CN1277199A - 四-氯苯基金属卟啉化合物及其制备方法和应用 - Google Patents
四-氯苯基金属卟啉化合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一类分子通式为C44H24N4Cl4M,其中,M为Cu、Co、Zn、Fe的四—氯苯基金属卟啉化合物及其制备方法和这类化合物在合成硝基苯甲酸反应中的应用。该类化合物的制备方法是在高压釜中,加入氯苯甲醛、M的无机盐和吡啶,在175℃下反应48小时,然后在氧化铝柱中进行柱层析分离,得到所需产物。该类化合物在合成硝基苯甲酸反应中用作催化剂,显著提高了合成产物的收率,此外,该类化合物除用在半导体、超导、特种功能高分子材料和抗癌药中间体等多个领域外,其最主要的用途之一是作为模拟生物酶催化剂催化氧化各种烃类使其功能化。
Description
本发明涉及一类四-氯苯基金属卟啉化合物及其制备方法和这类化合物在合成硝基苯甲酸反应中的应用。
金属卟啉类化合物具有许多独特的性质,除用作半导体、超导、特种功能高分子材料和抗癌药中间体等多个领域外,最重要的用途之一是广泛用作模拟生物酶催化剂催化氧化各种烃类使其功能化。
但金属卟啉类化合物的合成一向以收率低、提纯难而倍受人们的关注。目前,作为合成金属卟啉类化合物比较通用、成熟的Adler法-二步法(Adler A.D.;Longo F.R.;Finarelli J.D.et al.,J.Inorg.Nucl.Chem.,1970,33:2443),其步骤繁琐,产物不易分离提纯,因而,很难用这种方法合成多氯苯基金属卟啉类化合物。
本发明的目的在于提供一类四-氯苯基金属卟啉化合物及其制备方法和这类化合物在合成硝基苯甲酸反应中的应用。
本发明所提供的四-氯苯基金属卟啉化合物,具有以下分子通式:C44H24N4Cl4M,其中,M为Cu、Co、Zn、Fe。
本发明所提供的四-氯苯基金属卟啉化合物的制备方法,包括以下步骤:①在高压釜中,加入氯苯甲醛、M的无机盐和吡啶,在175℃下反应48小时;②在氧化铝柱中进行柱层析分离,分别以苯、苯/正己烷为洗脱剂,收集深色组分,得到所需产物。
上述四-氯苯基金属卟啉化合物在合成硝基苯甲酸反应中用作催化剂。
该合成反应是以清洁的氧气代替环境污染严重的重铬酸钠氧化剂,在接近室温的温和条件下,使用本发明所提供的催化剂催化氧化硝基甲苯制取硝基苯甲酸的新方法。同时,本发明所提供的催化剂显著地提高了合成产物的收率。
表1是四-氯苯基金属卟啉化合物在波数范围为2000-370cm-1的红外吸收光谱(KBr法)和紫外吸收光谱数据。从表1中可以看到,四-(邻/对-氯苯基)金属卟啉在1446-1470cm-1处均有苯环的vC=C振动的特征吸收峰,1313-1344cm-1处有卟啉环中vC-N振动的特征吸收峰,1001-1017cm-1处有吡络环中δC-H振动的特征吸收峰,748-751cm-1处有苯环的邻位取代,450-455cm-1处为vC-Cl振动的特征吸收峰。而四-(邻/对-氯苯基)金属卟啉在1486-1488cm-1处有苯环的vC=C振动的特征吸收峰,1322-1344cm-1处有卟啉环中vC-N振动的特征吸收峰,999-1014cm-1处有吡络环中δC-H振动的特征吸收峰,800-808cm-1处有苯环的对位取代特征峰,498-504cm-1处有vC-Cl振动的特征吸收峰,这些结果与四-(邻-氯苯基)金属卟啉应有的特征峰完全相符。此外,从表1中可以看出,八种卟啉类化合物的电子光谱在400nm附近均存在一个摩尔吸光系数较大的强吸收带-Soret吸收带,该带是由卟啉配体环上的π电子的π→π*跃迁产生的。这与卟啉的电子光谱特征完全相符。
表2是四-(邻/对-氯苯基)金属卟啉化合物质谱分析的负离子峰与计算值的比较结果。从表2中可以看到,理论值(M)(按平均分子量计算)与实测值(M-)吻合较好,而个别化合物的实测值与理论值差异是由于同位素存在造成的,这些结果说明所合成的产物的确是四-(邻/对-氯苯基)金属卟啉化合物。
表3是八种金属卟啉催化剂催化氧气氧化硝基甲苯制取硝基苯甲酸活性的对比,从表3中可以得出如下结论:添加四-氯苯基金属卟啉催化剂后,硝基苯甲酸的收率均超过50%,这说明四-氯苯基金属卟啉催化剂对氧气液相氧化硝基甲苯制取硝基苯甲酸均有显著的催化作用。
实施例:1、在高压釜中,加入10.3g邻(对)氯苯甲醛、4.9g无水醋酸锌、25ml吡络,在175℃下反应48小时。反应结束后,用适量吡啶溶解反应混合物,加入85%甲醇水溶液100ml,过滤,用石油醚洗至无吡啶,干燥,然后在氧化铝(100-200目)柱中进行柱层析分离:先将混合物溶于三氯甲烷,以苯作洗脱剂,收集深色组分;再将其溶于苯,以苯/正己烷(1∶1)作洗脱剂,收集深色组分,蒸出溶剂得粗产品。将其溶于适量苯中,加入85%甲醇水溶液进行重结晶,过滤、干燥,得到紫红色的四-(邻-氯苯基)锌卟啉化合物或紫色的四-(对-氯苯基)锌卟啉化合物。其红外及紫外吸收光谱数据见表1、质谱检测结果见表2。
在200ml高压釜内分别加入3.5g邻(对或间)硝基甲苯、8g NaOH、30ml甲醇、30ml苯和20mg上述所制备的催化剂,于3.0MPa、30℃下反应12h。反应结束后,加水溶解、过滤、加苯萃取。水相用盐酸酸化至pH<3。过滤、干燥得硝基苯甲酸,其收率见表3。2、在高压釜中,加入10.3g邻(对)氯苯甲醛、5.3g醋酸铜、25ml吡络,在175℃下反应48小时。反应结束后,用适量吡啶溶解反应混合物,加入85%甲醇水溶液100ml,过滤,用石油醚洗至无吡啶,干燥,然后在氧化铝(100-200目)柱中进行柱层析分离:先将混合物溶于三氯甲烷,以苯作洗脱剂,收集深色组分;再将其溶于苯,以苯/正己烷(1∶1)作洗脱剂,收集深色组分,蒸出溶剂得粗产品。将其溶于适量苯中,加入85%甲醇水溶液进行重结晶,过滤、干燥,得到紫红色的四-(邻-氯苯基)铜卟啉化合物或红色的四-(对-氯苯基)铜卟啉化合物。其红外及紫外吸收光谱数据见表1、质谱检测结果见表2。
在200ml高压釜内分别加入3.5g邻(对或间)硝基甲苯、8g NaOH、30ml甲醇、30ml苯和20mg上述所制备的催化剂,于3.0MPa、30℃下反应12h。反应结束后,加水溶解、过滤、加苯萃取。水相用盐酸酸化至pH<3。过滤、干燥得硝基苯甲酸,其收率见表3。3、在高压釜中,加入10.3g邻(对)氯苯甲醛、7.2g氯化铁、25ml吡络,在175℃下反应48小时。反应结束后,用适量吡啶溶解反应混合物,加入85%甲醇水溶液100ml,过滤,用石油醚洗至无吡啶,干燥,然后在氧化铝(100-200目)柱中进行柱层析分离:先将混合物溶于三氯甲烷,以苯作洗脱剂,收集深色组分;再将其溶于苯,以苯/正己烷(1∶1)作洗脱剂,收集深色组分,蒸出溶剂得粗产品。将其溶于适量苯中,加入85%甲醇水溶液进行重结晶,过滤、干燥,得到黑色的四-(邻-氯苯基)铁卟啉化合物或黑色的四-(对-氯苯基)铁卟啉化合物。其红外及紫外吸收光谱数据见表1、质谱检测结果见表2。
在200ml高压釜内分别加入3.5g邻(对或间)硝基甲苯、8g NaOH、30ml甲醇、30ml苯和20mg上述所制备的催化剂,于3.0MPa、30℃下反应12h。反应结束后,加水溶解、过滤、加苯萃取。水相用盐酸酸化至pH<3。过滤、干燥得硝基苯甲酸,其收率见表3。4、在高压釜中,加入10.3g邻(对)氯苯甲醛、4.7g无水醋酸钴、25ml吡络,在175℃下反应48小时。反应结束后,用适量吡啶溶解反应混合物,加入85%甲醇水溶液100ml,过滤,用石油醚洗至无吡啶,干燥,然后在氧化铝(100-200目)柱中进行柱层析分离:先将混合物溶于三氯甲烷,以苯作洗脱剂,收集深色组分;再将其溶于苯,以苯/正己烷(1∶1)作洗脱剂,收集深色组分,蒸出溶剂得粗产品。将其溶于适量苯中,加入85%甲醇水溶液进行重结晶,过滤、干燥,得到褐色的四-(邻-氯苯基)钴卟啉化合物或黑色的四-(对-氯苯基)钴卟啉化合物。其红外及紫外吸收光谱数据见表1、质谱检测结果见表2。
在200ml高压釜内分别加入3.5g邻(对或间)硝基甲苯、8g NaOH、30ml甲醇、30ml苯和20mg上述所制备的催化剂,于3.0MPa、30℃下反应12h。反应结束后,加水溶解、过滤、加苯萃取。水相用盐酸酸化至pH<3。过滤、干燥得硝基苯甲酸,其收率见表3。
表1
化合物名称 | IR/cm-1 | λmax/nm(1gε) |
四-(邻-氯苯基)锌卟啉 | 1590w,1564w,1526w,1476s,1433s,1335s,1203m,1125w,1068s,1037m,1003s,792s,748s,719m,646m,450m | 549(4.46),512(3.53),421(5.65),403(4.71),342(4.14),318(4.38) |
四-(邻-氯苯基)钴卟啉 | 1599w,1470s,1438s,1336s,1216w,1158w,1124w,1071s,1047s,1017s,989m,751s,725m,691m,452w | 513(4.03),388(4.97) |
四-(邻-氯苯基)铜卟啉 | 1593w,1562w,1472m,1432s,1344s,1206w,1127w,1070s,1035w,1001s,798s,752s,714m,647w,455m | 540(4.45),416(5.59),358(3.83),314(4.38) |
四-(邻-氯苯基)铁卟啉 | 1591m,1567m,1471s,1441s,1313b.s,1205w,1125b,1075b.s,1038b.s,1012b.s,790m,751s,653w,455m | 545(3.91),416(4.61),392(4.55),311(4.28),306(4.28) |
四-(对-氯苯基)锌卟啉 | 1484s,1394m,1338s,1207m,1176w,1091s,1000s,850w,800s,723s,498s | 589(3.78),550(4.37),511(3.81),422(5.56),320(4.49) |
四-(对-氯苯基)钴卟啉 | 1488s,1447m,1394w,1322m,1250w,1217w,1175w,1092s,1071m,1053m,1014s,808s,754m,725m,689m,504s | 553(3.96),508(4.00),393(4.92) |
四-(对-氯苯基)铜卟啉 | 1486s,1394w,1344s,1207w,1175w,1092s,1001s,801s,720m,501s | 539(4.40),417(5.61),311(4.24) |
四-(对-氯苯基)铁卟啉 | 1487s,1395w,1337m,1205w,1173w,1091s,999s,874m,801s,723m,498s | 570(3.76),411(4.90),341(4.33),317(4.34),301(4.31) |
表2
化合物名称 | 理论值(M) | 实测值(M) |
四-(邻-氯苯基)锌卟啉 | 815.70 | 815.9 |
四-(邻-氯苯基)钴卟啉 | 809.26 | 809.9 |
四-(邻-氯苯基)铜卟啉 | 813.87 | 812.8 |
四-(邻-氯苯基)铁卟啉 | 806.17 | 807.0 |
四-(对-氯苯基)锌卟啉 | 815.70 | 815.9 |
四-(对-氯苯基)钴卟啉 | 809.26 | 809.8 |
四-(对-氯苯基)铜卟啉 | 813.87 | 812.9 |
四-(对-氯苯基)铁卟啉 | 806.17 | 806.1 |
表3
催化剂名称 | 邻硝基苯甲酸收率(%) | 对硝基苯甲酸收率(%) |
无催化剂 | 0 | 18.5 |
四-(邻-氯苯基)锌卟啉 | 55.9 | 80.1 |
四-(邻-氯苯基)钴卟啉 | 66.8 | 73.9 |
四-(邻-氯苯基)铜卟啉 | 55.0 | 70.7 |
四-(邻-氯苯基)铁卟啉 | 54.0 | 70.4 |
四-(对-氯苯基)锌卟啉 | 51.4 | 66.6 |
四-(对-氯苯基)钴卟啉 | 62.0 | 72.1 |
四-(对-氯苯基)铜卟啉 | 52.4 | 60.1 |
四-(对-氯苯基)铁卟啉 | 52.3 | 61.6 |
Claims (5)
1、四-氯苯基金属卟啉化合物,具有以下分子通式:
C44H24N4Cl4M,其中,M为Cu、Co、Zn、Fe。
2、根据权利要求1所述的化合物,其中Cl处于苯基邻位。
3、根据权利要求1所述的化合物,其中Cl处于苯基对位。
4、根据权利要求1所述化合物的制备方法,包括以下步骤:①在高压釜中,加入氯苯甲醛、M的无机盐和吡啶,在175℃下反应48小时;②在氧化铝柱中进行柱层析分离,分别以苯、苯/正己烷为洗脱剂,收集深色组分,得到所需产物。
5、根据权利要求1所述的化合物在合成硝基苯甲酸反应中用作催化剂。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101948566A (zh) * | 2010-06-23 | 2011-01-19 | 中国科学院化学研究所 | 一种用于抗真菌、抗癌及细胞成像的多功能聚合物及其制备方法 |
CN102131581A (zh) * | 2008-08-11 | 2011-07-20 | 福留裕文 | 木质素分解用催化剂,芳族烃分解用催化剂,以及卟啉 |
CN102665908A (zh) * | 2009-09-28 | 2012-09-12 | 艾伯塔大学董事会 | 非均相铑金属催化剂 |
CN103694246B (zh) * | 2013-12-23 | 2015-06-17 | 北京工业大学 | A3b型不对称卟啉类化合物的制备方法 |
-
2000
- 2000-06-15 CN CN 00109300 patent/CN1277199A/zh active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102131581A (zh) * | 2008-08-11 | 2011-07-20 | 福留裕文 | 木质素分解用催化剂,芳族烃分解用催化剂,以及卟啉 |
CN102665908A (zh) * | 2009-09-28 | 2012-09-12 | 艾伯塔大学董事会 | 非均相铑金属催化剂 |
CN101948566A (zh) * | 2010-06-23 | 2011-01-19 | 中国科学院化学研究所 | 一种用于抗真菌、抗癌及细胞成像的多功能聚合物及其制备方法 |
CN103694246B (zh) * | 2013-12-23 | 2015-06-17 | 北京工业大学 | A3b型不对称卟啉类化合物的制备方法 |
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