5,17-二甲硫基-2,8,14,20-四氧杂苯[2]-嘧啶[2]杯芳烃衍生物的合成及其晶体结构
|
摘要
使用4,6-二氯-2-甲硫基嘧啶和相应的取代间苯二酚为原料,以碳酸铯为碱,N,N-二甲基甲酰胺为溶剂,在18-冠醚-6和碘化钾催化的条件下经缩合成环反应得到目标化合物。通过IR、1HNMR、13CNMR和HR-MS确证了化合物的结构,并通过X-射线衍射测定了5,17-二甲硫基-2,8,14,20-四氧杂苯[2]-嘧啶[2]杯芳烃的单晶结构。晶体结构结果表明化合物晶体属于单斜晶系,C2/c空间群,晶胞参数a=14. 529 5(18),b=12. 969 0(18),c=15. 523(2),α=90. 00°,β=112. 935(4)°,γ=90°,V=2 693. 8(6)3,Z=4,μ(Mo Kα)=0. 241 mm-1,F(000)=1 112。5,17-二甲硫基-2,8,14,20-四氧杂苯[2]-嘧啶[2]杯芳烃具有对称的环状结构,并通过分子间的π-π相互作用形成了二维网状结构。
The target compounds were synthesized via a cyclization of 4,6-dichloro-2-( methylthio) pyrimidine and 1,3-benzenediol in N,N-dimethylformamide with cesium carbonate as a base,18-crown-6 and potassium iodide as catalysts. Structures of the target compounds were comfirmed by IR,1 HNMR,13 CNMR,and HR-MS.Meanwhile,the crystal structure of 5,17-bis( methylsulfanyl)-2,8,14,20-tetraoxacalix [2] arene [2]-pyrimidine was obtained and determined by X-ray single-crystal diffraction. The compound crystallized in monoclinic crystal system and with space group C2/c with a = 14. 529 5( 18) ,b = 12. 969 0( 18) ,c = 15. 523( 2) ,α = 90. 00°,β = 112. 935( 4) °,γ = 90°,V = 2 693. 8( 6) 3,Z = 4,μ( Mo Kα) = 0. 241 mm-1,F( 000) = 1 112.The molecule of 5,17-bis( methylsulfanyl)-2,8,14,20-tetraoxacalix [2]arene [2]pyrimidine was interconnected by π-π interactions to aggregate 2 D framework.
The target compounds were synthesized via a cyclization of 4,6-dichloro-2-( methylthio) pyrimidine and 1,3-benzenediol in N,N-dimethylformamide with cesium carbonate as a base,18-crown-6 and potassium iodide as catalysts. Structures of the target compounds were comfirmed by IR,1 HNMR,13 CNMR,and HR-MS.Meanwhile,the crystal structure of 5,17-bis( methylsulfanyl)-2,8,14,20-tetraoxacalix [2] arene [2]-pyrimidine was obtained and determined by X-ray single-crystal diffraction. The compound crystallized in monoclinic crystal system and with space group C2/c with a = 14. 529 5( 18) ,b = 12. 969 0( 18) ,c = 15. 523( 2) ,α = 90. 00°,β = 112. 935( 4) °,γ = 90°,V = 2 693. 8( 6) 3,Z = 4,μ( Mo Kα) = 0. 241 mm-1,F( 000) = 1 112.The molecule of 5,17-bis( methylsulfanyl)-2,8,14,20-tetraoxacalix [2]arene [2]pyrimidine was interconnected by π-π interactions to aggregate 2 D framework.
引文
[1]徐雪梅,赵禹,马超,等.新型对叔丁基杯[4]芳烃1,2,3-三唑衍生物的合成[J].合成化学,2014,22(4):538-539.
[2]ROSSOM W V,CAERS J,ROBEYNS K,et al.(Thio)ureido anion receptors based on a 1,3-alternate oxacalix[2]arene[2]pyrimidine scaffold[J].J.Org.Chem.,2012,77(6):2 791-2 797.
