75

Chapter 3

Chemical studies of the rhizomes of

Curcuma caesia Roxb.

76

Chapter 3

Chemical studies of the rhizomes of Curcuma caesia Roxb.

3.1. Introduction

Curcuma caesia Roxb. (Black Tumeric) belongs to Zingiberaceae family. It is a

perennial herb of distinguishable bluish-black rhizome with a bitter and pungent

smell.1 It is widely cultivated as a medicinal plant in South East Asian countries.

The rhizomes of this plant are used as stimulants, anti-diarrheal, diuretic, anti-

emetic, wound cleaner and skin disorder in India.2 The rhizomes of this plant

were used in traditional medicines.3, 4 The plant was also used as a carminative

and for the treatment of headaches, rheumatic pains as well as being a stimulant.5-

7 The essential oil of this plant possessed antifungal activity.8, 9 The antimicrobial

efficacy of essential oil from this plant has also been reported.10 Leaves of this

plant yielded 0.8% oil. Fourteen constituents of the oil from the leaves were

identified; the major components were 1,8-cineole (27%), camphor (16.8%),

borneol (8.7%), -terpineol (5.2%) and -pinene (6.3%).11 The rhizome oil of this

plant contains 76.6% -camphor; it was also reported that rhizome oil of C.

caesia contained 1,8-cineole (9.06%), ocimene (15.66%), 1-ar-curcumene

(14.84%), -camphor (18.88%), -linalool (20.42%), -borneol (8.7%) and

zingiberol (12.60%).12 The volatile rhizomes oil of this plant was analysed by

GCMS, which resulted in the identification of 30 components, representing

97.48% of the oil, with camphor (28.3%), ar-turmerone (12.3%), (Z)- -ocimene

(8.2%), ar-curcumene (6.8%), 1,8-cineole (5.3%), -elemene (4.8%), borneol

77

(4.4%), bornyl acetate (3.3%) and -curcumene (2.82%) as the major

constituents.13 All the earlier reports have focused on the isolation of essential

oils from the leaves and rhizomes of C. caesia. Herein, the isolation and

characterization of sesquiterpenoids from the rhizomes of this plant are reported.

3.2. Results and Discussion

The present study describes the isolation and structural determination of

the constituents isolated from the rhizomes of the plant. The chloroform extract

was fractionated by column chromatography with silica gel 60-120 mesh (Merck)

to afford compounds 1-11 (figure 1).

O

O

O

O

O

O

O

1 2 3

O O

O OO

4 5 6

O

HO

OO

H

O

H

OH

7 8 9

O

O

O

O

O

O

O

O

2

OO

HO

HOHOOH

10 11

Figure 1. The structures of compounds 1-11

78

Compound 1 was isolated as a crystalline solid, m.p.149-150OC, and the

molecular formula was determined as C15H18O3 by the presence of a

pseudomolcular ion [M+H]+ at m/z 247.1332 in its TOF-MS (figure 2). The IR

spectrum (figure 3) of compound 1 exhibited absorption bands at 166.52 cm-1 due

to an , -unsaturated ketone. Its 1H NMR spectrum (figure 4) showed signals

due to three methyl protons at 1.34, 1.61 and 2.12 (Table 1). The spectrum

exhibited characteristic signals at 7.09 due to methine proton for a trisubstituted

