脱氢松香骨架上芳杂环的构建及其荧光性质研究
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摘要
脱氢松香酸是可再生资源松香异构体成分之一,广泛应用于涂料、胶粘剂、油墨、造纸、橡胶、食品添加剂及生物制品等领域。它是手性纯物质,含有三个手性碳原子;有一个反应性官能团——羧基;具有许多天然药物都具有的芳香型三环二萜结构。因此,利用脱氢松香的结构特点,在脱氢松香骨架上构建芳杂环,有望合成出多功能脱氢松香衍生物,开发新型手性荧光衍生试剂、高效低毒药物等具有高附加值的产品。这不仅符合绿色化学的要求,而且能带来良好的社会效益与经济效益。
首先,本文研究了脱氢松香酸的重排反应。它的甲酯、12 溴代甲酯分别通过7 位氧化,二氧化硒氧化,烯酮选择性还原成烯醇,最后在强路易斯酸作用下重排,得到了两个四氢蒽类化合物。对这两个产物荧光性质的研究表明,λ(ex) 在280-290nm 之间, λ_(em) 在345-355nm 之间,与脱氢松香酸甲酯相比,它们的激发波长与发射波长均有所红移。而12 溴代13 硝基脱异丙脱氢松香酸甲酯在同样条件下经过反应后生成了一个萘类化合物和一个四氢菲类化合物。我们用二维核磁对这两个化合物的精细结构进行了研究,结果表明生成的萘类化合物骨架,在脱氢松香酸酯的衍生物重排中还是首次被发现。我们还探讨了这类重排反应的机理,为控制重排产物的生成提供了理论基础。
其次,通过12 氨基脱氢松香酸甲酯,顺式12 氨基脱异丙基脱氢松香酸甲酯与2,4 二硝基邻氯苯甲酸偶联,得到两种灭酸。灭酸进一步关环,水解得到了三个深红色松香基吖啶酮化合物。另外还合成了三个重要中间体,可用来构建多种芳杂环。三个吖啶酮的荧光λ_(ex)/λ_(em)=280-290nm/310-330nm,与脱氢松香甲酯相比,有所红移,说明有了很大改善。这些产物颜色鲜艳有开发成新型颜料的优良性能。 再次,本文还通过顺式12 氨基脱异丙基脱氢松香酸甲酯与甘油脱水缩合,在松香骨架上构建了喹啉环,生成了两个喹啉异构体;通过对12-溴代-13,14-二硝基脱异丙基脱氢松香酸甲酯的还原,重氮化反应,合成了一个三唑化合物。松香基喹啉的荧光λ_(ex)/λ_(em)=255-260nm/370-380nm,松香基三唑的荧光λ_(ex)/λ_(em) =293.0nm/364.0nm。此外,还通过12 氨基、12 氨基14 硝基脱氢松香酸甲酯与马来酸酐反应,分别合成了两种N-取代马来酰亚胺。其热失重曲线表明起始失重温度分别为220℃和81℃,失重50%时的温度分别为466℃和442℃,说明具有良好的热稳定性能,有开发成高分子材料耐热改性剂的前景。14 硝基N?取代马来酰亚胺由于间硝基的影响而没有荧光,另一酰亚胺的荧光λ_(ex)/λ_(em) =268.0nm/402.0nm。总之,本论文共合成了16 个新化合物,它们的结构用红外光谱、核磁共振谱、质谱等分析手段进行了鉴定。研究表明,通过在脱氢松香骨架上构建芳杂环,脱氢松香的荧光性质和耐热性能能得到一定改善,这就为多功能脱氢松香衍生物的开发奠定了基础。这些化合物的生理活性还有待研究。
Dehydroabietic acid(DAA) is one of the isomerides in the renewable rosin. It is widely used in the fields such as paint, adhesives, printing ink, papermaking, rubber food, etc. Like some natural drug, it has a aromatic diterpene structure with three ring. It also has three chiral carbon atom and a reactive carboxy group. For these reasons, DAA might be hopefully modified to some multifunctional derivatives which can use as high added value products like novel fluorescence derivatization reagents and efficient but low toxic medicines through constructing aromatic or heteroaromatic ring on DAA’s skeleton. It not only meet with the de)and of green chemistry but also bring about favorable economical and social effects.
