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The N-2-phenylethylcinnamamide from Spilanthes ocymifolia
0031-9422/84S3 00+0 00 Q 1984PcrgamooPressLtd
Phytochemwry, Vol 23, No 11, PP 2671-2672, 1984
Pnotcd 10GreatBntam
THE N-2-PHENYLETHYLCINNAMAMIDE OCYMIFOLJA* J BORGES-DEL-CASTILLO, P VAZQUEZ-BUENO,
M
SECUNDINO-LUCAS, NATHAN?
FROM SPILANTHES
A I MARTINEZ-MARTIR and P JOSEPH-
Departamento de Quhmca OrgBmca, Fact&ad de Clencias, Umversldad Autdnoma de Madnd, Canto Blanco, Madnd-34, tDepartamento de Qulmlca de1 Centro de Investigach y de Estudios Avanzados, Institute Politecmco Naclonal, Apartado Postal 14-740, Mtx~o-14, D F , 07000 Mhco (Recetved
12 March 1984)
Key Word Index--Sphnthes ocymlfolra,Compositae, Hehantheae, N-2-phenylethylcmnamamlde, stigmasterol, taraxasteryl and lupe.yl acetates
Abstract-A simple amide, N-2-phenylethylcmnamamlde and three known compounds, stlgmasterol and taraxasteryl and lupeyl acetates, were isolated from the leaves of Spdanthes ocym~folzaThe structure of the cmnamamlde denvatlve was established by spectroscopic means and confirmed by synthesis
INTRODUCTION
Sphnthes ocymlfolza1s a Salvadorian
species which 1s a popular folk remedy for toothache and against the rabies disease, and It 1s known as ‘hlerba de la rabla’ (‘rabies grass’) [l] In previous work on this genus have been reported the presence of spllanthol m S oleracea [2], aand /I-amyrm esters and ntosterol-O-/I-D-glucoslde m S acmella [3] and ten acetylemc amides m S alba [4] The lsolatlon and characterlzatlon of a new amide, N-2phenylethylcmnamamlde, from S ocymlfolta IS described m the present commumcatlon It 1s interesting that this simple compound has not previously been found so far m nature though It has been described as a synthetic product
(J = 7 Hz) If the irradiated signal was that at 3 65 the triplet at 2 88 was converted into a singlet The amide compound was therefore, formulated as N-2-phenylethylcmnamamide and Its structure was confirmed by synthesis by heating cmnamlc acid with phenylethylamme (yield 25 %) A comparison of the “C NMR chemical shifts of this amide with the calculated values and with those of the amme and acid, respectively (Table 1) permitted assignment of structure 1
I31
Table 1 ‘“C NMR spectral data for compound 1 (CDCIJ, TMS as internal standard) Carbon
RESULTS AND DISCUSSION
The amide compound, C,,HI,NO, was obtained from the petrol and toluene extracts of the leaves of S ocymrfol~a as a crystalline product, mp 125-126” (cyclohexane), [M] + at m/z 251 Its IR spectrum had characterlstlc absorptlons at v=cm-’ 3300 (-NE&-) and 1670 (-C&NH-) The ‘H NMR spectrum showed two doublets of one proton each at 67 62 and 6 3 (J = 9 Hz) for olefimc protons and a multlplet centred around 7 53-7 0 for ten aromatic protons A triplet at 2 88 (J = 8 Hz) and a double triplet at 3 65 (J = 7 and J’ = 8 Hz) were assigned to the ethylene protons In addition there was a signal at 5 66 that disappeared with D1O which corresponds to the amide proton This was coupled with methylene protons at 3 65 When -NH- was irradiated the double tnplet at 3 65 appeared as a triplet (J = 8 Hz) and by lrradlatlon at 2 88 the double tnplet became a doublet
*Part 7 m the senes “Salvadonan Composltae” For Part 6 see 23, 859 (1984)
Phyfochemtstry
2671
1 2 3 4 5 6 7 1’ 2 3 4 5 6
6
1
165 6 1205 1408 1346 1286 1286 1294 356 407 138 6 127 6 128 5 1263
MC
Acid
1683 1175 1447 1361 1267 126 7 125 0 35 3 402 1442 1279 1284 1257
1727 1173 147 0 133 9 1289 128 3 1307
1
Amme
397 43 2 1395 1280 1284 125 7
2612
Short Reports
