CN105968374B - 一种铜(i)配位聚合物及其制备方法和用途 - Google Patents
一种铜(i)配位聚合物及其制备方法和用途 Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 32
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 32
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000012046 mixed solvent Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- UFSZPRQQIUALSF-UHFFFAOYSA-N 5-phenyl-1h-pyrimidine-2-thione Chemical class N1C(=S)N=CC(C=2C=CC=CC=2)=C1 UFSZPRQQIUALSF-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- -1 aryl boric acid class compound Chemical class 0.000 abstract description 15
- 150000002989 phenols Chemical class 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 230000000640 hydroxylating effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- 235000010338 boric acid Nutrition 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000004327 boric acid Substances 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 230000005855 radiation Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 239000003708 ampul Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical class CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical class CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LEMABCWCFKCYQC-UHFFFAOYSA-N OBO.C1=CC=CC2=CC=CC=C21 Chemical class OBO.C1=CC=CC2=CC=CC=C21 LEMABCWCFKCYQC-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000001543 aryl boronic acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZXDTWWZIHJEZOG-UHFFFAOYSA-N (2,6-dimethylphenyl)boronic acid Chemical class CC1=CC=CC(C)=C1B(O)O ZXDTWWZIHJEZOG-UHFFFAOYSA-N 0.000 description 1
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical class CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
- BJQCPCFFYBKRLM-UHFFFAOYSA-N (3-methylphenyl)boronic acid Chemical class CC1=CC=CC(B(O)O)=C1 BJQCPCFFYBKRLM-UHFFFAOYSA-N 0.000 description 1
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical class COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical class CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- 150000000345 2,6-xylenols Chemical class 0.000 description 1
- GQUMTQCSESILQU-UHFFFAOYSA-N 2-[10,15,20-tris(2-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical group OC(=O)c1ccccc1-c1c2ccc(n2)c(-c2ccccc2C(O)=O)c2ccc([nH]2)c(-c2ccccc2C(O)=O)c2ccc(n2)c(-c2ccccc2C(O)=O)c2ccc1[nH]2 GQUMTQCSESILQU-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LBAHHHQOJMMVQK-UHFFFAOYSA-N OBO.[O-][N+](=O)C1=CC=CC=C1 Chemical class OBO.[O-][N+](=O)C1=CC=CC=C1 LBAHHHQOJMMVQK-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002672 m-cresols Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- 150000002883 o-cresols Chemical class 0.000 description 1