furan ring and at 5.50 (dd, J=4 Hz, 12 Hz) due to vinylic proton. The 13C NMR

and DEPT spectra (figures 5 and 6) of 1 showed the presence of 15 carbon atoms,

a ketonic signal at 192.24, two oxygenated carbons at 64.01 and 66.54, three

methine, three methylene and three methyl groups (Table 1). The complete 1H-1H

COSY confirmed the structure of zederone14,15 which was reported to be found in

many species of Zingiberaceae family.16-21

79

Fig

ure

2. M

ass

Spe

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Fig

ure

3. I

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of

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d1

400

600

800

1000

1400

1800

2200

2600

3000

3400

1/cm

2030405060708090100

%T

2937.38

2474.50

2362.64

1662.52

1523.661460.01

1400.221369.37

1330.791232.43

1137.92

1020.27929.63864.05

808.12769.54

680.83607.54

576.68

466.74

pp02

81

Fig

ure

4.1 H

NM

R S

pect

rum

of

com

poun

d1

82

Fig

ure

5.13

C N

MR

Spe

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m o

f co

mpo

und

1

83

Fig

ure

6.13

C D

EP

T S

pect

rum

of

com

poun

d1

84

Fig

ure

7.1 H

-1H

CO

SY

Spe

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m o

f co

mpo

und

1

85

The structure of 1 was also confirmed by its direct conversion from

furanodienone, 3. The purity of the isolated compound 1 was found to be about

(99.12-99.54)% based on area normalization method. Its structure was elucidated

by spectroscopy, various NMR experiments, i.e., 1H NMR, 13C NMR, DEPT-

135, COSY, Electrospray Mass spectrometry and IR. It is the first report for the

isolation of zederone from C. caesia and to report the X-ray analysis.

The molecule of compound 1 having molecular formula C15H18O3 adopts a

folded conformation with the two methyl groups C8 and C13 occupy the axial

positions (figure 8). The furan ring adopts a twist conformation and the two rings

are cis fused.

Figure 8. An ORTEP view of a crystal structure of compound 1

Second Harmonic Generation (SHG) efficiency of the compound 1 was found to

be higher than that of KDP. It is the first report for the structure- nonlinearity

relationship of zederone from the rhizomes of C. caesia.

The physicochemical properties of glechomanolide(2), furanodienone(3),

germacrone(4), germacrane4,5-epoxide(5), isofuranodienone(6), curzerenone(7),

86

curcumenone(8), curcumenol(9) were confirmed by comparing with the

published data.22-31

Compound 10, white solid, m.p. 62-64oC, []20D -18.94, (c 10

percent chloroform), optical density - 0.01, was isolated from the

chloroform extract by elution with 2% EtOAc in petroleum ether and was

found to be an acyclic terpenoid ester, C32H54O12. IR spectrum (figure 9) of

10 showed characteristic absorption bands at 2918, 2849, 1734, 1462, 1177,

957, 920, 723 cm-1. The 1H-NMR (400MHZ, CDCl3) spectrum (figures 10

& 11) showed the presence of a triplet at H 4.05 (OCH2), a triplet at H 2.29

(CH2), a multiplet at H 1.61 (CH2) and methyl protons as triplet at H 0.88.

The 13C-NMR (100MHZ, CDCl3) spectrum (figures 12-15) showed peaks at

C 14.1, 22.7, 25.0, 29.5, 31.9, 34.4, 64.4 and 174.1.

O

O

O

O

O

O

O

O

2

Compound 10

87

Fig

ure

9.IR

Spe

ctru

m o

f co

mpo

und

10

88

Fig

ure

10.1

H N

MR

Spe

ctru

m o

f co

mpo

und

10

89

Fig

ure

11.1

H N

MR

Spe

ctru

m o

f co

mpo

und

10

90

Fig

ure

12.1

3 C N

MR

Spe

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m o

f co

mpo

und

10

91

Fig

ure

13.1

3 C N

MR

Spe

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m o

f co

mpo

und

10

92

200 180 160 140 120 100 80 60 40 20 0 ppm

14.1222.6925.0425.9428.6529.1629.2729.3729.7031.9334.4364.41

NAME PP-01EXPNO 3PROCNO 1Date_ 20130629Ti me 0. 42I NSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG dept135TD 65536SOLVENT CDCl 3NS 2000DS 4SWH 24038. 461 HzFI DRES 0. 366798 HzAQ 1. 3631988 secRG 16400DW 20. 800 usecDE 6. 50 usecTE 300. 0 KCNST2 145. 0000000D1 2. 00000000 secD2 0. 00344828 secD12 0. 00002000 secTD0 1======== CHANNEL f1 ========NUC1 13CP1 7. 00 usecP2 14. 00 usecPL1 0. 00 dBSFO1 100. 6228298 MHz======== CHANNEL f2 ========CPDPRG2 wal tz16NUC2 1HP3 11. 50 usecP4 23. 00 usecPCPD2 80. 00 usecPL2 -1. 00 dBPL12 16. 00 dBSFO2 400. 1316005 MHzSI 32768SF 100. 6127690 MHzWDW EMSSB 0LB 1. 00 HzGB 0PC 1. 40

