - a c e t y l D - t a t o s a m i n e as a h y g r o s c o p i c s u b s t a n c e It w a s c h a r a c t e r i z e d as t h e c r y s t a l l i n e llenyl~ydrazone which was formed more readily than from N-acetyl-D-galacto$mmixle. H y d r o l y s i s of t h e N - a c e t y l - n - t a l o s a m i n e w i t h dil. HC1 p r o d u c e d t h e k n o w n ~ - ~ n e h y d r o c h l o r i d e *. e p i m e r i z a t i o n w a s c a r r i e d o u t at p H I O - I I . P a p e r - c h r o m a t o g r a p h i c e x a m i nadtio,n i n d i c a t e d t h a t this p H w a s t h e best for t h e f o r m a t i o n of N - a c e t y l - o - t a l o s a m i n e . .At p i t 8 - 9 , t h e r e w a s little f o r m a t i o n of N - a c e t y l - D - t a l o s a m i n e , a n d N - a c e t y l t ~ L ~ e t o s . a m i n e r e m a i n e d l a r g e l y t m c h a n g e d , while a t p H 1 2 - 1 4 a n a d d i t i o n a l subwas formed. It migrated more rapidly than the two N-acetylhexosamines. ,~'-Acetyl-r~-galactosamine 9 (I 5 g) w a s t r e a t e d w i t h 4 ° m l of dil. N a O H ( p H IX) ffo~ 3; d a y s a t r o o m t e m p e r a t u r e . A f t e r p a s s i n g t h r o u g h a c o l u m n of A m b e r l i t e I R - I Z O ((H ÷ i~rm~ a n d a c o l u m n of A m b e r l i t e I R - 4 B ( O H - form), t h e r e a c t i o n s o l u t i o n w a s ¢¢meet~trated t o a s y r u p w h i c h w a s d i s s o l v e d in a m i x t u r e of 15 ml e a c h of m e t h a n o l ~mt e~ol. Additi, n of e t h y l - c e t a t e to a slight t u r b i d i t y a n d keeph~g t h e m i x t u r e in ~ r e f r i g e r a t o r s e p a r a t e d 12 g of t h e u n c h a n g e d N - a c e t y l - D - g a l a c t o s a m i n e . A f t e r ¢~neetI~ration of t h e filtrate a s y r u p r e m a i n e d w h i c h c o n t a i n e d a l m o s t p u r e N - a c e t y l D - t a l o s a m i n e a c c o r d i n g to p a p e r c h r o m a t o g r a p h y ; it w a s p r e c i p i t a t e d as a h y g r o s c o p i c $~mrder f r o m e t h a n o l w i t h e t h e r . ~ . o ~--- - - 4 '~ (c, I.O % / i n w a t e r ) . T i m s y r u p y N - a c e t y l - D - t a l o s a m J n e (I g) w a s d i s s o l v e d in I m l of w a t e r a n d to l t ~ w e r e a d d e d 0.5 g of p h e n y ! h y d r a z i n e a n d o.25 g of a c e t i c acid. A f t e r k e e p i n g t h e mLx-tttre a t r o o m t e m p e r a t u r e for 6 tt a c r y s t a l l i n e m a t t e r s e p a r a t e d w h i c h w a s ~e¢t, a f t e r s t a n d i n g o v e r n i g h t , b v filtration" t h e y.,eld w a s 1.5 g. I t w a s d i s s o l v e d 26~ m I of w a t e r , d e c o l o r i z e d ~ i t h c h a r c o a l , c o n c e n t r a t e d t o a b o u t 5 m l a n d k e p t a r e f r i g e r a t o r for c r y s t a l l i z a t i o n . T h e r e c r y s t a l l i z a t i o n wan r e p e a t e d o n c e m o r e a n d fmaI crsy-stals w e r e w a s h e d w i t h a little cold m e t h a n o l a n d d r i e d ; t h e 3deld w a s ~mg; m . p . I96°, [~]D = ~ I 6 ° --> + 5 °0 (c, Z.O% in w a t e r ) . [Calc. for C ~ , H , x N z O ~" C~ 54.o,x ; H, 6.8o; N, z3.5o. F o u n d : C, 53.9 o ; H, 7.oz ; N, z3.48 %.] Biochim. Biophys. Acta, 69 (x963) 572-573
SHORT COMMUNICATIONS
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Under similar reaction conditions, N-acetyl-D-galactosamine [tthm~_.tl~.5~ne was n o t o b t a i n e d , b u t r e f l u x i n g ;'~,2 g of N - a c e t y l - D - g a l a c t o s a n f i n e , rr.~5..~¢/lL-ii~n~th y d r a z i n e a n d I g of acetic a c i d in 2o a~xl of m e t h a n o l for z h, exm~p~fi,r,~. ,~f( r.,he s o l v e n t , t r e a t m e n t w i t h e t h e r a n d r e c r y s t a l l i z a t i o n f r o m h o t ethancil~m~er~eW_,',,m'.:, i. _ ~--- + 5 9 " (c, :x.o %,.in~a~:m~,~. (,_~t~ti h y d r a z o n e in a yield of i. 5 g; m. p. I 6 O - 1 6 2 °, [c,~r) - " ' .