1342 Notizen R o le o f th e H ydroxym ethyl G roup for
the Inhibitory A ctivity o f P en ien on e Y asu o K im u r a 3, T ak a sh i M iz u n o 3, T su y o sh i K a w a n o 3, a n d A ts u m i S him ada*-b
a D epartm ent of Agricultural Chemistry, Faculty of Agriculture, Tottori University. Koyama, Tottori 680-8553, Japan
b D epartm ent of Environm ental Chemistry, Faculty of Engineering, Kyushu Kyoritsu University, Yahatanishi, Kitakyushu 807-8585, Japan
* R eprint requests to Dr. A. Shimada.
Fax: (+81) 93-693-3201;
E-mail: jun@kyukyo-u.ac.jp
Z. Naturforsch. 54b, 1342-1344 (1999);
received June 7, 1999
Penicillium sp., Penienone, Growth Inhibitor, Lettuce
Penienone was isolated from the culture filtrate of Penicillium sp. No. 13 and completely inhibited hypocotyl elongation and root growth of lettuce seedlings at a concentration of 300 mg/1. In order to elucidate the active site of penienone, three de
rivatives were prepared and tested for their inhib
itory activity against the growth of lettuce seed
lings. The results indicated that hydroxymethyl group in the molecule of penienone was essential to exhibit the rem arkable inhibitory activity against the growth of lettuce seedlings.
Introduction
W e h a v e is o la te d a n d e lu c id a te d th e s tru c tu re s o f p e n ie n o n e (1) [1], p e n id ie n o n e [2] a n d p en ih y - d r o n e [1] fro m th e c u ltu re filtra te o f Penicillium sp. N o. 13 as th e g ro w th re g u la to rs o f le ttu c e s e e d lings. 1 show s th e in h ib ito ry a c tiv ity a g a in st th e g ro w th o f le ttu c e seedlings. P e n id ie n o n e show s w e a k e r in h ib ito ry ac tiv ity th a n 1, w hile p en ih y - d r o n e d o e s n o t sh o w a n y r e m a rk a b le in h ib ito ry activity. To e x p lo re th e s tru c tu ra l u n its e sse n tia l to th e in h ib ito ry ac tiv ity o f 1 in d e ta il, th r e e d e riv a tiv e s (Fig. 1) o f 1 w e re p r e p a r e d a n d te s te d fo r th e ir in h ib ito ry activity. H e r e w e d e s c rib e th e b io log ical a c tiv itie s o f p e n ie n o n e a n d its d e riv a tiv e s o n th e g ro w th o f le ttu c e seedlings.
Results and Discussion
P e n ie n o n e , p e n id ie n o n e a n d p e n ih y d ro n e w ere is o la te d fro m a c u ltu re filtra te o f P enicillium sp.
N o. 13 as d e s c rib e d p re v io u sly [1,2]. A c e ty la tio n
7 9 11 13
O 1: R 1=CH2OH 2: R i= CH2OCOCH3 3: R 1=H
7 9 11 13
O 4
Fig. 1.
(2 -4 ),
o f 1 w ith a c e tic a n h y d rid e in p y rid in e a ffo rd e d a m o n o a c e ty l d e riv a tiv e (2) w h ich w as c o n firm e d by th e r e s o n a n c e a t d 2.01 (O A c ) in th e *H N M R sp e c tru m o f 2. O x id a tio n o f 1 w ith J o n e s ’ r e a g e n t [3] a ffo rd e d a d e h y d ro x y m e th y l d e riv a tiv e (3).
T h e ° C N M R s p e c tru m o f 3 sh o w ed th e a b s e n c e o f a signal fo r th e h y d ro x y m e th y l g ro u p a n d th e a p p e a ra n c e o f a n ew sig n a l d u e to a m e th y le n e c a rb o n at 43.9 p p m , a d ja c e n t to a c a rb o n y l g roup.
