CN111138465B - 1-硼烷基甲基-6-芳基-3-苯磺酰基-3-氮杂双环己烷衍生物的合成方法 - Google Patents
1-硼烷基甲基-6-芳基-3-苯磺酰基-3-氮杂双环己烷衍生物的合成方法 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
- C07F5/025—Boronic and borinic acid compounds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种1‑硼烷基甲基‑6‑芳基‑3‑苯磺酰基‑3‑氮杂双环己烷衍生物的合成方法,以N‑炔丙基‑N‑(3‑芳基烯丙基)苯磺酰胺衍生物为原料,以二价钯为催化剂,联硼酸频那醇酯为硼试剂,合成得到目标产物,并对目标产物的结构通过IR、1H NMR、13C NMR和HRMS等方法进行了表征和分析。该方法具有原料易得、操作简单、后续处理方便等优点。
Description
技术领域
本发明属于有机合成领域,特别涉及一种1-硼烷基甲基-6-芳基-3-苯磺酰基-3-氮杂双环[3.1.0]己烷衍生物的简便合成方法。
背景技术
有机硼化合物在现代有机合成化学中起着举足轻重的作用,其广泛作为基本碳亲核体用于官能团的引入和碳-硼键形成过程。它们优于其他有机金属的特性表现在:1)其对氧气和水分的不敏感而易于操作;2)低毒性;3)具有高官能团相容性等。Suzuki-Miyaura交叉偶联反应的最新进展允许使用烷基硼烷或烷基三氟硼酸盐作为亲核试剂。烷基硼酸酯的合成通常通过烯烃的氢硼化或主要有机金属衍生物与硼酸酯的反应来完成。在后一种情况下,反应显示出较低的官能团相容性。最近,烷烃的C-H活化使得可以制备伯烷基硼酸酯。通常用于形成芳基和烯基硼衍生物的双(硼)化合物的Pd 催化反应尚未应用于烷基硼酸或其衍生物的制备,这对于我们来说具有一定的挑战性。
在已有的报道中,我们仅发现一例关于此类相似反应的合成。文献(Macro-Martinez J,Lopez-Carrillo V,Bunuel E,et al.Pd-Catalyzed BorylativeCyclization of 1,6-Enynes.J. Am.Chem.Soc.2007,129,7,1874-1875)以1,6-烯炔类化合物为原料,醋酸钯为催化剂,在甲苯溶剂中,50℃下反应,得到了相似的双环[3.1.0]己烷。此方法反应所得到的产物多为五元单环类硼化物,仅有两个底物得到了相似的双环[3.1.0]己烷。该反应中,底物适用性较差,产率较低,使得产物不能够多样化,很难用于工业生产。
发明内容
本发明的目的是提供一种简便合成1-硼烷基甲基-6-芳基-3-苯磺酰基-3-氮杂双环
[3.1.0]己烷衍生物的方法。
实现本发明目的的技术方案是:一种合成1-硼烷基甲基-6-芳基-3-苯磺酰基-3-氮杂双环[3.1.0]己烷衍生物的方法,将N-炔丙基-N-(3-芳基烯丙基)苯磺酰胺衍生物、硼试剂联硼酸频那醇酯、添加剂和钯催化剂加入到溶剂中,一定温度下进行搅拌,TLC监测反应进程,待反应完全后经柱层析分离提纯得到目标产物,
其中,R为甲苯磺酰基;Ar为芳基,如:3-甲基苯基、4-氯苯基、4-甲基苯基等。
进一步的,钯催化剂选自氯化烯丙基钯二聚物、二氯化钯(PdCl2)、1,1'-双二苯基膦二茂铁二氯化钯(PdCl2(dppf))、乙酰丙酮钯(Pd(acac)2)和醋酸钯(Pd(OAc)2)中任意一种,优选乙酰丙酮钯(Pd(acac)2)。
进一步的,钯催化剂用量为N-炔丙基-N-(3-芳基烯丙基)苯磺酰胺衍生物的1~20mol%,优选5mol%。
进一步的,添加剂选自冰醋酸、碳酸铯、硫酸钠、甲醇、甲酸中任意一种,优选冰醋酸。
进一步的,反应体系溶剂选自1,2-二氯乙烷(DCE)、甲苯(Toluene)、乙酸乙酯(EtOAc)、四氢呋喃(THF)、丙酮(acetone)、乙醇(EtOH)和乙腈(MeCN)中任意一种,优选1,2-二氯乙烷(DCE)。
进一步的,N-炔丙基-N-(3-芳基烯丙基)苯磺酰胺衍生物:硼试剂:添加剂的摩尔比例为1:1.2~3.0:1.0~3.0。
进一步的,反应温度为20~60℃,优选40℃。
与现有技术相比,本发明的优点和效果在于:(1)本发明对反应环境中氧气,水的含量要求不高;(2)本发明不需要高温,在室温条件下进行反应,且使用的催化剂用量少,而产率较高,符合绿色环保理念;(3)本发明操作简单方便,安全可靠,具有潜在的工业生产价值。
具体实施方式
实施例1
