CN110898856B - Pd(II)-NHC催化剂制备方法及在Suzuki-Miyaura反应中的应用 - Google Patents
Pd(II)-NHC催化剂制备方法及在Suzuki-Miyaura反应中的应用 Download PDFInfo
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Abstract
Pd(II)‑NHC催化剂制备方法及在Suzuki‑Miyaura反应中的应用,涉及一种催化剂制备方法及在反应中的应用,本发明公开了Pd(II)‑氮杂环卡宾(Pd(II)‑NHC)催化剂制备方法及其在Suzuki‑Miyaur反应中的应用。本发明中的两种Pd(II)‑NHC催化剂均以K2PdCl4为前体,配体H2L1,H2L2分别以二(1‑咪唑基)甲烷与N‑(2‑氯苯基)乙酰胺以及N‑(2‑氯‑(2,6‑二异丙基))乙酰胺反应缩合而得,通过分步合成法制得催化剂Pd‑(H2L1),Pd‑(H2L2)。两种新颖的催化剂结构明确,对水和空气稳定;在Suzuki‑Miyaura反应中,反应条件温和,后处理简单,具有很好的催化活性和选择性。
Description
技术领域
本发明涉及催化剂制备方法及在反应中的应用,特别是涉及Pd(II)-NHC催化剂制备方法及在Suzuki-Miyaura反应中的应用。
背景技术
氮杂环卡宾(NHC)由于其与过渡金属之间极强的络合能力,使其在催化反应中表现出非常好的稳定性,甚至在有水、有氧的情况下也可进行,且反应条件温和,因此氮杂环卡宾金属催化剂是催化剂中非常重要的一类。随着研究的进一步深入,新型氮杂卡宾被逐渐合成出来,NHC金属催化剂的应用范围正在不断拓展,不但在很多传统催化反应中表现突出,在环合反应、氟化反应和极性反转等反应中也表现出优异的催化性能。
过渡金属钯是经典的催化剂,已被广泛地应用于催化氧化、偶联、烯烃复分解等反应,多年来一直是催化剂领域的研究热点。使用钯催化的氧化反应、氧化脱氢形成的C-O,C-N,C-C键的反应,以及C-C键键裂产生的开环反应在杂环化学、药物合成、天然产物的合成等方面具有重要的意义。Suzuki-Miyaura反应(铃木-宫浦反应)是有机偶联反应,零价钯催化剂催化下,芳基或烯基硼酸或硼酸酯与氯、溴、碘代芳烃或烯烃发生交叉偶联。该反应在有机合成中的用途广,具有较强的底物适应性及官能团容忍性,常用于合成多烯烃、苯乙烯和联苯的衍生物,从而应用于众多天然产物、有机材料的合成中。
发明内容
本发明的目的在于提供Pd(II)-NHC催化剂制备方法及在Suzuki-Miyaura反应中的应用,本发明属于配位化学,即金属有机催化剂制备及其应用,两种钯催化剂合成方法简单,结构稳定;在催化醇氧化过程中,优化反应条件后,催化活性好;该催化剂作用下,芳基或烯基硼酸或硼酸酯与氯,溴,碘代芳烃或烯烃发生交叉偶联反应,该反应过程无论是在有机合成、精细化工或是在医药工业中都是一个重要反应。
本发明的目的是通过以下技术方案实现的:
Pd(II)-NHC催化剂制备方法,所述方法包括两种Pd(II)-NHC催化剂配合物都是以K2PdCl4为前体,配体H2L1,H2L2分别以二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺以及N-(2-氯-(2,6-二异丙基))乙酰胺反应缩合而得,通过分步合成法制得催化剂Pd- (H2L1),Pd-(H2L2);所制备的两种Pd(II)-NHC催化剂的结构通式如下式所示:
两种Pd(II)-NHC催化剂的具体制备步骤如下:
a)制备二(1-咪唑基)甲烷化合物
称取NaOH固体溶于乙腈溶液,升温至60℃,缓慢加入咪唑,用恒压滴液漏斗缓慢滴加二溴甲烷,滴加完毕后升温至80℃,回流反应3h;
b)制备N-(2-氯苯基)乙酰胺化合物
称取苯胺溶于DCM溶液中,用恒压滴液漏斗缓慢加入氯乙酰
氯,室温下搅拌3h;
c) N-(2-氯-(2,6-二异丙基))乙酰胺化合物的制备方法同上,但加入的是氯乙酰氯之前滴加3-5滴三乙胺;
d) 酰胺配体的制备
分别将二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺溶于乙腈溶液中,将N-(2-氯苯基)乙酰胺溶液缓慢加入到乙腈溶液中,滴加完毕后升温至100℃,搅拌24h,抽滤,用乙腈,叔甲醚溶液洗涤,得到H2L1配体;
