CN1035659A - 3，3-二芳基丙烯酸酰胺的制备 - Google Patents

3，3-二芳基丙烯酸酰胺的制备 Download PDF

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CN1035659A
CN1035659A CN89100850A CN89100850A CN1035659A CN 1035659 A CN1035659 A CN 1035659A CN 89100850 A CN89100850 A CN 89100850A CN 89100850 A CN89100850 A CN 89100850A CN 1035659 A CN1035659 A CN 1035659A
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CN1019971C (zh
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于尔根·库茨
路德维希·施罗德
鲍尔·郝尔得·布里若
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Beijing million green environment Technology Co., Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms

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Abstract

通过在碱存在下使二苯酮与乙酰胺反应制备3，3-二芳基丙烯酸酰胺，该方法的特征在于用醇钠作为碱。

Description

本发明涉及一种3，3-二芳基丙烯酸酰胺的制备方法。
EP0120321A1，EP0208999A1和EP0219756A1公开了某些3，3-二芳基丙烯酸酰胺和这类化合物的各种制备方法。这些化合物具有杀真菌活性并且特别适合于控制光合致病真菌。EP0294907公开了一种制备这类化合物的不同的方法，该方法包括最好在强碱（如叔丁酸钾，某种碱金属氢氧化物或碳酸盐，或叔丁基锂）存在下，使二苯酮与适当的乙酰胺反应。但是后一种方法的产率一般低于50%。
业已发现如果在EP0294907的方法中用叔醇钠作为碱，则产率可出人意料地增加到90%以上。因此，本发明提供一种制备通式Ⅰ的3，3-二芳基丙烯酸酰胺的方法，
Figure 891008500_IMG6
Figure 891008500_IMG7
其中
R1为C1-4-烷基，C1-4-烷氧基，NH2，NHC1-4-烷基，N（C1-4-烷基）2，C3-4-烯基，C3-4-炔基，C3-4-烯氧基，C3-4-炔氧基，或C3-6-环烷基;
R2为C1-4-烷基，C1-4-烷氧基或卤素;
R3为氢或卤素;
R4为氢，卤素，C1-4-烷基或C1-4-烷氧基;
R5为氢，被1个或多个选自C1-4-烷基，C1-4-烷氧基和卤素任意取代的苯基，被1个或多个卤原子任意取代的C1-12烷基，C3-7-环烷基，联苯基，或苯氧基苯基，各自被苯基任意取代的C2-6-烯基或C2-6-炔基，或萘基或C5-8-环烯基;
x为单键，-O-，-S（O）p-，-N＝N-，-CHR9O-OCHR9-，-CHR9S（O）p-，-S（O）pCHR9-，-（CH2）n-，-HC＝CH-，或-C＝C-;
R6为C1-4-烷基，C3-7-环烷基，苄基，C3-4-烯基或C3-4-炔基;
R7为C1-4-烷基;
R8为氢，C1-4-烷基或C1-4-烷氧基;
R9为氢或C1-4-烷基;
p为0，1或2;并且
n为1-10的整数
通过在碱存在下使式Ⅱ的二苯酮
Figure 891008500_IMG8
（其中A和B的含意同上）与式Ⅲ的乙酰胺
（其中Q的含意同上）反应进行制备，该方法的特征在于所用的碱是叔醇钠。
醇化物可从任何叔醇得到，但用式Ⅳ的化合物获得了良好的结果
