CN114524835B - 碳硼烷支撑的salen配体、巢式碳硼烷支撑的salen-Al催化剂及其制备和应用 - Google Patents
碳硼烷支撑的salen配体、巢式碳硼烷支撑的salen-Al催化剂及其制备和应用 Download PDFInfo
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- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 28
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Abstract
本发明公开碳硼烷支撑的salen配体、巢式碳硼烷支撑的salen‑Al催化剂及其制备和应用。碳硼烷支撑的salen配体分子结构式见式Ⅰ,巢式碳硼烷支撑的salen‑Al络合物分子结构式见式Ⅱ。二氨基邻碳硼烷与水杨醛反应得到含邻碳硼烷的salen配体;随后与三乙基铝反应,得到含巢式碳硼烷的salen‑Al配合物。本发明合成工艺简单,具有较好的选择性和收率。
Description
技术领域
本发明属于精细化学品和单体合成及催化应用技术领域,涉及一种新型salen配体及salen-Al配合物,特别涉及碳硼烷支撑的salen配体、巢式碳硼烷支撑的salen-Al催化剂及其制备方法和应用,具体是NN骨架为巢式碳硼烷的苯环上不同取代基的系列salen-Al配合物。
背景技术
Salen配体是二胺分子和一类特定的醛--水杨醛,反应生成的含有[ONNO]的四齿希夫碱类配体。salen配体由于其易于制备,并且可以通过改变NN之间桥连的基团,及水杨醛苯环上的取代基去修饰配体空间和电子效应。同时salen配体可以和很多过渡金属发生配位,生成salen金属配合物,催化多种反应,这些特质使salen配体可以被称为配位化学领域的“优势配体”。
环状碳酸酯作为有机碳酸盐的重要组成部分,可用作锂离子电池的电解质以及精细化学品生产的中间体,应用广泛。以二氧化碳为原料生成环状碳酸酯的反应是减少碳排放的有效途径,因此二氧化碳和环氧丙烷生成环状碳酸酯的反应也是目前化学家研究的热点。
环状碳酸酯的合成通常使用路易斯酸或路易斯碱催化剂进行,这一般需要高温和高压。从能源和经济角度来看,这些条件都是催化过程的局限性。如果要大幅增加环状碳酸酯的利用率,则需要开发接近大气压和接近室温下可行的催化剂和方法,以使环状碳酸酯生产总成本中的能源价格占比最小化。所以开发新型高效的催化剂是十分有必要的。
但目前为止,还没有含碳硼烷的Salen-Al的化合物报道,碳硼烷是多面体的硼烷上的硼原子被碳原子取代后的一类分子簇化合物。碳硼烷的硼笼内电子云高度离域,使其具有三维芳香性。这使得它可以看作是二维芳香苯的三维类似物。同时由于碳硼烷封闭多面体的结构,自身庞大的空间体积可以有效屏蔽一些有机物,所以碳硼烷又兼具稳定性和刚性,同时其配合物还具有溶解性好、易于结晶等优点,可以用于多种催化体系。在此基础上,本发明提出以二氨基碳硼烷为原料成功的和系列水杨醛反应成功得到了一些含碳硼烷的salen配体,并用其和三乙基铝反应合成了含巢式碳硼烷的salen-Al化合物,成功以较高活性在温和条件下催化了二氧化碳和环氧化物的反应。
发明内容
本发明的第一个目的是针对现有技术的不足,提供碳硼烷支撑的salen配体。
本发明碳硼烷支撑的[ONNO]型salen配体,其分子结构式如下:
其中R1选自H或tBu,R2选自H或OMe,R3选自H或tBu。
作为优选,碳硼烷支撑的salen配体的分子结构式如下式L1-L4中的一种:
碳硼烷支撑的[ONNO]型salen配体,是NN之间桥连部分为具有刚性同时兼有三维芳香性的邻碳硼烷。其中,salen配体是指一分子二胺和两分子水杨醛发生缩和反应生成的含有[ONNO]四种原子的四齿希夫碱;邻碳硼烷为1,2-二碳代十二硼烷。
