CN102491977B - 一类具有除草活性的多取代嘧啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶及制备 - Google Patents
一类具有除草活性的多取代嘧啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶及制备 Download PDFInfo
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Abstract
通式见下式具有除草活性的1-取代苯氧亚甲基-8-烷硫基-10-甲硫基嘧啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶类化合物,式中R1表示烷基、R2表示取代苯基。本化合物对单子叶和双子叶植物的生长具有显著的抑制作用,是除草剂的有效成分。
Description
技术领域
本发明涉及具有除草活性的1-取代苯氧亚甲基-8-烷硫基-10-甲硫基嘧啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶类化合物及其制备方法,以及它作为除草剂的生物活性。
背景技术
杂环类农药以其灵活多变的结构和高活性、低毒而与未来农药发展的要求相适应,且杂环化合物的研究趋向于复杂结构的杂环、双杂环以及多杂环的化合物。含氮杂环化合物因其具有良好的生物活性,在医药和农药等人类健康和农业生产中发挥着重要的作用。嘧啶类杂环衍生物是一类十分重要的含氮杂环化合物,广泛存在于动植物体内,并对动植物体的新陈代谢起着至关重要的作用,例如胞嘧啶、脲嘧啶和胸腺嘧啶等都是核糖核酸的重要组成部分。同时,嘧啶杂环作为十分有效的活性因子广泛存在于已经商品化的医药、农药以及正在开发的医药和农药的品种结构中。嘧啶杂环在农药中的影响远远高于医药,仅就已经商品化的高效含嘧啶农药可达数十乃至上百种之多,其专利已达 400 多项,商品化品种已超过 30个,代表了除草剂的发展方向和前途。
嘧啶并嘧啶类杂环衍生物由于其分子结构中同时包含了两个嘧啶活性结构单元,并且以其显著的生物活性成为当今化学界研究的热点之一,药理学研究表明: 这类化合物在杀菌、抗真菌、抗肿瘤、抗癌症、抗过敏、抗心血管疾病、杀虫剂、抗叶酸、抗病毒等方面具有很好的药效作用。嘧啶并嘧啶类化合物尤以其抗肿瘤和杀菌而受到人们的关注,它们是二氢叶酸还原酶的(DHFR)抑制剂,可用于治疗各种肿瘤、癌症、白血病。
嘧啶并三唑并嘧啶类化合物同时含有嘧啶并嘧啶及三唑并嘧啶两个高药理活性的骨架,从目前文献报道来看,此类化合物骨架非常新颖。
通过我们对近几十年的文献跟踪发现,嘧啶并三唑并嘧啶类化合物在合成方法、药理学及农药学活性等方面的报道非常少。因此我们对此类新型化合物的合成方法进行了研究,发明了一条比较成熟且环境友好的方法合成了嘧啶并三唑并嘧啶类化合物,并且对其进行了除草活性测试,从中找到了具有优良除草活性的化合物。
发明内容
本发明的目的在于探索和发现具有新结构并具有除草活性的多取代嘧啶并[5, 4-e]-1, 2, 4-三唑并[1, 5-c]嘧啶,提供一类具有除草活性的嘧啶并三唑并嘧啶衍生物及其合成方法。
本发明的化合物的结构通式如I:
式中,R1表示C1,C2,C3,C4,C5的烷基;R2表示苯基、邻甲基苯基、间甲基苯基、对甲基苯基、对氯苯基、2, 4-二氯苯基等取代苯基。
本发明所提出的的化合物的结构均没有其他专利或文献报道。
本发明的具有上述通式I的化合物对单子叶和双子叶杂草具有显著的抑制作用,可用作为除草剂的有效成分。
以通式I表示的多取代嘧啶并[5, 4-e]-1, 2, 4-三唑并[1, 5-c]嘧啶衍生物的制备方法是使通式Ⅱ所表示的化合物与原甲酸三乙酯反应生成中间体Ⅲ,Ⅲ再与苯氧乙酰肼、邻甲基苯氧乙酰肼、间甲基苯氧乙酰肼、对甲基苯氧乙酰肼、对氯苯氧乙酰肼、2,4-二氯苯氧乙酰肼反应,在乙二醇甲醚中加热回流关环,即可获得好产率。
式Ⅱ和R2OCH2CONHNH2中,R1、R2的定义与权力要求1所述的通式I中的定义相同。
上述反应中的Ⅱ与原甲酸三乙酯摩尔比为1:3-4,采用原甲酸三乙酯即为反应物又为溶剂在120℃之间反应9小时,得到中间体Ⅲ,中间体Ⅲ再与R2OCH2CONHNH2以摩尔比1:1,有机溶剂为乙二醇甲醚,在 125℃ 反应5小时,即可获得较好的收率。
下面通过实例来具体地说明本发明I的化合物的制备方法,对这些实施例仅对本发明进行说明,而不是对本发明进行限制。
实施例1 化合物1的制备
2-苯氧亚甲基-8, 10-二甲硫基嘧啶并[5, 4-e]-1, 2, 4-三唑并[1,5-c]嘧啶的制备
在50mL的圆底烧瓶中,加入0.05mol 4-氨基-5-氰基-2,6二甲硫基嘧啶、0.015mol原甲酸三乙酯和催化量的三氟乙酸,搅拌加热回流9小时。反应完后减压除去没有反应的原甲酸三乙酯,残余物用石油醚洗涤数次既得淡黄色固体4-乙氧基亚甲基氨基-5-氰基-2,6-二甲硫基嘧啶,熔点128-129℃,产率70%
将0.001mol 4-乙氧基亚甲基氨基-5-氰基-2,6-二甲硫基嘧啶,0.001mol苯氧乙酰肼和10mL乙二醇甲醚加入到50mL的圆底烧瓶中,搅拌加热回流5小时。冷却,抽滤。滤饼用少量的乙醚洗涤数次,烘干既得黄色固体,收率为76%,m.p.270-271℃。
C16H14N6OS2
