李 婷,張 敏,鮑永團(tuán),陳國燕,李 吉,仰榴青
(江蘇大學(xué) 化學(xué)化工學(xué)院,江蘇 鎮(zhèn)江 212013)
·研究論文·
新型橙酮肟(醚)衍生物的合成及其除草活性*
李 婷,張 敏,鮑永團(tuán),陳國燕,李 吉,仰榴青
(江蘇大學(xué) 化學(xué)化工學(xué)院,江蘇 鎮(zhèn)江 212013)
間苯二酚和氯乙腈經(jīng)Houben-Hoesch反應(yīng)制得2,4-二羥基-α-氯代苯乙酮(2);2與芳醛經(jīng)環(huán)化和縮合反應(yīng)制得6-羥基橙酮衍生物(4a~4e);4a~4e依次分別與一氯丙酮和NH2OR1·HCl反應(yīng)合成了12個新型的橙酮肟(醚)衍生物(1a~1l),其結(jié)構(gòu)經(jīng)1H NMR,IR和元素分析的表征。初步的生物活性測試結(jié)果表明:在用藥量為100μg·mL-1時,(Z)-2-(3-三氟甲基苯基)亞甲基-6-[(Z,E)-2-(乙氧基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1l)對油菜根長的生長抑制率為78.2%。
橙酮;肟/肟醚;合成;除草活性
橙酮[2-苯基亞甲基-3-(2H)-苯并呋喃酮]是植物體內(nèi)的次生代謝產(chǎn)物,屬類黃酮化合物,大多存在于玄參科、菊科、苦苣苔科以及單子葉植物中的莎草科和海洋生物中。與其它類黃酮化合物(如黃酮、查耳酮等)相比,橙酮類化合物的研究尚處于起步階段,但呈不斷上升趨勢[1-2],其研究主要集中在抗腫瘤活性[3-5]、抗氧化活性[6-7]、緩解和治療糖尿病綜合癥[8]以及對昆蟲的拒食活性[9]等方面。
在前期研究工作中,本課題組設(shè)計(jì)并合成了一系列4,6-二取代橙酮以及6-取代橙酮衍生物,且部分化合物表現(xiàn)出良好的除草活性[10-11],說明橙酮可能是一個新的除草活性結(jié)構(gòu),通過對其結(jié)構(gòu)的進(jìn)一步修飾和除草活性的深入研究,有望開發(fā)出新型的除草劑。
肟類化合物具有優(yōu)良的殺蟲(如辛硫磷、涕滅威)、殺菌(如肟菌酯、烯肟菌酯)和除草(如稀禾啶、烯草酮和環(huán)苯草酮)等活性,而且有些化合物還具有高效、低毒、低殘留等優(yōu)點(diǎn)。目前肟類化合物的分子設(shè)計(jì)、合成與生物活性研究仍然是農(nóng)藥創(chuàng)制的熱點(diǎn)之一[12-14]。此外,將氟原子或含氟基團(tuán)引入農(nóng)藥分子中,可以提高化合物的穩(wěn)定性、增強(qiáng)其疏水性以及對膜和生物組織的滲透性等[15-16],在農(nóng)藥研究中占有非常重要的地位。
為了尋找新型、高效的農(nóng)藥先導(dǎo)化合物,本文采用活性亞結(jié)構(gòu)拼接原理,利用氟原子有利于增強(qiáng)化合物的疏水性以及對膜和生物組織的滲透性等特點(diǎn),設(shè)計(jì)并合成了一系列新型的含氟橙酮肟(醚)衍生物。即間苯二酚和氯乙腈經(jīng)Houben-Hoesch反應(yīng)制得2,4-二羥基-α-氯代苯乙酮(2);2與芳醛(3a~3e)經(jīng)縮合反應(yīng)制得6-羥基橙酮衍生物(4a~4e);4a~4e依次分別與一氯丙酮和NH2OR1·HCl(5a,5f和5k)反應(yīng)合成了12個新型的橙酮肟(醚)衍生物(1a~1l,Scheme 1),其結(jié)構(gòu)經(jīng)1H NMR,IR和元素分析的表征。并對其除草活性進(jìn)行了研究。
1.1 儀器與試劑
數(shù)字顯微熔點(diǎn)儀(溫度未校正);Brucker Avance AM 400MHz型核磁共振儀(DMSO-d6為溶劑,TMS為內(nèi)標(biāo));Nexus 670型傅立葉變換紅外光譜儀(KBr壓片);EA-1112A型元素分析儀。
2和4a~4e按文獻(xiàn)[10-11]方法制備;其余所用試劑均為分析純。
1.21a~1l的合成通法[17]
在圓底燒瓶中加入42.5mmol,K2CO30.50g(3.6mmol)和DMF 5mL,攪拌下加入一氯丙酮0.30mL(3.8mmol),于室溫反應(yīng)過夜(TLC 檢測)。倒入雙蒸水200mL中,過濾,濾餅用乙酸乙酯重結(jié)晶得A。
