CN104529716A - 1,1’,1”-三羟基三蝶烯及其合成方法 - Google Patents
1,1’,1”-三羟基三蝶烯及其合成方法 Download PDFInfo
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- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 15
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 1,8-disubstituted anthraquinone Chemical class 0.000 claims abstract description 12
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 8
- VBQNYYXVDQUKIU-UHFFFAOYSA-N 1,8-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC(Cl)=C2C(=O)C2=C1C=CC=C2Cl VBQNYYXVDQUKIU-UHFFFAOYSA-N 0.000 claims abstract description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012312 sodium hydride Substances 0.000 claims abstract description 6
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 6
- WEUFQISIJPSTBM-UHFFFAOYSA-N 2-bromo-6-methoxyphenol Chemical compound COC1=CC=CC(Br)=C1O WEUFQISIJPSTBM-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 5
- 229960001867 guaiacol Drugs 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 20
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
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- 150000008064 anhydrides Chemical class 0.000 claims description 4
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- 230000009467 reduction Effects 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000662429 Fenerbahce Species 0.000 description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- CROLBRYGLOVQCD-UHFFFAOYSA-N 6-methoxyhexan-1-ol Chemical compound COCCCCCCO CROLBRYGLOVQCD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GNWXVOQHLPBSSR-UHFFFAOYSA-N oxolane;toluene Chemical compound C1CCOC1.CC1=CC=CC=C1 GNWXVOQHLPBSSR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 238000010898 silica gel chromatography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
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- C07—ORGANIC CHEMISTRY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
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- C07C2602/00—Systems containing two condensed rings
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- C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms
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Abstract
