CN110240607B - 1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐及其制备方法 - Google Patents
1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
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- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract
本发明公开了一种1,3‑二金刚烷‑4,5‑二氢咪唑二氯亚铜盐及其制备方法,将1,3‑二金刚烷‑4,5‑二氢咪唑溶解在THF溶液中,加入一定量的叔丁醇钾作为碱,选择氯化亚铜作为金属前体,将金属前体缓慢加入,加入完毕后搅拌12h以上制得1,3‑二金刚烷‑4,5‑二氢咪唑二氯亚铜盐。本发明采用的配体二氢咪唑盐的两个侧臂为给电子能力较强的极性较小的金刚烷基团,有利于配体与金属配位反应的稳定和增加催化剂的脂溶性;配体与金属通过简单的共生反应生成目标产物,制备方法简便易行;目标产物适用于醇的有氧氧化反应,在温和的反应条件下,可获得很高的产率。
Description
技术领域
本发明属于催化化学领域,具体涉及一种1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备及其在醇氧化制备醛酮类化合物的应用。
背景技术
醛酮类化合物是生物学,制药学,农药化学以及天然产品中一个重要的原料。在农药,染料,医药等方面有重要意义。因此醛酮类化合物不仅在理论上,在实际应用上也有重要作用。而由醇氧化生成相应的醛酮类化合物是现代有机化学反应中重要的官能化反应,也是合成醛酮类化合物的一种重要方法。
经典的氧化醇生成醛酮化合物的催化剂一般是高价过渡金属的盐或其氧化物,如Jones试剂、重铬酸吡啶盐(PDC)、Dess-Martin高碘试剂(DMP)等,但是使用这类催化剂一般要过量,而且重金属的大量使用会对环境造成污染。后来人们发现了过氧化物-金属催化体系,大大降低了催化剂的用量,并且双氧水催化反应的副产物是水,所以被认为是一种绿色高效的催化剂,随后这种方法得到了充分发展,但是也发现其氧化醇的反应选择性较低,容易产生过氧化副产物。近年来的研究发现,氧气作为一种容易得到的资源可以作为很好的氧化剂,但其反应活性不高,一般需要过渡金属来进行活化,其中主要的过渡金属-有氧氧化体系一般是Pd、Ru、Cu催化体系或其共催化体系。
金属铜是一种储量丰富、价格便宜、具有Cu0,CuI,CuII,CuIII不同的氧化态,使其能够与不同的官能团通过π-共轭或者路易斯酸碱配位而交联在一起,其在催化有氧氧化反应中有着广泛的应用。开始用于醇的有氧氧化为铜盐的配位体系,如CuCl/TEMPO、CuCl/Phen、CuCl/bipyridine等,但是这种配位的稳定性不高,催化效果不好。后来人们发现卡宾与金属Cu形成的稳定的卡宾铜催化剂可以高效地催化一系列醇的有氧氧化反应。但是,这些均相金属催化剂制备工艺较复杂。
由于卡宾铜均相催化剂的成本太高,限制了在工业上的应用,因此,研究开发新的催化体系,以克服均相催化体系的这些弊端,成为研究的热点。
发明内容
本发明的目的在于提供一种1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐、制备方法及其催化制备醛酮类化合物的应用。
本发明所采用的技术方案是:1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐,其结构式如下:
上述目标化合物的制备方法,包括将配体1,3-二金刚烷-4,5-二氢咪唑与氯化亚铜发生配位反应制备1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的步骤,
具体制备方法包括:将1,3-二金刚烷-4,5-二氢咪唑溶解在THF溶液中,加入一定量的叔丁醇钾作为碱,选择氯化亚铜作为金属前体,将金属前体缓慢加入,加入完毕后搅拌12h以上制得1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐。
进一步的,1,3-二金刚烷-4,5-二氢咪唑与叔丁醇钾与氯化亚铜的摩尔比为1:1:1。
上述目标化合物在制备醛酮类化合物中的应用,以氢氧化钾为碱,以1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐为铜催化剂,对醇进行有氧氧化反应。
