CN1130344C - 取代的喹啉除草剂中间体及制备方法 - Google Patents

取代的喹啉除草剂中间体及制备方法 Download PDF

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CN1130344C
CN1130344C CN96106657A CN96106657A CN1130344C CN 1130344 C CN1130344 C CN 1130344C CN 96106657 A CN96106657 A CN 96106657A CN 96106657 A CN96106657 A CN 96106657A CN 1130344 C CN1130344 C CN 1130344C
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吴文学
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Wyeth Holdings LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C07D215/32—Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C07D215/32—Esters
    • C07D215/34—Carbamates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Quinoline Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

本发明是合成除草剂2-(4-异丙基-4-甲基-5-氧-2-咪唑烷基)-5-甲氧基甲基烟酸有用的取代喹啉中间体及其制备方法。

Description

取代的喹啉除草剂中间体 及制备方法
本发明是合成除草剂2-(4-异丙基-4-甲基-5-氧-2-咪唑烷基)-5-甲氧基甲基烟酸有用的取代喹啉中间体及制备除草剂中间体3-甲氧基甲基-7-或8-羟基喹啉的方法。
本发明是下式所示除草剂中间体化合物
Figure C9610665700051
其中X为直链或支链C1-C6烷基、苯基、-O-苯基、-O-C1-C4直链或支链烷基或
Figure C9610665700052
，其中Y和Z各自为H、直链或支链C1-C6烷基或苯基；B为H、卤素或季铵卤化物；以及制备下式I化合物的方法
Figure C9610665700053
包括(1)将如下式II化合物
Figure C9610665700061
其中X为直链或支链C1-C6烷基、苯基、-O-苯基、-O-C1-C4直链或支链烷基或
Figure C9610665700062
其中Y和Z各自为H、直链或支链C1-C6烷基或苯基与基团卤化剂，其中卤素为溴或氯，进行反应，生成如下式III化合物
Figure C9610665700063
(2)将化合物III与无活性β-氢的叔胺反应，生成下式IV化合物其中，B为季铵卤化物；
(3)在密闭的反应器中，在约120℃至约180℃温度范围内，将化合物IV和一种碱在甲醇中反应，生成式I化合物；或在密闭的反应器中，在约65℃至约180℃温度范围内，在过渡金属盐的存在下，将化合物IV和一种碱在甲醇中反应，生成式I化合物。
化合物3-甲氧基甲基-8-羟基喹啉在用于合成美国专利5,334,576的除草剂2-(4-异丙基-4-甲基-5-氧-2-咪唑烷基)-5-甲氧基甲基烟酸的5-甲氧基甲基-2，3-吡啶二羧酸中间体的制备上是有用的。
本发明在下面的实施例中进一步加以说明，但不能认为受这些
实施例的限制。
                    实施例1
          酰化的8-羟基-3-甲基喹啉的制备
将8-羟基-3-甲基喹啉盐酸盐(200g，1.02mol)和氢氧化钠(102g，2.55mol)在1000ml水中的混合物用乙酐(208g，2.04mol)0-10℃处理1小时以上，室温搅拌1小时。再加入部分乙酐(50g，0.49mol)，所得混合物再搅拌1小时。滴加饱和碳酸氢钠(100ml)。滤集粗产物，水洗，60℃真空干燥，从乙酸乙酯和庚烷中重结晶，得白色针状体(168.5g，得率82％)。
Figure C9610665700081
将8-羟基-3-甲基喹啉盐酸盐(10g，0.051mol)和三乙胺(15.5g，0.15mol)在100ml二氯甲烷中的混合物用苯甲酰氯(10.8g，0.077mol)0-10℃处理1小时以上，室温搅拌3小时。加水，有机相用水洗三次，用硫酸镁干燥。蒸发，从庚烷/甲苯中重结晶，得产物淡黄色结晶(8.8g，得率65％)。
同样制得其它酰化的8-羟基-3-甲基喹啉。
                     实施例2
