CN114656352B - 半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法 - Google Patents
半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法 Download PDFInfo
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Abstract
本发明公开了一种半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其以介孔硼氮碳材料为光催化剂,在室温和常压、可见光光照条件下,实现二氧化碳的固定制备苯丙酸类衍生物。本发明将介孔硼氮碳材料用于光催化二氧化碳的固定与转化。在可见光下进行,反应操作简单,条件温和,成本低,符合实际生产需要,避免金属残留,具有极大的应用潜力。本方法较传统的二氧化碳加成反应具有更高的区域选择性、更温和的反应条件以及更强的经济适用性。
Description
技术领域
本发明属于光催化有机合成技术领域,具体涉及一种利用半导体光催化活化二氧化碳合成苯丙酸类衍生物的方法。
背景技术
二氧化碳是温室效应的主要来源,同时也是一种廉价,无毒且自然界中储量最丰富的C1资源,实现二氧化碳的资源化利用,获得具有高价值的化工产品,不仅符合绿色化学的要求,也是缓解二氧化碳持续增加所带来的日益严重的温室效应的手段之一。
苯丙酸类化合物是一类重要的苯丙素类化合物,具有抗氧化,抑菌,增强免疫力,抗癌,抗病毒,抗炎,降血脂,治疗心血管疾病等生物学活性,广泛应用于食品,医药,香料,化妆品,农业等领域。目前苯丙酸类化合物的制备方法主要有以下三种:(1)肉桂酸衍生物氢化法;(2)铬酸盐氧化丙苯衍生物;(3)苯乙烯类衍生物的氢羧化法。肉桂酸衍生物氢化法需要用到有毒的钠汞齐或者较为危险的氢气气体(
ChemCatChem2019, 11, 1313-1319; 有机化合物合成手册,2011. 8, ISBN 978-122-11519-5);铬酸盐氧化法可以一步从丙苯衍生物制备得到苯丙酸类衍生物,但反应废料重金属铬盐污染环境,处理步骤较多且效率较低(有机化合物合成手册,2011. 8, ISBN 978-122-11519-5);由CO2参与的苯乙烯类化合物氢羧化法具有明显的优势,但需要用到强还原剂Zn或者Mn且区域选择性较难控制(
J.
Am. Chem. Soc.2017, 139, 12161−12164)。
太阳光驱动的CO2转化是解决CO2排放并加以利用合成高附加值化学品的一种绿色有效的途径,符合绿色合成化学的要求(专利CN110028403A)。König课题组报道了一种均相四咔唑间二苯腈(4-CzIPN)光敏剂与镍配合物协同催化的方法,在可见光下成功地将苯乙烯类底物氢羧基化为苯丙酸类衍生物,不过这种方法有过渡金属参与,催化剂无法循环利用且反应产率一般 (
J. Am. Chem. Soc.2018, 140, 3198−3201.)。Jamison课题组建立了以三联苯为催化剂的光催化流动反应体系,提高了整体反应效率,然而该体系需要高能量紫外光驱动(
J. Am. Chem. Soc.2017, 139, 13969−13972.)。因此,需要发展一种催化剂可重复使用、反应操作简便、反应条件温和、绿色环保以及成本低廉的创新方法,实现二氧化碳的转化以制备高附加值的苯丙酸类衍生物。
发明内容
为了解决以上现有技术的缺点和不足之处,本发明提供了一种利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法。
为实现上述目的,本发明采用如下技术方案:
一种利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其是以介孔硼氮碳材料为光催化剂,在室温和常压、可见光光照条件下,将二氧化碳活化并与苯乙烯加成生成苯丙酸类衍生物;其反应方程式如下:
;
所述硼氮碳为富含介孔的类石墨结构,其制备包括以下步骤:
(1)将尿素、硼酸、柠檬酸和硅溶胶以质量比(1-10):(1-5):(1-5):(1-5)混合均匀并搅干;