其中,反应在氧气氛围下进行,反应温度为室温条件,反应时间为12h,n(醇):n(氢氧化钾)=1:2,1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐用量为醇的3mol%,反应溶剂为二氯甲烷。
与现有技术相比,本发明具有以下显著优点:
(1)配体二氢咪唑盐的两个侧臂为给电子能力较强的极性较小的金刚烷基团,有利于配体与金属配位反应的稳定和增加催化剂的脂溶性。
(2)配体与金属通过简单的共生反应生成目标产物,制备方法简便易行。
(3)目标产物适用于醇的有氧氧化反应,在温和的反应条件下,可获得很高的产率。
附图说明
图1为目标产物1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的单分子晶体结构图。
具体实施方式
本发明中目标产物的合成路线如下:
具体制备方法包括:
(1)N,N’-二金刚烷基乙二亚胺的制备:取适量1-金刚烷胺溶于乙醇水溶液中,冰水浴条件下搅拌15min,滴加适量的乙二醛水溶液,滴加结束后搅拌反应1h,过滤,乙醇水洗涤滤饼,得到二亚胺产物。
(2)N,N’-二金刚烷基乙二胺的制备:将制得的二亚胺溶于甲醇中,冰水浴条件下搅拌15min,缓慢加入适量的硼氢化钠,搅拌反应过夜,多步处理得到二亚胺的还原产物,干燥备用。
(3)1,3-二金刚烷-4,5-二氢咪唑氯化盐的制备:向烧瓶中加入上述二亚胺还原产物,原甲酸三甲酯,氯化铵,氮气保护下,于110℃回流反应12h,反应结束后经多步处理得到二氢咪唑盐产物,干燥备用。
(4)1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备:将二氢咪唑盐溶解在THF溶液中,加入一定量的叔丁醇钾作为碱,选择氯化亚铜作为金属前体,将金属前体缓慢加入,加入完毕后搅拌12h制得1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐。
实施例1
1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备方法如下:
(1)N,N’-二金刚烷基乙二亚胺的制备:在500mL烧瓶中,将6.3g1-金刚烷胺完全溶解于250mL水:乙醇(1:1)体系中,将烧瓶在冰水浴中冷却并搅拌30min。用恒压滴液漏斗滴加3.0mL乙二醛水溶液,滴加结束后,开始沉淀出无色固体。继续搅拌1h以提供足够的时间使产物完全沉淀。硅藻土过滤,收集无色固体产物,用50mL水:乙醇(1:1)洗涤,干燥,得4.8g产物,收率72.5%。
核磁分析结果:1H NMR(500MHz,CDCl3)δ:7.92(s,2H),2.14(s,6H),1.74-1.64(m,24H)ppm;13C NMR(101MHz,CDCl3)δ:158.13,58.19,43.05,36.67,29.66ppm.
(2)N,N’-二金刚烷基乙二胺的制备:在250mL圆底烧瓶中加入4.0g上述二亚胺产物,100mL甲醇,并加热使其完全溶解,将烧瓶在冰水浴中冷却并搅拌30min,氮气保护条件下,缓慢加入1.9g硼氢化钠,保持冰水浴条件反应12h。饱和氯化铵溶液淬灭,二氯甲烷萃取(2×100mL),加水洗涤(2×30mL),无水硫酸钠干燥,减压蒸馏去除溶剂,得4.2g粗产物。将粗产物溶于50mL二氯甲烷,滴加6mol/L盐酸水溶液使体系呈现酸性,加水萃取(2×50mL),水相中滴加饱和碳酸钠溶液直至溶液呈碱性,二氯甲烷萃取(2×100mL),旋转蒸发仪除溶剂,真空干燥,得3.2g产物,收率80%。
核磁分析结果:1H NMR(500MHz,CDCl3)δ:2.68(s,4H),2.06(s,6H),1.67-1.58(m,24H)ppm;13C NMR(101MHz,CDCl3)δ:50.71,43.04,41.41,37.00,29.85ppm.
(3)1,3-二金刚烷-4,5-二氢咪唑氯盐的制备:在250mL圆底烧瓶中加入3.0g上述二胺产物,100mL原甲酸三甲酯,0.59g氯化铵,氮气保护下,于110℃回流反应12h。反应结束后,降至室温,有白色固体析出,静置,吸出上层液体,石油醚洗涤除去原甲酸三甲酯,减压蒸馏去除溶剂,得到粗产物2.5g。粗品用二氯甲烷溶解,滤纸过滤除去剩余氯化铵,减压蒸馏去除溶剂,真空干燥,得2.3g产物,收率65%。
核磁分析结果:1H NMR(500MHz,CDCl3)δ:8.41(s,1H),4.05(s,4H),2.21(s,6H),2.05-2.04(m,10H),1.97(s,4H),1.70-1.69(m,10H)ppm;13C NMR(101MHz,CDCl3)δ:152.47,57.59,44.08,41.03,35.76,29.41ppm.
