np020154n.beech root phenolics.pdf

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Five New Phenolics from the Roots ofF i c u s b e ec h e ya n a

Tzong-Hu ei Lee, Yuh-Chi Kuo, G uei-J ane Wa ng, Yueh-Hsiung Kuo, Chi-I Chang, Chung-Kung Lu,| a n dChing -Kuo Lee*,|

I n st i t ut e of B ot any, A cademi a S i n i ca, Nank ang, Tai pei , T ai wan 115, Nat i onal Research I nst i t ut e of Chi n ese Medi ci ne,

S hi h-P ai , Tai pei , Tai wan 112, Depart ment of Chemi st ry, Nat i onal Tai wan Uni versi t y, Tai pei , Tai wan 106, S chool of

P harm acy, Tai pei M edi cal Un i versi t y, No. 250, Wu-Hsi ng S t . , Tai pei 110-31, Tai w an, and S hu Zen Col l ege of Medi ci ne &

M anagement , K aohsi un g, Tai w an 821, Republ i c of Chi na

Received April 10, 2002

From the ethanolic extract of the roots of Ficus beecheyana, threo-2,3-bis(4-hydroxy-3-methoxyphenyl)-3-ethoxypropan-1-ol (1), erythro-2,3-bis(4-hy dr oxy-3-met hoxy phen yl)-3-eth oxypr opan -1-ol (2), t r a n s -4,5-bis(4-hyd roxy-3-meth oxyphenyl)-1,3-dioxacyclohexa ne (3), threo-3-(4-hydroxy-3,5-dimethoxyphenyl)-3-eth oxypropan e-1,2-diol (4), 2,3-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone (5), a nd 3-hydr oxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone (6) were isolated. The stru ctures of the new compounds1-5 were elucidated by the analysis of their spectroscopic data.

Ficus beecheyanaH ook. & Arn. (Mora ceae) is a semide-ciduous tree with br own, tomentose bran ches and is w idelydis t r ibut ed in ea s t A s ia , es pecia lly in m a inla nd China ,Hong Kong, Vietnam, a nd Taiw an .1 Its r hizomes ha ve longb e e n u s e d a s a f o l k m e d i c i n e t o t r e a t r h e u m a t i s m a n d

d i a b et e s , a n d a s a c a r m in a t i v e,2 but no phyt ochemica lstudies ha ve been car ried out on this plant part . The rootsof F. beecheyana a re clos ely rela t ed t o t he rhizomes a nda g a i n h a v e n ot b ee n i n ve st i g a t e d p h y t och e m ic a ll y . Achemical investiga tion on an etha nolic extra ct of the rootsof F. beecheyanaw a s t h u s u n d er t a k e n a n d h a s l ed t o t h eisolation and characterization of five new phenolics (1-5)along w ith one known compound (6). This report describest he is ola t ion a nd s t ruct ura l elucida t ion of t he new com-pounds.

The etha nolic extra ct from t he roots ofF . beecheyanaw a ssuspended in H 2O and then partit ioned sequentially usingn-hexane, CH Cl 3, a nd n-BuOH. The CHCl3-soluble fractionwas then subjected to silica gel flash column chromatog-

raphy and HP LC t o give five new phenolics (1-5), t ogetherwit h one kn own compound , 3-hyd roxy-1-(4-hyd roxy-3,5-dimet hoxypheny l)-1-propan one (6).3