本发明的第二个目的是提供碳硼烷支撑的salen配体的制备方法,具体是
在催化剂量的酸性催化剂条件下,将溶解于溶剂的二氨基碳硼烷与水杨醛类化合物(Ⅲ)在100℃-140℃下加热至反应体系回流,加热回流一定时间,旋蒸除去溶剂,乙醇重结晶,得到碳硼烷支撑的salen配体。
作为优选,酸性催化剂采用三氟乙酸。
作为优选,溶剂为甲苯。
作为优选,反应温度为125-135℃;
水杨醛类化合物(Ⅲ)的结构式如下:
本发明的第三个目的是提供含巢式碳硼烷的salen-Al络合物,其分子结构式如下:
其中R1选自H或tBu,R2选自H或OMe,R3选自H或tBu,sol为含氧配位溶剂。
作为优选,所述含氧配位溶剂为THF,EtOH,MeOH,H2O中的一种。
作为优选,含巢式碳硼烷的salen-Al络合物分子结构式如下式L5-L8中的一种:
本发明的第四个目的是提供含巢式碳硼烷的salen-Al络合物的制备方法,具体如下:
将溶解于无水溶剂的碳硼烷支撑的salen配体(I),在氩气保护,低温条件下,缓慢滴加三乙基铝,搅拌后缓慢升温至室温,然后加入一定量溶剂,并于一定温度(优选为-30至-50℃)条件下加热至回流;反应完全后,加入乙醇或甲醇(甲醇),随后旋蒸除去多余溶剂,甲醇重结晶得到黄色固体,即目标产物,含巢式碳硼烷的salen-Al化合物(Ⅱ)。
作为优选,所述无水溶剂为二氯甲烷、甲苯、四氢呋喃中的一种。
作为优选,所述低温为-30℃到常温。
本发明的第5个目的是提供含巢式碳硼烷的salen-Al络合物在温和条件下催化二氧化碳和环氧化物反应上的应用。
作为优选,上述应用具体是环氧化物和二氧化碳的反应体系中含巢式碳硼烷的salen-Al络合物(Ⅱ)作为主催化剂,季铵盐作为助催化剂。
作为优选,上述应用具体是环氧化物和二氧化碳的反应体系中反应条件为温度25-75℃,常压;更为优选温度优选为50℃,常压。
作为优选,季铵盐助催化剂为四丁基溴化铵。
作为优选,含巢式碳硼烷的salen-Al络合物(Ⅱ)与环氧化物的摩尔比为0.0001-0.02:1;
作为优选,含巢式碳硼烷的salen-Al络合物(Ⅱ)与季铵盐助催化剂的摩尔比为0.01-2:2。
本发明碳硼烷支撑的salen配体所需溶剂为甲苯,无需特殊处理。所述配合物溶于氢化钙处理过的除水无水溶剂,即无水二氯甲烷、甲苯、四氢呋喃等。
本发明用简单步骤,高选择性、高收率合成了含巢式碳硼烷的salen-Al化合物。本发明合成工艺简单,反应具有较高选择性和收率,容易实现工业化。
附图说明
图1为化合物5的单晶结构图;
图2为化合物6的单晶结构图;
图3为化合物7的单晶结构图;
图4为化合物8的单晶结构图。
具体实施方式
下面通过实施例进一步具体描述本发明,本发明并不局限于下述实施例。
实施例1:配体L1的合成
于100ml的圆底烧瓶中加入将二氨基碳硼烷(1.85g),和水杨醛(3.24g),加入60ml甲苯使其溶解,再加入0.8ml的三氟乙酸,圆底烧瓶瓶口连接分水器支口下端,分水器另一端连接回流冷凝管,用油浴130℃加热至反应体系回流,反应6h撤去油浴,旋蒸除去多余溶剂,所得黑色固体用乙醇重结晶,过滤得到黄色固体(2.80g,产率:70%)。
1H NMR(400.13MHz,CDCl3):δ11.15(s,2H,OH),8.71(s,2H,N=CH),7.47–7.42(m,4H,HPh),7.03–6.96(m,4H,HPh);
13C{1H}NMR(100.61MHz,CDCl3):δ170.96(N=CH),161.26(CPh),135.57(CPh),133.91(CPh),119.92(CPh),117.94(CPh),117.81(CPh),93.43(Co-carb);
11B{1H}NMR(160.46MHz,DMSO-d6):δ-7.35,-9.27,-12.12.