IR (KBr, υ/cm-1): 1567, 1424, 1340, 1122, 1069, 955, 864, 777;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 2.76 (s, 6H, SCH 3), 5.48 (s, 2H, O-CH 2), 7.00 (s, 1H, Ar-H), 7.09 (d, J = 8.0HZ, 2H, Ar-H), 7.33 (d, J = 8.0HZ, 2H, Ar-H), 9.34 (s, 1H, CH =N); MS ( EI, m/z, % ): 370 (M+); Anal. Calcd.(%) for C16H14N6OS2: C 51.87, H 3.81, N 22.69; Found C 51.91, H 3.95, N 22.79.
化合物6、11、16、21、26按化合物1类似的方法制得,其结构鉴定数据如下:
化合物6
2-邻甲基苯氧亚甲基-8,10-二甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为76%,m.p.278-280℃
C17H16N6OS2
IR (KBr, υ/ cm-1): 1569, 1427, 1337, 1147, 945, 857, 779;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 2.33 (s, 3H, ArCH 3), 2.59 (s, 3H, SCH 3), 2.76 (s, 3H, SCH 3), 5.48 (s, 2H, O-CH 2), 6.92-7.18 (m, 4H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 384 (M+); Anal. Calcd.(%) for C17H16N6OS2: C 53.11, H 4.19, N 21.86; Found C 53.32, H 4.33, N 21.94.
化合物11
2-间甲基苯氧亚甲基-8,10-二甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为76%,m.p.250-251℃
C17H16N6OS2
IR (KBr, υ/ cm-1): 1567, 1413, 1323, 1145, 954, 853, 780;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz):2.34 (s, 3H, ArCH 3), 2.53 (s, 3H, SCH 3), 2.76 (s, 3H, SCH 3), 5.46 (s, 2H, O-CH 2), 6.83 (d, J = 8.0HZ, 1H, Ar-H), 6.87-6.92 (m, 1H, Ar-H), 6.93 (s, 1H, Ar-H), 7.18 (d, J = 8.0HZ, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 384 (M+); Anal. Calcd.(%) for C17H16N6OS2: C 53.11, H 4.19, N 21.86; Found C 53.31, H 4.24, N 21.98.
化合物16
2-对甲基苯氧亚甲基-8,10-二甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为74%,m.p.259-260℃
C17H16N6OS2
IR (KBr, υ/ cm-1): 1569, 1427, 1353, 1138, 1069, 953, 867;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 2.53 (s, 3H, ArCH 3), 2.76 (s, 6H, SCH 3), 5.49 (s, 2H, O-CH 2), 6.99 (d, J = 12.0HZ, 2H, Ar-H), 7.11 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 384 (M+); Anal. Calcd.(%) for C17H16N6OS2: C 53.11, H 4.19, N 21.86; Found C 53.29, H 4.27, N 21.93.
化合物21
2-对氯苯氧亚甲基-8,10-二甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为76%,m.p.273-275℃
C16H13ClN6OS2
IR (KBr, υ/ cm-1): 1528, 1421, 1357, 1154, 953, 874, 677;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 2.79 (s, 6H, SCH 3), 5.45 (s, 2H, O-CH 2), 7.02 (d, J = 8.0HZ, 2H, Ar-H), 7.27 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 405 (M+); Anal. Calcd.(%) for C16H13ClN6OS2: C 47.46, H 3.24, N 20.76; Found C 47.55, H 3.37, N 20.87.