In addltlon, the petrol extract afforded stlgmasterol and taraxasteryl and lupeyl acetates The physical constants and spectroscopic data of these compounds were conslstent with those reported m the literature [6-81 EXPERIMENTAL Mps was measured with a Buchl apparatus and are uncorr The IR spectrum was recorded m KBr Extractton and zsolatlon Spdanthes ocymlfolta was collected m 1979 m El Salvador Leaves (3 3 kg) were extracted with EtOH The matenal obtamed after removal of the EtOH was diluted with H20, and extracted x 3 with petrol and then x 3 with toluene, for 30 hr The petrol extract (10 g) waschromatographed on a column of sdlca gel eluted with mcreasmg proportIons of toluene followed by EtOAc, yleldmg the following compounds m order of elution taraxasteryl acetate, lupeyl acetate, stlgmasterol and N-2-phenylethylcmnamam~de (1) The toluene extract (7 5 g) was chromatographed on a slhca gel column with CHCl,-Me&O mixtures as eluents, yleldmg stlgmasterol and IV-2-phenylethylcmnamarmde (1) m order of elutlon The previously known products were ldentlfied by their mp and spectroscopic (IR, ‘H NMR, ‘“C NMR and MS) data N-2-phenylethylclnnamamlde White needles, mp 125-126” (cyclohexane) IR vz cm-’ 3300, 3100, 3060, 2960, 2960, 1670, 1620, 1570, 1460, 1350, 1230, 1000, 870, 770, 750, 730, 700, etc ‘HNMR see Results and DIscussIon “CNMR see
Phytochemtstry, Vol 23, No
11, pp
2672-2673,
Results and DIscussIon MS (direct Inlet) m/z (rel mt) 252 [M + l]+ (18 8), 251 [Ml+ (42 l), 160 [M -C,H,]+ (21 1), 146 [M-C,H,-CH2]+ (120),131 [M-C,H,,N]+ (100),103[M -C,H,,NO]+ (23 3) Acknowledgements-We are Indebted to the Orgamsatlon of American States for a grant to one of us (A I M M ) from the Depto de Farmacla, Facultad de Quhmca y Farmaaa, Umversldad Naclonal de El Salvador, El Salvador, and to Professor Jorge A Lagos of the same umverslty, for botanrcal classlficatlon REFERENCES Standley, P C and Calderon, S (1944)f.l~la Preltmmar de las Plantas de El Salvador 217 Jacobson, M (1957) Chem Ind 50 Knshnaswamy, N R , Prasanna, S, Seshadn, T R and Vedantham, T N C (1975) Phytochemlstry 14, 1666 Bohlmann, F , Zlesche, J , Robmson, H and Kmg, R M (1980) Phytochemlsfry 19, 1535 Braun, V (1927) Ber Dtsch Chem Ges 60,358 Ilda, T ,Tamura, T and Matsumoto, T (1980).I Ltpld Res 21, 326 Lehn, J M and Ourlsson, G (1962) Mem Sot Chrm serve 5a, 1137 Gonzalez, A G , Velazquez, J M and Breton, J L (1983) An Qulm
79,470
0031-9422/84$3 00 +0 00 Q 1984Pergamon Press Ltd
1984
Pnnted m Great Bntam
LAUREQUINONE,
A CYCLOLAURANE SESQUITERPENE ALGA LAURENCIA NIDIFZCA
FROM THE RED
YOSHIKAZU SHIZURI, ATSUSHI YAMADA and KIYOYUKI YAMADA Department of Chemistry, Faculty of Science, Nagoya Umverslty, Chlkusa, Nagoya 464, Japan (Recewed
Key Word Index-burencza
29 March
1984)
tudrfca, Rhodomelaceae, red alga, cyclolaurane-type sesqmterpene, laurequmone
Abstract-From the red alga Laurencta ndtjica a new sesqulterpene of cyclolaurane-type structure elutidated by spectra1 analyses and chemical means
INTRODUCTION Previous
Investlgatlons
of the red alga Luurencza ndzjica
(Rhodomelaceae, Rhodophyta) have revealed that this alga 1s a rich source of halogenated and nonhalogenated sesqmterpenes, and halogenated Cl5 nonterpenold compounds [l-3] The present paper describes the lsolatlon of a new cyclolaurane sesquiterpene, laurequmone (1) together with aplysm [4-6], debromoaplysm [4-6], laurmterol [7-lo] and debromolaurmterol [7, S]
was isolated, and the
RESULTS AND DISCUSSION The fresh alga was extracted with acetone and the
resulting extract was further extracted with ethyl acetate The oily extract was separated by column chromatography, TLC and HPLC to afford a new compound, laurequmone (1) Laurequmone (l), C15H1s02, pale yellow oil, [a]g - 53 5” (c 0 91, CHCl,) The presence of either a 2-methyl5-alkyl-1,Cbenzoqumone group or a 2-methyld-alkyl-
Phytochemwry, Vol 23, No 11, PP 2671-2672, 1984
Pnotcd 10GreatBntam
THE N-2-PHENYLETHYLCINNAMAMIDE OCYMIFOLJA* J BORGES-DEL-CASTILLO, P VAZQUEZ-BUENO,
M
SECUNDINO-LUCAS, NATHAN?