In this paper, we firstly studied the rearrang_(em)ent of DAA derivatives. Its’methyl ester and 12 bromo methyl ester were respectively oxidized, reduced and then rearranged under the existence of lewis acid to tetrahydroanthracene derivatives with fluorescent λex/λ_(em) of 280-290nm/345-355nm. Compared with DAA’s methyl ester, both the products’maximal excitation wavelengths andemission wavelengths are red shifted. Methyl 12-bromo-13-nitro-deisopropyldehydroabietate was lastly rearranged to different products under the same conditions however. One of the products was naphthalene compound and the other was tetrahydrophenanthrene compound. Using 2D-NMR, we studied their fine structures. Among them, the naphthalene compound has a skeleton firstly observed in DAA’s rearrangement products. A possible mechanism of the rearrangement reactions is discussed.
Then, 12-aminodehydroabietate and cis-12-aminodeisopropyldehydroabietate were coupled respectively with 2-chloro-3,5-dinitrobenzoic acid. Their products were cyclized with POCl3 and further hydrolyzed to red acridones. Three other intermediate compounds which can be used to the synthesis of other acridones were also synthesized. The three acridonesemit fluorescence of 310-330 nm ifexcited by a violet light ranging 280-290 nm. These bright-coloured products have good properties forexploiting novel dyes. By coupled with glycerol, cis-12-aminodeisopropyldehydroabietate were converted to quinolines with fluorescent λ_(ex)/ λ_(_(em)) of 255-260nm/370-380nm. 12-bromo-13,14-dinitro-deisopropyldehydroabietate was reduced , diazotized to triazoles with fluorescent λ_(ex)/λ_(em) of 293nm/364nm.
In addition, two N-DAAmaleimides were synthesized by the reaction of 12-aminodehydroabietate, 12-amino-14-nitrodehydroabietate with maleic anhydride respectively. The TGA curves showed that two products lost half weight at 466℃and 442℃respectively. It indicates products’good thermostability. The nitromaleimide is nonfluorescent substance and the another maleimideemit fluorescence of 402 nm ifexcited by a violet light ranging 268 nm.
In summary, 16 new compounds were synthesized and characterized by IR, NMR and MS in this paper. Our study shows that DAA’s properties such as fluorescence, thermostability were improved through constructing aromatic or heteroaromatic ring on DAA’s skeleton. All that laid the groundwork for futureexploitation of multifunctional reagents.
首先,本文研究了脱氢松香酸的重排反应。它的甲酯、12 溴代甲酯分别通过7 位氧化,二氧化硒氧化,烯酮选择性还原成烯醇,最后在强路易斯酸作用下重排,得到了两个四氢蒽类化合物。对这两个产物荧光性质的研究表明,λ(ex) 在280-290nm 之间, λ_(em) 在345-355nm 之间,与脱氢松香酸甲酯相比,它们的激发波长与发射波长均有所红移。而12 溴代13 硝基脱异丙脱氢松香酸甲酯在同样条件下经过反应后生成了一个萘类化合物和一个四氢菲类化合物。我们用二维核磁对这两个化合物的精细结构进行了研究,结果表明生成的萘类化合物骨架,在脱氢松香酸酯的衍生物重排中还是首次被发现。我们还探讨了这类重排反应的机理,为控制重排产物的生成提供了理论基础。
其次,通过12 氨基脱氢松香酸甲酯,顺式12 氨基脱异丙基脱氢松香酸甲酯与2,4 二硝基邻氯苯甲酸偶联,得到两种灭酸。灭酸进一步关环,水解得到了三个深红色松香基吖啶酮化合物。另外还合成了三个重要中间体,可用来构建多种芳杂环。三个吖啶酮的荧光λ_(ex)/λ_(em)=280-290nm/310-330nm,与脱氢松香甲酯相比,有所红移,说明有了很大改善。这些产物颜色鲜艳有开发成新型颜料的优良性能。 再次,本文还通过顺式12 氨基脱异丙基脱氢松香酸甲酯与甘油脱水缩合,在松香骨架上构建了喹啉环,生成了两个喹啉异构体;通过对12-溴代-13,14-二硝基脱异丙基脱氢松香酸甲酯的还原,重氮化反应,合成了一个三唑化合物。松香基喹啉的荧光λ_(ex)/λ_(em)=255-260nm/370-380nm,松香基三唑的荧光λ_(ex)/λ_(em) =293.0nm/364.0nm。此外,还通过12 氨基、12 氨基14 硝基脱氢松香酸甲酯与马来酸酐反应,分别合成了两种N-取代马来酰亚胺。其热失重曲线表明起始失重温度分别为220℃和81℃,失重50%时的温度分别为466℃和442℃,说明具有良好的热稳定性能,有开发成高分子材料耐热改性剂的前景。14 硝基N?取代马来酰亚胺由于间硝基的影响而没有荧光,另一酰亚胺的荧光λ_(ex)/λ_(em) =268.0nm/402.0nm。总之,本论文共合成了16 个新化合物,它们的结构用红外光谱、核磁共振谱、质谱等分析手段进行了鉴定。研究表明,通过在脱氢松香骨架上构建芳杂环,脱氢松香的荧光性质和耐热性能能得到一定改善,这就为多功能脱氢松香衍生物的开发奠定了基础。这些化合物的生理活性还有待研究。
