CN107868018A - N,n,n′,n′‑四[4‑(4′‑羧基)联苯基)]‑ 9,10‑蒽二胺合成法 - Google Patents
N,n,n′,n′‑四[4‑(4′‑羧基)联苯基)]‑ 9,10‑蒽二胺合成法 Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 52
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 26
- 239000004305 biphenyl Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- PQCXFUXRTRESBD-UHFFFAOYSA-N (4-methoxycarbonylphenyl)boronic acid Chemical compound COC(=O)C1=CC=C(B(O)O)C=C1 PQCXFUXRTRESBD-UHFFFAOYSA-N 0.000 claims abstract description 9
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 9
- 238000001308 synthesis method Methods 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- DEJGCXGGTKKUEK-UHFFFAOYSA-N 9-n,9-n,10-n,10-n-tetrakis(4-bromophenyl)anthracene-9,10-diamine Chemical compound C1=CC(Br)=CC=C1N(C=1C2=CC=CC=C2C(N(C=2C=CC(Br)=CC=2)C=2C=CC(Br)=CC=2)=C2C=CC=CC2=1)C1=CC=C(Br)C=C1 DEJGCXGGTKKUEK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 10
- RZGMFRRDBNHLJU-UHFFFAOYSA-N 9-n,9-n,10-n,10-n-tetraphenylanthracene-9,10-diamine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C2C=CC=CC2=1)C1=CC=CC=C1 RZGMFRRDBNHLJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- -1 aromatic tetracarboxylic acid compound Chemical class 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 1
- 229920006389 polyphenyl polymer Polymers 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004896 high resolution mass spectrometry Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000013336 microporous metal-organic framework Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明的N,N,N′,N′‑四[4‑(4′‑羧基)联苯基)]‑9,10‑蒽二胺合成方法,9,10‑二溴蒽与二苯胺经Buchwald‑Hartwig芳胺化反应生成N,N,N′,N′‑四苯基‑9,10‑蒽二胺(A),A与NBS反应生成N,N,N′,N′‑四(4‑溴苯基)‑9,10‑苯二胺(B)。化合物B与4‑甲氧羰基苯硼酸在惰性气体保护条件下加入催化剂反应生成N,N,N′,N′‑四[4‑(4′‑甲氧羰基)联苯基)]‑9,10‑蒽二胺(C)。化合物C经水解反应生成目标化合物D:N,N,N′,N′‑四[4‑(4′‑羧基)联苯基)]‑9,10‑蒽二胺。本发明合成一个尚无文献报道的多苯环芳香四羧酸化合物,具有合成方法简单,合成成本低、产率高、产品纯度高的优点。目标化合物D如下式:
Description
技术领域
本发明涉及有机化学技术领域,尤其涉及一种四元羧酸N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺的合成方法。
背景技术
金属有机框架(Metal-organic frameworks)是由有机桥联配体与金属离子通过配位键或辅以其它弱作用力而形成的具有高度规整且无限扩展结构的一类配位化合物,这类化合物有时也被称为配位聚合物(Coordination polymers)。近年来,四元羧酸类桥联配体构筑的金属有机框架的研究受到广泛关注,其原因是羧基配体的溶解性相对较好,配位能力强,生成多孔骨架热稳定高,配位模式易于调控,生成的多孔结构富于变化。此类配体中,长链脂肪族羧酸柔性大,网络容易产生互穿较难形成高维的刚性孔道结构,骨架内孔隙率往往小于。而芳香族多羧酸配体具有更大的刚性,不仅有利于晶体的生长,也有助于合成出具有特殊的光、电、磁等功能复合的刚性金属有机框架材料。随着合成技术的不断发展,采用芳香性羧酸合成的金属有机框架越来越多。
