交趾黃檀心材的黃酮類和三萜類成分

鐘艷霞, 陳郊, 莫新良, 徐志防, 邱聲祥, 劉新紅

交趾黃檀心材的黃酮類和三萜類成分

鐘艷霞1a, 陳郊2, 莫新良1a, 徐志防3, 邱聲祥3, 劉新紅1b*

(1. 茅臺(tái)學(xué)院, a. 釀酒工程系; b. 資源環(huán)境系, 貴州 仁懷 564507；2. 貴州茅臺(tái)酒股份有限公司，貴州 仁懷 564507；3. 中國(guó)科學(xué)院華南植物園，廣州 510650)

為研究交趾黃檀()的化學(xué)成分，采用有機(jī)溶劑提取、萃取及多種色譜分離技術(shù)，從其心材中分離得到5個(gè)新黃酮和7個(gè)其他類型成分。根據(jù)理化性質(zhì)和波譜數(shù)據(jù)，其結(jié)構(gòu)分別鑒定為：7-hydroxy-2?,3?,4?-trimethoxyisoflavan (1)、6,4?-dihydroxy-7-methoxyflavan (2)、-dalbergiphenol (3)、-4-methoxydalbergione (4)、mimosifoliol (5)、-5--methyllatifolin (6)、-latifolin (7)、maackiain (8)、secundiflorol Ι (9)、3,9-dimethoxy-6- benzofufo[3,2-c]chromen-6-one (10)、mucodianin C (11)、lup-(20)29-ene-2,3-diol (12)?；衔?、5、8～12為首次從交趾黃檀植物中分離得到。

交趾黃檀；心材；黃酮類；新黃酮類；三萜類

交趾黃檀()主要產(chǎn)于泰國(guó)、老撾、越南、柬埔寨等東南亞地區(qū)，其木材表面具有光澤，木質(zhì)結(jié)構(gòu)均勻且細(xì)膩，硬度大, 強(qiáng)度高，具有很強(qiáng)的抗蟲(chóng)性能和耐腐蝕性能，適于制作精美工藝品、高檔紅木家具、高級(jí)樂(lè)器等[1–2]。交趾黃檀心材在泰國(guó)有作為民間藥材使用[3]，據(jù)報(bào)道，其主要含有二氫黃酮、異黃酮、新黃酮、二氫異黃酮、查爾酮、苯并呋喃、酚類等成分。有學(xué)者已從交趾黃檀中分離鑒定出65個(gè)化合物，包括9個(gè)二氫黃酮、8個(gè)異黃酮、7個(gè)新黃酮、3個(gè)二氫異黃酮、5個(gè)查爾酮、3個(gè)黃烷、2個(gè)黃酮、1個(gè)異黃烷、6個(gè)酚類、5個(gè)苯甲酸及苯甲酮類、4個(gè)苯并呋喃類、2個(gè)甾體類、3個(gè)萜類、1個(gè)紫檀烷類、2個(gè)糖苷及其苷元、1個(gè)菲醌類、1個(gè)氧雜蒽酮、1個(gè)二苯乙烯類、1個(gè)叔醇類[4–14]。本課題組在前期研究的基礎(chǔ)上進(jìn)一步對(duì)其心材進(jìn)行化學(xué)成分研究，從中分離得到12個(gè)化合物。

1 材料和方法

1.1 材料

試驗(yàn)材料于2011年由老撾進(jìn)口，為佛山市家禾木家具有限公司彭慶明提供，由中國(guó)科學(xué)院華南植物園鄧云飛研究員鑒定為交趾黃檀()心材。

1.2 儀器和試劑

美國(guó)Applied Biosystems公司生產(chǎn)的API2000 LC/MS/MS質(zhì)譜儀；瑞士Bruker公司生產(chǎn)的DRX- 400(500)型核磁共振波譜儀，內(nèi)標(biāo)為四甲基硅烷試劑，化學(xué)位移用ppm表示，偶合常數(shù)用Hz表示。

柱色譜硅膠(100～200和200～300目)；柱色譜反相硅膠Rp-C18(50和70m)；柱色譜用凝膠Sepha- dex LH-20 (日本三菱)；薄層硅膠層析板(煙臺(tái)黃務(wù))；反相硅膠層析板(德國(guó)Merck)；氯仿、乙酸乙酯、甲醇、鹽酸等試劑均為分析純。

