CN108676027A - 基于膦硼阴离子的离子液体及其合成方法 - Google Patents

基于膦硼阴离子的离子液体及其合成方法 Download PDF

Info

Publication number
CN108676027A
CN108676027A CN201810421650.1A CN201810421650A CN108676027A CN 108676027 A CN108676027 A CN 108676027A CN 201810421650 A CN201810421650 A CN 201810421650A CN 108676027 A CN108676027 A CN 108676027A
Authority
CN
China
Prior art keywords
cdcl
nmr
ionic liquid
liquid
cat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810421650.1A
Other languages
English (en)
Other versions
CN108676027B (zh
Inventor
刘天林
张庆华
燕超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemical Material of CAEP
Original Assignee
Institute of Chemical Material of CAEP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Material of CAEP filed Critical Institute of Chemical Material of CAEP
Priority to CN201810421650.1A priority Critical patent/CN108676027B/zh
Publication of CN108676027A publication Critical patent/CN108676027A/zh
Application granted granted Critical
Publication of CN108676027B publication Critical patent/CN108676027B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms

Abstract

本发明公开了基于膦硼阴离子的离子液体的合成方法，包括如下步骤：用硼烷和亚磷酸酯络合得到硼烷磷酸酯，经过氢氧化钾水解得到硼烷磷酸酯单钾盐；再与咪唑溴盐、吡咯溴盐和四丁基溴化铵离子交换，得到各种基于膦硼阴离子的离子液体。本发明还公开了基于膦硼阴离子的离子液体。本发明获得了几种全新的基于膦硼阴离子的离子液体，开拓了新的绿色火箭推进剂材料。