DEPT 135, PP-01, CDCL3, 28/06/13, SAIF, NEHU, DRW

14151617181920212223242526272829303132333435 ppm

14.1222.6925.0425.9428.6529.1629.2729.3729.7031.9334.43

DEPT 135, PP- 01, CDCL3, 28/ 06/ 13, SAI F, NEHU, DRW

Figure 14. DEPT 135 Spectrum of compound 10

93

200 180 160 140 120 100 80 60 40 20 0 ppm

14.1222.6925.0325.9428.6529.1629.2729.3629.7031.9334.4364.42NAME PP-01EXPNO 1PROCNO 1Date_ 20130628Ti me 19. 00I NSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG dept45TD 65536SOLVENT CDCl 3NS 2000DS 4SWH 24038. 461 HzFI DRES 0. 366798 HzAQ 1. 3631988 secRG 16400DW 20. 800 usecDE 6. 50 usecTE 300. 0 KCNST2 145. 0000000D1 2. 00000000 secD2 0. 00344828 secD12 0. 00002000 secTD0 1======== CHANNEL f1 ========NUC1 13CP1 7. 00 usecP2 14. 00 usecPL1 0. 00 dBSFO1 100. 6228298 MHz======== CHANNEL f2 ========CPDPRG2 wal tz16NUC2 1HP3 11. 50 usecP4 23. 00 usecPCPD2 80. 00 usecPL2 -1. 00 dBPL12 16. 00 dBSFO2 400. 1316005 MHzSI 32768SF 100. 6127690 MHzWDW EMSSB 0LB 1. 00 HzGB 0PC 1. 40

DEPT 45, PP-01, CDCL3, 28/06/13, SAIF, NEHU, DRW

23242526272829303132333435 ppm

22.6925.0325.9428.6529.1629.2729.3629.7031.9334.43

DEPT 45, PP- 01, CDCL3, 28/ 06/ 13, SAI F, NEHU, DRW

Figure 15. DEPT 45 Spectrum of compound 10

94

ppm

8 7 6 5 4 3 2 1 0 ppm8

7

6

5

4

3

2

1

0

NAME PP-01EXPNO 4PROCNO 1Date_ 20130629Time 0.42INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG cosygpqfTD 2048SOLVENT CDCl3NS 8DS 8SWH 5341.880 HzFIDRES 2.608340 HzAQ 0.1917428 secRG 64DW 93.600 usecDE 6.50 usecTE 300.0 KD0 0.00000300 secD1 1.48689198 secD13 0.00000400 secD16 0.00020000 secIN0 0.00018720 sec======== CHANNEL f1 ========NUC1 1HP0 11.50 usecP1 11.50 usecPL1 -1.00 dBSFO1 400.1324057 MHz====== GRADIENT CHANNEL =====GPNAM1 SINE.100GPZ1 10.00 %P16 1000.00 usecND0 1TD 128SFO1 400.1324 MHzFIDRES 41.733440 HzSW 13.350 ppmFnMODE QFSI 1024SF 400.1300000 MHzWDW SINESSB 0LB 0.00 HzGB 0PC 1.00SI 1024MC2 QFSF 400.1300000 MHzWDW SINESSB 0LB 0.00 HzGB 0

