| 查看: 742 | 回复: 6 | |||
| 当前主题已经存档。 | |||
wtqua铁杆木虫 (著名写手)
|
[交流]
求助论文摘要翻译
|
||
|
喹啉是一类非常重要的杂环化合物，广泛应用于农药，医药，染料，颜料等的合成和开发。近年来，喹啉类衍生物应用于抗癌，抗HIV病毒等药物的开发以及用于有机电致光材料的合成。使得这类化合物的开发具有十分重要的意义。本文以巴豆醛为原料，与苯胺类衍生物反应，分别在氯苯、盐酸或硫酸介质中成功地合成了喹哪啶、8-氯喹哪啶、8-溴喹哪啶、8-羟基喹哪啶、8-羧基喹哪啶和8-甲氧基喹哪啶一系列喹哪啶类衍生物。并分别以喹哪啶、8-氯喹哪啶、8-溴喹哪啶和8-羟基喹哪啶为原料对8-氨基喹哪啶的合成进行了详细的研究进而以8-氨基喹哪啶为原料合成颜料黄C.I.138；最后以8-羟基喹哪啶为原料合成了具有抗癌，抗HIV病毒活性的Lavendamycin及其衍生物。 1. 喹哪啶及8-取代喹哪啶的合成 以来苯胺和2-取代苯胺为原料与巴豆醛反应，合成了喹哪啶、8-氯喹哪啶、8-溴喹哪啶、8-羟基喹哪啶、8-羧基喹哪啶和8-甲氧基喹哪啶一系列喹哪啶类衍生物 。 该反应用18%盐酸代替氯苯为介质，使用方便，降低了生产成本，反应收率由57%左右提高至85-96%。 工艺路线新颖、反应条件温和，易于控制，成本较低，具有很好的可行性和操作性。 2. 8-氨基喹哪啶的合成 本文分别研究了以邻硝基苯胺与巴豆醛反应制取8-硝基喹哪啶再经还原制8-氨基喹哪啶；8-氯喹哪啶和8-羟基喹哪啶在亚硫酸铵催化下与28%氨水发生亲核取代反应制8-氨基喹哪啶；8-羟基喹哪啶在Pd催化下与氢气和氨气作用制备8-氨基喹哪啶；上述研究均取得一定成果但结果未达预期目标，最后以8-溴喹哪啶为原料在乙酰丙酮铜、碳酸铯和乙酰丙酮的催化下在N-甲基吡咯烷酮中与25%氨水反应得到目标产物，收率74.0 %，产物经1HNMR、IR和MS确证。 3. `Lavendamycin类化合物的合成 8-羟基喹哪啶为原料，经硝化、氢化还原、催化酰化、重铬酸钾氧化得7-乙酰氨基-5，8-二酮-2-甲基喹啉，再甲基氧化得7-乙酰氨基-5，8-二酮-2-甲醛基喹啉，总收率29.27%。L-色氨酸与醇在氯化氢催化作用下发生酯化反应得到对应的色氨酸酯；再将所得色氨酸酯与7-乙酰氨基-5，8-二酮-2-甲醛基喹啉反应制得目标分子。 7-乙酰氨基-5，8-二酮-2-甲醛基喹啉的合成 有机溶剂中混合酸硝化收率82.2 %；还原反应采用催化氢化法，无水乙醇作溶剂，5 %钯-炭催化，产物不经分离，将所得反应液在无水乙酸钠和无水亚硫酸钠作用下与乙酐发生乙酰化；收率82.6%。将酰化产物溶于乙酸与重铬酸钾在室温下反应得7-乙酰氨基-5，8-二酮-2-甲基喹啉，收率50.8%；再将所得的二酮产物在二氧六环和水的混合溶液中以二氧化硒氧化得7-乙酰氨基-5，8-二酮-2-甲醛基喹啉，收率86.1 %。 色氨酸酯的制备 考察了不同结构的醇与色氨酸发生酯化反应并探讨了酯化反应催化剂的选择，以氯化氢为催化剂操作简便，反应完全，后处理方便，产物易于纯化，具有普遍适用性，制备了10种色氨酸醇酯中间体，结构经1HNMR、IR等确证。并对色氨酸氨基保护后与含卤化合物在碱性条件下进行反应制备3种相应的取代酯 环合反应 将7-乙酰氨基-5，8-二酮-2-甲醛基喹啉和色氨酸酯于干燥苯甲醚中进行环合反应得到了12种新型Lavendamycin类化合物，结构经1HNMR等确证。反应条件温和、操作简单，方法新颖。 单晶X-射线衍射分析 8-氯喹哪啶的单晶X-射线衍射分析进一步确定了化合物结构，并由单晶分析可知：8-氯喹哪啶属于正交晶系，Pca21空间群。喹啉的两个六元环所构成的二面角为2.03°，N1—C9—C8形成键角为119.62 (16)。化合物结构中Cl1—C8的键长为1.730 (2)；N1—C1的键长为1.316 (3)，N1—C9的键长为1.367 (2)，可以看出N1—C1是双键；C3—C4的键长为1.421 (2)，而C2—C3的键长为1.359 (3)，C4—C5的键长为1.410 (3)，可以看出C3—C4是单键，表明合环成功。 8-溴喹哪啶的单晶X-射线衍射分析亦进一步确定了化合物结构，由单晶分析可知：8-溴-2-甲基喹啉属于单斜晶系，P21/c空间群。喹啉的两个六元环所构成的二面角为0.49 (16)°，N1—C8—C1形成键角为120.5 (5)。化合物结构中Br1—C1的键长为1.889 (6)；N1—C7的键长为1.318 (8)，N1—C8的键长为1.365 (7)，可以看出N1—C7是双键；C9—C5的键长为1.422 (9)，而C9—C4的键长为1.411 (9)，C5—C6的键长为1.344 (10)，可以看出C9—C5是单键，证明合环成功。 |
回复此楼» 猜你喜欢
081700化学工程与技术 一志愿中海洋 323 求调剂学校
已经有12人回复
-
385分 生物学（071000）求调剂
已经有7人回复
-
材料专硕283求调剂
已经有3人回复
-
0703求调剂383分
已经有5人回复
-
323求调剂
已经有3人回复
-
26考研调剂0710 0860
已经有8人回复
-
081700学硕，323分，一志愿中国海洋大学求调剂学校
已经有3人回复
-
一志愿北京化工大学，初试成绩350求调剂
已经有5人回复
-
一志愿0817化学工程与技术，求调剂
已经有22人回复
-
085600，专业课化工原理，321分求调剂
已经有10人回复
ysm56789
荣誉版主 (知名作家)
骆驼
- 翻译EPI: 1
- 应助: 416 (硕士)
- 贵宾: 3.503
- 金币: 21031.5
- 散金: 124
- 红花: 41
- 沙发: 7
- 帖子: 5778
- 在线: 665.9小时
- 虫号: 173752
- 注册: 2006-01-21
- 性别: GG
- 专业: 流行病学方法与卫生统计
- 管辖: 海外博后
2楼2010-02-01 04:12:59
lengbingyu
金虫 (小有名气)
- 翻译EPI: 1
- 应助: 0 (幼儿园)
- 金币: 537.6
- 帖子: 272
- 在线: 42分钟
- 虫号: 948501
- 注册: 2010-01-25
- 性别: MM
- 专业: 英语语言学
3楼2010-02-01 21:48:56
lengbingyu
金虫 (小有名气)
- 翻译EPI: 1
- 应助: 0 (幼儿园)
- 金币: 537.6
- 帖子: 272
- 在线: 42分钟
- 虫号: 948501
- 注册: 2010-01-25
- 性别: MM
- 专业: 英语语言学
4楼2010-02-01 21:49:51
pharmjackie
木虫 (正式写手)
- 翻译EPI: 21