Description

基于膦硼阴离子的离子液体及其合成方法
技术领域
本发明涉及一种材料及其制备方法，具体涉及一种基于膦硼阴离子的离子液体及其合成方法，属于含能材料制备领域。
背景技术
推进剂用离子液体是将离子液体含能化并应用于液体推进剂，用更加安全环保的离子液体替代剧毒的肼类燃料。当前液体动力推进系统仍然广泛使用剧毒的肼类衍生物作为动力燃料。肼类推进剂由于其高致癌性、高挥发性、使用维护不便等缺点，越来越无法满足现代动力技术的要求。因此，液体推进系统的无毒化、快响应、低成本、系统简单、可维护性强等需求就成为了航天技术中亟待解决的技术难题。近年来美国、欧盟等相继启动了绿色先进空间推进创新计划，提出了发展基于离子液体技术的先进火箭推进剂材料。该离子液体火箭燃料，由于分子间强的正、负离子相互作用而具有极低的蒸汽压，不仅比肼类燃料更安全、绿色环保、可操作的液态区间宽，同时燃烧时仅释放出环境友好的气体产物如水蒸气、氮气和二氧化碳等，具有低特征信号的优势。此外，离子液体推进剂对外界刺激如撞击，摩擦，静电，冲击波等的敏感度很低，安全性高。更特别的是，由于组成离子液体的阴、阳离子搭配具有成千上万种可能，极大地拓展了离子液体推进剂材料的开发空间。因此，离子液体推进剂有望取代传统的肼类物质，用于空间推进系统、高性能姿轨控发动机、应急动力装置等。而目前离子液体推进剂的研发还处于初级阶段，其性能还不如传统燃料，亟需开发性能更优异的离子液体材料。
发明内容
针对现有技术的不足，本发明的目的在于提供一种新型基于膦硼阴离子的离子液体的合成方法。
为了实现上述目的，本发明采用的技术方案是：
基于膦硼阴离子的离子液体的合成方法，包括如下步骤：
用硼烷和亚磷酸酯络合得到硼烷磷酸酯，即
经过氢氧化钾水解得到硼烷磷酸酯单钾盐
再与咪唑溴盐、吡咯溴盐和四丁基溴化铵离子交换，得到各种基于膦硼阴离子的离子液体；当R为甲基时离子液体是当R为乙基时离子液体是
其中，Cat+是
本发明还提供了一种基于膦硼阴离子的离子液体，是通过本发明的制备方法制备得到的。所述的基于膦硼阴离子的离子液体具有如下结构：
其中，R是甲基或乙基，Cat+是
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ9.99(s,1H),7.59–7.49(m,2H),4.35(q,J＝7.4Hz,2H),4.04(s,3H),3.53(d,J＝10.3Hz,6H),1.58(t,J＝7.4Hz,3H),0.61–0.08(m,3H)；13C-NMR(151MHz,CDCl3)δ135.82,121.71,119.95,47.69(d),43.08,34.43,13.62；Anal.calcd for C8H20BN2O3P:C 41.06,H 8.61,N11.97；found:C 40.91,H 8.72,N 11.89。
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ10.09(s,1H),7.54–7.38(m,2H),4.27(t,J＝7.4Hz,2H),4.04(s,3H),3.54(d,J＝10.3Hz,6H),1.93–1.85(m,2H),1.42–1.35(m,2H),0.96(t,J＝7.4Hz,3H),0.60–0.09(m,3H)；13C-NMR(151MHz,CDCl3)δ138.42,123.51,121.94,49.71(d),36.47,32.13,19.46,13.44；Anal.calcd for C10H24BN2O3P:C45.83,H 9.23,N 10.69；found:C 45.70,H 9.31,N10.58。
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.71–3.61(m,6H),3.51(d,J＝10.2Hz,6H),3.17(s,3H),2.36–2.20(m,4H),1.44(t,J＝7.2Hz,3H),0.58–0.05(m,3H)；13C-NMR(151MHz,CDCl3)δ63.88,59.44,49.58(d),47.92,21.63,9.50；Anal.calcd for C9H25BNO3P:C 45.59,H 10.63,N 5.91；found:C 45.25,H10.74,N 5.85。
当R是甲基，Cat+是时，离子液体为无色液体,colorless liquid,91％yield；1H-NMR(600MHz,CDCl3)δ3.74–3.65(m,4H),3.55–3.43(m,8H),3.19(s,3H),2.34–2.23(m,4H),1.94–1.80(m,2H),1.05(t,J＝7.4Hz,3H),0.63–-0.03(m,3H)；13C-NMR(151MHz,CDCl3)δ65.33,64.06,49.21(d),48.14,21.33,17.21,10.54；Anal.calcd forC10H27BNO3P:C 47.83,H 10.84,N 5.58；found:C 47.77,H 10.90,N 5.54。
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.74–3.66(m,4H),3.49(d,J＝10.3Hz,6H),3.19(s,3H),2.33–2.25(m,4H),1.83–1.75(m,2H),1.49–1.41(m,2H),1.00(t,J＝7.4Hz,3H),0.64–-0.06(m,3H)；13C-NMR(101MHz,CDCl3)δ64.08,63.80,49.27,49.25(d),25.63,21.35,19.44,13.44；Anal.calcdfor C11H29BNO3P:C 49.83,H 11.03,N 5.28；found:C 49.61,H 11.11,N 5.23。