Dehydroabietic acid(DAA) is one of the isomerides in the renewable rosin. It is widely used in the fields such as paint, adhesives, printing ink, papermaking, rubber food, etc. Like some natural drug, it has a aromatic diterpene structure with three ring. It also has three chiral carbon atom and a reactive carboxy group. For these reasons, DAA might be hopefully modified to some multifunctional derivatives which can use as high added value products like novel fluorescence derivatization reagents and efficient but low toxic medicines through constructing aromatic or heteroaromatic ring on DAA’s skeleton. It not only meet with the de)and of green chemistry but also bring about favorable economical and social effects.
In this paper, we firstly studied the rearrang_(em)ent of DAA derivatives. Its’methyl ester and 12 bromo methyl ester were respectively oxidized, reduced and then rearranged under the existence of lewis acid to tetrahydroanthracene derivatives with fluorescent λex/λ_(em) of 280-290nm/345-355nm. Compared with DAA’s methyl ester, both the products’maximal excitation wavelengths andemission wavelengths are red shifted. Methyl 12-bromo-13-nitro-deisopropyldehydroabietate was lastly rearranged to different products under the same conditions however. One of the products was naphthalene compound and the other was tetrahydrophenanthrene compound. Using 2D-NMR, we studied their fine structures. Among them, the naphthalene compound has a skeleton firstly observed in DAA’s rearrangement products. A possible mechanism of the rearrangement reactions is discussed.
Then, 12-aminodehydroabietate and cis-12-aminodeisopropyldehydroabietate were coupled respectively with 2-chloro-3,5-dinitrobenzoic acid. Their products were cyclized with POCl3 and further hydrolyzed to red acridones. Three other intermediate compounds which can be used to the synthesis of other acridones were also synthesized. The three acridonesemit fluorescence of 310-330 nm ifexcited by a violet light ranging 280-290 nm. These bright-coloured products have good properties forexploiting novel dyes. By coupled with glycerol, cis-12-aminodeisopropyldehydroabietate were converted to quinolines with fluorescent λ_(ex)/ λ_(_(em)) of 255-260nm/370-380nm. 12-bromo-13,14-dinitro-deisopropyldehydroabietate was reduced , diazotized to triazoles with fluorescent λ_(ex)/λ_(em) of 293nm/364nm.
In addition, two N-DAAmaleimides were synthesized by the reaction of 12-aminodehydroabietate, 12-amino-14-nitrodehydroabietate with maleic anhydride respectively. The TGA curves showed that two products lost half weight at 466℃and 442℃respectively. It indicates products’good thermostability. The nitromaleimide is nonfluorescent substance and the another maleimideemit fluorescence of 402 nm ifexcited by a violet light ranging 268 nm.
In summary, 16 new compounds were synthesized and characterized by IR, NMR and MS in this paper. Our study shows that DAA’s properties such as fluorescence, thermostability were improved through constructing aromatic or heteroaromatic ring on DAA’s skeleton. All that laid the groundwork for futureexploitation of multifunctional reagents.
引文
1.Chen Gangfung D. Developments in the field of rosin chemistry and its implications in coatings[J]. Prog Org Coat, 1992, 20(2):139-167.
2.Bhatnagar M S. Applications of rosin-part 1 : Surface coatings and inks[J]. Paint Resin,1983,53(6):45-49.
3.Bhatnagar M S. Applications of rosin-part 2 : Adhesives[J]. Paint Resin, 1984, 54(1):42-43.
4. 邹志琛, 普绍芬. 光学纯去氢枞酸的制备与表征[J]. 化学试剂, 1996,18(4):241-242.
5.阎丽萍, 欧阳福承. 松香歧化的研究[J]. 吉林化工学院学报, 1994, 11(1):40-43.