Compound 1 w a s is ola t ed a s a n a morphous pow der. Apseudomolecular ion of m/z272.1042, revealed by HRE IMS ,led to its elementa l formula , C 16H 16O4, consistent with t heelimination of -C H 2O H a n d -OC H 2C H 3 u n i t s f r om t h emolecule. I t s I R a bs orpt ion ma xima a t 3412, 1605, a nd1516 cm-1 an d a U V absorption peak at 280 nm suggestedthe presence of an oxygenat ed ar omatic ring. The 1H NMRspectrum (Table 1) of 1 exhibit ed t w o s et s of A B X-t ypesignals [H 6.29 (1H, br s), 6.48 (1H, br d, J) 8.1 Hz); 6.71(1H, d , J ) 8.1 Hz); H 6.51 (1H, br d, J ) 8.2 Hz), 6.52(1H, br s), and 6.69 (1H, d, J ) 8.2 Hz)] an d t wo meth oxys ig n a l s [H 3 .68 a n d 3.72], indica t ing t ha t 1 ha s t w oguaiacyl groups.4 In the aliphatic region, ABMX-type andethoxyl signals [H 2.98 (1H, ddd, J) 8.8, 8.8, 3.8 H z, H -2),3.83 (1H, dd, J ) 10.9, 3.8 Hz, H a -1), 4.15 (1H, dd, J )10.9, 8.8 Hz, H b-1), and 4.39 (1H, d, J ) 8.8 Hz, H-3); 1.19 (3H, d d, J ) 7.0, 7.0 Hz), 3.34 (1H , m), a nd 3.40 (1H,

m)]w ere observed. Among 19 13 C NMR signals, 12 aromatics ig n a l s (s i x C a n d s ix C H ; w i t h f ou r 1 ,2 -d i ox y g en a t e dc a r b o n s a t C 144.3, 144.9, 146.2, an d 146.3) a nd tw ophenolic met hyl s igna ls (C 55.8, 55.9) (Table 2) w erepresent. The rema ining five aliphat ic signa ls included three

oxygena t ed ca rbons [C 64.3 (CH 2), 66.9 (CH 2), and 87.9(CH)], one C H 3(C 15.3), and one CH (C 54.8). The signala t H 2.98 (C-2 resonated at C 54. 8) w a s a s s igned t o abenzylic met hine prot on due t o HB M C correla t ions w it hC-1, C-3, C-1, C-1, C -2, and C-6. The proton resonatingat lower field at 4.39 (H-3) wa s considered a s being linkedw it h a n et hoxyl group a nd a gua ia cyl group. The H-3 (4.39) resonance exhibited correlations with C-1, C-2, C-1 ,C -2, C-6, C-1, a n d C - 1 i n t h e H M B C s p e c t r u m a n dh e lp ed t o con f ir m t h e a s s i gn e d p a r t i a l s t r u ct u r e. Th eNOESY s pect rum revea led mut ua l correla t ions bet w eenH 3-7/H -2a nd H 3-7/H -2. These correlat ions permitted thestructural assignment of 1 a s 2,3-bis(4-hy dr oxy-3-met hox-ypheny l)-3-ethoxypropa n-1-ol. Compa rison of th e coupling

con s t a n t b et w e en H -2 a n d H -3 (J2,3 )

8 . 8 H z ) w i t hpublished data of related phenolic isomers provided evi-dence for t he det ermina t ion of t he threo configura tion ofthe C -2 and C-3 substituents. 4,5 Additionally, t he chemicalshifts of C-1, C-2, C-3, H-2, and H-3 of 1 w e r e a l s o i na ccorda nce w it h t hos e of threo-2,3-bis(4-hydroxy-3-meth-oxyphenyl)-3-met hoxypropan -1-ol isolat ed from A r a l i a b i - p i n n a t a .5 Thus, 1 w a s con cl u de d t o b e threo-2,3-bis(4-hy droxy -3-met hoxyph enyl)-3-eth oxypropa n-1-ol. To ourknowledge, compound 1 ha s been is ola t ed from a na t ura lsource for t he first t ime, alth ough this compound h as beens ynt hes ized by Gellerst edt a nd Agnemo, but t he s pect ra ld a t a of 1 were not included in their report. 6

