CN111377978B - 双齿膦[2Fe2S]二铁络合物及其制备方法与应用 - Google Patents
双齿膦[2Fe2S]二铁络合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及双齿膦[2Fe2S]二铁络合物及其制备方法与应用。氮气氛围下，将反应物(μ‑dmedt)[Fe2(CO)6]与三甲基膦PMe3混合并注入有机溶剂，搅拌反应，然后加入氧化三甲胺，在相同温度下继续搅拌反应，反应产物经分离，得到双齿膦螯合[2Fe2S]二铁络合物。本发明采用双齿膦螯合[2Fe2S]二铁络合物(μ‑dmedt)[Fe2(CO)6](PMe3)2为催化剂,乙睛为溶剂,以双氧水为羟基化试剂,一步法将苯羟基化制备成苯酚，催化产率可达18.6％，仅得到产品苯酚，选择性100％，无副产物产生。
Description
技术领域
本发明涉及金属酶仿生合成化学和催化应用领域，具体是含P配体的金属络合物催化剂的制备方法和其在温和条件下直接一步法催化苯变苯酚的应用研究。
背景技术
苯酚是一种具有特殊气味的无色针状晶体，作为工业原料广泛应用于橡胶、塑胶、合成纤维、农药乳化、医药、添加剂、香料、涂料、染料、炼油以及其他精细化工品的合成领域。有多种方法可以合成对苯酚,现在工业上生产苯酚采用主要方法为异丙苯法、磺化法和甲苯苯甲酸法。三种方法中异丙苯法是最有前途使用最广泛的方法，将苯和丙烯转化成更具工业生产、应用价值的苯酚是具有实际应用价值。异苯丙法首先是苯与丙烯在酸催化下，通过傅-克反应加成生成异丙苯；随后，在自由基作用下，异丙苯被空气氧化生成过氧化氢异丙苯；最后，过氧化氢异丙苯在酸性环境下水解为苯酚和丙酮。但丙烯的生产大多来源于石油的裂解产生，但是我们石油资源紧缺并且石油裂解加工能力较差，因此丙烯原料的来源大多数来源于进口，因此提升丙烯产量十分困难，苯酚的产量难以提升。并且此方法步骤较长,废水较多，总产率偏低并且有大量的副产物生成。此方法耗能较高,成本较高。因此需要原料易得、反应步骤短,废水较少,副产物更少的制备苯酚的方法。
催化剂最好可以定位生产苯酚，减少副产物的生成。一些催化剂如铁络合物、TS-1分子筛和Py4PMo11V型复合催化剂被设计出来直接用于催化苯羟基化反应。但总体的研究尚处于实验室的阶段。此外，中国专利文件CN101434515A公开了一种苯酚的制备方法，其特征在于在温度为0～150℃和压力为0.1～3.0MPa的条件下，将苯、氧气、氢气、稀释气体、溶剂和催化剂混合接触反应，苯与氧气、氢气、稀释气体的摩尔比为1∶(0.1～10)∶(0.1～10)∶(0～100)，苯与催化剂的质量比为(0.5-50)∶1，溶剂与催化剂的质量比为(20～1000)∶1，所说的催化剂为一种微孔钛硅材料或含有该微孔钛硅材料的组合物，微孔钛硅材料的组成用氧化物的形式表示为xTiO2·100SiO2·yEmOn·zE，其中x值为0.001～50.0、(y+z)值为0.005～20.0且y/z<1，E表示选自Ru、Rh、Pd、Re、Os、Ir、Pt和Au中的一种或几种贵金属，m和n为满足E氧化态所需的数，该材料晶粒部分或全部为空心结构。
中国专利文件CN101440021A公开了一种苯酚的制备方法，具体涉及杂多酸盐纳米粒子在介孔材料中的定向自组装法合成苯酚的方法，以分子氧为氧化剂，将大孔SBA-15分子筛在高真空的条件下，用过渡金属盐或有机盐的水溶液浸泡24h，然后将分子筛外表面的水去除，加入磷钼钒醚合物，在水热条件下原位生成杂多酸盐的纳米粒子，然后再以分子筛负载的杂多酸盐纳米粒子为催化剂，以分子氧为氧化剂一步氧化苯合成苯酚。
中国专利文件CN108424353A公开了一种苯羟基化制苯酚的合成方法，乙腈、苯、双氧水、Cu-Cu2O纳米颗粒、N，N—二甲基乙酰胺、水合氧氯化锆和2-磺酸对苯二甲酸钠为主要原料，采用磁控溅射的方法制备一种具有特殊结构的纳米颗粒,其中颗粒作为核,它的周围被所包裹形成壳体,该结构的纳米颗粒进行水合配位后形成MOFs多孔骨架空间结构，具有一定的晶型、晶粒大小、孔隙结构、比表面积以及高机械强度，相比传统催化剂活性中心，其具有更多的界面面积和缺陷浓度,并且容易通过调节制备工艺来调节缺陷浓度,从而达到提高催化活性，延长催化剂使用寿命的效果，对苯羟基化反应制备苯酚具有优异的催化效果。
