苯直接胺化合成苯胺按新催化体系研究
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摘要
把苯的C-H键活化,将氨基直接引人苯环合成苯胺的研究,近年来引起广泛关注,苯的直接胺化合成苯胺,将多步反应变为一步,可明显提高苯胺化反应的原子利用率。但如何实现温和条件下C-H键的选择性活化,并引入氨基官能团仍然是合成化学和绿色化学所面临的重大挑战之一,因此寻找苯直接胺化绿色合成方法仍旧是研究者的考察焦点。
本文共设计制备了三种类型的非均相催化剂,并应用于苯的直接胺化反应,系统考察了他们对苯直接胺化反应过程的影响,具体内容如下：
1.设计制备MCM-41和负载矾的V-MCM-41催化剂,通过XRD、FT-IR和低温N2吸附测试手段对以上介孔材料的组成和结构、表面物理化学性质进行了表征,结果表明：当矾添加量适当的时候,V-MCM-41的基本结构未发生改变；产品是具有高度有序的介孔材料；与母体材料相比,负载矾的V-MCM-41,随着矾含量的增加,样品的孔道结构发生了变化,这可能是由于样品中的部分V没有进入到分子筛的骨架中去,而是负载在分子筛的内表面上,占据了更多的孔道空间,从而引起孔道变窄,孔径分布的不均匀程度增加,导致孔比表面积、孔径和孔容的减小。
把所制得的催化剂应用于以盐酸羟铵为胺化剂的苯直接胺化反应,系统探究了V-MCM-41介孔催化剂的催化性能,考察了V-MCM-41的矾负载量、溶剂种类、介质酸性、反应温度、原料配比、反应时间和催化剂用量对苯胺收率的影响,结果表明,当矾含量为V-MCM-41(40)时,苯胺的收率最大,为67.7%。以V-MCM-41(40)为催化剂,考察了溶剂种类、介质酸性、反应温度、原料配比、反应时间和催化剂用量对苯胺收率的影响,结果表明,以70v01.%的乙酸介质,70℃,催化剂量为0.05g,反应2小时,羟胺与苯摩尔比为1：1,苯胺的收率最高为67.7%。
在参考文献的基础上,分析了苯直接胺化的反应历程,提出了质子化的氨自由基·NU3+是苯胺化的活性物种。
2.采用燃烧法设计制备了多种SO42-/MxOy型固体强酸,通过酸强度、XRD、FT-IR、 NH3-TPD分析可知,所合成的SO42-/Fe2O3-TiO2(SFT)和SO42-/Fe2O3-TiO2-Nd2O3(SFTN)样品的表面硫与金属氧化物是以螯合双配位的方式结合的,具有超强酸性。添加了金属钕的SFTN催化剂样品的酸强度高于SFT样品。TEM分析表明,三元样品SFTN的粒度更小,直径大约是30nm。
把它们应用于以盐酸羟胺为胺化剂,在温和条件下由苯一步合成苯胺的反应体系中,系统探究了SO42-/MxOy型固体强酸的催化剂性能,考察了催化剂制备条件、反应温度、原料配比、反应时间和催化剂用量对苯胺收率的影响。结果表明,当反应温度70℃,羟胺与苯摩尔比为1：1,催化剂量为0.05g,反应2小时,获得最佳的苯胺收率为62%。
3.采用改良的胶体沉积法制备了不同三氧化二铝负载量的纳米金粒子,通过对样品SEM和XPS的分析表明,在所研究的载体使用量范围内,金纳米粒子覆盖载体颗粒的程度,随着载体颗粒加入量的减少而增加；传统胶体沉积法制得的纳米金样品,虽然可以观察到金纳米粒子几乎均匀地附着在载体颗粒表面,但是金纳米粒子的覆盖量与改良法所制得的样品相比,明显较少。
把改良胶体沉积法制得的纳米金催化剂应用于,以氨水为胺化剂、双氧水为氧化剂的苯直接胺化反应中。考察了反应温度、氨水用量、双氧水用量、双氧水加料方式和反应时间对苯胺收率的影响。结果表明,催化剂2.0g,反应温度50℃,反应时间2小时,氨水与苯的摩尔比为3：1,双氧水与苯的摩尔比为1.5：1,25mL苯时,苯胺的产量最多为1.96mg。
Single-step amination of benzene to aniline by the activation of C-H bond of benzene attracts much attention recently. Direct amination of benzene to aniline can make multi-step processes change into single-step process, which can improve atom utilization. However, how to carry out activation of C-H bond, furthermore, the introduction of-NH2into benzene, still is a challenging topic in the field of synthetic chemistry and green chemistry. Therefore looking for direct amination of benzene under mild conditions is still the researchers'study focus.