H2L2配体的制备方法同上;
e) Pd(II)-NHC催化剂的制备
将K2PdCl4和H2L1按1:1比例加入到反应瓶中,再加入DMSO,温度设置95℃,反应时间升3天降2天;得到Pd-(H2L1)配合物;
Pd-(H2L2)配合物的制备方法同上,其中Pd-(H2L2)反应溶剂换为DMSO与水的混合溶液。
Pd(II)-NHC催化剂在Suzuki-Miyaura反应中的应用,所述以上合成的配合物,以苯硼酸为底物对两种催化剂进行Suzuki-Miyaura反应,溶剂为水和乙醇的混合溶液,催化剂与底物比为1:100,反应温度为80℃;Pd-(H2L1)催化剂在此条件下催化转化率达到83.77%, 而Pd-(H2L2)在此条件下的催化转化率达到91.05%;同时在此反应条件下,Pd-(H2L1),Pd-(H2L2)的催化产物选择性分别是99.27%、99.82%;两种配合物中的酰胺配体的不同,对催化性起到了不同的作用。
本发明的优点与效果是:
1、本发明中的两种Pd(II)-NHC催化剂均以K2PdCl4为前体,配体H2L1,H2L2分别以二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺以及N-(2-氯-(2,6-二异丙基))乙酰胺反应缩合而得,通过分步合成法制得催化剂Pd- (H2L1),Pd-(H2L2)。通过水热法分步合成制得催化剂Pd- (H2L1),Pd-(H2L2)。配合物中的不同酰胺配体对催化Suzuki-Miyaura反应条件有改进作用。
2、两种新型Pd(II)-NHC催化剂结构明确,对催化Suzuki-Miyaura反应有较好的催化效果,且反应条件温和,后处理简单,是一类有价值的Suzuki-Miyaura反应催化剂。
3、对所合成的两种新型配合物催化剂进行了活性测试,通过优化温度、溶剂、催化剂用量、氧化剂用量等参数,对Pd(II)-NHC催化剂催化Suzuki-Miyaura反应时的影响进行研究,结果表明配合物Pd-(H2L2)的催化活性最高,催化剂与底物比为1:100,反应温度为80℃反应条件下,催化转换率达91.05%,选择性接近99.82%。
具体实施方式
下面结合实施例对本发明进行详细说明。
1、具有催化Suzuki-Miyaura反应的新型Pd(II)-NHC催化剂的制备方法和反应条件
a)制备二(1-咪唑基)甲烷化合物。称取NaOH(0.02mol)固体溶于乙腈溶液,升温至60℃,缓慢加入咪唑(0.02mol),用恒压滴液漏斗缓慢滴加二溴甲烷(0.01mol),滴加完毕后升温至80℃,回流反应3h。
制备N-(2-氯苯基)乙酰胺化合物。称取苯胺(0.01mol)溶于DCM溶液中,用恒压滴液漏斗缓慢加入氯乙酰氯(0.01mol),室温下搅拌3h。
N-(2-氯-(2,6-二异丙基))乙酰胺化合物的制备方法同上。称取2,6-二异丙基苯胺(0.01mol),氯乙酰氯(0.011mol)。不同的是加入氯乙酰氯之前滴加3-5滴三乙胺。
b) 酰胺配体的制备。分别将二(1-咪唑基)甲烷(0.001mol)与N-(2-氯苯基)乙酰胺(0.0021mol)溶于乙腈溶液中,将N-(2-氯苯基)乙酰胺溶液缓慢加入到乙腈溶液中,滴加完毕后升温至100℃,搅拌24h,抽滤,用乙腈,叔甲醚溶液洗涤,得到白色固体,在真空干燥箱中干燥24h,温度设置为45℃。得到H2L1配体。
H2L2配体的制备方法同上。分别将二(1-咪唑基)甲烷(0.001mol)与N-(2-氯-(2,6-二异丙基))乙酰胺(0.0021mol)溶于乙腈溶液中,将N-(2-氯-(2,6-二异丙基))乙酰胺溶液缓慢加入到乙腈溶液中,滴加完毕后升温至100℃,搅拌24h,抽滤,用乙腈,叔甲醚溶液洗涤,得到白色固体,干燥,得到H2L2配体。
c) Pd(II)-NHC催化剂的制备。将K2PdCl4(0.1mmol)与H2L1(0.1mmol)按照1:1比例加入到反应瓶中,再加入DMSO,温度设置95℃,反应时间升3天降2天。反应结束后在显微镜下观察,看到透明长条晶体。即Pd-(H2L1)配合物。
