CN110437269B - 一种b(4,5)烷基取代碳硼烷化合物的合成方法 - Google Patents
一种b(4,5)烷基取代碳硼烷化合物的合成方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种碳硼烷化合物的合成方法,适用于B(4,5)烷基取代碳硼烷化合物的合成方法。其合成步骤包括:以1‑羧基‑2‑(取代)碳硼烷和丙烯醇类为原料,在催化剂和添加剂的存在下,反应温度为70℃~130℃,反应时间为1h~36h,在溶剂中发生交叉偶联反应生成B(4,5)烷基取代碳硼烷。本发明所涉及的反应物具有很好的普适性,底物的官能团具有很好的兼容性;本发明使用较为便宜的丙烯醇类作为烷基化试剂,相对成本较低;本发明提供的合成方法的选择性和产率较高,反应体系组成单一,后处理简单,易于实施。
Description
技术领域
本发明涉及一种碳硼烷的合成方法,尤其涉及一种B(4,5)烷基取代碳硼烷化合物的合成方法。
背景技术
碳硼烷为多面体闭型笼状结构,具有热值高、硼含量高、良好的热稳定性和化学稳定性等特点,是一类性能优异的高燃速催化剂,另外,碳硼烷在配位化学领域和医学领域用作金属配体和中子吸收材料;该类化合物常温下为液体,它们在固体推进剂中除主要起燃速调节作用外,还兼具增塑剂的功能。
目前,常用碳硼烷类燃速催化剂有正丁基碳硼烷、正己基碳硼烷(NHC)及碳硼烷基甲基丙酸酯等。研究较多的是NHC,其燃烧热达到56MJ/kg。国外用NHC研制了系列高燃速推进剂,其中催化剂添加量大多为10~14%,例如美国“蝮蛇”反坦克导弹的丁羟推进剂采用添加质量分数13.1%的NHC作燃速催化剂,配方燃速为144mm/s,压强指数为0.65(13.8MPa)。1-正己基-1,2-碳硼烷由于它在高燃速推进剂配方中具有优良的全面综合性能,已成了一个大量生产和应用的碳硼烷燃速调节剂品种。对于丁羟推进剂上功能化的碳硼烷衍生物,目前的改性主要集中在碳原子上,由于选择性的问题以及保证高燃烧热值所需要引入特定的官能基团,对于硼原子上的改性应用则少有报道。但正是因为硼数量的优势,使得修饰的可能性增加,并且空间上多取代的活性基团对整体性能影响较小等优点决定了在硼原子上引入官能化基团将为其在丁羟推进剂中的使用提供更好的应用前景。
发明内容
为了解决现有技术的不足和缺陷,本发明提供一种高选择性、高收率及反应物普适性好的B(4,5)烷基取代碳硼烷化合物的合成方法。
本发明提供的一种B(4,5)烷基取代碳硼烷化合物的合成方法,以1-羧基-2-(取代)碳硼烷为原料,反应方程式如下:
其中R1为直链烷基或芳基,R2为直链烷基或芳基。
该方法以1-羧基-2-(取代)碳硼烷和丙烯醇类为原料,包括以下步骤:
1-羧基-2-(取代)碳硼烷和烯丙醇类在催化剂和添加剂的存在下,在溶剂中发生交叉偶联反应生成B(4,5)烷基取代碳硼烷,其中催化剂为一价铑盐或三价铑盐,添加剂为银盐,1-羧基-2-(取代)碳硼烷与催化剂摩尔比为1~50:1,1-羧基-2-(取代)碳硼烷与与添加剂摩尔比为1:1~20,1-羧基-2-(取代)碳硼烷与烯丙醇类摩尔比为1:1~20,反应温度为70℃~130℃,反应时间为1h~36h。
本发明所述1-羧基-2-(取代)碳硼烷优选1-羧基-2-甲基碳硼烷,1-羧基-2-正丁基碳硼烷,1-羧基-2-正己基碳硼烷,1-羧基-2-苯基碳硼烷;丙烯醇类为丙烯醇,3-丁烯-2-醇,1-戊烯-3-醇,2-甲基-2-丙烯-1-醇,3-甲基-2-丁烯-1-醇,1-芳基-2-丙烯-1-醇,其中芳基为苯基、取代苯基,苯环上含有一个或多个取代基,苯环上取代基为甲基、甲氧基、卤素、三氟甲基、甲酯基。
本发明所述催化剂优选二氯五甲基茂基合铑二聚体,添加剂为醋酸银,氧化银,优选溶剂为1,4-二氧六环。
本发明1-羧基-2-(烷基)碳硼烷与催化剂摩尔比优选1~50:1,1-羧基-2-(烷基)碳硼烷与与添加剂摩尔比优选1:1~20,1-羧基-2-(烷基)碳硼烷与烯丙醇类摩尔比优选1:1~20,反应温度优选70℃~130℃,反应时间优选1h~36h。
与现有技术相比,本发明具有下列优势:
1、本发明使用较为便宜的丙烯醇类作为烷基化试剂,相对成本较低。
2、本发明方法所涉及的反应物具有很好的普适性,烯丙醇类试剂可以是烯丙醇,3-丁烯-2-醇,1-戊烯-3-醇,2-甲基-2-丙烯-1-醇,3-甲基-2-丁烯-1-醇,1-芳基-2-丙烯-1-醇,其中芳基为苯基、取代苯基,苯环上含有一个或多个取代基,苯环上取代基为甲基、甲氧基、卤素、三氟甲基、甲酯基。
3、本发明方法所涉及的反应的选择性和产率较高,反应体系组成单一,后处理比较简单。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1:2-正己基-4,5-双(3-丁酮)-1,2-碳硼烷的合成
取20mL的Schlenk管装入磁子,取20mL的Schlenk管装入磁子,依次加入1-羧基-2-正己基邻碳硼烷55mg(0.2mmol),二氯五甲基茂基合铑二聚体6mg(0.02mmol),133mg醋酸银(0.8mmol),然后加入5mL1,4-二氧六环,在90℃条件下搅拌下电磁加热搅拌器上反应12小时,反应结束后,蒸除溶剂,通过柱层析纯化得到2-正己基-4,5-双(3-丁酮)-1,2-碳硼烷66mg,收率85%。
结构鉴定:
1HNMR(500MHz,氘代氯仿,δ/ppm)δ7.36(d,J=8.4Hz,2H),7.13(d,J=8.1Hz,2H),3.92(s,1H),2.34(s,3H).13C NMR(126MHz,氘代氯仿,δ/ppm)δ140.3,130.8,129.6,127.6,60.4,21.1.11B NMR(160MHz,氘代氯仿,δ/ppm)δ-2.93(2B),-3.57(1B),-5.13(1B),-9.86(2B),-12.07(2B),-14.79(2B).
