CN114057545A - 一种催化四氢吡喃醚脱保护为羟基化合物的绿色方法 - Google Patents
一种催化四氢吡喃醚脱保护为羟基化合物的绿色方法 Download PDFInfo
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- -1 hydroxyl compound Chemical class 0.000 title claims abstract description 26
- 238000010511 deprotection reaction Methods 0.000 title claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title abstract description 14
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 title abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- HUHXLHLWASNVDB-UHFFFAOYSA-N 2-(oxan-2-yloxy)oxane Chemical compound O1CCCCC1OC1OCCCC1 HUHXLHLWASNVDB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000006239 protecting group Chemical group 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical group [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229930192474 thiophene Chemical group 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
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- 239000003960 organic solvent Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
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- 230000002153 concerted effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical class CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
本发明提供了一种催化四氢吡喃醚脱保护为羟基化合物的绿色方法,属于绿色有机化学领域。该方法在在中性、敞口、室温条件下,以乙腈作反应溶剂,FeBr2或FeBr3作催化剂,H2O2作氧化剂,短时间内将四氢吡喃醚类衍生物转化为羟基化合物。本发明所用催化剂FeBr2、FeBr3,氧化剂H2O2和溶剂乙腈价廉易得,反应时间短且条件温和,具有广泛的官能团相容性,后处理简单,容易操作,是当前绿色、环保、安全的四氢吡喃醚类衍生物脱保护成羟基化合物的方法,具有广阔的应用前景。
Description
技术领域
本发明属于绿色化学和有机合成技术领域,具体涉及一种催化四氢吡喃醚脱保护为羟基化合物的绿色方法。
背景技术
在多步有机合成反应中,常见的官能团,如羰基、羟基和羧酸等都需要保护。在现有的关于羟基保护的方法中,四氢吡喃基(THP)是最常见的保护基团之一。
目前,关于四氢吡喃醚衍生物的脱保护方法有很多。但是,这些方法通常使用无机酸的水溶液,或使用有机酸的非水溶液作为反应溶剂,反应很少在中性条件下进行。此外,这些方法还存在着一些缺点,如反应时间长、试剂价格昂贵、毒性大等,在合成过程中产生大量的副产物,对环境造成了一定的污染。
因此,开发一种绿色环保、对环境友好且成本较低的四氢吡喃醚脱保护为羟基化合物的方法具有重要意义。
发明内容
本发明的目的是,开发一种催化四氢吡喃醚脱保护为羟基化合物的通用、绿色的方法。
本发明采用的技术方案为:
一种催化四氢吡喃醚脱保护为羟基化合物的绿色方法:
在中性、室温、敞口条件下,以乙腈作为反应溶剂,以FeBr2或FeBr3作催化剂,H2O2作氧化剂,短时间内完成四氢吡喃醚为转化为相应羟基化合物的脱保护反应。
反应以四氢吡喃醚类衍生物为原料,所述衍生物的结构如式I所示:
反应底物为不同类型的四氢吡喃醚类衍生物,反应底物具有的官能团可为氢基、烷基、烯基、炔基、芳基、酯基、脂环烃等不同官能团或呋喃、吡啶、噻吩、吡咯以及其他杂环等不同取代基,也可为常用的保护基团如Ac、Bn、Boc和TBS等。反应生成的羟基化合物包括伯醇、仲醇和叔醇。反应于催化剂条件下进行,所用催化剂为FeBr2、FeBr3以及FeSO4-KBr、Fe(NO3)2-KBr、FeCl2-KBr、FeCl3-KBr、Fe(NO3)3-KBr等Fe3+和Fe2+与Br-组成的金属盐组合。
具体操作时,提供一种方案:将四氢吡喃醚类衍生物加入到乙腈中,两者混匀后加入催化剂FeBr2或FeBr3(0.05-0.1eq)搅拌均匀,然后向混合物中加入H2O2水溶液(30%,0.6-2eq),反应混合物在室温下继续搅拌反应10-30min。反应完成后用稀释的Na2S2O3溶液(0.1M)淬灭,淬灭后用乙酸乙酯萃取。收集有机相,水相用乙酸乙酯萃取2-3次。合并有机相后依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得产物。
本发明的有益效果:
本发明与现有技术相比具有以下优点和效果:
本发明首次实现了以FeBr2和FeBr3催化四氢呋喃醚类衍生物转化为羟基化合物的反应,是一种脱除羟基保护基的绿色方法。本发明以乙腈作为反应溶剂,在中性敞口的条件下由协同催化体系CeBr3-H2O2催化氧化进行脱保护反应,反应生成H2O,对环境友好。此外本发明还具有原料易得、成本低、反应快、底物适用范围广、路线简单、容易操作等特点,比之前所有的方法更具优势,具有良好的应用前景。有望在有机合成领域中得到广泛应用。
附图说明
图1和图2是实施例1的1H-NMR及13C-NMR谱图
图3和图4是实施例2的1H-NMR及13C-NMR谱图
图5和图6是实施例3的1H-NMR及13C-NMR谱图
图7和图8是实施例4的1H-NMR及13C-NMR谱图
图9和图10是实施例5的1H-NMR及13C-NMR谱图
具体实施方式
下面用具体实施方案详述本发明,但本发明的保护范围不仅限于此。
以下实施例中的1H-NMR及13C-NMR谱均在室温条件下测定,记录在400MHz光谱仪上,1H为400MHz,13C为100MHz,光谱仪来自布鲁克公司。
实施例1
将乙腈4ml、1a(0.80mmol,0.15g)依次加入25ml圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.08mmol,0.017g)或FeBr3(0.08mmol,0.024g),H2O2水溶液(30wt%,0.81mmol,81ul),在室温下搅拌反应10min。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,乙酸乙酯萃取依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物1b(产率:98.7%)。该化合物的表征数据如下:1H-NMR(400MHz,Chloroform-d)δ3.96(dt,J=11.7,4.4Hz,2H),3.85(tt,J=9.1,4.3Hz,1H),3.49-3.39(m,2H),1.94-1.86(m,2H),1.75(s,1H),1.57(qd,J=9.5,4.8Hz,2H).13C-NMR(100MHz,Chloroform-d)δ67.1,65.8,35.6.
实施例2
将乙腈3ml、2a(0.52mmol,0.15g)依次加入25ml圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.05mmol,0.011g)或FeBr3(0.05mmol,0.015g),H2O2水溶液(30wt%,0.52mmol,53ul),在室温下搅拌反应20min。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物2b(产率:78.9%)。该化合物的表征数据如下:1H-NMR(400MHz,Chloroform-d)δ7.45-7.35(m,4H),3.66(t,J=6.4Hz,2H),2.76(t,J=7.8Hz,2H),1.88(m,2H),1.53(s,1H).13C-NMR(100MHz,Chloroform-d)δ142.9,132.0,130.7(q,J=32.0Hz),128.9,125.2(q,J=3.8Hz),124.4(q,J=120.0Hz),122.9(q,J=3.8Hz),62.0,34.1,32.0.
实施例3
将乙腈5ml、3a(0.97mmol,0.15g)依次加入25ml圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.10mmol,0.021g)或FeBr3(0.10mmol,0.029g),H2O2水溶液(30wt%,0.97mmol,98ul),在室温下搅拌反应15min。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物2b(产率:94.2%)。该化合物的表征数据如下:1H NMR(400MHz,Chloroform-d)δ3.83(t,J=6.1Hz,1H),3.16(s,1H),2.58(t,J=6.1Hz,1H).13C-NMR(101MHz,Chloroform-d)δ118.5,57.7,21.5.
实施例4
将乙腈4ml、4a(0.75mmol,0.15g)依次加入25ml圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.08mmol,0.016g)或FeBr3(0.08mmol,0.022g),H2O2水溶液(30wt%,0.75mmol,76ul),在室温下搅拌反应15min。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物4b(产率:56.9%)。该化合物的表征数据如下:1H-NMR(400MHz,Chloroform-d)δ3.38(d,J=6.4Hz,2H),2.26(s,1H),1.73-1.61(m,5H),1.47-1.38(m,1H),1.26-1.10(m,3H),0.93-0.83(m,2H).13C-NMR(100MHz,Chloroform-d)δ68.8,40.5,29.6,26.6,25.9.
实施例5
将乙腈4ml、5a(0.68mmol,0.126g)依次加入25ml圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.07mmol,0.015g)或FeBr3(0.07mmol,0.020g),H2O2水溶液(30wt%,0.68mmol,69ul),在室温下搅拌反应15min。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物5b(产率:97.1%)。该化合物的表征数据如下:1H-NMR(400MHz,Chloroform-d)δ7.52-7.48(m,2H),7.37-7.32(m,2H),7.26(m,1H),1.59(s,6H).13C-NMR(101MHz,Chloroform-d)δ149.2,128.3,126.8,124.5,72.6,31.9.
Claims (9)
2.根据权利要求1所述的方法,其特征在于:反应于溶剂中进行,所用溶剂可为乙腈、乙醇、四氢呋喃等,四氢吡喃醚类衍生物与溶剂的用量为1mmol/5-10ml。
3.根据权利要求1所述的方法,其特征在于:反应在催化剂条件下进行,所用催化剂为FeBr2、FeBr3以及FeSO4-KBr、Fe(NO3)2-KBr、FeCl2-KBr、FeCl3-KBr、Fe(NO3)3-KBr等Fe3+和Fe2 +与Br-组成的金属盐组合中的任意一种,所述的四氢吡喃醚类衍生物与催化剂的摩尔比为1∶0.05-0.1。
4.根据权利要求1所述的方法,其特征在于,所述氧化剂为过氧化氢,浓度为3-30%,H2O2与四氢吡喃醚类衍生物的摩尔比为0.6-2∶1。
5.根据权利要求1所述的方法,其特征在于:反应在pH为中性条件下进行。
6.根据权利要求1所述的方法,其特征在于:反应在不排除空气和水分的情况下即可进行,即敞口条件下进行,反应温度为室温。
7.根据权利要求1所述的方法,其特征在于:所述反应较佳反应时间为10-15min。
8.根据权利要求1所述的方法,其特征在于:具体操作时将四氢吡喃醚类衍生物、催化剂和乙腈依次加入到圆底烧瓶中搅拌,然后加入H2O2水溶液,反应混合物在室温下继续搅拌反应10-15min,完成四氢吡喃醚类衍生物的脱保护反应。
9.根据权利要求1所述的方法,其特征在于:所述四氢吡喃醚类衍生物脱保护成相应羟基化合物反应的后处理方法为,反应完成后用Na2S2O3溶液淬灭,乙酸乙酯萃取,收集有机相,水相再用有机溶剂萃取2-3次,合并有机相后依次用水洗,无水硫酸钠干燥,过滤,减压浓缩,即可得相应的羟基化合物。
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