周 婷, 王道林, 錢建華
(渤海大學(xué) 化學(xué)化工學(xué)院 遼寧省功能化合物合成與應(yīng)用重點(diǎn)實(shí)驗(yàn)室,遼寧 錦州 121003)
·快遞論文·
DABCO-促進(jìn)新型呋喃并[3,2-c]喹啉酮類化合物的合成
周 婷, 王道林*, 錢建華
(渤海大學(xué) 化學(xué)化工學(xué)院 遼寧省功能化合物合成與應(yīng)用重點(diǎn)實(shí)驗(yàn)室,遼寧 錦州 121003)
在1,4-二氮雜二環(huán)[2.2.2]辛烷(DABCO)促進(jìn)下,以水為反應(yīng)介質(zhì),通過3-溴乙?;?4-羥基-1-甲基-2-喹啉酮與芳香醛的親核取代、分子內(nèi)環(huán)化及消除的串聯(lián)反應(yīng),合成了9個(gè)新型的呋喃并[3,2-c]喹啉酮類化合物,其結(jié)構(gòu)經(jīng)1H NMR,13C NMR, IR, MS(ESI)和元素分析表征。
喹啉; 3-溴乙?;?4-羥基-1-甲基-2-喹啉酮; 呋喃并[3,2-c]喹啉酮; 1,4-二氮雜二環(huán)[2.2.2]辛烷; 串聯(lián)反應(yīng); 合成
2-喹啉酮類衍生物是一類重要的喹啉化合物,存在于大量天然產(chǎn)物中,表現(xiàn)出抗癌[1]、抗瘧[2]、抗病毒[3]、抗高血壓[4]和治療心血管[5]等多種生物活性和藥理活性。雜環(huán)稠合的喹啉酮類化合物作為潛在的藥物已引起研究人員的關(guān)注[6-8],其中,呋喃并喹啉是一類重要的稠雜環(huán)化合物,多數(shù)表現(xiàn)出強(qiáng)的生物活性和藥理活性,如抗病毒、抗炎鎮(zhèn)痛和抗菌等[9],臨床上用于光化治療領(lǐng)域[10]?;瘜W(xué)合成已成為獲得該類物質(zhì)的重要途徑。其中,以4-羥基-2-喹啉酮為原料,通過與乙烯基醚[11]的過渡金屬催化、與硝基乙烯[12-13]的堿催化、以及與異腈類化合物[14]的環(huán)化反應(yīng),成為合成呋喃并喹啉酮的主要途徑。另外,鈀催化下N-呋喃酰基苯胺的分子內(nèi)環(huán)化方法[15-16]也日益受到關(guān)注。但過渡金屬及一些特殊試劑的使用使得該類方法的應(yīng)用受到限制。
最近,本課題組以喹啉類雜環(huán)化合物為研究對(duì)象,合成了具有潛在生物活性的含有噻吩[17]、嘧啶[18]和香豆素[19]等結(jié)構(gòu)單元的喹啉類稠雜環(huán)化合物。作為該項(xiàng)工作的進(jìn)一步拓展,本文對(duì)新型呋喃并[3,2-c]喹啉酮類衍生物的合成方法進(jìn)行探討。以1,4-二氮雜二環(huán)[2.2.2]辛烷(DABCO)為促進(jìn)劑,水為反應(yīng)介質(zhì),通過3-溴乙酰基-4-羥基-1-甲基-2-喹啉酮(1)與芳香醛(2a~2i)的親核取代、分子內(nèi)環(huán)化及消除的串聯(lián)反應(yīng),合成了9個(gè)新型的呋喃并[3,2-c]喹啉酮類化合物(3a~3i, Scheme 1),其結(jié)構(gòu)經(jīng)1H NMR,13C NMR, IR, MS(ESI)和元素分析表征。
Scheme 1
1.1 儀器與試劑
WRS-1B型數(shù)字熔點(diǎn)儀(溫度未校正);Bruker DPX-400 MHz型核磁共振儀(CDCl3為溶劑,TMS為內(nèi)標(biāo));BIO-RAD FTS-40型傅立葉變換紅外光譜儀(KBr壓片);ZAB-HS型質(zhì)譜儀;Vario EL型元素分析儀。
1[收率76%, m.p.176~178 ℃(174~176 ℃[20])]參照文獻(xiàn)[20]方法合成;其余所用試劑均為分析純。
1.2 3a~3i的合成通法
將1 1.00 mmol, 2a~2i 1.2 mmol和DABCO 0.2 mmol加至水(20 mL)中,攪拌下回流反應(yīng)3~6 h(TLC監(jiān)測(cè))。冷卻至室溫,過濾,濾餅用水洗滌,干燥后用冰乙酸重結(jié)晶得3a~3i。
N-甲基-2-苯基亞甲基-5H-呋喃[3,2-c]喹啉-3,4-二酮(3a): 黃色晶體,產(chǎn)率75%, m.p.175~177 ℃;1H NMR(400 MHz)δ: 6.97(s, 1H), 7.44~7.48(m, 2H), 7.61~7.64(m, 3H), 7.75(t,J=7.6 Hz, 1H), 7.90~7.92(m, 2H), 8.16(d,J=8.0 Hz, 1H);13C NMR(100 MHz)δ: 95.8, 116.6, 120.6, 122.9, 124.0, 125.3, 127.7, 129.0, 129.8, 133.8, 13, 134.7, 137.9, 152.4, 161.9, 170.4, 179.5; IRν: 1 678(C=O), 1 622(C=O) cm-1; MS(ESI)m/z: 304{[M+H]+}; Anal.calcd for C19H13NO3: C 75.24, H 4.32, N 4.62, found C 75.31, H 4.33, N 4.63。