Compounds 2a nd 3 w ere is ola t ed a s a mixt ure. Thismixt ure w a s a cet yla t ed us ing pyridine a nd A c2O, t hen t he

products were subjected to a normal-phase HPLC separa-t i on t o y i el d t h e ir p er a c et y l a t e d d e ri va t i v es 7 a nd 8,respectively. Compound 7 w a s obt a ined a s a n a morphousp ow d e r , a n d i t s m o l ecu l a r f or m u l a w a s d e t er m i n ed a sC 25H 30O9 b y t h e H R E I M S d a t a a n d f r o m i t s 13C N M Rs pect rum. I t s 1H NMR spectrum (Table 1) exhibited twosets of acetyl guaia cyl groups [H 6.58 (1H, d, J ) 1.4 Hz),6.63 (1H, dd, J ) 8.1, 1.4 Hz), 6.85 (1H, d, J ) 8.1 Hz),3.67 (3H, s ), an d 2.26 (3H, s);H 6.40 (1H, d , J ) 1.4 Hz),6.66 (1H, dd, J ) 8.0, 1.4 Hz), 6.89 (1H, d, J ) 8.0 Hz),3.57 (3H, s), and 2.26 (3H, s)], a 1,2,3,3-tetrasubstitutedpropane group [H 3.10 (1H, d dd, J) 7.5, 7.0, 4.3 H z, H -2),

* To wh om correspondence sh ould be a ddressed. Tel: 886-2-27361661.Fa x: 886-2-23638146. E-mail: cklee1962@ya hoo.com.tw .

Ins t i t u t e o f B o t a ny , Ac a de m ia S i ni ca . National Research Insti tute of Chinese Medicine. D e p a r t m e nt o f C he m i s t r y , N a t i o na l Ta i wa n U ni v e r s it y . Shu Zen College of Medicine & Management.| School of Pharmacy, Taipei Medical University.

1497J . N a t . P r od . 2002, 65 , 1497-1500

10.1021/np020154n CC C: $22.00 2002 American Ch emical Society a nd American S ociety of Pha rma cognosyP ubli she d on Web 08/16/2002


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4.30 (1H, dd, J ) 11.0, 7.0 Hz, H a -1), 4.53 (1H, dd, J )

11.0, 7.5 H z, H b-1), 4.56 (1H, d, J ) 4.3 Hz, H -3), a nd 2.00

(3H, s ); t he cons ecut ive prot ons w ere revea led from t heCOS Y spectrum ], an ethoxyl group [1.19 (3H ), 3.26 (1H ,

m), and 3.41 (1H, m)], a nd a n a cetyl group [H 2.00 (s)]. Itpossessed spectr oscopic da ta closely compa ra ble wit h th ose

of1 except for having t hree acetoxyl groups instead of thr eeh y d r ox y l g r ou ps . I t s h ow e d a s m a l l cou p li n g c on s t a n t

between H -2 and H-3 (J2,3 ) 4.3 Hz), revealing a n erythro

configurat ion in contra st to the thr eoconfigura tion signals

b et w e e n H -2 a n d H -3 (J2,3 ) 8.8 Hz) observed for 1.7,8

Therefore, the structure of 7 w a s e st a b l i sh e d a s erythro-2,3-bis(4-a cetoxy-3-met hoxyph eny l)-3-eth oxypropa n-1-ol a c-

et a t e.