(2)将步骤(1)得到的混合粉末在氨气气氛下1000~1200 ℃煅烧1-6 h,后用氟氢化铵去除硅球模板,从而得到介孔硼氮碳光催化剂。
所述利用半导体光催化活化二氧化碳制备苯丙酸类衍生物,其具体操作是将光催化剂,碱、苯乙烯类原料和溶剂直接加入反应管,后充入二氧化碳气体至反应管中,在室温、可见光光照条件下搅拌反应20-40 h;反应结束后用盐酸酸化反应液,滤去光催化剂并用二氯甲烷或乙酸乙酯对反应液进行萃取,合并有机相,干燥,过滤,减压蒸馏溶剂,得粗产物,再经柱层析提纯得到苯丙酸类衍生物。
其中,所用光催化剂和苯乙烯类原料的质量比为0.3:1。
所述二氧化碳压力为常压。
所述光催化剂为具有介孔结构的硼氮碳。
所述柱层析提纯采用体积比为20:1~5:1的石油醚与乙酸乙酯(含0.5 v%乙酸)混合溶剂作为洗脱液。
介孔硼氮碳(mp-BCN)是一种富含介孔(5~20 nm,图2)的可见光响应的非金属半导体光催化剂,其具有廉价易得、化学稳定性好、对有机物吸附能力强、无毒无害以及禁带宽度和能带位置适宜等优点。本发明以苯乙烯及其衍生物为原料,在可见光照下,利用光催化剂对CO2进行活化,将其加成至苯乙烯类化合物从而制备苯丙酸及其衍生物。
所述苯乙烯类原料包括苯乙烯类原料为苯乙烯、茚、1,2-二苯乙烯、1,1-二苯乙烯、N-(3-苯氧基苄基)-4-乙烯基苯胺中的一种,但不仅限于以上几种。
本发明具有如下优点及有益效果:
(1)本发明合成方法避免了含金属催化剂的使用,方法简单易行,条件温和,绿色安全;
(2)本发明合成方法无需加热,在室温、可见光照下就能得到较高的收率,节能环保;
(3)本发明合成方法原子经济性高,反应条件温和,具有良好的工业、农业以及医药界应用前景。
(4)本发明所用催化剂简单易得,可重复使用且光催化活性稳定。
(5)高温热解法制备得到的硼氮碳材料具有较大的比表面积和丰富的微孔结构,然而该类材料的孔径太小(<1.0 nm),难以使有机分子充分进入到催化剂的孔道中参与反应,同时在某种程度上降低了其可见光的利用能力,这限制了其在光催化反应中的应用。本发明制备得到的介孔硼氮碳材料,具有高表面积,充分暴露的表面活性位点和易于接近的反应孔道(2~50 nm),这有利于反应物和产物的传质与扩散,并且入射光能在催化剂孔道内进行反射,使可见光利用率大大提高,是一种潜在的苯乙烯氢羧化制备苯丙酸衍生物的高活性催化剂。
附图说明
图1为本发明的介孔硼氮碳材料的氮气吸脱附曲线图(由图可得,所制备硼氮碳材料的比表面积约为144 m2/g);
图2为本发明的介孔硼氮碳材料的孔径分布图(由图可得,所制备的硼氮碳材料的孔径分布约为5~20 nm);
图3为本发明制得的介孔硼氮碳材料的紫外-可见吸收光谱图(由图可得,所制备的硼氮碳材料吸收带边在400-600 nm)。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
所述介孔硼氮碳为富含介孔的类石墨结构,其制备包括以下步骤:
(1)将尿素、硼酸、柠檬酸和硅溶胶以质量比5:1:1:2混合均匀并搅干;
(2)将步骤(1)得到的混合粉末在氨气气氛下1100 ℃煅烧5 h,后用氟氢化铵水溶液浸泡所得粉末,并在室温下搅拌24 h以去除硅球模板,从而得到介孔硼氮碳光催化剂。其比表面积为144 m2/g(图1),孔径为5~20 nm(图2),吸收带边在400-600 nm(图3)。
实施例1
在反应器中,加入50 mg苯乙烯,15 mg介孔硼氮碳光催化剂,30 mg 碳酸钾,3 mlN,N-二甲基甲酰胺,后充入二氧化碳气体,室温光照下搅拌反应20 h,反应结束后用盐酸酸化并用乙酸乙酯萃取,合并有机相,干燥,过滤,减压蒸去溶剂得粗产物,再以体积比为10:1的石油醚-乙酸乙酯混合溶剂(含0.5 v%乙酸)进行柱层析提纯,获得54.1 mg 3-苯丙酸()的无色油状液体,产率75%。
1(600 MHz,CDCl3):δ 7.33 – 7.28 (m, 2H), 7.22 (t,
J= 7.2 Hz, 3H), 2.97(t,
J= 7.8 Hz, 2H), 2.73 – 2.65 (m, 2H)。13C NMR(151 MHz,CDCl3):δ 178.90,140.29, 128.71, 128.41, 126.52, 35.68, 30.72。MS(m/z,EI):150。
