CN105884570A - 含氟二芳基碘盐及其用途 - Google Patents
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Abstract
本发明涉及一种含氟二芳基碘盐及其制备方法和用途。所述含氟二芳基碘盐具有式Ⅰ所示结构,且其作为芳基化试剂。本发明提供的含氟二芳基碘盐具有易于制备及其用于芳基化反应时,芳基化反应的条件较为温和及芳基化产物的选择性好等优点。式Ⅰ中,R1为芳环基或芳杂环基,或取代的芳环基或芳杂环基;Y为一价的有机或无机酸根离子。
Description
技术领域
本发明涉及一种含氟二芳基碘盐及其制备方法和用途,具体地说,涉及一种含五氟苯基的二芳基碘盐及其制备方法和用途。
背景技术
二芳基碘盐被公认为一种良好的芳基化试剂,广泛应用于有机(特别是药物)合成中(Eleanor A.Merritt,Berit Olofsson.Diaryliodonium Salts:A Journey fromObscurity to Fame,Angew.Chem.Int.Ed.2009,48,9052–9070.)。
然而,现有二芳基碘盐(特别是含氟的二芳基碘盐)存在的不足是:①难于制备,②用于芳基化反应时,芳基化反应的条件较为苛刻及芳基化产物的选择性较差。
鉴于此,提供一种易于制备、且在芳基化反应时,反应条件温和及芳基化产物的选择性好的二芳基碘盐成为本发明需要解决的技术问题。
发明内容
本发明一个目的在于,提供一种结构新颖的含氟二芳基碘盐,克服现有技术存在的缺陷。
本发明所述的含氟二芳基碘盐,其为式Ⅰ所示化合物:
式Ⅰ中,R1为芳环基或芳杂环基,或取代的芳环基或芳杂环基;Y为一价的有机或无机酸根离子。
本发明另一个目的在于,揭示上述式Ⅰ所示化合物一种用途。即:式Ⅰ所示化合物作为芳基化试剂的应用。
此外,本发明还有一个目的在于,提供一种制备式Ⅰ所示化合物的方法,所述方法包括如下步骤:
(1)由五氟碘苯(式Ⅱ所示化合物)经氧化反应,制备式Ⅲ所示化合物的步骤;
(2)由式Ⅲ所示化合物制备式Ⅳ所示化合物的步骤;及
(3)由式Ⅳ所示化合物与取代或未取代的芳环烃或芳杂环烃(R1H)于含氟有机溶剂中反应,得到目标化合物(式Ⅰ所示化合物)的步骤。
其中,R1和Y的定义与前文所述相同。
具体实施方式
在本发明一个优选的技术方案中,R1为C4~C10的芳环基或芳杂环基,或取代的C4~C10的芳环基或芳杂环基;
其中,所述的芳杂环基的杂原为氧(O)或/和硫(S),杂原子数为1或2;
所述取代的C4~C10的芳环基或芳杂环基的取代基选自:C1~C6烷基,C1~C6烷氧基,卤素(F、Cl、Br或I),或中一种或两种以上(含两种),取代基个数为1~5的整数,曲线标记处为取代位(下同)。
在进一步优选的技术方案中,R1为噻吩基,苯基,取代苯基或萘基;
所述取代苯基的取代基选自:C1~C3烷基,C1~C3烷氧基,卤素(F、Cl、Br或I),或中一种或两种以上(含两种),取代基个数为1~3的整数。
在更进一步的优选的技术方案中,R1为噻吩基,苯基,取代苯基或萘基;
所述取代苯基的取代基选自:甲基,乙基,正丙基,异丙基,甲氧基,F,Cl,Br,或中一种或两种以上(含两种),取代基个数为1~3的整数。
本发明推荐的R1为下列基团中一种:
在本发明另一个优选技术方案中,所述一价的有机或无机酸根离子包括(但不限于):对甲苯磺酸根阴离子(OTs),F,Cl,Br,四氟硼酸根阴离子(BF4 -),三氟甲磺酸根阴离子(OTf),十二烷基苯磺酸根阴离子(ABS),ClO4 -,三氟乙酸根阴离子(CF3COO-)或HSO4 -等。
下面通过实施例对本发明作进一步阐述,目的仅在于更好理解本发明的内容。所举之例不限制本发明的保护范围。
实施例中所述常温或室温为15℃~25℃。
实施例1
(1)三氟乙酸五氟碘苯(式Ⅲ所示化合物)的合成:
五氟碘苯(1.47g,5mmol,1equiv.),5ml~10ml氯仿和三氟乙酸(15ml,400equiv.)置于反应器中,搅拌10-30min,温度降低至0℃,分批加入过一硫酸氢钾复合盐(Oxone)(4.61g,7.5mmol,1.5equiv.),加毕,升温至室温,在室温条件下,搅拌1-10h,过滤,用二氯甲烷洗涤滤饼(3×20ml),合并滤液,经蒸除去溶剂及干燥,得到2.39g淡黄色固体(式Ⅲ所示化合物),Mp:95.5-96.5℃,产率92%。
19F NMR(300MHz,DMSO-d6):δ-73.9(s),-123.6(s),-144.8(s),-157.3(s).