在圓底燒瓶中加入A和無水乙醇5mL,攪拌使其溶解;加入NH2·OR1鹽酸鹽3.0mmol和K2CO30.48g(3.5mmol),于室溫反應(yīng)(1a~1e)或回流反應(yīng)(1f~1l)至終點(diǎn)(TLC檢測)。加雙蒸水100mL,過濾,濾餅晾干,用DMF重結(jié)晶后經(jīng)硅膠柱層析[洗脫劑:V(石油醚)∶V(乙酸乙酯)=10∶1]純化得1a~1l。
(Z)-2-苯基亞甲基-6-[(Z)-2-(羥基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1a):白色粉末,收率73.8%,m.p.135℃~136℃;1H NMRδ:1.87(s,3H,CH3),5.03(s,2H,CH2),6.87(s,1H,=CH),6.89(dd,J=8.4Hz,2.0Hz,1H,ArH),7.12(d,J=2.0Hz,1H,ArH),7.42~7.55(m,3H,ArH),7.74(d,J=8.4Hz,1H,ArH),7.95~8.01(m,2H,ArH),11.06(s,1H,OH);IRν:3265,3076,1688,1645,1601,1439,1349,1311,1267,1157,1131,1100,1018cm-1;Anal.calcd for C18H15NO4:C 69.89,H 4.89,N 4.53;found C 69.75,H 5.11,N 4.43。
(Z)-2-(2-氟苯基)亞甲基-6-[(E)-2-(羥基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1b):白色固體,收率66.8%,m.p.152℃~153℃;1H NMRδ:1.86(s,3H,CH3),4.77(s,2H,CH2),6.82(s,1H,=CH),6.91(dd,J=8.4Hz,2.0Hz,1H,ArH),7.17~7.22(m,1H,ArH),7.32~7.42(m,2H,ArH),7.48~7.56(m,1H,ArH),7.72(d,J=8.4Hz,1H,ArH),8.17~8.27(m,1H,ArH),11.10(s,1H,OH);IRν:3333,3106,2962,1686,1651,1604,1499,1445,1352,1298,1272,1135,1004cm-1;Anal.calcd for C18H14NO4F:C 66.05,H 4.31,N 4.28;found C 66.27,H 4.43,N 4.04。
(Z)-2-(3-氟苯基)亞甲基-6-[(Z)-2-(羥基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1c):白色粉末,收率 80.1%,m.p.133℃~134℃;1H NMRδ:1.86(s,3H,CH3),5.00(s,2H,CH2),6.80~6.89(m,2H,=CH,ArH),7.11(d,J=1.6Hz,1H,ArH),7.24~7.30(m,1H,ArH),7.45~7.55(m,1H,ArH),7.69(d,J=8.4Hz,1H,ArH),7.72~7.80(m,2H,ArH),11.05(s,1H,OH);IRν:3258,3067,3019,1688,1644,1601,1448,1375,1347,1294,1267,1159,1133,1100,1018cm-1;Anal.calcd for C18H14NO4F:C 66.05,H 4.31,N 4.28;found C 66.34,H 3.99,N 4.24。
(Z)-2-(4-氟苯基)亞甲基-6-[(E)-2-(羥基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1d):黃色針狀固體,收率82.2%,m.p.172℃~173℃;1H NMRδ:1.87(s,3H,CH3),4.77(s,2H,CH2),6.89~6.92(m,2H,=CH,ArH),7.18(d,J=1.6Hz,1H,ArH),7.34~7.39(m,2H,ArH),7.71(d,J=8.8Hz,1H,ArH),8.02~8.05(m,2H,ArH),11.10(s,1H,OH);IRν:3321,3098,1687,1650,1608,1509,1445,1349,1274,1239,1136,1115cm-1;Anal.calcd for C18H14NO4F:C 66.05,H 4.31,N 4.28;found C 66.00,H 4.59,N 4.29。