N-甲基-2-(4-甲基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3b): 黃色晶體,產(chǎn)率78%, m.p. 274~276 ℃;1H NMR(400 MHz)δ: 2.42(s, 3H, CH3), 3.70(s, 3H, NCH3), 6.99(s, 1H), 7.28~7.37(m, 2H), 7.41~7.45(m, 2H), 7.78~7.80(m, 3H), 8.13(d,J=7.6 Hz, 1H);13C NMR(100 MHz)δ: 20.1, 27.4, 106.1, 109.2, 113.4, 113.8, 120.9, 122.2, 127.1, 128.3, 130.1, 133.8, 139.6, 141.6, 144.6, 155.5, 171.7, 178.7; IRν: 1 679(C=O), 1 628(C=O) cm-1; MS(ESI)m/z: 318{[M+H]+}; Anal. calcd for C20H15NO3: C 75.70, H 4.76, N 4.41, found C 75.79, H 4.77, N 4.42。
N-甲基-2-(2,4-二甲基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3c): 黃色晶體,產(chǎn)率72%, m.p.>300 ℃;1H NMR(400 MHz)δ: 2.37(s, 3H, CH3), 2.48(s, 3H, CH3), 3.71(s, 3H, NCH3), 7.09(s, 1H), 7.12(s, 1H), 7.17(d,J=8.0 Hz, 1H), 7.38(t,J=7.6 Hz, 1H), 7.45(dd,J=8.0 Hz, 8.4 Hz, 1H), 7.80(d,J=8.0 Hz, 1H), 8.10~8.12(m, 2H);13C NMR(100 MHz)δ: 20.3, 21.6, 29.0, 107.8, 110.0, 110.9, 112.4, 115.4, 122.5, 123.7, 127.3, 127.4, 131.1, 131.8, 135.4, 139.9, 141.0, 143.3, 157.2, 173.5, 180.3; IRν: 1 676(C=O), 1 630(C=O) cm-1; MS(ESI)m/z: 332{[M+H]+}; Anal. calcd for C21H17NO3: C 76.12, H 5.17, N 4.23, found C 76.20, H 5.18, N 4.24。
N-甲基-2-(2-甲氧基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3d): 黃色晶體,產(chǎn)率80%, m.p 297~299 ℃;1H NMR(400 MHz)δ: 3.69(s, 3H, OCH3), 3.89(s, 3H, NCH3), 6.93 (d,J=8.4 Hz, 1H), 7.08(d,J=7.6 Hz, 1H), 7.11(s, 1H), 7.35~7.41(m, 2H), 7.42(d,J=8.4 Hz, 1H), 7.80(t,J=8.0 Hz, 1H), 8.11(d,J=8.0 Hz, 1H), 8.22(d,J=8.0 Hz, 1H);13C NMR(100 MHz)δ: 28.9, 55.6, 107.8, 109.1, 109.2, 110.9, 111.0, 115.4, 120.5, 120.9, 122.5, 123.7, 131.8, 132.2, 135.4, 143.3, 157.2, 159.2, 173.2, 180.2; IRν: 1 681(C=O), 1 631(C=O) cm-1; MS(ESI)m/z: 334{[M+H]+}; Anal. calcd for C20H15NO4: C 72.06, H 4.54, N 4.20, found C 72.11, H 4.55, N 4.22。
N-甲基-2-(4-甲氧基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3e): 黃色晶體,產(chǎn)率85%, m.p.294~296 ℃;1H NMR(400 MHz)δ: 3.71(s, 3H, NCH3), 3.88(s, 3H, OCH3), 7.01~7.02(m, 3H), 7.37~7.39(m, 2H), 7.75~7.79(m, 1H), 7.88(d,J=8.0 Hz, 2H), 8.15(d,J=8.0 Hz, 1H);13C NMR(100 MHz)δ: 29.0, 55.5, 110.9, 113.9, 114.7, 115.0, 115.4, 122.2, 123.6, 124.2, 130.2, 133.7, 135.3, 143.3, 145.6, 161.5, 173.0, 180.2; IRν: 1 672(C=O), 1 625(C=O) cm-1; MS(ESI)m/z: 334{[M+H]+}; Anal. calcd for C20H15NO4: C 72.06, H 4.54, N 4.20, found C 72.15, H 4.55, N 4.21。