Ana lys is of t he HR EI M S , DEP T, a nd 13C NMR spectra

of 8 ga ve a molecula r formula of C22H 24O8, indica t ing 11

indices of hydrogen deficiency. The IR absorption bandsa t 16 05 a n d 1 50 7 c m-1 s u g ge st e d t h e p r es en ce of a naromatic functionality. The 1H NMR spectrum (Table 1)revealed partia l structural chara cteristics such as a romaticprot on s igna ls [ 6.62 (br s), 6.64 (br d), and 6.83 (d); 6.34 (br s), 6.66 (br d), and 6.90 (d)], two phenolic acetylgroups ( 2.24 an d 2.25), a nd tw o phenolic methyl groups( 3 .64 a nd 3.65). The NOESY s pect rum of 8 showedcorrelat ions betw een 6.34 (br s)/3.65 (OC H 3) a n d 6.62(br s)/3.64 (OCH 3), revealing the relative positions of thet w o s u bs t i t u en t s i n t h e p h en y l g r ou p w h i ch cou l d b eestablished as an acetyl guaiacyl unit . The residual struc-t ura l unit s included t w o oxygena t ed m et hylenes (C 94.1,an d 71.2), tw o methines (C83.9, a nd 49.6), a nd t wo oxygena t oms . The rema ining index of hydrogen deficiency w a sconsistent wit h t he presence of a 1,3-dioxacyclohexane unit,a nd t he s igna l a t C 94.1 wa s a ssigned to a m ethylenedioxycarb on. The contig uous seq uence of H -4, -5, a nd -6 (Ta ble1 ) w a s r e ve a l ed f r om C O S Y c or r e la t i on s . I n a H M B Cexperiment, correlations between H-4 and C-2, -5, -6, -1 ,-2, -6, -1 a nd H-5 a nd C-4, -6, -1, -1, -2, -6 w ereobserved. Therefore, the stru cture of 8 wa s assigned as 4,5-bis(4-a cetoxy-3-met hoxyph eny l)-1,3-dioxa cyclohexa ne. Thestereochemistry of8 w a s es t a blis hed by a combina t ion of

ob s er v ed c ou pl in g c on s t a n t s a n d d a t a f r om i t s N O E S Yspectrum . The H-4 signa l wa s assign ed to a benzy lic protonwith an axial orientat ion due to the la rge coupling consta nt( 4.59, d, J ) 9.6 Hz) with H-5 ( 3.05). The H-5 protonw a s l inked t o a met hylene (H 2-6) group from its couplingcons t a nt s (J ) 11.2, 9.6, 4.5 Hz). The NO ES Y spectru m of8 showed correlations between H-5 and H eq-6, H a x-6 andH a x-2, and H-4 and H a x-2 (as in t he chair conformat ion of8). Th e se d a t a w e r e s u p por t i v e of h a v i n g t h e t w o a r y lg r ou p s b ot h i n t h e e q u a t or i a l or i en t a t i o n . Th e r ef or e ,compound 8 w a s a s s i g n e d a s t r a n s -4,5-bis(4-a cet oxy-3-methoxyphenyl)-1,3-dioxacyclohexane.

Compound 4, o b t a i n ed a s a n a m o r ph ou s p ow d e r , w a sa s s i gn e d i n i t s 13C N M R s pe ct r u m 1 3 c a r b on s ig n a l s

including t w o oxygena t ed met hylenes (C 62.4 and 64.3)(Table 2), two methoxyls (C56.3 2), one meth yl (C15.3),t w o ox y g en a t e d m e t h in e s (C 7 5. 4 a n d 8 2. 6), a n d s ixa roma t ic ca rbons (C 103.9 2, 129.4, 134.6, 147.2 2 ).I n t h e 1H NM R s pect rum, t w o s inglet phenyl prot ons (6.54), two phenolic methyl groups ( 3 . 87, 6H), a nd a nexcha ngeable phenolic proton ( 5.50) suggested the pres-ence of a 4-hydroxy-3,5-dimethoxyphenyl moiety. A NOESYcorrelat ion betweenH 6.54 an d 3.87 indicated the presenceof a syringyl group. An ethoxyl group attached to a chiralcarbon was revealed from the 1H NM R [H 1.18 (3H, t , J)7.0 Hz), 3.33, 3.44 (each 1H, m)] and 13C N M R (C 15.3a n d 6 4. 3) d a t a . A d o ub le t s i gn a l a t H 4.19 (1H , H-3)showed a HMB C correlation with C 64.3 (-OCH 2C H 3) a ndNOESY correla t ions w it h s igna ls a t H 3.33 and 3.44, and