In this dissertation, Three different types of non-homogeneous catalysts have been prepared and utilized as catalysts for single-step amination of benzene to aniline. The influences of these catalysts on the activity and selectivity for amination were studied. Specific contents are as follows:
1. In this paper, MCM-41and a series of ordered mesoporous composite materials V-MCM-41have been prepared for single-step amination of benzene to aniline using NH2OH as aminating agent under mild conditions. The composite materials were well characterized by FT-IR, X-ray diffraction analysis, and nitrogen adsorption analysis. The results confirm that V-MCM-41with the appropriate amount of V still had highly ordered mesoporous structure. Compared with MCM-41prepared, as the amounts of V in the catalytic samples increased, the pore structure of the V-MCM-41samples changed. This may be the result that a part of V species wasn't able to be incorporated into the molecular sieve skeleton, but was introduced onto the inner surface of the molecular sieve, they occupied more pore volume, leading to narrows in pore channel, reductions in pore size,pore volume and specific surface area.
These materials were subsequently utilized as the catalysts for direct amination of benzene to aniline with NH2OH as an aminating agent under mild conditions. The influences of key reaction parameters, including loadings of V, solvents, media acidity, reaction temperature, the molar ratios of raw materials, reaction time and the catalyst amount on the activity and selectivity for the amination, were also studied. Based on the extensive literatures, the reaction mechanism was studied, thus the free-radical mechanism has been proposed for the amination of benzene, the protonated amino radical NH3+is the active aminating species for the amination of benzene.
2. Using combustion method, a series of SO42-/MxOy solid super acid have been prepared for single-step amination of benzene to aniline with NH2OH as an aminating agent under mild conditions. The prepared materials doped and undoped by Nd were characterized by means of TG-DTG, XRD, FT-IR, NH3-TPD and TEM techniques. The results showed that the samples kept the typical covalence S=O bond structure of SO42-/MxOy (SM) solid acids, and both Lewis and Br(?)nsted acid sites existed; SFTN exhibited higher activity for the amination of benzene to aniline. TEM and HRTEM observation indicate that the introduction of Nd made the grains size considerably smaller, down to30nm.
These materials were subsequently utilized as the catalysts for direct amination of benzene to aniline with NH2OH as an aminating agent. The influences of key reaction parameters, including catalytic preparation conditions, reaction temperatures, the molar ratios of raw materials, reaction time and the catalyst amount on the activity and selectivity for the reaction were also studied, the optimum conditions were determinded
3.Gold nanoparticles (AuNPs) have been prepared by a modified colloidal deposition method, SEM and XPS analysis showed that the coverage of alumina particles by AuNPs increased as the amount of alumina decreased; AuNPs onto alumina particles by the conventional colloidal deposition method were also prepared, whose TEM showed that the coverage of AuNPs was evidently smaller than that in the case of modified colloidal deposition method, although the AuNPs were spread almost uniformly over the surface of alumina particles.