6.段文贵,岑波. 去氢枞酸基新型甜菜碱类两性表面活性剂的合成[J]. 现代化工, 2004, 24(4):39-42.
7.梁梦兰, 叶建峰等. 松香衍生物的季铵盐阳离子表面活性剂的合成与性能测定[J]. 化学世界, 2000, 3:138-141.
8.王延, 宋湛谦. N-脱氢枞酸氨基酸类两性表面活性剂合成及其结构与性质关系研究[J]. 林产化学与工业, 1996, 16(3):1-5.
9.Cannon L C. Penicillin salts of amines derived from rosin[P]. US 2585436, 1952.
10.Kalser A, Scheer M. Process for the preparation of L-DOPA[P]. US 3969397, 1976.
11. Riff T, Marle H R, Hodingol A. Process for the resolution of racemic half esters[P]. CN 85106365, 1987.
12.林东恩, 蔡玉壁等. 菊酸构型的转化及消旋反式菊酸的光学拆分[J]. 华南理工大学学报, 1999, 27(3):100-105.
13.张静夏, 周永言等. 手性胺-铜配合物的合成及其在菊酸不对称合成中的应用[J]. 分子催化, 1997,11(1):41-44.
14.林向成, 王恒山等. 新型手性衍生试剂脱氢松香酸酰氯用于氨基酸的毛细管电泳拆分研究[J]. 广西师范大学学报, 2003, 21(3):269-270.
15.Tkachev A V, Denisoc A Y. Oxidative Decarboxylation by Hydrogen Peroxide and a Mercury(II) Salt: a Simple Route Route to nor-Derivatives of Acetyloleanolic, Acetyllursolic and Dehydroabietic Acids[J]. Tetrahedron, 1994, 50(8):2591-2598.
16.史新利, 郭学申. 1-脱氢松香酮的合成[J]. 河南电大, 1995, 4:10, 6.
17.王延, 周永红, 宋湛谦. 盐酸介质中脱氢松香基咪唑啉对Q235 钢缓蚀性能研究[J]. 腐蚀与防护, 1998, 19(6):247-249.
18.Feio S S, Gigante B, Roseiro J C. Method on multiwell plates for the evaluation of the antimicrobial activity of resin acid derivatives[J]. J Microbiol Methods, 1999, 35:201-206.
19.Tahara A, Akita H. Diterpenoids. XXX. Reaction of Methyl Dehydroabietate Derivatives with Aluminum Chloride under Effect of Electron-donating Group[J]. Chem Pharm Bull, 1975, 23(9):1976-1983.
20.Fonseca T, Gigante B. A short synthesis of phenanthro[2,3-d]imidazoles from dehydroabietic acid. Application of the methodology as a convenient route to benzimidazoles[J]. Tetrahedron, 2001, 57:1793-1799.
21.Baleizao C, Pires N, Gigante B. Friedel-Crafts reactiona in ionic liquids: the counter-ion effect on the dealkylation and acylation of methyl dehydroabietate[J].
Tetrahedron Letters, 2004, 45:4375-4377.
22.Pereira C, Alvarez F, Stud Surf Sci Cata, 1993, 78:581-586.
23.Fonseca T, Gigante B. Synthesis and antiviral evaluation of benzimidazoles, quinoxalines and indoles from dehydroabietic acid[J]. Bioorganic & Medicinal Chmistry, 2004, 12:103-112.
24.Esteves M A, Narender N, Gigante B. Microporous solids for the selective bromination of a diterpene resin acid[J]. Synth Commun, 1999, 29:275-280.
25.Wada H, Kodato S, Kawamori M. Antiulcer Activity of Dehydroabietic Acid Derivatives[J]. Chem Parm Bull, 1985, 33(4):1472-1487.
26.Matsumoto T, Tanaka Y. Rearrangement of the Angular Methyl Group in Dehydroabietic Acid[J]. Chem Pharm Bull, 1993, 41(11):1960-1964.
27.Gigante B, Lobo A M, Prabhakar S. New selective synthesis of oxidized diterpene resin acid derivatives[J]. Synthetic Communications, 1991, 21:1959-1966.
28.Akita H, Mori K,Tahara A. Diterenoids. XLV. Ozonolysis of phenolic dehydroabietic acid derivatives[J]. Chem Pharm Bull, 1977,25:974.