                    季盐的制备
Figure C9610665700082
将8-乙酸基-3-甲基喹啉(168.5g，0.84mol)、N-溴丁二酰亚胺(NBS)(177.9g，1.00mol)和2，2′-偶氮二异丁腈(AIBN)(6.7g，0.004mol)在1675ml氯苯中的溶液用氮气吹扫，在氮气下80-90℃加热2小时，冷却至室温并过滤。滤液与丙酮(700ml)混合，并用三甲胺(75.4mg，1.28ml)0-5℃处理，5-10℃搅拌30分钟，然后室温搅拌1小时，过滤。滤饼用丙酮洗涤，60℃真空干燥，得白色固体(180g，总收率63％)。获得的最高收率为77％。
其它酰化的8-乙酸基-3-甲基喹啉以相似的收率得到相应的季盐。
季盐制备的条件变异和关键因素
(1)氯苯是推荐的溶剂。
(2)浓度可低至0.2g乙酸酯/10ml溶剂，或高至1g乙酸酯/10ml溶剂。它可更加浓缩，只要所有的反应剂在反应温度下均溶解。
(3)温度通常限制在80-95℃。温度低于此范围时反应缓慢，高于此范围时出现副反应。
(4)AIBN的量可为2％-10％。
(5)与三甲胺的反应通常在-10-10℃进行。
(6)母体化合物8-羟基-3-甲基喹啉抑制溴化作用，因而其含量应限制在5％以下。
(7)溴化作用在氮气氛围下进行。氧气可阻滞该反应。
                     实施例3
             8-羟基-3-甲氧基甲基喹啉
Figure C9610665700091
将溴化(8-乙酸基喹啉-3-基)甲基三甲铵(80g，0.24mol)的15％甲醇钠甲醇液(250g，0.69mol)在加压反应器中120℃加热18小时，减压浓缩。残渣用水稀释，将pH调至7-8，过滤。滤饼用水洗，60℃真空干燥，得一棕黄色固体(收率91％)。
实施例4-17阐述采用不同条件的甲氧基化反应。将溴化季铵的甲醇溶液和3当量碱，可任选一催化剂，在密封的反应器中65-180℃加热16-96小时，减压浓缩。残渣用水稀释，pH调至7-8，过滤。滤饼用水洗涤，60℃真空干燥，得棕黄色固体产物。实施例          条件              时间(小时)     收率4     无催化剂，NaOMe，65℃        31          4％5     无催化剂，LiOMe，65℃        31          50％6     5％CuSO4，NaOMe，65℃       31          65％7     10％CuSO4，NaOMe，65℃      22          94％8     10％CuSO4，K2CO3，65℃   96          73％9     50％CuSO4，K2CO3，65℃   47          98％10    5％FeSO4，K2CO3，65℃    96          67％11    10％ZnCl2，NaOMe，65℃      20          38％12    1-2％CuSO4，K2CO3，150℃ 22          69-91％13    1-2％CuSO4，NaOMe，120℃    17-21       ～80％14    无催化剂，13％NaOMe，120℃   19          73％15    无催化剂，15％NaOMe，120℃   18          74％16    无催化剂，NaOMe，150℃       17          73％17    无催化剂，NaOMe，180℃       16          69％18    无催化剂，K2CO3，150℃    16.5        65％
当式IV的X＝Ph时，季盐和碳酸钾在甲醇中150℃加热18小时后，得到粗收率82％的终产物。
当式IV的X＝OMe时，季盐和碳酸钾在10％CuSO4存在下，在回流甲醇中加热22小时，得到粗收率90％的终产物。
甲氧基化的条件变异和关键因素
(1)过渡金属例如，但不限于，CuSO4、FeSO4、ZnSO4、ZnCl2催化此反应。
(2)反应温度可在65℃-180℃间变化。更高的温度可引起副反应，更低的温度则反应可能非常缓慢。
(3)甲醇是较佳的溶剂。二甘醇二甲醚或DMSO，和NaOMe一起，也可用作溶剂。
(4)甲醇钠和碳酸钾对于反应是最佳的，虽然其它碱，如LiOMe、KOMe、Ca(OMe)2、Mg(OMe)2、NaHCO3、Na2CO3、KHCO3、CaCO3、Me3N、Et3N和吡啶可在适当的条件，如较高的温度下使用。事实上，反应可不加碱而进行，因为在反应过程中产生碱(Me3N)。
(5)浓度不是关键性的。所采用的最高浓度是15％NaOMe，或3g季盐/10ml甲醇，最低浓度是0.2g季盐/10ml甲醇。