高分辨质谱:质荷比C16B10H36O2Na[M+Na]+,理论值:393.3538;实测值:393.3564。
上述结构表征数据证实所得化合物是2-正己基-4,5-双(3-丁酮)-1,2-碳硼烷的合成。
实施例2~13
实施例2~13按照实施例1中相同的方法合成2-正己基-4,5-双(3-丁酮)-1,2-碳硼烷,通过调整添加剂、溶剂和时间等参数,研究反应条件对产物收率的影响,验结果见下表:
实施例14:2-正丁基-4,5-双(3-丁酮)-1,2-碳硼烷的合成
取20mL的Schlenk管装入磁子,取10mL的Schlenk管装入磁子,依次加入1-羧基-2-正丁基邻碳硼烷49mg(0.2mmol),二氯五甲基茂基合铑二聚体6mg(0.02mmol),133mg醋酸银(0.8mmol),然后加入5mL1,4-二氧六环,在90℃条件下搅拌下电磁加热搅拌器上反应12小时,反应结束后,蒸除溶剂,通过柱层析纯化得到2-正丁基-4,5-双(3-丁酮)-1,2-碳硼烷58mg,收率80%。
结构鉴定:
1HNMR(500MHz,氘代氯仿,δ/ppm)δ3.56(s,1H),2.57(t,J=7.8Hz,5H),2.15(s,6H),2.14–2.12(m,2H),1.41–1.34(m,2H),1.28–1.25(m,2H),1.16–1.10(m,2H),1.06–1.00(m,2H),0.88(t,J=7.3Hz,3H).13C NMR(126MHz,氘代氯仿,δ/ppm)δ209.42,74.83,64.31,42.46,37.84,31.16,29.60,22.07,13.57.11B NMR(160MHz,氘代氯仿,δ/ppm)δ-2.81(2B),-3.53(1B),-5.09(1B),-9.81(2B),-11.99(2B),-14.72(2B).高分辨质谱:质荷比C14B10H33O2[M+H]+,理论值:343.3406;实测值:343.3402。
上述结构表征数据证实所得化合物是2-正丁基-4,5-双(3-丁酮)-1,2-碳硼烷。
实施例15~22
实施例15~22按照实施例14中相同的方法合成B(4,5)烷基取代碳硼烷,通过调整烯丙醇偶联试剂,研究反应条件对产物收率的影响,实验结果见下表:
实施例 | 烯丙醇偶联试剂 | 产率 |
15 | 丙烯醇 | 90% |
16 | 1-戊烯-3-醇 | 78% |
17 | 1-苯基-2-丙烯醇 | 72% |
18 | 1-(4-甲基苯基)-2-丙烯醇 | 76% |
19 | 1-(4-甲氧基苯基)-2-丙烯醇 | 77% |
20 | 1-(4-氯苯基)-2-丙烯醇 | 80% |
21 | 1-(4-氟苯基)-2-丙烯醇 | 73% |
22 | 1-(3-氯苯基)-2-丙烯醇 | 75% |
Claims (6)
2.根据权利要求1所述的B(4,5)烷基取代碳硼烷化合物的合成方法,其特征在于,所述1-羧基-2-(取代)碳硼烷为1-羧基-2-甲基碳硼烷,1-羧基-2-正丁基碳硼烷,1-羧基-2-正己基碳硼烷,或1-羧基-2-苯基碳硼烷。
3.根据权利要求1所述的B(4,5)烷基取代碳硼烷化合物的合成方法,其特征在于,所述的丙烯醇类为丙烯醇,3-丁烯-2-醇,1-戊烯-3-醇,2-甲基-2-丙烯-1-醇,3-甲基-2-丁烯-1-醇,1-芳基-2-丙烯-1-醇,其中芳基为苯基、取代苯基,取代苯基指的是苯环上含有一个或多个取代基,苯环上取代基为甲基、甲氧基、卤素、三氟甲基、甲酯基。
4.根据权利要求1所述的B(4,5)烷基取代碳硼烷化合物的合成方法,其特征在于,所述添加剂为醋酸银,碳酸银,氧化银或三氟乙酸银。
5.根据权利要求1所述的B(4,5)烷基取代碳硼烷化合物的合成方法,其特征在于,所述溶剂为1,4-二氧六环、甲苯、邻二甲苯或1,2-二氯乙烷。
6.根据权利要求1所述的B(4,5)烷基取代碳硼烷化合物的合成方法,其特征在于反应温度为70℃~130℃,反应时间为1h~36h。
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