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- 238000011913 photoredox catalysis Methods 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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Abstract
本发明公开了一种铜(I)配位聚合物及其制备方法和用途。具体而言,本发明的铜(I)配位聚合物的化学式为[Cu6I2(μ4‑I)2(μ4‑5‑phpymt)2]n,其中5‑phpymt为5‑苯基‑2‑巯基嘧啶中的巯基失去质子后形成的阴离子,n为任一正整数。该配位聚合物能够在可见光照射下催化芳基硼酸类化合物至酚类化合物的转化,具有转化效率高、适用范围广、反应条件温和等特点。转化反应结束后,从反应体系中离心分离出铜(I)配位聚合物,经简单水洗即可进行下一轮反应,至少循环5次后仍能保持稳定,并且其催化活性也未出现明显降低。
Description
技术领域
本发明属于催化化学技术领域,涉及一种铜(I)配位聚合物,特别是一种包含5-苯基-2-巯基嘧啶阴离子桥联配体的铜(I)配位聚合物,其制备方法,及其在光催化芳基硼酸类化合物制备酚类化合物中的用途。
背景技术
苯酚是一种应用广泛的有机化工原料,用于制造医药、化学农产品、天然产物人工替代品、染料、香料和炸药。工业生产苯酚的传统工艺主要包括异丙苯法、甲苯-苯甲酸法、磺化法、苯一步氧化法等,但这些方法本身存在不足之处,例如原子利用率较低、反应复杂、副产物较多、容易造成环境污染等。
为了克服上述缺点,越来越多的研究都集中在利用过渡金属催化剂来实现苯酚的高效合成,例如利用金属催化剂实现卤代芳烃的羟基化、利用氧化剂实现芳基硼酸的氧化羟基化、利用过渡金属催化剂实现苯硼酸的羟基化等,但这些反应大都需要氧化剂或无机碱,并且转化效率相对较低。
近年来,很多课题组使用钌联吡啶配合物、亚甲基蓝(MB)、玫瑰红(RB)等作为可见光光催化剂,实现了苯硼酸到苯酚的高效转化,这种方法的反应条件非常温和,并且具备绿色环保的特点。但是,所使用的催化剂不易分离,无法实现催化剂的循环利用(参见Zou, Y.Q., Chen, J. R., Xiao, W. J., et al., Highly Efficient Aerobic OxidativeHydroxylation of Arylboronic Acids: Photoredox Catalysis Using Visible Light[J], Angew. Chem. Int. Ed., 2012, 51(3):784-788)。目前,仅有极少数文献报道了在可见光照射下使用异相催化剂催化苯硼酸的氧化羟基化反应(参见Toyao, T., Ueno, N.,Matsuoka, M., et al., Visible-light, photoredox catalyzed, oxidativehydroxylation of arylboronic acids using a metal-organic framework containingtetrakis(carboxyphenyl)porphyrin groups[J], Chem. Commun., 2015, 51, 16103-16106)。
发明内容
针对上述情况,本发明的目的在于提供一种铜(I)配位聚合物及其制备方法和用途。以该配位聚合物为光催化剂,在水和乙腈的混合溶剂中,可以在可见光照射下催化芳基硼酸类化合物的氧化羟基化(oxidative hydroxylation)反应,最终制得酚类化合物。另外,在上述反应体系中,作为光催化剂使用的铜(I)配位聚合物可以被循环利用5次以上,循环5次后仍然稳定,并且其催化活性也未出现明显降低,是一种有效且高效的光催化剂。
为了实现上述目的,本发明采用如下技术方案:
一种铜(I)配位聚合物,其化学式为[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n,其中5-phpymt为5-苯基-2-巯基嘧啶中的巯基失去质子后形成的阴离子,n为任一正整数。
该配位聚合物基本上呈二维层状分布,以n=1时的重复结构单元为例:5-苯基-2-巯基嘧啶结构大致分别处于二维平面的两侧,每1个S原子与2个Cu原子配位,每1个N原子与1个Cu原子配位,构成μ4-5-phpymt桥联配位;4个I原子中的2个各自与4个Cu原子配位,构成μ4-I桥联配位,剩余的2个各自仅与1个Cu原子配位;6个Cu原子中的4个各自与1个S原子、1个N原子和1个I原子配位,剩余的2个各自与3个I原子配位;6个Cu原子和4个I原子构成[Cu6I2(μ4-I)2]单元,每个[Cu6I2(μ4-I)2]单元通过μ4-5-phpymt配体与其他单元连接,形成二维结构。
该配位聚合物的晶体属于单斜晶系,空间群为C2/m,晶胞参数为a = 12.5100(9)Å,b = 9.4515(6) Å,c = 12.0472(9) Å,α = 90.00 °,β= 107.004(8) °,γ = 90.00 °,V= 1362.16(17) nm3,Z = 1。