(Z)-2-(3-三氟甲基苯基)亞甲基-6-[(E)-2-(羥基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1e):淡黃色粉末,收率75.0%,m.p.163℃~165℃;1H NMRδ:1.87(s,3H,CH3),4.76(s,2H,CH2),6.85~6.91(m,2H,=CH,ArH),7.16(d,J=2.0Hz,1H,ArH),7.31~7.38(m,2H,ArH),7.65~7.72(m,1H,ArH),7.97~8.02(m,2H,ArH),11.09(s,1H,OH);IRν:3279,3098,2966,1702,1655,1609,1444,1329,1262,1158,1130,1114,937cm-1;Anal.calcd for C19H14NO4F3:C 60.48,H 3.74,N 3.71;found C 60.34,H 3.99,N 3.64。
(Z)-2-苯基亞甲基-6-[(Z,E)-2-(甲氧基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1f):乳白色粉末,收率41.1%,m.p.118℃~119℃;1H NMRδ:1.97[s,2.35H,(E)-CH3],2.00[s,0.65H,(Z)-CH3],3.92[s,0.70H,(Z)-OCH3],3.93[s,2.30H,(E)-OCH3],4.65[s,1.58H,(E)-CH2],4.95[s,0.42H,(Z)-CH2],6.76~6.84(m,3H,=CH,ArH ),7.36~7.42(m,1H,ArH),7.42~7.50(m,2H,ArH),7.68~7.75(m,1H,ArH),7.86~7.95(m,2H,ArH);IRν:2966,2938,1713,1695,1662,1595,1494,1444,1263,1155,1126,1103,1043,1030cm-1;Anal.calcd for C19H17NO4:C 70.58,H 5.30,N 4.33;found C 70.34,H 5.08,N 4.61。
(Z)-2-(2-氟苯基)亞甲基-6-[(Z,E)-2-(甲氧基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1g):淡黃色粉末,收率52.4%,m.p.129℃~130℃;1H NMRδ:1.97[s,2.32H,(E)-CH3],2.00[s,0.68H,(Z)-CH3],3.92[s,0.68H,(Z)-OCH3],3.93[s,2.32H,(E)-OCH3],4.65[s,1.56H,(E)-CH2],4.95[s,0.44H,(Z)-CH2],6.76~6.85(m,2H,ArH),7.09~7.16(m,2H,=CH,ArH),7.22~7.29(m,1H,ArH),7.33~7.41(m,1H,ArH),7.69~7.75(m,1H,ArH),8.24~8.31(m,1H,ArH);IRν:3096,2966,2938,2810,1697,1654,1611,1495,1443,1303,1267,1155,1128,1098,1039,999cm-1;Anal.calcd for C19H16NO4F:C 66.86,H 4.72,N 4.10;found C 66.74,H 4.98,N 4.24。