~. for C14H21NaOs" C, 5 4 . o i ; H, 6.80; N, I3.5o. F o u n d " C, 5 4 . i 6 ; H , , 6 ~ O ~ ; ~ , ~,-~:'*~:. : The sirupy N-acetyl-D-talosamine prepared from N-acet#~~mmline (I5 g) w a s h y d r o l y z e d in o. 5 N HC1 for 6 h on a b o i l i n g - w a t e r ba~h~antltflimti~. 0[taoL~,~ s a t e e v a p o r a t e d to a s m a l l v o l u m e . I t w a s a p p l i e d to a c o l m n n :(2o .~ ~m0 n m 0 ) o f D o w e x s o w X 8 (H + form) a n d e l u t c d w i t h o.33 N HCI. T h e f r a c t i o n s ~ t t i i ~ w~r,e p o s i t i v e to t h e ELSON--MORGAN r e a c t i o n ~° w e r e c o m b i n e d a n d e v a p o r a t ~ t ~ v d t r 3 m ~ s s ~ T h e r e s i d u e w a s d i s s o l v e d in IO ml of w a t e r a n d a g a i n applietl ~to ~ , ~ d l m l m ((m, < 400 m m ) of D o w e x 5 o W X 8 (H + form) a n d e l u t e d similarly. T h e ~-a~lii~m~ l ~ ~ e to t h e ELSON--MORGAN r e a c t i o n w e r e a g a i n c o m b i n e d , concentrated~mI{t~ttttm~]]and~ e t h y l a c e t a t e w e r e a d d e d to t h e r e s i d u e u n t i l a t u r b i d i t y w a s o b t a i n e t l . ~ ~ n ~ in a r e f r i g e r a t o r , D - t a l o s a m i n e h y d r o c h l o r i d e w a s o b t a i n e d in c r 3 ~ l ! ! i ~ e ~ r m i~, a, yield of 460 m g . I t w a s r e p e a t e d l y r e c r y s t a l l i z e d f r o m a mix'tu~e ,~ff ~ttttxm~|l andl m e t h a n o l b y c a r e f u l a d d i t i o n ot' e t h y l a c e t a t e . T h e final p r o d u c t ((,3kiellfl ,-,~ m ~ ) ~ e a single s p o t in p a p e r - c h r o m a t o g r a p h i c a s s a y n. I t h a d m . p . x - S x - ~ ° (0tim~rrrL~)),~ad~ l a i d = - - 5 . 0 ° (c, ~.O % in w a t e r ) . [Calc. for C ~ H I s N O ~. HCI" C, 33~t.~:;lIB~,0B.~g~:~-'~K,8,5o: F o u n d " C, 33.84; H , 6.62; N, 6 . I 3 %. ] KUHN ~,~D FISCHER 4 r e p o r t e d for t h i s c o m p o u n d m . p . x-~d~x~x-~~ ~ (0[h~uath~))and~ l a i d = ~* 3.4 ° --~ - - 5 . 7 °. T h e i n f r a r e d s p e c t r u m of o u r p r o d u c t . w a s i i t t e m ~ r ~ ] ~ t ~ a ~ of D - t a l o s a m i n e h y d r o c h l o r i d e s y n t h e s i z e d a n d s u p p l i e d b y ~ . [ K ~ . IM~tmtL~ t h a t an a b s o r p t i o n at 1485 c m -1 in t h e s p e c t r u m of D - t a l o s a m i n e i l ~ y & - m ~ i m i i ~ a ~ c h a r a c t e r i s t i c of t h i s a m i n o s u g a r , b e i n g a b s e n t f r o m t h a t of *.he ~ . , ~ , ; l , , , ; i r , ~ o~ ,-galactosamine, D-glucosamine and D-mannosamine. W e are g r e a t l y i n d e b t e d t o Dr. KUHN for his g e n e r o u s g i f t c f f ! ~ , M l ~ t t ~ l ~ - c h l o r i d e , a n d we w i s h to t h a n k Dr. K. ONODERA a n d Dr. S. K I ~ A o K ~ t f f tK~ritt~ ~Tniv v e r s i t y for t h e i r a d v i c e a n d e n c o u r a g e m e n t . R e s c a r c h L a b o r a t o r y , K a k e n - y a k u - k a k o Co. L t d . , Kyoto (Japan) I p . ~I. CARROLLAND J. ~,V. CORNFORTH, Biochim. Biophys. Acta, 39 (I06o) .~f~l. -~C. T. SPIVAK AND S. ROSEMAN,J. A m . Chem. Sot., 8x (i959) 2403. 3 M. J. CRUMPTON, Nature, i8o (I9.57) 605.
4 R . K U H N AND H . F I S C H E R , A n n . Chem,, 6 1 2 (I9.57) 6 5 . I~[. K U H N AND J . c . J o c H I , M S , A n n . Chem., 6 4 x ( I 9 6 I ) x43. ¢ R. "~V. JEANLOZ, Z. T. GLAZER AND D. A. JEANLOZ, J. Org. Chem., 26 (I061)~32-. R . HEYXVORTtl, H. R. P E R K I N S AND P . G . "~VALKER, Nature, I 9 o ( I 9 6 I ) ~ G x . s I-]. K U S H I D A , S. F U J I I AND T . O F U j I , S e i k a g a k u , 3 3 ( I 9 6 I ) 2 3 7 , S, ROSEMAN AND J , LUDO~VIEG, J. A m . Chem, Sot., 7 6 ( 1 9 5 4 ) 3 o x . 10 L . A. EL-~ON AND VV. T . J . MORGAN, Biochem. J . , 27 ( 1 9 3 3 ) i 8 2 4 . it R . K U H N , Vv'. B i t T E R AND H . F I S C H E R , A n n . Chem., 6 1 7 (T958) IO9.
R e c e i v e d O c t o b e r I o t h , 1962 Biochim. Biophys. ,B eta, ~69 ( ~ )
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