C a ta ly tic h y d ro g e n a tio n o v e r p la tin u m o x id e o f 1 a ffo rd e d a h e x a h y d ro -d e riv a tiv e (4). T h e i3C N M R s p e c tru m o f 4 s h o w e d six sig n als d u e to m e th y le n e c a r b o n a to m s in s te a d o f six d o u b le b o n d e d m e th in e c a rb o n a to m s in 1.
P e n ie n o n e in h ib ite d h y p o c o ty l e lo n g a tio n a n d r o o t g ro w th o f le ttu c e s e e d lin g s by 3 4 % a n d 23%
a t a c o n c e n tra tio n o f 30 mg/1, resp ectiv ely . C om - O
Penihydrone
Constitution of penienone (1), three derivatives penidienone and penihydrone.
0932-0776/99/1000-1342 $06.00 © 1999 Verlag der Zeitschrift für Naturforschung, Tübingen • www.znaturforsch.com D
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Notizen 1343 p le te in h ib itio n w as f o u n d a t a c o n c e n tra tio n o f
300 mg/1. T h e in h ib ito ry a c tiv ity o f c o m p o u n d 2 (300 mg/1) o n h y p o c o ty l e lo n g a tio n a n d r o o t g ro w th w as w e a k e r th a n th a t o f p e n ie n o n e a t a c o n c e n tra tio n o f 30 mg/1. C o m p o u n d 3 d id n o t sh o w a n y re m a rk a b le in h ib ito ry a c tiv ity a g a in st h y p o c o ty l e lo n g a tio n a n d r o o t g ro w th a t a c o n c e n tr a tio n o f 300 mg/1. C o m p o u n d 4 c o m p le te ly in h ib ite d h y p o c o ty l e lo n g a tio n a n d r o o t g ro w th a t th e sa m e c o n c e n tra tio n , b u t sh o w e d n o in h ib ito r y a c tivity a t a c o n c e n tra tio n o f 30 mg/1 (Fig. 2). T h e se re su lts in d ic a te d th a t th e h y d ro x y m e th y l g r o u p o f 1 w as e s se n tia l to e x h ib it th e r e m a rk a b le in h ib i
to ry ac tiv ity a g a in st th e g ro w th o f le ttu c e s e e d lings.
E x p e rim e n ta l
U V a n d IR sp e c tra w e re re c o rd e d o n a H ita c h i 1 0 0 - 5 0 a n d a J A S C O F T /IR -7 0 0 0 s p e c tro m e te rs , resp e ctiv ely . 'H - N M R a n d 13C -N M R s p e c tr a w e re o b ta in e d o n a J E O L JN M G X -2 7 0 s p e c tr o m e te r a t 270.05 M H z a n d 67.80 M H z, resp e ctiv ely . M S s p e c tra w e re ta k e n o n a IN C O S 50 in s tru m e n t.
P rep a ra tio n o f (5S, 6 R )- 5 - [ (lE , 3 E )-l,3 -h e p ta d i- en y l]-6-(a c e to x y m e th y l) -2-c y c lo h e x e n o n e (2)
P e n ie n o n e (1) (20 m g ) w as a c e ty la te d w ith a c e tic a n h y d rid e (0.5 m l) a n d p y rid in e (1.0 m l) fo r 24 h a t ro o m te m p e r a tu re a n d w o rk e d u p in th e u su a l m a n n e r to y ield 2 (18 m g ) as a c o lo rle ss oil.
C o m p o u n d 2: U V ( E t O H ) n m (e): 230 (22,500);
IR (K B r) c m - 1: 2964 (C = C ), 1743 ( 0 - C = 0 ) , 1680
Hypocotyl length (%) Hypocotyl length (%)
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
--- 1--- 1--- 1--- 1---1---1___________ i ---1--- 1___________ i___________ i___________ i___________ i___________i
Root growth <%) Root ^ QWth (%)
Fig. 2. Effect of penienone (1) and three derivatives (2 -4 ) on the growth of lettuce seedlings.
Concentration: (left) 30 mg/1, (right) 300 mg/1.