(Z)-2-(3-氟苯基)亞甲基-6-[(Z,E)-2-(甲氧基亞氨基)丙氧基]-3(2H)-苯并呋喃 酮(1h):淡黃色粉末,收率52.6%,m.p.84℃~85℃;1H NMRδ:1.98[s,2.31H,(E)-CH3],2.00[s,0.69H,(Z)-CH3],3.93[s,0.69H,(Z)-OCH3],3.94[s,2.31H,(E)-OCH3],4.66[s,1.56H,(E)-CH2],4.95[s,0.44H,(Z)-CH2],6.76(s,1H,=CH),6.77~6.88(m,2H,ArH),7.05~7.13(m,1H,ArH),7.37~7.44(m,1H,ArH),7.54~7.59(m,1H,ArH),7.66~7.74(m,2H,ArH);IRν:3089,2958,2946,2815,1697,1654,1615,1494,1446,1338,1290,1268,1248,1148,1124,1101cm-1;Anal.calcd for C19H16NO4F:C 66.86,H 4.72,N 4.10;found C 66.84,H 4.79,N 4.07。
(Z)-2-(4-氟苯基)亞甲基-6-[(Z,E)-2-(甲氧基亞氨基)丙氧基]-3(2H)-苯并呋喃 酮(1i):淺粉色粉末,收率 54.8%,m.p.127℃~128℃;1H NMRδ:1.98[s,2.27H,(E)-CH3],2.01[s,0.63H,(Z)-CH3],3.93[s,0.63H,(Z)-OCH3),3.94[s,2.27H,(E)-OCH3],4.66[s,1.57H,(E)-CH2],4.96[s,0.43H,(Z)-CH2],6.77~6.86(m,3H,=CH,ArH),7.12~7.18(m,2H,ArH),7.69~7.76(m,1H,ArH),7.87~7.94(m,2H,ArH);IRν:3056,2929,2819,1698,1656,1602,1510,1446,1344,1293,1267,1235,1156,1132,1106,1070,1045,1001cm-1;Anal.calcd for C19H16NO4F:C 66.86,H 4.72,N 4.10;found C 66.69,H 4.79,N 4.19。
(Z)-2-(3-三氟甲基苯基)亞甲基-6-[(Z,E)-2-(甲氧基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1j):黃色固體,收率 59.3%,m.p.95℃~96℃;1H NMRδ:1.98[s,2.33H,(E)-CH3],2.00[s,0.67H,(Z)-CH3],3.94(s,3H,OCH3),4.68[s,1.56H,(E)-CH2],4.96[s,0.44H,(Z)-CH2],6.78~6.91(m,3H,=CH,ArH),7.54~7.66(m,2H,ArH),7.70~7.76(m,1H,ArH),7.97~8.04(m,1H,ArH),8.17~8.22(m,1H,ArH);IRν:3056,2938,1711,1662,1610,1495,1444,1346,1296,1261,1159,1121,1100,1071cm-1;Anal.calcd for C20H16NO4F3:C 61.38,H 4.12,N 3.58;found C 61.34,H 3.99,N 3.82。
(Z)-2-(2-氟苯基)亞甲基-6-[(Z,E)-2-(乙氧基亞氨基)丙氧基]-3(2H)-苯并呋喃 酮(1k):白色固體,收率 54.2%,m.p.91℃~92℃;1H NMRδ:1.30[t,J=7.2Hz,2.35H,(E)-CH3in Et],1.33[t,J=7.2Hz,0.65H,(Z)-CH3in Et],1.98[s,2.35H,(E)-CH3],1.99[s,0.65H,(Z)-CH3],4.18(q,J=7.2Hz,2H,CH2in Et),4.67[s,1.56H,(E)-CH2],4.96[s,0.44H,(Z)-CH2],6.77~6.88(m,2H,ArH),7.09~7.16(m,2H,=CH,ArH),7.21~7.29(m,1H,ArH),7.33~7.40(m,1H,ArH),7.69~7.75(m,1H,ArH),8.24~8.31(m,1H,ArH);IRν:3060,2983,2929,2880,1700,1656,1610,1493,1443,1263,1237,1156,1129,1100,1050cm-1;Anal.calcd for C20H18NO4F:C 67.60,H 5.11,N 3.94;found C 67.34,H 4.99,N 4.24。