13C NMR(125.6MHz,DMSO-d6):δ159.7(q,JCF=37Hz),148.2(m),146.3(m),138.2(m),136.2(m),115.6(q,JCF=289Hz).
(2)五氟碘苯Koser盐(式Ⅳ-1所示化合物)的合成
将一水合对甲苯磺酸(1.21g,6.35mmol,1.5equiv.)和20ml乙腈置于反应器中,在0℃条件下,分批将式Ⅲ所示化合物(2.20g,4.23mmol,1equiv.)加入该反应器中,加毕,升温至室温,搅拌至有白色固体析出,继续搅拌2h,过滤,并用乙腈洗涤滤饼(2×10ml),将滤饼干燥后,得到1.96g五氟碘苯的Koser盐(式Ⅳ-1所示化合物),Mp:160℃,产率96%。
1H NMR(500MHz,CD3CN/DMSO-d6,20:1):δ=7.57(d,J=8.7Hz,2H),7.24(d,J=8.7Hz,2H),2.39(s,3H).
13C NMR(125.6MHz,CDCl3/DMSO-d6,24:1):δ=141.1,140.4,128.8,125.9,21.3.
19F NMR(282MHz,CD3CN/DMSO-d6,20:1):δ=-120.5(s),-153.9(s),-160.4(s).
(3)目标化合物的制备:
将式Ⅳ-1所示化合物(2.41g,5mmol,1equiv.)和20ml六氟异丙醇或六氟异丙醇与二氯甲烷等体积混合物置于反应器中,将1,3,5-三甲基苯(5mmol,1equiv.)该反应器中,搅拌1~5min,再加入20ml甲醇,随后除去溶剂,再加入50ml乙醚,搅拌10-30min,沉淀析出,过滤,滤饼经用乙醚洗涤(3×10ml)及干燥后,得到2.63g白色固体(式Ⅰ-1所示化合物),产率90%,Mp:162℃。
1H NMR(300MHz,DMSO-d6):δ=2.33(s,3H),2.36(s,3H),2.68(s,6H,),7.18-7.21(m,4H,),7.58(d,J=7.8Hz,2H).
13C NMR(125.7MHz,DMSO-d6):δ=21.0,21.3,26.9,123.3,126.8,129.8,131.4,141.8,143.3,143.9,146.4,154.6,154.9,155.0,155.2.