29.Matsumoto T, Takeda Y. Skeletal Rearrangement of the Dehydroabietic Acid Derivative[J]. Bull Chem Soc Jpn, 1995, 68:2349-2353.
30.Gigante B, Santos C, Silva A M. Catechols from Abietic Acid: Synthesis and Evaluation as Bioactive Compounds[J]. Bioorganic & Medicinal Chmistry, 2003, 11:1631-1638.
31.Esteves A M, Narender N. Synthetic Derivatives of Abietic Acid with Radical Scavenging Activity[J]. J Nat Prod, 2001, 64:761-763.
32.Zaharescu T, Jipa S, Setnescu R. Synergistic effects on thermal stability of ethylene-propylene elastomers stabilized with hidered phenols and secondary amines[J]. Polymer Testing, 2002,21:149-153.
33.Ochiai E, Ohta M.Azaditerpenoids. I. Nitrogen Derivatives of Dehydroabietic Acid[J]. J Pharm Soc(Japan), 1954, 74:203-206.
34.Matsumoto T, Imai S. Synthesis of Ar-abietatrien-12,16-oxide and Its C-15 Epimer[J]. Bull Chem Soc Jpn, 1987, 60:2401-2407.
35.Gigante B, Lobo A M, Prabhakar S. Heterogeneous Catalysis and Fine Chemicals II[M]. Amsterdam: Eisevier), 1991, 209.
36.Tahara A, Shimagaki M. Formation of steroidal skeleton from resin acid[J]. Chemistry Letters, 1974,651-654.
37.Matsumoto T, Takeda Y. A New Synthesis of 3-Oxosapriparaquinone,a Diterpene from Salvia prionitisHance(Labiatae) [J]. Chem Pharm Bull, 1996, 44(8):1583-1590.
38.史新利, 张文戈, 韩玉谦等. 8-硝基脱氢松香酸的合成[J]. 郑州纺织工学院学报, 1996, 7(3):55-57.
39.Matsumoto T, Imai S. The Conversion of (+)-Dehydroabietic acid into Steroidal Hormones[J]. Bull Chem Soc Jpn, 1988, 61:723-727.
40.Noah J H, Ray V L. J. Org. Chem., 1966, 31 (12) : 4246?4249.
41. Fieser L F, J.Amer.Chem.Soc., 1938, 60:159.
42.Wenkert E, Jackson B G, J.Amer.Chem.Soc., 1958, 80:211.
43.Wenkert E, Carney R W J, J.Amer.Chem.Soc., 1961, 83:4440.
44.Tahara A, Akita H, Chem. Pharm. Bull., 1974, 22(7):1547-1554.
45.Acheson M, Orgel L K,“The Chemistry of Heterocyclic Compounds: The Acridines”, Interscine, New York, 1956, 362-389.
46.Samarin A S, Vereiskaya T A, Perm Politekh(Russ), 1965, 18:148-150.
47.Dean A C R, Chem.Heterocycl.Compounds, 1973, 9:789-813.
48.Burkhatter J H, Tendick F H, Jones E M, J.Am.Chem.Soc., 1948, 70:1363.
49.Mehte V K, Patel S R, J.Indian Chem.Soc., 1966, 43:235.
50.Kimura M, Okabayashi I, Kato A, Chem.Pharm.Bull., 1989, 37:697.
51.Demondiaux P, Laayoun A, Demeunynck M, J.Med.Chem., 1989, 32:31.
52.Wilson W R, Thompson L H, Anderson R F, J.Med.Chem., 1989, 32:31.
53.Bastianelli C, Caia N, Cum G, J.Chem.Soc.Perkin Trans.2, 1991, 679-683.
54.谢克勤, 许建刚. 药学学报, 1984,19(6):8-11.
55.Jaycox D, Gribble G W, J.Heterocycl.Chem., 1987, 24:1405.
56.张秀平, 时惠麟,颜闵. 医药工业, 1984(3):8-11.
57.Dodeigne C, Talanta, 2000, 51:415-439.
58.Peck R M, J.Med.Chem., 1968, 11:315.
59.Baguley B C, J.Med.Chem., 1981, 24:170.
60.Cain B F, Atwell G. J, Eur.A.Cancer, 1974, 10:539.
61.Fulong N B, Sato J, Browon T, Cancer Res., 1978, 38:1329.
62.Legha S S, Gutterman J U, Hall S W, Canter Res., 1978, 38:3712.
63.Cain B F, Canter Res., 1975, 18:1110.