- 应助: 2 (幼儿园)
- 金币: 2210
- 帖子: 312
- 在线: 180.4小时
- 虫号: 302356
- 注册: 2006-12-02
- 性别: GG
- 专业: 有机合成
5楼2010-02-01 22:40:54
pharmjackie
木虫 (正式写手)
- 翻译EPI: 21
- 应助: 2 (幼儿园)
- 金币: 2210
- 帖子: 312
- 在线: 180.4小时
- 虫号: 302356
- 注册: 2006-12-02
- 性别: GG
- 专业: 有机合成
wtqua(金币+100): 2010-02-02 18:15
|
Quinolines is an important calss of heterocycles widely found in agrochemicals, pharmaceuticals, dyes and paints. Recently quinoline derivatives are found in anticancer, anti-HIV drugs and organic electroluminescent materials. All these make the development of this class of compounds of great significance. We successfully obtained a series of quinaldine derivatives, including quinaldine, 8-chloroquinaldine, 8-bromoquinaldine, 8-hydroxylquinaldine, 8-carboxylquinaldine, 8-methoxylquinaldine from reaction crotonaldehyde with aniline derivatives in chlorobenzene, hydrochloric acid, sulfuric acid medium respectively. Starting from quinaldine, 8-chloroquinaldine, 8-bromoquinaldine, 8-hydroxylquinaldine, we studied the synthesis of 8-aminoquinaldine, from which we obtained pigment yellow C.I. 138, and from 8-hydroxylquialdine Lavendamyci and its derivatives that possess anticancer, anti-HIV bioactivity. 1. The synthesis of quinaldine and 8-substituted quinaldine Quinaldine derivatives include quinaldine, 8-chloroquinaldine, 8-bromoquinaldine, 8-hydroxylquinaldine, 8-carboxylquinaldine, 8-methoxylquinaldine were obtained from 2-substituted aniline and crotonaldehyde. The reaction was undertaken in 18% hydrochloric acid instead of chlorobenzene. It’s a new synthetic route noted for its easiness to handle, mild reaction conditions, low cost, good feasibility and higher yield 85-96% compared to 57%. 2. The synthesis of 8-aminoquialdine 8-aminoquialdine can be effected by either of the following method: 1) 2-nitroaniline was reacted with crotonaldehyde and reduced to provide 8-aminoquialdine. 2) 8-chloroquinaldine and 8-hydroxylquinaldine underwent SN reaction with 28% aqueous ammonia in the presence of ammonium sulfite to give 8-aminoquinaldine. 3) Pd catalyzed 8-hydroxylquinaldine reaction with hydrogen and ammonia gas. Although significant improvements had been made, the above study was to a certain extent limited. The target material was finally obtained through the reaction of 8-bromoquinaldine with 25% aqueous ammonia catalyzed by copper acetylacetonate, caesium carbonate and acetylacetone in NMP with a 74.0% yield. The product was confirmed by 1HNMR, IR and MS. 3．