t h i s w a s a s s i g n e d a s g e m i n a l t o a n e t h o x y g r o u p . T h econtiguous protons to H-2 [ 3.68 (1H, ddd, J ) 8.2, 4.5,3.2 Hz)] an d t hen t o H-1 [3.35 (1H, dd, J ) 11.8, 4.5 H z)and 3.55 (1H, dd, J ) 11.8, 3.2 Hz)] were established fromt h e C O S Y s pe ct r u m . F u r t h er m or e , t h e l a r g e c ou pl in gconsta nt betw een H-2 and H -3 (J) 8.2 Hz) revealed a threoconfiguration.9 The aryl group in 4 w a s loca t ed a t C-3 onthe basis of the HMB C correlat ions of H-3/C-1, -2, a n d-6. H ence, 4 w a s det ermined t o be thr eo-3-(4-hydroxy-3,5-dimethoxyphenyl)-3-ethoxypropane-1,2-diol.

Compound 5 w a s a s s i gn e d a m ol ecu l a r f or m u la ofC 11H 14O6by HREI MS, two carbons and six hydrogen atomsl e s s t h a n 4. I t s I R s pect rum indica t ed t he pres ence ofhyd roxyl (3431 cm-1), aroma tic (1605 and 1516 cm-1), an d

1498 J ou r n al of N at u r al Pr od u ct s, 2002, V ol . 65, N o. 10 N ot es
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conjugat ed carbonyl (1667 cm-1) groups. Besides signalsfor a 3,5-dimethoxy-4-hydr oxyphenyl unit , the rema iningt hree ca rbon s igna ls w ere one conjuga t ed ca rbonyl (C197.4) and tw o oxygenat ed carbons (C 65.9 and 74.0). TheU V peak at 287 nm a lso confirmed the presence of a 3,4,5-trioxygenated benzoyl group.10 Comparison of the 13C NMRd a t a o f 5 w it h t hos e of 4 revea led t ha t t he et hoxyl groupin 4 was replaced by an oxo function (C 197.4) (Table 2).Therefore, 5 w a s a n 1-o xo a n a l o g ue of 4. Th e H M B Cspectrum of 5displaying correlat ions betw een C-1/H 2-1,

H-2, H -2, a n d H - 6 w a s s upport ive of t his conclus ion.Consequently, 5 wa s esta blished as 2,3-dihydroxy-3-(4-hyd roxy-3,5-dimet hoxypheny l)-1-propanone.

Experimental Section

General Experimental Procedures. Optical rotationswere mea sured using a J ASCO DIP -180 digital spectropola-rimeter. UV spectra were measured in MeOH on a Shima dzuU V-1601PC spectrophotometer. The IR spectra were r ecordedon a Nicolet 510P FT-IR spectrometer. The NMR spectra wererecorded in CDCl3 a t r oom t e m pe r at ur e on a B r uke r DM X -

500 SB spectrometer, and t he solvent resonance was used asi nt er nal shi ft r e fe r enc e (TM S as st and a r d ). The 2D NM Rspectra were recorded using sta ndar d pulse sequences. EIMSand H R E I M S w e r e r e cor de d on a Fi nnig an TS Q -700 a nd aJ EOL S X-102A spectromet er, respectively. TLC wa s performedusing si l ica gel 60 F254 plates (200 m , M e r c k). H P L C w asperformed using a Hichrosorb Si 60 (10 m) column (250 10 mm).

Plant Material. The roots of F . beecheyana were collectedat Nankang in north Taiwan in J une 1999 and were identifiedby Mr. Chii-Cheng Liao of the Department of Botany, NationalTaiwan University. Voucher specimens (No. 19990615) havebeen deposited a t C hung Hw ai C ollege of Medical Technology,Tainan, Taiwan.