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.47(d,J＝10.3Hz,6H),3.38(q,7.3Hz,8H),1.36(t,J＝7.3Hz,12H),0.52–0.00(m,3H)；13C-NMR(151MHz,CDCl3)δ50.64,47.36(d),5.72；Anal.calcd for C10H29BNO3P:C 47.45,H11.55,N 5.53；found:C 47.25,H 11.60,N 5.50。
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ10.34(s,1H),7.45–7.34(m,2H),4.35(q,J＝7.4Hz,2H),4.03(s,3H),3.97–3.88(m,4H),1.57(t,J＝7.4Hz,3H),1.23(t,J＝7.1Hz,6H),0.60–0.10(m,3H)；13C-NMR(151MHz,CDCl3)δ138.77,123.33,121.42,58.10(d),45.09,36.51,16.88(d),15.57；Anal.calcd forC10H24BN2O3P:C 45.83,H 9.23,N 10.69；found:C 45.70,H 9.28,N 10.61。
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ10.41(s,1H),7.36(s,1H),7.28(s,1H),4.28(t,J＝7.4Hz,2H),4.04(s,3H),3.96–3.90(m,4H),1.94–1.84(m,2H),1.42–1.34(m,2H),1.24(t,J＝7.1Hz,6H),0.96(t,J＝7.4Hz,3H),0.61–0.10(m,3H)；13C-NMR(151MHz,CDCl3)δ139.31,123.10,121.49,58.09(d),49.74,36.53,32.11,19.46,16.85(d),13.41；Anal.calcd for C12H28BN2O3P:C 49.67,H9.73,N 9.65；found:C 49.45,H 9.80,N 9.59。
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.92–3.83(m,4H),3.73–3.63(m,6H),3.19(s,3H),2.33–2.24(m,4H),1.44(t,J＝7.2Hz,3H),1.22(t,J＝7.1Hz,6H),0.60–0.06(m,3H)；13C-NMR(151MHz,CDCl3)δ63.87,59.37,57.88(d),47.97,21.63,16.89(d),9.52；Anal.calcd for C11H29BNO3P:C 49.83,H 11.03,N5.28；found:C 49.67,H 11.09,N 5.24。
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.93–3.84(m,4H),3.76–3.65(m,4H),3.53–3.42(m,2H),3.20(s,3H),2.36–2.22(m,4H),1.96–1.74(m,2H),1.22(t,J＝7.1Hz,6H),1.05(t,J＝7.3Hz,3H),0.58–0.07(m,3H)；13C-NMR(151MHz,CDCl3)δ65.57,64.33,57.86(d),21.60,17.46,16.87(d),10.77；Anal.calcd for C12H31BNO3P:C 51.63,H 11.19,N 5.02；found:C 51.50,H 11.21,N 4.99。
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.92–3.84(m,4H),3.76–3.65(m,4H),3.53–3.48(m,2H),3.20(s,3H),2.36–2.22(m,4H),1.84–1.70(m,2H),1.51–1.40(m,2H),1.22(t,J＝7.1Hz,6H),0.99(t,J＝7.4Hz,3H),0.60–0.06(m,3H)；13C-NMR(151MHz,CDCl3)δ64.33,63.99,57.84(d),48.58,25.89,21.61,19.69,16.88(d),13.64；Anal.calcd for C13H33BNO3P:C 53.26,H 11.35,N 4.78；found:C 53.10,H 11.39,N 4.76。
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.91–3.85(m,4H),3.39(q,J＝7.3Hz,8H),1.35(t,J＝7.3Hz,12H),1.22(t,J＝7.1Hz,6H),0.61–0.07(m,3H).；13C-NMR(151MHz,CDCl3)δ55.87,50.70,15.01(d),5.77；Anal.calcdfor C12H33BNO3P:C 51.26,H 11.83,N 4.98；found:C 51.12,H 11.90,N 4.96。
本发明提供了一种基于基于膦硼阴离子的离子液体材料及其合成方法，获得了几种全新的绿色推进剂用离子液体，开拓了航天领域肼类燃料绿色替代物的可选范围。
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
本发明的具体详细的合成路线如下：
选用化合物亚磷酸酯(1)作为起始原料，与硼烷二甲硫醚溶液在室温下搅拌4小时得到化合物2；然后在醇溶液中用氢氧化钾(KOH)对2进行水解得到钾盐3；最后在乙腈溶液中与咪唑溴盐、吡咯溴盐和四丁基溴化铵离子交换得到新型离子液体4a-1–4a-6和4b-1–4b-6。
