h- and c - nmr spectra were recorded on jeol al-400 ( h at 400 and c at 100 mhz , respectively ) and bruker avance-400 ( h at 400 and c at 100 mhz , respectively ) spectrometers . hr - ms spectra were taken under electron impact ( ei ) conditions using a jeol jms - sx102a spectrometer by direct inlet . cd spectrum was measured on a jasco j-600 spectrophotometer . for column chromatography , kieselgel 60 ( merck ) and cosmosil ( nakarai tesk ) were used . for preparative tlc , preparative hplc was performed on a jai lc-908 and tosoh sd-8023 instruments with lichrosorb si 60 columns and a mightsil c-18 column . scytosiphon lomentaria was collected at aikappu in akkeshi , hokkaido on 1 july 1989 by dr . the prostrate - branched filaments were kept as unialgal culture at the laboratory of kochi prefectural deep seawater laboratory . in order to induce the erect thalli , the filaments were cultured as free - floating form in glass vessels containing 500 ml of pes medium with continuous aeration at 10 c in short day length ( 10:14 h light : dark cycle ) with white fluorescent light of 4060 mol ms . several erect thallus germlings occurred in a filament and became  germling clusters , each of which contained 10100 germlings . when the germling clusters grew to more than 5 mm diameter , they were transplanted as free - floating forms to an outdoor tank and cultured with continuous aeration and deep seawater supply at a rate of 3 volume exchanges per day . the brown alga scytosiphon lomentaria ( japanese name : kayamonori ; 15 kg wet weight ) was obtained as unialgal culture at the laboratory of muroto dsw , kochi prefecture , japan , in 2002 . the whole plant was immediately soaked in meoh and extracted at rt for 4 d. the meoh extract was concentrated under a reduced pressure to give a residue . the aqueous suspension was partitioned with hexane , dichloromethane ( dcm ) , and ethyl acetate ( etoac ) . a part of the dcm - soluble portion ( 1.6 g ) was subjected to flash column chromatography ( fcc ) eluting with a mixed solvent ( chcl3-acetone - meoh 100:10:1)-etoac ( 7:3 ) to give five fractions ( frs.1 - 1~1 - 5 ) . fraction 1 - 3 was applied to preparative tlc with 5% meoh in hexane - etoac ( 1:1 ) to give five fractions ( frs.2 - 1~2 - 5 ) . fraction 2 - 3 was purified by preparative hplc [ 5% meoh in hexane - etoac ( 1:1 ) ] to