实施例2
根据实施例1的教导,除采用不同酸(如:三氟甲磺酸、十二烷基苯磺酸、HCl、H2SO4或四氟硼酸等)替换实施例1步骤(2)一水合对甲苯磺酸,或/和不同的取代或未取代的芳环烃或芳杂环烃(如:甲氧基苯、溴苯、氟苯、噻吩、对二甲苯、间二甲苯、邻二甲苯、苯、甲苯、萘或1,3,5-三异丙基苯等替换实施例1步骤(3)中1,3,5-三甲基苯外,其它步骤与条件与实施例1相似。可制得表1所示化合物。
表1
续表1
芳基化反应实施例
实施例3
含五氟苯基二芳基碘盐(化合物Ⅰ-1)与苯甲酸的反应:
将化合物Ⅰ-1(0.584g,1mmol),苯甲酸(0.122g,1mmol),醋酸银(0.167g,1mmol)和四氢呋喃(5ml)置于反应器中,在40℃状态保持2-4个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=10/1),得0.216克苯甲酸均三甲苯酯,产率为90%。
1H NMR(400MHz,CDCl3)δ:8.27–8.25(m,2H),7.68–7.64(m,1H),7.56–7.52(m,2H),6.93(s,2H),2.31(s,3H),2.17(s,6H);
13C NMR(100MHz,CDCl3)δ:164.7,146.3,135.5,133.7,130.3,130.0,129.6,129.4,128.8,21.0,16.5。
对比例1
T.B.Petersen,R.Khan,B.Olofsson报道的方法(Org.Lett,2011,13,3462–3465):
将化合物A(0.536g,1mmol),苯甲酸(0.122g,1mmol),叔丁醇钾(0.112g,1mmol)和甲苯(5ml)置于反应器中,在120℃状态下回流1小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=10/1),得0.230克苯甲酸均三甲苯酯,产率为96%。
实施例4
含五氟苯基二芳基碘盐(化合物Ⅰ-1)与苯硼酸的反应:
将化合物Ⅰ-1(0.584g,1mmol),苯硼酸(0.122g,1mmol),醋酸钯(0.022g,0.1mmol),三乙胺(0.101g,1mmol)和四氢呋喃(5ml)置于反应器中,在60℃状态保持2-4个小时,蒸除溶剂,残余物经柱层析分离(石油醚),得0.167克2,4,6-三甲基联苯,产率为85%。
1H-NMR(400MHz,CDCl3)δ:7.38-7.43(m,2H),7.30-7.34(m,1H),7.12-7.15(d,2H),6.94(s,2H),2.33(s,3H),2.00(s,6H).
13C NMR(100MHz,CDCl3),δ:141.11,139.07,136.55,135.97,129.31,128.36,128.05,126.50,21.02,20.73.
实施例5
含五氟苯基二芳基碘盐(化合物Ⅰ-15)与苯乙炔的反应:
将化合物Ⅰ-15(0.556g,1mmol),苯乙炔(0.102g,1mmol),无水硫酸铜(0.016g,0.1mmol),叠氮化钠(0.065g,1mmol)和乙腈(5ml)置于反应器中,在常温下反应2-4个小时,蒸除溶剂,残余物经柱层析分离出(石油醚/乙酸乙酯=10/1),得到0.212克产物,产率为90%。
1H NMR(500MHz,CDCl3)δ:8.15(s,1H),7.81-7.78(m,4H),7.56-7.53(m,2H),7.46-7.44(m,1H),7.27(d,J=6.5Hz,2H),2.40(s,3H);
13C NMR(CDCl3,125MHz)δ:148.47,138.31,137.09,129.75,129.59,128.69,127.38,125.73,120.49,117.21,21.32.
实施例6
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与苯胺的反应:
将化合物Ⅰ-14(0.542g,1mmol),苯胺(0.093g,1mmol),碳酸钾(0.138g,1mmol)和乙腈(5ml)置于反应器中,在常温下反应6个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.155克产物,收率为92%。
1H NMR(400MHz,CDCl3)δ:7.34-7.26(m,4H),7.14-7.07(m,4H),7.01-6.92(m,2H),5.73(br,s,1H);
13C NMR(CDCl3,100MHz)δ:143.2,129.5,121.1,117.9.
