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Preparation of butyryl-β-methylcholine perchlorate
366
D . H . ADAMS, V. P. WHITTAKER
VOL. 3
(I949)
S UMMA R Y I. T h e specificity of h u m a n p l a s m a c h o l i n e s t e r a s e freed from a c c o m p a n y i n g aliesterase by partial purification h a s been s t u d i e d u s i n g s o m e .l o choline a n d non-choline esters. 2. In c o n t r a s t to t h e h u n l a n e r y t h r o c y t e cholinest~,rase, t h e p l a s m a e n z y m e h y d r o l y s e s butyr,lt~,s m o s t r a p i d l y in a n y series of esters. T h e "alcohol st~,cificity' of the e n z y m e (except in r , . s w c t of s u b s t i t u t i o n in t h e cart)on a t o m a d j a c e n t to the ester link) is, howevcr, s i m i l a r to t h a t of tlw c r v t h r o c y t e e n z y m e , a l i p h a t i c esters'l~fing more r a p i d l y split the more closely t h e y apl~roach t h e c'holim. configuration. R gsu.~iI~ I. La spdcificit4 de 1,t cholinestdrase du p l a s m a de l ' h o m m e , lib6r6e de l'alicst~)rase qui l'accomp a g n e p a r u n e purification partielle, a 6t6 6tudide "a. l'aide d ' e n v i r o n 4 ° esters choliniques et noncholiniques. 2. C o n t r a i r e m e n t b. la cholinest6rase des 6 r y t h r o c y t e s de l ' h o m m e , l ' e n z y m e du p l a s m a h y d r o l y s e los b u t y r a t e s avec la plus g r a n d e rapidit6 d a n s routes les sdries d'esters. La "sFeeificit6 x'is-'2t-vis (le l'alcool" de l ' e n z v m e (sauf en ce q u i concerne la s u b s t i t u t i o n de l ' a t o m e tie e a r b o n e a d j a c e n t ~ la liaison ester) e s t e e p e n d a n t proche de celle de l ' e n z y m e globulaire, les esters a l i p h a t i q u e s 6 t a n t d ' a u t a n t plus r a p i d e m e n t hydrolysds qu'ils se r a p p r o c h e n t plus de la configuration tie la choline. ZUSAMMENFASSIJN(; i. Die Spezifizit/it der m c n s c h l i c h e n l ' l a s m a - C h o l i n e s t e r a s e w u r d e nach A b t r e n n u n g der beg l e i t e n d e n Aliesterase (durch partielle Reinigung) u n t e r s u c h t u n d 4 ° Cholin- u n d N i c h t c h o l i n e s t e r verwandt. 2. I m G e g e n s a t z zur Cholinesterase der l n e n s c h l i c h e n E r y t h r o c y t e n , h y d r o l y s i e r t d a s P l a s m a ~.nzym B u t } r a t e a m s c h n e l l s t e n in allen Serien yon E s t e r n . Die Alkoholspezifizit/tt des E n z y m s ( a u s g e n o m m e n h i n s i c h t l i c h des E r s a t z e s des Kohlc n s t o f f a t o m s n a h e der E s t e r b i n d u n g ) ist jedoch 5.hnlich d e m E n z y m der E r y t h r o c y t e n . A l i p h a t i s c h e E s t e r w e r d e n u m so schnelIer gespalten, je nS.her sie d e r C h o l i n k o n f i g u r a t i o n k o m m e n . REI,ERENCES 1 (;. 2 B. 3 ]). 4 l). 5 I). s D. 7 L. s D. 9 ]1. 10 |). IX D. lz F. 13 R. x4 C. 15 K. 16 E.
A. ALLES AND R. C. HAWES, J. Biol. Chem.. 133 (194o) 375. MENDEL AND H. RODWEV, Biochem. J., 37 (1943) 59. I~'ACItl~IANSOIIlN"AND ~'[. A. ]{OTIIENBERG, f . Biol. Chem., INS (I945) 653. NACHMANSOtlN AND H. ,~CHNEEMANN, J. Biol. Chem., t59 (I945) 239. H. ADAMS AND V. P. WHITTAKER, Biochem. J., 43 (Igl 8) pag. XlV. H. ADAMS, Biochim. Biophys. Acla 3 (I949) 7. H. EASSON AND E. STEDMAN, Proc. Roy. Soc.. I 2 I B (1936-7) i42. GLICK, J. B*ol. Chem., I37 (I941 ) 357VAItLQUIST, Skand. Arch. Physiol., 72 (I935) I35. RICHTER AND P. (;. CROFT, Biochem. J.. 36 (lo.t2) 746. H. ADAMS AND V. P. WHITTAKER, Biochem. J. 44 (I949) 6". STRELITZ, Biochem. J., 38 (I944) 86. AM~tON, Pfl~igers Arch. ges. Physiol., 233 (I933) 486. H. SAWYER, Science, i o i (I945) 385 • B. AUGUSTINSSON, Nature, 162 (I9,t8) I94. A. ZELLER, Heh,. Physiol. et Pharmacol. Acta, 6 (I948) c 36. AI)I)ENI)I'M PREPARATION
OF BUTYRYL-fl-METHYLCHOLINE
PEI(CHLORATE
by J. M.