其中每个R各为1-4个碳原子的烷基。最好是两个R为甲基，而剩下的R为甲基，乙基，丙基或丁基。就式Ⅰ化合物的产率而言，用得自戊醇和丁醇的醇化物获得了极好的结果。醇化物可现场制备或加入制备好的化合物，醇化物可按已知方法，例如在惰性溶剂（如甲苯）存在下使氢化钠与叔醇反应来制备。
本发明的方法可在惰性溶剂（如甲苯，苯，乙醚，二甘醇二甲醚，四氢呋喃，N，N-二甲基甲酰胺）存在下进行。也可用某一种过量的反应成分作为溶剂。根据各成分的反应性，可在冷却，室温或提高温度至反应混合物的回流温度下进行反应。一般说来，反应在10°～150℃的温度下发生。
过量的醇钠（最好是1.5-2倍）和/或过量的乙酰胺是有利的。后者可被回收并再参加反应。
本发明的方法可被用于制备通式Ⅰ的所有化合物，但是它特别适用于式Ⅰ中的各基团如下所示的式Ⅰ化合物
在基团A中：
R1为C1-4-烷氧基，C1-4-烷基或氨基
R2为C1-4-烷氧基，C1-4-烷基或卤素
R3为氢或卤素
在基团B中：
R4为氢或卤素
R5为氢，苯基或卤苯基
x为单键或-O-
Q表示其中R8和R9均为氢的吗啉基。卤素或卤-取代基可以是氟，氯，溴或碘原子，但最好是氯或溴原子。
在基团A中，苯环上的取代最好在3位和4位或在3，4和5位上，这种取代的特别优选的实例为3，4-二甲氧基，3-乙氧基-4-甲氧基，3-氯-4-甲氧基，3-溴-4-甲氧基，3-甲基-4-甲氧基，3-乙基-4-甲氧基，3-丙基-4-甲氧基，3，4-二甲基，3-氨基-4-甲氧基，3，5-二氯-4-氨基和3-甲氧基-4-甲基。其中，苯环的3，4-二甲氧基取代是特别优选的。
本发明的方法可通过以下实施例来进一步说明。
实施例1
3-（4-氯苯基）-3-（3，4-二甲氧苯基）丙烯酸酰吗啉
将4-氯-3′，4′-二甲氧基二苯酮（6.29g，25mmol），叔戊基化钠（5，50g，50mmol），乙酰吗啉（23.90g，185mmol），和无水甲苯（50ml）回流搅拌8小时。冷却后，用水洗涤该溶液两次，干燥，并在旋转式蒸发器上蒸馏除去甲苯。在50℃下将粘性残余物与二异丙醚（40ml）一起搅拌。从而使该物质固化，将其冷却至室温后，将粗产物粉碎，抽滤，用二异丙醚洗涤（2×5ml）并干燥。
产率：8.1g＝83.5%理论上薄层层析纯的产物。
实施例2
3-〔4-（4-氯苯氧基）苯基〕-3-（3，4-二甲氧苯基）丙烯酸酰吗啉
将氢化钠（具有20%石蜡油;2.25g，75mmol）与无水甲苯（50ml）一起回流搅拌并在30分钟内逐滴加入叔戊醇（7.25g，82.5mmol）。当溶液冷却至100℃时，加入4-（4-氯苯氧基）-3′，4′-二甲氧基二苯酮（9.22g，25mmol）和乙酰吗啉（16.17g，125mmol）并将该混合物回流搅拌8小时。
冷却至室温后，该溶液用水洗涤（2×100ml），干燥并加到硅胶（50g）柱上。用甲苯（200ml）和甲苯-丙酮混合物（各200ml;90∶10，80∶20，70∶30）洗脱产物。将含有Rf值为0.47的物质的级分（甲苯-丙酮70∶30）合并并在旋转式蒸发器上浓缩。粗产率：11g含有甲苯的粘性油状物。将该油状物与二异丙醚（30ml）一起搅拌，从而使所需化合物缓慢地结晶。
产率：8.7g＝72.5%理论值
熔点：115～127℃
异构体比E/Z：45/55。
实施例3
3-（4-氯苯基）-3-（3，4-二甲氧苯基）丙烯酸酰吗啉
将氢化钠（具有20%石蜡油;8.0g，100mmol）与无水甲苯（70ml）一起搅拌并逐滴加入叔丁醇（8.15g，110mmol）于无水甲苯（30ml）中的溶液。溶液变清后，加入4-氯-3′，4′-二甲氧基二苯酮（13.84g，50mmol）和乙酰吗啉（19.37g，150mmol），并在搅拌下将混合物回流8小时。当溶液冷却至室温时，用水洗涤两次，干燥并在旋转式蒸发器上浓缩。从而得到24.9g粘性油状物，该油状物在二异丙醚（50ml）中搅拌而缓慢地结晶。用异丙醇/二异丙醚重结晶。
产率：19.0g＝92.8%理论值。
熔点：123～145℃。