FROM SPILANTHES
A I MARTINEZ-MARTIR and P JOSEPH-
Departamento de Quhmca OrgBmca, Fact&ad de Clencias, Umversldad Autdnoma de Madnd, Canto Blanco, Madnd-34, tDepartamento de Qulmlca de1 Centro de Investigach y de Estudios Avanzados, Institute Politecmco Naclonal, Apartado Postal 14-740, Mtx~o-14, D F , 07000 Mhco (Recetved
12 March 1984)
Key Word Index--Sphnthes ocymlfolra,Compositae, Hehantheae, N-2-phenylethylcmnamamlde, stigmasterol, taraxasteryl and lupe.yl acetates
Abstract-A simple amide, N-2-phenylethylcmnamamlde and three known compounds, stlgmasterol and taraxasteryl and lupeyl acetates, were isolated from the leaves of Spdanthes ocym~folzaThe structure of the cmnamamlde denvatlve was established by spectroscopic means and confirmed by synthesis
INTRODUCTION
Sphnthes ocymlfolza1s a Salvadorian
species which 1s a popular folk remedy for toothache and against the rabies disease, and It 1s known as ‘hlerba de la rabla’ (‘rabies grass’) [l] In previous work on this genus have been reported the presence of spllanthol m S oleracea [2], aand /I-amyrm esters and ntosterol-O-/I-D-glucoslde m S acmella [3] and ten acetylemc amides m S alba [4] The lsolatlon and characterlzatlon of a new amide, N-2phenylethylcmnamamlde, from S ocymlfolta IS described m the present commumcatlon It 1s interesting that this simple compound has not previously been found so far m nature though It has been described as a synthetic product
(J = 7 Hz) If the irradiated signal was that at 3 65 the triplet at 2 88 was converted into a singlet The amide compound was therefore, formulated as N-2-phenylethylcmnamamide and Its structure was confirmed by synthesis by heating cmnamlc acid with phenylethylamme (yield 25 %) A comparison of the “C NMR chemical shifts of this amide with the calculated values and with those of the amme and acid, respectively (Table 1) permitted assignment of structure 1
I31
Table 1 ‘“C NMR spectral data for compound 1 (CDCIJ, TMS as internal standard) Carbon
RESULTS AND DISCUSSION
The amide compound, C,,HI,NO, was obtained from the petrol and toluene extracts of the leaves of S ocymrfol~a as a crystalline product, mp 125-126” (cyclohexane), [M] + at m/z 251 Its IR spectrum had characterlstlc absorptlons at v=cm-’ 3300 (-NE&-) and 1670 (-C&NH-) The ‘H NMR spectrum showed two doublets of one proton each at 67 62 and 6 3 (J = 9 Hz) for olefimc protons and a multlplet centred around 7 53-7 0 for ten aromatic protons A triplet at 2 88 (J = 8 Hz) and a double triplet at 3 65 (J = 7 and J’ = 8 Hz) were assigned to the ethylene protons In addition there was a signal at 5 66 that disappeared with D1O which corresponds to the amide proton This was coupled with methylene protons at 3 65 When -NH- was irradiated the double tnplet at 3 65 appeared as a triplet (J = 8 Hz) and by lrradlatlon at 2 88 the double tnplet became a doublet
*Part 7 m the senes “Salvadonan Composltae” For Part 6 see 23, 859 (1984)
Phyfochemtstry
2671
1 2 3 4 5 6 7 1’ 2 3 4 5 6
6
1
165 6 1205 1408 1346 1286 1286 1294 356 407 138 6 127 6 128 5 1263
MC
Acid
1683 1175 1447 1361 1267 126 7 125 0 35 3 402 1442 1279 1284 1257
1727 1173 147 0 133 9 1289 128 3 1307
1
Amme
397 43 2 1395 1280 1284 125 7
2612
Short Reports