构筑羧酸类金属有机框架材料的主要策略是SUB策略和以此为基础形成的目标性网格合成策略”。羧基不仅可以采取多种方式与金属离子配位,部分配位点还可以将金属离子连接成具有特定构型的多核簇次级结构单元(SUB),SUB在反应过程中能够保持结构的完整性,且具有金属离子所不具备的功能。与金属离子相比,它具有以下优点:SUB呈电中性,可以与中性桥联配体相互连接生成中性的结构骨架,受抗衡离子影响小,有利于目标产物的设计和预测;SUB体积较大,且具有较好的刚性和稳定性,能有效避免网络穿插,构造出一些含大孔洞的刚性结构骨架;当SUB端基位点的配位基团被含有相同配位基团的桥联配体取代后,可将刚性的SUB拓展成更高维度的结构,并且可根据SUB和配位点之间间隔基的结构和功能信息,预测出目标产物的拓扑结构和功能;含有弱端基配位基的SUB有利于生成含不饱和配位中心的金属活性中心,在催化领域具有潜在的应用前景。利用SUB策略设计合成具有特定形状的金属有机框架多孔材料成为该领域的研究热点,通过选用不同的金属离子、不同构型的配体分子或加入辅助试剂,人们己经成功设计合成出从双核单元到十一核单元甚至无限的M-C-O棒状SUB。延长的刚性四角羧酸配体通常能得到结构新颖、比表面积大的多微孔MOFs材料,并能改变微孔结构,使其微孔内电子环境得到优化从而提高上述应用性能,因此,设计合成结构新颖的延长四元羧酸配体并应用于MOFs材料的合成已成为当今研究的热点之一。然而,大尺寸的刚性四元羧酸化合物合成比较困难。因此本发明中所涉及的结构新颖的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺是一种具有巨大潜在应用价值的配体。目前尚无文献报道该化合物。
发明内容
本发明的目的是提供一种合成成本低、产率高、产品纯度高的新型N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺的合成方法。
本发明的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺的合成方法,合成步骤为:
(ⅰ)以9,10-二溴蒽和二苯胺为原料,加入一定量叔丁醇钠和适量催化剂,加入甲苯作为溶剂,在氮气或氩气保护下快速加入三叔丁基膦,摩尔比9,10-二溴蒽:二苯胺:叔丁醇钠为1:2.5~3.2:2.1~2.8,9,10-二溴蒽与甲苯的用量比是1毫摩:10~15毫升。加完后在100~140℃油浴加热反应10~16小时,反应结束蒸出甲苯,加20~40mL水稀释,二氯甲烷萃取(40~60mL×3),收集有机相并用无水亚硫酸钠对其进行除水处理,过滤,真空浓缩,最后以石油醚和二氯甲烷按体积比为50:0.8~1.2的混合溶剂为洗脱剂用柱色谱法分离提纯得到化合物A:N,N,N′,N′-四苯基-9,10-蒽二胺;
(ⅱ)N,N,N′,N′-四苯基-9,10-蒽二胺和NBS(N-溴代丁二酰亚胺)按摩尔比1:3.0~5.5混合后溶于一定溶剂中,N,N,N′,N′-四苯基-9,10-蒽二胺与溶剂的用量比是1毫摩:10.0~15.0毫升,在0~30℃反应2~10小时,反应结束后加饱和亚硫酸钠溶液10.0~20.0毫升,加水10~30毫升稀释,收集有机相并用无水硫酸镁对其进行除水处理,过滤,真空浓缩,最后用10~30mL无水乙醇重结晶纯化3次,过滤、干燥得化合物B:N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺;
(ⅲ)在氩气或氮气保护下,在250mL三口瓶中分别加入N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺、4-甲氧羰基苯硼酸、碳酸钾和一定量的二氧六环,摩尔比N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺:4-甲氧羰基苯硼酸:碳酸钾为1:5.0~10.0:5.0~10.0,N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺与溶剂的比为1毫摩:15.0~30.0毫升。加入一定量的钯盐作为催化剂,90℃反应30~50小时,反应结束蒸出1,4-二氧六环,加20~40mL水稀释,二氯甲烷萃取(30~70mL×3),收集有机相并用无水亚硫酸钠对其进行除水处理,过滤,蒸出二氯甲烷溶剂得粗产物,最后以石油醚和二氯甲烷按体积比为20:0.8~1.2的混合溶剂为洗脱剂用柱色谱法分离提纯得到化合物C:N,N,N′,N′-四[4-(4’-甲氧羰基)联苯基)]-9,10-蒽二胺;
(ⅳ)将N,N,N′,N′-四[4-(4’-甲氧羰基)联苯基)]-9,10-蒽二胺和NaOH按摩尔比1:20~40加入1,4-二氧六环和水的混合溶剂中,体积比为3~5:1,95℃回流8~15小时,蒸除过量1,4-二氧六环,加水稀释,加入过量的稀HCl酸化至pH=2,析出黄色固体,真空干燥得最终化合物D:N,N,N′,N′-四[4-(4’-羧基)联苯基)]-9,10-蒽二胺。