HRMS(ESI):m/z calcd.for[C16H22B9N2O2]+372.2572,found[M-B]+372.2588.
实施例2:配体L2的合成
于100ml的圆底烧瓶中加入将二氨基碳硼烷(1.00g),和三五二叔丁基水杨醛(3.00g),加入60ml甲苯使其溶解,再加入0.8ml的三氟乙酸,圆底烧瓶瓶口连接分水器支口下端,分水器另一端连接回流冷凝管,用油浴135℃加热至反应体系回流,反应6h撤去油浴,旋蒸除去多余溶剂,所得黑色固体用乙醇重结晶,过滤得到黄色固体(2.70g,产率:77%)。
1H NMR(400.13MHz,DMSO-d6):δ11.62(s,2H,OH),8.70(s,2H,N=CH),7.50(s,2H,HPh),7.20(s,2H,HPh),1.38(s,18H,tBu),1.32(s,18H,tBu);
13C{1H}NMR(100.61MHz,CDCl3):δ171.72(N=CH),158.66(CPh),141.47(CPh),137.72(CPh),130.54(CPh),128.14(CPh),117.14(CPh),94.08(Co-carb),35.30(CMe3),34.36(CMe3),31.48(CMe3),29.52(CMe3);
11B{1H}NMR(160.46MHz,DMSO-d6):δ-7.68,-12.22.
HRMS(ESI):m/z calcd.for[C32H54B9N2O2]+596.5086,found[M-B]+596.5096.
实施例3:配体L3的合成
于100ml的圆底烧瓶中加入将二氨基碳硼烷(2.37g),和四甲氧基水杨醛(4.76g),加入60ml甲苯使其溶解,再加入0.8ml的三氟乙酸,圆底烧瓶瓶口连接分水器支口下端,分水器另一端连接回流冷凝管,用油浴125℃加热至反应体系回流,反应6h撤去油浴,旋蒸除去多余溶剂,所得黑色固体用甲醇重结晶,过滤得到黄色固体(3.70g,产率:62%)。
1H NMR(400.13MHz,DMSO-d6):δ11.55(s,2H,OH),8.52(s,2H,N=CH),7.22(s,2H,HPh),6.49-6.44(m,4H,HPh),3.79(s,6H,OMe);
13C{1H}NMR(100.61MHz,CDCl3):δ169.47(N=CH),165.69(CPh),163.81(CPh),135.21(CPh),111.89(CPh),108.45(CPh),101.23(CPh),94.04(Co-carb),55.75(OMe);
11B{1H}NMR(160.46MHz,DMSO-d6):δ-7.51,-13.37.
HRMS(ESI):m/z calcd.for[C18H25B9N2O4]+432.2684,found[M-B]+432.2650.
实施例4:配体L4的合成
于100ml的圆底烧瓶中加入将二氨基碳硼烷(1.50g),和三叔丁基水杨醛(3.38g),加入60ml甲苯使其溶解,再加入0.8ml的三氟乙酸,圆底烧瓶瓶口连接分水器支口下端,分水器另一端连接回流冷凝管,用油浴135℃加热至反应体系回流,反应6h撤去油浴,旋蒸除去多余溶剂,所得黑色固体用乙醇重结晶,过滤得到黄色固体(3.10g,产率:73%)。
1H NMR(400.13MHz,DMSO-d6):δ11.77(s,2H,OH),8.72(s,2H,N=CH),7.46(dd,2H,HPh),7.28(dd,2H,HPh),6.91(t,2H,HPh),1.39(s,18H,tBu);
13C{1H}NMR(100.61MHz,CDCl3):δ171.43(N=CH),160.76(CPh),138.34(CPh),132.76(CPh),132.24(CPh),119.20(CPh),117.89(CPh),93.83(Co-carb),35.13(CMe3),29.45(CMe3);
11B{1H}NMR(160.46MHz,DMSO-d6):δ-7.64,-12.17.