Claims (7)

1、一种制备通式I的3，3-二芳基丙烯酸酰胺的方法
Figure 891008500_IMG1
其中
A表示
Figure 891008500_IMG2
B表示
Figure 891008500_IMG3
Q表示
Figure 891008500_IMG4
其中
R1为C1-4-烷基，C1-4-烷氧基，NH2，NHC1-4-烷基，N(C1-4-烷基)2，C3-4-烯基，C3-4-炔基，C3-4-烯氧基，C3-4-炔氧基，或C3-6-环烷基；
R2为C1-4-烷基，C1-4-烷氧基或卤素；
R3为氢或卤素；
R4为氢，卤素，C1-4-烷基或C1-4烷氧基；
R5为氢，被1个或多个选自C1-4烷基，C1-4-烷氧基和卤素任意取代的苯基，被1个或多个卤原子任意取代的C1-12烷基，C3-7-环烷基，联苯基，或苯氧基苯基，各自被苯基任意取代的C2-6-烯基或C2-6-炔基，或萘基或C5-8-环烯基；
x为单键，-O-，-S(O)p-，-N=N-，-CHR9O-，-OCHR9-，-CHR9S(O)p，-S(O)pCHR9-，-(CH2)n-，-HC=CH-，或-C=C-；
R6为C1-4-烷基，C3-7-环烷基，苄基，C3-4-烯基或C3-4-炔基；
R7为C1-4-烷基；
R8为氢，C1-4-烷基或C1-4-烷氧基；
R9为氢或C1-4-烷基；
p为0，1或2；并且
n为1-10的整数
通过在碱存在下使式Ⅱ的二苯酮
(其中A和B的含意同上)与式Ⅲ的乙酰胺
(其中Q的含意同上)反应进行制备，该方法的特征在于所用的碱是叔醇钠。
2、权利要求1所述的方法，其特征在于叔醇钠得自通式Ⅳ的醇
其中每个R均为1-4个碳原子的烷基。
3、权利要求1或2所述的方法，其特征在于叔醇钠得自戊醇或丁醇。
4、权利要求1-3任一项所述的方法，其特征在于醇钠是过量的。
5、前述权利要求任一项所述的方法，其特征在于式Ⅲ的乙酰胺是过量的。
6、前述权利要求任一项所述的方法，其特征在于使用一种惰性溶剂。
7、前述权利要求任一项所述的方法，其中反应温度为10°～150℃。
CN89100850A 1988-02-19 1989-02-17 3，3-二芳基丙烯酸酰胺的制备 Expired - Lifetime CN1019971C (zh)

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DE3805235A DE3805235A1 (de) 1988-02-19 1988-02-19 Verfahren zur herstellung von 3,3-diarylacrylsaeureamiden

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US (1) US4920222A (zh)
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JP (1) JP2573872B2 (zh)
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CN (1) CN1019971C (zh)
AT (1) ATE105286T1 (zh)
BR (1) BR8900689A (zh)
DE (2) DE3805235A1 (zh)
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JPS5421067A (en) * 1977-07-15 1979-02-16 Keigo Kishimoto Ash receiving chute with damper for refuse incinerator
DE3817711A1 (de) * 1988-05-25 1989-11-30 Shell Int Research Verfahren zur herstellung von 3,3-diphenylacrylsaeureamiden
US5071166A (en) * 1990-01-12 1991-12-10 Thomas Marino Environmentally designed transportable holding tank
AU660205B2 (en) 1991-12-23 1995-06-15 Virbac, Inc Systemic control of parasites
IL106122A (en) * 1992-07-10 1997-04-15 Shell Int Research Preparation of 3, 3-diaryl acrylic acid amides
CN101637176B (zh) * 2009-08-27 2013-09-18 深圳诺普信农化股份有限公司 农药悬浮剂

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DE3128574C2 (de) * 1981-07-20 1984-03-29 Deutsche Texaco Ag, 2000 Hamburg Verfahren zur Herstellung von N-substituierten Acryl- und Methacrylamiden
CS244440B2 (en) * 1983-02-28 1986-07-17 Celamerck Gmbh & Co Kg Method of acrylic acids' new amides production
DE3689506D1 (de) * 1985-10-09 1994-02-17 Shell Int Research Neue Acrylsäureamide.
DE3536029A1 (de) * 1985-10-09 1987-04-09 Celamerck Gmbh & Co Kg Neue acrylsaeureamide
DE3719488A1 (de) * 1987-06-11 1988-12-29 Shell Agrar Gmbh & Co Kg Verfahren zur herstellung von 3,3-diarylacrylsaeureamiden
DE3817711A1 (de) * 1988-05-25 1989-11-30 Shell Int Research Verfahren zur herstellung von 3,3-diphenylacrylsaeureamiden

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JP2573872B2 (ja) 1997-01-22
EP0329256A1 (en) 1989-08-23
IL89331A (en) 1993-06-10
US4920222A (en) 1990-04-24
JPH023639A (ja) 1990-01-09
KR970011285B1 (ko) 1997-07-09
HK1000116A1 (en) 1997-12-05
DE68915025D1 (de) 1994-06-09
CN1019971C (zh) 1993-03-03
DE3805235A1 (de) 1989-08-31
KR890012988A (ko) 1989-09-20
ES2056188T3 (es) 1994-10-01
ATE105286T1 (de) 1994-05-15
IL89331A0 (en) 1989-09-10
EP0329256B1 (en) 1994-05-04
DE68915025T2 (de) 1994-08-25

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