CN1174834A - 制备酰基氯化合物的方法 - Google Patents
制备酰基氯化合物的方法 Download PDFInfo
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- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
Abstract
本发明涉及一种有效地制备式Ⅰ的吖嗪酰氯化合物的方法(环Az在说明书中定义)。在该方法中,在酸性催化剂存在下,用酸处理式Ⅱ的三氯甲基吖嗪,该酸可形成在反应过程中可减压馏去的酰基氯。本发明还涉及将该方法制得的式Ⅰ化合物用于制备(杂)芳氧基吖嗪基甲酰胺。
Description
本发明涉及一种从三氯甲基吖嗪制备吖嗪酰氯(azinyl acid chloride)化合物的方法，其中，在酸性催化剂存在下用酸处理三氯甲基吖嗪，该酸能够形成在反应过程中可减压馏去的酰基氯。
吖嗪酰氯化合物是制备大量不同化合物的合适中间体，这些化合物可用作农用化学品、药物或液晶。特别是，它们是制备如EP 0 447 004A中所述的除草剂吡啶甲酰胺(pyridinecarboxamide)的关键中间体。
美国专利No.3,875,226公开了一种方法，其中在路易斯酸存在下用二氧化硫处理三氯甲基化合物，从而形成酰基氯化合物和亚硫酰氯。
然而，该方法几乎不能以技术规模加以应用，因为二氧化硫在正常条件下是气态的，因而必须在冷却和/或加压条件下进行，这些条件对于大规模生产是不适用的。
欧洲专利申请EP 0 646 666揭示，在氯化烃和路易斯酸存在下，用水来水解三氯甲基吖嗪。
然而，该方法在配料率和精确地确定等摩尔量的水方面存在问题。过量的水会导致所需的酰基氯化合物的水解，从而降低产率。
此外，最近因为环境问题所以使用氯化烃是不好的，而且在已有技术的程序中所使用的溶剂量很大。另外，使用水/1，2-二氯乙烷时所需的反应时间非常长(24小时)。
EP 0 091 022公开了，使用三氯乙酸和五氟化锑或氯化铁作为路易斯酸，从5-三氯甲基异噁唑制备异噁唑-5-羧酸。
然而，没有暗示表明该方法可以应用于其他的三氯甲基吖嗪和其他的羧酸。尽管使用五氟化锑的反应在2小时内完成，但是使用氯化铁需8小时。该方法的缺点之一是，昂贵的五氯化锑是有毒的，因而该方法不能用于技术规模的生产。此外，如果使用五氯化锑制备吖嗪酰氯(azinoyl chloride)时，产率低。
德国专利申请DE 30 04 693公开了一种通过芳族磺酸与三氯甲基芳烃的反应而同时制备芳族磺酰卤和苯甲酰卤的方法。
然而，分离这些产物需要非常复杂的蒸馏技术。
待解决的问题是，提供一种高产率地制备吖嗪酰氯的方法，它避免了使用造成环境问题的溶剂和长反应时间。
令人意外的是，式I的吖嗪酰氯化合物
其中Az为任意取代的吖嗪基，可以在一种方法的协助下高产率地轻易制备，该方法包括：在酸性催化剂存在下，加热式II的三氯甲基吖嗪和一种酸，
Az-CCl3 (II)
其中Az的定义如上，而该酸形成在反应过程中可减压馏去的酰基氯，较佳地是在酸性催化剂存在下和减压下，加热式II的该三氯甲基吖嗪和式III的酸
R1-X-OH (III)
其中，R1为C1-6烷基或C1-6卤代烷基，而X为CO或SO2。
因此，本发明的一个目的是提供一种制备吖嗪酰氯化合物的有效新方法。