(Z)-2-(3-三氟甲基苯基)亞甲基-6-[(Z,E)-2-(乙氧基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1l):白色固體,收率 57.7%,m.p.124℃~126℃;1H NMRδ:1.30[t,J=7.2Hz,2.30H,(E)-CH3in Et],1.34[t,J=6.8Hz,0.70H,(Z)-CH3in Et],1.98[s,2.30H,(E)-CH3],1.99[s,0.70H,(Z)-CH3],4.18[q,J=7.2Hz,1.56H,(E)-CH2in Et],4.19[q,J=6.8Hz,0.44H,Z)-CH2in Et],4.69[s,1.56H,(E)-CH2],4.98[s,0.44H,(Z)-CH2],6.79~6.92(m,3H,=CH,ArH),7.54~7.60(m,1H,ArH),7.61~7.66(m,1H,ArH),7.69~7.74(m,1H,ArH),7.97~8.03(m,1H,ArH),8.17~8.22(m,1H,ArH);IRν:3101,2978,2941,1712,1662,1609,1444,1345,1295,1263,1158,1119,1100cm-1;Anal.calcd for C21H18NO4F3:C 62.22,H 4.48,N 3.46;found C 62.34,H 4.22,N 3.48。
2.1 合成
在干燥氯化氫和無水氯化鋅的存在下,間苯二酚與氯乙腈發(fā)生Houben-Hoesch反應(yīng),經(jīng)水解得中間體2;2與芳醛經(jīng)環(huán)化和縮合反應(yīng)得6-羥基橙酮衍生物(4)[10-11]。在碳酸鉀作用下,4與一氯丙酮發(fā)生親核取代反應(yīng)得烷基化產(chǎn)物,然后在堿作用下與NH2OR2·HCl反應(yīng)得目標(biāo)化合物1a~1l。由于橙酮肟衍生物1a~1e極性較大,需用DMF重結(jié)晶純化,而橙酮肟醚衍生物1f~1l則采用柱層析[V(石油醚)∶V(乙酸乙酯)=10∶1]分離純化。對于1f~1l初始的設(shè)計(jì)合成思路是對1a~1e的肟羥基在堿性條件下進(jìn)行烷基化。當(dāng)我們采用該路徑時,常溫下基本不反應(yīng),但當(dāng)升溫至50℃反應(yīng)一段時間后卻得到了6(Chart 1),而不是1,這與文獻(xiàn)[13]報道的結(jié)果是一致的。
2.2 幾何異構(gòu)體
1的結(jié)構(gòu)中均含有環(huán)外C=C和C=N雙鍵,也就有異構(gòu)體的存在。對于C=C雙鍵,其Z或E構(gòu)型可以通過1H NMR進(jìn)行確認(rèn),一般認(rèn)為雙鍵上的δ在6.7左右時為Z構(gòu)型,δ>7.0為E構(gòu)型[10-11]。除1k和1g外,其余1的C=CH雙鍵上氫的δ均在6.70~6.90,說明該雙鍵以Z構(gòu)型存在。1k和1g的C=CH雙鍵上氫的δ在7.10左右,也被指認(rèn)為Z構(gòu)型。是因?yàn)樗鼈兊谋江h(huán)上有鄰位取代基,異常的鄰位效應(yīng)使C=CH雙鍵上氫的δ向低場移動[11]。同樣,C=N雙鍵也存在著Z式和E式兩種異構(gòu)體,在E異構(gòu)體中,OCH2上的氫將會向高場移動,一般出現(xiàn)在δ4.70左右;反之向低場移動,一般出現(xiàn)在δ5.0左右[17]。1a~1e通過DMF重結(jié)晶得Z式單體(1a和1c)或E式單體(1b,1d和1e)。而1f~1l存在兩種幾何異構(gòu)體,通過計(jì)算1H NMR譜圖上兩個幾何異構(gòu)體同一質(zhì)子相應(yīng)吸收峰積分面積[13],計(jì)算1f~1l中兩種幾何異構(gòu)體的比例(E/Z)在(3.6/1.0)~(3.3/1.0)。
2.3 除草活性