COSY, PP-01, CDCL3, 28/06/13, SAIF, NEHU, DRW

ppm

0.60.81.01.21.41.61.82.02.22.4 ppm

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

NAME PP-01EXPNO 4PROCNO 1Date_ 20130629Time 0.42INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG cosygpqfTD 2048SOLVENT CDCl3NS 8DS 8SWH 5341.880 HzFIDRES 2.608340 HzAQ 0.1917428 secRG 64DW 93.600 usecDE 6.50 usecTE 300.0 KD0 0.00000300 secD1 1.48689198 secD13 0.00000400 secD16 0.00020000 secIN0 0.00018720 sec======== CHANNEL f1 ========NUC1 1HP0 11.50 usecP1 11.50 usecPL1 -1.00 dBSFO1 400.1324057 MHz====== GRADIENT CHANNEL =====GPNAM1 SINE.100GPZ1 10.00 %P16 1000.00 usecND0 1TD 128SFO1 400.1324 MHzFIDRES 41.733440 HzSW 13.350 ppmFnMODE QFSI 1024SF 400.1300000 MHzWDW SINESSB 0LB 0.00 HzGB 0PC 1.00SI 1024MC2 QFSF 400.1300000 MHzWDW SINESSB 0LB 0.00 HzGB 0

COSY, PP-01, CDCL3, 28/06/13, SAIF, NEHU, DRW

Figure 16. 1H-1H COSY spectrum of compound10

95

Figure 17. Mass Spectrum of compound 10

96

Compound 11, white solid, was isolated from the chloroform extract by

elution with PE:EA, 4:1 v/v and was found to be a steroid indicated by

Libermann Burchard (LB) test, C40H62O10. IR spectrum of 11 (figure 18) showed

characteristic absorption bands at 3360, 2940, 1460, 1369, 1070, 1024 cm-1. The

1H-NMR (400MHZ, DMSO-d6) spectrum (figure 19) showed the presence of six

methyl groups at 0.63, 0.76, 0.81, 0.88, 0.95 and 1.11; presence of one olefinic

proton was evident at 5.30 (1H, m). The signal at C-3 showing multiplet (seven

peaks) was found at 3.40. From the analysis of 13C-NMR (100MHz, DMSO-d6)

spectrum (figures 19 & 20) with DEPT spectra (figures 21-24), 11 showed twenty

nine carbon signals including 6CH3, 12CH2, 14CH and 3C. On the basis of

physical constant, IR, 1H-NMR, 13C-NMR with DEPT spectral data; and by

comparing with the authentic sample, 11 was established as -sitosterol--D-

glucoside.

OO

HO

HOHOOH

-Sitosterol--D-glucoside, 11

97

Fig

ure

18. I

R S

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of

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d11

98

Fig

ure

19.1

H N

MR

Spe

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m o

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und

11

99

Fig

ure

20.1

3 C N

MR

Spe

ctru

m o

f co

mpo

und

11

100

Fig

ure

21.1

3 C N

MR

Spe

ctru

m o

f co

mpo

und

11

101

Fig

ure

22.1

3 C D

EP

T S

pect

rum

of

com

poun

d11

102

Fig

ure

23.1

3 C D

EP

T 1

35 S

pect

rum

of

com

poun

d11

103

Fig

ure

24.1

3 C D

EP

T 9

0 S

pect

rum

of

com

poun

d11

104

Fig

ure

25.1

3 C D

EP

T 4

5 S

pect

rum

of

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d11

105

Fig

ure

26.1

3 C D

EP

T 4

5 S

pect

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of

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d11

106

Fig

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27. M

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107

3.3. Experimental

3.3.1. General Procedure

Melting points were measured on a melting point apparatus (VMP-I) and are

uncorrected. Optical rotations were measured on an Autopol II: Rudolph

Research Analytical. Silica gel 60-120 mesh (Merck) were used for column

chromatography; Ethyl acetate/petroleum ether as an eluent was used for TLC

and the spots were detected by spraying LB reagent, followed by heating. The

purity of compounds were performed by reverse phase HPLC: Merck Hitachi

(Lichrosphere RP-18 column). The HPLC eluents were acetonitrile: water

(75:25). IR spectra :Shimazdu IR-408 spectrometer, absorption maxima were

recorded in wave numbers (cm-1); 1H NMR spectra:Bruker AC-400

spectrometers; 13C NMR spectra:Bruker AC-100MHz spectrometers, residual

non-deuterated solvent was used as an internal reference and all chemical shifts

(H and C) are quoted in parts per million (ppm) downfield from

tetramethylsilane (TMS); Mass spectra :Jeol-D 300 mass spectrometer and Water

ZQ-4000 mass spectrometer. The SHG efficiency of the grown crystals was

measured with respect to urea and KDP by powder technique developed by Kurtz

and Perry32 using a Quanta Ray Spectra Physics model:Prolab 170 Nd:YAG 10

ns laser with the first harmonic output of 1064 nm at the pulse repetition rate of