1344 Notizen ( C = 0 ) ; M S: m /z ( % ) = 262 (M +,20), 202 (38), 189
(47), 173 (17), 159 (100), 145 (63), 133 (57), 117 (34), 107 (43), 91 (73), 77 (49), 6 8 (65); 13C N M R (C D C lV T M S ): ö = 13.7 (C -1 3 ), 20.8 (C H3-C O ), 22.3 (C -1 2 ), 32.4 (C -4 ), 34.6 ( C - l l ) , 40.5 (C -5), 50.5 (C -6), 60.6 ( C H2-O A c ), 129.5 (C -9 ), 129.6 (C - 2), 131.0 (C -7 ), 132.4 (C -8), 135.0 (C -1 0 ), 148.7 (C - 3), 170.8 ( C H3- C O ), 197.1 ( C - l) p p m ; 2H N M R (C D C lV T M S ): <5 = 0.91 (t, 3 H , J = 7.3, 13-H ), 1.41 (tq , 2 H , J = 7.3, 7.3, 12 -H ), 2.01 (s, 3 H , O A c), 2.03 (d t, 2 H , J = 7.3, 7.3, 11-H ), 2.43 (m , 3H , 4-H , 6- H ), 2.82 (m , 1H , 5 -H ), 4.20 (d d , 1H , J = 11.1, 3.9, C H2-O A c ), 4.58 (d d , 1H , J = 14.7, 7.3, C H2-O A c ), 5.46 (d d , 1H , J = 14.7, 8.8, 7 -H ), 5.65 (d t, 1H, J = 14.7, 7.3, 10-H ), 5.96 (m , 1H , 9 -H ), 6.05 (m , 1H , 2- H ), 6.08 (m , 1H , 8-H ), 6.95 p p m (d d d , 1H , / = 10.3, 5.5, 2.4, 3 -H ).
P rep a ra tio n o f (5 S )-5 -[ (lE , 3 E )-l,3 -h e p ta d ie n y lJ - 2 -c y c lo h e x e n o n e (3)
P e n ie n o n e (1) (40 m g ) w as tr e a te d w ith J o n e s ’ re a g e n t [3] in a c e to n e (2.0 m l) fo r 12 h in an ice- c o o le d w a te r b a th a n d w o rk e d u p in th e u su a l m a n n e r to yield 3 ( 6 m g ) as a c o lo rle ss oil.
C o m p o u n d 3: U V ( E t O H ) n m (e): 225 (1,900);
IR (K B r) c m “ 1: 2930 (C = C ), 1678 ( C = 0 ) ; MS: m / z ( % ) = 190 (M +, 49), 161 (8), 147 (14), 133 (16), 122 (23), 110 (34), 91 (61), 79 (100), 6 8 (62); 13C N M R (C D C I3/T M S ): Ö = 13.7 (C -1 3 ), 22.4 (C -12), 32.1 (C -4 ), 34.7 ( C - l l ) , 38.0 (C -5 ), 43.9 (C -6), 129.7 (C -9 ), 129.8 (C -2 ), 130.4 (C -7 ), 132.8 (C -8), 134.6 (C -1 0 ), 149.3 (C -3 ) a n d 199.1 ( C - l) pp m ; JH N M R (C D C I3/T M S ): <3 = 0.91 (t, 3 H , J = 7.3, 13- H ), 1.41 (tq , 2 H , J = 7.3, 7.3, 12 -H ), 2.06 (d t, 2H , J = 7.3, 7.3, 11 -H ), 2.28 (m , 2 H , 4 -H ), 2.52 (m , 2H ,
6-H ), 2.81 (m , 1H , 5 -H ), 5.54 (d d , 1H , J = 14.4, 6.8, 7 -H ), 5.66 (d t, 1H , J = 14.2, 7.3, 1 0-H ), 6.03 (m , 3H , 2-, 8-, 9 -H ), 6.95 p p m (d d d , 1H , J = 10.3, 5.6, 2.4, 3 -H ).