本发明的另一目的是用本发明方法获得的吖嗪酰氯制备(杂)芳氧基吖嗪基甲酰胺。
通过下列的描述和所附的权利要求，本发明的其他目的和优点对于本领域的技术人员而言是明显的。
一般而言，除非另外说明，否则术语“任意取代的吖嗪基”在本文中用于Az时，指具有至少一个氮原子的6元杂环基团，尤其是吡啶基或嘧啶基，它们可被一个或多个卤素原子、硝基、氰基、烷基(较佳地为C1-6烷基)、烷氧基(较佳地C1-6烷氧基)、4-烷基-环己基(较佳地4-C1-6烷基-环己基)、或卤代烷基(较佳地C1-6卤代烷基)所任意取代。
通常，被至少一个吸电子基，尤其是一个或多个卤素原子、硝基、氰基或卤代烷基所取代的杂芳族基是优选的。
在一个具体的优选例子中，Az为式V的任意取代的吡啶基，
其中，R2是氢或卤素原子或烷基或卤代烷基，以及
Z是卤素原子。
一般而言，除非另外说明，否则术语“烷基或卤代烷基”在本文中用于基团或分子一部分时，指直链或支链的基团或分子部分。通常，这样的基团有10个之内，尤其是6个之内的碳原子。合适的烷基或卤代烷基部分有1-6个碳原子，较佳地为1-3个碳原子。优选的烷基部分是乙基或特别优选的甲基。
优选的卤代烷基是式-(CX2)n-Y的多卤代或全卤代烷基，其中n是1-10，较佳地1-6，更佳地1-3的整数，X是氟或氯，而Y是氢或X。优选的多卤代烷基部分是五氟乙基、五氯乙基，或尤其是二氟-或三氟甲基，或二氯-或三氯甲基基团。
任意取代的部分可以是未取代的，或者具有1至最大可能数目的取代基。一般，存在0-2个取代基。
此外，本发明的优选例子是这样的方法，其中：
(a)该方法中，Az是被一个卤素原子取代并且任选地被一个烷基或卤代烷基所取代的吖嗪基，较佳地是式V的取代吡啶基，
其中，R2是氢原子或烷基或卤代烷基，以及
Z是卤素原子，尤其是6-卤代吡啶-2-基。
(b)该方法中，R1为任选地被一个或多个氯原子取代的甲基。
(c)该方法中，酸性催化剂选自硫酸、FeCl3和ZnCl2。
(d)该方法中，加热基本上由式II的三氯甲基吖嗪、式III的酸和酸性催化剂所构成的反应混合物，而且在反应过程中形成的式IV酰基氯被减压馏去
R1-X-Cl (IV)
其中，R1和X的定义如上。
(e)该方法中，1摩尔式II三氯甲基吖嗪用0.4-1.2摩尔式III的酸进行处理。
(f)该方法中，X为SO2而酸性催化剂是含水量小于5重量％的硫酸。
(g)该方法中，1摩尔的式II三氯甲基芳烃在0.01-0.10摩尔酸性催化剂存在下用式III的酸进行处理。
在室温和反应混合物的回流温度之间进行反应，较佳地在升高的温度下，更佳地在回流温度下，更佳地在75-160℃之间，尤其是85-130℃之间的温度下进行。
本发明的另一方面是，
用式I化合物制备式VI的(杂)芳氧基-杂芳基甲酰胺
其中，
Az是可任选地被一个烷基或卤代烷基取代的吖嗪基，较佳地是可任意取代的吡啶基，
Ar是任意取代的芳基或杂芳基，较佳地是被至少一个卤素原子或卤代烷基或卤代烷氧基所取代的苯基，尤其是吡啶-2，6-二基，特别是3-三氟甲基苯基，
R3是氢原子或烷基，较佳地是氢原子，以及
R4是任意取代的烷基、芳基、杂芳基或环烷基，较佳地是被至少一个卤素原子或卤代烷基或卤代烷氧基所取代的苯基，尤其是4-氟苯基，其中，
(a)式I的单卤代吖嗪酰氯是根据权利要求1-10中任一权利要求，用式II的单卤代吖嗪基三氯甲烷制备的，