实施例2
在反应器中,加入50 mg 茚,15 mg介孔硼氮碳光催化剂,30 mg 碳酸钾,3 ml N,N-二甲基甲酰胺,后充入二氧化碳气体,室温光照下搅拌反应20 h,反应结束后用盐酸酸化并用乙酸乙酯萃取,合并有机相,干燥,过滤,减压蒸去溶剂得粗产物,再以体积比为10:1的石油醚-乙酸乙酯混合溶剂(含0.5 v%乙酸)进行柱层析提纯,获得57.3 mg 2-茚羧酸()的白色固体,产率82%。
1(600 MHz,CDCl3):δ 7.24 (dt,
J= 7.1, 3.5 Hz, 2H), 7.21 – 7.16 (m, 2H),3.44 – 3.36 (m, 1H),3.35 – 3.22 (m, 4H)。13C NMR(151 MHz,CDCl3):δ 181.47,141.47, 126.83, 124.49, 43.46, 36.14。MS(m/z,EI):162。
实施例3
在反应器中,加入50 mg 1,2-二苯乙烯,15 mg介孔硼氮碳光催化剂,30 mg 碳酸钾,3 ml N,N-二甲基甲酰胺,后充入二氧化碳气体,室温光照下搅拌反应20 h,反应结束后用盐酸酸化并用乙酸乙酯萃取,合并有机相,干燥,过滤,减压蒸去溶剂得粗产物,再以体积比为10:1的石油醚-乙酸乙酯混合溶剂(含0.5 v%乙酸)进行柱层析提纯,获得50.2 mg 2,3-二苯基丙酸()的白色固体,产率80%。
1(600 MHz,CDCl3):δ 7.34 (d,
J= 4.4 Hz, 4H), 7.30 (dt,
J= 8.4, 4.0 Hz,1H), 7.27 – 7.23 (m, 2H), 7.20 (t,
J= 7.3 Hz, 1H), 7.13 (d,
J= 7.1 Hz, 2H),3.89 (dd,
J= 8.2, 7.2 Hz, 1H), 3.44 (dd,
J= 13.9, 8.4 Hz, 1H), 3.07 (dd,
J=13.9, 7.1 Hz, 1H)。13C NMR(151 MHz,CDCl3):δ 179.70, 138.77, 138.01, 129.04,128.83, 128.50, 128.23, 127.76, 126.59, 53.60, 39.35。MS(m/z,EI):226。
实施例4
在反应器中,加入50 mg 1,1-二苯乙烯,15 mg介孔硼氮碳光催化剂,30 mg 碳酸钾,3 ml N,N-二甲基甲酰胺,后充入二氧化碳气体,室温光照下搅拌反应20 h,反应结束后用盐酸酸化并用乙酸乙酯萃取,合并有机相,干燥,过滤,减压蒸去溶剂得粗产物,再以体积比为10:1的石油醚-乙酸乙酯混合溶剂(含0.5 v%乙酸)进行柱层析提纯,获得53.4 mg 3,3-二苯基丙酸()的白色固体,产率85%。
1(600 MHz,CDCl3):δ 7.31 – 7.27 (m, 4H), 7.25 – 7.17 (m, 6H), 4.54 (t,
J= 7.9 Hz, 1H), 3.10 (d,
J= 7.9 Hz, 2H)。13C NMR(151 MHz,CDCl3):δ 177.76,143.37, 128.76, 127.75, 126.77, 46.75, 40.52。MS(m/z,EI):226。
实施例5
在反应器中,加入50 mg N-(3-苯氧基苄基)-4-乙烯基苯胺,15 mg介孔硼氮碳光催化剂,30 mg 碳酸钾,3 ml N,N-二甲基甲酰胺,后充入二氧化碳气体,室温光照下搅拌反应30 h,反应结束后用盐酸酸化并用乙酸乙酯萃取,合并有机相,干燥,过滤,减压蒸去溶剂得粗产物,再以体积比为5:1的石油醚-乙酸乙酯混合溶剂(含0.5 v%乙酸)进行柱层析提纯,获得37.5 mg 3-(4-((3-苯氧基苄基)胺)苯基)丙酸(GW9508,)的浅黄色固体,产率65%。
1(600 MHz,CDCl3):δ 7.34 – 7.31 (m, 2H), 7.29 (t,