HRMS(ESI):m/z calcd.for[C24H38B9N2O2]+484.3829,found[M-B]+484.3818.
实施例5:合成化合物5
氩气保护下,于100ml的schlenk瓶中加入配体L1(0.43g),加入40ml无水二氯甲烷,在-30℃加入三乙基铝的甲苯溶液(1.8mmol,0.8ml)。低温半小时,常温反应1h,加入甲醇,常压继续常温2h,45℃加热回流10h,旋蒸除去溶剂。用二氯甲烷正己烷重结晶,过滤,得黄色固体(0.44g,产率84%)。图1为化合物5的单晶结构图。
1H NMR(400.13MHz,Acetone):δ8.21(s,2H,N=C-H),7.36(dd,J=8.0,2.0Hz,2H,Ar-H),7.32–7.25(m,2H,Ar-H),6.71–6.67(m,4H,Ar-H),-2.21(s,1H,B-H-B).
13C NMR(126MHz,Acetone):δ164.08(s),161.80(d,J=3.78Hz),134.57(s),133.98(s),121.15(d,J=7.56Hz),119.74(s),115.96(d,J=6.3Hz).
11B{1H}NMR(160.46MHz,Acetone):δ=-8.59,-20.15,-31.42,-34.33.
实施例6:合成化合物6
氩气保护下,于100ml的schlenk瓶中加入配体L2(0.91g),加入40ml无水二氯甲烷,在-30℃加入三乙基铝的甲苯溶液(1.8mmol,1ml)。低温半小时,常温反应1h,加入乙醇,常压继续常温2h,45℃加热回流10h,旋蒸除去溶剂。用甲醇重结晶,过滤,滤液旋干,黄色固体(0.60g,产率58%)。
图2为化合物6的单晶结构图。
1H NMR(400.13MHz,CDCl3):δ8.40(s,2H,N=C-H),7.51(d,J=2.4Hz,2H,Ar-H),7.1(d,J=2.4Hz,2H,Ar-H),1.50(s,18H,Ar-t-Bu),1.31(s,18H,Ar-t-Bu),-2.37(s,1H,B-H-B).
13C NMR(100.61MHz,CDCl3):δ164.26(s),160.88(s),139.97(s),139.21(s),131.00(s),128.29(s),118.49(s),35.56(s),34.10(s),31.38(s),29.67(s).
11B{1H}NMR(160.46MHz,CDCl3):δ=-8.63,-22.77,-36.71,-40.41.
实施例7:合成化合物7
氩气保护下,于100ml的schlenk瓶中加入配体L3(0.80g),加入40ml无水二氯甲烷,在-30℃加入三乙基铝的甲苯溶液(1.8mmol,1ml)。低温半小时,常温反应1h,加入乙醇,常压继续常温2h,45℃加热回流10h,旋蒸除去溶剂。用二氯甲烷正己烷重结晶,过滤,得黄色固体(0.82g,产率85%)。
图3为化合物7的单晶结构图。
1HNMR(400.13MHz,Acetone):δ8.15(s,2H,N=C-H),7.30(d,J=8.7Hz,2H,Ar-H),6.30(dd,J=8.8Hz,2.4Hz,2H,Ar-H),6.17(d,J=2.0Hz,2H,Ar-H),3.78(s,6H,Ar-OCH3),-2.29(s,1H,B-H-B).
13C NMR(100.61MHz,Acetone):δ167.30(s),166.51(s),161.41(s),135.96(s),114.82(s),106.10(s),104.27(s),55.61(s).
11B{1H}NMR(160.46MHz,Acetone):δ=-9.35,-20.62,-31.30,-31.88.
实施例8:合成化合物8
氩气保护下,于100ml的schlenk瓶中加入配体L4(0.84g),加入40ml无水二氯甲烷,在-30℃加入三乙基铝的甲苯溶液(1,8mmol,1ml)。低温半小时,常温反应1h,加入无水甲醇,常压继续常温2h,45℃加热回流10h,旋蒸除去溶剂。用甲醇重结晶,过滤,滤液旋干,黄色固体(0.61g,产率71%)。图4为化合物8的单晶结构图。
1H NMR(400.13MHz,CDCl3):δ8.36(s,2H,N=C-H),7.42(dd,J=7.2,1.2Hz,2H,Ar-H),7.18(dd,J=7.6Hz,1.2Hz,2H,Ar-H),6.74(t,J=7.6Hz,2H,Ar-H),1.47(s,18H,Ar-t-Bu),-2.34(s,1H,B-H-B).
13C NMR(100.66MHz,CDCl3):δ163.54(s),162.98(s),140.68(s),132.73(d,J=9.01Hz),119.44(s),116.83(s),35.38(s),29.59(s).
11B{1H}NMR(160.46MHz,CDCl3):δ=-8.98,-22.78,-36.65,-40.50.
实施例9:
于四个5ml反应管A-D中,均加入丁基环氧乙烷(0.6ml,5.00mmol),百分之二摩尔占比的含巢式碳硼烷的salen-Al络合物(四个反应管A-D分别加入化合物5(39.5mg,0.1mmol),化合物6(69.1mg,0.1mmol),化合物7(48.9mg,0.1mmol),化合物8(55.5mg,0.1mmol)),百分之二摩尔占比的助催化剂四丁基溴化铵(32.0mg,0.1mmol),50℃反应3h,反应管口用橡胶塞封闭,插入充满二氧化碳的气球,封口膜密封管口。转化率:98%,55%,83%,66%。
实施例10:
于5ml反应管A-D中,分别加入丁基环氧乙烷(0.6ml,5.00mmol),加入百分之一摩尔占比的含巢式碳硼烷的salen-Al络合物(其中反应管A-D分别加入化合物5(19.78mg,0.05mmol)、化合物6(34.5mg,0.05mmol),化合物7(24.5mg,0.05mmol),化合物8(27.7mg,0.05mmol)),百分之二摩尔占比的助催化剂四丁基溴化铵(32.0mg,0.1mmol),50℃反应一定时间。
反应管A组反应时间为3h,转化率:97%;反应管B-D组反应时间为6h,转化率分别为:81%,98%,94%。
实施例11:
于5ml反应管A-D中,分别加入丁基环氧乙烷(0.6ml,5.00mmol),加入百分之一摩尔占比的含巢式碳硼烷的salen-Al络合物(其中反应管A-D分别加入化合物5(19.78mg,0.05mmol)、化合物6(34.5mg,0.05mmol),化合物7(24.5mg,0.05mmol),化合物8(27.7mg,0.05mmol)),百分之一摩尔占比的助催化剂四丁基溴化铵(16.0mg,0.05mmol),50℃反应一定时间。
反应管A组反应时间为3h,转化率:68%;反应管B-D组反应时间为6h,转化率分别为:48%,75%,71%。
实施例12:
于5ml反应管中,分别加入丁基环氧乙烷(0.6ml,5.00mmol),分别加入百分之二摩尔占比的化合物5(39.6mg,0.1mmol),不加助催化剂,50℃反应3h,反应管口用橡胶塞封闭,插入充满二氧化碳的气球,封口膜密封管口。转化率:0%。
实施例13:
于两个5ml反应管A-B中,分别加入丁基环氧乙烷(0.6ml,5mmol),分别加入百分之一摩尔占比的化合物5(19.8mg,0.05mmol),百分之二摩尔占比的助催化剂四丁基溴化铵(32.0mg,0.1mmol),在不同温度下反应3h,反应管口用橡胶塞封闭,插入充满二氧化碳的气球,封口膜密封管口。反应管A组反应温度为25℃,转化率:66%;反应管B组反应温度为75℃,转化率:98%。
实施例14:
于五个5ml反应管A-F中,按照表1加入环氧化物、百分之一摩尔占比的化合物5、百分之二摩尔占比的助催化剂四丁基溴化铵,50℃反应3h,反应管口用橡胶塞封闭,插入充满二氧化碳的气球,封口膜密封管口。
表1
实施例15:
于5ml反应管A-F中,按照表2加入丁基环氧乙烷,不同用量的含巢式碳硼烷的salen-Al络合物(其中反应管A-F分别加入0.5%,0.25%,0.1%,0.05%,0.03%,0.01%摩尔占比的化合物5),助催化剂四丁基溴化铵,50℃反应3h,反应管口用橡胶塞封闭,插入充满二氧化碳的气球,封口膜密封管口。
表2
上述实施例并非是对于本发明的限制,本发明并非仅限于上述实施例,只要符合本发明要求,均属于本发明的保护范围。
Claims (9)
6.权利要求4或5所述的含巢式碳硼烷的salen-Al络合物的制备方法,其特征在于具体如下:
将溶解于无水溶剂的权利要求1或2所述碳硼烷支撑的[ONNO]型salen配体,在氩气保护,-30℃到常温条件下,缓慢滴加三乙基铝,搅拌后缓慢升温至室温,然后加入一定量溶剂并于一定温度条件下加热至回流;脱硼反应完全后,加入含氧配位溶剂,随后旋蒸除去多余溶剂,甲醇重结晶得到黄色固体,即目标产物,含巢式碳硼烷的salen-Al络合物。
7.权利要求4或5所述的含巢式碳硼烷的salen-Al络合物在温度25-75℃、常压条件下催化二氧化碳和环氧化物反应上的应用。
8.如权利要求7所述的应用,其特征在于环氧化物和二氧化碳的反应体系中含巢式碳硼烷的salen-Al络合物作为主催化剂,季铵盐作为助催化剂。
9.如权利要求7或8所述的应用,其特征在于含巢式碳硼烷的salen-Al络合物(Ⅱ)与环氧化物的摩尔比为0.0001-0.02:1;含巢式碳硼烷的salen-Al络合物(Ⅱ)与季铵盐助催化剂的摩尔比为0.01-2:2。
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Citations (2)
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CN103170365A (zh) * | 2013-01-29 | 2013-06-26 | 沈阳金久奇科技有限公司 | 一种高活性双功能催化剂及其制备方法和应用 |
CN104418832A (zh) * | 2013-09-06 | 2015-03-18 | 中国科学院大连化学物理研究所 | 一类环氧乙烷及其衍生物与co2生成环状碳酸酯的反应 |
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Non-Patent Citations (4)
Title |
---|
Carboranylimine-complexed titanium (IV) organometallics: An investigation of synthesis, structure and catalytic polymerization;Zhu Yinghuai et al.;《Journal of Organometallic Chemistry》;20121231;第721-722卷;第119-123页 * |
Intramolecularly two-centered cooperation catalysis for the synthesis of cyclic carbonates from CO2 and epoxides;Xiang Zhang et al.;《Tetrahedron Letters》;20081111;第49卷;第6589-6592页 * |
Ligand-Assisted Rate Acceleration in Transacylation by a Yttrium-Salen Complex. Demonstration of a Conceptually New Strategy for Metal-Catalyzed Kinetic Resolution of Alcohols;Mei-Huey Lin et al.;《Organic Letters》;20020328;第4卷(第9期);第1607-1610页 * |
Robust Zinc Complexes that Contain Pyrrolidine-Based Ligands as Recyclable Catalysts for the Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides;Elisabet Mercade et al.;《ChemCatChem》;20151126;第8卷;第234-243页 * |
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