Extraction and Isolation. The dried crude EtOH extract

of the roots of F. beecheyana (12 kg) was a gift from Dr. An-P a ng L i n, J e n-Ai C hi nese M ed i cal Uni t e d C l ini c, Tai pei ,Taiwan. The ethanolic extract (81 g) was suspended in H 2O(500 mL) and then parti t ioned sequential ly using n-hexane,C H C l3, and n-B uOH (500 mL 3). The CHCl3-soluble fractionwas evaporated under a vacuum to give an oily residue (39 g),wh ich wa s chromat ograph ed over silica gel 60 (230-400 mesh)and e lut e d se q ue nt ial l y w i t h n-hexane-EtOAc (5:3), n-hex-a ne-EtOAc (5:7), and EtOAc to give subfractions I , II , andIII , respectively. Subfra ction I wa s purified by using t he samecolumn with n-hexane-Et OAc (1:5) as eluent to yield 1 (26mg) and a mixture of 2 a nd 3 (4 mg). The mixture of 2 a nd 3was dissolved in pyridine (3 mL) and Ac 2O (3 m L ) and l ef tovernight at room temperature. Then, the reaction mixturew a s pour e d i nt o i ce w at e r (30 m L ) and st i r r ed for 1 h. Theresultant suspension wa s extracted with ethyl a ceta te (30 mL

Table 1. 1H NMR Data for Compounds 1, 4, 5, 7, a n d 8 (CDCl3, 500 MHz)a

position 1 4 5 7 8

1 3.83 dd (10.9, 3.8) 3.35 dd (11.8, 4.5) 4.30 dd (11.0, 7.0)4.15 dd (10.9, 8.8) 3.55 dd (11.8, 3.2) 4.53 dd (11.0, 7.5)

2 2 .9 8 d d d (8 .8 , 8 .8, 3 .8 ) 3 .6 8 d d d (8 .2 , 4. 5, 3 .2 ) 5 .1 0 d d (5. 4, 3 .4 ) 3 .1 0 d d d (7 .5 , 7 .0 , 4 .3 ) 4 .9 7 d (6. 5)5.31 d (6.5)

3 4.39 d (8.8) 4.19 d (8.2) 3.70 dd (11.6, 5.4) 4.56 d (4.3)3.99 dd (11.6, 3.4)

4 4.59 d (9.6)5 3.05 ddd (11.2, 9.6, 4.5)

6 3.98 dd (11.2, 11.2)4.24 dd (11.2, 4.5)2 6.52 br s 6.54 s 7.20 s 6.40 d (1.4) 6.62 br s5 6.69 d (8.2) 6.89 d (8.0) 6.83 d (8.0)6 6.51br d (8.2) 6.54 s 7.20 s 6.66 dd (8.0, 1.4) 6.64 br d (8.0)7 3.72 s 3.87 s 3.94 s 3.57 s 3.64 s8 3.87 s 3.94 s1 3.33 m

3.44 m2 6.29 br s 1.18 t (7.0) 6.58 d (1.4) 6.34 br s5 6 .71 d (8.1) 6.85 d (8.1) 6.90 d (8.3)6 6.48 br d (8.1) 6.63 dd (8.1, 1.4) 6.66 br d (8.3)7 3.68 s 3.67 s 3.65 s1 3.34 m 3.26 m

3.40 m 3.41 m2 1.19 dd (7.0, 7.0) 1.11 dd (7.0, 7.0)C H 3C O- 2.00 s 2.24 s

2.26 s 2.25 s2.26 s

a Signals without mult iplicity were assigned from the COSY or HMQC spectrum.