化合物26
2-(2,4-二氯苯氧亚甲基)-8,10-二甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为74%,m.p.275-276℃
C16H12Cl2N6OS2
IR (KBr, υ/ cm-1): 1551, 1485, 1392, 1064, 874, 785;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz) :2.73 (s, 3H, SCH 3), 2.77 (s, 3H, SCH 3), 5.52 (s, 2H, O-CH 2), 7.11 (d, J = 8.0HZ, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 7.41 (s, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 439 (M+); Anal. Calcd.(%) for C16H12Cl2N6OS2: C 43.74, H 2.75, N 19.13; Found C 43.87, H 2.89, N 19.30.
实施例2
化合物2的制备
2-苯氧亚甲基-8-乙硫基-10-甲硫基嘧啶并[5, 4-e]-1,2,4-三唑并[1,5-c]嘧啶
在50mL的圆底烧瓶中,加入0.05mol 2-乙硫基-4-氨基-5-氰基-6-二甲硫基嘧啶、0.015mol原甲酸三乙酯和催化量的三氟乙酸,搅拌加热回流9小时。反应完后减压除去没有反应的原甲酸三乙酯,残余物用石油醚洗涤数次既得淡黄色固体2-乙硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,熔点72-73℃,产率76%
将0.001mol 2-乙硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,0.001mol苯氧乙酰肼和10mL乙二醇甲醚加入到50mL的圆底烧瓶中,搅拌加热回流5小时。冷却,抽滤。滤饼用少量的乙醚洗涤数次,烘干既得黄色固体,收率为73%,m.p.249-251℃。
C17H16N6OS2
IR (KBr, υ/ cm-1): 1567, 1424, 1340, 1122, 1069, 955, 864, 777;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.45-1.51 (m, 3H, SCH2 CH 3), 2.76 (s, 3H, SCH 3), 3.31-3.36 (m, 2H, SCH 2CH3), 5.48 (s, 2H, OCH 2), 7.00 (s, 1H, Ar-H), 7.09 (d, J = 8.0HZ, 2H, Ar-H), 7.33 (d, J = 8.0HZ, 2H, Ar-H), 9.34 (s, 1H, CH=N); 13C NMR (δ/ppm, TMS,CDCl3/ CF3COOD, 100MHz): 13.2, 14.8, 27.2, 63.2, 112.8, 114.5, 114.6, 114.7, 115.7, 118.5, 129.8, 151.9, 156.3, 157.1, 162.1, 179.8; MS ( EI, m/z, % ): 384 (M+); Anal. Calcd.(%) for C17H16N6OS2: C 53.11, H 4.19, N 21.86; Found C 53.33, H 4.09, N 21.97.
化合物7、12、17、22、27按化合物2类似的方法制得,其结构鉴定数据如下:
化合物7
2-邻甲基苯氧亚甲基-8-乙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为79%,m.p.258-260℃
C18H18N6OS2
IR (KBr, υ/ cm-1): 1568, 1431, 1341, 1146, 953, 853, 776;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.37-1.40 (m, 3H, SCH2 CH 3), 2.33 (s, 3H, ArCH 3), 2.76 (s, 3H, ArCH 3), 3.30-3.34 (m, 2H, SCH 2CH3), 5.48 (s, 2H, OCH 2), 6.92-7.18 (m, 4H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 398 (M+); Anal. Calcd.(%) for C18H18N6OS2: C 54.25, H 4.55, N 21.09; Found C 54.45, H 4.75, N 21.28.
化合物12
2-间甲基苯氧亚甲基-8-乙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为73%,m.p.247-249℃
C18H18N6OS2
IR (KBr, υ/ cm-1): 1570, 1401, 1340, 1146, 954, 857, 777;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.40-1.46 (m, 3H, SCH2 CH 3), 2.34 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.32-3.34 (m, 2H, SCH 2CH3), 5.46 (s, 2H, OCH 2), 6.83 (d, J = 8.0HZ, 1H, Ar-H), 6.87-6.92 (m, 1H, Ar-H), 6.93 (s, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 398 (M+); Anal. Calcd.(%) for C18H18N6OS2: C 54.25, H 4.55, N 21.09; Found C 54.42, H 4.74, N 21.28.