对比例2
M.A.Carroll,R.A.Wood报道的方法(Tetrahedron 2007,63,11349–11354):
将苯胺(0.093g,1mmol)、化合物B(0.452g,1mmol)和DMF(5ml)置于反应器中,在130度下回流24小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.140克产物,收率为83%。
实施例7
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与苯酚的反应:
将化合物Ⅰ-14(0.542g,1mmol),苯酚(0.094g,1mmol),碳酸钾(0.138g,1mmol)和乙腈(5ml)置于反应器中,在40℃状态保持6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.168克产物(联苯醚),收率为99%。
1H NMR(400MHz,CDCl3)δ:7.41-7.32(m,4H),7.17-7.10(m,2H),7.08-7.02(m,4H);13C NMR(CDCl3,100MHz)δ:157.4,129.9,123.3,119.0。
实施例8
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与咔唑的反应:
将化合物Ⅰ-14(0.542g,1mmol),咔唑(0.167g,1mmol),叔丁醇钾(0.112g,1mmol),和甲苯(5ml)置于反应器中,在常温下反应2个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.231克产物(氮苯基的咔唑),收率为95%。
1H NMR(400MHz,CDCl3)δ:8.13(d,J=8.0Hz,2H),7.54-7.60(m,4H),7.36-7.46(m,5H),7.24-7.30(m,2H).
13C NMR(CDCl3,100MHz)δ:141.0,137.8,129.9,127.5,127.2,126.0,123.4,120.3,119.9,109.8。
对比例3
F.Guo,L.Wang,P.Wang,J.Yu,J.Han报道的方法(Asian J.Org.Chem.2012,1,218-221):
将化合物C(0.452g,1mmol),咔唑(0.167g,1mmol),叔丁醇钾(0.112g,1mmol),和甲苯(5ml)置于反应器中,在50度下反应10个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.109克产物(氮苯基的咔唑),收率为45%。
实施例9
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与苄胺的反应:
将化合物Ⅰ-14(0.542g,1mmol),苄胺(0.107g,1mmol),碳酸钾(0.138g,1mmol)和甲苯(5ml)置于反应器中,在80~100℃状态保持6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.165克产物(氮苯基苄胺),收率为90%。
1H NMR(400MHz,CDCl3)δ:7.40–7.31(m,4H),7.32–7.26(m,1H),7.22–7.12(m,2H),6.72(m,1H),6.69–6.60(m,2H),4.33(s,2H),4.02(s,br,1H);
13C NMR(CDCl3,100MHz)δ:148.3,148.3,139.5,129.4,128.7,127.6,127.3,117.7,112.9,48.4.
实施例10
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与苯乙炔的反应:
将化合物Ⅰ-14(0.542g,1mmol),苯乙炔(0.102g,1mmol),碳酸钾(0.138g,1mmol),醋酸钯(0.22g,0.1mmol)和N,N-二甲基甲酰胺(5ml)置于反应器中,在常温下反应6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.164克产物(苯基苯乙炔),收率为92%。
1H NMR(400MHz,CDCl3)δ:7.55-7.51(m,4H),7.36-7.31(m,6H);
13C NMR(CDCl3,100MHz)δ:131.6,128.3,128.2,123.3,89.4.
实施例11
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与茚的反应:
将化合物Ⅰ-14(0.542g,1mmol),茚(0.116g,1mmol),碳酸钾(0.138g,1mmol),醋酸钯(0.22g,0.1mmol)和N,N-二甲基甲酰胺(5ml)置于反应器中,在氮气保护及60~80℃状态保持6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.171克产物(苯基取代茚),收率为89%。
1H NMR(400MHz,CDCl3)δ:7.69(d,2H,J=8.1Hz),7.53(d,1H,J=7.3Hz),7.42-7.48(m,3H),7.30-7.36(m,2H),7.28(s,1H),7.25(dt,1H,J=7.4,1.1Hz),3.84(s,2H);
13C NMR(CDCl3,100MHz)δ:146.4,145.3,143.1,135.9,128.6,127.4,126.6,126.5,125.6,124.7,123.6,120.9,38.9。
实施例12
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与苯甲醛的反应:
将化合物Ⅰ-14(0.542g,1mmol),苯甲醛(0.106g,1mmol),碳酸钾(0.138g,1mmol),醋酸钯(0.22g,0.1mmol),N卡宾催化剂(0.1mmol)和N,N-二甲基甲酰胺(5ml)置于反应器中,在氮气保护及60~80℃状态保持6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.155克产物(二苯甲酮),收率为85%。
1H NMR(400MHz,CDCl3)δ:7.83-7.78(m,4H),7.61-7.55(m,2H),7.50-7.44(m,4H);13C NMR(CDCl3,100MHz)δ:196.6,137.5,132.3,129.9,128.2.
