CN1040757C - 双环三唑除草剂制备方法 - Google Patents
双环三唑除草剂制备方法 Download PDFInfo
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Abstract
本发明涉及制备式(Ⅰ)化合物的方法,其中Q和Z如说明书中所定义。
Description
发明背景
US4,925,481,US4,213,773和US4,881,967公开了四氢三唑并吡啶-3-酮除草剂及其制备方法,但未公开本方法。
发明概述
R1是H,卤素,OH,C1-C6烷基,C1-C6卤代烷基,C1-C6烷氧基,C1-C6卤代烷氧基,C1-C6烷硫基,C1-C6卤代烷硫基,C2-C6链烯氧基,C2-C6链烯硫基,C2-C6卤代链烯氧基,C2-C6卤代链烯硫基,C3-C6炔氧基,C3-C6炔硫基,C3-C6卤代炔氧基,C3-C6卤代炔硫基,C2-C6烷羰基,C2-C6烷氧羰基,C4-C8链烯氧基羰基,C3-C8烷羰基烷氧基,C3-C8烷羰基烷硫基,C3-C8烷氧羰基烷氧基,C3-C8烷氧羰基烷硫基,C5-C8链烯氧羰基烷氧基,C5-C8链烯氧基羰基烷硫基,苯氧基和苯硫基,其中苯基可任选地带卤素取代基;
R4是H,C1-C3烷基和卤素;
R5是H,卤素,C1-C3卤代烷基,环丙基,乙烯基,C2炔基,CN,C(O)R6,C(O)2R6,C(O)NR6R7,CR8R9CN,CR8R9C(O)R6,CR8R9C(O)2R6,CR8R9C(O)NR6R7,CHR8OH,CHR8OC(O)R6和OCHR8OC(O)NR6R7;
R6和R7独立表示H和C1-C4烷基;
R8和R9独立表示H和C1-C4烷基;
W是O和S;
Z是CH2和O;
m是1-5和
n是1-3;当m或n大于1时,R1可以相同或独立选自上面定义的取代基;
该方法涉及下述反应;
第二,使式IV化合物与式III的肼或其盐反应,
Q-NHNH2
III其中Q定义同上;生成式II化合物,其中R2定义同上;以及
在上述定义中,术语“烷基”,不论是单独使用或在复合词(如“烷硫基”或“卤代烷基”)中使用时,都包括直链或支链烷基,例如甲基,乙基,正丙基,异丙基或各种丁基、戊基和己基异构体。“烷氧基”,不论单独使用或在复合词(如“卤代烷氧基”)中使用,都包括甲氧基,乙氧基,正丙氧基,异丙氧基,和各种丁氧基、戊氧基和己氧基异构体。“链烯基”,不论单独使用或在复合词(如“卤代链烯基”或“链烯基硫基”)中使用,都包括直链或支链烯类,如乙烯基,1-丙烯基,2-丙烯基,3-丙烯基和各种丁烯基、戊烯基和己烯基异构体。“炔基”,不论单独使用或在复合词(如“卤代炔基”或“炔硫基”)中使用,都包括直链或支链炔类,如1-丙炔基,3-丙炔基和各种丁炔基、戊炔基和己炔基异构体。“烷硫基”包括甲硫基,乙硫基和各种丙硫基、丁硫基、戊硫基和己硫基异构体。
术语“卤素”,不论单独使用或在复合词(如“卤代烷基”)中使用,是指氟、氯、溴或碘。此外,当其用在复合词(如“卤代烷基”)中、并且所述烷基可以被卤原子部分或全部取代时,该卤原子可以相同或不同。卤代烷基的实例包括CF3,CH2CH2F,CF2CF3,CH2CHFCl,和CHBrCH3。术语“卤代链烯基”和“卤代炔基”按“卤代烷基”的类似方法进行定义。
取代基中碳原子总数用前缀Ci-Cj表明,其中i和j为1-8的数。例如,C3炔氧基表示OCH2C≡CH,C4炔氧基包括OCH2C≡CCH3,OCH2CH2C≡CH,和OCH(CH3)C≡CH;C2烷羰基表示C(O)CH3,C4烷羰基包括C(O)CH2CH2CH3和C(O)CH(CH3)2;C2烷氧羰基表示C(O)2CH3,C4烷氧羰基包括C(O)2CH2CH2CH3和C(O)2CH(CH3)2;C3烷羰基烷氧基表示OCH2C(O)CH3,C4烷羰基烷氧基包括OCH2C(O)CH2CH3,OCH(CH3)C(O)CH3,和OCH2CH2C(O)CH3;C3烷氧羰基烷氧基表示OCH2C(O)2CH3,C4烷氧羰基烷氧基包括OCH2C(O)2CH2CH3,OCH(CH3)C(O)2CH3和OCH2CH2C(O)2CH;C3烷羰基烷硫基表示SCH2C(O)CH,C4烷羰基烷硫基包括SCH2C(O)CH2CH3,SCH(CH3)C(O)CH3和SCH2CH2C(O)CH3;最后一个实例C3烷氧羰基烷硫基表示SCH2C(O)2CH3,C4烷氧羰基烷硫基包括SCH2C(O)2CH2CH3,SCH(CH3)C(O)2CH3和SCH2CH2C(O)2CH3。