所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,制备A时,在氮气或氩气保护下快速加入三叔丁基膦,摩尔比1,4-二溴苯:二苯胺:叔丁醇钠为1:2.5~3.2:2.1~2.8,1,4-二溴苯与甲苯的用量比是1毫摩:10~15毫升。
所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,制备A以甲苯作为溶剂,在100~140℃油浴加热反应10~16小时,反应结束蒸出甲苯,加20~40mL水稀释,二氯甲烷萃取(20~40mL×3),柱层析纯化A以石油醚和二氯甲烷按体积比为50:0.8~1.2。
所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,其特征在于:制备化合物A使用的催化剂为双(二亚苄基丙酮)钯,用量为1,4-二溴苯摩尔数的1~5%。所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,制备化合物B时,A和NBS的摩尔比为1:3.0~5.5,A与溶剂的用量比是1毫摩:10.0~15.0毫升。所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,其特征在于:制备化合物B时,纯化B用10~30mL无水乙醇重结晶3次。
所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,制备化合物C时,摩尔比B:4-甲氧羰基苯硼酸:碳酸钾为1:5.0~10.0:5.0~10.0。B与溶剂的比为1毫摩:15.0~30.0毫升。纯化B用石油醚和二氯甲烷按体积比为20:0.8~1.2的混合溶剂为洗脱剂。
所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,制备化合物C使用的催化剂为四(三苯基膦)钯,用量为B的物质的量的1~5%。
所述的一种四元羧酸N,N,N′,N′-四(4′-羧基联苯基)-9,10-蒽二胺的合成方法,制备化合物D时,C和NaOH按摩尔比1:20~40,溶剂1,4-二氧六环和水的混合溶剂中,体积比为3~5:1,酸化至pH=2。
用本方法合成结构新颖的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺的有益效果是:延长的刚性四元羧酸类配体广泛应用于MOFs材料的合成中,这类材料通常具有有序的孔道结构、大的比表面积,使这类材料在气体储藏与分离、化学传感、催化及药物缓释等不同领域具有潜在应用。延长的刚性四羧酸配体通常能得到结构新颖、比表面积大的多微孔MOFs材料,并能改变微孔结构,使其气孔内电子环境得到优化从而提高上述应用性能。因此,设计合成结构新颖的延长四元羧酸配体并应用于MOFs材料的合成已成为当今研究的热点之一。然而,大尺寸的刚性四元多羧酸化合物合成比较困难。因此,用本方法合成结构新颖的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺是一种具有巨大潜在应用价值的四元羧酸配体。
附图说明
图1本发明中目标化合物D的结构式示意图。
图2本发明中化合物A和B的合成示意图。
图3本发明中化合物C的合成示意图。
图4本发明中化合物D的合成示意图。
具体实施方式
本发明的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺的合成方法,合成步骤为:
以9,10-二溴蒽,二苯胺为原料经Buchwald-Hartwig芳胺化反应生成N,N,N',N'-四苯基-9,10-蒽二胺(A),A与NBS溴化反应生成N,N,N',N'-四(4-溴苯基)-9,10-蒽二胺(B),合成路线如图2所示。B与对甲氧羰基苯硼酸经Suzuki偶联反应生成N,N,N′,N′-四[4-(4′-甲氧羰基)联苯基)]-9,10-蒽二胺(C),合成路线如图3所示。C最后水解得到目标化合物N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺(D),合成路线如图4所示。
具体实施例如下:
(ⅰ)如图2所示:依次称取9,10-二溴蒽(1.0g,3.0mmol)、二苯胺(1.5g,9.0mmol)、双(二亚苄基酮)钯(0.1g,0.17mmol)、叔丁醇钠(0.71g,7.4mmol)加入150mL三口瓶中,加入30mL甲苯,置换氩气三次后加入3.5mL三叔丁基膦,氩气保护下130℃回流反应12h。反应结束蒸出甲苯,加30mL水,二氯甲烷萃取(50mL×3),收集有机层,无水Na2SO3干燥、过滤,蒸出溶剂得反应粗产物,干燥后经硅胶柱层析(洗脱剂:石油醚/二氯甲烷=50/1)纯化,得黄色粉末A(1.12g),产率73%。熔点:>300℃。