Claims (9)

1.下式所示化合物
Figure C9610665700021
其中X为直链或支链C1-C6烷基、苯基、-O-苯基、-O-C1-C4直链或支链烷基或其中Y和Z各自为H、直链或支链C1-C6烷基或苯基；
B为H、卤素或季铵卤化物。
2.按权利要求1所述的化合物，其中X为-CH3，且-OCOX在8位上，B为溴或溴化叔铵。
3.按权利要求1所述的化合物，其中X为苯基，B为溴或溴化叔铵。
4.按权利要求1所述的化合物，其中X为叔丁基，B为溴或溴化叔铵。
5.按权利要求1所述的化合物，其中X为8位上的-OCH3，B为溴。
6.按权利要求1所述的化合物，其中X为-OCH3，B为溴化季铵。
7.权利要求1所述化合物的制备方法，其特征在于：
(1)当所述化合物为式III化合物时
将如下式II化合物
Figure C9610665700032
其中X为直链或支链C1-C6烷基、苯基、-O-苯基、-O-C1-C4直链或支链烷基或其中Y和Z各自为H、直链或支链C1-C6烷基或苯基与基团卤化剂，其中卤素为溴或氯，进行反应；
(2)当所述化合物为式IV化合物时其中，B为季铵卤化物，将式III化合物
Figure C9610665700035
与无活性β-氢的叔胺反应。
8.按权利要求7所述的方法，其中式II、III、IV化合物的XOCO-在8位上，用于生成式III化合物的基团卤化剂为N-溴丁二酰亚胺，用于生成式IV化合物的叔胺为三甲胺。
9.按权利要求7所述的方法，其中用于生成式II化合物的酰化剂为乙酐，用于生成式III化合物的基团卤化剂为N-溴丁二酰亚胺，用于生成式IV化合物的叔胺为三甲胺。
CN96106657A 1995-06-05 1996-05-24 取代的喹啉除草剂中间体及制备方法 Expired - Lifetime CN1130344C (zh)

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US08/461,786 US5633380A (en) 1995-06-05 1995-06-05 Substituted quinoline herbicide intermediates and process

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Citations (2)

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Publication number Priority date Publication date Assignee Title
DE1223393B (de) * 1958-09-02 1966-08-25 Metalsalts Corp Verfahren zur Herstellung von Carbonsaeuresalzen von Carbonsaeureestern des gegebenenfalls substituierten 8-Hydroxychinolins
US3362960A (en) * 1964-06-04 1968-01-09 Geigy Chem Corp O-quinolyl-(8)-n-methyl carbamic acid esters

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Publication number Priority date Publication date Assignee Title
US3297525A (en) * 1962-10-19 1967-01-10 Merck & Co Inc Fungicidal compositions comprising salicylates of 8 hydroxy quinoline carboxylic esters
GB2192877A (en) * 1986-07-22 1988-01-27 Shell Int Research Herbicidal imidazolinyl compounds
US5288866A (en) * 1991-12-20 1994-02-22 American Cyanamid Company 5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for the preparation of 5- (substituted methyl)-2,3-pyridinedicarboxylic acids
US5281713A (en) * 1991-12-20 1994-01-25 American Cyanamid Company Process for the manufacture of 2-alkoxymethylacrolein

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1223393B (de) * 1958-09-02 1966-08-25 Metalsalts Corp Verfahren zur Herstellung von Carbonsaeuresalzen von Carbonsaeureestern des gegebenenfalls substituierten 8-Hydroxychinolins
US3362960A (en) * 1964-06-04 1968-01-09 Geigy Chem Corp O-quinolyl-(8)-n-methyl carbamic acid esters

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TR199600442A1 (tr) 1996-12-21
DK0747362T3 (da) 2003-01-06
IL118503A (en) 2001-01-11
CN1138034A (zh) 1996-12-18
HU9601520D0 (en) 1996-07-29
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AR002304A1 (es) 1998-03-11
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SK283842B6 (sk) 2004-03-02
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IL118503A0 (en) 1996-09-12
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US5633380A (en) 1997-05-27
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