采用油菜平皿法和稗草小杯法,按文獻(xiàn)[18]方法進(jìn)行測定。以甲基磺草酮(Mesotrione)為對照藥進(jìn)行除草活性測試并計(jì)算抑制率,其結(jié)果見表1。從表1可以看出,大部分化合物對油菜根長的生長抑制率高于對稗草株高的生長抑制率,且含氟基團(tuán)和肟醚結(jié)構(gòu)的引入對稗草株高的生長抑制率均無顯著影響。橙酮肟醚衍生物(1f~1l)對油菜根長的生長抑制活性明顯高于橙酮肟衍生物(1a~1e),這可能是由于橙酮肟的極性大和溶解性差的原因造成的。與1f相比,氟原子的引入提高了化合物對油菜根長的生長抑制活性,而且氟原子所在位置不同對除草活性也有影響,如在用藥量為100μg·mL-1時,當(dāng)R1為Me時,1h(55.4%,R=3-F)>1g(32.2%,R=2-F)>1i(16.5%,R=4-F)>1f(11.9%,R=H)。值得注意的是,CF3基團(tuán)的引入對除草活性有明顯的促進(jìn)作用,含有CF3的1j和1l在用藥量為1000μg·mL-1時,對油菜根長的生長抑制率分別為83.6%和90.6%,略低于甲基磺草酮(93.4%);但當(dāng)用藥量降低至100μg·mL-1時,活性下降較多,分別為65.0%和78.2%。另外,通過與文獻(xiàn)[10]對比發(fā)現(xiàn),在橙酮的6-位引入肟甲(乙)醚結(jié)構(gòu)可以提高化合物的除草活性。
表1 1a~1l 的除草活性Table1 Herbicidal activities of 1a~1l
*μg·mL-1
設(shè)計(jì)并合成了12個新型的橙酮肟(醚)衍生物,其結(jié)構(gòu)經(jīng)1H NMR,IR和元素分析的表征。初步的生物活性測試結(jié)果表明:在用藥量為100μg·mL-1時,(Z)-2-(3-三氟甲基苯基亞甲基)-6-[(Z,E)-2-(乙氧基亞氨基)丙氧基]-3(2H)-苯并呋喃酮(1l)對油菜根長的生長抑制率為78.2%。
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SynthesisandHerbicidalActivitiesofNovelAuroneOxime(Ether)Derivatives
LI Ting, ZHANG Min,BAO Yong-tuan, CHEN Guo-yan, LI Ji, YANG Liu-qing
(School of Chemistry and Chemical Engineering,Jiangsu University,Zhenjiang 212013,China)
6-Hydroxylaurone derivatives(4a~4e)were prepared by reaction ofm-dihydroxybenzene with chloroacetonitrile,and then cyclization and condensation with aromatic aldehyde.Twelve novel aurone oxime(ether)derivatives(1a~1l)were synthesized by4a~4ewith 1-chloroacetone and NH2OR1·HCl,respectively.The structures were characterized by1H NMR,IR and elemental analysis.The preliminary bioassay results showed that some of them displayed certain herbicidal activity.For example,inhibition of (Z)-2-(3-trifluoromethylphenyl)methylene-6-[(Z,E)-2-(ethoxy imino)propoxy]-3(2H)-benzofuranone(1l)was 78.2% againstBrasicacampestrisat 100μg·mL-1.
aurone;oxime(ether);synthesis;herbicidal activity
2014-03-05;
2014-05-15
中國博士后科學(xué)基金資助項(xiàng)目(2012M521021);江蘇大學(xué)高級專業(yè)人才科研啟動基金資助項(xiàng)目(09JDG064)
李婷(1988-),女,漢族,河南商丘人,碩士研究生,主要從事有機(jī)合成的研究。
張敏,博士,副教授,E-mail:zhangmin@ujs.edu.cn;仰榴青,博士,教授,E-mail:yangliuqing@ujs.edu.cn
O626;O621.3
A
1005-1511(2014)04-0453-06