N-甲基-2-(3,4-二甲氧基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3f): 黃色晶體,產(chǎn)率86%, m.p. 285~287 ℃;1H NMR(400 MHz)δ: 3.69(s, 3H, NCH3), 3.95(s, 3H, OCH3), 3.99(s, 3H, OCH3), 6.95~6.97(m, 2H), 7.37~7.44(m, 2H), 7.47~7.49(m, 2H), 7.79(d,J=8.0 Hz, 1H), 8.09(d,J=8.0 Hz, 1H);13C NMR(100 MHz)δ: 29.0, 55.8, 56.0, 107.9, 110.9, 111.3, 113.6, 115.2, 115.5, 122.6, 123.2, 124.4, 126.4, 135.3, 143.3, 145.6, 149.1, 151.3, 157.2, 172.8, 180.1; IRν: 1 677(C=O), 1 618(C=O) cm-1; MS(ESI)m/z: 364{[M+H]+}; Anal. calcd for C21H17NO5: C 69.41, H 4.72, N 3.85, found C 69.48,
H 4.73, N 3.86。
N-甲基-2-(2,4,5-三甲氧基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3g): 黃色晶體,產(chǎn)率80%, m.p.>300 ℃;1H NMR(400 MHz)δ: 3.72(s, 3H, NCH3), 3.90(s, 3H, OCH3), 3.96(s, 3H, OCH3), 4.02(s, 3H, OCH3), 7.35~7.46(m, 3H), 7.58(s, 1H), 7.78(d,J=8.0 Hz, 1H), 7.86(s, 1H), 7.98(d,J=8.0 Hz, 1H);13C NMR(100 MHz)δ: 29.0, 56.0, 56.1, 56.4, 96.1, 96.2, 108.1, 109.7, 109.8, 111.1, 112.1, 113.8, 113.9, 115.5, 115.6, 122.5, 122.9, 135.1, 143.2, 152.9, 170.8, 173.2; IRν: 1 675(C=O), 1 627(C=O) cm-1; MS(ESI)m/z: 394{[M+H]+}; Anal. calcd for C22H19NO6: C 67.17, H 4.87, N 3.56, found C 67.23, H 4.89, N 3.57。
N-甲基-2-(4-羥基苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3h): 黃色晶體,產(chǎn)率76%, m.p.>300 ℃;1H NMR(400 MHz)δ: 3.58(s, 3H, NCH3), 6.92~6.95(m, 3H), 7.65(d,J=8.4 Hz, 1H), 7.89(t,J=8.0 Hz, 1H), 7.87~7.94(m, 3H), 8.25(d,J=8.0 Hz, 1H), 10.35(s, 1H, OH);13C NMR(100 MHz)δ: 29.1, 107.4, 110.6, 111.4, 116.6, 116.8, 122.7, 123.1, 123.9, 134.7, 136.1, 143.2, 145.1, 156.7, 160.6, 173.0, 179.7; IRν: 3 341(OH), 1 672(C=O), 1 619(C=O) cm-1; MS(ESI)m/z: 320{[M+H]+}; Anal. calcd for C19H13NO4: C 71.47, H 4.10, N 4.39, found C 71.54, H 4.11, N 4.40。
N-甲基-2-(4-氯苯基亞甲基)-5H-呋喃[3,2-c]喹啉-3,4-二酮(3i): 黃色晶體,產(chǎn)率74%, m.p.>300 ℃;1H NMR(400 MHz)δ: 3.72(s, 3H, NCH3), 6.97(s, 1H), 7.39~7.47(m, 4H), 7.80~7.85(m, 3H), 8.13(d,J=7.6 Hz, 1H);13C NMR(100 MHz)δ: 29.1, 107.6, 109.9, 110.7, 113.3, 115.5, 122.7, 123.6, 129.4, 130.0, 132.8, 135.8, 136.6, 140.2, 143.5, 173.7, 180.2; IRν: 1 683(C=O), 1 628(C=O) cm-1; MS(ESI)m/z: 338{[M+H]+}; Anal. calcd for C19H12NO3Cl: C 67.56, H 3.58, N 4.15, found C 67.65, H 3.59, N 4.17。
Scheme 2
2.1 合成