实施例13
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与吲哚的反应:
将化合物Ⅰ-14(0.542g,1mmol),吲哚(0.117g,1mmol),三氟甲磺酸铜(0.036g,0.1mmol),2,6-二叔丁基吡啶(0.191g,1mmol)和1,2-二氯乙烷(5ml)置于反应器中,在氮气保护及60~80℃状态保持6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.166克产物,收率为86%。
1H NMR(400MHz,CDCl3)δ:8.12(br,s,1H),8.00(d,J=7.8Hz,1H),7.71(dd,J=1.2,8.2,2H),7.49(t,J=7.7Hz,2H),7.42(d,J=7.8Hz,1H),7.31-7.35(m,2H),7.28(m,1H),7.24(m,1H);
13C NMR(CDCl3,100MHz)δ:136.6.135.5,128.7,127.5,126.0,125.7,122.4,121.7,120.3,119.8,118.3,111.4.
实施例14
含五氟苯基二芳基碘盐(化合物Ⅰ-14)与吲哚的反应:
将化合物Ⅰ-14(0.542g,1mmol),吲哚(0.117g,1mmol),醋酸钯(0.22g,0.1mmol)和乙酸(5ml)置于反应器中,在氮气保护及80~100℃状态保持6~8个小时,蒸除溶剂,残余物经柱层析分离(石油醚/乙酸乙酯=20/1),得到0.170克产物,收率为88%。
1H NMR(400MHz,CDCl3)δ:8.3(br,s,1H),7.65(t,J=7.8Hz,3H),7.44(dd,J=1.2,8.2Hz,2H),7.39(d,J=7.8Hz,1H),7.33(t,J=7.8Hz,1H),7.21(m,1H),7.14(t,J=7.6Hz,1H),6.83(d,J=7.4Hz,1H);
13C NMR(CDCl3,100MHz)δ:137.9,136.9,132.4,129.4,129.0,127.7,125.2,122.5,120.7,120.3,110.9,100.0。
Claims (7)
1.一种含氟二芳基碘盐,其为式Ⅰ所示化合物:
式Ⅰ中,R1为芳环基或芳杂环基,或取代的芳环基或芳杂环基;Y为一价的有机或无机酸根离子。
2.如权利要求1所述的含氟二芳基碘盐,其特征在于,其中R1为C4~C10的芳环基或芳杂环基,或取代的C4~C10的芳环基或芳杂环基;
其中,所述的芳杂环基的杂原为氧或/和硫,杂原子数为1或2;
所述取代的C4~C10的芳环基或芳杂环基的取代基选自:C1~C6烷基,C1~C6烷氧基,卤素,或中一种或两种以上,取代基个数为1~5的整数。
3.如权利要求2所述的含氟二芳基碘盐,其特征在于,其中R1为噻吩基,苯基,取代苯基或萘基;
所述取代苯基的取代基选自:C1~C3烷基,C1~C3烷氧基,卤素,或中一种或两种以上,取代基个数为1~3的整数。
4.如权利要求3所述的含氟二芳基碘盐,其特征在于,其中所述取代苯基的取代基选自:甲基,乙基,正丙基,异丙基,甲氧基,F,Cl,Br,或中一种或两种以上。
5.如权利要求4所述的含氟二芳基碘盐,其特征在于,其中R1为下列基团中一种:
6.如权利要求1所述的含氟二芳基碘盐,其特征在于,其中Y,OTs,F,Cl,Br,BF4 -,OTf,ABS,ClO4,CF3COO或HSO4。
7.如权利要求1~6中任意一项所述的含氟二芳基碘盐作为芳基化试剂的应用。
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CN109705012B (zh) * | 2019-01-25 | 2022-04-05 | 西北师范大学 | 一种2,5-二芳基五元杂环芳烃的制备方法 |
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