称取4-甲基-N-炔丙基-N-(3-间甲苯基烯丙基)苯磺酰胺68.0mg(0.2mmol)、硼试剂联硼酸频那醇酯67.0mg(0.24mmol),乙酰丙酮钯3.0mg(5mol%),冰醋酸11μL(0.2mmol)于10mL的无色透明反应管中,加入2mL 1,2-二氯乙烷溶剂,然后在氮气保护,40℃下搅拌反应,TLC检测反应进度,约18h待反应完全后,经柱层析分离提纯(石油醚: 乙酸乙酯=9:1),得到白色固体,即为产物1,产率:77%。
产物1的结构表征如下:
白色固体;1H NMR(400MHz,CDCl3)δ7.73(d,J=7.9Hz,2H),7.34(d,J=7.7Hz,2H),7.12(t,J=7.5Hz,1H),6.96(d,J=7.3Hz,1H),6.88(s,1H),6.83(d,J=7.4Hz,1H),3.73(d,J=9.1Hz,1H),3.66(d,J=8.9Hz,1H),3.25–3.16(m,1H),2.97(d,J=9.1Hz, 1H),2.44(s,3H),2.29(s,3H),2.12(s,1H),1.25(d,J=7.7Hz,1H),1.05(s,6H),1.04(s, 6H),0.69(s,2H);13C NMR(CDCl3,100MHz)δ:143.2,137.4,133.4,129.7,129.5,127.9, 127.7,126.7,125.6,83.0,55.3,55.2,50.9,31.6,29.4,26.6,24.6,24.6,21.5,21.5,21.4,21.4。; IR(neat):ν=2979,2928,2861,1604,1350,1161,1102,968,812,667,590,548cm-1;HRMS (ESI)理论计算值[C26H34BNNaO4S]+[M+Na]+:490.2194,实际测量值:490.2239。
由以上数据可知,本发明成功地合成了化合物1-((4,4,5,5-四甲基-1,3,2-二氧杂硼硼烷-2-基)甲基)-6-(间甲苯基)-3-甲苯磺酰基-3-氮杂[3.1.0]己烷。
反应条件同实施例1,使用不同种类的催化剂,产物产率如下表1所示:
表1不同种类的催化剂时产物的产率
由上表可知,当其他反应条件不变,以乙酰丙酮钯为催化剂时产物的产率最高。
反应条件同实施例1,使用不同用量的催化剂时,产物产率如下表2所示:
表2不同当量的添加剂时产物的产率
催化剂(equiv) | 0.01 | 0.02 | 0.05 | 0.10 | 0.20 |
产率(%) | 42 | 51 | 77 | 65 | 61 |
由上表可知,当其他反应条件不变,使用0.05当量的催化剂时产物的产率最高。
反应条件同实施例1,当其他反应条件不变,改变硼试剂的用量,产物产率如下表3所示:
表3不同当量的硼试剂时产物的产率
硼试剂(equiv) | 0.6 | 1.0 | 1.2 | 1.5 | 2.0 | 3.0 |
产率(%) | 28 | 56 | 77 | 74 | 73 | 72 |
由上表可知,当其他反应条件不变,硼试剂的用量为1.2和1.5-3.0倍当量的时候产率相当,考虑经济性问题,所以选择1.2倍当量为最佳反应条件。
反应条件同实施例1,使用不同种类的添加剂,产物产率如下表4所示:
表4不同种类的添加剂时产物的产率
添加剂(1.0equiv) | 冰醋酸 | 硫酸钠 | 甲醇 | 碳酸铯 | 甲酸 |
产率(%) | 77 | <5% | 46 | <5% | 58 |
由上表可知,当其他反应条件不变,以冰醋酸为添加剂时产物的产率最高。
反应条件同实施例1,使用不同量的冰醋酸时,产物产率如下表5所示:
表5不同当量的添加剂时产物的产率
冰醋酸(equiv) | 0.8 | 1.0 | 1.5 | 2.0 | 3.0 |
产率(%) | 69 | 77 | 74 | 71 | 68 |
由上表可知,当其他反应条件不变,使用1.0倍当量的冰醋酸为添加剂时产物的产率最高。
反应条件同实施例1,使用不同种类的溶剂,产物产率如下表6所示:
表6不同种类的溶剂时产物的产率
由上表可知,当其他反应条件不变,溶剂为1,2-二氯乙烷时,产物的产率最高。
反应条件同实施例1,改变反应温度,产物产率如下表7所示:
表7不同反应温度时产物的产率
温度(℃) | 20 | 30 | 40 | 60 |
产率(%) | 61 | 70 | 77 | 75 |
由上表可知,当其他反应条件不变,温度为20-60℃时,产物产率均大于60%,其中,温度为40℃时,产物的产率较高。
实施例2
采用实施例1相同的方法和反应条件,当4-甲基-N-炔丙基-N-(3-苯基烯丙基)苯磺酰胺反应原料时,得到如下目标产物2,产率:79%。
产物2结构表征如下:
白色固体:1H NMR(400MHz,CDCl3)δ7.73(d,J=7.1Hz,2H),7.34(d,J=7.8Hz,2H),7.22(d,J=7.5Hz,2H),7.16(d,J=6.8Hz,1H),7.06(d,J=7.3Hz,2H),3.74(d,J=8.9Hz,1H),3.67(d,J=8.9Hz,1H),3.21(d,J=8.8Hz,1H),2.97(d,J=9.6Hz,1H),2.44(s,3H),2.18(s,1H),1.67(s,1H),1.05(s,6H),1.03(s,6H),0.69(s,2H).13C NMR(151 MHz,CDCl3)δ143.3,137.6,133.3,129.6,128.8,128.0,127.7,126.0,83.1,55.3,50.9,31.7,29.7,29.5,29.3,27.2,26.7,24.7,24.6,21.5.IR(neat):ν=3771,3655,2927,2855,1600,1350,1242 1152,1022,822,666cm-1;HRMS(ESI)理论计算值[C25H32BNO4S]+[M+Na]+:470.2037,实际测量值:470.2046.
实施例3
采用实施例1相同的方法和反应条件,当4-甲基-N-炔丙基-N-对氯苯基烯丙基苯磺酰胺反应原料时,得到如下目标产物3,产率:64%。
产物3结构表征如下:
白色液体:1H NMR(400MHz,CDCl3)δ7.72(d,J=7.6Hz,2H),7.34(d,J=7.6Hz,2H),7.20(d,J=8.0Hz,2H),7.00(d,J=7.9Hz,2H),3.73(d,J=9.1Hz,1H),3.67(d,J=8.8Hz,1H),3.18(d,J=7.7Hz,1H),2.93(d,J=9.2Hz,1H),2.43(s,3H),2.17(s,1H),1.62(s,1H),1.05(s,6H),1.03(s,6H),0.66(s,2H).13C NMR(101MHz,CDCl3)δ143.4,136.2,133.2,131.8,130.1,129.6,128.1,127.7,83.2,65.6,55.1,50.7,31.7,28.8,26.8,24.7,24.6, 21.5,19.2.IR(neat):ν=2978,2861,1489,1348,1158,1098,1020,826,663,595,546,531 cm-1;HRMS(ESI)理论计算值[C25H31BClNNaO4S]+[M+Na]+:510.1648,实际测量值:510.1658.
实施例4
采用实施例1相同的方法和反应条件,当4-甲基-N-炔丙基-N-(3-对甲苯基烯丙基)苯磺酰胺反应原料时,得到如下目标产物4,产率:73%。
产物4结构表征如下:
黄色固体:1H NMR(400MHz,CDCl3)δ7.72(d,J=7.8Hz,2H),7.33(d,J=7.8Hz,2H),7.04(d,J=7.6Hz,2H),6.94(d,J=7.7Hz,2H),3.72(d,J=9.1Hz,1H),3.66(d,J=8.8Hz,1H),3.20(d,J=5.4Hz,1H),2.96(d,J=9.1Hz,1H),2.43(s,3H),2.28(s,3H),2.13(s,1H),1.63(d,J=4.5Hz,1H),1.05(s,6H),1.03(s,6H),0.67(d,J=5.5Hz,2H).13C NMR(151MHz,CDCl3)δ143.3,140.3,139.7,136.4,133.5,129.6,129.0,128.6,128.5, 128.1,127.6,127.0,126.0,124.0,83.6,50.5,50.0,47.7,24.7,24.4,21.5.IR(neat):ν=2980,2864,1349,1159,1103,1026,967 821,746,665,601,549cm-1;HRMS(ESI)理论计算值[C26H34BNNaO4S]+[M+Na]+:490.2194,实际测量值:490.2236.
由以上数据可知,本发明成功地提供了一种合成1-硼烷基甲基-6-芳基-3-苯磺酰基 -3-氮杂双环[3.1.0]己烷衍生物的有效路径。
Claims (3)
2.如权利要求1所述的方法,其特征是,N-炔丙基-N-(3-芳基烯丙基)苯磺酰胺衍生物:联硼酸频那醇酯:添加剂的摩尔比例为1 : 1.2~3.0 : 1.0~3.0。
3.如权利要求1所述的方法,其特征是,反应温度为20~60 ℃。
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