1.3 提取和分離

交趾黃檀心材5.0 kg用工業(yè)酒精浸提3次，依次為72、48和48 h，減壓濃縮后合并得到總浸膏，再溶于適量水中得懸濁液，倒入分液漏斗加入乙酸乙酯溶劑進(jìn)行萃取，合并3次萃取液再減壓濃縮,最后得到乙酸乙酯部分250.0 g。

取乙酸乙酯部分235.0 g，采用硅膠(100～200目)柱色譜進(jìn)行分離，依次以正己烷-乙酸乙酯(7∶1～1∶1)為洗脫劑進(jìn)行梯度洗脫，每次1 L收集洗脫液，各洗脫液減壓濃縮后用TLC板檢查，合并主點(diǎn)相似洗脫液，共計(jì)得到13個(gè)組分Fr-1～Fr-13。Fr-2采用硅膠柱色譜分離，以正己烷-乙酸乙酯(50∶1～10∶1)為洗脫劑進(jìn)行梯度洗脫，收集洗脫液，合并相似組分，共計(jì)得到8個(gè)亞組分Fr-2-1～Fr-2-8。Fr-2-8采用ODS-C18反相柱層析分離，以97%甲醇-水為流動(dòng)相，從洗脫液中析出白色針狀結(jié)晶，即為化合物10 (2.5 mg) (圖1)。Fr-3采用硅膠柱色譜分離, 以正己烷-乙酸乙酯(50∶1～1∶1)為洗脫劑進(jìn)行梯度洗脫，共計(jì)得到6個(gè)亞組分Fr-3-1～Fr-3-6。其中Fr-3-4采用凝膠(甲醇)柱色譜等度洗脫得到化合物3 (7.5 mg)。Fr-3-6先后采用凝膠柱色譜(氯仿-甲醇)等度洗脫、ODS反相柱色譜(甲醇-水)梯度洗脫, 得化合物4 (10.2 mg)。Fr-4采用凝膠柱(氯仿-甲醇1∶3)色譜分離，得到7個(gè)亞組分Fr-4-1～Fr-4-7。Fr-4-3采用正相硅膠柱色譜、Sephadex LH-20凝膠柱色譜和制備薄層硅膠層析，得到化合物5 (15.3 mg)、6 (18.2 mg)和12 (2.1 mg)。Fr-5采用硅膠柱(氯仿-甲醇100∶1～10∶1)色譜分離，依次梯度洗脫后經(jīng)過(guò)合并得亞組分Fr-5-1～Fr-5-17。有無(wú)色結(jié)晶從Fr- 5-4中析出來(lái)，即為化合物7 (20.0 mg)。Fr-5-6采用硅膠柱色譜分離，經(jīng)正己烷-乙酸乙酯(4∶1～1∶1)梯度洗脫得13個(gè)亞組分，F(xiàn)r-5-6-10經(jīng)反復(fù)凝膠柱色譜和硅膠柱色譜分離，得到化合物8 (25.5 mg)。Fr-5-6-12采用硅膠柱色譜分離，以正己烷-丙酮(8∶1～3∶1)梯度洗脫得到56個(gè)組分，其中Fr-5-6-12-6經(jīng)硅膠柱色譜分離，以正己烷-乙酸乙酯(4∶1)等度洗脫，得到化合物1 (11.1 mg)，F(xiàn)r-5-6-12-11經(jīng)凝膠柱(甲醇)層析及薄層硅膠層析板制備得到化合物2(2.5 mg)和9 (3.2 mg)。Fr-7采用硅膠柱色譜(氯仿-甲醇500∶1～50∶1)和凝膠(甲醇)柱色譜分離，有淡黃色結(jié)晶從組分Fr-7-11-18中析出，即為化合物11 (3.8 mg)。

圖1 化合物1～12的結(jié)構(gòu)