化合物17
2-对甲基苯氧亚甲基-8-乙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为75%,m.p.250-252℃
C18H18N6OS2
IR (KBr, υ/ cm-1): 1569, 1425, 1356, 1138, 1070, 953, 864;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.45-1.51 (m, 3H, SCH2 CH 3), 2.53 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.32-3.34 (m, 2H, SCH 2CH3), 5.45 (s, 2H, OCH 2), 6.99 (d, J = 12.0HZ, 2H, Ar- H), 7.11 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 398 (M+); Anal. Calcd.(%) for C18H18N6OS2: C 54.25, H 4.55, N 21.09; Found C 54.44, H 4.66, N 21.20.
化合物22
2-对氯苯氧亚甲基-8-乙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为73%,m.p.259-261℃
C17H15ClN6OS2
IR (KBr, υ/ cm-1): 1570, 1424, 1355, 1157, 954, 860, 677;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.45-1.51 (m,3 H, SCH2 CH 3), 2.79 (s, 3H, SCH 3), 3.29-3.35 (m, 2H, SCH 2CH3), 5.45 (s, 2H, OCH 2), 7.02 (d, J = 8.0HZ, 2H, Ar-H), 7.27 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS (EI, m/z, % ): 419 (M+); Anal. Calcd.(%) for C17H15ClN6OS2: C 48.74, H 3.61, N 20.06; Found C 48.87, H 3.77, N 20.30.
化合物27
2-(2,4-二氯苯氧亚甲基)-8-乙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为75%,m.p.249-250℃
C17H14 Cl2N6OS2
IR (KBr, υ/ cm-1): 1541, 1482, 1391, 1070, 954, 874, 785;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.47-1.51 (m, 3H, SCH2 CH 3), 2.76 (s, 3H, ArCH 3), 3.30-3.36 (m, 2H, SCH 2CH3), 5.52 (s, 2H, OCH 2), 7.11 (d, J = 8.0HZ, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 7.41 (s, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 453 (M+); Anal. Calcd.(%) for C17H14Cl2N6OS2: C 45.04, H 3.11, N 18.54; Found C 45.29, H 3.09, N 18.73.
实施例3
化合物3的制备
2-苯氧亚甲基-8-正丙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
在50mL的圆底烧瓶中,加入0.05mol 2-正丙硫基-4-氨基-5-氰基-6-二甲硫基嘧啶、0.015mol原甲酸三乙酯和催化量的三氟乙酸,搅拌加热回流9小时。反应完后减压除去没有反应的原甲酸三乙酯,残余物用石油醚洗涤数次既得淡黄色固体2-正丙硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,熔点69-71℃,产率83%
将0.001mol 2-正丙硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,0.001mol苯氧乙酰肼和10mL乙二醇甲醚加入到50mL的圆底烧瓶中,搅拌加热回流5小时。冷却,抽滤。滤饼用少量的乙醚洗涤数次,烘干既得黄色固体,收率为81%,m.p.263-265℃。
C18H18N6OS2
IR (KBr, υ/cm-1): 1568, 1422, 1343, 1160, 1073, 954, 860, 777;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.05-1.25 (m, 3H, SCH2CH2 CH 3), 1.84-1.89 (m, 2H, SCH2 CH 2CH3), 2.74 (s, 3H, SCH 3), 3.30-3.34 (m, 2H, SCH 2CH2 CH3), 5.47 (s, 2H, OCH 2), 7.00 (s, 1H, Ar-H), 7.09 (d, J = 8.0HZ, 2H, Ar-H), 7.31 (d, J = 8.0HZ, 2H, Ar-H), 9.39 (s, 1H, CH=N); MS ( EI, m/z, % ): 398 (M+); Anal. Calcd.(%) for C18H18N6OS2: C 54.25, H 4.55, N 21.09; Found C 54.39, H 4.71, N 21.30.
化合物8、13、18、23、28按化合物3类似的方法制得,其结构鉴定数据如下:
化合物8
2-邻甲基苯氧亚甲基-8-正丙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为81%,m.p.214-216℃
C19H20N6OS2
IR (KBr, υ/ cm-1): 1568, 1428, 1340, 1144, 949, 857, 780;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.94-1.00 (m, 3H, SCH2CH2 CH 3), 1.81-1.86 (m, 4H, SCH 2 CH 2 CH3), 2.33 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.28-3.33 (m, 2H, SCH 2CH2CH3), 5.48 (s, 2H, OCH 2), 6.92-7.18 (m, 4H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 426 (M+); Anal. Calcd.(%) for C20H22N6OS2: C 56.31, H 5.20, N 19.70; Found C 56.52, H 5.39, N 19.82.