Table 2. 13C NMR Data for Compounds 1, 4, 5, 7, a n d 8(CDCl3, 125 MHz)a

position 1 4 5 7 8

1 66.9 t 62.4 t 197.4 s 65.0 t2 54.8 d 75.4 d 74.0 d 51.6 d 94.1 t3 87.9 d 82.6 d 65.9 t 81.1 d 83.9d45 49.6d6 71.2 t1 132. 4 s 129.4 s 124.7 s 139. 1 s 139.2 s2 109. 4 d 103. 9 d 106. 0 d 111. 0 d 110. 8 d3 146. 3 s 147.2 s 147.1 s 139. 0 s 138.0 s

4 144. 9 s 134.6 s 140.9 s 150. 8 s 150.6 s5 113. 7 d 147.2 s 147.1 s 122. 1 d 122.2 d6 120. 3 d 103. 9 d 106. 0 d 119. 1 d 118. 8 d7 55.9 q 56.3 q 56.6 q 55.8 q 55.9 q 8 56.3 q 56.6 q 1 131.2 s 64.3 t 136.2 s 135.9 s2 111.6 d 15.3 q 114.1 d 113.6 d3 146.2 s 138.9 s 138.9 s4 144.3 s 150.3 s 151.0 s5 114.2 d 121.9 d 122.7 d6 120.6 d 121.6 d 119.6 d7 55.8 q 55.8 q 55.9 q 1 64.3 t 64.7 t2 15.3 q 15.1 q CH 3C O- 20.6 q 20.6 q

20.6 q 20.6 q 20.9 q

C H 3CO- 1 68. 9 s 17 1. 7 s1 68. 9 s 17 1. 7 s171.0 s

a Multiplicit ies w ere obtained from DE PT experiments.

N ot es J ou r n al of N at u r al P r od u ct s, 2002, V ol . 65, N o. 10 1499


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2). The e t hy l ac e t at e l ay e r w as w a she d w i t h 1 N H C l , 3%aq ue ous NaH C O3, and t he n b r i ne w at e r , se q ue nt i al l y . T heorganic layer wa s purified on si l ica gel chromat ography w ithn-hexane-EtOAc (2:1) as eluent to yield the pure peracety-lated derivatives 7 (3 mg) and 8 (2 mg). Subfraction II waspurified by using the same chromatographic procedure withn-hexane-EtOAc-C 6H 6 (2:20:1) as eluent to give 6 (7 mg).Subfra ction II I w as purified by using silica gel chromat ographyw i t h n-hexane-EtOAc-Me 2CO (1:20:2) as eluent to afford 4(3 mg) an d 5 (10 mg).

t h r e o -2,3-Bis(4-hydroxy-3-methoxyphenyl)-3-ethoxypro-

pan-1-ol (1): amorphous white powder; [R]25D +16 (c 0.13,C H C l3); IR (KBr )ma x 3412, 1605, 1516, 1377, 1264 cm -1; U V(MeOH) ma x (log ) 280.2 (3.39) nm; 1H a n d 13C N M R d a t a ,see Tables 1 a nd 2; E IMS m/z272 [(M - C 3H 8O2)]+ (16), 181(100), 167 (17), 149 (43), 137 (9); HREIMS m/z[M - (C 3H 8O2)]+

272.1042 (calcd for C 16H 16O4 272.1049).t h r eo-3-(4-Hydroxy-3,5-dimethoxyphenyl)-3-ethoxypro-

pane-1,2-diol (4): amorphous white powder; [R]25D +28 (c0.10, CHC l3); IR (KB r)ma x3420, 2930, 1612, 1518, 1460, 1329,1215, 1115 cm-1; UV (MeOH) ma x (log ) 271 (3.59) nm; 1Ha n d 13C NMR da ta , see Tables 1 and 2; EIMS m/z272 (M+, 3),226 (2), 211 (100), 196 (3), 183 (10), 167 (35), 123 (12); HREIMSm/z 272.1250 (calcd for C 13H 20O6 272.1260).