1.4 結(jié)構(gòu)鑒定

化合物1 無(wú)色結(jié)晶；ESI-MS: 339 [M + Na]+, 655 [2M + Na]+, 315 [M - H]–，分子式為C18H20O5;1H NMR (400 MHz, CDCl3):6.94 (1H, d,= 8.1 Hz, H-5), 6.80 (1H, d,= 8.6 Hz, H-6?), 6.66 (1H, d,= 8.7 Hz, H-5?), 6.40 (1H, dd,= 8.1, 2.5 Hz, H-6), 6.37 (1H, d,= 2.4 Hz, H-8), 5.17 (br s, -OH), 4.28 (1H, ddd,= 10.4, 3.4, 1.6 Hz, H-2a), 3.99 (1H, t,= 10.3 Hz, H-2b), 3.90 (3H, s, H-2?), 3.89 (3H, s, H-3?), 3.85 (3H, s, H-4?), 3.54 (1H, m, H-3), 2.89 (2H, m, H-4);13C NMR (100 MHz, CDCl3):155.1 (C-7), 155.0 (C-9), 152.6 (C-4?), 151.9 (C-2?), 142.3 (C-3?), 130.4 (C-5), 127.3 (C-1?), 121.4 (C-6?), 114.6 (C-10), 108.0 (C-6), 107.5 (C-5?), 103.2 (C-8), 70.4 (C-2), 61.3 (2?-OCH3), 60.8 (3?-OCH3), 56.0 (4?-OCH3), 31.8 (C-3), 31.3 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[15]報(bào)道一致, 故鑒定為7-hydroxy-2?,3?,4?-trimethoxyisoflavan。

化合物2 無(wú)色結(jié)晶；ESI-MS: 273 [M + H]+, 295 [M + Na]+, 567 [2M + Na]+, 271 [M - H]–, 分子式為C16H16O4;1H NMR [500 MHz, (CD3)2CO]:8.58 (1H, s, 4′-OH), 7.27 (2H, d,= 8.4 Hz, H-2′, 6′), 7.09 (1H, s, 6-OH), 6.84 (2H, d,= 8.5 Hz, H-3′, 5′), 6.54 (1H, s, H-5), 6.40 (1H, s, H-8), 4.87 (1H, dd,= 10.3, 2.0 Hz, H-2), 3.78 (3H, s, 7-OCH3), 2.86 (1H, m, H-4a), 2.63 (1H, ddd,= 16.2, 5.3, 2.9 Hz, H-4b), 2.10 (1H, m, H-3a), 1.96 (1H, m, H-3b);13C NMR [125 MHz, (CD3)2CO]:158.0 (C-4′), 149.2 (C-7), 147.6 (C-9), 141.2 (C-6), 134.2 (C-1′), 128.3 (C-2′, 6′), 116.0 (C-3′, 5′), 115.9 (C-5), 114.2 (C-10), 101.8 (C- 8), 78.2 (C-2), 56.4 (7-OCH3), 31.0 (C-3), 25.4 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[6]報(bào)道基本一致，故鑒定為6,4?- dihydroxy-7-methoxyflavan。

化合物3 棕色油狀固體；ESI-MS: 269 [M - H]–，271 [M + H]+, 293 [M + Na]+, 分子式為C17H18O3;1H NMR (400 MHz, CDCl3):7.22～7.09 (5H, m, B-ring), 6.65 (1H, s, H-6), 6.43 (1H, s, H-3), 6.18 (1H, ddd,= 17.0, 10.1, 6.7 Hz, H-8), 5.11 (2H, overlapped, H-9a, -OH), 5.00 (1H, d,= 6.6 Hz, H-7), 4.84 (1H, d,= 17.1 Hz, H-9b), 3.81 (3H, s, -OCH3), 3.64 (3H, s, -OCH3);13C NMR (100 MHz, CDCl3):150.3 (C-2), 144.8 (C-4), 143.0 (C-1′), 140.2 (C-8), 139.1 (C-5), 128.3 (C-3′, 5′), 127.9 (C-2′, 6′), 125.7 (C-4′), 124.4 (C-1), 115.7 (C-9), 115.0 (C-6), 97.1 (C- 3), 56.7 (4-OCH3), 55.9 (2-OCH3), 46.7 (C-7)。以上數(shù)據(jù)與文獻(xiàn)[16]報(bào)道一致，故鑒定為-dalbergiphenol。