提出了一个新化合物1,1’,1”-三羟基三蝶烯A。本发明产物的合成通过:(1)利用乙二醇单甲醚、金属钠和1,8-二氯蒽醌生成1,8-二取代蒽醌;(2)用锌粉还原1,8-二取代蒽醌得到1,8-二取代蒽;(3)同时,用溴素、叔丁胺与愈创木酚反应生成2-溴代-6-甲氧基苯酚,并将2-溴代-6-甲氧基苯酚与氢化钠、三甲基氯硅烷、正丁基锂、及三氟甲磺酸酐反应得到苯炔前体;(4)最后1,8-二取代蒽与苯炔前体反应生成三蝶烯,将粗品三蝶烯与三溴化硼进行去保护反应,得到产物1,1’,1”-三羟基三蝶烯。本发明合成的产物1,1’,1”-三羟基三蝶烯,具有独特的空间结构,将在化学仿生学、分子识别、有机材料、具有特殊功能的高分子等领域具有潜在的应用价值。
Description
技术领域
本发明提出了一种新的化合物以及其化学合成方法,具体化合物是1,1’,1”-三羟基三蝶烯。
背景技术
三蝶烯是由三个苯环组成的具有独特结构的立体分子,在空间结构上三个苯环形成互为120°的夹角,具有D3h对称性,它具有独特的三维刚性Y型构架以及3个开放式的富电子空腔。
三蝶烯因其独特的特点,可以在化学仿生、分子机器、功能材料等领域有广泛的应用:以宏观尺度的实体为模型,可设计合成其微观尺度上的分子机器;三蝶烯由于其独特的空间几何构架,可以通过桥头堡碳原子的三次对称轴旋转,是一个天然的分子转子模型,可构建分子齿轮、分子马达等这类分子机器模型;对三蝶烯基块加以功能化和结构修饰后的衍生物往往都具有一定的特殊性能,这些高性能化合物已经在发光材料、储气材料、传感材料等众多材料化学领域取得了广泛的应用。
然而,目前对三蝶烯骨架结构上进行官能化的修饰,绝大多数是在其β位上进行的,极少有在α位进行,其主要原因是β位的空阻比α位的空阻小很多。另外,对三蝶烯骨架上特定取向的官能化还很少能实现,例如,对三蝶烯上同一个方向上的三个α位的修饰。本专利提出并成功合成了具有特定取向的三羟基化的三蝶烯衍生物-1,1’,1”-三羟基三蝶烯A,是将三蝶烯骨架上的三个同取向的α位上的氢原子用羟基取代。使用羟基作为取代基,目的是可以在此基础上进一步进行官能化,从而可以得到一系列具有特定取向的分子结构,将可在有机合成、分子器件和功能材料等领域具有良好的应用前景。
发明内容
1、本发明的主要目的:针对在三蝶烯α位进行官能化的报道比较少,尤其是在同一取向的三个α位官能化的化合物。本发明实现了在三蝶烯的三个苯环臂上的同一取向上的α位的官能化,得到了一个全新化合物1,1’,1”-三羟基三蝶烯,并给出了此一化合物的化学合成途径。对该化合物进行进一步修饰,将可在配位化学、功能材料、分子器件、分子识别等领域有潜在利用价值。
2、本发明的原理:以1,8-二氯蒽醌为原料,与乙二醇甲醚进行取代反应得到1,8-二烷氧基蒽醌;将1,8-二烷氧基蒽醌还原成1,8-二烷氧基蒽;再使用1,8-二烷氧基蒽与3-甲氧基苯炔进行区域选择性的[4+2]环加成反应得到羟基保护的三羟基三蝶烯;最后,将保护基去除得到1,1’,1”-三羟基三蝶烯。
具体实施方式:
下面结合具体方式,进一步说明本发明。
1、1,8-二烷氧基蒽醌2的合成:在0℃下,将金属钠(7.47g,324mmol,3.0equiv.)分批加入己二醇单甲醚(170.76mL,2163mmol,20.0equiv.)中,待金属钠消失之后,将1,8-二氯蒽醌(30.0g,108mmol,1.0equiv.)加入到上述溶液中,将反应温度升至60℃搅拌8h。
后处理:待反应完毕后,将反应温度缓慢降低至0℃,加入水(100mL)搅拌约10min,随后再加入DCM(100mL)使反应物分层。用分液漏斗取有机相,并将水相用DCM萃取(200mL×3)。有机相合并之后用饱和NaCl溶液洗(200mL×1),随后用无水Na2SO4干燥并且过滤。所得粗产品经柱层析纯化,得到31.6克黄色固体,产率82%。
2、1,8-二取代蒽3的合成:将1,8-二取代蒽醌(15.0g,41.85mmol,1.0equiv.)和锌粉(18.0g,275.3mmol,6.5equiv.)依次放入1000mL三颈烧瓶中,量取300mL 10%的NaOH溶液,加热至回流搅拌,直至原料1,8-二取代蒽醌完全反应完后停止反应,进行后处理。
后处理:将三颈烧瓶冷却至室温,静置,分离上层红棕色液体。将下层灰色固体进行抽滤,抽滤过程中用DCM清洗滤渣,直至固体滤渣里面没有附着的黄色产物为止,可看到抽滤流出的液体为无色。水相用DCM萃取(约100mL×4,直到DCM萃取的颜色很浅为止)。合并得到的两部分有机相。将有机相先用10%的HCl进行中和至pH=7,再用饱和NaCl洗(100mL),最后用无水Na2SO4干燥并过滤。旋干即可得到浅黄色粗产物。所得粗产品经柱层析纯化,得到10.9克黄色固体,产率80%。
3、2-溴-6-甲氧基苯酚7的合成:取一个1000mL的三颈瓶,量取350mL的甲苯,加入叔丁基胺(30.4mL,290mmol,3.0equiv.),混合后在冰水浴里搅拌。缓慢加入液溴(6.5mL,135mmol,1.3equiv.),然后把反应瓶降低温度并保持到-30℃左右,缓慢加入愈创木酚6(12.0g,97mmol,1.0equiv.),之后保持低温,让其反应10min左右,TLC监测至反应完全,后处理。
后处理:
加入适量10%HCl,调节水相pH为1.0左右,分出甲苯相,用饱和Na2S2O3(200mL×2)溶液洗甲苯相,再用乙酸乙酯(EtOAc)(100mL×4)萃取,把萃取后的乙酸乙酯相用Na2S2O3洗(200mL×2),合并有机相。加入无水Na2SO4干燥,过滤,浓缩,所得粗产品经柱层析纯化,得到15.9克白色固体,产率81%。
4、3-甲氧基苯炔前体4的合成:
取一干燥的500mL单口圆底烧瓶,在冰水浴条件下加入60%氢化钠(2.76g,68.92mmol,1.4equiv.),再加入无水四氢呋喃(THF)(60mL),将2-溴-6-甲氧基苯酚7(10.0g,49.23mmol,1.0equiv.)溶解于THF(100mL)中,并将其缓慢加入到氢化钠的四氢呋喃混合物中。紧接着缓慢滴加三甲基氯硅烷(TMSCl)(8.09g,63.99mmol,1.3equiv.),并在室温搅拌过夜。
将上述混合物冷却至-78℃,缓慢滴加正丁基锂(nBuLi)(2.5M,25.59ml,63.99mmol,1.3equiv.),保持温度在-78℃反应5分钟,再缓慢加入三氟甲磺酸酐(Tf2O)(10.0mL,59.04mol,1.2equiv.)。保持反应在-78℃一小时,再缓慢升温。缓慢加入10%Na2CO3溶液,直至加入Na2CO3时没有气泡产生为止。向烧瓶中的溶液中加入约100mL的乙醚进行萃取,最后合并的有机相,用饱和NaCl溶液洗涤,无水硫酸钠干燥,过滤,浓缩,得到深紫色的油状液体。
纯化:将得到的油状液体抽干,经快速硅胶柱层析,得10.6克浅黄色油状液体,产率65%。
5、1,1’,1”-三羟基三蝶烯5的合成:a)取100mL干燥的梨形单口烧瓶,依次加入乙腈(50mL),1,8-二取代蒽(1.5g,4.6mmol,1.0equiv.),氟化铯(CsF)(1.75g,11.5mmol,2.5equiv.),3-甲氧基苯炔前体(3.02g,4.6mmol,1.0equiv.),回流,并适当补加CsF及3-甲氧基苯炔前体,至蒽被完全消耗掉。
后处理:过滤,滤液浓缩后,抽干。
b)取250mL干燥的单口圆底烧瓶,加入上述粗品三蝶烯(2g)以及DCM(100mL),在冰水浴条件下,滴加三溴化硼(BBr3)(2.18mL,23.01mol,5.0equiv.),室温搅拌7天左右,至反应完全。
后处理:冰水浴条件下,缓慢滴加蒸馏水和DCM,充分搅拌,后将混合物转入一升烧杯中,加水至液面到500mL左右,充分搅拌3小时,抽滤,将滤纸上固体用丙酮溶解后浓缩、抽干,所得固体用少量丙酮溶解后,加入200mL DCM析出1,1’,1”-三羟基三蝶烯,再抽滤,得1,1’,1”-三羟基三蝶烯粗品。1,1’,1”-三羟基三蝶烯粗品用DCM和MeOH混合溶剂进行硅胶柱层析,可纯化得到白色1,1’,1”-三羟基三蝶烯固体。从1,8-二取代蒽到1,1’,1”-三羟基三蝶烯两步的产率是40%。
附图说明
图1为三蝶烯的结构以及α位和β位的标示
图2为本发明所合成的1,1’,1”-三羟基三蝶烯的合成路线
图3为具体实施中所用的苯炔前体的合成路线图
化合物性质
1、1,8-二烷氧基蒽醌2
Mp:108-110℃;1H NMR(500MHz,CDCl3)δ9.34(s,1H),8.31(s,1H),7.58(d,J=8.5Hz,2H),7.45–7.29(m,2H),6.72(d,J=7.4Hz,2H),4.48–4.21(m,4H),4.07–3.85(m,4H),3.60(s,6H)ppm;13C NMR(125MHz,CDCl3)δ155.22,133.09,125.71,125.23,124.64,120.61,116.31,102.73,71.29,68.12,59.65ppm;IR(thin film)2922,1674,1588,1437,1312,1133,1069,1022,895,864,790,741,666cm-1;HRMS-MALDI(m/z)calcd for[C20H22NaO6]+,379.11576;found,379.1153.
2、1,8-二烷氧基蒽3
Mp:127-129℃;1H NMR(500MHz,CDCl3)δ7.86(d,J=7.5Hz,1H),7.63(s,1H),7.36(d,J=8.0Hz,1H),4.42–4.20(m,2H),4.05–3.81(m,2H),3.57(s,3H)ppm;13C NMR(125MHz,CDCl3)δ183.88,182.09,158.59,134.74,133.68,124.89,120.42,119.49,70.94,69.80,59.54ppm;IR(thin film)2923,1623,1568,1443,1269,1120,1083,900,853,787,744,618cm-1;HRMS-MALDI(m/z)calcd for[C20H22NaO4]+,349.14158;found,349.1413.
3、1,1’,1”-三羟基三蝶烯A
Mp:>360℃;1H NMR(500MHz,DMSO)δ9.44(s,3H),6.87(dd,J=54.8,6.5Hz,6H),6.68–6.45(m,4H),5.42(s,1H),3.68(s,1H)ppm;13C NMR(125MHz,DMSO)δ151.81,148.52,131.28,125.17,115.01,112.68,53.85,33.21ppm;IR(thin film)1603,1460,1392,1256,1161,1060,757,726,570cm-1;HRMS-MALDI(m/z)calcd for[C20H14NaO3]+,325.08406;found,325.0837.
使用的药品
试剂名称 | CAS号 | 纯度 | 规格 | 厂家 |
1,8-二氯蒽醌 | 82-43-9 | 97.50% | 1000g | 南京康满林 |
乙二醇单甲醚 | 109-86-4 | AR | 500mL | 科龙 |
钠 | 7440-23-5 | AR | 250g | 科龙 |
锌粉 | 7440-66-6 | AR | 500g | 科龙 |
氢氧化钠 | 1310-73-2 | AR | 500g | 科龙 |
氟化铯 | 13400-13-0 | 99% | 100g | 阿拉丁 |
三溴化硼 | 10294-33-4 | 99% | 1Kg | 阿拉丁 |
二氯甲烷 | 75-09-2 | AR | 500mL | 科龙 |
乙腈 | 75-05-8 | AR | 500mL | 科龙 |
叔丁基胺 | 75-64-9 | 99% | 500mL | Adamas |
溴 | 7726-95-6 | AR | 500mL | 科龙 |
甲苯 | 108-88-3 | AR | 500mL | 科龙 |
愈创木酚 | 90-05-1 | AR | 500g | 阿拉丁 |
氢化钠 | 7646-69-7 | AR | 250g | Adamas |
三甲基氯硅烷 | 75-77-4 | 99% | 500mL | Adamas |
四氢呋喃 | 109-99-9 | AR | 500mL | 科龙 |
正丁基锂(2.5M) | 109-72-8 | 2.5M | 100mL | Acros |
三氟甲磺酸酐 | 358-23-6 | RG | 500g | Adamas |
相关缩写的中英文对照
英文缩写 | 中文 |
DCM | 二氯甲烷 |
NaH | 氢化钠 |
TMSCl | 三甲基氯硅烷 |
BBr3 | 三溴化硼 |
CsF | 氟化铯 |
t-BuNH2 | 叔丁基胺 |
EtOAc | 乙酸乙酯 |
PhMe | 甲苯 |
THF | 四氢呋喃 |
n-Buli | 正丁基锂 |
Tf2O | 三氟甲磺酸酐 |
Claims (1)
- 发明名称1,1’,1”-三羟基三蝶烯及其合成方法2.1,1’,1”-三羟基三蝶烯的合成,其特征在于具体步骤如下:(1)1,8-二取代蒽醌的合成乙二醇单甲醚与金属钠反应生成醇钠,再与1,8-二氯蒽醌发生取代反应生成1,8-二取代蒽醌,产率为82%。(2)1,8-二取代蒽的合成1,8-二取代蒽醌和锌粉在氢氧化钠(NaOH)水溶液中回流搅拌,还原得到1,8-二取代蒽,经柱层析纯化产率为80%。(3)2-溴代-6-甲氧基苯酚的合成溴与叔丁胺反应生成叔丁基溴化铵,再与愈创木酚反应生成2-溴代-6-甲氧基苯酚,经柱层析纯化产率81%。(4)含3-甲氧基的苯炔前体的合成将2-溴代-6-甲氧基苯酚依次与氢化钠(NaH)、三甲基氯硅烷(TMSCl)、正丁基锂(n-BuLi)、及三氟甲磺酸酐(Tf2O)反应后,经柱层析纯化得浅黄色油状3-甲氧基的苯炔前体,经柱层析纯化产率65%。(5)1,1’,1”-三羟基三蝶烯A的合成上述1,8-二取代蒽与3-甲氧基的苯炔前体在氟化铯(CsF)存在下发生[4+2]环加成反应生成三蝶烯,再将此三蝶烯粗品直接与过量的三溴化硼(BBr3)反应,将苯酚的保护基去保护后生成1,1’,1”-三羟基三蝶烯,经柱层析纯化,从1,8-二取代蒽到1,1’,1”-三羟基三蝶烯两步的产率是40%。
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