J= 7.9 Hz, 1H), 7.12– 7.08 (m, 2H), 7.04 – 6.99 (m, 5H), 6.91 – 6.88 (m, 1H), 6.58 – 6.54 (m,2H), 4.29 (s,2H), 2.88 – 2.80 (m, 2H), 2.65 – 2.58 (m, 2H)。13C NMR(151 MHz,CDCl3):δ 178.41, 157.71, 157.16, 146.55, 141.82, 130.05, 129.88, 129.45,129.20, 123.44, 122.28,119.08, 117.90, 117.60, 113.24, 48.37, 36.08, 29.97。MS(m/z,EI):347。
对比例1
体相硼氮碳的制备包括以下步骤:
(1)将尿素、硼酸和柠檬酸以质量比5:1:1混合均匀并搅干;
(2)将步骤(1)得到的混合粉末在氨气气氛下1100 ℃煅烧5 h从而得到体相硼氮碳光催化剂。其比表面积为568 m2/g,孔径为0.5~1.0 nm,吸收带边在400-450 nm。
在反应器中,加入50 mg苯乙烯,15 mg体相硼氮碳光催化剂,30 mg 碳酸钾,3 mlN,N-二甲基甲酰胺,后充入二氧化碳气体,室温光照下搅拌反应20 h,反应结束后用盐酸酸化并用乙酸乙酯萃取,合并有机相,干燥,过滤,减压蒸去溶剂得粗产物,再以体积比为10:1的石油醚-乙酸乙酯混合溶剂(含0.5 v%乙酸)进行柱层析提纯,获得13.0 mg 3-苯丙酸的无色油状液体,产率18%。
由实施例1和对比例1比较可知,介孔硼氮碳材料的应用显著提高了光催化活化二氧化碳制备苯丙酸类衍生物的产率。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的催化剂制备所用的前驱体比例变化、催化剂与反应底物用量变化,皆应属本发明的涵盖范围。
Claims (7)
1.一种利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:以介孔硼氮碳为光催化剂,在室温、碱和可见光光照条件下,实现二氧化碳的活化并与苯乙烯类有机分子加成从而生成苯丙酸类衍生物;
所述硼氮碳为富含介孔的类石墨结构,其比表面积为140-600 m2/g,孔径为5~20 nm,吸收带边在400-600 nm;
所述介孔硼氮碳的制备包括以下步骤:
(1)将尿素、硼酸、柠檬酸和硅溶胶以质量比(1-10):(1-5):(1-5):(1-5)混合均匀并搅干;
(2)将步骤(1)得到的混合粉末在氨气气氛下1000~1200 ℃煅烧1-6 h,后用氟氢化铵去除硅球模板,从而得到介孔硼氮碳光催化剂。
2. 根据权利要求1所述的利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:其具体是将介孔硼氮碳光催化剂,碱和苯乙烯类原料直接加入溶剂中,后充入二氧化碳气体,在室温、可见光光照条件下搅拌反应20-40 h;反应结束后用盐酸酸化反应液,滤去光催化剂并用二氯甲烷或乙酸乙酯对反应液进行萃取,合并有机相,干燥,过滤,减压蒸馏溶剂,得粗产物,再经柱层析提纯得到苯丙酸类衍生物。
3.根据权利要求2所述的利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:苯乙烯类原料为苯乙烯、茚、1,2-二苯乙烯、1,1-二苯乙烯、N-(3-苯氧基苄基)-4-乙烯基苯胺中的一种。
4.根据权利要求2所述的利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:所用碱为碳酸钾。
5.根据权利要求2所述的利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:所用溶剂为N,N-二甲基甲酰胺。
6.根据权利要求2所述的利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:所用光催化剂和苯乙烯类原料的质量比为0.3:1。
7.根据权利要求2所述的利用半导体光催化活化二氧化碳制备苯丙酸类衍生物的方法,其特征在于:二氧化碳压力为常压。
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