In addltlon, the petrol extract afforded stlgmasterol and taraxasteryl and lupeyl acetates The physical constants and spectroscopic data of these compounds were conslstent with those reported m the literature [6-81 EXPERIMENTAL Mps was measured with a Buchl apparatus and are uncorr The IR spectrum was recorded m KBr Extractton and zsolatlon Spdanthes ocymlfolta was collected m 1979 m El Salvador Leaves (3 3 kg) were extracted with EtOH The matenal obtamed after removal of the EtOH was diluted with H20, and extracted x 3 with petrol and then x 3 with toluene, for 30 hr The petrol extract (10 g) waschromatographed on a column of sdlca gel eluted with mcreasmg proportIons of toluene followed by EtOAc, yleldmg the following compounds m order of elution taraxasteryl acetate, lupeyl acetate, stlgmasterol and N-2-phenylethylcmnamam~de (1) The toluene extract (7 5 g) was chromatographed on a slhca gel column with CHCl,-Me&O mixtures as eluents, yleldmg stlgmasterol and IV-2-phenylethylcmnamarmde (1) m order of elutlon The previously known products were ldentlfied by their mp and spectroscopic (IR, ‘H NMR, ‘“C NMR and MS) data N-2-phenylethylclnnamamlde White needles, mp 125-126” (cyclohexane) IR vz cm-’ 3300, 3100, 3060, 2960, 2960, 1670, 1620, 1570, 1460, 1350, 1230, 1000, 870, 770, 750, 730, 700, etc ‘HNMR see Results and DIscussIon “CNMR see
Phytochemtstry, Vol 23, No
11, pp
2672-2673,
Results and DIscussIon MS (direct Inlet) m/z (rel mt) 252 [M + l]+ (18 8), 251 [Ml+ (42 l), 160 [M -C,H,]+ (21 1), 146 [M-C,H,-CH2]+ (120),131 [M-C,H,,N]+ (100),103[M -C,H,,NO]+ (23 3) Acknowledgements-We are Indebted to the Orgamsatlon of American States for a grant to one of us (A I M M ) from the Depto de Farmacla, Facultad de Quhmca y Farmaaa, Umversldad Naclonal de El Salvador, El Salvador, and to Professor Jorge A Lagos of the same umverslty, for botanrcal classlficatlon REFERENCES Standley, P C and Calderon, S (1944)f.l~la Preltmmar de las Plantas de El Salvador 217 Jacobson, M (1957) Chem Ind 50 Knshnaswamy, N R , Prasanna, S, Seshadn, T R and Vedantham, T N C (1975) Phytochemlstry 14, 1666 Bohlmann, F , Zlesche, J , Robmson, H and Kmg, R M (1980) Phytochemlsfry 19, 1535 Braun, V (1927) Ber Dtsch Chem Ges 60,358 Ilda, T ,Tamura, T and Matsumoto, T (1980).I Ltpld Res 21, 326 Lehn, J M and Ourlsson, G (1962) Mem Sot Chrm serve 5a, 1137 Gonzalez, A G , Velazquez, J M and Breton, J L (1983) An Qulm
79,470
0031-9422/84$3 00 +0 00 Q 1984Pergamon Press Ltd
1984
Pnnted m Great Bntam
LAUREQUINONE,
A CYCLOLAURANE SESQUITERPENE ALGA LAURENCIA NIDIFZCA
FROM THE RED
YOSHIKAZU SHIZURI, ATSUSHI YAMADA and KIYOYUKI YAMADA Department of Chemistry, Faculty of Science, Nagoya Umverslty, Chlkusa, Nagoya 464, Japan (Recewed
Key Word Index-burencza
29 March
1984)
tudrfca, Rhodomelaceae, red alga, cyclolaurane-type sesqmterpene, laurequmone
Abstract-From the red alga Laurencta ndtjica a new sesqulterpene of cyclolaurane-type structure elutidated by spectra1 analyses and chemical means
INTRODUCTION Previous
Investlgatlons
of the red alga Luurencza ndzjica
(Rhodomelaceae, Rhodophyta) have revealed that this alga 1s a rich source of halogenated and nonhalogenated sesqmterpenes, and halogenated Cl5 nonterpenold compounds [l-3] The present paper describes the lsolatlon of a new cyclolaurane sesquiterpene, laurequmone (1) together with aplysm [4-6], debromoaplysm [4-6], laurmterol [7-lo] and debromolaurmterol [7, S]
was isolated, and the
RESULTS AND DISCUSSION The fresh alga was extracted with acetone and the
resulting extract was further extracted with ethyl acetate The oily extract was separated by column chromatography, TLC and HPLC to afford a new compound, laurequmone (1) Laurequmone (l), C15H1s02, pale yellow oil, [a]g - 53 5” (c 0 91, CHCl,) The presence of either a 2-methyl5-alkyl-1,Cbenzoqumone group or a 2-methyld-alkyl-