The synthesis of Lavendamycin and it derivatives 8-hydroxylquialdine was nitrated, hydrogenated, acylated and then oxidized with potassium dichromate to give 7-acetylamino-5,8-dione-2-methylquinoline, oxidization of the methyl group of the product give 7-acetylamino-5,8-dione-2-formylquinaldine {N-(2-formyl-5,8-dioxo-5,8-dihydroquinolin-7-yl)acetamide with a yield of 29.27%. L-tryptophan was esterified with alcohol catalyzed by chlorine hydride and then reacted with 7-acetylamino-5,8-dione-2-formylquinaldine to give the target molecule. The synthesis of 7-acetyl-5,8-dione-2-formylquinoline The yield of nitration with mixed acids is 82.2%, while that of the catalyzed hydrogenation with 5% Pd-C in absolute alcohol is 82.6% in which the reaction mixture, without isolation, was acetylated with acetic anhydride in the presence of anhydrous sodium acetate and anhydrous sodium sulfite, the acylates was dissolved in acetic acid and reacted with potassium dichromate to give 7-acetylamino-5,8-dione-2-methylquinoline with a yield of 50.8%, which was further oxidized with selenium dioxide in a mixture of dioxane and water to give 7-acetylamino-5,8-dione-2-formylquinoline in 86.1% yield. The preparation of tryptophan ester We screened the esterification of alcohol with different structure moiety in different catalyst. The most convenient is one using chlorine hydride as the catalyst. The reaction condition was characterized by easiness to operate, highly conversion, easily work-up, wide functionality compatibility. The obtained 10 intermediate were confirmed by 1HNMR, IR. Reaction of halo-substituted compounds with amino group protected tryptophan gave 3 corresponding esters. Cyclization reaction 7-acetylamino-5,8-dione-2-formylquinoline was cyclized with tryptophan esters in dry anisole to give 12 novel Lavendamycin derivatives, and their structures were confirmed by 1HNMR. The reaction was novel, operated under mild reaction condition, easy to handle. Single crystal X-ray diffraction 8-chloroquinaldine was confirmed by its single crystal X-ray diffraction. It’s a orthorhombic system, pca 21 space group. The dihedral angle of the two six-membered rings is 2.03。， the bond angle of N1-C7-C8 is 19.62(16). The bond lengths of 1.730(2) of C11-C8, 1.316(3) of N1-C1, 1.367(2) of N1-C9 indicate that N1-C1 is a double bond and C3-C4 is a single bond can be inferred from the bond length of 1.412(2) of C3-C4, 1.359(2) of C2-C3, 1.410(3) of C4-C5. This suggests that the cyclization was successful. 8-bromoquinaldine was confirmed by its single crystal X-ray diffraction. From the diffraction test, we know that 8-romo-2-methylquinoline was monoclinic system, p2/c space group. Its dihedral angle of the two six-memebered ring of the quinoline is 0.49。, the bond angle of N1-C8-C1 is 120.5(5). The bond lengths of 1.889(6) of Br1-C1, 1.318(8) of N1-C, 1.365(7) of N1-C8 indicate that N1-C7 is double bonded. While the bond length of 1.422 (9) of C9-C5, 1.411 (9) of C9—C4, 1.344 (10) of C5—C6, support that C9-C5 is single bonded. All these indicate the successful completion of the Cyclization reaction. |
6楼2010-02-02 17:32:20
wtqua
铁杆木虫 (著名写手)
- 应助: 38 (小学生)
- 金币: 26414.4
- 散金: 100
- 红花: 1
- 帖子: 1725
- 在线: 125.3小时
- 虫号: 357022
- 注册: 2007-04-27
- 性别: GG
- 专业: 应用有机化学
7楼2010-02-02 18:16:46