10Hz. The crystal was ground to homogenous powder and tightly packed in a

micro capillary tube and mounted in the path of the laser beam of pulse energy

3.9mJ obtained by split beam technique. The SHG was confirmed by the

emission of green light (=532nm) collected by photomultiplier tube (PMT-

108

HAMAMATSU R2059) and displayed on the oscilloscope (Tektronics TDS

3052B). The SHG measurement was first carried out in KDP, urea. Throughout

the experiment the laser (Prolab170) power was kept constant. Signal amplitude

in milli volts (mv) on the oscilloscope indicates the SHG efficiency of the

sample.

3.3.2. Plant materials

The rhizomes of Curcuma caesia Roxb. were collected from Nambol, Bishupur

and Senapati districts of Manipur. A voucher specimen (IBSD/-19) has been

deposited in Institute of Bioresources and Sustainable Development, Takyelpat,

Imphal.

Curcuma caesia Roxb.(a) Leaves and flower, (b) rhizome, (c) vertical section ofrhizome.

3.3.3. Extraction and Isolation

The air-dried powdered rhizomes of Curcuma caesia Roxb (2.5 kg) were

subjected to extraction in a Soxhlet apparatus with light Petroleum ether (bp 60-

80 C) and chloroform successively. After filtration, the extraction solvents were

removed under reduced pressure.

109

Before packing in an open column, a preliminary examination of the

crude extract mass was subjected for chemical profiling using Thin Layer

Chromatography (TLC). This examination gave an idea for elution of the column

and the presence of different number of compounds. The TLC plates were

prepared manually.

The Chloroform extract was a thick dark brown in color. Its slurry was

prepared by mixing with minimum amount of Silica gel (60 120 mesh) and the

solvent was evaporated at room temperature on a glass Petridish till the slurry

was powdery. The chloroform extract was subjected to silica gel column

chromatography with gradient mixture of petroleum ether (PE) and ethyl acetate

(EA) of increasing polarity (table 1). All fractions were monitored using TLC

with Iodine-chamber/Liebermann-Burchart reagent/UV lamp/potassium

permanganate spray. Fractions with interesting chemical constituents were re-

chromatographed. The compounds were further purified using preparative TLC

(PTLC) and High Performance Liquid Chromatography (HPLC). Fractions eluted

with PE (100%) gave the essential oil fractions (1-39) and fractions (40-56) were

re-chromatographed on silica gel to afford compound (10). Eluted with PE:EA

(49:1, v/v) gave fractions (57-77) which were re-crystallized to yield 3 and

fractions (92-109) were collected and re-crystallized to give zederone 1. Elution

with PE:EA (97:3, v/v) gave fractions (120-129) were collected to afford

glechomanolide, 2. Further elution with PE:EA (19:1,v/v) gave fractions (130-

148), which were concentrated, purified with PTLC and re-chromatographed to

afford 4 and 5. Fractions (149-156) were combined and purified with PTLC to

110

give 6. Further fractions (157-165) were concentrated and then, purified with

PTLC to afford 7. Elution with PE:EA (9:1, v/v) gave fractions (166-174), which

were combined to give 8; fractions (175-187) were concentrated and further

purified using PTLC to give 9. Further elution with PE:EA (4:1, v/v) gave

fractions (188-201) which were concentrated to afford 11.