化合物13
2-间甲基苯氧亚甲基-8-正丙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为76%,m.p.258-260℃
C19H20N6OS2
IR (KBr, υ/ cm-1): 1567, 1422, 1342, 1144, 952, 859, 779;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.07-1.23 (m, 3H, SCH2CH2 CH 3), 1.83-1.87 (m, 2H, SCH2 CH 2CH3), 2.33 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.29-3.33 (m, 2H, SCH 2CH2CH3), 5.46 (s, 2H, OCH 2), 6.83 (d, J = 12.0HZ, 1H, Ar-H), 6.86 -6.91 (m, 1H, Ar-H), 6.92 (s, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 412 (M+); Anal. Calcd.(%) for C19H20N6OS2: C 55.32, H 4.89, N 20.37; Found C 55.43, H 4.98, N 20.56.
化合物18
2-对甲基苯氧亚甲基-8-正丙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为80%,m.p. >300℃
C19H20N6OS2
IR (KBr, υ/ cm-1): 1568, 1424, 1357, 1158, 1069, 954, 859, 779;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.07-1.23 (m, 3H, SCH2CH2 CH 3), 1.85-1.87 (m, 2H, SCH2 CH 2CH3), 2.30 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.29-3.33 (m, 2H, SCH 2CH2CH3), 5.45 (s, 2H, OCH 2), 6.99(d, J = 12.0HZ, 2H, Ar-H), 7.11 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 412 (M+); Anal. Calcd.(%) for C19H20N6OS2: C 55.32, H 4.89, N 20.37; Found C 55.41, H 4.96, N 20.47.
化合物23
2-对氯苯氧亚甲基-8-正丙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为80%,m.p.263-265℃
C18H17ClN6OS2
IR (KBr, υ/ cm-1): 1529, 1420, 1357, 1154, 954, 873, 678;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.09-1.13 (m, 3H, SCH2CH2 CH 3), 1.84-1.87 (m, 2H, SCH2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.29-3.33 (m, 2H, SCH 2CH2 CH3), 5.45 (s, 2H, OCH 2), 7.02 (d, J = 8.0HZ, 2H, Ar-H), 7.27 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); 13C NMR (δ/ppm, TMS, CDCl3/CF3COOD, 100MHz): 12.9, 15.2, 34.2, 34.4, 63.4, 112.9, 115.7, 115.9, 118.5, 116.1, 118.5, 129.6, 154.5, 155.4, 155.9, 161.9, 179.5; MS ( EI, m/z, % ): 433 (M+); Anal. Calcd.(%) for C18H17ClN6OS2: C 49.93, H 3.96, N 19.41; Found C 49.81, H 3.99, N 19.65.
化合物28
2-(2,4-二氯苯氧亚甲基)-8-正丙硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为79%,m.p.251-253℃
C18H16 Cl2N6OS2
IR (KBr, υ/ cm-1): 1552, 1486, 1394, 1063, 965, 869, 785;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 1.05-1.09 (m, 3H, SCH2CH2 CH 3), 1.76-1.84 (m, 2H, SCH2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.13-3.16 (m, 2H, SCH 2CH2 CH3), 5.52 (s, 2H, OCH 2), 7.11(d, J = 4.0HZ, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 7.41 (s, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 467 (M+); Anal. Calcd.(%) for C18H16Cl2N6OS2: C 46.25, H 3.45, N 17.98; Found C 46.38, H 3.62, N 17.91.
实施例4
化合物4的制备
2-苯氧亚甲基-8-正丁硫基-10-甲硫基嘧啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
在50mL的圆底烧瓶中,加入0.05mol 2-正丁硫基-4-氨基-5-氰基-6-二甲硫基嘧啶、0.015mol原甲酸三乙酯和催化量的三氟乙酸,搅拌加热回流9小时。反应完后减压除去没有反应的原甲酸三乙酯,残余物用石油醚洗涤数次既得淡黄色固体2-正丁硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,熔点68-69℃,产率80%
将0.001mol 2-正丁硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,0.001mol苯氧乙酰肼和10mL乙二醇甲醚加入到50mL的圆底烧瓶中,搅拌加热回流5小时。冷却,抽滤。滤饼用少量的乙醚洗涤数次,烘干既得黄色固体,收率为80%,m.p.277-278℃。
C19H20N6OS2
IR (KBr, υ/cm-1): 1568, 1423, 1342, 1160, 1075, 951, 860, 778;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.95-0.99 (m, 3H, SCH2CH2CH2 CH 3), 1.46-1.78 (m, 4H, SCH2 CH 2 CH 2CH3), 2.74 (s, 3H, SCH 3), 3.28-3.32 (m, 2H, SCH 2CH2CH2CH3), 5.47 (s, 2H, OCH 2), 7.01 (s, 1H, Ar-H), 7.09 (d, J = 8.0HZ, 2H, Ar-H), 7.35 (d, J = 8.0HZ, 2H, Ar-H), 9.39 (s, 1H, CH=N); MS ( EI, m/z, % ): 412 (M+); Anal. Calcd.(%) for C19H20N6OS2: C 55.32, H 4.89, N 20.37; Found C 55.40, H 4.97, N 20.47.