一种上述铜(I)配位聚合物的制备方法,其包括如下步骤:
按照碘化亚铜:5-苯基-2-巯基嘧啶=2~5:1的摩尔比,将碘化亚铜、5-苯基-2-巯基嘧啶和溶剂加入到反应容器中,通入惰性气体0.5~1小时后,密闭反应容器,加热至100~140℃并反应24~72小时;反应结束后,将反应体系的温度降至室温,经过滤、洗涤、干燥,得到所述铜(I)配位聚合物。
优选的,在上述制备方法中,所述碘化亚铜和所述5-苯基-2-巯基嘧啶之间的摩尔比为4:1。
优选的,在上述制备方法中,所述惰性气体选自氮气、氖气、氩气中的任意一种,优选氮气。
优选的,在上述制备方法中,所述溶剂为乙腈和N,N-二甲基甲酰胺的混合溶剂,优选所述乙腈和所述N,N-二甲基甲酰胺之间的体积比为20:1。
优选的,在上述制备方法中,所述加热通过烘箱来完成。
优选的,在上述制备方法中,所述反应的温度为120℃,时间为48小时。
上述铜(I)配位聚合物在光催化芳基硼酸类化合物制备酚类化合物中的用途,其中所述芳基硼酸类化合物选自苯硼酸、烷基取代苯硼酸(优选甲基取代苯硼酸)、烷氧基取代苯硼酸(优选甲氧基取代苯硼酸)、酰基取代苯硼酸(优选乙酰基取代苯硼酸)、硝基取代苯硼酸、萘硼酸、苯二硼酸中的任意一种。
具体而言,上述用途可以具体表现为一种利用上述铜(I)配位聚合物由芳基硼酸类化合物制备酚类化合物的方法,其包括如下步骤:
按照硼酸基:铜(I)配位聚合物:碱=1:0.01~0.03:1的摩尔比,将芳基硼酸类化合物、铜(I)配位聚合物、碱和溶剂加入到配备搅拌装置的反应容器中,在可见光照射下,于室温敞口反应24~72小时;反应结束后,采用乙酸乙酯萃取,合并有机相,经干燥、过滤、减压浓缩、硅胶柱色谱纯化,得到酚类化合物。
优选的,在上述方法中,所述硼酸基、所述铜(I)配位聚合物和所述碱之间的摩尔比为1:0.02:1。
优选的,在上述方法中,所述芳基硼酸类化合物选自苯硼酸、烷基取代苯硼酸(优选甲基取代苯硼酸)、烷氧基取代苯硼酸(优选甲氧基取代苯硼酸)、酰基取代苯硼酸(优选乙酰基取代苯硼酸)、硝基取代苯硼酸、萘硼酸、苯二硼酸中的任意一种。
优选的,在上述方法中,所述碱选自三乙胺、N,N-二异丙基乙胺、N,N-二异丙基异丁胺中的任意一种,优选三乙胺。
优选的,在上述方法中,所述溶剂为乙腈和水的等体积混合溶剂。
优选的,在上述方法中,所述搅拌装置为磁力搅拌装置。
优选的,在上述方法中,所述可见光的光源为荧光灯,优选45W荧光灯。
优选的,在上述方法中,所述反应的时间为48小时。
与现有技术相比,采用上述技术方案的本发明具有下列优点:
(1)本发明首次披露了一种作为光催化剂的铜(I)配位聚合物,其能够在可见光照射下催化芳基硼酸类化合物至酚类化合物的转化;
(2)本发明中记载的芳基硼酸类化合物至酚类化合物的转化具有转化效率高(结构简单的芳基硼酸能够达到80%,甚至95%以上的转化率,并且空间位阻较高的芳基硼酸的转化率也能够达到75%左右)、适用范围广(不仅适合苯硼酸的转化,而且适合于其他稠环芳基硼酸的转化,并且能够实现多种不同取代基取代的苯硼酸的转化)、反应条件温和(室温下敞口反应即可,无需除水除氧过程)等特点;
(3)转化反应结束后,从反应体系中离心分离出铜(I)配位聚合物,经简单水洗即可加入到盛有芳基硼酸类化合物、碱和混合溶剂的反应容器中,用于进行下一轮反应,该铜(I)配位聚合物能够至少循环5次,循环5次后仍能保持稳定,并且其催化活性也未出现明显降低;以苯硼酸为例,循环5次的产率依次为95%、91%、89%、84%和79%,并且循环催化后的粉末衍射实验表明催化剂的结构保持不变。
附图说明
图1为本发明的铜(I)配位聚合物的晶体结构示意图。
图2为本发明的铜(I)配位聚合物循环催化苯硼酸氧化羟基化的产率对比图。
图3为本发明的铜(I)配位聚合物的粉末衍射模拟图以及循环催化苯硼酸氧化羟基化后的粉末衍射实测图。
具体实施方式
下面将结合附图和具体实施例对本发明做出进一步的描述。除非另有说明,下列实施例中所使用的试剂、材料、仪器等均可通过商业手段获得。
实施例1:[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n的制备。
将碘化亚铜(19.0 mg,0.10 mmol)、5-苯基-2-巯基嘧啶(4.7 mg, 0.025 mmol)、乙腈(2 mL)和N,N-二甲基甲酰胺(0.1 mL)加入到10 mL耐热玻璃管中,鼓入氮气0.5 h后,封管,放入烘箱中并于120℃反应48 h;反应结束后,以5℃/h的速率慢慢降温,降至室温后,过滤反应液,滤饼经乙腈、乙醚洗涤并干燥后,得到橙色块状晶体[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(产量:12.2 mg;产率:58%,以Cu计算)。
元素分析(%):C40H28Cu12I8N8S4(n=2的情况),理论值:C 19.01,H 1.12,N 4.43;实验值:C 18.88,H 1.32,N 4.36。
IR(KBr压片,cm-1):3031 (w), 1601 (m), 1551 (w), 1525 (w), 1489 (w),1367 (s), 1348 (m) 1164 (s), 1151 (m), 762 (m), 693 (m)。
对所得产物进行单晶X射线衍射试验,其晶体学参数如表1所示,晶体结构如图1所示。
上述数据表明,本实施例成功得到了目标产物[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n。
实施例2:可见光照射下苯硼酸的氧化羟基化。
将苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1 mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3 mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5 mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物苯酚(产率95%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 9.32 (s, 1H), 7.36-7.02 (m, 2H), 6.75 (d,J = 7.5 Hz, 3H);
13C-NMR (100 MHz, DMSO-d6) δ 157.20, 129.10, 118.68, 114.77。
通过离心的方式,从反应体系中分离出[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n,经简单水洗后加入到盛有苯硼酸、Et3N以及水和乙腈(v/v=1:1)的混合溶剂的装有磁力搅拌子的石英管中,用于进行下一轮转化反应;按照上述过程对光催化剂进行循环利用,循环5次的产率依次为95%、91%、89%、84%和79%(其结果如图2所示),并且循环催化后的粉末衍射实验表明催化剂的结构保持不变(其结果如图3所示)。
实施例3:可见光照射下4-甲氧基苯硼酸的氧化羟基化。
将4-甲氧基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物4-甲氧基苯酚(产率97%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 8.88 (s, 1H), 6.74 (d, J = 8.7 Hz, 2H),6.67 (d, J = 8.6 Hz, 2H), 3.65 (s, 3H);
13C-NMR (100 MHz, DMSO-d6) δ 151.98, 151.09, 115.69, 114.39, 55.31。
实施例4:可见光照射下2-甲基苯硼酸的氧化羟基化。
将2-甲基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物2-甲基苯酚(产率81%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 9.24 (s, 1H), 7.11-6.96 (m, 2H), 6.85 (m,1H), 6.70 (d, J = 6.0 Hz, 1H), 2.18 (s, 3H);
13C-NMR (100 MHz, DMSO-d6) δ 155.51, 130.63, 126.68, 123.89, 118.86,114.70, 16.06。
实施例5:可见光照射下3-甲基苯硼酸的氧化羟基化。
将3-甲基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物3-甲基苯酚(产率91%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 9.98 (s, 1H), 7.51 (d, J = 6.2 Hz, 2H),7.41 (s, 1H), 7.30-7.25 (m, 1H), 3.82 (s, 3H);
13C-NMR (100 MHz, DMSO-d6) δ 157.45, 138.48, 129.30, 119.86, 116.26,112.71, 21.17。
实施例6:可见光照射下4-甲基苯硼酸的氧化羟基化。
将4-甲基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物4-甲基苯酚(产率96%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 9.06 (s, 1H), 6.95 (d, J = 7.9 Hz, 2H),6.64 (d, J = 8.1 Hz, 2H), 2.17 (s, 3H);
13C-NMR (100 MHz, DMSO-d6) δ 154.55, 129.75, 127.17, 114.76, 19.96。
实施例7:可见光照射下2,6-二甲基苯硼酸的氧化羟基化。
将2,6-二甲基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1 mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物2,6-二甲基苯酚(产率75%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 8.17 (s, 1H), 6.90 (d, J = 7.4 Hz, 2H),6.64 (t, J = 7.4 Hz, 1H), 2.10 (s, 6H);
13C-NMR (100 MHz, DMSO-d6) δ 152.97, 127.89, 124.27, 119.14, 16.48。
实施例8:可见光照射下2,4,6-三甲基苯硼酸的氧化羟基化。
将2,4,6-三甲基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1 mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3 mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5 mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物2,4,6-三甲基苯酚(产率74%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 7.89 (s, 1H), 6.69 (s, 2H), 2.11 (s, 9H);