中国专利文件CN101817726A公开了一种苯酚的制备方法，采用Keggin型磷钼钒杂多酸作为催化剂，或以四丁基溴化铵提供有机反核阳离子的Keggin型磷钼钒多金属氧酸盐作为催化剂，在上述催化剂中，钒原子数目为0～3；以苯与双氧水作为反应物，反应温度为45～85℃，反应时间为1～7小时，制得苯酚。
综上分析，分子筛类催化剂的合成周期长，成本较高，不利于未来大规模利用；杂多酸催化剂作用下苯酚的收率偏低，反应时间过长，原子利用率低；金属氧化物类催化剂的催化反应温度要求过高，苯酚的选择性和产率不高。铁基催化剂的合成成本较低，反应活性较高，反应条件温和。氧化剂的选择方面，O2的氧化能力较弱且用量较大；N2O来源较少且价格较贵；用H2O2做氧化剂，反应副产物为水，不存在二次环境污染等问题，且H2O2也较易得，氧化能力比O2和N2O强，使用条件比较温和。
在众多催化剂中，铁基催化剂由于制备成本便宜、环境的危害较小、低毒性和在氧化反应中表现出的高选择性和高转化率等特点，格外引起了人们的关注。[Fe-Fe]-氢化酶模型化合物作为一种铁基催化剂，能够在温和条件下高效的催化H2的产生和其氧化过程相关的理论研究和前期类似的研究。表明[FeFe]-氢化酶模型配合物的[Fe-Fe]键有将氧原子转移到芳香族底物的能力。其有催化苯羟基化一步法制备苯酚的潜力。为此，提出本发明。
发明内容
针对现有技术的不足，尤其是现有催化剂的制备成本过高，环境友好性较差，选择性和转化率较低的特点。构建具有双三甲基膦配体的高供电子特性的铁基催化剂，使用苯和双氧水为原料提出了绿色一步法制备苯酚的新催化体系。催化剂的制备过程简单，原料易得且性能稳定可长期使用，催化条件比较温和，催化装置简单，催化反应时间短，在常压和较低温度下就可以进行反应，是一种环境友好的酚类绿色合成工艺。而且，本发明属于铁基催化剂制备成本便宜、环境的危害较小、毒性低。
本发明的技术方案如下：
双齿膦[2Fe2S]二铁络合物，具有如下所示结构：
本发明的双齿膦[2Fe2S]二铁络合物的化学式为(μ-dmedt)[Fe2(CO)4](PMe3)2。
根据本发明，上述双齿膦[2Fe2S]二铁络合物的制备方法，包括步骤如下：
氮气氛围下，将反应物(μ-dmedt)[Fe2(CO)6]与三甲基膦PMe3混合并注入有机溶剂，搅拌反应，然后加入氧化三甲胺，在相同温度下继续搅拌反应，反应产物经分离，得到双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2。
根据本发明，优选的，所述的有机溶剂为甲苯。
根据本发明，优选的，反应物(μ-dmedt)[Fe2(CO)6]、三甲基膦PMe3与氧化三甲胺的摩尔比为1：(1-3)：(1-3)，优选1:2:2；有机溶剂与反应物(μ-dmedt)[Fe2(CO)6]的摩尔比为(700-900)：1，优选800:1。
根据本发明，优选的，搅拌反应的温度为100-120℃，进一步优选110℃。
根据本发明，优选的，(μ-dmedt)[Fe2(CO)6]与三甲基膦PMe3的搅拌反应时间为20min-60min，加入氧化三甲胺后，搅拌反应时间为10-15h。
根据本发明，优选的，反应产物分离的方法为色谱分离，进一步优选为：反应产物减压抽干,用二氯甲烷提作为展开剂进行薄层色谱分离,收集主色带,得到红色物质即为双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2。
本发明双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2的反应路线如下：
根据本发明，上述双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2在催化苯和双氧水反应制备苯酚中的应用。
一种苯酚的制备方法，包括步骤如下：
以双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2为催化剂，苯为进行羟基化反应的反应原料，乙腈为反应溶剂，双氧水为羟基化试剂，对苯进行定向催化直接反应生成苯酚。
根据本发明，优选的，常温常压在溶剂乙睛溶液中,加入双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2催化剂，待其充分溶解之后，升高溶剂的温度至55-65℃，优选60℃，并在此温度下加入苯和双氧水，继续保持这个温度进行搅拌反应，即可产生苯酚。