NISBET
t~-Methyl choline perchlorate was h e a t e d on a w a t e r - b a t h u n d e r reflux for three h o u r s with excess redistilled b u t y r y l chloride. T h e reaction m i x t u r e solidified on cooling, a n d was e x t r a c t e d w i t h d r y e t h e r several t i m e s a n d t h e n recrystallized twice from ethanol. Colourless crystals, m.p. IoI ° C. ( F o u n d : C, 41.95; H, 7.7 ° Cx0H•OsNC1 requires C, 41.74; H, 7.65%)Received
November
25th, 1948
D . H . ADAMS, V. P. WHITTAKER
VOL. 3
(I949)
S UMMA R Y I. T h e specificity of h u m a n p l a s m a c h o l i n e s t e r a s e freed from a c c o m p a n y i n g aliesterase by partial purification h a s been s t u d i e d u s i n g s o m e .l o choline a n d non-choline esters. 2. In c o n t r a s t to t h e h u n l a n e r y t h r o c y t e cholinest~,rase, t h e p l a s m a e n z y m e h y d r o l y s e s butyr,lt~,s m o s t r a p i d l y in a n y series of esters. T h e "alcohol st~,cificity' of the e n z y m e (except in r , . s w c t of s u b s t i t u t i o n in t h e cart)on a t o m a d j a c e n t to the ester link) is, howevcr, s i m i l a r to t h a t of tlw c r v t h r o c y t e e n z y m e , a l i p h a t i c esters'l~fing more r a p i d l y split the more closely t h e y apl~roach t h e c'holim. configuration. R gsu.~iI~ I. La spdcificit4 de 1,t cholinestdrase du p l a s m a de l ' h o m m e , lib6r6e de l'alicst~)rase qui l'accomp a g n e p a r u n e purification partielle, a 6t6 6tudide "a. l'aide d ' e n v i r o n 4 ° esters choliniques et noncholiniques. 2. C o n t r a i r e m e n t b. la cholinest6rase des 6 r y t h r o c y t e s de l ' h o m m e , l ' e n z y m e du p l a s m a h y d r o l y s e los b u t y r a t e s avec la plus g r a n d e rapidit6 d a n s routes les sdries d'esters. La "sFeeificit6 x'is-'2t-vis (le l'alcool" de l ' e n z v m e (sauf en ce q u i concerne la s u b s t i t u t i o n de l ' a t o m e tie e a r b o n e a d j a c e n t ~ la liaison ester) e s t e e p e n d a n t proche de celle de l ' e n z y m e globulaire, les esters a l i p h a t i q u e s 6 t a n t d ' a u t a n t plus r a p i d e m e n t hydrolysds qu'ils se r a p p r o c h e n t plus de la configuration tie la choline. ZUSAMMENFASSIJN(; i. Die Spezifizit/it der m c n s c h l i c h e n l ' l a s m a - C h o l i n e s t e r a s e w u r d e nach A b t r e n n u n g der beg l e i t e n d e n Aliesterase (durch partielle Reinigung) u n t e r s u c h t u n d 4 ° Cholin- u n d N i c h t c h o l i n e s t e r verwandt. 2. I m G e g e n s a t z zur Cholinesterase der l n e n s c h l i c h e n E r y t h r o c y t e n , h y d r o l y s i e r t d a s P l a s m a ~.nzym B u t } r a t e a m s c h n e l l s t e n in allen Serien yon E s t e r n . Die Alkoholspezifizit/tt des E n z y m s ( a u s g e n o m m e n h i n s i c h t l i c h des E r s a t z e s des Kohlc n s t o f f a t o m s n a h e der E s t e r b i n d u n g ) ist jedoch 5.hnlich d e m E n z y m der E r y t h r o c y t e n . A l i p h a t i s c h e E s t e r w e r d e n u m so schnelIer gespalten, je nS.her sie d e r C h o l i n k o n f i g u r a t i o n k o m m e n . REI,ERENCES 1 (;. 2 B. 3 ]). 4 l). 5 I). s D. 7 L. s D. 9 ]1. 10 |). IX D. lz F. 13 R. x4 C. 15 K. 16 E.
A. ALLES AND R. C. HAWES, J. Biol. Chem.. 133 (194o) 375. MENDEL AND H. RODWEV, Biochem. J., 37 (1943) 59. I~'ACItl~IANSOIIlN"AND ~'[. A. ]{OTIIENBERG, f . Biol. Chem., INS (I945) 653. NACHMANSOtlN AND H. ,~CHNEEMANN, J. Biol. Chem., t59 (I945) 239. H. ADAMS AND V. P. WHITTAKER, Biochem. J., 43 (Igl 8) pag. XlV. H. ADAMS, Biochim. Biophys. Acla 3 (I949) 7. H. EASSON AND E. STEDMAN, Proc. Roy. Soc.. I 2 I B (1936-7) i42. GLICK, J. B*ol. Chem., I37 (I941 ) 357VAItLQUIST, Skand. Arch. Physiol., 72 (I935) I35. RICHTER AND P. (;. CROFT, Biochem. J.. 36 (lo.t2) 746. H. ADAMS AND V. P. WHITTAKER, Biochem. J. 44 (I949) 6". STRELITZ, Biochem. J., 38 (I944) 86. AM~tON, Pfl~igers Arch. ges. Physiol., 233 (I933) 486. H. SAWYER, Science, i o i (I945) 385 • B. AUGUSTINSSON, Nature, 162 (I9,t8) I94. A. ZELLER, Heh,. Physiol. et Pharmacol. Acta, 6 (I948) c 36. AI)I)ENI)I'M PREPARATION
OF BUTYRYL-fl-METHYLCHOLINE
PEI(CHLORATE
by J. M.
NISBET
t~-Methyl choline perchlorate was h e a t e d on a w a t e r - b a t h u n d e r reflux for three h o u r s with excess redistilled b u t y r y l chloride. T h e reaction m i x t u r e solidified on cooling, a n d was e x t r a c t e d w i t h d r y e t h e r several t i m e s a n d t h e n recrystallized twice from ethanol. Colourless crystals, m.p. IoI ° C. ( F o u n d : C, 41.95; H, 7.7 ° Cx0H•OsNC1 requires C, 41.74; H, 7.65%)Received
November
25th, 1948