afford a new terpenoid ( 2 , 2.5 mg ) . fraction 1 - 4 was purified by preparative tlc with chcl3-etoac ( 7:3 ) to afford fucoxanthin ( 1 , 3.2 mg ) . other part of the dcm - soluble portion ( 2.4 g ) was subjected to fcc eluting with a mixed solvent ( chcl3-acetone - meoh 100:10:1)-etoac ( 7:3 ) to give seven fractions ( frs.3 - 1~3 - 7 ) . fraction 3 - 4 was subjected to fcc eluting with hexane - etoac ( 1 : 1 ) to give seven fractions ( frs.4 - 1~4 - 7 ) . fraction 4 - 4 was purified by recycle hplc [ hexane - etoac ( 1:1 ) ] to afford apo-9-fucoxanthinone ( 3 , 3.1 mg ) and apo-13-fucoxanthinone ( 4 , 0.6 mg ) . fraction 4 - 5 was purified by recycle hplc [ hexane - etoac ( 1:1 ) ] to afford apo-9-fucoxanthinone ( 3 , 1.1 mg ) . fraction 3 - 5 ( 930.2 mg ) mainly consisting of fucoxanthin ( 1 ) was obtained . fraction 4 - 6 was subjected to fcc eluting with 3% meoh in hexane - etoac ( 1:1 ) to give seven fractions ( frs.5 - 1~5 - 7 ) . fraction 5 - 4 was applied to sep - pak eluting with meoh - distilled water ( 9:1 ) to give two fractions ( frs.6 - 1~2 ) . fraction 6 - 2 was purified by hplc with meoh - distilled water ( 95:5 ) to afford 1 ( 4.0 mg ) . max ( etoh ) : 449.5 [ e ( 1% , 1 cm ) 1174.1 ] , h - nmr : ( cdcl3 , 400 mhz ) :  0.95 ( s , me-17 ) , 1.02 ( s , me-16 ) , 1.06 ( s , me-17 ) , 1.21 ( s , h-18 ) , 1.34 ( s , h-18 ) , 1.36 ( dd , j=8.7 , 14.2 hz , h-2ax ) , 1.37 ( s , me-16 ) , 1.41 ( dd , j=10.4 , 14.9 hz , h-2ax ) , 1.49 ( dd , j=2.9 , 14.2 hz , h-2eq ) , 1.53 ( dd , j=10.4 , 14.9 hz , h-4ax ) , 1.77 ( dd , j=8.7 , 14.2 hz , h-4ax ) , 1.80 ( s , h-19 ) , 1.93 ( s , h-19 ) , 1.98 ( s , h-20 ) , 1.98 ( s , h-20 ) , 2.00 ( dd , j=2.9 , 14.9 hz , h-2eq ) , 2.03 ( s , me , c-3oac ) , 2.29 ( dd , j=2.9 , 17.8 hz , h-4eq ) , 2.29 ( dd , j=2.9 , 17.8 hz , h-4eq ) , 2.59 ( d , j=20.4 hz , h-7 ) , 3.64 ( d , j=20.4 hz , h-7 ) , 3.80 ( m , h-3 ) , 5.37 ( tt , j=8.8 , 12.0 hz , h-3 ) , 6.04 ( s , h-8 ) , 6.12 ( d , j=11.6 hz , h-10 ) , 6.26 ( d , j=11.6 hz , h-14 ) , 6.34 ( d , j=11.6 hz , h-12 ) , 6.40 ( d , j=11.6 hz , h-14 ) , 6.58 ( m , h-11 ) , 6.66 ( t , j=12.8 hz , h-12 ) , 6.67 ( m , h-15 ) , 6.71 ( dd , j=12.0 , 14.2 hz , h-15 ) , 6.71 ( t , j=12.0 hz , h-11 ) , 7.14 ( d , j=12.8 hz , h-10 ) . c - nmr : ( cdcl3 , 100 mhz ) :  11.7 ( c-19 ) , 12.6 ( c-20 ) , 12.80 ( c-20 ) , 13.9 ( c-19 ) , 21.0 ( c-18 ) , 21.3 ( me , c-3oac ) , 24.9 ( c-16 ) , 28.0 ( c-17 ) , 29.0 ( c-16 ) , 31.1 ( c-18 ) , 31.9 ( c-17 ) , 35.0 ( c-1 ) , 35.6 ( c-1 ) , 40.6 ( c-7 ) , 41.5 ( c-4 ) , 45.1 ( c-4 ) , 45.2 ( c-2 ) , 46.9 ( c-2 ) , 64.2 ( c-3 ) , 66.0 ( c-5 ) , 66.9 ( c-6 ) , 67.8 ( c-3 ) , 72.6 ( c-5 ) , 103.2 ( c-8 ) , 117.3 ( c-6 ) , 123.2 ( c-11 ) , 125.5 ( c-11 ) , 128.4 ( c-10 ) , 129.3 ( c-15 ) , 132.0 ( c-14 ) , 132.4 ( c-9 ) , 132.4 ( c-15 ) , 134.3 ( c-9 ) , 135.3 ( c-13 ) , 136.6 ( c-14 ) , 137.0 ( c-12 ) , 138.0 ( c-13 ) , 139.0 ( c-10 ) , 144.9 ( c-12 ) , 170.4 ( c-8 ) , 197.7 ( c = o , c-3oac ) , 202.2 ( c-7 ) . ir 1669 cm ( -c = o ) , eihrms m / z 306.1813 ( calcd for c18h26o4 ; 306.1831 ) . h nmr : ( c6d6 , 400 mhz ) :  0.96 ( s , h-15 ) , 1.10 ( s , h-14 ) , 1.20 ( s , me-16 ) , 1.36 ( dd , j=9.1 , 11.6 hz , h-2ax ) , 1.41 ( ddd , j=1.8 , 4.8 , 11.6 hz , h-2eq ) , 1.69 ( dd , j=9.1 , 13.6 hz , h-4ax ) , 1.69 ( s , me-17 ) , 1.88 ( s , h-18 ) , 2.24 ( ddd , j=1.8 , 4.8 , 13.6 hz , h-4eq ) , 2.56 ( d , j=18.8 hz , h-7 ) , 3.39 ( d , j=18.8 hz , h-7 ) , 3.81 ( tt , j=4.8 , 9.1 hz , h-3 ) , 6.02 ( d , 15.4 hz , h-12 ) , 6.66 ( d , j=11.1 hz h-10 ) , 7.16 ( dd , j=11.1 , 15.4 hz , h-11 ) . ( c-17 ) , 21.1 ( c-16 ) , 25.1 ( c-14 ) , 27.7 ( c-18 ) , 28.2 ( c-15 ) , 35.2 ( c-1 ) , 41.7 ( c-7 ) , 42.1 ( c-4 ) , 47.7 ( c-2 ) , 63.9 ( c-3 ) , 65.8 ( c-5 ) , 66.4 ( c-6 ) , 134.3 ( c-10 ) , 135.5 ( c-12 ) , 136.0 ( c-11 ) , 142.9 ( c-9 ) , 195.8 ( c-13 ) , 197.7 ( c-8 ) . orange oil . h - nmr : ( c6d6 , 400 mhz ) :  0.94 ( s , h-10 ) , 1.01 ( s , me-12 ) , 1.25 ( ddd , j=2.0 , 4.3 , 12.4 hz , h-2eq ) , 1.26 ( dd , j=11.2 , 12.4 hz , h-4ax ) , 1.32 ( s , me-11 ) , 1.76 ( s , h-13 ) , 1.91 ( s , me , c-3oac ) , 1.95 ( ddd , j=2.0 , 4.3 , 12.4 hz , h-4eq ) , 2.21 ( dd , j=11.2 , 12.4 hz , h-2ax ) , 5.59 ( tt , j=4.3 , 11.2 hz , h-3 ) , 5.81 ( s , h-8 ) . c - nmr : ( c6d6 , 100 mhz ) :  20.9 ( me , c-3oac ) , 26.2 ( c-11 ) , 26.3 ( c-13 ) , 28.8 ( c-12 ) , 30.3 ( c-10 ) , 35.8 ( c-1 ) , 45.2 ( c-4 ) , 45.3 ( c-2 ) , 67.4 ( c-3 ) , 71.4 ( c-5 ) , 100.8 ( c-8 ) , 118.2 ( c-6 ) , 169.4 ( c = o , c-3oac ) , 196.0 ( c-9 ) , 209.0 ( c-7 ) . h - nmr :  ( cd2cl2 , 400 mhz ) : 1.10 ( s , me-14 ) , 1.36 ( s , me-15 ) , 1.40 ( s , h-16 ) , 1.41 ( dd , j=8.0 , 10.0 hz , h-2ax ) , 1.52 ( dd , j=8.0 , 10.0 hz , h-4ax ) , 1.93 ( s , h-17 ) , 1.98 ( ddd , j=1.9 , 5.0 , 