根据本发明，优选的，反应中各物料的配比为：n(H2O2):n(苯)＝(5～8)：1(摩尔比)；水：苯＝(20～25)：1(体积比)；催化剂：苯＝(1～2)：2(摩尔比)；催化羟基化反应的反应时间为1～4小时。
本发明苯直接羟基化反应合成苯酚的路线图如下：
本发明的双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2作为催化剂，在该催化剂作用下,将双氧水与苯反应,定向催化生产苯酚。克服了以往合成苯酚工艺反应步骤繁琐、副产物过多、原子利用率低等缺点。使用本发明制备的催化剂,可以在温和的条件下从苯一步催化合成苯酚，该方法具有环境友好、简单、三废排放少、定向反应生成苯酚收率高的特点。
本发明的有益效果：
1、本发明提供了一种新的用于定向苯羟基化催化反应生成苯酚的金属络合物催化剂双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2。拥有较高的催化活性，可以在温和条件下定向高效催化苯一步法羟基化制备苯酚，催化剂制备简单成本较低，催化装置简单，催化反应时间短，选择性达到100％。
2、本发明采用双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2为催化剂,乙睛为溶剂,以双氧水为羟基化试剂,一步法将苯羟基化制备成苯酚，催化产率可达18.6％，仅得到产品苯酚，选择性100％，无副产物产生。
3、本发明双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2催化剂制备简单，易于工业化生产，催化合成苯酚，选择性100％，一步法反应，无副产物，反应条件温和，环保。
附图说明
图1本发明实施例2中双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2的晶体结构图。
图2本发明实施例2中双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2的核磁H谱图。
图3本发明实施例2中双齿膦螯合[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2的核磁C谱图。
图4本发明实施例4中产物气相色谱法分析检测图。
具体实施方式：
下面通过具体实施例对本发明做进一步说明，但不限于此。
实施例1、(μ-dmedt)[Fe2(CO)6]的合成
氮气氛围下，100mL Schlenk瓶中依次加入甲苯(55mL)、Fe(CO)5(13.4g,68.6mmol)和2,3-丁二硫醇(2.77g,22.7mmol)，搅拌回流29h。冷却至室温，于140℃下，减压蒸馏除去溶剂。真空条件下抽干反应溶剂。再用硅胶柱分离纯化，以正己烷为洗脱剂对其进行洗脱提纯，收集第一带产物，得到红色固体配合物1(3.439g,37.9％)。
配合物1的分析：1H NMR(CDCl3)；δ＝2.21(m，2H，SCH)，1.33(d，6H，CH3C)。元素分析；测定值；C，30.07；H，2.12。理论值(C10H8O6Fe2S2)；C，30.03；H，2.02。质谱；测定值401.2；理论值400.7.1H NMR(CDCl3)；δ＝2.21(m，2H，SCH)，1.33(d，6H，CH3C)。
实施例2、催化剂(μ-dmedt)[Fe2(CO)4](PMe3)2的合成
氮气保护下，将PMe3(0.46mmol,31.2mg)，(μ-dmedt)[Fe2(CO)6](0.23mmol,90mg)以及Me3NO(46mg,0.46mmol)加入到50mL的圆底希莱克烧瓶中，无水无氧操作(抽换氮气三次)后保持氮气氛围的条件下加入20mL的甲苯溶液。然后保持在甲苯回流温度下(110 0C)氮气氛围下持续搅拌反应12个小时，溶液颜色变为暗红色停止反应蒸干溶剂。得到红色固体运用硅胶柱层析法进行分离提纯，以二氯甲烷溶液为洗脱液，其中第一带为未反应的(μ-dmedt)[Fe2(CO)6]带和单取代产物带，其中第二带为产品带。对产品带旋蒸后得到固体54.02mg，产率42％。
产物结构分析如下(图1-图3)：