(b)与式VII的胺反应
HNR3R4 VII
其中R3和R4的定义如上，该反应可任选地在惰性溶剂和/或碱存在下进行，和
(c)在碱存在下，形成的单卤代吖嗪基甲酰胺与式VIII的芳族或杂芳族羟基化合物反应，
Ar-OH VIII
其中，Ar具有所给出的定义，尤其是根据权利要求1-10中任一权利要求而获得的式I的卤代吖嗪酰氯与式VII的胺反应而不必进一步纯化。
通常，在减压下进行反应，以便蒸馏在反应过程中形成的式IV化合物。最佳地，反应是在20-400毫巴(mbar)，尤其是25-250毫巴的压力下进行。
在本发明方法的特别优选的例子中，将1当量式II三氯甲基吖嗪(更佳地其中Az是取代的吡啶基，尤其是Nitrapyrin)与0.05-0.15当量的催化剂(尤其是FeCl3)混合，然后加热至80-150℃，更佳地为110-130℃。接着将0.8-1.2当量的式III的酸(其中X为CO，尤其是一氯乙酸、二氯乙酸或三氯乙酸)加入保持于减压条件下的反应混合物中。蒸馏出相应的式IV酰基氯，直至反应结束。
通常，在这种优选的反应条件下，反应可在1-5小时，更佳地在1.5-4小时内完成。
在本发明方法的另一个特别优选例子中，将1当量式II三氯甲基吖嗪(更佳地其中Az是取代的吡啶基，尤其是Nitrapyrin)与0.01-0.05当量的催化剂(尤其是H2SO4)混合，然后加热至80-150℃，更佳地为110-130℃。接着将0.2-0.8当量式III的酸(其中X为SO2，尤其是甲磺酸)加入保持于减压条件下的反应混合物中。蒸馏出相应的烷磺酰氯，直至反应结束。
如果反应是用等摩尔量的式II杂环三氯甲基吖嗪和式III烷磺酸进行，那么会得到焦油样的副产物，这样便降低了所实现的产率并在纯化程序中造成麻烦。因此，使用过量的三氯甲基吖嗪是有利的，因为这可避免形成这些副产物。
在本发明的一个特别优选的例子中，在0.01-0.05摩尔硫酸(96-98重量％)存在下，过量1-4当量的Nitrapyrin与1摩尔甲磺酸反应。
通常，在这种优选的反应条件下，反应可在0.05-5小时，更佳地在0.3-3小时内完成。
剩下的吖嗪酰氯可用作制备所需终产物的中间体，而不必进一步纯化。也可以用标准方法纯化它们，例如结晶或蒸馏，尤其是在减压下特别是在1-100毫巴的压力下进行蒸馏。
这个新方法可用价廉的、容易获得的析出物，在技术规模上高产率地生产吖嗪酰氯。此外，在新方法中用作试剂的式III酸，可以通过将水加入反应中形成的相应酰基氯而再循环。因此，新方法仅需少量试剂。
为了便于理解本发明，给出下列阐述性的实施例。本发明并不限于所描述或阐述的具体实施例，它包括所附权利要求书的全部范围。
实施例1
制备2-氯-6-吡啶碳酰氯
[Az＝式I化合物中的2-氯-6-吡啶基]
将200mmol Nitrapyrin(2-氯-6-三氯甲基吡啶)与给定数量催化剂组成的混合物加热至90-130℃之间的温度。将200mmol有机酸在减压下加入混合物中。在反应时间内馏去反应所形成的有机酰基氯。反应通过GC分析而监测。通过常规后处理和减压蒸馏而获得产物，是无色晶体，并显示如下物理性质：
熔点74-75℃，沸点80℃/2.6Pa
1H-NMR(DMSO，300MHz)：δ(ppm)＝8.11(m，2H，3-，5-CH)，7.80(m，1H，4-CH).