化合物4 棕黃色粉末；ESI-MS: 255 [M + H]+, 277 [M + Na]+, 531 [2M + Na]+, 253 [M - H]–, 分子式為C16H14O3;1H NMR (400 MHz, CDCl3):7.34～7.16 (5H, m, B-ring), 6.49 (1H, s, H-6), 6.10 (1H, ddd,= 17.0, 10.2, 6.7 Hz, H-8), 5.92 (1H, s, H-3), 5.28 (1H, d,= 10.2 Hz, H-9a), 5.00 (1H, d,= 17.2 Hz, H-9b), 3.81 (1H, s, -OCH3) , 4.93 (1H, d,= 6.6 Hz, H-7);13C NMR (100 MHz, CDCl3):186.5 (C-2), 182.6 (C-5), 158.7 (C-4), 151.2 (C-1), 139.5 (C-1′), 137.4 (C-8), 131.8 (C-4′), 129.0 (C-3′, 5′), 128.8 (C-2′, 6′), 127.4 (C-6), 118.4 (C-9), 108.1 (C-3), 56.5 (4-OCH3), 47.2 (C-7)。以上數(shù)據(jù)與文獻(xiàn)[17]報(bào)道一致，故鑒定為-4-methoxydalbergione。

化合物5 棕黃色油狀固體；ESI-MS: 271 [M + H]+, 293 [M + Na]+, 563 [2M + Na]+, 269 [M -H]–，分子式為C17H18O3;1H NMR (400 MHz, CDCl3):7.39～7.17 (5H, m, B-ring), 6.58 (1H, s, H-6), 6.45 (1H, s, H-3), 6.31 (1H, ddd,= 16.9, 10.2, 6.5 Hz, H-8), 5.30 (1H, d,= 10.2 Hz, H-9a), 5.02 (1H, d,= 17.2 Hz, H-9b), 4.88 (2H, overlapped, H-7, -OH), 3.80 (3H, s, 2-OCH3), 3.75 (3H, s, 5-OCH3);13C NMR (100 MHz, CDCl3):148.5 (C-2), 147.6 (C-4), 142.9 (C-5), 141.5 (C-1?), 139.5 (C-8), 128.6 (C-3?, 5?), 128.5 (C-2?,6?), 126.7 (C-4?), 119.7 (C-1), 116.9 (C-9), 113.3 (C-6), 101.6 (C-3), 56.5 (5-OCH3), 55.8 (2- OCH3), 48.9 (C-7)。以上數(shù)據(jù)與文獻(xiàn)[18]報(bào)道一致, 故鑒定為mimosifoliol。

化合物6 無(wú)色結(jié)晶；ESI-MS: 301 [M + H]+, 323 [M + Na]+, 623 [2M + Na]+, 299 [M - H]–, 分子式為C18H20O4;1H NMR (400 MHz, CDCl3):7.18～7.10 (2H, m, B-ring), 6.90～6.83 (2H, m, B-ring), 6.69 (1H, s, H-6), 6.55 (1H, s, H-3), 6.34 (1H, m, H-8), 6.06 (1H, s, 2?-OH), 5.29 (1H, d,= 10.3 Hz, H-9a), 5.22 (1H, d,= 5.6 Hz, H-7), 5.04 (1H, d,= 17.2 Hz, H-9b), 3.76 (3H, s, -OCH3), 3.87 (3H, s, -OCH3), 3.86 (3H, s, -OCH3);13C NMR (100 MHz, CDCl3):150.1 (C-2), 153.8 (C-2?), 148.5 (C-4), 143.7 (C-5), 139.0 (C-8), 129.2 (C-1?), 128.3 (C-4?), 127.7 (C-6?), 121.3 (C-1), 120.6 (C-5?), 116.8 (C-9), 116.3 (C-3?), 113.2 (C-6), 97.9 (C-3), 57.0 (4-OCH3), 56.6 (5-OCH3), 56.1 (2-OCH3), 40.2 (C-7)。以上數(shù)據(jù)與文獻(xiàn)[19]報(bào)道一致，故鑒定為-5--methyllatifolin。

化合物7 無(wú)色結(jié)晶；ESI-MS: 287 [M + H]+, 309 [M + Na]+, 595 [2M + Na]+, 285 [M - H]–, 分子式為C17H18O4;1H NMR (400 MHz, CDCl3):7.18～7.10 (2H, m, B-ring), 6.89～6.81 (2H, m, B-ring), 6.75 (1H, s, H-6), 6.52 (1H, s, H-3), 6.32 (1H, m, H-8), 6.05 (1H, s, 2?-OH), 5.32～5.22 (2H, overlapped, H-9a, 5-OH), 5.19 (1H, d,= 5.8 Hz, H-7), 5.04 (1H, dt,= 17.1, 1.4 Hz, H-9b), 3.87 (3H, s, -OCH3), 3.85 (3H, s, -OCH3);13C NMR (100 MHz, CDCl3):153.7 (C-2?), 149.4 (C-2), 145.5 (C-4), 140.1 (C-5), 139.0 (C-8), 129.4 (C-1?), 128.4 (C-4?), 127.7 (C-6?), 122.5 (C-1), 120.6 (C-5?), 116.7 (C-9), 116.3 (C-3?), 115.2 (C-6), 97.0 (C-3), 57.1 (4-OCH3), 56.1 (2-OCH3), 40.0 (C- 7)。以上數(shù)據(jù)與文獻(xiàn)[19]報(bào)道一致，故鑒定為-lati- folin。

化合物8 白色粉末；ESI-MS: 283 [M -H]–, 307 [M + Na]+, 285 [M + H]+, 分子式為C16H12O5;1H NMR (400 MHz, CDCl3):7.36 (1H, d,= 8.4 Hz, H-1), 6.72 (1H, s, H-7), 6.55 (1H, dd,= 8.4, 2.4 Hz, H-2), 6.44 (1H, s, H-11), 6.42 (1H, d,= 2.4 Hz, H-4), 5.92 (1H, d,= 0.9 Hz, H-9), 5.90 (1H, d,= 0.9 Hz, H-9), 5.47 (1H, d,= 6.9 Hz, H-12a), 5.42 (1H, s, -OH), 4.22 (1H, dd,= 11.0, 5.0 Hz, H-6), 3.64 (1H, t,= 11.0 Hz, H-6), 3.47 (1H, m, H-6a);13C NMR (100 MHz, CDCl3) δ: 157.1 (C-3), 156.6 (C-4a), 154.2 (C-11a), 148.1 (C-10a), 141.7 (C-7a), 132.1 (C-1), 117.9 (C-6b), 112.6 (C-12b), 109.8 (C-2), 104.7 (C-7), 103.6 (C-4), 101.3 (C-9), 93.8 (C-11), 78.5 (C-12a), 66.4 (C-6), 40.1 (C-6a)。以上數(shù)據(jù)與文獻(xiàn)[20]報(bào)道基本一致，故鑒定為maackiain。

化合物9 棕色粉末；ESI-MS: 301 [M + H]+, 323 [M + Na]+, 623 [2M + Na]+, 299 [M - H]–, 分子式為C17H16O5;1H NMR [500 MHz, (CD3)2CO]:8.75 (1H, s, 3-OH), 7.29 (1H, d,= 8.4 Hz, H-1), 7.00 (1H, s, H-7), 6.55 (1H, dd,= 8.4, 2.4 Hz, H-2), 6.48 (1H, s, H-10), 6.36 (1H, d,= 2.3 Hz, H-4), 5.46 (1H, d,= 7.0 Hz, H-11a), 4.26 (1H, dd,= 10.6, 4.5 Hz, H-6), 3.75 (3H, s, 9-OCH3), 3.74 (3H, s, 8-OCH3), 3.56 (1H, m, H-6a), 3.63 (1H, m, H-6);13C NMR [125 MHz, (CD3)2CO]:159.8 (C-3), 157.8 (C-4a), 155.1 (C-10a), 151.8 (C-9), 145.0 (C-8), 133.1 (C-1), 118.7 (C-6b), 113.1 (C-11b), 111.6 (C-7), 110.6 (C-2), 104.1 (C-4), 96.9 (C-10), 79.1 (C-11a), 67.2 (C-6), 57.7 (8-OCH3), 56.5 (9-OCH3), 41.4 (C-6a)。以上數(shù)據(jù)與文獻(xiàn)[21]報(bào)道一致，故鑒定為secundiflorol Ι。

化合物10 白色針狀結(jié)晶；ESI-MS: 297 [M + H]+, 319 [M + Na]+, 615 [2M + Na]+, 295 [M -H]–，分子式為C17H12O5;1H NMR (400 MHz, CDCl3):7.96 (1H, d,= 8.6 Hz, H-1), 7.89 (1H, d,= 8.4 Hz, H-7), 7.18 (1H, d,= 1.8 Hz, H-10), 7.05 (1H, dd,= 8.4, 2.0 Hz, H-8), 6.99 (2H, m, H-2, 4), 3.92 (3H, s, -OCH3), 3.91 (3H, s, -OCH3);13C NMR (100 MHz, CDCl3):162.6 (C-3), 160.1 (C-11a), 159.2 (C-9), 158.5 (C-6), 156.5 (C-10a), 155.1 (C-4a), 122.4 (C-7), 121.6 (C-1), 116.6 (C-6b), 113.2 (C-2), 113.0 (C-8), 106.1 (C-11b), 103.5 (C-6a), 101.4 (C-4), 96.8 (C-10), 55.9 (-OCH3), 55.8 (-OCH3)。以上數(shù)據(jù)與文獻(xiàn)[22]報(bào)道一致，故鑒定為3,9-dimethoxy-6H-benzofufo[3,2-c] chromen-6-one。

化合物11 黃色粉末；ESI-MS/: 317 [M + H]+, 339 [M + Na]+, 655 [2M + Na]+, 315 [M - H]–, 分子式為C17H16O6;1H NMR (400 MHz, DMSO-6):7.24 (1H, d,= 8.8 Hz, H-6?), 7.04 (1H, s, H-4), 6.99 (1H, s, H-3), 6.93 (1H, s, H-7), 6.73 (1H, d,= 8.8 Hz, H-5?), 3.78 (3H, s, 5-OCH3), 3.81 (3H, s, 2?- OCH3), 3.80 (3H, s, 3?-OCH3);13C NMR (100 MHz, DMSO-6):148.6 (C-2?), 150.4 (C-4?), 148.2 (C-2), 145.2 (C-7a), 145.0 (C-5), 144.6 (C-6), 139.7 (C-3?), 120.5 (C-3a), 117.2 (C-1?), 115.4 (C-6?), 107.2 (C-5?), 103.8 (C-3), 102.6 (C-4), 97.7 (C-7), 58.9 (3?-OCH3), 56.0 (2?-OCH3), 55.8 (5-OCH3)。以上數(shù)據(jù)與文獻(xiàn)[23]報(bào)道一致，故鑒定為mucodianin C。

化合物12 白色粉末；ESI-MS: 441 [M -H]–, 465 [M + Na]+, 907 [2M + Na]+, 分子式為C30H50O2;1H NMR (400 MHz, CDCl3):4.57 (1H, s, H-29b), 4.69 (1H, d,= 2.0 Hz, H-29a), 3.98 (1H, ddd,= 14.7, 7.1, 4.1 Hz, H-2), 3.42 (1H, s, H-3), 2.38 (1H, td,= 11.0, 5.8 Hz, H-19), 2.04 (1H, d,= 2.8 Hz, H-21), 1.69 (3H, s, H-30), 1.02 (3H, s, H-26), 1.00 (3H, s, H-27), 0.95 (3H, s, H-24), 0.88 (3H, s, H-25), 0.84 (3H, s, H-23), 0.78 (3H, s, H-28);13C NMR (100 MHz, CDCl3):150.9 (C-20), 109.4 (C-29), 79.0 (C-3), 66.7 (C-2), 50.1 (C-9), 48.3 (C-5), 48.2 (C-18), 48.0 (C-19), 43.0 (C-14), 42.9 (C-17), 42.1 (C-1), 41.0 (C-8), 40.0 (C-22), 38.6 (C-10), 38.3 (C-4), 38.0 (C-13), 35.6 (C- 16), 34.0 (C-7), 29.8 (C-21), 28.5 (C-23), 27.4 (C-15), 25.0 (C-12), 21.6 (C-24), 20.9 (C-11), 19.3 (C-30), 18.0 (C-6, 28), 17.1 (C-25), 16.0 (C-26), 14.6 (C-27)。以上數(shù)據(jù)與文獻(xiàn)[24-25]報(bào)道基本一致，故鑒定為lup-(20) 29-ene-2,3-diol。

2 結(jié)果和討論

從交趾黃檀心材中分離鑒定得到12個(gè)化合物,分別為：7-hydroxy-2?,3?,4?-trimethoxyisoflavan (1), 6, 4?-dihydroxy-7-methoxyflavan (2),-dalbergiphenol (3),-4-methoxydalbergione (4), mimosifoliol (5),- 5--methyllatifolin (6),-latifolin (7), maackiain (8), secundiflorol Ι (9), 3,9-dimethoxy-6H-benzofufo [3,2- c] chromen-6-one (10), mucodianin C (11)和lup-(20) 29-ene-2,3-diol (12)。化合物1、5、8～12為首次從交趾黃檀心材中分離得到。

在抗骨質(zhì)疏松試驗(yàn)中，化合物3能顯著提高骨細(xì)胞的礦化能力，顯著上調(diào)BMP-2和RunX2的mRNA水平，并能顯著提高骨鈣素和I型膠原的mRNA表達(dá)水平[26]?；衔?、6和7能顯著抑制5-還原酶活性，并能競(jìng)爭(zhēng)性抑制二氫睪酮與受體的形成，從而有望治療雄激素活性過(guò)高所致的疾病,包括多毛癥、痤瘡、前列腺肥大、前列腺癌等[5]?；衔?對(duì)-葡萄糖醛酸苷酶和NO生成均表現(xiàn)出不錯(cuò)的抑制效果，提示其具有較強(qiáng)的抗炎活性。此外，有報(bào)道指出，化合物4還具有抗腫瘤、抗過(guò)敏、抗菌及瘧原蟲(chóng)抑制活性[27]。化合物5在DNA鏈斷裂試驗(yàn)中顯示出較弱的活性[18]。本課題從交趾黃檀中分離得到的這5個(gè)已知新黃酮類成分，特征性明顯，生物活性多樣，將為進(jìn)一步發(fā)掘該屬植物中潛在的新藥資源提供參考價(jià)值。

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Flavonoid and Triterpenoid Compounds from the Heartwood of

ZHONG Yanxia1a, CHEN Jiao2, MO Xinliang1a, XU Zhifang3, QIU Shengxiang3, LIU Xinhong1b*

(1a. Department of Brewing Engineering; 1b. Department of Resources and Environment, Moutai Institute,Renhuai 564507, Guizhou, China; 2. Kweichow Moutai Co. Ltd,Renhuai 564507, Guizhou, China; 3. South China Botanical Garden, Chinese Academy of Sciences,Guangzhou 510650, China)

To investigate the chemical constituents of, five neoflavonoids and seven other compounds were isolated from its heartwood by various methods, such as organic solvent extraction, fractionation and chromatographic separation techniques. Based on physical and chemical properties and spectral data, their structures were identified as 7-hydroxy-2?,3?,4?-trimethoxyisoflavan (1), 6,4?-dihydroxy-7-methoxy- flavan (2),-dalbergiphenol (3),-4-methoxydalbergione (4), mimosifoliol (5),-5--methyllatifolin (6),- latifolin (7), maackiain (8), secundiflorol Ι (9), 3,9-dimethoxy-6H-benzofufo[3,2-c]chromen-6-one (10), muco- dianin C (11), lup-(20)29-ene-2,3-diol (12). Compounds 1, 5 and 8-12 were isolated fromfor the first time.

; Heartwood; Flavonoids; Neoflavonoid; Triterpenoid

10.11926/jtsb.4435

2021-04-26

2021-06-08

貴州省教育廳青年科技人才成長(zhǎng)項(xiàng)目(KY[2018]449, KY[2018]465)；貴州省特色重點(diǎn)實(shí)驗(yàn)室項(xiàng)目(KY[2018]003)；貴州省科技計(jì)劃項(xiàng)目([2019]1295)資助

This work was supported by the Project for Growth of Young Talents in Guizhou Educational Committee (Grant No. KY[2018]449, KY[2018]465), the Project of Guizhou Key Laboratory (Grant No. KY[2018]003), and the Project for Science and Technology Planning in Guizhou (Grant No. KY[2019]1295).

鐘艷霞，女，碩士，講師，研究方向?yàn)樘烊划a(chǎn)物化學(xué)。E-mail: 290827232@qq.com

. E-mail: liuxinhong@mtxy.edu.cn