[3]ADDEPALLI Y,YANG X H,ZHOU M H,et al.Synthesis and anticancer activity evaluation of novel azacalix[2]arene[2]pyrimidines[J].Eur.J.Med.Chem.,2018,151:214-225.
[4]张刚,高光宇,李清寒,等.4,6-二甲基嘧啶-2-硫基乙酰腙类化合物的合成及抗菌活性研究[J].化学试剂,2014,36(7):594-598.
[5]商琳琳,贾云宏,蔡东.5-二乙氨甲基-6-甲基-2,4-二羟基嘧啶的合成及抗炎活性[J].化学世界,2010,51(6):355-358.
[6]周根,刘欢欢,王丹丹,等.嘧啶拼接3-烯键氧化吲哚衍生物的合成及其抗肿瘤活性[J].合成化学,2017,25(3):185-189.
[7]LI J T,WANG D X,ZHAO L,et al.Synthesis of functionalized azacalix[3]aromatics from azacalix[4]pyrimidine:unexpected macrocyclic transannular reactions[J].Tetra.Lett.,2014,55(21):3 259-3 262.
[8]XU R B,HOU B Y,WANG D X,et al.Synthesis and selfassembly of novel oxacalix[2]arene[2]triazine amphiphiles[J].Sci.China Chem.,2016,59(10):1 306-1 310.
[9]WANG X D,WANG D X,HUANG Z T,et al.One-pot synthesis of oxygen and nitrogen-bridged calix[2]arene[2]triazines[J].Supramol.Chem.,2014,26(7/8):601-606.
[10]SHELDRICK G M.SHELXL-97,Program for the refinement of crystal structures[M].G9ttingen:University of G9ttingen,1997.
[11]SHELDRICK G M.SHELXS-97,Program for the refinement of crystal structures[M].G9ttingen:University of G9ttingen,1997.
[2]ROSSOM W V,CAERS J,ROBEYNS K,et al.(Thio)ureido anion receptors based on a 1,3-alternate oxacalix[2]arene[2]pyrimidine scaffold[J].J.Org.Chem.,2012,77(6):2 791-2 797.
[3]ADDEPALLI Y,YANG X H,ZHOU M H,et al.Synthesis and anticancer activity evaluation of novel azacalix[2]arene[2]pyrimidines[J].Eur.J.Med.Chem.,2018,151:214-225.
[4]张刚,高光宇,李清寒,等.4,6-二甲基嘧啶-2-硫基乙酰腙类化合物的合成及抗菌活性研究[J].化学试剂,2014,36(7):594-598.
[5]商琳琳,贾云宏,蔡东.5-二乙氨甲基-6-甲基-2,4-二羟基嘧啶的合成及抗炎活性[J].化学世界,2010,51(6):355-358.
[6]周根,刘欢欢,王丹丹,等.嘧啶拼接3-烯键氧化吲哚衍生物的合成及其抗肿瘤活性[J].合成化学,2017,25(3):185-189.
[7]LI J T,WANG D X,ZHAO L,et al.Synthesis of functionalized azacalix[3]aromatics from azacalix[4]pyrimidine:unexpected macrocyclic transannular reactions[J].Tetra.Lett.,2014,55(21):3 259-3 262.
[8]XU R B,HOU B Y,WANG D X,et al.Synthesis and selfassembly of novel oxacalix[2]arene[2]triazine amphiphiles[J].Sci.China Chem.,2016,59(10):1 306-1 310.
[9]WANG X D,WANG D X,HUANG Z T,et al.One-pot synthesis of oxygen and nitrogen-bridged calix[2]arene[2]triazines[J].Supramol.Chem.,2014,26(7/8):601-606.
[10]SHELDRICK G M.SHELXL-97,Program for the refinement of crystal structures[M].G9ttingen:University of G9ttingen,1997.
[11]SHELDRICK G M.SHELXS-97,Program for the refinement of crystal structures[M].G9ttingen:University of G9ttingen,1997.