2,3-Dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone (5): am or phous w hi t e pow d er ; [R]25D 0 (c 0.5,C H C l3); IR (KBr) ma x3431, 2928, 2855, 1667, 1605, 1516, 1464,

1423, 1271, 1119, 1034 cm-1; UV (MeOH)ma x(log ) 286 (3.61)nm; 1H a n d 13C NMR da ta , see Tables 1 and 2; EIMS m/z24 2(M+, 4), 212 (8), 196 (4), 181 (100), 153 (13), 137 (7); HREIMSm/z 242.0791 (calcd for C 11H 14O6 242.0790).

er yt h r o-2,3-Bis(4-acetoxy-3-methoxyphenyl)-3-ethox-ypropan-1-ol acetate (7): amorphous powder; [R]25D -14(c0.14, CH Cl 3); IR (KBr) ma x 2973, 1767, 1740, 1605, 1510,1370, 1198, 1034 cm-1; UV (MeOH)ma x(log ) 279 (3.48) nm;1H a n d 13C NMR da ta , see Tables 1 and 2; EIMS m/z474 (M+,2), 272 (3), 232 (88), 181 (100), 153 (21), 135 (5), 93 (10);H R E I M S m/z 474.1883 (calcd for C 25H 30O9 474.1890).

t r a n s -4,5-Bis(4-acetoxy-3-methoxyphenyl)-1,3-dioxacy-clohexane (8): a m or phous pow d e r ; [R]25D -46 (c 0.08,C H C l3); IR (KBr ) ma x2924, 2853, 1761, 1605, 1507, 1372, 1198,1028 cm-1; U V (MeOH)ma x (log ) 273 (3.35) nm ; 1H a n d 13CNM R d at a , se e Tab l e s 1 and 2; E I M S m/z 416 (M+, 36), 374(68), 253 (93), 239 (62), 225 (68), 211 (90), 197 (100); HREIMSm/z 416.1489 (calcd for C 22H 24O8 486.1471).

Acknowledgment. This research wa s supported by gra nt

from the National Science Council of the Republic of China

(NSC 89-2320-B -273-006). We a re gr a teful to D r. An-Pa ng L infor his kind help in the plant collection and extraction. We

al so t hank M s. S hou- L i ng H uang and S hu- Yun S un for t he

N M R d a t a a c q u is it i on a n d H R E I M S m ea s u r em en t i n t h e

Instrumentation Center of the College of Science, National

Taiwan University.

References and Notes

(1) H u a ng , T. C . , Ed. F l o r a o f T a i w a n ; National Science Council of theRepublic of C hina: Taipei , 1996; Vol. 2, p 154.

(2) Chiu, N. Y.; Chang, K. H. TheIllustr ated Medicinal Plants of Taiwan;SMC Pu blishing Inc.: Taipei , 1992; Vol. 3, p 40.

(3) N a ka s o ne , Y . ; Ta ka r a , K . ; W a da , K . ; Ta na ka , J . ; Y o g i, S . Biosci.Biotech. Biochem. 1996, 6 0, 1714-1716.

(4) Yoshikawa , K.; Mimura, N.; Arihara , S.J. Nat. Pr od. 1998, 61, 1137-1139.

(5) Hsiao, J .-J .; C hian g, H .-C. Phytochemistry 1995, 3 9, 899-902.(6) Gellerstdt , G .; Agnemo, R. Acta Chem. Scand. B1980, 3 4, 461-462.(7) Fa ng, J .-M.; Lee, C.-K.; Cheng, Y.-S. Phytochemistry1992, 31, 3659-

3661.(8) To fe r n, B . ; J e net t -S ie m s , K. ; S i e m s , K. ; J a ku p ov i c, J . ; Ei c h, E.

Phytochemistry 2000, 5 3, 119-128.(9) Kikuzaki, H.; Hara, S.; Kawai , Y.; Nakatani , N.Phytochemistry1999,

52, 1307-1312.(1 0) S i l ve r st e in , R . M . ; B a s s le r , G . C . ; M or r i ll , T. C . Spectrometric

Identif ication of Or ganic Compounds, 5th ed.; J ohn Wiley & Sons:New York, 1991; p 309.

NP020154N

1500 J ou r n al of N at u r al Pr od u ct s, 2002, V ol . 65, N o. 10 N ot es

np020154n.beech root phenolics.pdf

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