13C-NMR(DMSO)：δ(ppm)＝164.7(q，COCl)，150.2(q，6-C)，148.8(q，2-C)，141.0(t，4-C)，127.9(t，3-C)，124.0(t，5-C)
实验数据列于下表，其中使用下列缩写：CPA 6-氯吡啶基-2-羧酸 AA 乙酸DCAA 二氯乙酸 CAA 一氯乙酸TCAA 三氯乙酸 PA 丙酸表1
| 有机酸 | 催化剂 | mol％催化剂 | T(℃) | p(毫巴) | t(小时) | 产率(面积％) | CPA产率(面积％) |
| AA | FeCl3 | 20 | 110 | 700 | 8 | 52 | 3 |
| CAA | FeCl3 | 20 | 120 | 180 | 1.5 | 87 | - |
| DCAA | FeCl3 | 10 | 115 | 170 | 4 | 85 | - |
| TCAA | FeCl3 | 10 | 120 | 180 | 2 | 95 | - |
| TCAA | ZnCl2 | 10 | 120 | 150 | 3 | 41 | - |
| PA | FeCl3 | 10 | 120 | 室温 | 10 | 46 | 25 |
| PA | ZnCl2 | 10 | 120 | 室温 | 10 | 30 | 15 |
实施例2
制备2-氯-6-吡啶碳酰氯
[Az＝式I化合物中的2-氯-6-吡啶基]
将给定数量的Nitrapyrin(简称NP，2-氯-6-三氯甲基吡啶)与0.005mmol催化剂组成的混合物加热至125-140℃之间的温度。将0.1mol甲磺酸在减压下加入混合物中。在0.5-2小时内馏去反应所形成的甲烷磺酰氯。反应通过GC分析而监测。获得产物，它是未反应的NP(NP的用量是过量的)和所需产物的混合物。该混合物不需进一步纯化便可用于制备除草剂吡啶甲酰胺。通过蒸馏获得产物，它是无色晶体，并显示如下物理性质：
熔点74-75℃，沸点80℃/2.6Pa
1H-NMR(DMSO，300MHz)：δ(ppm)＝8.11(m，2H，3-，5-CH)，7.80(m，1H，4-CH).
13C-NMR(DMSO)：δ(ppm)＝164.7(q，COCl)，150.2(q，6-C)，148.8(q，2-C)，141.0(t，4-C)，127.9(t，3-C)，124.0(t，5-C)
实验数据列于下表，其中从获得的、由NP和产物所构成的混合物确定产率。表2
| 实施例 | NP(mol) | 催化剂 | T(℃) | p(毫巴) | 产率(理论值的％) |
| 2a) | 0.2 | FeCl3 | 130 | 100-50 | 78 |
| 2b) | 0.2 | FeCl3 | 135 | 50-45 | 88 |
| 2c) | 0.2 | H2SO4 | 135 | 50-45 | 92 |
| 2d) | 0.2 | H2SO4 | 135 | 50-40 | 90 |
| 2e) | 0.2 | H2SO4 | 135 | 40 | 92 |
| 2f) | 0.4 | H2SO4 | 135 | 40 | 97 |
对比实施例
制备2-氯-6-吡啶碳酰氯
将200mmol Nitrapyrin与10mmol SbCl5组成的混合物加热至120℃。将200mmol三氯乙酸在常压下加入混合物中。在15小时内馏去反应所形成的三氯乙酰氯。反应通过GC分析而监测。GC显示9％产物和4％6-氯吡啶-2-基羧酸。
用途实施例
制备N-(4-氟苯基)6-(3-三氟甲基苯氧基)-吡啶-2-基甲酰胺
将实施例2e)中获得的粗产物稀释于甲苯(200毫升)中，然后在65℃加至4-氟苯胺(250mmol)中。随后将混合物加热1小时至100℃。然后冷却混合物至20℃，用稀盐酸洗涤并水蒸汽蒸馏(stripped)，得到基本上由N-(4-氟苯基)6-氯吡啶-2-基甲酰胺和未反应的NP所构成的油状物。未反应的NP被减压馏去。获得的粗产物(49.5克，87％)被稀释于甲苯(200毫升)中，并不进行进一步纯化而直接加入由碳酸钾(210mmol)、3-三氟甲基苯酚(200mmol)和二甲基乙酰胺(120mmol)所组成的混合物中。馏去甲苯，将反应混合物加热至160℃，4小时。馏去溶剂，用甲苯稀释残留物。混合物用碳酸氢钠洗涤，干燥并浓缩。在甲醇中重结晶残留物，得到标题化合物(58.2克，85％)，熔点105-107℃。
Claims (10)
1.一种制备式I的吖嗪酰氯化合物的方法，
其中Az为任意取代的吖嗪基，其特征在于，该方法包括：
在酸性催化剂存在下，加热式II的三氯甲基吖嗪和一种酸，
Az-CCl3 (II)