其中，化合物1-3的合成可以参考文献报道的方法，化合物4以及4a-1至4a-6以及4b-1至4b-6是本发明实施例获得的新化合物。
为了更详细的说明本发明的技术方案，下面对每一个具体步骤进行详细说明。
实施例2.化合物2a的合成
向250mL圆底烧瓶中加入亚磷酸三甲酯(24.8g,200mmol)和二氯甲烷(50mL),冰浴冷却，搅拌下滴加硼烷二甲硫醚溶液(10mol/L,21mL，200mmol),室温反应4小时，旋蒸除去溶剂和多余的二甲硫醚溶液，得到无色透明液体产物2a(26.2g,95％)。
实施例3.化合物2b的合成
将亚磷酸三甲酯替换为亚磷酸三乙酯，其他条件与实施例2相同，得到产物2b。
实施例4.化合物3a的合成
将化合物2a(20.7g,150mmol)加入甲醇中(100mL)，冰浴冷却，然后向溶液中加入氢氧化钾(8.3g，148mmol)，室温搅拌半小时，然后升温至60度反应5小时，旋蒸除去溶剂，向剩余物中加入石油醚搅拌半小时，过滤石油醚洗涤，干燥得到白色固体3a(22.9g,96％)。
实施例5.化合物3b的合成
将化合物2a替换为2b，其他同实施例4，得到白色固体3b。
实施例6.化合物4a-1–4a-6的合成
取六个100mL圆底烧瓶，在每个100mL圆底烧瓶中均加入3a(3.24g，20mmol)和乙腈(40mL),然后在六个100mL圆底烧瓶中分别加入1-乙基-3-甲基咪唑溴盐(3.82g，20mmol)，1-丁基-3-甲基咪唑溴盐(4.38g，20mmol)，1-乙基-1-甲基-吡咯溴盐(3.88g，20mmol)，1-丙基-1-甲基-吡咯溴盐(4.16g，20mmol)，1-丁基-1-甲基-吡咯溴盐(4.44g，20mmol)和四乙基溴化铵(4.2g，20mmol)，室温搅拌2天，过滤，旋蒸除去溶剂，得到无色液体产物4a-1–4a-6。
化合物4a-1，无色液体(4.21g,90％),1H-NMR(600MHz,CDCl3)δ9.99(s,1H),7.59–7.49(m,2H),4.35(q,J＝7.4Hz,2H),4.04(s,3H),3.53(d,J＝10.3Hz,6H),1.58(t,J＝7.4Hz,3H),0.61–0.08(m,3H)；13C-NMR(151MHz,CDCl3)δ135.82,121.71,119.95,47.69(d),43.08,34.43,13.62；Anal.calcd for C8H20BN2O3P:C 41.06,H 8.61,N 11.97；found:C40.91,H 8.72,N 11.89。
化合物4a-2，无色液体(4.82g,92％),1H-NMR(600MHz,CDCl3)δ10.09(s,1H),7.54–7.38(m,2H),4.27(t,J＝7.4Hz,2H),4.04(s,3H),3.54(d,J＝10.3Hz,6H),1.93–1.85(m,2H),1.42–1.35(m,2H),0.96(t,J＝7.4Hz,3H),0.60–0.09(m,3H)；13C-NMR(151MHz,CDCl3)δ138.42,123.51,121.94,49.71(d),36.47,32.13,19.46,13.44；Anal.calcd forC10H24BN2O3P:C 45.83,H 9.23,N 10.69；found:C 45.70,H 9.31,N 10.58。
化合物4a-3，无色液体(4.17g,88％),1H-NMR(600MHz,CDCl3)δ3.71–3.61(m,6H),3.51(d,J＝10.2Hz,6H),3.17(s,3H),2.36–2.20(m,4H),1.44(t,J＝7.2Hz,3H),0.58–0.05(m,3H)；13C-NMR(151MHz,CDCl3)δ63.88,59.44,49.58(d),47.92,21.63,9.50；Anal.calcdfor C9H25BNO3P:C 45.59,H 10.63,N5.91；found:C 45.25,H 10.74,N 5.85.
化合物4a-4，无色液体(4.57g,91％),,colorless liquid,91％yield；1H-NMR(600MHz,CDCl3)δ3.74–3.65(m,4H),3.55–3.43(m,8H),3.19(s,3H),2.34–2.23(m,4H),1.94–1.80(m,2H),1.05(t,J＝7.4Hz,3H),0.63–-0.03(m,3H)；13C-NMR(151MHz,CDCl3)δ65.33,64.06,49.21(d),48.14,21.33,17.21,10.54；Anal.calcd for C10H27BNO3P:C47.83,H 10.84,N 5.58；found:C 47.77,H 10.90,N 5.54.
化合物4a-5，无色液体(4.93g,93％),1H-NMR(600MHz,CDCl3)δ3.74–3.66(m,4H),3.49(d,J＝10.3Hz,6H),3.19(s,3H),2.33–2.25(m,4H),1.83–1.75(m,2H),1.49–1.41(m,2H),1.00(t,J＝7.4Hz,3H),0.64–-0.06(m,3H)；13C-NMR(101MHz,CDCl3)δ64.08,63.80,49.27,49.25(d),25.63,21.35,19.44,13.44；Anal.calcd for C11H29BNO3P:C 49.83,H11.03,N 5.28；found:C 49.61,H 11.11,N 5.23。