Au-immobilized alumina particles (Alumina=200mg) were subsequently utilized as the catalysts for direct amination of benzene to aniline with NH3H2O as an aminating agent and H2O2as an oxidant under mild conditions. The influences of key reaction parameters, including reaction temperatures, NH3H2O amount, H2O2amount, feed motheds and reaction time on the activity and selectivity for the reaction were also studied, the reaction conditions were optimized.
本文共设计制备了三种类型的非均相催化剂,并应用于苯的直接胺化反应,系统考察了他们对苯直接胺化反应过程的影响,具体内容如下：
1.设计制备MCM-41和负载矾的V-MCM-41催化剂,通过XRD、FT-IR和低温N2吸附测试手段对以上介孔材料的组成和结构、表面物理化学性质进行了表征,结果表明：当矾添加量适当的时候,V-MCM-41的基本结构未发生改变；产品是具有高度有序的介孔材料；与母体材料相比,负载矾的V-MCM-41,随着矾含量的增加,样品的孔道结构发生了变化,这可能是由于样品中的部分V没有进入到分子筛的骨架中去,而是负载在分子筛的内表面上,占据了更多的孔道空间,从而引起孔道变窄,孔径分布的不均匀程度增加,导致孔比表面积、孔径和孔容的减小。
把所制得的催化剂应用于以盐酸羟铵为胺化剂的苯直接胺化反应,系统探究了V-MCM-41介孔催化剂的催化性能,考察了V-MCM-41的矾负载量、溶剂种类、介质酸性、反应温度、原料配比、反应时间和催化剂用量对苯胺收率的影响,结果表明,当矾含量为V-MCM-41(40)时,苯胺的收率最大,为67.7%。以V-MCM-41(40)为催化剂,考察了溶剂种类、介质酸性、反应温度、原料配比、反应时间和催化剂用量对苯胺收率的影响,结果表明,以70v01.%的乙酸介质,70℃,催化剂量为0.05g,反应2小时,羟胺与苯摩尔比为1：1,苯胺的收率最高为67.7%。
在参考文献的基础上,分析了苯直接胺化的反应历程,提出了质子化的氨自由基·NU3+是苯胺化的活性物种。
2.采用燃烧法设计制备了多种SO42-/MxOy型固体强酸,通过酸强度、XRD、FT-IR、 NH3-TPD分析可知,所合成的SO42-/Fe2O3-TiO2(SFT)和SO42-/Fe2O3-TiO2-Nd2O3(SFTN)样品的表面硫与金属氧化物是以螯合双配位的方式结合的,具有超强酸性。添加了金属钕的SFTN催化剂样品的酸强度高于SFT样品。TEM分析表明,三元样品SFTN的粒度更小,直径大约是30nm。
把它们应用于以盐酸羟胺为胺化剂,在温和条件下由苯一步合成苯胺的反应体系中,系统探究了SO42-/MxOy型固体强酸的催化剂性能,考察了催化剂制备条件、反应温度、原料配比、反应时间和催化剂用量对苯胺收率的影响。结果表明,当反应温度70℃,羟胺与苯摩尔比为1：1,催化剂量为0.05g,反应2小时,获得最佳的苯胺收率为62%。
3.采用改良的胶体沉积法制备了不同三氧化二铝负载量的纳米金粒子,通过对样品SEM和XPS的分析表明,在所研究的载体使用量范围内,金纳米粒子覆盖载体颗粒的程度,随着载体颗粒加入量的减少而增加；传统胶体沉积法制得的纳米金样品,虽然可以观察到金纳米粒子几乎均匀地附着在载体颗粒表面,但是金纳米粒子的覆盖量与改良法所制得的样品相比,明显较少。
把改良胶体沉积法制得的纳米金催化剂应用于,以氨水为胺化剂、双氧水为氧化剂的苯直接胺化反应中。考察了反应温度、氨水用量、双氧水用量、双氧水加料方式和反应时间对苯胺收率的影响。结果表明,催化剂2.0g,反应温度50℃,反应时间2小时,氨水与苯的摩尔比为3：1,双氧水与苯的摩尔比为1.5：1,25mL苯时,苯胺的产量最多为1.96mg。
Single-step amination of benzene to aniline by the activation of C-H bond of benzene attracts much attention recently. Direct amination of benzene to aniline can make multi-step processes change into single-step process, which can improve atom utilization. However, how to carry out activation of C-H bond, furthermore, the introduction of-NH2into benzene, still is a challenging topic in the field of synthetic chemistry and green chemistry. Therefore looking for direct amination of benzene under mild conditions is still the researchers'study focus.