Pd-(H2L2)配合物的制备方法同上。称取K2PdCl4(0.1mmol)与H2L2(0.1mmol)反应。不同的是,其中Pd-(H2L2)配合物反应溶剂换为DMSO与水的混合溶液。
2、Pd(II)-NHC催化剂催化醇氧化反应
对所合成出的新型催化剂进行了催化性能测试。以温度、溶剂、催化剂用量、氧化剂用量为参数,对新型的钯催化剂催化Suzuki-Miyaura反应的影响进行研究。结果表明,两种配合物均具有催化活性,其活性最高的是Pd-(H2L2)催化剂,其催化转换率达91.05%,选择性接近99.82%。
本发明中的两种Pd(II)-NHC催化剂均以K2PdCl4为前体,配体H2L1,H2L2分别以二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺以及N-(2-氯-(2,6-二异丙基))乙酰胺反应缩合而得,通过分步合成法制得催化剂Pd- (H2L1),Pd-(H2L2)。通过水热法分步合成制得催化剂Pd- (H2L1),Pd-(H2L2)。配合物中的不同酰胺配体对催化Suzuki-Miyaura反应条件有改进作用。活性最高的Pd-(H2L2)配合物,其催化转换率达91.05%,选择性接近99.82%,说明这类催化剂对催化Suzuki-Miyaura反应有较好的催化效果,是一类有价值的Suzuki-Miyaura反应催化剂。
两种新型Pd(II)-NHC催化剂,均以K2PdCl4为前体,配体H2L1,H2L2分别以二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺以及N-(2-氯-(2,6-二异丙基))乙酰胺反应缩合而得,通过水热法分步合成制得催化剂Pd- (H2L1),Pd-(H2L2)。
Claims (2)
1.Pd(II)-NHC催化剂制备方法,其特征在于,所述方法包括两种Pd(II)-NHC催化剂配合物都是以K2PdCl4为前体,配体H2L1,H2L2分别以二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺以及N-(2-氯-(2,6-二异丙基))乙酰胺反应缩合而得,通过分步合成法制得催化剂Pd-(H2L1),Pd-(H2L2);所制备的两种Pd(II)-NHC催化剂的结构通式如下图所示:
R= H ,C3H7
两种Pd(II)-NHC催化剂的具体制备步骤如下:
a)制备二(1-咪唑基)甲烷化合物
称取NaOH固体溶于乙腈溶液,升温至60℃,缓慢加入咪唑,用恒压滴液漏斗缓慢滴加二溴甲烷,滴加完毕后升温至80℃,回流反应3h;
b)制备N-(2-氯苯基)乙酰胺化合物
称取苯胺溶于DCM溶液中,用恒压滴液漏斗缓慢加入氯乙酰
氯,室温下搅拌3h;
c) N-(2-氯-(2,6-二异丙基))乙酰胺化合物的制备方法同上,但加入的是氯乙酰氯之前滴加3-5滴三乙胺;
d) 酰胺配体的制备
分别将二(1-咪唑基)甲烷与N-(2-氯苯基)乙酰胺溶于乙腈溶液中,将N-(2-氯苯基)乙酰胺溶液缓慢加入到乙腈溶液中,滴加完毕后升温至100℃,搅拌24h,抽滤,用乙腈,叔甲醚溶液洗涤,得到H2L1配体;
H2L2配体的制备方法同上;
e) Pd(II)-NHC催化剂的制备
将K2PdCl4和H2L1按1:1比例加入到反应瓶中,再加入DMSO,温度设置95℃,反应时间升3天降2天;得到Pd-(H2L1)配合物;
Pd-(H2L2)配合物的制备方法同上,其中Pd-(H2L2)反应溶剂换为DMSO与水的混合溶液。
2. Pd(II)-NHC催化剂在Suzuki-Miyaura反应中的应用,其特征在于,所述以上合成的配合物,以苯硼酸为底物对两种催化剂进行Suzuki-Miyaura反应,溶剂为水和乙醇的混合溶液,催化剂与底物比为1:100,反应温度为80℃;Pd-(H2L1)催化剂在此条件下催化转化率达到83.77%, 而Pd-(H2L2)在此条件下的催化转化率达到91.05%;同时在此反应条件下,Pd-(H2L1),Pd-(H2L2)的催化产物选择性分别是99.27%、99.82%;两种配合物中的酰胺配体的不同,对催化性起到了不同的作用。
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