化合物9、14、19、24、29按化合物4类似的方法制得,其结构鉴定数据如下:
化合物9
2-邻甲基苯氧亚甲基-8-正丁硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为82%,m.p.202-204℃
C20H22N6OS2
IR (KBr, υ/ cm-1): 1568, 1428, 1340, 1144, 949, 857, 780;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.94-1.00 (m, 3H, SCH2CH2CH2 CH 3), 1.81-1.86 (m, 4H, SCH2 CH 2 CH 2CH3), 2.33 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.28-3.33 (m, 2H, SCH 2CH2CH2CH3), 5.48 (s, 2H, OCH 2), 6.92-7.18 (m, 4H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 426 (M+); Anal. Calcd.(%) for C20H22N6OS2: C 56.31, H 5.20, N 19.70; Found C 56.52, H 5.39, N 19.82.
化合物14
2-间甲基苯氧亚甲基-8-正丁硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为80%,m.p.210-212℃
C20H22N6OS2
IR (KBr, υ/ cm-1): 1567, 1418, 1323, 1139, 954, 862, 779;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.96-1.00 (m, 3H, SCH2CH2CH2 CH 3), 1.51-1.83 (m, 4H, SCH2 CH 2 CH 2CH3), 2.34 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.31-3.35 (m, 2H, SCH 2CH2CH2CH3), 5.46 (s, 2H, OCH 2), 6.83 (d, J = 12.0HZ, 1H,Ar-H), 6.86-6.91 (m, 1H, Ar-H), 6.92 (s, 1H, Ar -H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 426 (M+); Anal. Calcd.(%) for C20H22N6OS2: C 56.31, H 5.20, N 19.70; Found C 56.44, H 5.34, N 19.88.
化合物19
2-对甲基苯氧亚甲基-8-正丁硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为76%,m.p.225-226℃
C20H22N6OS2
IR (KBr, υ/ cm-1): 1567, 1424, 1357, 1138, 1069, 955, 864;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.96-1.00 (m, 3H, SCH2CH2CH2 CH 3), 1.40-1.73 (m, 4H, SCH2 CH 2 CH 2CH3), 2.30 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.28-3.33 (m, 2H, SCH 2CH2CH2CH3), 5.45 (s, 2H, OCH 2), 6.99 (d, J = 8.0HZ, 2H, Ar-H), 7.12 (d, J = 12.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 426 (M+); Anal. Calcd.(%) for C20H22N6OS2: C 56.31, H 5.20, N 19.70; Found C 56.50, H 5.34, N 19.88.
化合物24
2-对氯苯氧亚甲基-8-正丁硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为81%,m.p.242-244℃
C19H19ClN6OS2
IR (KBr, υ/ cm-1): 1569, 1423, 1355, 1160, 954, 860;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.96-1.00 (m, 3H, SCH2CH2CH2 CH 3), 1.53-1.81 (m, 4H, SCH2 CH 2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.31-3.35 (m, 2H, SCH 2CH2CH2CH3), 5.44 (s, 2H, OCH 2), 7.02 (d, J = 8.0HZ, 2H, Ar-H), 7.27 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 447 (M+); Anal. Calcd.(%) for C19H19ClN6OS2: C 51.05, H 4.28, N 18.80; Found C 51.27, H 4.39, N 18.96.
化合物29
2-(2,4-二氯苯氧亚甲基)-8-正丁硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为81%,m.p.207-208℃
C19H18 Cl2N6OS2
IR (KBr, υ/ cm-1): 1554, 1484, 1392, 1143, 954, 861, 785;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.94-1.00 (m, 3H, SCH2CH2CH2 CH 3), 1.49-1.81 (m, 4H, SCH2 CH 2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.41-3.53 (m, 2H, SCH 2 CH2CH2CH3), 5.52 (s, 2H, OCH 2), 7.10 (d, J = 8.0HZ, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 7.41 (s, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 481 (M+); Anal. Calcd.(%) for C19H18Cl2N6OS2: C 47.40, H 3.77, N 17.46; Found C 47.52, H 3.99, N 17.55.