化合物4a-6，无色液体(4.25g,84％),,1H-NMR(600MHz,CDCl3)δ3.47(d,J＝10.3Hz,6H),3.38(q,7.3Hz,8H),1.36(t,J＝7.3Hz,12H),0.52–0.00(m,3H)；13C-NMR(151MHz,CDCl3)δ50.64,47.36(d),5.72；Anal.calcd for C10H29BNO3P:C 47.45,H 11.55,N5.53；found:C 47.25,H 11.60,N 5.50。
实施例7.化合物4b-1–4b-6的合成方法
取六个100mL圆底烧瓶，在每个100mL圆底烧瓶中均加入3b(3.80g，20mmol)和乙腈(40mL),然后在六个100mL圆底烧瓶中分别加入1-乙基-3-甲基咪唑溴盐(3.82g，20mmol)，1-丁基-3-甲基咪唑溴盐(4.38g，20mmol)，1-乙基-1-甲基-吡咯溴盐(3.88g，20mmol)，1-丙基-1-甲基-吡咯溴盐(4.16g，20mmol)，1-丁基-1-甲基-吡咯溴盐(4.44g，20mmol)和四乙基溴化铵(4.2g，20mmol)，室温搅拌2天，过滤，旋蒸除去溶剂，得到无色液体产物。
化合物4b-1，无色液体(4.72g,90％),1H-NMR(600MHz,CDCl3)δ10.34(s,1H),7.45–7.34(m,2H),4.35(q,J＝7.4Hz,2H),4.03(s,3H),3.97–3.88(m,4H),1.57(t,J＝7.4Hz,3H),1.23(t,J＝7.1Hz,6H),0.60–0.10(m,3H)；13C-NMR(151MHz,CDCl3)δ138.77,123.33,121.42,58.10(d),45.09,36.51,16.88(d),15.57；Anal.calcd for C10H24BN2O3P:C 45.83,H 9.23,N 10.69；found:C 45.70,H 9.28,N 10.61.
化合物4b-2，无色液体(5.34g,92％),,1H-NMR(600MHz,CDCl3)δ10.41(s,1H),7.36(s,1H),7.28(s,1H),4.28(t,J＝7.4Hz,2H),4.04(s,3H),3.96–3.90(m,4H),1.94–1.84(m,2H),1.42–1.34(m,2H),1.24(t,J＝7.1Hz,6H),0.96(t,J＝7.4Hz,3H),0.61–0.10(m,3H)；13C-NMR(151MHz,CDCl3)δ139.31,123.10,121.49,58.09(d),49.74,36.53,32.11,19.46,16.85(d),13.41；Anal.calcd for C12H28BN2O3P:C 49.67,H 9.73,N 9.65；found:C 49.45,H 9.80,N 9.59.
化合物4b-3，无色液体(4.82g,91％),1H-NMR(600MHz,CDCl3)δ3.92–3.83(m,4H),3.73–3.63(m,6H),3.19(s,3H),2.33–2.24(m,4H),1.44(t,J＝7.2Hz,3H),1.22(t,J＝7.1Hz,6H),0.60–0.06(m,3H)；13C-NMR(151MHz,CDCl3)δ63.87,59.37,57.88(d),47.97,21.63,16.89(d),9.52；Anal.calcd for C11H29BNO3P:C 49.83,H 11.03,N 5.28；found:C49.67,H 11.09,N 5.24。
化合物4b-4，无色液体(4.97g,89％),,1H-NMR(600MHz,CDCl3)δ3.93–3.84(m,4H),3.76–3.65(m,4H),3.53–3.42(m,2H),3.20(s,3H),2.36–2.22(m,4H),1.96–1.74(m,2H),1.22(t,J＝7.1Hz,6H),1.05(t,J＝7.3Hz,3H),0.58–0.07(m,3H)；13C-NMR(151MHz,CDCl3)δ65.57,64.33,57.86(d),21.60,17.46,16.87(d),10.77；Anal.calcd for C12H31BNO3P:C51.63,H 11.19,N 5.02；found:C 51.50,H 11.21,N 4.99。
化合物4b-5，无色液体(5.44g,92％),,1H-NMR(600MHz,CDCl3)δ3.92–3.84(m,4H),3.76–3.65(m,4H),3.53–3.48(m,2H),3.20(s,3H),2.36–2.22(m,4H),1.84–1.70(m,2H),1.51–1.40(m,2H),1.22(t,J＝7.1Hz,6H),0.99(t,J＝7.4Hz,3H),0.60–0.06(m,3H)；13C-NMR(151MHz,CDCl3)δ64.33,63.99,57.84(d),48.58,25.89,21.61,19.69,16.88(d),13.64；Anal.calcd for C13H33BNO3P:C 53.26,H 11.35,N 4.78；found:C 53.10,H 11.39,N4.76.
化合物4b-6，无色液体(4.78g,85％),1H-NMR(600MHz,CDCl3)δ3.91–3.85(m,4H),3.39(q,J＝7.3Hz,8H),1.35(t,J＝7.3Hz,12H),1.22(t,J＝7.1Hz,6H),0.61–0.07(m,3H)；13C-NMR(151MHz,CDCl3)δ55.87,50.70,15.01(d),5.77；Anal.calcd for C12H33BNO3P:C51.26,H 11.83,N 4.98；found:C 51.12,H11.90,N 4.96。
尽管这里参照本发明的解释性实施例对本发明进行了描述，上述实施例仅为本发明较佳的实施方式，本发明的实施方式并不受上述实施例的限制，应该理解，本领域技术人员可以设计出很多其他的修改和实施方式，这些修改和实施方式将落在本申请公开的原则范围和精神之内。