Table 1: Fractionation of the Chloroform - extract

Eluent % (Column Polarity) Fraction No. InferencePE 100% 1 - 34 Viscous dark violet oil (mixture)

35 -39 Viscous oil(mixture)

40 -56 Viscous light yellow (10)Two spots

PE:EA, 49:1 v/v 57 - 77 Viscous yellowFour spots

78 - 91 Viscous light yellow (3)Three spots

92 - 109 Viscous light greenish yellowSingle spot (1)

PE:EA, 97:3 v/v 110 - 119 Viscous light yellow oilThree spots

120 - 129 Viscous light yellow (2)Two spots

PE:EA, 19:1 v/v 130 - 148 Viscous light yellowFour spots (4, 5)

149 - 156 Viscous light yellowThree spots (6)

157 - 165 Viscous yellowTwo spots (7)

PE:EA, 9:1 v/v 166 - 174 Mixture of three spot (8)175 - 187 Mixture of two spots (9)

PE:EA, 4:1 v/v 188 - 201 Mixture of three spots (11)PE:EA, 3:2 v/v 202 - 215 Mixture of viscous oilsPE:EA, 1:1 v/v 216 - 228 Mixture of three spotsPE:EA, 1:4 v/v 229 - 237 Gummy brown solid mixture

111

3.3.4. Zederone(1)

White crystal (ethyl acetate), m.p. 149-150oC, []D32 +0.43. IR (max, cm-1):

2937.38, 1662.52, 1523.66, 1400.22, 1020.27, 769.54; 1H NMR & 13C NMR are

listed below (table 2); TOF MS: m/z 247.1332[M+H]+ ; 229.11, 201.12, 175.07,

139.02, 123.03, 121.02, 107.08.

Table 2. 1H NMR & 13C NMR values of the compound 1

Position H C

1 5.50 (dd, J = 12.0, 4.0 Hz) 131.202 2.24 (br d), 2.54 (br d) 24.643 1.26 (m), 2.30 (dt, J = 13.0, 3.5 Hz) 37.964 - 64.015 3.82 (s) 66.536 - 192.247 - 122.208 - 157.119 3.67 (d, J = 16.0 Hz), 3.75 (d, J = 16.0 Hz) 41.8710 - 131.0511 - 123.2312 7.09 (s) 138.0613 1.61 (s) 15.7414 1.35 (s) 15.1415 2.12 (s)

3.3.5. X-ray crystal structure analysis

X-ray analysis data collection: Bruker SMART; cell refinement: Bruker SMART;

data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97;

program(s) used to refine structure: SHELXL97; molecular graphics: Bruker

SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

All the non-H atoms were refined in the anisotropic approximation against F2 of

all reflections. The H-atoms were placed at their calculated positions and refined

in the isotropic approximation Crystallographic data collection was made at room

112

temperature. Crystallographic data for the structure reported in this paper have

been deposited in the Cambridge Crystallographic Data Centre as supplementary

publication number CCDC790473 (table 3). Copies of the data can be obtained,

free of charge, on application to the Director, CCDC, 12 Union Road, Cambridge

CB 1EZ, UK (fax 44-(0)1223336 033 or Email:deposit@ccdc.cam.ac.uk).

Table 3. The crystal data and refinement parameters of compound 1

C15H18O3 Dx = 1.276 Mg m3

Mr = 246.29 Melting point: 149-150oC

Orthorhombic, P212121Mo K radiation = 0.71073 Cell parameters from 5202 reflections

a = 11.617 (2) = 0.000.00b = 11.400 (2) = 0.09 mm1

c = 9.6834 (18) T = 296 (2) KV = 1282.4 (4) 3

Z = 4 Blocks, colorlessF000 = 528 0.48 0.24 0.19 mmCCD area detectordiffractometer

2356 independent reflections

Radiation source: fine-focus sealedtube

1887 reflections with I > 2(I)

Monochromator: graphite Rint = 0.082max = 26.0

T = 296(2) K min = 2.5h = 13 14

phi and scans k = 13 14Absorption correction: none l = 11 119559 measured reflections