实施例5
化合物5的制备
2-苯氧亚甲基-8-正戊硫基-10-甲硫基嘧啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
在50mL的圆底烧瓶中,加入0.05mol 2-正戊硫基-4-氨基-5-氰基-6-二甲硫基嘧啶、0.015mol原甲酸三乙酯和催化量的三氟乙酸,搅拌加热回流9小时。反应完后减压除去没有反应的原甲酸三乙酯,残余物用石油醚洗涤数次既得淡黄色固体2-正戊硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,熔点64-65℃,产率81%
将0.001mol 2-正戊硫基-4-乙氧基亚甲基氨基-5-氰基-6-甲硫基嘧啶,0.001mol苯氧乙酰肼和10mL乙二醇甲醚加入到50mL的圆底烧瓶中,搅拌加热回流5小时。冷却,抽滤。滤饼用少量的乙醚洗涤数次,烘干既得黄色固体,收率为77%,m.p.216-218℃。
C20H22N6OS2
IR (KBr, υ/ cm-1): 1569, 1433, 1339, 1161, 1076, 951, 861, 777;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.91-0.95 (m, 3H, SCH2CH2CH2CH2 CH 3), 1.38-1.84 (m, 6H, SCH2 CH 2 CH 2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.31-3.34 (m, 2H, SCH 2CH2CH2CH2 CH3), 5.47 (s, 2H, OCH 2), 7.00 (s, 1H, Ar-H), 7.09 (d, J = 12.0HZ, 2H, Ar-H), 7.33 (d, J = 8.0HZ, 2H, Ar-H), 9.39 (s, 1H, CH=N); MS ( EI, m/z, % ): 426 (M+); Anal. Calcd.(%) for C20H22N6OS2: C 56.31, H 5.20, N 19.70; Found C 56.41, H 5.33, N 19.88.
化合物10、15、20、25、30按化合物5类似的方法制得,其结构鉴定数据如下:
化合物10
2-邻甲基苯氧亚甲基-8-正戊硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为76%,m.p.183-185℃
C21H24N6OS2
IR (KBr, υ/ cm-1): 1567, 1423, 1336, 1147, 950, 859, 787;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.96-0.99 (m, 3H, SCH2CH2CH2 CH2 CH 3), 1.81-1.88 (m, 6H, SCH2 CH 2 CH 2 CH 2CH3), 2.33 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.30-3.34 (m, 2H, SCH 2CH2CH2CH2CH3), 5.48( s, 2H, OCH 2), 6.92-7.18 (m, 4H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 440 (M+); Anal. Calcd.(%) for C21H24N6OS2: C 57.25, H 5.49, N 19.07; Found C 57.36, H 5.66, N 19.18.
化合物15
2-间甲基苯氧亚甲基-8-正戊硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为77%,m.p.202-203℃
C21H24N6OS2
IR (KBr, υ/ cm-1): 1567, 1417, 1356, 1145, 954, 856, 779;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.91-0.94 (m, 3H, SCH2CH2CH2CH2 CH 3), 1.25-1.84 (m, 6H, SCH2 CH 2 CH 2 CH 2CH3), 2.34 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.31-3.34 (m, 2H, SCH 2CH2CH2CH2CH3), 5.46 (s, 2H, OCH 2), 6.813 (d, J = 12.0HZ, 1H, Ar-H), 6.86-6.91 (m, 1H, Ar -H), 6.92 (s, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 440 (M+); Anal. Calcd.(%) for C21H24N6OS2: C 57.25, H 5.49, N 19.07; Found C 57.34, H 5.59, N 19.25.
化合物20
2-对甲基苯氧亚甲基-8-正戊硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为82%,m.p.240-242℃
C21H24N6OS2
IR (KBr, υ/ cm-1): 1565, 1432, 1360, 1135, 1069, 953, 779;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.95-0.99 (m, 3H, SCH2CH2CH2CH2 CH 3), 1.33-1.74 (m, 6H, SCH2 CH 2 CH 2 CH 2CH3), 2.29 (s, 3H, ArCH 3), 2.76 (s, 3H, SCH 3), 3.30-3.34 (m, 2H, SCH 2CH2CH2CH2CH3), 5.47 (s, 2H, OCH 2), 6.98 (d, J = 8.0HZ, 2H, Ar-H), 7.12 (d, J = 12.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 440 (M+); Anal. Calcd.(%) for C21H24N6OS2: C 57.25, H 5.49, N 19.07; Found C 57.44, H 5.64, N 19.34.