64.张葆询. 药学学报, 1980, 15:40.
65.Gurseille P C, Busetta B, Hospotal M, Acta Cryst., 1973, 29:2349.
66.Sakore T D, Reddy B S, Sobdl H M, J.Mol.Biol., 1979, 135:763.
67.Peddy B S, Seshadri T P, Sakore T D, J.Mol.Biol., 1979, 135:787.
68.Drozdov N S, Cherntzov M O, J.Gen.Chem., 1935, 5:1576.
69.Ochiai E, Ohta M, J. Pharm. Soc.(Japan), 1954, 74:203-206.
70.Cornelis A, Laslo P, Synthesis, 1985, 909-918.
71.Alfred S, Levinson A, J. Org. Chem., 1971, 36(20):3063.
72.金熙等. 工业水处理技术问答及常用数据. 北京:化学工业出版社,1997,314-315.
73.赵树斌等.精细化工,1988, 5:23-25.
74.肖进新等. 陕西化工,1990, 3:10-23.
75.丁著明等. 天津化工,1991, 1:34-38.
76.施庆宁等. 武汉化工,1991, 3:4-6.
77.赵树斌等. 石油化工,1989, 12:863-865.
78.Maiti S, Das S, Maiti M et al. Polymer Application of Renew?Resource Material. (New York: Plenum New York) , 1983, 129.
79.Maiti M, Maiti S. J. Macromol. Sci. Chem., 1983, 20 (1) : 109.
80.Kong Z W, Xia J L, Huang F. Journal of Chemical Industy of Forest Products (Linchan Huagong Tongxun), 2002, 36 (5) : 21?28.
81.Li C C, Song Z Q. China Plastics Industry (Suliao Gongye) , 1996, 94?96.
82.Ochiai E, Ohta M. J. Pharm. Soc. (Japan) , 1954, 74 : 203?206.
83. Gigante B, Santos L, Marcelo?Curto M J. Magn Reson Chem., 1995, 33: 318?321.
2.Bhatnagar M S. Applications of rosin-part 1 : Surface coatings and inks[J]. Paint Resin,1983,53(6):45-49.
3.Bhatnagar M S. Applications of rosin-part 2 : Adhesives[J]. Paint Resin, 1984, 54(1):42-43.
4. 邹志琛, 普绍芬. 光学纯去氢枞酸的制备与表征[J]. 化学试剂, 1996,18(4):241-242.
5.阎丽萍, 欧阳福承. 松香歧化的研究[J]. 吉林化工学院学报, 1994, 11(1):40-43.
6.段文贵,岑波. 去氢枞酸基新型甜菜碱类两性表面活性剂的合成[J]. 现代化工, 2004, 24(4):39-42.
7.梁梦兰, 叶建峰等. 松香衍生物的季铵盐阳离子表面活性剂的合成与性能测定[J]. 化学世界, 2000, 3:138-141.
8.王延, 宋湛谦. N-脱氢枞酸氨基酸类两性表面活性剂合成及其结构与性质关系研究[J]. 林产化学与工业, 1996, 16(3):1-5.
9.Cannon L C. Penicillin salts of amines derived from rosin[P]. US 2585436, 1952.
10.Kalser A, Scheer M. Process for the preparation of L-DOPA[P]. US 3969397, 1976.
11. Riff T, Marle H R, Hodingol A. Process for the resolution of racemic half esters[P]. CN 85106365, 1987.
12.林东恩, 蔡玉壁等. 菊酸构型的转化及消旋反式菊酸的光学拆分[J]. 华南理工大学学报, 1999, 27(3):100-105.
13.张静夏, 周永言等. 手性胺-铜配合物的合成及其在菊酸不对称合成中的应用[J]. 分子催化, 1997,11(1):41-44.
14.林向成, 王恒山等. 新型手性衍生试剂脱氢松香酸酰氯用于氨基酸的毛细管电泳拆分研究[J]. 广西师范大学学报, 2003, 21(3):269-270.
15.Tkachev A V, Denisoc A Y. Oxidative Decarboxylation by Hydrogen Peroxide and a Mercury(II) Salt: a Simple Route Route to nor-Derivatives of Acetyloleanolic, Acetyllursolic and Dehydroabietic Acids[J]. Tetrahedron, 1994, 50(8):2591-2598.
16.史新利, 郭学申. 1-脱氢松香酮的合成[J]. 河南电大, 1995, 4:10, 6.