当一个化合物由一个带有下标(该下标表示所述取代基数目可能大于1)的取代基取代时,所述取代基(超过1个时)独立地选自所限定的上述一组取代基。
制备最有使用价值的产品的特别优选的方法是:
A).制备Q是Q-1的式I化合物的方法。
B).制备选自下述式I化合物的方法A中的优选方法:
2-[2,4-二氯-5-(2-丙炔基氧)苯基]-5,6,7,8-四氢
-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮;
[[2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑
并[4,3-a]吡啶-2(3H)-基)苯基]硫代]乙酸乙酯;
2-(2,4-二氯-5-羟基苯基)-5,6,7,8-四氢-1,2,4-三
唑并[4,3-a]吡啶-3(2H)-酮。
C).制备Q是Q-2的式I化合物的方法。
D).制备下述式I化合物的方法C中的优选方法:
2-(5,7-二氯-2,3-二氢-2-甲基-4-苯并呋喃基)-5,6,
7,8-四氢-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮。
E).制备Q是Q-3的式I化合物的方法。
F).制备Q是Q-4的式I化合物的方法。
G).制备下述式I化合物的方法F中的优选方法:
6-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2
(3H)-基)-4-(2-丙炔基)-2H-1,4-苯并噁嗪-3(4H)-酮。
由本发明方法制得的化合物对于在栽培作物中选择性和/或普遍的阔叶和禾本杂草控制是一种有效的除草剂,这些作物包括咖啡,可可树,油棕榈,橡胶树,糖苷蔗,柠檬,葡萄,果树,坚果树,香蕉,大蕉,波萝,针叶松,例如火炬松,和turf species Kentucky bluegrass,St.Augustine grass,Kentucky fescue and bermudagrass。
本发明中间体本身可用于生产本发明活性除草剂的方法
本发明的详细描述
该方法的第一阶段(a)(反应示意式I)原则性地概括了下述的反应:在-40℃至40℃温度下,较好是5-15℃,或在惰性烃类、氯代烃类中,或在醚类溶剂中,较好的是甲苯,含有或不含有溶剂,使1当量或多当量无水卤化氢,较好是2-2.5当量氯化氢与式V化合物(较好是氨基甲酸甲酯)接触。溶剂的用量最好是原料V的100至2000%(重量),该反应可以在大气压或高于大气压条件下、在连续或分批条件下进行。通常,分离式IV化合物的方法通常是减压除去多余的卤代烃,然后除去溶剂,或通过过滤并且用适合的含氧溶剂(如四氢呋喃)洗涤。或者,在除去多余的卤化氢后,该产品不经纯化而直接使用。式V的氨基甲酸酯或是已知物,或可通过本领域技术人员已知的各种方法制得。例如,Synthesis,(1984)831中描述了式V的氨基甲酸酯的制备方法,即烯类和酰胺类进行酰胺汞化作用-还原性烷基化作用。
反应示意式I阶段(a)其中R2、X和Z如前面所定义。
该方法的第二阶段(b)如反应示意式II所示,它原则性地概括了下述反应:在适当的非反应溶剂(较好的是乙腈或醇类,如甲醇,但不限于此)中,在-40至80℃温度下,较好是-20℃至30℃,使式IV的氢卤酸盐与大约等摩尔量的式III的肼化合物或其盐以及足量的酸结合剂(以维持有效的pH值于3.5-7.0、较好是4.5-5.5之间)进行接触。所用的酸结合剂可以是任何弱碱性无水物质,但较好的是弱叔胺碱,如吡啶,或碱金属羧酸盐,如乙酸钠,并且较好的用量是0.5-1.5当量-以式III和IV化合物中被结合的酸的总量为计算基础。式III的肼或是已知物,或是可用本领域技术人员已知的各种方法制得。例如US4,881,967以及其中所引用文献中叙述了由本领域已知的适当取代的胺通过重氮化作用制备肼的方法。
反应示意式II
阶段(b)其中Q的定义如前所述。