In this dissertation, Three different types of non-homogeneous catalysts have been prepared and utilized as catalysts for single-step amination of benzene to aniline. The influences of these catalysts on the activity and selectivity for amination were studied. Specific contents are as follows:
1. In this paper, MCM-41and a series of ordered mesoporous composite materials V-MCM-41have been prepared for single-step amination of benzene to aniline using NH2OH as aminating agent under mild conditions. The composite materials were well characterized by FT-IR, X-ray diffraction analysis, and nitrogen adsorption analysis. The results confirm that V-MCM-41with the appropriate amount of V still had highly ordered mesoporous structure. Compared with MCM-41prepared, as the amounts of V in the catalytic samples increased, the pore structure of the V-MCM-41samples changed. This may be the result that a part of V species wasn't able to be incorporated into the molecular sieve skeleton, but was introduced onto the inner surface of the molecular sieve, they occupied more pore volume, leading to narrows in pore channel, reductions in pore size,pore volume and specific surface area.
These materials were subsequently utilized as the catalysts for direct amination of benzene to aniline with NH2OH as an aminating agent under mild conditions. The influences of key reaction parameters, including loadings of V, solvents, media acidity, reaction temperature, the molar ratios of raw materials, reaction time and the catalyst amount on the activity and selectivity for the amination, were also studied. Based on the extensive literatures, the reaction mechanism was studied, thus the free-radical mechanism has been proposed for the amination of benzene, the protonated amino radical NH3+is the active aminating species for the amination of benzene.
2. Using combustion method, a series of SO42-/MxOy solid super acid have been prepared for single-step amination of benzene to aniline with NH2OH as an aminating agent under mild conditions. The prepared materials doped and undoped by Nd were characterized by means of TG-DTG, XRD, FT-IR, NH3-TPD and TEM techniques. The results showed that the samples kept the typical covalence S=O bond structure of SO42-/MxOy (SM) solid acids, and both Lewis and Br(?)nsted acid sites existed; SFTN exhibited higher activity for the amination of benzene to aniline. TEM and HRTEM observation indicate that the introduction of Nd made the grains size considerably smaller, down to30nm.
These materials were subsequently utilized as the catalysts for direct amination of benzene to aniline with NH2OH as an aminating agent. The influences of key reaction parameters, including catalytic preparation conditions, reaction temperatures, the molar ratios of raw materials, reaction time and the catalyst amount on the activity and selectivity for the reaction were also studied, the optimum conditions were determinded
3.Gold nanoparticles (AuNPs) have been prepared by a modified colloidal deposition method, SEM and XPS analysis showed that the coverage of alumina particles by AuNPs increased as the amount of alumina decreased; AuNPs onto alumina particles by the conventional colloidal deposition method were also prepared, whose TEM showed that the coverage of AuNPs was evidently smaller than that in the case of modified colloidal deposition method, although the AuNPs were spread almost uniformly over the surface of alumina particles.
Au-immobilized alumina particles (Alumina=200mg) were subsequently utilized as the catalysts for direct amination of benzene to aniline with NH3H2O as an aminating agent and H2O2as an oxidant under mild conditions. The influences of key reaction parameters, including reaction temperatures, NH3H2O amount, H2O2amount, feed motheds and reaction time on the activity and selectivity for the reaction were also studied, the reaction conditions were optimized.
引文
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