近年來,以水作為有機(jī)反應(yīng)介質(zhì)的綠色有機(jī)合成方法已有大量文獻(xiàn)報(bào)道,如Claisen重排反應(yīng)、Aldol縮合反應(yīng)、Diels-Alder反應(yīng)、Michael加成反應(yīng)及Knoevenagel縮合反應(yīng)等[21]。DABCO作為一種無毒、價(jià)格低廉和市售的有機(jī)堿、親核試劑,在有機(jī)合成反應(yīng)中應(yīng)用廣泛[22-23]。為了合成新型喹啉類化合物,本文探討以水作為反應(yīng)介質(zhì),在DABCO作用下,通過3-乙?;?4-羥基-1-甲基-2-喹啉酮1與芳香醛2的縮合反應(yīng)合成呋喃并[3,2-c]喹啉酮類化合物。
從實(shí)驗(yàn)結(jié)果可以看出,3-溴乙?;?4-羥基-1-甲基-2-喹啉酮與含有不同取代基團(tuán)的芳香醛反應(yīng),以良好收率(72%~86%)獲得9種呋喃并[3,2-c]喹啉酮類衍生物。同時(shí)還發(fā)現(xiàn),在芳香醛中,無論取代基為供電子基(如甲氧基、甲基、羥基等),還是吸電子基(如鹵素),反應(yīng)在較短時(shí)間內(nèi)(3~6 h)均得以順利進(jìn)行。
2.2 表征
目標(biāo)產(chǎn)物3a~3i的結(jié)構(gòu)經(jīng)1H NMR,13C NMR, IR, MS(ESI)和元素分析表征。IR分析表明,3a~3i的共同特征為在1 672~1 683 cm-1出現(xiàn)喹啉2-位羰基的伸縮振動(dòng)吸收峰,1 618~1 631 cm-1處的吸收峰為喹呋喃環(huán)3-位羰基的伸縮振動(dòng)吸收峰。在1H NMR譜圖中,δ6.97~7.12處的單峰為芳基亞甲基質(zhì)子的特征吸收峰。在13C NMR譜圖中,δ170~180處吸收峰為喹啉環(huán)2-位羰基碳及呋喃環(huán)3-位羰基碳的特征吸收峰。
2.3 反應(yīng)機(jī)理
依據(jù)實(shí)驗(yàn)結(jié)果及相關(guān)文獻(xiàn)[24],我們對(duì)反應(yīng)機(jī)理(Scheme 2)進(jìn)行了如下推測(cè):首先DABCO作為親核試劑與1反應(yīng)生成季銨鹽A; A經(jīng)過分子內(nèi)環(huán)化得到環(huán)化產(chǎn)物B,緊接著在DABCO作為堿的作用下,B與醛通過Knoevenagel縮合反應(yīng)生成加成物C,進(jìn)而消除一分子的水生成目標(biāo)產(chǎn)物3。
在DABCO促進(jìn)下,通過3-溴乙酰基-4-羥基-1-甲基-2-喹啉酮與芳香醛的串聯(lián)反應(yīng),成功地合成了一系列新型呋喃并[3,2-c]喹啉酮類化合物,為構(gòu)建新型喹啉類稠雜環(huán)衍生物提供了有效的合成策略。該方法以水為反應(yīng)介質(zhì),反應(yīng)條件溫和、操作簡便、選擇性良好,有較好的實(shí)用價(jià)值及應(yīng)用前景。
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DABCO-Promoted Synthesis of Novel Furo[3,2-c]quinolinones
ZHOU Ting, WANG Dao-lin*, QIAN Jian-hua
(Key Laboratory of Synthesis & Application of Functional Compound,College of Chemistry, Chemical Engineering, Bohai University, Jinzhou 121003, China)
A simple and efficient method for the synthesis of novel furo[3,2-c]quinolinone derivatives was developed by a domino nucleophilic/cyclization/elimination reaction in H2O of 3-bromoacetyl-4-hydroxy-1-methylquinolin-2-one with aryl aldehydes, in the presence of 1,4-diazabicyclo[2.2.2]octane(DABCO). The structures were characterized by1H NMR,13C NMR, IR, MS(ESI) and elemental analysis.
quinoline; 3-bromoacetyl-4-hydroxy-1-methylquinolin-2-one; furo[3,2-c]quinolinone; 1,4-diazabicyclo[2.2.2]octane; domino reaction; synthesis
2016-12-12;
2017-05-16
遼寧省教育廳創(chuàng)新團(tuán)隊(duì)項(xiàng)目(2015001)
周婷(1992-),女,漢族,黑龍江佳木斯人,碩士研究生,主要從事有機(jī)合成的研究。 Tel. 0416-3400329, E-mail: 784804238@qq.com
王道林,教授, Tel. 0416-3400329, E-mail: wangdaolin@sina.com
O626; O621.3
A
10.15952/j.cnki.cjsc.1005-1511.2017.07.16309