烯基

The cytotoxicity of these compounds were valuated by MTT and SRB methods using three cancer cell lines: HL-60, A-549, P-388. Cyclo-shikonin, and cyclo-alkannin have high cytotoxicity against HL-60.The chiral center of side chain has no effect on their activity. 2- 1-(Acetyloxy-4-methyl-3-pentenyl -5, 8-dihydroxy-1, 4-naphthoquinone (105) has strong inhibition effect on P-388 cells. 2- 1-(isooctyloxy-4-methyl-3-pentenyl -5, 8-dihydroxy-1, 4-naphthoquinone (108) and 2- 1-(2-furoyloxy-4-methyl-3-pentenyl -5, 8-dihydroxy-1, 4-naphthoquinone (112) have high inhibition on A-549.Shikonin (1), alkannin (2), and their derivatives have the structural features of a planar chromophores and short side chain. We examined the ability to inhibit the telomerase.

抗肿瘤活性初步筛选测试采用小鼠白血病P-388肿瘤细胞和人肺癌A-549肿瘤细胞进行，结果表明侧链羟基的手性对抗肿瘤活性无明显影响；有数个化合物具有很好的体外抑制活性，特别是化合物2-（1-异辛酰氧基-4-甲基-3-戊烯基）-5，8-二羟基-1，4-萘醌（108）和2-[1-（2-呋喃甲酰氧基）-4-甲基-3-戊烯基]-5，8-二羟基-1，4-萘醌（112）体外显示对人肺癌A-549肿瘤细胞有强效；2-（1-乙酰氧基-4-甲基-3-戊烯基）-5，8-二羟基-1，4-萘醌（105）对小鼠白血病P-388肿瘤细胞有强效；环紫草素和环异紫草素对人白血病HL-60细胞有强烈抑制作用。

The method involves exposing the cells to a compound having the formula I in which: w is a nucleic acid x is a non-amino acid or non-peptide nucleic acid binding group y is a spacer having a chain length equivalent to 1-30 carbon-carbon single covalent bonds or is absent R4 is H or halogen or CH2O-R3; and R1, R2 and R3 are the same or different and are either hydrogen, methyl, ethyl, alkyl, alkenyl, hydroxylated alkyl, hydroxylated alkenyl groups or ether containing alkyl, alkenyl, hydroxylated alkyl or hydroxylated alkenyl groups optionally being an acyl group having a carbon chain length equivalent to 3-24 carbon atoms saturated or unsaturated, with the proviso that at least one of R1, R2 or R3 includes a group having a carbon chain of 3-24 carbon atoms saturated or unsaturated, or to a compound having the formula II in which: w is a nucleic acid x is a non-amino acid or non-peptide nucleic acid binding group y is a space having a chain length equivalent to 1-30 carbon-carbon single covalent bonds or is absent, R5 is alkyl, alkenyl, hydroxylated alkyl, hydroxylated alkenyl group or ether containing alkyl, alkenyl, hydroxylated alkyl or hydroxylated alkenyl group optionally being an acyl group having a carbon chain length equivalent to 3-24 carbon atoms saturated or unsaturated, with the proviso that R5 includes a group having a carbon chain of 3-24 carbon atoms saturated or unsaturated.

该方法包括使细胞暴露于具有式的化合物，在式中：w是核酸，x是非氨基酸或者非肽核酸结合基团，y是具有等于1―30个碳―碳单共价键的链长的间隔基或者不存在，R4是H或者卤素或者CH2O－R3；R1、R2和R3是相同的或者不同的并且是氢、甲基、乙基、烷基、链烯基、羟基化烷基、羟基化链烯基或者包含烷基、链烯基、羟基化烷基或羟基化链烯基的醚，任选地是来源于具有等于3―24个碳原子的碳链长的饱和或不饱和脂肪酸的酰基，其条件是R1、R2或者R3的至少一个包括具有3―24个碳原子的饱和或不饱和碳链的基团，或者使细胞暴露于具有式的化合物，在式中：w是核酸，x是非氨基酸或者非肽核酸结合基团，y是具有等于1―30个碳―碳单共价键的链长的间隔基或者不存在，R5是烷基、链烯基、羟基化烷基、羟基化链烯基或者包含烷基、链烯基、羟基化烷基或羟基化链烯基的醚，任选地是具有等于3―24个碳原子的饱和或不饱和碳链的链长的酰基，其条件是R5包括具有3―24个碳原子的饱和或不饱和碳链的基团。

They are 4-(2- hydroxy-3-butynlenoxy) benzoic acid (1, WA), 5-chloro-7, 8-dihydroxy-7-methyl- 6-oxo-3- [ -3, 4-dihydroxy-3, 5-dimethyl-l-heptylene] -1H-8, 8a-dihydrobenzo [2, 3-c] pyran (2, WB),-2-(2-methyl-2-dibutene diamido)-2-butenoic acid (3, B5262), 3, 4-dihydro-9, 10-dihydroxy-7-methoxy-3-methyl-1H-naphtho [2, 3- c] pyran-1-one (4, A73 semi-Vioxanthin), 8, 8'-bis (6, 9-dioxo-3,4-dihydro-10- hydroxy-7-methoxy-3-methyl-1H-naphtho [2, 3-c] pyran-1-one)(5, A122 Xanthomegnin), 2, 5-dioxo-3a-hydroxymethyl-3, 3a, 6, 6a-tetrahydro-furo [2, 3-b] furan (6, 1003-2), 7-acety1-5-chloro-6, 8-dioxo-7-methyl-3- [ -3, 5-dimethyl-1, 3- diheptylene] -4aH-benzo [2, 3-c] pyran (7, M2-2 sclerotiorin), respectively.

它们分别被命名为4-（2-羟基-3-丁炔氧基）苯甲酸（1，WA）、5-氯-7，8-二羟基-7-甲基-6-氧代-3-[-3，4-二羟基-3，5-二甲基-1-庚烯基]-1H-8，8a-二氢苯并[2，3-c]吡喃（2，WB）、-2-（2-甲基-2-丁烯二酰亚胺基）-2-丁烯酸（3，B5262）、3，4-氢-9，10-二羟基-7-甲氧基-3-甲基-1H-萘并［2，3-c］吡喃-1-酮（semi-Vioxanthin，4，A73）、8，8'-双（6，9-二氧代-3，4-二氢-10-羟基-7-甲氧基-3-甲基-1H-萘并［2，3-c］吡喃-1-酮）（Xanthomegnin，5，A122）、2，5-二氧代-3a-羟甲基-3，3a，6，6a-四氢-呋喃并［2，3-b］呋喃（6，1003-2），7-乙酰基-5-氯-6，8-二氧代-7-甲基-3-［-3，5-二甲基-1，3-庚二烯基］-4aH-苯并2，3-c］吡喃（Sclerotiorin，7，M2-2）。

A process for the carbonylation of allylic butenyl ether (for example, methyl crotyl ether, 3-methoxybutene-1 and mixtures thereof) or mixture of butadiene and alcohol and production of beta-gamma unsaturated carboxylic acid esters (for example, methyl-3-pentenoate) utilizing a rhodium-containing catalyst for example, dicarbonylacetylacetonate rhodium(I or the like promoted with an iodide-containing compound (for example, HI, AlI3, SnI4, TiI4, CrI3, and CoI2 or the like).

一种将烯丙型丁烯基醚(如甲基巴豆基醚、3－甲氧基丁烯－1及其混合物)或者丁二烯与醇的混合物羰基化的方法，以及由含碘化物化合物(如HI、AlI3、SnI4、TiI4、CrI3和CoI2或等效物)促进，用含铑催化剂如二羰基乙酰丙酮酸铑(I或其等效物制备β－γ不饱和羧酸酯(如甲基－3－戊烯酸酯)的方法。

However, the first one enzyme 1-deoxy-D-xylulose 5-phosphate synthase gene and the second one enzyme 1-deoxy-D-xylulose 5-phosphate reductoisomerase gene in MEP pathway had been reported and expressed in the latex of rubber tree, indicating that MEP pathway may be involved in rubber biosynthesis.4 - hydroxy -3 - methyl -2 -- butenyl -4 - phosphate reductaseis the last enzyme that catalytic 4 - hydroxy -3 - methyl -(2E)- butenyl -4 - phosphate to generate isopentenyl pyrophosphate.

然而已有报道MEP途径中第1个酶1-脱氧-D-木酮糖-5-磷酸合成酶（1-deoxy-D-xylulose 5-phosphate synthase，DXS）基因和第2个酶1-脱氧-D-木酮糖-5-磷酸还原酶（1-deoxy-D-xylulose 5-phosphate reductoisomerase ，DXR）基因在橡胶树胶乳中的表达，这表明MEP途径可能参与橡胶的生物合成。4-羟基-3-甲基-2--丁烯基-4-磷酸还原酶（4-hydroxy -3-methyl-2--butenyl-4-diphosphate reductase，HDR）是异戊烯基焦磷酸合成途径之一甲基赤藓糖磷酸（methylerythritol phosphate，MEP）途径中的最后一个酶，催化4-羟基-3-甲基-(2E)-丁烯基-4-磷酸生成异戊烯基焦磷酸。

Firstly, 3-ethylthiobutanal was prepared from crotonaldehyde reacting with ethanehiol in triethylamine with high yield. Secondly, methyl acetoacetate was converted to 6-ethylthiohept-3-en-2-one by three steps via hydrolysis, condensation with 3-ethyltio-butanal and dehydration, then 6-ethylthiohept-3-en-2-one was cycloco ndensed with dimethyl malonate by Michael addition and Claisen condensation, followed by saponification and decarboxylation to give the intermediate of 5-(2-ethylthiopropyl)-cyclohexane-1,3-dione.

首先，以巴豆醛与乙硫醇为原料，在三乙胺的催化作用下高收率制得3-乙硫基丁醛；然后从乙酰乙酸甲酯出发，通过碱水解、与3-乙硫基丁醛缩合、脱水三步反应合成6-乙硫基-3-烯-2-庚酮，接着6-乙硫基-3-烯-2-庚酮与丙二酸二甲酯通过Michael加成和Claisen缩合成环，再通过皂化和脱羧反应生成中间体5-[2-丙基]-1，3-环己二酮；再与丙酸酐反应丙酰化，最后与0-3-氯-2-丙烯基羟胺肟化，得到目标化合物烯草酮。

The chapter two was focused on the samarium diiodide promoted organic reactions and their applications in organic synthesis, firstly, a new synthesis of highly substituted cyclopentadienes from a,β-alkynone promoted by samarium diiodide was investigated and the highly substituted cyclopentadienes were prepared in moderate to good yields under mild conditions. Secondly, the Michael addition and Michael-aldol tandem reaction of diorganyl diselenides or diorganyl disulfides with α,β-alkynones mediated by samarium diiodide were studied and a series of alkenylsulfides and alkenylselenides were prepared in good yields. Then the highly regioselecfive nucleophilic addition of the allylsamarium bromide to α,β-alkynones were explored. We found that the allylsamarium bromide reacts with α,β-alkynones to afford regiospecificly 1. 2-nucleophilic addition products in good yields under mild condition. At last we studied the coupling reaction of aryl halides promoted by NiCl〓/PPh〓/Sm〓.

第二章 研究了二碘化钐、金属钐促进的有机反应：1、二碘化钐促进下α，β-炔基酮的偶联环化反应，提供了一种制备多取代环戊二烯的新方法；2、二碘化钐促进下的二硫醚、二硒醚与α，β-炔基酮的Michael加成反应，为高产率地制备多取代的烯基硫或烯基硒化合物提供了方便可靠的新方法；3、二碘化钐促进下的二硫醚、二硒醚与α，β-炔基酮和醛、酮的Michael—aldol串联反应，提供了一种一锅法高产率地制备多取代的含硫的烯丙基醇或含硒的烯丙基醇类化合物的方便可靠的原子经济性的新方法；4、烯丙基溴化钐与α，β-炔基酮的高度区域选择性的1，2-亲核加成反应；5、NiCl〓/PPh〓/Sm〓促进的卤代芳烃的偶联反应-一种从各种卤代芳烃制备联苯类化合物的有效方法。

Chapter 2 has analysized the conversly synthetic means of solanesol and designed novelly synthetic routes of solanesol and key intermediate Chapter 3 has summarized the preparation of trans-3-methyl-4-hydroxy (bromo-2-butenyl oxy methyl benzene In chapter 4 ,a novel technology of important intermediate(all trans-8-bromo geranyl acetate),which is suitable for industrial procedure , was found .meanwhile,an another new way has been invented ,of which the key intermediate (all trans-8-hydroxy geranyl acetate) has been produced.

第二部分分析了茄尼醇的逆合成方法，设计了一条适合于合成茄尼醇的合成路线及其重要中间体的合成路线。第三部分研究了重要中间体[Trans-3-甲基-4-羟基-2-丁烯基乙酰基(苄基，2，3-二氢吡喃基)醚]的合成新方法，找到了一条适合于工业化生产的制备反式-3-甲基-4-羟基-2-丁烯基苄基醚的新方法。第四部分研究了重要中间体[-3，7-二甲基-8-羟基-2，6-辛二烯-1-醇乙酸酯、-3，7-二甲基-8-溴-2，6-辛二烯-1-醇乙酸酯]的合成新方法，找到了一条适合于工业化生产的制备它们的新方法；同时研究了一条制备-3，7-二甲基-8-羟基-2，6-辛二烯-1-醇乙酸酯的另一新方法。

These compounds were identified as follows:chrysophanol (FP-1),physcion(FP-2),eriosematin(FP-3),scoparone(FP-4),lupeol(FP-5),betulinic acid(FP-6),3\',4\'-Dihydroxy-trans-cinamic acid octacosyl ester(FP-7),β-sitosterol (FP-8),flemiphilippinone A(FP-9),monopalmitin(FP-10),emodin(FP-11),islandicin (FP-12),salicylic acid(FP-13),p-methoxyphenylpropionic acid(FP-14),trideca-1, 3-diene(FP-15),lupinifolin(FP-16),flemichin D(FP-17),flemiphilippinin A(FP-18), auriculasin(FP-19),erythrinin B(FP-20),6-C-prenylluteolin(FP-21), 8-(1,1-dimethylallyl) genistein(FP-22),flemiphilippinin E(FP-23),flemiphilippinin F (FP-24),5,7,3\',4\'-tetrahydroxy-6,8-diprenylisoflavone(FP-25),flemiphilippinin D (FP-26),dorsmaninsⅠ(FP-27),osajin(FP-28),6,8-diprenyleriodictyol(FP-29), lupinalbin A(FP-30),genistein(FP-31),3\'-O-methylorobol(FP-32),orobol(FP-33), 5,7,2\',3\',4\'-pentahrdroxyflavone(FP-34),the mixture of biochanin A and prunetin (FP-35 and 36),genistin(FP-37),sophororicoside(FP-38),3\'-O-methylorobol-7-glucoside(FP-39),the mixture of sissotrin and prunetin 4\'-O-β-D-glucoside(FP-40 and 41),adenosine(FP-42) and luteoloside(FP-43,mixture).

这些化合物分别为大黄酚(FP-1)、大黄素甲醚(FP-2)、eriosematin(FP-3)、滨蒿内酯(FP-4)、羽扇豆醇(FP-5)、白桦酸(FP-6)、咖啡酸二十八烷酯(FP-7)、β-谷甾醇(FP-8)、蔓性千斤拔酮A(FP-9)、单棕榈酸甘油酯(FP-10)、大黄素(FP-11)、islandicin(FP-12)、水杨酸(FP-13)、对甲氧基苯丙酸(FP-14)、十三烷-1，4-二烯烃(FP-15)、lupinifolin(FP-16)、千斤拔素D(FP-17)、蔓性千斤拔素A(FP-18)、auriculasin(FP-19)、erythrinin B(FP-20)、6-C-异戊烯基木犀草素(FP-21)、8-(1，1-二甲烯丙基)-染料木黄酮(FP-22)、蔓性千斤拔素E(FP-23)、蔓性千斤拔素F(FP-24)、5，7，3′，4′-四羟基-6，8-双异戊烯基异黄酮(FP-25)、蔓性千斤拔素D(FP-26)、dorsmaninsⅠ(FP-27)、osajin(FP-28)、6，8-双异戊烯基圣草素(FP-29)、lupinalbin A(FP-30)、染料木黄酮(FP-31)、3\'-O-甲基香豌豆苷元(FP-32)、奥洛醇(FP-33)、5，7，2′，3′，4′-五羟基黄酮(FP-34)、鹰嘴豆素甲和樱黄素的混合物(FP-35和FP-36)、染料木苷(FP-37)、槐属苷(FP-38)、7-葡萄糖基-3\'-O-甲基香豌豆苷(FP-39)、印度黄檀苷和樱黄素4′-O-β-D-葡萄糖苷的混合物(FP-40和FP-41)、腺嘌呤核苷(FP-42)和木犀草苷(FP-43，混合物)。

Laba garlic, the formation of green pigment and red onion with a certain degree of similarity, diallyl sulfide and propylene oxide exists at the same time, Green took place, there is Propylene oxide sulfide, there is no oxidation of allyl sulfur objects when changes occur red.

腊八蒜绿色素的形成与洋葱红变具有一定的相似性，烯丙基与丙烯基硫氧化物同时存在时，就发生绿变，存在丙烯基硫氧化物，不存在烯丙基硫氧化物时，就发生红变。

For a big chunk of credit-card losses; the number of filings (and thus charge-off rates) would be rising again, whether

年美国个人破产法的一个改动使得破产登记急速下降，而后引起了信用卡大规模的亏损。

Eph. 4:23 And that you be renewed in the spirit of your mind

弗四23 而在你们心思的灵里得以更新