Claims (4)

1.基于膦硼阴离子的离子液体的合成方法，其特征在于包括如下步骤：
用硼烷和亚磷酸酯络合得到硼烷磷酸酯，即
经过氢氧化钾水解得到硼烷磷酸酯单钾盐
再与咪唑溴盐、吡咯溴盐和四丁基溴化铵离子交换，得到各种基于膦硼阴离子的离子液体；当R为甲基时离子液体是当R为乙基时离子液体是
其中，Cat+是
2.基于膦硼阴离子的离子液体，其特征在于：是通过权利要求1所述基于膦硼阴离子的离子液体的合成方法制备得到的。
3.根据权利要求2所述基于膦硼阴离子的离子液体，其特征在于：所述离子液体具有如下结构：
其中，R是甲基或乙基，Cat+是
4.根据权利要求3所述基于膦硼阴离子的离子液体，其特征在于：
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ9.99(s,1H),7.59–7.49(m,2H),4.35(q,J＝7.4Hz,2H),4.04(s,3H),3.53(d,J＝10.3Hz,6H),1.58(t,J＝7.4Hz,3H),0.61–0.08(m,3H)；13C-NMR(151MHz,CDCl3)δ135.82,121.71,119.95,47.69(d),43.08,34.43,13.62；Anal.calcd for C8H20BN2O3P:C 41.06,H 8.61,N11.97；found:C 40.91,H 8.72,N 11.89；
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ10.09(s,1H),7.54–7.38(m,2H),4.27(t,J＝7.4Hz,2H),4.04(s,3H),3.54(d,J＝10.3Hz,6H),1.93–1.85(m,2H),1.42–1.35(m,2H),0.96(t,J＝7.4Hz,3H),0.60–0.09(m,3H)；13C-NMR(151MHz,CDCl3)δ138.42,123.51,121.94,49.71(d),36.47,32.13,19.46,13.44；Anal.calcd for C10H24BN2O3P:C 45.83,H 9.23,N 10.69；found:C 45.70,H 9.31,N10.58；
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.71–3.61(m,6H),3.51(d,J＝10.2Hz,6H),3.17(s,3H),2.36–2.20(m,4H),1.44(t,J＝7.2Hz,3H),0.58–0.05(m,3H)；13C-NMR(151MHz,CDCl3)δ 63.88,59.44,49.58(d),47.92,21.63,9.50；Anal.calcd for C9H25BNO3P:C 45.59,H 10.63,N 5.91；found:C 45.25,H10.74,N 5.85；
当R是甲基，Cat+是时，离子液体为无色液体,colorless liquid,91％yield；1H-NMR(600MHz,CDCl3)δ3.74–3.65(m,4H),3.55–3.43(m,8H),3.19(s,3H),2.34–2.23(m,4H),1.94–1.80(m,2H),1.05(t,J＝7.4Hz,3H),0.63–-0.03(m,3H)；13C-NMR(151MHz,CDCl3)δ65.33,64.06,49.21(d),48.14,21.33,17.21,10.54；Anal.calcd forC10H27BNO3P:C 47.83,H 10.84,N 5.58；found:C 47.77,H 10.90,N 5.54；
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.74–3.66(m,4H),3.49(d,J＝10.3Hz,6H),3.19(s,3H),2.33–2.25(m,4H),1.83–1.75(m,2H),1.49–1.41(m,2H),1.00(t,J＝7.4Hz,3H),0.64–-0.06(m,3H)；13C-NMR(101MHz,CDCl3)δ64.08,63.80,49.27,49.25(d),25.63,21.35,19.44,13.44；Anal.calcd for C11H29BNO3P:C 49.83,H 11.03,N 5.28；found:C 49.61,H 11.11,N 5.23；
当R是甲基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.47(d,J＝10.3Hz,6H),3.38(q,7.3Hz,8H),1.36(t,J＝7.3Hz,12H),0.52–0.00(m,3H)；13C-NMR(151MHz,CDCl3)δ50.64,47.36(d),5.72；Anal.calcd for C10H29BNO3P:C 47.45,H 11.55,N5.53；found:C 47.25,H 11.60,N 5.50；