R e d u c tio n o f p e n ie n o n e
P e n ie n o n e (1) (30 m g ) w as r e d u c e d by c a ta ly tic h y d ro g e n a tio n o v e r p la tin u m o x id e (30 m g) in e t h an o l (5.0 m l) a n d w o rk e d u p in th e usual m a n n e r to y ield 4 ( 8 m g ) as a c o lo rle ss oil.
C o m p o u n d 4: I R (K B r) c m -1 : 3412 (O -H ), 2930 (C = C ), 1704 ( C = 0 ) ; M S: m /z ( % ) = 226 (M +, 13), 208 (28), 137 (22), 127 (73), 110 (77), 97 (100), 83 (6 8), 67 (73); 13C N M R (C D C 13/T M S ): (3 = 14.1 (C -1 3 ), 22.6 ( C - 7 -1 2 ) , 25.9 (C -4 ), 26.0 (C -5), 29.2 (C -7 -1 2 ) , 29.8 ( C -7 -1 2 ), 30.3 (C -7 -1 2 ) , 31.8 (C - 7 - 1 2 ) , 33.5 ( C - 7 -1 2 ) , 40.3 (C -3 ), 42.1 (C -6), 56.8 (C -2 ), 59.7 (C -1 4 ), 215.5 ( C - l ) p p m ; JH N M R (C D C I3/T M S ): (3 - 0.88 (t, 3 H , J = 7.3, 13-H ), 1.27 (br. s, 12H , 7 - 1 2 - H ) , 1.45 (d d d , 1H , J = 13.7, 3.7, 2.0, 4 -H ), 1.62 (m , 1H , 5 -H ), 1.70 (m , 1H , 3 -H ), 1.97 (d d d , 1H , J = 13.7, 3.7, 2.0, 4 -H ), 2.09 (d d d , 1H , J = 14.7, 7.1, 3.7, 5 -H ), 2.25 (d d d , 1H , J = 11.5, 6.5, 2.8, 2 -H ), 2.32 (m , 1H , 6-H ), 2.38 (m , 1H , 6- H ), 2.70 (m , 1H , O H ), 3.71 (m , 1H , 14 -H ), 3.85 p p m (m , 1 H , 14-H ).
B io a ssa y
T h e g ro w th o f le ttu c e se e d lin g s tr e a te d w ith th e c o m p o u n d s w as e x a m in e d b y th e e s ta b lish e d m e th o d [4], T h e h y p o c o ty l a n d r o o t le n g th s o f th e se ed lin g s a f te r tr e a tm e n t w e re m e a s u re d a n d c o m p a r e d w ith th e v a lu e s fo r a n u n tr e a te d c o n tro l.
B io a ssa y w as p e r f o rm e d th r e e tim e s a n d th e m e a n v a lu e s a re sh o w n in Fig. 2.
A c k n o w le d g e m e n ts
W e w ish to th a n k D r F. S u g a w a ra (R IK E N , T h e I n s titu te o f P h y sica l a n d C h e m ic a l R e se a rc h , Sai- ta m a ) fo r MS. T h is w o rk w as s u p p o r te d in p a r t by a G ra n t-in -A id fo r E n c o u r a g e m e n t o f Y o u n g S cie n tists fro m th e M in istry o f E d u c a tio n , S cience, S p o rts, a n d C u ltu re (N o. 10760073) to A . S., a n d by th e P la n t S c ie n c e R e s e a r c h F o u n d a tio n o f th e F acu lty o f A g ric u ltu re , K y o to U n iv e rs ity to Y. K..
[1] Y. Kimura, T. Mizuno, A. Shimada, Tetrahedron [3] W. Dalziel, B. Hesp, K. M. Stevenson, J. Chem. Soc.,
Lett. 38. 469 (1997). Perkin Trans. I 2841 (1973).
[2] Y. Kimura, T. Mizuno, A. Shimada, T. Kawano, Phy- [4] B. Frankland, P. F. Wareing, N ature 185. 255 (1960).
tochem. 47, 323 (1998).