13C-NMR (100 MHz, DMSO-d6) δ 150.75, 128.79, 127.47, 123.97, 19.66,16.06。
实施例9:可见光照射下4-乙酰基苯硼酸的氧化羟基化。
将4-乙酰基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物对4-乙酰基苯酚(产率86%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 10.34 (s, 1H), 7.84 (d, J = 8.2 Hz, 2H),6.85 (d, J = 8.2 Hz, 2H), 2.47 (s, 3H);
13C-NMR (100 MHz, DMSO-d6) δ 195.75, 161.79, 130.69, 128.49, 115.13,25.86。
实施例10:可见光照射下4-硝基苯硼酸的氧化羟基化。
将4-硝基甲基苯硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1 mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物4-硝基苯酚(产率81%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 11.03 (s, 1H), 8.11 (d, J = 7.8 Hz, 2H),6.92 (d, J = 8.5 Hz, 2H);
13C-NMR (100 MHz, DMSO-d6) δ 163.89, 139.61, 126.16, 115.77。
实施例11:可见光照射下2-萘硼酸的氧化羟基化。
将2-萘硼酸(1 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1 mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3 mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5 mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物2-萘酚(产率86%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 9.71 (s, 1H), 7.78-7.72 (m, 2H), 7.67 (d,J = 8.2 Hz, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.25 (t, J = 7.4 Hz, 1H), 7.12-7.05 (m, 2H);
13C-NMR (100 MHz, DMSO-d6) δ 155.25, 134.57, 129.26, 127.70, 127.51,126.07, 125.95, 122.60, 118.58, 108.61。
实施例12:可见光照射下1,4-苯二硼酸的氧化羟基化。
将1,4-苯二硼酸(0.5 mmol)、[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(0.02 mmol)、Et3N(1mmol)加入到装有磁力搅拌子的石英管中,然后加入水和乙腈(v/v=1:1)的混合溶剂(3mL),在45W荧光灯的照射下,于室温敞口反应48 h;反应结束后,用乙酸乙酯萃取(3×5mL),合并有机相,用无水硫酸钠干燥,过滤,用旋转蒸发仪浓缩滤液后,再用硅胶色谱柱法进行分离纯化,得到目标产物1,4-苯二酚(产率75%)。
所得产物的核磁数据如下:
1H-NMR (400 MHz, DMSO-d6) δ 8.61 (s, 2H), 6.55 (s, 4H);
13C-NMR (100 MHz, DMSO-d6) δ 149.73, 115.46。
Claims (5)
1.一种铜(I)配位聚合物,其化学式为[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n,其中5-phpymt为5-苯基-2-巯基嘧啶中的巯基失去质子后形成的阴离子,n为任一正整数。
2.根据权利要求1所述的铜(I)配位聚合物,其特征在于:
所述铜(I)配位聚合物的晶体属于单斜晶系,空间群为C2/m,晶胞参数为a = 12.5100(9) Å,b = 9.4515(6) Å,c = 12.0472(9) Å,α = 90.00 °,β= 107.004(8) °,γ = 90.00°,V = 1362.16(17) nm3,Z = 1。
3.一种根据权利要求1或2所述的铜(I)配位聚合物的制备方法,其包括如下步骤:
按照碘化亚铜:5-苯基-2-巯基嘧啶=2~5:1的摩尔比,将碘化亚铜、5-苯基-2-巯基嘧啶和溶剂加入到反应容器中,通入惰性气体0.5~1小时后,密闭反应容器,加热至100~140℃并反应24~72小时;反应结束后,将反应体系的温度降至室温,经过滤、洗涤、干燥,得到所述铜(I)配位聚合物。
4.根据权利要求3所述的制备方法,其特征在于:
所述碘化亚铜和所述5-苯基-2-巯基嘧啶之间的摩尔比为4:1。
5.根据权利要求3所述的制备方法,其特征在于:
所述惰性气体选自氮气、氖气、氩气中的任意一种;
所述溶剂为乙腈和N,N-二甲基甲酰胺的混合溶剂;
所述加热通过烘箱来完成;
所述反应的温度为120℃,时间为48小时。
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