其中Az的定义如上，而该酸形成在反应过程中可减压馏去的酰基氯。
2.如权利要求1所述的方法，其持征在于，该酸是式III化合物
R1-X-OH (III)
其中，
R1为C1-6烷基或C1-6卤代烷基，而
X为CO或SO2。
3.如权利要求1所述的方法，其特征在于，Az是被一个卤素原子取代并且任选地被一个烷基或卤代烷基所取代的吖嗪基。
4.如权利要求1所述方法，其特征在于，酸性催化剂选自：硫酸、FeCl3和ZnCl2。
5.如权利要求1所述方法，其特征在于，Az为式V的取代的吡啶基，
其中，
R2是氢原子或烷基或卤代烷基，以及
Z是卤素原子。
6.如权利要求5所述的方法，其特征在于，Az是6-卤代吡啶-2-基。
7.如权利要求5所述的方法，其特征在于，1摩尔式II三氯甲基吖嗪用0.4-1.2摩尔式III的酸进行处理。
8.如权利要求5所述的方法，其特征在于，1摩尔的式II三氯甲基芳烃在0.01-0.10摩尔酸性催化剂存在下，用式III的酸进行处理。
9.式I化合物用于制备式VI的(杂)芳氧基杂芳基甲酰胺的用途，
其中，
Az的定义如上述任一权利要求中所述，和
Ar是任意取代的芳基或杂芳基，
R3是氢原子或烷基，以及
R4是任意取代的烷基、芳基、杂芳基或环烷基，其特征在于，
(a)式I的单卤代吖嗪酰氯是根据权利要求1-10中任一权利要求，用式II的单卤代吖嗪基三氯甲烷制备的，
(b)与式VII的胺反应
HNR3R4 VII
该反应可任选地在惰性溶剂和/或碱存在下进行，和
(c)在碱存在下，将形成的单卤代吖嗪基甲酰胺与式VIII的芳族或杂芳族羟基化合物反应，
Ar-OH VIII
其中，Ar具有所给出的定义。
10.如权利要求9所述的用途，其特征在于，式I的卤代吖嗪酰氯与式VII的胺反应而不必进一步纯化。
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| EP96113531.6 | 1996-08-23 | ||
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| EP96117863.9 | 1996-11-07 |
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| US1921767A (en) * | 1929-05-20 | 1933-08-08 | Dow Chemical Co | Method of making acid halides |
| US1965556A (en) * | 1930-03-06 | 1934-07-03 | Dow Chemical Co | Method for the preparation of acid halides |
| US2856425A (en) * | 1956-04-06 | 1958-10-14 | Du Pont | Production of aromatic acid halides |
| US3875226A (en) * | 1969-10-17 | 1975-04-01 | Dow Chemical Co | Preparation of acid halides |
| DE3004693A1 (de) * | 1980-02-08 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von aromatischen sulfonsaeurehalogeniden |
| IL68187A0 (en) * | 1982-04-01 | 1983-06-15 | Basf Ag | 5-trichloromethylisoxazole,its preparation and its use for the preparation of 5-isoxazolecarboxylic acid |
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| ZA947672B (en) * | 1993-10-05 | 1995-06-29 | Shell Internationale Researchm | Process for the preparation of acid chloride compounds. |
| JPH07291891A (ja) * | 1994-04-28 | 1995-11-07 | Tokuyama Corp | カルボン酸クロライドの製造方法 |
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