Refinement on F2Hydrogen site location: inferred fromneighbouring sites

Least-squares matrix: full H-atom parameters constrained

R[F2 > 2(F2)] = 0.043 w = 1/[2(Fo

2) + (0.0827P)2]where P = (Fo

2 + 2Fc2)/3

wR(F2) = 0.135 (/)max < 0.001S = 1.05 max = 0.20 e 32356 reflections min = 0.20 e 3

167 parametersExtinction correction: SHELXL,Fc*=kFc[1+0.001xFc23/sin(2)]-1/4Extinction coefficient: 0.049 (7)

113

3.3.6. Determination of Second Harmonic Generation efficiency

The SHG measurement was first carried out in KDP, urea. Throughout the

experiment the laser power was kept constant. Signal amplitude in milli volts

(mv) on the oscilloscope indicates the SHG efficiency of the sample. The

compound 1 gives 17.5mv; reference compounds, urea=176mv and KDP=13mv,

beam energy is 3.9 mj/pulse.

3.3.7. Polymeric compound (10)

White solid, m.p. 62-64oC, []20D -18.94, (c 10 percent chloroform), optical

density - 0.01; IR (max, cm-1) at 2918, 2849, 1734, 1462, 1177, 957, 920, 723;

1H NMR (400 MHz, CDCl3) : H 4.05 (t, J = 7.5 Hz, 2H, OCH2), 2.29 (t, J = 7.5

Hz, 2H, CH2), 1.61 (m, 2H, CH2), 0.88 (t, J = 7.2 Hz, 3H, CH3);13C NMR (100

MHz, CDCl3) : C 14.1, 22.7, 25.0, 29.5, 31.9, 34.4, 64.4, 174.1; EIMS : m/z 955,

642, 536, 240.

3.3.8. -Sitosterol--D-glucoside (11)

White solid; m.p. 255-260oC(d); IR (max, cm-1) 3360, 2940, 1460, 1369, 1070,

1024; 1H NMR (400 MHz, DMSO-d6) : H 0.63, 0.76, 0.81, 0.88, 0.95, 1.11 (s,

3H each, 6xCH3), 2.89 (m, 1H, H-3), 3.62 (m, 1H, CH of glucose), 3.10 (m, 1H,

CH of glucose), 3.04 (m, 1H, CH of glucose), 4.20 (d, J = 7.5 Hz, 1H, CH of

glucose), 4.48 (m, 1H, CH of glucose), 4.92 (m, 2H, CH2 of glucose), 5.03 (m,

1H, H-1), 5.30 (m, 1H, H-6); 13C NMR (100 MHz, DMSO-d6) : C 37.3 (C-1),

29.7 (C-2), 77.4 (C-3), 40.0 (C-4), 140.9 (C-5), 121.7 (C-6), 31.8 (C-7), 29.7 (C-

8), 50.0 (C-9), 36.6 (C-10), 21.0 (C-11), 39.2 (C-12), 42.3 (C-13), 56.6 (C-14),

114

25.8 (C-15), 29.1 (C-16), 55.8 (C-17), 12.1 (C-18), 19.1 (C-19), 35.9 (C-20), 19.4

(C-21), 35.9 (C-22), 33.8 (C-23), 45.5 (C-24), 29.6 (C-25), 19.4 (C-26), 20.2 (C-

27), 28.0 (C-28), 12.2 (C-29), 101.2 (C-1), 70.5 (C-2), 77.4 (C-3), 73.8 (C-4),

77.1 (C-5), 61.5 (C-6); EIMS : m/z 475, 453, 301, 172.

Conclusion

Curcuma caesia Roxb. is used as traditional medicine. This plant showed the

antimicrobial activities in previous report. Nine sesquiterpenoids (1-9) were

isolated along with a naturally polymer compound (10) and a steroid (11) from

the dried rhizomes of Curcuma caesia Roxb. The structure-nonlinearity

relationship of zederone (1) was determined using Second Harmonic Generation

(SHG) efficiency and found to be higher than that of KDP. The isolated

compounds could be exploited for medicinal uses as well as other non-linear

properties.

115

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