化合物25
2-对氯苯氧亚甲基-8-正戊硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为77%,m.p.245-246℃
C20H21ClN6OS2
IR (KBr, υ/ cm-1): 1530, 1420, 1357, 1155, 955, 873, 677;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.96-1.00 (m, 3H, SCH2CH2CH2CH2 CH 3), 1.45-1.83 (m, 6H, SCH2 CH 2 CH 2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.3-3.35 (m, 2H, SCH 2CH2CH2CH2CH3), 5.44 (s, 2H, OCH 2), 7.02 (d, J = 8.0HZ, 2H, Ar-H), 7.27 (d, J = 8.0HZ, 2H, Ar-H), 9.40 (s, 1H, CH=N); MS ( EI, m/z, % ): 461 (M+); Anal. Calcd.(%) for C20H21ClN6OS2: C 52.11, H 4.59, N 18.23; Found C 52.32, H 4.52, N 18.33.
化合物30
2-(2,4-二氯苯氧亚甲基)-8-正戊硫基-10-甲硫基嘧啶啶并[5,4-e]-1,2,4-三唑并[1,5-c]嘧啶
所得纯品为黄色固体,收率为78%,m.p.286-287℃
C20H20 Cl2N6OS2
IR (KBr, υ/ cm-1): 1553, 1486, 1392, 1063, 955, 873, 785;
1H NMR (δ/ppm, CDCl3, TMS, 400MHz): 0.94-0.99 (m, 3H, SCH2CH2CH2CH2 CH 3), 1.51-1.82 (m, 6H, SCH2 CH 2 CH 2 CH 2CH3), 2.76 (s, 3H, SCH 3), 3.40-3.45 (m, 2H, SCH 2CH2CH2CH2CH3), 5.48 (s, 2H, OCH 2), 7.10 (d, J = 8.0HZ, 1H, Ar-H), 7.18 (d, J = 4.0HZ, 1H, Ar-H), 7.41 (s, 1H, Ar-H), 9.40(s, 1H, CH=N); MS ( EI, m/z, % ): 495 (M+); Anal. Calcd.(%) for C20H20Cl2N6OS2: C 48.48, H 4.07, N 16.96; Found C 48.26, H 4.12, N 17.12.
采用上述类似的方法,可以制备其他的化合物。表1中所列的为本发明合成的部分化合物。
表中省略的符号的含义:Me-甲基、Et-乙基、n-Pr-正丙基、n-Bu-正丁基、n-Amyl-正戊基、Ph-苯基
表1已合成的部分化合物
本发明式1的化合物制成粒剂、水合剂、乳剂、可流动剂来使用。也可与其它除草剂、杀菌剂、杀虫剂、杀螨剂、植物生长调节剂、肥料以及土壤改良剂混合使用或同时并用。
实施例6
除草活性试验
试验仪器:
电子天平一台、烧杯、滴管、移液管、洗耳球、培养皿、圆形滤纸、刻度尺、蒸馏水、DMF、乳化剂(吐温-80)、待测样品。供试植物为小麦(Wheat,单叶子杂草(Monocotyledonous weeds))、稗草(Barnyard grass,单叶子杂草(Monocotyledonous weeds))、萝卜(Radish , 双子叶杂草(Dicotyledonous weeds))、黄瓜(Cucumber,双子叶杂草(Dicotyledonous weeds))。
测试方法:
表面皿离体除草活性测试法:
用电子天平称量3-5mg待测样品,加入少量DMF溶解,滴加1滴乳化剂(吐温-80),加3-5mL蒸馏水配成1000mg/mL的溶液,取此溶液1mL加蒸馏水稀释到10mL,即配成100mg/mL的试样溶液,同样取1mL100mg/mL的试样溶液加蒸馏水稀释到10 mL,即配成10mg/mL的试样溶液。用直径为9cm的培养皿,内置两层滤纸及15-20粒小麦、稗草、萝卜和黄瓜的种子,分别加入100mg/mL(100ppm)和10mg/mL(10ppm)的试样溶液作培养液。用上述方法,不用药样溶液,直接用蒸馏水作培养液,作空白对照,用盖子盖上培养皿。将培养皿水平放置在人工培养箱中培养,温度为25℃,培养三天后,每天光照8小时,处理8天后调查测试情况。测定植株根及茎的长度,取其中10株的平均值计算结果。结果为正值说明药剂具有抑制作用,为负值说明药剂具有促进作用。
效果=[(空白平均长度-处理平均长度)/空白平均长度]*100
活性标准:A级:≥90%, B级:≥70%, C级:≥50% ,D级:<50%
I化合物的测试结果见表:
Claims (5)
3.权利要求1所述通式I表示的化合物的应用,其特征是作为除草剂的有效成分。
4.权利要求1所述通式I表示的化合物的应用,其特征是作为单子叶植物除草剂的有效成分。
5.权利要求1所述通式I表示的化合物的应用,其特征是作为双子叶植物除草剂的有效成分。
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