17.王延, 周永红, 宋湛谦. 盐酸介质中脱氢松香基咪唑啉对Q235 钢缓蚀性能研究[J]. 腐蚀与防护, 1998, 19(6):247-249.
18.Feio S S, Gigante B, Roseiro J C. Method on multiwell plates for the evaluation of the antimicrobial activity of resin acid derivatives[J]. J Microbiol Methods, 1999, 35:201-206.
19.Tahara A, Akita H. Diterpenoids. XXX. Reaction of Methyl Dehydroabietate Derivatives with Aluminum Chloride under Effect of Electron-donating Group[J]. Chem Pharm Bull, 1975, 23(9):1976-1983.
20.Fonseca T, Gigante B. A short synthesis of phenanthro[2,3-d]imidazoles from dehydroabietic acid. Application of the methodology as a convenient route to benzimidazoles[J]. Tetrahedron, 2001, 57:1793-1799.
21.Baleizao C, Pires N, Gigante B. Friedel-Crafts reactiona in ionic liquids: the counter-ion effect on the dealkylation and acylation of methyl dehydroabietate[J].
Tetrahedron Letters, 2004, 45:4375-4377.
22.Pereira C, Alvarez F, Stud Surf Sci Cata, 1993, 78:581-586.
23.Fonseca T, Gigante B. Synthesis and antiviral evaluation of benzimidazoles, quinoxalines and indoles from dehydroabietic acid[J]. Bioorganic & Medicinal Chmistry, 2004, 12:103-112.
24.Esteves M A, Narender N, Gigante B. Microporous solids for the selective bromination of a diterpene resin acid[J]. Synth Commun, 1999, 29:275-280.
25.Wada H, Kodato S, Kawamori M. Antiulcer Activity of Dehydroabietic Acid Derivatives[J]. Chem Parm Bull, 1985, 33(4):1472-1487.
26.Matsumoto T, Tanaka Y. Rearrangement of the Angular Methyl Group in Dehydroabietic Acid[J]. Chem Pharm Bull, 1993, 41(11):1960-1964.
27.Gigante B, Lobo A M, Prabhakar S. New selective synthesis of oxidized diterpene resin acid derivatives[J]. Synthetic Communications, 1991, 21:1959-1966.
28.Akita H, Mori K,Tahara A. Diterenoids. XLV. Ozonolysis of phenolic dehydroabietic acid derivatives[J]. Chem Pharm Bull, 1977,25:974.
29.Matsumoto T, Takeda Y. Skeletal Rearrangement of the Dehydroabietic Acid Derivative[J]. Bull Chem Soc Jpn, 1995, 68:2349-2353.
30.Gigante B, Santos C, Silva A M. Catechols from Abietic Acid: Synthesis and Evaluation as Bioactive Compounds[J]. Bioorganic & Medicinal Chmistry, 2003, 11:1631-1638.
31.Esteves A M, Narender N. Synthetic Derivatives of Abietic Acid with Radical Scavenging Activity[J]. J Nat Prod, 2001, 64:761-763.
32.Zaharescu T, Jipa S, Setnescu R. Synergistic effects on thermal stability of ethylene-propylene elastomers stabilized with hidered phenols and secondary amines[J]. Polymer Testing, 2002,21:149-153.
33.Ochiai E, Ohta M.Azaditerpenoids. I. Nitrogen Derivatives of Dehydroabietic Acid[J]. J Pharm Soc(Japan), 1954, 74:203-206.
34.Matsumoto T, Imai S. Synthesis of Ar-abietatrien-12,16-oxide and Its C-15 Epimer[J]. Bull Chem Soc Jpn, 1987, 60:2401-2407.
35.Gigante B, Lobo A M, Prabhakar S. Heterogeneous Catalysis and Fine Chemicals II[M]. Amsterdam: Eisevier), 1991, 209.
36.Tahara A, Shimagaki M. Formation of steroidal skeleton from resin acid[J]. Chemistry Letters, 1974,651-654.
37.Matsumoto T, Takeda Y. A New Synthesis of 3-Oxosapriparaquinone,a Diterpene from Salvia prionitisHance(Labiatae) [J]. Chem Pharm Bull, 1996, 44(8):1583-1590.
38.史新利, 张文戈, 韩玉谦等. 8-硝基脱氢松香酸的合成[J]. 郑州纺织工学院学报, 1996, 7(3):55-57.