式I化合物制备方法(阶段(c))原则性地概括了下述反应:任选地在一种溶剂中,在0-150℃温度区间内,优选地在一种酸催化剂存在下,或大气压下、低于大气压下或高于大气压力下,使式II化合物发生反应(反应示意式III)。有很多种溶剂可供选用,但优选的是非酮化合物、中性或仅为弱酸性的化合物。特别好的是甲苯、丙酮、乙酸乙酯和乙酸异丙酯,优选的用量是100-2,000%。该反应任选地进行酸催化,可以使用0.01-100摩尔当量的甲酸、乙酸、丙酸及其类似物,优选用量为0.1-3当量,本方法优选的操作温度为25-100℃。然后通过冷却反应混合物、任选地加入一种非极性溶剂(如己烷)并过滤沉淀的产物,可分离出本方法的最终产品式I化合物。
或者,式I化合物也可以通过加热阶段(b)的反应混合物由25-150℃来制得,但优选的是先分离式II中间化合物,再进行阶段(c)中所述的反应。
实施例1
A步:制备2-亚氨基-1-哌啶甲酸甲酯盐酸盐
在0-5℃往5.1千克5-氰基戊酰胺和4.45千克甲醇钠在27.5千克甲醇中的溶液的液面下加入6.5千克溴。将所得混合物慢慢转移到24千克热的(60℃)甲醇中,并在50-65℃下保温。蒸馏除去大部分甲醇。加入甲苯30千克,继续蒸馏,直至除去所有甲醇。然后将混合物过滤,得到大约18%(重量)的4-氰基丁基氨基甲酸甲酯的甲苯溶液。取一部分该溶液(259克)于15-20℃保温,同时用2小时鼓泡通入33克无水氯化氢。在150托压力下清除该两相混合物中过量的HCl,加入100毫升四氢呋喃。将产品滤出并用四氢呋喃洗涤以除去残留的HCl。得到标题化合物,为53克(95%)白色晶状固体。熔点118-119℃(分解)。1H NMR(CDCl3)δ1.7(t,2H),1.8(t,2H),3.15(t,2H),3.8(t,2H),3.82(s,3H),10.2(br s,1H),12.75(br s,1H).
B步:制备2-[[2,4-二氯-5-(2-丙炔氧基)苯基]亚肼基]-1-哌啶甲酸甲酯
往12.3克无水乙酸钠和80毫升乙腈的混合物中加入13.3克91%2,4-二氯-5-(炔丙基氧基)苯基-肼盐酸盐,剧烈搅拌30分钟以后,将混合物冷至0-5℃,然后加入10.0克A步的产品。该混合物在5-10℃剧烈搅拌1小时,然后倒入200毫升冷水中。将产品滤出,先后用30毫升冷水和30毫升冷的异丙醇洗涤,干燥后得16.0克(95%)固体标题化合物。熔点137-138℃。1H NMR(CDCl3)δ1.74(m,2H),1.82(m,2H),2.46(t,2H,J=6Hz),2.52(d,1H,J=2.4Hz),3.68(t,2H,J=6Hz),3.73(s,3H),4.75(d,2H,J=2.4Hz),7.13(s(1H),7.23(s,1H),7.26(br s,1H).
C步:制备2-[2,4-二氯-5-(2-丙炔基氧基)苯基]-5,6,7,8-四氢-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮
将10.0克B步产品和0.50克冰醋酸在50毫升甲苯中的混合物在100℃加热2小时,同时用氮气流除去甲醇蒸气。于70℃加入50毫升己烷,在25℃滤出产品,用己烷洗涤,得8.0克(94%)标题化合物,熔点168-169℃。1H NMR(CDCl3)δ1.9(m,4H),2.55(t,1H,J=2.4Hz),2.74(t,2H,J=6Hz),3.67(t,2H,J=6Hz),4.74(d,2H,J=2.4Hz),7.13(s,1H),7.50(s,1H).
实施例2
A步:制备2-[2,4-二氯-5-羟基苯基)亚肼基]-1-哌啶甲酸甲酯
将18.5克乙酸钠和320毫升干燥甲醇混合物冷至-20℃,加入实施例1A步产品28.8克,然后加入34.8克96%纯的2,4-二氯-5-肼基苯酚盐酸盐。该混合物在-10-0℃搅拌1小时,然后倒入500毫升冰水中。将产品滤出,用三份100毫升水洗涤,真空干燥得44.6克标题化合物,为橙色固体。熔点158-159℃。1H NMR(DMSO-d6)δ1.7(m,4H),2.5(t,2H,J=5.4Hz),3.57(t,2H,J=5.4Hz),3.64(s,3H),7.00(s,1H),7.25(s,1H),8.15(br s,1H),10.3(br s,1H).