1H NMR(400MHz,CDCl3):δ＝1.09,1.28(m,6H,CH3),δ＝2.70,3.07(s,2H,CH-CH)，δ＝1.46(d,18H,CH3)；
13C NMR(CDCl3):δCO＝210.08,δdalkyl＝13.92,20.93,22.36,54.58,δP(CH3)3＝30.04,32.06；
31P NMR(400MHz,CDCl3):18.78(s).Anal.Calc.for C14H26Fe2O4P2S2:C,33.89；H,5.28；Found:C,33.92；H,5.30。
实施例3、苯酚的合成
常温常压下，将3.0mL的CH3CN加入到带有磁力搅拌的25mL单口烧瓶中，依次加入0.05mmol催化剂、1mmol苯、6mmol双氧水(H2O2)后均匀搅拌，使催化剂在反应溶剂中充分溶解，控制反应体系的温度为60℃。反应2个小时。反应结束,将反应液自然冷却至室温，离心5min(8000r/min)，将催化剂从体系中分离出来，取样经过气相色谱法分析,苯酚收率13.6％，选择性100％。
实施例4、苯酚的合成
常温常压下，将2.0mL的CH3CN加入到带有磁力搅拌的25mL单口烧瓶中，依次加入0.05mmol催化剂、1mmol苯、6mmol双氧水(H2O2)后均匀搅拌，使催化剂在反应溶剂中充分溶解，控制反应体系的温度为60℃。反应3个小时。反应结束,将反应液自然冷却至室温，离心5min(8000r/min)，将催化剂从体系中分离出来，取样经过气相色谱法分析(图4),苯酚收率18.6％,选择性100％。
Claims (10)
1.双齿膦[2Fe2S]二铁络合物，其特征在于，该络合物具有如下所示结构：
2.权利要求1所述的双齿膦[2Fe2S]二铁络合物的制备方法，包括步骤如下：
氮气氛围下，将反应物(μ-dmedt)[Fe2(CO)6]与三甲基膦PMe3混合并注入有机溶剂，搅拌反应，然后加入氧化三甲胺，在相同温度下继续搅拌反应，反应产物经分离，得到双齿膦[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2；
所述的反应物(μ-dmedt)[Fe2(CO)6]的结构式如下：
3.根据权利要求2所述的双齿膦[2Fe2S]二铁络合物的制备方法，其特征在于，所述的有机溶剂为甲苯。
4.根据权利要求2所述的双齿膦[2Fe2S]二铁络合物的制备方法，其特征在于，反应物(μ-dmedt)[Fe2(CO)6]、三甲基膦PMe3与氧化三甲胺的摩尔比为1：(1-3)：(1-3)，有机溶剂与反应物(μ-dmedt)[Fe2(CO)6]的摩尔比为(700-900)：1。
5.根据权利要求2所述的双齿膦[2Fe2S]二铁络合物的制备方法，其特征在于，搅拌反应的温度为100-120℃。
6.根据权利要求2所述的双齿膦[2Fe2S]二铁络合物的制备方法，其特征在于，(μ-dmedt)[Fe2(CO)6]与三甲基膦PMe3的搅拌反应时间为20min-60min，加入氧化三甲胺后，搅拌反应时间为10-15h。
7.权利要求1所述的双齿膦[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2在催化苯和双氧水反应制备苯酚中的应用。
8.一种苯酚的制备方法，包括采用权利要求1所述的双齿膦[2Fe2S]二铁络合物作为催化剂，包括步骤如下：
以双齿膦[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2为催化剂，苯为进行羟基化反应的反应原料，乙腈为反应溶剂，双氧水为羟基化试剂，对苯进行定向催化直接反应生成苯酚。
9.根据权利要求8所述的苯酚的制备方法，其特征在于，常温常压在溶剂乙腈溶液中,加入双齿膦[2Fe2S]二铁络合物(μ-dmedt)[Fe2(CO)4](PMe3)2催化剂，待其充分溶解之后，升高溶剂的温度至55-65℃，并在此温度下加入苯和双氧水，继续保持这个温度进行搅拌反应，即得苯酚。
10.根据权利要求8所述的苯酚的制备方法，其特征在于，反应条件符合如下条件中的一项或多项：
A、反应中各物料的摩尔配比为：H2O2:苯＝(5～8)：1；
B、催化剂：苯的摩尔比＝(1～2)：2；
C、催化羟基化反应的反应时间为1～4小时。
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