39.Matsumoto T, Imai S. The Conversion of (+)-Dehydroabietic acid into Steroidal Hormones[J]. Bull Chem Soc Jpn, 1988, 61:723-727.
40.Noah J H, Ray V L. J. Org. Chem., 1966, 31 (12) : 4246?4249.
41. Fieser L F, J.Amer.Chem.Soc., 1938, 60:159.
42.Wenkert E, Jackson B G, J.Amer.Chem.Soc., 1958, 80:211.
43.Wenkert E, Carney R W J, J.Amer.Chem.Soc., 1961, 83:4440.
44.Tahara A, Akita H, Chem. Pharm. Bull., 1974, 22(7):1547-1554.
45.Acheson M, Orgel L K,“The Chemistry of Heterocyclic Compounds: The Acridines”, Interscine, New York, 1956, 362-389.
46.Samarin A S, Vereiskaya T A, Perm Politekh(Russ), 1965, 18:148-150.
47.Dean A C R, Chem.Heterocycl.Compounds, 1973, 9:789-813.
48.Burkhatter J H, Tendick F H, Jones E M, J.Am.Chem.Soc., 1948, 70:1363.
49.Mehte V K, Patel S R, J.Indian Chem.Soc., 1966, 43:235.
50.Kimura M, Okabayashi I, Kato A, Chem.Pharm.Bull., 1989, 37:697.
51.Demondiaux P, Laayoun A, Demeunynck M, J.Med.Chem., 1989, 32:31.
52.Wilson W R, Thompson L H, Anderson R F, J.Med.Chem., 1989, 32:31.
53.Bastianelli C, Caia N, Cum G, J.Chem.Soc.Perkin Trans.2, 1991, 679-683.
54.谢克勤, 许建刚. 药学学报, 1984,19(6):8-11.
55.Jaycox D, Gribble G W, J.Heterocycl.Chem., 1987, 24:1405.
56.张秀平, 时惠麟,颜闵. 医药工业, 1984(3):8-11.
57.Dodeigne C, Talanta, 2000, 51:415-439.
58.Peck R M, J.Med.Chem., 1968, 11:315.
59.Baguley B C, J.Med.Chem., 1981, 24:170.
60.Cain B F, Atwell G. J, Eur.A.Cancer, 1974, 10:539.
61.Fulong N B, Sato J, Browon T, Cancer Res., 1978, 38:1329.
62.Legha S S, Gutterman J U, Hall S W, Canter Res., 1978, 38:3712.
63.Cain B F, Canter Res., 1975, 18:1110.
64.张葆询. 药学学报, 1980, 15:40.
65.Gurseille P C, Busetta B, Hospotal M, Acta Cryst., 1973, 29:2349.
66.Sakore T D, Reddy B S, Sobdl H M, J.Mol.Biol., 1979, 135:763.
67.Peddy B S, Seshadri T P, Sakore T D, J.Mol.Biol., 1979, 135:787.
68.Drozdov N S, Cherntzov M O, J.Gen.Chem., 1935, 5:1576.
69.Ochiai E, Ohta M, J. Pharm. Soc.(Japan), 1954, 74:203-206.
70.Cornelis A, Laslo P, Synthesis, 1985, 909-918.
71.Alfred S, Levinson A, J. Org. Chem., 1971, 36(20):3063.
72.金熙等. 工业水处理技术问答及常用数据. 北京:化学工业出版社,1997,314-315.
73.赵树斌等.精细化工,1988, 5:23-25.
74.肖进新等. 陕西化工,1990, 3:10-23.
75.丁著明等. 天津化工,1991, 1:34-38.
76.施庆宁等. 武汉化工,1991, 3:4-6.
77.赵树斌等. 石油化工,1989, 12:863-865.
78.Maiti S, Das S, Maiti M et al. Polymer Application of Renew?Resource Material. (New York: Plenum New York) , 1983, 129.
79.Maiti M, Maiti S. J. Macromol. Sci. Chem., 1983, 20 (1) : 109.
80.Kong Z W, Xia J L, Huang F. Journal of Chemical Industy of Forest Products (Linchan Huagong Tongxun), 2002, 36 (5) : 21?28.
81.Li C C, Song Z Q. China Plastics Industry (Suliao Gongye) , 1996, 94?96.
82.Ochiai E, Ohta M. J. Pharm. Soc. (Japan) , 1954, 74 : 203?206.
83. Gigante B, Santos L, Marcelo?Curto M J. Magn Reson Chem., 1995, 33: 318?321.