化合物A核磁1H NMR、13C NMR和高分辨质谱数据:1H NMR(400MHz,CDCl3)δ8.18(dd,J=6.8,3.0Hz,4H),7.34(dd,J=6.8,3.0Hz,4H),7.19(t,J=7.6Hz,8H),7.11(d,J=8.0Hz,8H),6.90(t,J=7.1Hz,4H).13C NMR(101MHz,CDCl3)δ147.67,137.36,131.81,129.23,126.72,125.03,121.29,120.25。HRMS(ESI),C38H28N2,实测值(计算值),m/z:513.6415[M+H]+(513.6423)。
(ⅱ)如图2所示:称取N,N,N',N'-四苯基-9,10-蒽二胺(1.05g,2.05mmol)加入100mL三口瓶中,缓慢向三口瓶中加入30mL氯仿,加入N-溴代丁二酰亚胺(1.71g,9.6mmol),室温避光搅拌4h,停止反应,加入饱和Na2SO3溶液,收集有机相,无水MgSO4干燥、过滤,蒸出氯仿得反应粗产物,无水乙醇重结晶3次,干燥得黄色粉末B(1.63g),产率96%。熔点:187-189℃。
化合物B核磁1H NMR、13C NMR和高分辨质谱数据:1H NMR(400MHz,CDCl3)δ8.06(dd,J=6.7,3.1Hz,4H),7.39(dd,J=6.7,3.0Hz,4H),7.28(d,J=8.6Hz,8H),6.93(d,J=8.6Hz,8H).13C NMR(101MHz,CDCl3)δ146.25,135.38,132.40,131.15,127.33,124.61,121.84,118.94。HRMS(ESI),C38H24Br4N2,实测值(计算值),m/z:829.2272[M+H]+(829.2266)。
(ⅲ)如图3所示:在100mL三口瓶中分别加入N,N,N',N'-四(4-溴苯基)-9,10-蒽二胺(1.5g,1.8mmol)、4-甲氧羰基苯硼酸(2.6g,14.4mmol)、碳酸钾(1.74g,12.6mmol)、40mL1,4-二氧六环、6mL水和四(三苯基膦)钯(104mg,5mol%),置换氩气三次后,氩气保护下90℃反应48h,反应结束蒸出1,4-二氧六环,加30mL水稀释,二氯甲烷萃取(60mL×3),收集有机层,无水Na2SO3干燥、过滤,蒸出二氯甲烷得反应粗产物,干燥后经硅胶柱层析(洗脱剂:石油醚/二氯甲烷=20/1)纯化,得黄色粉末C(1.23g,1.17mmol),产率65%。熔点:195-197℃。
化合物C核磁1H NMR、13C NMR和高分辨质谱数据:1H NMR(400MHz,CDCl3)δ8.05(d,J=8.0Hz,8H),7.96(d,J=8.0Hz,8H),7.62(d,J=8.1Hz,8H),7.49(d,J=11.2Hz,8H),7.31(d,J=7.9Hz,8H),3.93(s,6H),3.89(s,6H).13C NMR(101MHz,CDCl3)δ166.90,166.50,144.54,142.95,139.60,132.97,131.52,130.16,129.38,129.26,129.05,128.41,127.66,126.25,117.77,52.22,52.06。HRMS(ESI),C70H52N2O8,实测值(计算值),m/z:1050.1715[M+H]+(1050.1705)。
(ⅳ)如图4所示:在250mL的圆底烧瓶里依次加入N,N,N′,N′-四[4-(4′-甲氧羰基)联苯基)]-9,10-蒽二胺(1.0g,1.0mmol)、NaOH(1.0g,25mmol)、60mL 1,4-二氧六环和20mL水,95℃反应12h,蒸出1,4-二氧六环,加入适量的水溶解羧酸钠盐,过滤,滤液中加稀HCl酸化至pH为2左右,析出沉淀,静置,倾倒上层清液,抽滤、水洗干燥得黄色粉末D(0.94g,0.9mmol),产率98%。熔点:256-258℃。
化合物D核磁1H NMR、13C NMR和高分辨质谱数据:1H NMR(400MHz,DMSO)δ12.91(s,4H),7.93(t,J=7.2Hz,16H),7.76(d,J=7.6Hz,8H),7.61(d,J=8.6Hz,4H),7.54(s,8H),7.18(d,J=8.5Hz,4H).13C NMR(101MHz,DMSO)δ167.61,167.52,143.97,143.55,140.90,132.52,132.18,130.36,130.17,130.00,129.46,127.74,126.49,120.30。HRMS(ESI),C66H44N2O8[M-H]+,实测值(计算值),m/z:992.0458(992.0462)。以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (7)
1.一种N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于,合成步骤为:
(ⅰ)以9,10-二溴蒽和二苯胺为原料,加入一定量叔丁醇钠和适量催化剂,加入甲苯作为溶剂,在氮气或氩气保护下快速加入三叔丁基膦,摩尔比9,10-二溴蒽:二苯胺:叔丁醇钠为1:2.5~3.2:2.1~2.8,9,10-二溴蒽与甲苯的用量比是1毫摩:10~15毫升,加完后在100~140℃油浴加热反应10~16小时,反应结束蒸出甲苯,加20~40mL水稀释,二氯甲烷萃取(40~60mL×3),收集有机相并用无水亚硫酸钠对其进行除水处理,过滤,真空浓缩,最后以石油醚和二氯甲烷按体积比为50:0.8~1.2的混合溶剂为洗脱剂用柱色谱法分离提纯得到化合物A:N,N,N′,N′-四苯基-9,10-蒽二胺;