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ10.34(s,1H),7.45–7.34(m,2H),4.35(q,J＝7.4Hz,2H),4.03(s,3H),3.97–3.88(m,4H),1.57(t,J＝7.4Hz,3H),1.23(t,J＝7.1Hz,6H),0.60–0.10(m,3H)；13C-NMR(151MHz,CDCl3)δ138.77,123.33,121.42,58.10(d),45.09,36.51,16.88(d),15.57；Anal.calcd forC10H24BN2O3P:C 45.83,H 9.23,N 10.69；found:C 45.70,H 9.28,N 10.61；
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ10.41(s,1H),7.36(s,1H),7.28(s,1H),4.28(t,J＝7.4Hz,2H),4.04(s,3H),3.96–3.90(m,4H),1.94–1.84(m,2H),1.42–1.34(m,2H),1.24(t,J＝7.1Hz,6H),0.96(t,J＝7.4Hz,3H),0.61–0.10(m,3H)；13C-NMR(151MHz,CDCl3)δ139.31,123.10,121.49,58.09(d),49.74,36.53,32.11,19.46,16.85(d),13.41；Anal.calcd for C12H28BN2O3P:C 49.67,H 9.73,N9.65；found:C 49.45,H 9.80,N 9.59；
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.92–3.83(m,4H),3.73–3.63(m,6H),3.19(s,3H),2.33–2.24(m,4H),1.44(t,J＝7.2Hz,3H),1.22(t,J＝7.1Hz,6H),0.60–0.06(m,3H)；13C-NMR(151MHz,CDCl3)δ63.87,59.37,57.88(d),47.97,21.63,16.89(d),9.52；Anal.calcd for C11H29BNO3P:C 49.83,H 11.03,N5.28；found:C 49.67,H 11.09,N 5.24；当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ 3.93–3.84(m,4H),3.76–3.65(m,4H),3.53–3.42(m,2H),3.20(s,3H),2.36–2.22(m,4H),1.96–1.74(m,2H),1.22(t,J＝7.1Hz,6H),1.05(t,J＝7.3Hz,3H),0.58–0.07(m,3H)；13C-NMR(151MHz,CDCl3)δ65.57,64.33,57.86(d),21.60,17.46,16.87(d),10.77；Anal.calcd for C12H31BNO3P:C 51.63,H 11.19,N 5.02；found:C51.50,H 11.21,N 4.99；
当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ3.92–3.84(m,4H),3.76–3.65(m,4H),3.53–3.48(m,2H),3.20(s,3H),2.36–2.22(m,4H),1.84–1.70(m,2H),1.51–1.40(m,2H),1.22(t,J＝7.1Hz,6H),0.99(t,J＝7.4Hz,3H),0.60–0.06(m,3H)；13C-NMR(151MHz,CDCl3)δ64.33,63.99,57.84(d),48.58,25.89,21.61,19.69,16.88(d),13.64；Anal.calcd for C13H33BNO3P:C 53.26,H 11.35,N 4.78；found:C 53.10,H 11.39,N 4.76；当R是乙基，Cat+是时，离子液体为无色液体,1H-NMR(600MHz,CDCl3)δ 3.91–3.85(m,4H),3.39(q,J＝7.3Hz,8H),1.35(t,J＝7.3Hz,12H),1.22(t,J＝7.1Hz,6H),0.61–0.07(m,3H).；13C-NMR(151MHz,CDCl3)δ55.87,50.70,15.01(d),5.77；Anal.calcd for C12H33BNO3P:C 51.26,H 11.83,N 4.98；found:C 51.12,H 11.90,N 4.96。
CN201810421650.1A 2018-05-04 2018-05-04 基于磷硼阴离子的离子液体及其合成方法 Active CN108676027B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810421650.1A CN108676027B (zh) 2018-05-04 2018-05-04 基于磷硼阴离子的离子液体及其合成方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810421650.1A CN108676027B (zh) 2018-05-04 2018-05-04 基于磷硼阴离子的离子液体及其合成方法