B步:制备2-(2,4-二氯-5-羟基苯基)-5,6,7,8-四氢-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮
将50克A步产品和乙酸在甲苯中的5%溶液(100毫升)的混合物在65-70℃加热3小时,同时用氮气流除去甲醇。然后加入50毫升己烷,将混合物在室温下过滤,依次用50毫升己烷和两份5毫升冷异丙醇洗涤,干燥后得到37克标题化合物,熔点214-216℃(218-219℃,用含水乙醇重结晶)。1H NMR(DMSO-d6)δ1.8(m,4H),2.6(t,2H,J=6Hz),3.50(t,2H,J=6Hz),7.09(s,1H),10.9(br s,1H).
Claims (10)
R1是H,卤素,OH,C1-C6烷基,C1-C6卤代烷基,C1-C6烷氧基,C1-C6卤代烷氧基,C1-C6烷硫基,C1-C6卤代烷硫基,C2-C6链烯氧基,C2-C6链烯硫基,C2-C6卤代链烯氧基,C2-C6卤代链烯硫基,C3-C6炔氧基,C3-C6炔硫基,C3-C6卤代炔氧基,C3-C6卤代炔硫基,C2-C6烷羰基,C2-C6烷氧羰基,C4-C8链烯氧基羰基,C3-C8烷羰基烷氧基,C3-C8烷羰基烷硫基,C3-C8烷氧羰基烷氧基,C3-C8烷氧羰基烷硫基,C5-C8链烯氧羰基烷氧基,C5-C8链烯氧基羰基烷硫基,苯氧基或苯硫基,其中苯基可任选地带卤素取代基;
R2是C1-C6烷基;
R3是H,C1-C6烷基,C1-C6卤代烷基,C2-C6烷氧基烷基,C3-C6链烯基,C3-C6炔基或
R4是H,C1-C3烷基或卤素;
R5是H,卤素,C1-C3烷基,C1-C3卤代烷基,环丙基,乙烯基,C2炔基,CN,C(O)R6,C(O)2R6,C(O)NR6R7,CR8R9CN,CR8R9C(O)R6,CR8R9C(O)2R6,CR8R9C(O)NR6R7,CHR8OH,CHR8OC(O)R6或OCHR8OC(O)NR6R7;
R6和R7独立表示H或C1-C4烷基;
R8和R9独立表示H或C1-C4烷基;
W是O或S:
Z是CH2或O;
m是1-5,和
n是1-3;当m或n大于1时,R1可以相同或独立选自规定的取代基。
4.权利要求1所述的方法,其中Q是Q-1。
5.权利要求4所述的方法,其中式I化合物选自下面一组化合物:
2-[2,4-二氯-5-(2-丙炔基氧)苯基]-5,6,7,8-四氢-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮;
[[2-氯-4-氟-5-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)苯基]硫代]乙酸乙酯;和
2-(2,4-二氯-5-羟基苯基)-5,6,7,8-四氢-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮。
6.权利要求1所述的方法,其中Q是Q-2。
7.权利要求6所述的方法,其中式I化合物是2-(5,7-二氯-2,3-二氢-2-甲基-4-苯并呋喃基)-5,6,7,8-四氢-1,2,4-三唑并[4,3-a]吡啶-3(2H)-酮。
8.权利要求1所述的方法,其中Q是Q-3。
9.权利要求1所述的方法,其中Q是Q-4。
10.权利要求9所述的方法,其中式I化合物是6-(5,6,7,8-四氢-3-氧代-1,2,4-三唑并[4,3-a]吡啶-2(3H)-基)-4-(2-丙炔基)-2H-1,4-苯并噁嗪-3(4H)-酮。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US3721793A | 1993-03-26 | 1993-03-26 | |
US08/037,217 | 1993-03-26 | ||
US08/037217 | 1993-03-26 |
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CN1119857A CN1119857A (zh) | 1996-04-03 |
CN1040757C true CN1040757C (zh) | 1998-11-18 |
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US (1) | US5705639A (zh) |
EP (1) | EP0690844B1 (zh) |
JP (1) | JPH08508485A (zh) |
KR (1) | KR100291007B1 (zh) |
CN (1) | CN1040757C (zh) |
AU (1) | AU6444394A (zh) |
BR (1) | BR9406187A (zh) |
DE (1) | DE69406437T2 (zh) |
ES (1) | ES2108439T3 (zh) |
HU (1) | HUT72001A (zh) |
IL (1) | IL108968A (zh) |
PL (1) | PL310823A1 (zh) |
TW (1) | TW275623B (zh) |
WO (1) | WO1994022828A1 (zh) |
ZA (1) | ZA941965B (zh) |
Families Citing this family (2)
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EP0784053A1 (de) * | 1996-01-15 | 1997-07-16 | Degussa Aktiengesellschaft | Verfahren zur Herstellung von Triazolinonherbiziden |
DE19754322B4 (de) * | 1997-12-08 | 2006-01-26 | Degussa Ag | Verfahren zur Herstellung von Salzen cyclischer Amidine |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4139364A (en) * | 1977-08-09 | 1979-02-13 | E. I. Du Pont De Nemours And Company | Triazolone herbicides |