(ⅱ)N,N,N′,N′-四苯基-9,10-蒽二胺和NBS(N-溴代丁二酰亚胺)按摩尔比1:3.0~5.5混合后溶于一定溶剂中,N,N,N′,N′-四苯基-9,10-蒽二胺与溶剂的用量比是1毫摩:10.0~15.0毫升,在0~30℃反应2~10小时,反应结束后加饱和亚硫酸钠溶液10.0~20.0毫升,加水10~30毫升稀释,收集有机相并用无水硫酸镁对其进行除水处理,过滤,真空浓缩,最后用10~30mL无水乙醇重结晶纯化3次,过滤、干燥得化合物B:N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺;
(ⅲ)在氩气或氮气保护下,在250mL三口瓶中分别加入N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺、4-甲氧羰基苯硼酸、碳酸钾和一定量的二氧六环,摩尔比N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺:4-甲氧羰基苯硼酸:碳酸钾为1:5.0~10.0:5.0~10.0,N,N,N′,N′-四(4-溴苯基)-9,10-蒽二胺与溶剂的比为1毫摩:15.0~30.0毫升。加入一定量的钯盐作为催化剂,90℃反应30~50小时,反应结束蒸出1,4-二氧六环,加20~40mL水稀释,二氯甲烷萃取(30~70mL×3),收集有机相并用无水亚硫酸钠对其进行除水处理,过滤,蒸出二氯甲烷溶剂得粗产物,最后以石油醚和二氯甲烷按体积比为20:0.8~1.2的混合溶剂为洗脱剂用柱色谱法分离提纯得到化合物C:N,N,N′,N′-四[4-(4′-甲氧羰基)联苯基)]-9,10-蒽二胺;
(ⅳ)将N,N,N′,N′-四[4-(4′-甲氧羰基)联苯基)]-9,10-蒽二胺和NaOH按摩尔比1:20~40加入1,4-二氧六环和水的混合溶剂中,体积比为3~5:1,95℃回流8~15小时,蒸除过量1,4-二氧六环,加水稀释,加入过量的稀HCl酸化至pH=2,析出黄色固体,真空干燥得最终化合物D:N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺,它的化学结构式为:
2.根据权利要求1所述的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于:制备A时,在氮气或氩气保护下快速加入三叔丁基膦,摩尔比1,4-二溴苯:二苯胺:叔丁醇钠为1:2.5~3.2:2.1~2.8,1,4-二溴苯与甲苯的用量比是1毫摩:10~15毫升。
3.根据权利要求1所述的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于:制备化合物A使用的催化剂为双(二亚苄基丙酮)钯,用量为1,4-二溴苯摩尔数的1~5%。
4.根据权利要求1所述的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于:制备化合物B时,A和NBS的摩尔比为1:3.0~5.5,A与溶剂的用量比是1毫摩:10.0~15.0毫升。
5.根据权利要求1所述的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于:制备化合物C时,摩尔比B:4-甲氧羰基苯硼酸:碳酸钾为1:5.0~10.0:5.0~10.0,B与溶剂的比为1毫摩:15.0~30.0毫升,纯化B用石油醚和二氯甲烷按体积比为20:0.8~1.2的混合溶剂为洗脱剂。
6.根据权利要求1所述的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于:制备化合物C使用的催化剂为四(三苯基膦)钯,用量为B的物质的量的1~5%。
7.根据权利要求1所述的N,N,N′,N′-四[4-(4′-羧基)联苯基)]-9,10-蒽二胺合成法,其特征在于:C和NaOH按摩尔比1:20~40,溶剂1,4-二氧六环和水的混合溶剂中,体积比为3~5:1,酸化至pH=2。
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CN107325017A (zh) * | 2017-07-28 | 2017-11-07 | 遵义医学院 | 一种四元羧酸n,n,n′,n′‑四(4′‑羧基联苯基)‑1,4‑苯二胺的合成方法 |
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---|---|---|---|---|
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CN107325017A (zh) * | 2017-07-28 | 2017-11-07 | 遵义医学院 | 一种四元羧酸n,n,n′,n′‑四(4′‑羧基联苯基)‑1,4‑苯二胺的合成方法 |
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