Publications (2)

Publication Number Publication Date
CN108676027A true CN108676027A (zh) 2018-10-19
CN108676027B CN108676027B (zh) 2020-07-07

Family

ID=63802830

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810421650.1A Active CN108676027B (zh) 2018-05-04 2018-05-04 基于磷硼阴离子的离子液体及其合成方法

Country Status (1)

Country Link
CN (1) CN108676027B (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005072062A2 (en) * 2004-02-02 2005-08-11 Bar-Ilan University Inorganic boranophosphate salts
WO2005085272A1 (ja) * 2004-03-05 2005-09-15 Takeshi Wada ボラノホスフェートモノマーおよびそれを用いたオリゴヌクレオチド誘導体の製造方法
WO2011005860A2 (en) * 2009-07-07 2011-01-13 Alnylam Pharmaceuticals, Inc. 5' phosphate mimics

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005072062A2 (en) * 2004-02-02 2005-08-11 Bar-Ilan University Inorganic boranophosphate salts
WO2005085272A1 (ja) * 2004-03-05 2005-09-15 Takeshi Wada ボラノホスフェートモノマーおよびそれを用いたオリゴヌクレオチド誘導体の製造方法
WO2011005860A2 (en) * 2009-07-07 2011-01-13 Alnylam Pharmaceuticals, Inc. 5' phosphate mimics

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAZUKI SATO ET AL: ",2- Trans-Selective Synthesis of Glycosyl Boranophosphates and Their Utility as Building Blocks for the Synthesis of Phosphodiester-Linked Disaccharides", 《J. ORG. CHEM.》 *
MAMORU SHIMIZU ET AL: "Solid-phase Synthesis of Oligodeoxyribonucleoside Boranophosphates by the Boranophosphotriester Method", 《J. ORG. CHEM.》 *

Also Published As

Publication number Publication date
CN108676027B (zh) 2020-07-07

Similar Documents

Publication Publication Date Title
US3032584A (en) p-bis-(2-chloroethyl) aminophenylalanine and the process for the production thereof
Krakowiak et al. Preparation of triaza-, tetraaza-and peraza-crown compounds containing aminoalkyl side groups or unsubstituted ring nitrogen atoms
KR20100092938A (ko) 플루오로알킬기 유도체를 함유하는 겔화제
ES2856268T3 (es) Proceso para preparar (9E,11Z)-9,11-hexadecadienal
CN108676027A (zh) 基于膦硼阴离子的离子液体及其合成方法
CN105884626B (zh) 一种2‑氨基茚满衍生物的合成方法及其产品
CH641671A5 (it) Processo per la preparazione dell'acido 2-(6'-metossi-2'-naftil)-propionico.
Asano et al. The Synthesis of α-Amino Phosphonic Acids
Quin et al. Synthesis of Unsymmetrical Diarylphosphinous Chlorides and Their Conversion to Secondary Phosphine Oxides1, 2
US4427599A (en) Method for preparation of N-phosphonomethylglycine
US2460144A (en) Hydroxyphenyl alkanolamines
Drake et al. The Mercuration of 5-Nitroguaiacol1, 2
EP0694526B1 (en) Process for preparation of fluorinated beta-keto ester
US3660460A (en) Process for preparing n n-bis-cyanoethylated derivatives of aliphatic primary amine branched at the alpha-position
EP0174844B1 (en) Method for production of alpha-aryl-alkanoic acid
Cheng et al. A new synthesis of hordenine and other p-dialkylaminoethylphenols and some of their derivatives
SHECHTER et al. Addition reactions of trinitromethane and α, β-unsaturated ethers
Savignac et al. α-Cuprophosphonates. V. The Reaction of 3 and 4-Oxoalkane Phosphonates and Their Use in Aminoalkanephosphonic Acids Synthesis
DE2264903C3 (de) Piperidinderivate und ihre Herstellung
JPH0710813A (ja) α−フェネチルアミン化合物の光学分割法
CN108299239A (zh) 一种1，6-（对脒基苯基）己二醚新的合成方法
WATANABE The Chemical Structure of the Intermediate Metabolites of Catechin. III Synthesis of the Intermediate Metabolites (G and H)
CN108440287B (zh) 一种制备2-[4-(2-乙氧基乙基)-2,3-二甲基苯氧基]乙基胺的方法
US3718684A (en) Method for synthesizing alpha-haloacrylonitrile acid
JP2001261595A (ja) 光学活性１，３−プロパンジオール類の製造方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant