CN110467636B - 一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法及应用 - Google Patents
一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法及应用 Download PDFInfo
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- CN110467636B CN110467636B CN201910761155.XA CN201910761155A CN110467636B CN 110467636 B CN110467636 B CN 110467636B CN 201910761155 A CN201910761155 A CN 201910761155A CN 110467636 B CN110467636 B CN 110467636B
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- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 4
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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Abstract
本发明属于精细化工技术领域,一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法及应用,其中制备方法,是以过渡金属盐中的Co2+作为节点,以L作为配体反应制得金属有机三棱柱化合物,其合成路线如下:Co2++L→Co‑L,所述配体L选自H4PTPC,所述过渡金属盐选自硝酸钴,高氯酸钴,四氟硼酸钴或三氟甲磺酸钴中的一种;本发明方法制备的金属有机三棱柱化合物原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中。作为化合物Co‑PTPC在还原间硝基苯乙酮制间氨基苯乙酮和还原对硝基苯乙酮制对氨基苯乙酮方面中的应用,其TON最高可达到36000,选择性大于99%。
Description
技术领域
本发明涉及一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法及应用,属于精细化工技术领域。
背景技术
氨基芳烃类化合物是化工工业生产中最重要的中间体之一,在染料工业中可用于制造酸性墨水蓝G、金光红、酚菁红等;在农药工业中用于生产许多杀虫剂、杀菌剂如DDV、除草醚、毒草胺等。其中,对氨基苯乙酮是一种非常重要的医药中间体用以合成克喘素和氟比布洛芬。克喘素可用于治疗支气管哮喘,慢性喘息型支气管炎和肺气肿等疾病。氟比布洛芬是一种非留体抗炎镇痛药可以用于风湿性关节炎、骨关节炎及弯曲性脊椎炎等。目前,工业中通过还原硝基芳烃类制取氨基芳烃类主要有三种方法:(1)气相加氢,此法不需使用溶剂、铜催化剂价廉易得、生产稳定、易实现自动化,但需要在较高的氢气压力下才能进行。另外实验需要维持在中性条件下进行,因此酸性或其他碱性的基团的化合物会对反应活性存在影响。另外要求仪器加压密闭,操作要求严格。其催化的还原选择性较差,仅适用于沸点低、容易气化且稳定的芳香族硝基化合物的还原,当硝基化合物分子中含有其它易被氢化的基团,如碳—碳双键时,也不能采用此法。(2)液相加氢,液相加氢还原法具有温度低,产物易分离,副产物污染性小,且不受硝基物沸点的限制的特点。但其需要在实际生产过程中使用易燃的催化剂雷尼镍或贵金属催化剂铂、钯、铑等,因此生产安全性不高,且生产成本高,选择性也有待提高。(3)电解还原法,芳香族硝基化合物通常在无机酸电解液、溶剂、润滑剂、促进剂(常用氯化亚锡、氯化铜、二氯化钛等)作用下,在阴极(金属材质铜、镍、钯等)电解产生了活性的原子氢,原子氢进而对硝基化合物进行还原芳胺类化合物,但原子氢活性极高,此法仍收到其他其它易被氢化的官能团的影响。
发明内容
为了克服现有技术中存在的不足,本发明目的是提供一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法及应用。采用该种方法制备的基于金属有机三棱柱化合物具有足够大的空腔,包合具有递氢能力的醌氢醌电对,以为水和抗坏血酸作为氢源替代高压氢气,在可见光照射下实现硝基芳烃的选择性的氢化,制取含有各类其他官能团的氨基芳香类化合物。
为了实现上述发明目的,解决现有技术中所存在的问题,本发明采取的技术方案是:一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法,以过渡金属盐中的Co2+作为节点,以L作为配体反应制得金属有机三棱柱化合物,其合成路线如下:
Co2++L→Co-L;
所述配体L选自H4PTPC;
所述过渡金属盐选自硝酸钴,高氯酸钴,四氟硼酸钴或三氟甲磺酸钴中的一种;
所述配体H4PTPC具有如下(A)分子结构式,
式中:R1为苯基,R2为氢,R3为氢,X为亚甲基;
所述一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法,包括以下步骤:
步骤1、将间苯二甲酸与95%的多聚甲醛按1:0.45~0.55的摩尔比溶解于90~110mL 20%的发烟硫酸中,混合物在110~130℃下搅拌4~8小时,之后冷却至室温;将混合物倒在冰水上,过滤沉淀,用水清洗,在真空中干燥,得到黄色固体,再将黄色固体溶解于90~110mL的甲醇中,加入200~250mL盐酸并回流20~40分钟,将混合物冷却至0~15℃,然后对出现的固体产物进行过滤,用冷甲醇洗涤并干燥,得到白色固体产物;
步骤2、将步骤1所得白色固体产物与水合肼按1:60~100的摩尔比混合,在80~100℃温度下回流搅拌10~15小时,反应结束后抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到白色粉末;
步骤3、将步骤2所得白色粉末与2-双苯基膦苯甲醛按照1:4.2~4.4的摩尔比加入到80~120mL乙醇中混合,再加入5~6滴冰醋酸,将混合溶液在80~100℃温度下回流搅拌10~15小时,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H4PTPC;
步骤4、将配体H4PTPC与过渡金属钴盐按照1:2~3的摩尔比加入到25~35mL甲醇、乙醇和乙腈的混合溶剂中,室温下搅拌4~6小时,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙红色固体,制得目标化合物Co-PTPC,所述甲醇、乙醇和乙腈的体积比为1:0.8~1.2:0.5~2。
所述制备方法制备的Co-PTPC在还原间硝基苯乙酮制间氨基苯乙酮和还原对硝基苯乙酮制对氨基苯乙酮方面中的应用。
本发明有益效果是:一种用于催化还原硝基芳烃制胺基芳烃的金属有机三棱柱状化合物的制备方法及应用,其中制备方法,是以过渡金属盐中的Co2+作为节点,以L作为配体反应制得金属有机三棱柱化合物,其合成路线如下:Co2++L→Co-L,所述配体L选自H4PTPC;所述过渡金属盐选自硝酸钴,高氯酸钴,四氟硼酸钴或三氟甲磺酸钴中的一种;与已有技术相比,采用该方法制备金属有机三棱柱化合物原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中。作为化合物Co-PTPC在还原间硝基苯乙酮制间氨基苯乙酮和还原对硝基苯乙酮制对氨基苯乙酮方面中的应用,其TON最高可达到36000,选择性大于99%。
附图说明
图1是实施例1化合物Co-PTPC的晶体结构图。
图2是实施例1化合物Co-PTPC溶液的高分辨质谱图。
图3是实施例6化合物Co-PTPC光照条件下选择性还原对硝基苯乙酮制取对氨基苯乙酮的反应TON值随时间的变化图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
将间苯二甲酸(33.0g,0.20mol)与95%的多聚甲醛(3.1g,0.10mol)溶解于100mL20%的发烟硫酸中,混合物在118℃下搅拌6小时。之后冷却至室温,将混合物倒在冰水上,过滤沉淀,用水清洗,在真空中干燥得到黄色固体。再将得到的黄色固体溶解于100mL甲醇中,加入220mL盐酸并回流30分钟。将混合物冷却至10℃,然后将出现的固体产物过滤,用冷甲醇洗涤并干燥。得到白色固体产物4.40g,产率11%。1H-NMR(400MHz,CDCl3):δ8.55(t,J=1.6Hz,2H),8.05(d,J=1.6Hz,4H),4.16(s,2H),3.93(s,12H).ESI-MS质谱,精确分子量400.1158,实际峰值401.1237[M+H]+,423.1068[M+Na]+.
将白色固体产物(4.00g,10mmol)与800mmol水合肼混合后,在95℃下回流搅拌12小时。反应结束后抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到白色粉末3.96g,产率99%。1H-NMR(400MHz,DMSO-d6,ppm)δ9.74(s,4H),8.07(s,2H),7.83(d,J=1.6Hz,4H),4.51(s,8H),4.09(s,2H).ESI-MS质谱,精确分子量400.1608,实际峰值401.1689[M+H]+,423.1494[M+Na]+.
将白色粉末(2.00g,5mmol)与2-双苯基膦苯甲醛(6.38g,22mmol)加入到100mL乙醇中混合,加入5滴冰醋酸后,将混合溶液在95℃下回流搅拌12小时。反应结束后进行抽滤并用甲醇洗涤滤饼,真空干燥洗涤后的滤饼,得到黄色粉末6.50g,产率87.2%,即配体H4PTPC。1H-NMR(400MHz,DMSO-d6,ppm)δ12.11(s,4H),8.24(s,2H),8.07(d,J=4.8Hz,4H),7.98(s,4H),7.83(s,4H),7.51(t,J=6.0Hz,8H),7.40(t,J=8.0Hz,24H),7.19(d,J=1.6Hz,16H),6.86(d,J=4.4Hz,4H),4.08(s,2H).ESI-MS质谱,精确分子量1489.47,实际峰值1512.46[M+Na]+.
将Co(NO3)2·6H2O(29.6mg,0.1mmol)和配体H4PTPC(74.5mg,0.05mmol)溶于30mL甲醇,乙醇和乙腈比例为1:1:1的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙红色固体,即可制得目标化合物Co-PTPC49.6mg,产率40.1%。晶体结构图,如图1所示。ESI-MS质谱:m/z:801.66[Co6(PTPC)3]6+,974.38[Co6(PTPC)3·NO3 -]5+和1233.48[Co6(PTPC)3·2NO3 -]4+,如图2所示。
实施例2
将Co(ClO4)2·6H2O(36.6mg,0.1mmol)与实施例1制备的配体H4PTPC(74.5mg,0.05mmol)溶于30mL甲醇,乙醇和乙腈比例为1:0.9:2的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙红色固体,即可制得目标化合物Co-PTPC27.3mg,产率21.9%。ESI-MS质谱:m/z:801.66[Co6(PTPC)3]6+。
实施例3
将Co(BF4)2·6H2O(34.1mg,0.1mmol)与实施例1制备的配体H4PTPC(74.5mg,0.05mmol)溶于30mL甲醇,乙醇和乙腈比例为1:1:1.5的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙红色固体,即可制得目标化合物Co-PTPC 22.4mg,产率18.2%。ESI-MS质谱:m/z:801.66[Co6(PTPC)3]6+。
实施例4
将Co(CF3SO3)2(35.7mg,0.1mmol),实施例1制备的配体H4PTPC(74.5mg,0.05mmol)溶于30mL甲醇,乙醇和乙腈比例为1:0.8:2的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙红色固体,即可制得目标化合物Co-PTPC,产率15.4mg,12.5%。ESI-MS质谱:m/z:801.66[Co6(PTPC)3]6+。
实施例5利用Co-PTPC还原间硝基苯乙酮制间氨基苯乙酮
在20mL的光反应管中,加入5mL乙腈/水=1:1的溶液,之后加入2.2mg的Ru(bpy)3(PF6)2,12.5微升的Co-PTPC的1mmol/L的乙腈溶液,88.0mg抗坏血酸,用硫酸和氢氧化钠溶液调节pH值至4.75。后加入31mg醌氢醌与33mg的间硝基苯乙酮,将反应器置于氩气氛围中,利用500W氙灯光照10h,氙灯光强150,波长大于420nm,间硝基苯乙酮有93%转化为间氨基苯乙酮,选择性大于99%。TON可达到19200。
实施例6利用Co-PTPC还原对硝基苯乙酮制对氨基苯乙酮
在50mL的光反应管中,加入20mL乙腈/水=1:1的溶液,之后加入2.2mg的Ru(bpy)3(PF6)2,12.5微升的Co-PTPC的1mmol/L的乙腈溶液,88.0mg抗坏血酸,用盐酸和氢氧化钠溶液调节pH值至4.75。后加入31mg苯醌与82.5mg的对硝基苯乙酮,将反应器置于氩气氛围中,利用500W氙灯光照60h,氙灯光强150,波长大于400nm,每隔10小时加入88.0mg抗坏血酸,60小时反应的TON可达到36000,选择性大于99%,如图3所示。
Claims (1)
1.一种金属有机三棱柱状化合物的制备方法,其特征在于:以过渡金属盐中的Co2+作为节点,以L作为配体反应制得金属有机三棱柱化合物,其合成路线如下:
Co2++L→Co-L;
所述配体L选自H4PTPC;
所述过渡金属盐选自硝酸钴,高氯酸钴,四氟硼酸钴或三氟甲磺酸钴中的一种;
所述配体H4PTPC具有如下(A)分子结构式,
式中:R1为苯基,R2为氢,R3为氢,X为亚甲基;
制备方法,包括以下步骤:
步骤1、将间苯二甲酸与95%的多聚甲醛按1:0.45~0.55的摩尔比溶解于90~110mL20%的发烟硫酸中,混合物在110~130℃下搅拌4~8小时,之后冷却至室温;将混合物倒在冰水上,过滤沉淀,用水清洗,在真空中干燥,得到黄色固体,再将黄色固体溶解于90~110mL的甲醇中,加入200~250mL盐酸并回流20~40分钟,将混合物冷却至0~15℃,然后对出现的固体产物进行过滤,用冷甲醇洗涤并干燥,得到白色固体产物;
步骤2、将步骤1所得白色固体产物与水合肼按1:60~100的摩尔比混合,在80~100℃温度下回流搅拌10~15小时,反应结束后抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到白色粉末;
步骤3、将步骤2所得白色粉末与2-双苯基膦苯甲醛按照1:4.2~4.4的摩尔比加入到80~120mL乙醇中混合,再加入5~6滴冰醋酸,将混合溶液在80~100℃温度下回流搅拌10~15小时,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H4PTPC;
步骤4、将配体H4PTPC与过渡金属钴盐按照1:2~3的摩尔比加入到25~35mL甲醇、乙醇和乙腈的混合溶剂中,室温下搅拌4~6小时,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙红色固体,制得目标化合物Co-PTPC,所述甲醇、乙醇和乙腈的体积比为1:0.8~1.2:0.5~2。
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