10.0 hz , h-2eq ) , 2.03 ( s , me , c-3oac ) , 2.27 ( s , h-18 ) , 2.28 ( ddd , j=1.9 , 5.0 , 10.0 hz , h-4eq ) , 5.31 ( m , h-3 ) ,  6.12 ( s , h-8 ) , 6.15 ( d , j=15.6 hz , h-10 ) , 6.21 ( d , j=10.5 hz , h-12 ) , 7.47 ( dd , j=10.5 , 15.6 hz , h-11 ) . h- and c - nmr spectra were recorded on jeol al-400 ( h at 400 and c at 100 mhz , respectively ) and bruker avance-400 ( h at 400 and c at 100 mhz , respectively ) spectrometers . hr - ms spectra were taken under electron impact ( ei ) conditions using a jeol jms - sx102a spectrometer by direct inlet . cd spectrum was measured on a jasco j-600 spectrophotometer . for column chromatography , kieselgel 60 ( merck ) and cosmosil ( nakarai tesk ) were used . for preparative tlc , preparative hplc was performed on a jai lc-908 and tosoh sd-8023 instruments with lichrosorb si 60 columns and a mightsil c-18 column . scytosiphon lomentaria was collected at aikappu in akkeshi , hokkaido on 1 july 1989 by dr . the prostrate - branched filaments were kept as unialgal culture at the laboratory of kochi prefectural deep seawater laboratory . in order to induce the erect thalli , the filaments were cultured as free - floating form in glass vessels containing 500 ml of pes medium with continuous aeration at 10 c in short day length ( 10:14 h light : dark cycle ) with white fluorescent light of 4060 mol ms . several erect thallus germlings occurred in a filament and became  germling clusters , each of which contained 10100 germlings . when the germling clusters grew to more than 5 mm diameter , they were transplanted as free - floating forms to an outdoor tank and cultured with continuous aeration and deep seawater supply at a rate of 3 volume exchanges per day . the brown alga scytosiphon lomentaria ( japanese name : kayamonori ; 15 kg wet weight ) was obtained as unialgal culture at the laboratory of muroto dsw , kochi prefecture , japan , in 2002 . the whole plant was immediately soaked in meoh and extracted at rt for 4 d. the meoh extract was concentrated under a reduced pressure to give a residue . the aqueous suspension was partitioned with hexane , dichloromethane ( dcm ) , and ethyl acetate ( etoac ) . a part of the dcm - soluble portion ( 1.6 g ) was subjected to flash column chromatography ( fcc ) eluting with a mixed solvent ( chcl3-acetone - meoh 100:10:1)-etoac ( 7:3 ) to give five fractions ( frs.1 - 1~1 - 5 ) . fraction 1 - 3 was applied to preparative tlc with 5% meoh in hexane - etoac ( 1:1 ) to give five fractions ( frs.2 - 1~2 - 5 ) . fraction 2 - 3 was purified by preparative hplc [ 5% meoh in hexane - etoac ( 1:1 ) ] to afford a new terpenoid ( 2 , 2.5 mg ) . fraction 1 - 4 was purified by preparative tlc with chcl3-etoac ( 7:3 ) to afford fucoxanthin ( 1 , 3.2 mg ) . other part of the dcm - soluble portion ( 2.4 g ) was subjected to fcc eluting with a mixed solvent ( chcl3-acetone - meoh 100:10:1)-etoac ( 7:3 ) to give seven fractions ( frs.3 - 1~3 - 7 ) . fraction 3 - 4 was subjected to fcc eluting with hexane - etoac ( 1 : 1 ) to give seven fractions ( frs.4 - 1~4 - 7 ) . fraction 4 - 4 was purified by recycle hplc [ hexane - etoac ( 1:1 ) ] to afford apo-9-fucoxanthinone ( 3 , 3.1 mg ) and apo-13-fucoxanthinone ( 4 , 0.6 mg ) . fraction 4 - 5 was purified by recycle hplc [ hexane - etoac ( 1:1 ) ] to afford apo-9-fucoxanthinone ( 3 , 1.1 mg ) . fraction 3 - 5 ( 930.2 mg ) mainly consisting of fucoxanthin ( 1 ) was obtained . fraction 4 - 6 was subjected to fcc eluting with 3% meoh in hexane - etoac ( 1:1 ) to give seven fractions ( frs.5 - 1~5 - 7 ) . fraction 5 - 4 was applied to sep - pak eluting with meoh - distilled water ( 9:1 ) to give two fractions ( frs.6 - 1~2 ) . fraction 6 - 2 was purified by hplc with meoh - distilled water ( 95:5 ) to afford 1 ( 4.0 mg ) . max ( etoh ) : 449.5 [ e ( 1% , 1 cm ) 1174.1 ] , h - nmr : ( cdcl3 , 400 mhz ) :  0.95 ( s , me-17 ) , 1.02 ( s , me-16 ) , 1.06 ( s , me-17 ) , 1.21 ( s , h-18 ) , 1.34 ( s , h-18 ) , 1.36 ( dd , j=8.7 , 14.2 hz , h-2ax ) , 1.37 ( s , me-16 ) , 1.41 ( dd , j=10.4 , 14.9 hz , h-2ax ) , 1.49 ( dd , j=2.9 , 14.2 hz , h-2eq ) , 1.53 ( dd , j=10.4 , 14.9 hz , h-4ax ) , 1.77 ( dd , j=8.7 , 14.2 hz , h-4ax ) , 1.80 ( s , h-19 ) , 1.93 ( s , h-19 ) , 1.98 ( s , h-20 ) , 1.98 ( s , h-20 ) , 2.00 ( dd , j=2.9 , 14.9 hz , h-2eq ) , 2.03 ( s , me , c-3oac ) , 2.29 ( dd , j=2.9 , 17.8 hz , h-4eq ) , 2.29 ( dd , j=2.9 , 17.8 hz , h-4eq ) , 2.59 ( d , j=20.4 hz , h-7 ) , 3.64 ( d , j=20.4 hz , h-7 ) , 3.80 ( m , h-3 ) , 5.37 ( tt , j=8.8 , 12.0 hz , h-3 ) , 6.04 ( s , h-8 ) , 6.12 ( d , j=11.6 hz , h-10 ) , 6.26 ( d , j=11.6 hz , h-14 ) , 6.34 ( d , j=11.6 hz , h-12 ) , 6.40 ( d , j=11.6 hz , h-14 ) , 6.58 ( m , h-11 ) , 6.66 ( t , j=12.8 hz , h-12 ) , 6.67 ( m , h-15 ) , 6.71 ( dd , j=12.0 , 14.2 hz , h-15 ) , 6.71 ( t , j=12.0 hz , h-11 ) , 7.14 ( d , j=12.8 hz , h-10 ) . c - nmr : ( cdcl3 , 100 mhz ) :  11.7 ( c-19 ) , 12.6 ( c-20 ) , 12.80 ( c-20 ) , 13.9 ( c-19 ) , 21.0 ( c-18 ) , 21.3 ( me , c-3oac ) , 24.9 ( c-16 ) , 28.0 ( c-17 ) , 29.0 ( c-16 ) , 31.1 ( c-18 ) , 31.9 ( c-17 ) , 35.0 ( c-1 ) , 35.6 ( c-1 ) , 40.6 ( c-7 ) , 41.5 ( c-4 ) , 45.1 ( c-4 ) , 45.2 ( c-2 ) , 46.9 ( c-2 ) , 64.2 ( c-3 ) , 66.0 ( c-5 ) , 66.9 ( c-6 ) , 67.8 ( c-3 ) , 72.6 ( c-5 ) , 103.2 ( c-8 ) , 117.3 ( c-6 ) , 123.2 ( c-11 ) , 125.5 ( c-11 ) , 128.4 ( c-10 ) , 129.3 ( c-15 ) , 132.0 ( c-14 ) , 132.4 ( c-9 ) , 132.4 ( c-15 ) , 134.3 ( c-9 ) , 135.3 ( c-13 ) , 136.6 ( c-14 ) , 137.0 ( c-12 ) , 138.0 ( c-13 ) , 139.0 ( c-10 ) , 144.9 ( c-12 ) , 170.4 ( c-8 ) , 197.7 ( c = o , c-3oac ) , 202.2 ( c-7 ) . ir 1669 cm ( -c = o ) , eihrms m / z 306.1813 ( calcd for c18h26o4 ; 306.1831 ) . h nmr : ( c6d6 , 400 mhz ) :  0.96 ( s , h-15 ) , 1.10 ( s , h-14 ) , 1.20 ( s , me-16 ) , 1.36 ( dd , j=9.1 , 11.6 hz , h-2ax ) , 1.41 ( ddd , j=1.8 , 4.8 , 11.6 hz , h-2eq ) , 1.69 ( dd , j=9.1 , 13.6 hz , h-4ax ) , 1.69 ( s , me-17 ) , 1.88 ( s , h-18 ) , 2.24 ( ddd , j=1.8 , 4.8 , 13.6 hz , h-4eq ) , 2.56 ( d , j=18.8 hz , h-7 ) , 3.39 ( d , j=18.8 hz , h-7 ) , 3.81 ( tt , j=4.8 , 9.1 hz , h-3 ) , 6.02 ( d , 15.4 hz , h-12 ) , 6.66 ( d , j=11.1 hz h-10 ) , 7.16 ( dd , j=11.1 , 15.4 hz , h-11 ) . c nmr : ( c6d6 , 100 mhz ) :     ( c-17 ) , 21.1 ( c-16 ) , 25.1 ( c-14 ) , 27.7 ( c-18 ) , 28.2 ( c-15 ) , 35.2 ( c-1 ) , 41.7 ( c-7 ) , 42.1 ( c-4 ) , 47.7 ( c-2 ) , 63.9 ( c-3 ) , 65.8 ( c-5 ) , 66.4 ( c-6 ) , 134.3 ( c-10 ) , 135.5 ( c-12 ) , 136.0 ( c-11 ) , 142.9 ( c-9 ) , 195.8 ( c-13 ) , 197.7 ( c-8 ) . orange oil . cd spectrum ( etoh ) :  255 6.07 . h - nmr : ( c6d6 , 400 mhz ) :  0.94 ( s , h-10 ) , 1.01 ( s , me-12 ) , 1.25 ( ddd , j=2.0 , 4.3 , 12.4 hz , h-2eq ) , 1.26 ( dd , j=11.2 , 12.4 hz , h-4ax ) , 1.32 ( s , me-11 ) , 1.76 ( s , h-13 ) , 1.91 ( s , me , c-3oac ) , 1.95 ( ddd , j=2.0 , 4.3 , 12.4 hz , h-4eq ) , 2.21 ( dd , j=11.2 , 12.4 hz , h-2ax ) , 5.59 ( tt , j=4.3 , 11.2 hz , h-3 ) , 5.81 ( s , h-8 ) . c - nmr : ( c6d6 , 100 mhz ) :  20.9 ( me , c-3oac ) , 26.2 ( c-11 ) , 26.3 ( c-13 ) , 28.8 ( c-12 ) , 30.3 ( c-10 ) , 35.8 ( c-1 ) , 45.2 ( c-4 ) , 45.3 ( c-2 ) , 67.4 ( c-3 ) , 71.4 ( c-5 ) , 100.8 ( c-8 ) , 118.2 ( c-6 ) , 169.4 ( c = o , c-3oac ) , 196.0 ( c-9 ) , 209.0 ( c-7 ) . h - nmr :  ( cd2cl2 , 400 mhz ) : 1.10 ( s , me-14 ) , 1.36 ( s , me-15 ) , 1.40 ( s , h-16 ) , 1.41 ( dd , j=8.0 , 10.0 hz , h-2ax ) , 1.52 ( dd , j=8.0 , 10.0 hz , h-4ax ) , 1.93 ( s , h-17 ) , 1.98 ( ddd , j=1.9 , 5.0 , 10.0 hz , h-2eq ) , 2.03 ( s , me , c-3oac ) , 2.27 ( s , h-18 ) , 2.28 ( ddd , j=1.9 , 5.0 , 10.0 hz , h-4eq ) , 5.31 ( m , h-3 ) ,  6.12 ( s , h-8 ) , 6.15 ( d , j=15.6 hz , h-10 ) , 6.21 ( d , j=10.5 hz , h-12 ) , 7.47 ( dd , j=10.5 , 15.6 hz , h-11 ) . red paste . max ( etoh ) : 449.5 [ e ( 1% , 1 cm ) 1174.1 ] , h - nmr : ( cdcl3 , 400 mhz ) :  0.95 ( s , me-17 ) , 1.02 ( s , me-16 ) , 1.06 ( s , me-17 ) , 1.21 ( s , h-18 ) , 1.34 ( s , h-18 ) , 1.36 ( dd , j=8.7 , 14.2 hz , h-2ax ) , 1.37 ( s , me-16 ) , 1.41 ( dd , j=10.4 , 14.9 hz , h-2ax ) , 1.49 ( dd , j=2.9 , 14.2 hz , h-2eq ) , 1.53 ( dd , j=10.4 , 14.9 hz , h-4ax ) , 1.77 ( dd , j=8.7 , 14.2 hz , h-4ax ) , 1.80 ( s , h-19 ) , 1.93 ( s , h-19 ) , 1.98 ( s , h-20 ) , 1.98 ( s , h-20 ) , 2.00 ( dd , j=2.9 , 14.9 hz , h-2eq ) , 2.03 ( s , me , c-3oac ) , 2.29 ( dd , j=2.9 , 17.8 hz , h-4eq ) , 2.29 ( dd , j=2.9 , 17.8 hz , h-4eq ) , 2.59 ( d , j=20.4 hz , h-7 ) , 3.64 ( d , j=20.4 hz , h-7 ) , 3.80 ( m , h-3 ) , 5.37 ( tt , j=8.8 , 12.0 hz , h-3 ) , 6.04 ( s , h-8 ) , 6.12 ( d , j=11.6 hz , h-10 ) , 6.26 ( d , j=11.6 hz , h-14 ) , 6.34 ( d , j=11.6 hz , h-12 ) , 6.40 ( d , j=11.6 hz , h-14 ) , 6.58 ( m , h-11 ) , 6.66 ( t , j=12.8 hz , h-12 ) , 6.67 ( m , h-15 ) , 6.71 ( dd , j=12.0 , 14.2 hz , h-15 ) , 6.71 ( t , j=12.0 hz , h-11 ) , 7.14 ( d , j=12.8 hz , h-10 ) . c - nmr : ( cdcl3 , 100 mhz ) :  11.7 ( c-19 ) , 12.6 ( c-20 ) , 12.80 ( c-20 ) , 13.9 ( c-19 ) , 21.0 ( c-18 ) , 21.3 ( me , c-3oac ) , 24.9 ( c-16 ) , 28.0 ( c-17 ) , 29.0 ( c-16 ) , 31.1 ( c-18 ) , 31.9 ( c-17 ) , 35.0 ( c-1 ) , 35.6 ( c-1 ) , 40.6 ( c-7 ) , 41.5 ( c-4 ) , 45.1 ( c-4 ) , 45.2 ( c-2 ) , 46.9 ( c-2 ) , 64.2 ( c-3 ) , 66.0 ( c-5 ) , 66.9 ( c-6 ) , 67.8 ( c-3 ) , 72.6 ( c-5 ) , 103.2 ( c-8 ) , 117.3 ( c-6 ) , 123.2 ( c-11 ) , 125.5 ( c-11 ) , 128.4 ( c-10 ) , 129.3 ( c-15 ) , 132.0 ( c-14 ) , 132.4 ( c-9 ) , 132.4 ( c-15 ) , 134.3 ( c-9 ) , 135.3 ( c-13 ) , 136.6 ( c-14 ) , 137.0 ( c-12 ) , 138.0 ( c-13 ) , 139.0 ( c-10 ) , 144.9 ( c-12 ) , 170.4 ( c-8 ) , 197.7 ( c = o , c-3oac ) , 202.2 ( c-7 ) . ir 1669 cm ( -c = o ) , eihrms m / z 306.1813 ( calcd for c18h26o4 ; 306.1831 ) . h nmr : ( c6d6 , 400 mhz ) :  0.96 ( s , h-15 ) , 1.10 ( s , h-14 ) , 1.20 ( s , me-16 ) , 1.36 ( dd , j=9.1 , 11.6 hz , h-2ax ) , 1.41 ( ddd , j=1.8 , 4.8 , 11.6 hz , h-2eq ) , 1.69 ( dd , j=9.1 , 13.6 hz , h-4ax ) , 1.69 ( s , me-17 ) , 1.88 ( s , h-18 ) , 2.24 ( ddd , j=1.8 , 4.8 , 13.6 hz , h-4eq ) , 2.56 ( d , j=18.8 hz , h-7 ) , 3.39 ( d , j=18.8 hz , h-7 ) , 3.81 ( tt , j=4.8 , 9.1 hz , h-3 ) , 6.02 ( d , 15.4 hz , h-12 ) , 6.66 ( d , j=11.1 hz h-10 ) , 7.16 ( dd , j=11.1 , 15.4 hz , h-11 ) . ( c-17 ) , 21.1 ( c-16 ) , 25.1 ( c-14 ) , 27.7 ( c-18 ) , 28.2 ( c-15 ) , 35.2 ( c-1 ) , 41.7 ( c-7 ) , 42.1 ( c-4 ) , 47.7 ( c-2 ) , 63.9 ( c-3 ) , 65.8 ( c-5 ) , 66.4 ( c-6 ) , 134.3 ( c-10 ) , 135.5 ( c-12 ) , 136.0 ( c-11 ) , 142.9 ( c-9 ) , 195.8 ( c-13 ) , 197.7 ( c-8 ) . orange oil . cd spectrum ( etoh ) :  255 6.07 . h - nmr : ( c6d6 , 400 mhz ) :  0.94 ( s , h-10 ) , 1.01 ( s , me-12 ) , 1.25 ( ddd , j=2.0 , 4.3 , 12.4 hz , h-2eq ) , 1.26 ( dd , j=11.2 , 12.4 hz , h-4ax ) , 1.32 ( s , me-11 ) , 1.76 ( s , h-13 ) , 1.91 ( s , me , c-3oac ) , 1.95 ( ddd , j=2.0 , 4.3 , 12.4 hz , h-4eq ) , 2.21 ( dd , j=11.2 , 12.4 hz , h-2ax ) , 5.59 ( tt , j=4.3 , 11.2 hz , h-3 ) , 5.81 ( s , h-8 ) . c - nmr : ( c6d6 , 100 mhz ) :  20.9 ( me , c-3oac ) , 26.2 ( c-11 ) , 26.3 ( c-13 ) , 28.8 ( c-12 ) , 30.3 ( c-10 ) , 35.8 ( c-1 ) , 45.2 ( c-4 ) , 45.3 ( c-2 ) , 67.4 ( c-3 ) , 71.4 ( c-5 ) , 100.8 ( c-8 ) , 118.2 ( c-6 ) , 169.4 ( c = o , c-3oac ) , 196.0 ( c-9 ) , 209.0 ( c-7 ) . h - nmr :  ( cd2cl2 , 400 mhz ) : 1.10 ( s , me-14 ) , 1.36 ( s , me-15 ) , 1.40 ( s , h-16 ) , 1.41 ( dd , j=8.0 , 10.0 hz , h-2ax ) , 1.52 ( dd , j=8.0 , 10.0 hz , h-4ax ) , 1.93 ( s , h-17 ) , 1.98 ( ddd , j=1.9 , 5.0 , 10.0 hz , h-2eq ) , 2.03 ( s , me , c-3oac ) , 2.27 ( s , h-18 ) , 2.28 ( ddd , j=1.9 , 5.0 , 10.0 hz , h-4eq ) , 5.31 ( m , h-3 ) ,  6.12 ( s , h-8 ) , 6.15 ( d , j=15.6 hz , h-10 ) , 6.21 ( d , j=10.5 hz , h-12 ) , 7.47 ( dd , j=10.5 , 15.6 hz , h-11 ) .
three metabolites of fucoxanthin were isolated from a brown alga , scytosiphon lomentaria , and the structure of a new compound was determined by nmr . 
 the content of fucoxanthin , a biologically active carotenoid , in four edible brown algae , cultivated in deep seawater , was studied .