US4925481A (en) * | 1987-11-27 | 1990-05-15 | Schering Aktiengesellschaft | Substituted bicyclic triazole herbicides |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4213773A (en) * | 1977-11-17 | 1980-07-22 | E. I. Du Pont De Nemours And Company | Herbicidal substituted bicyclic triazoles |
US4080192A (en) * | 1977-04-14 | 1978-03-21 | E. I. Du Pont De Nemours And Company | Substituted bicyclic triazines |
US4881967A (en) * | 1986-12-10 | 1989-11-21 | E. I. Du Pont De Nemours And Company | Heterocyclic 2,3-dihydrobenzofuran herbicides |
-
1994
- 1994-03-08 AU AU64443/94A patent/AU6444394A/en not_active Abandoned
- 1994-03-08 PL PL94310823A patent/PL310823A1/xx unknown
- 1994-03-08 DE DE69406437T patent/DE69406437T2/de not_active Expired - Fee Related
- 1994-03-08 WO PCT/US1994/002497 patent/WO1994022828A1/en active IP Right Grant
- 1994-03-08 EP EP94912194A patent/EP0690844B1/en not_active Expired - Lifetime
- 1994-03-08 US US08/525,502 patent/US5705639A/en not_active Expired - Fee Related
- 1994-03-08 KR KR1019950704092A patent/KR100291007B1/ko not_active IP Right Cessation
- 1994-03-08 BR BR9406187A patent/BR9406187A/pt not_active IP Right Cessation
- 1994-03-08 ES ES94912194T patent/ES2108439T3/es not_active Expired - Lifetime
- 1994-03-08 JP JP6522080A patent/JPH08508485A/ja active Pending
- 1994-03-08 HU HU9502812A patent/HUT72001A/hu unknown
- 1994-03-08 CN CN94191580A patent/CN1040757C/zh not_active Expired - Fee Related
- 1994-03-14 IL IL108968A patent/IL108968A/xx active IP Right Grant
- 1994-03-21 TW TW083102509A patent/TW275623B/zh active
- 1994-03-21 ZA ZA941965A patent/ZA941965B/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4139364A (en) * | 1977-08-09 | 1979-02-13 | E. I. Du Pont De Nemours And Company | Triazolone herbicides |
US4925481A (en) * | 1987-11-27 | 1990-05-15 | Schering Aktiengesellschaft | Substituted bicyclic triazole herbicides |
Also Published As
Publication number | Publication date |
---|---|
AU6444394A (en) | 1994-10-24 |
EP0690844B1 (en) | 1997-10-22 |
IL108968A (en) | 1997-06-10 |
DE69406437D1 (de) | 1997-11-27 |
HUT72001A (en) | 1996-03-28 |
JPH08508485A (ja) | 1996-09-10 |
DE69406437T2 (de) | 1998-05-07 |
EP0690844A1 (en) | 1996-01-10 |
PL310823A1 (en) | 1996-01-08 |
BR9406187A (pt) | 1999-06-01 |
TW275623B (zh) | 1996-05-11 |
US5705639A (en) | 1998-01-06 |
ES2108439T3 (es) | 1997-12-16 |
CN1119857A (zh) | 1996-04-03 |
WO1994022828A1 (en) | 1994-10-13 |
IL108968A0 (en) | 1994-06-24 |
ZA941965B (en) | 1995-09-21 |
KR100291007B1 (ko) | 2001-09-17 |
HU9502812D0 (en) | 1995-11-28 |
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