(4)1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备:在氮气氛围下,于50mL茄形瓶中加入1.0g上述二氢咪唑盐,20mL四氢呋喃,再加入0.3g叔丁醇钾和0.3g氯化亚铜,溶液呈绿色,室温反应12h。反应结束后体系呈淡蓝色,停止反应,滤纸过滤除去固体,用旋转蒸发仪去除溶剂,得粘稠液体,用20mL无水乙醚洗涤三次,旋转蒸发仪去除溶剂,得粗产物0.7g。粗产物用1,2-二氯乙烷重结晶,得0.6g固体产物,收率47.6%。
单晶衍射结果如附图1。
实施例2
仅将实施例1中的步骤4中1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备方法作如下改变,其他步骤与实施例1一致。
在氮气氛围下,于100mL茄形瓶中加入2.0g上述二氢咪唑盐,38mL四氢呋喃,再加入0.7g叔丁醇钾和0.6g氯化亚铜,溶液呈绿色,室温反应15h。反应结束后体系呈淡蓝色,停止反应,滤纸过滤除去固体,用旋转蒸发仪去除溶剂,得粘稠液体,用40mL无水乙醚洗涤三次,旋转蒸发仪去除溶剂,得粗产物1.2g。粗产物用1,2-二氯乙烷重结晶,得1.0g固体产物,收率42.3%。
实施例3
仅将实施例1中的步骤4中1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备方法作如下改变,其他步骤与实施例1一致。
在氮气氛围下,于50mL茄形瓶中加入1.0g上述二氢咪唑盐,20mL四氢呋喃,再加入0.2g叔丁醇钾和0.3g氯化亚铜,溶液呈绿色,室温反应12h。反应结束后体系呈淡蓝色,停止反应,滤纸过滤除去固体,用旋转蒸发仪去除溶剂,得粘稠液体,用20mL无水乙醚洗涤三次,旋转蒸发仪去除溶剂,得粗产物0.6g。粗产物用1,2-二氯乙烷重结晶,得0.5g固体产物,收率40.0%。
实施例4
仅将实施例1中的步骤4中1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐的制备方法作如下改变,其他步骤与实施例1一致。
在氮气氛围下,于50mL茄形瓶中加入1.0g上述二氢咪唑盐,20mL四氢呋喃,再加入0.4g叔丁醇钾和0.3g氯化亚铜,溶液呈绿色,室温反应12h。反应结束后体系呈淡蓝色,停止反应,滤纸过滤除去固体,用旋转蒸发仪去除溶剂,得粘稠液体,用20mL无水乙醚洗涤三次,旋转蒸发仪去除溶剂,得粗产物0.5g。粗产物用1,2-二氯乙烷重结晶,得0.4g固体产物,收率38.6%。
实施例5
1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐在醇的有氧氧化反应中的应用:
在反应管中加入苯甲醇(1.0mmol),KOH(2.0mmol),1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐(0.03mmol)、4A分子筛,抽真空,再冲入干燥氧气,使体系处于氧气氛围下,再加入10mL二氯甲烷,室温条件下反应12h。反应结束后,滤纸过滤,饱和氯化钠水溶液洗涤,无水硫酸钠干燥,旋转蒸发仪去除溶剂,使用石油醚与乙酸乙酯柱层析分离得到目标产物苯甲醛,收率为65.1%。
实施例6
反应步骤与实施例5完全相同,不同之处在于:
氢氧化钾的使用量为1mmol,苯甲醛收率为39.2%。
实施例7
反应步骤与实施例5完全相同,不同之处在于:
氢氧化钾的使用量为3mmol醋酸钯,苯甲醛收率为63.2%。
实施例8
反应步骤与实施例5完全相同,不同之处在于:
碱为2mmol叔丁醇钾,苯甲醛收率为59.4%。
实施例9
反应步骤与实施例5完全相同,不同之处在于:
反应温度为40℃,苯甲醛收率为62.7%。
实施例10
反应步骤与实施例5完全相同,不同之处在于:
反应温度为10℃,苯甲醛收率为52.6%。
实施例11
反应步骤与实施例5完全相同,不同之处在于:
反应溶剂为10mL甲苯,苯甲醛收率为57.5%。
实施例12
反应步骤与实施例5完全相同,不同之处在于:
反应时间为6h,苯甲醛收率为45.1%。
实施例13
反应步骤与实施例5完全相同,不同之处在于:
反应时间为18h,苯甲醛收率为64.5%。
Claims (10)
3.如权利要求2所述的制备方法,其特征在于,反应体系采用THF溶液为反应溶剂。
4.如权利要求2所述的制备方法,其特征在于,1,3-二金刚烷-4,5-二氢咪唑与叔丁醇钾与氯化亚铜的摩尔比为1:1:1。
5.如权利要求1所述的1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐在制备醛酮类化合物中的应用。
6.如权利要求5所述的应用,其特征在于,以氢氧化钾为碱,以1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐为铜催化剂,对醇进行有氧氧化反应。
7.如权利要求6所述的应用,其特征在于,反应在氧气氛围下进行。
8.如权利要求6所述的应用,其特征在于,反应时间为12h。
9.如权利要求6所述的应用,其特征在于,n(醇):n(氢氧化钾)=1:2;1,3-二金刚烷-4,5-二氢咪唑二氯亚铜盐用量为醇的3mol%。
10.如权利要求6所述的应用,其特征在于,氧化反应的反应溶剂为二氯甲烷。
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