CN1070170C - 4-卤代-2'-硝基丁酰苯化合物的制备方法 - Google Patents
4-卤代-2'-硝基丁酰苯化合物的制备方法 Download PDFInfo
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- CN1070170C CN1070170C CN95114849A CN95114849A CN1070170C CN 1070170 C CN1070170 C CN 1070170C CN 95114849 A CN95114849 A CN 95114849A CN 95114849 A CN95114849 A CN 95114849A CN 1070170 C CN1070170 C CN 1070170C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
- C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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Abstract
本发明提供了制备式Ⅰ的4-卤代-2′-硝基丁酰苯化合物的方法。式Ⅰ化合物是制备氨磺酰脲除草剂的重要中间体。
Description
本发明涉及4-卤代-2′-硝基丁酰苯化合物的制备方法。
在美国专利第4,622,065号、5,009,699和5,280,007号及其它中述及了除草剂氨磺酰脲化合物。在美国专利第5,009,699号中揭示了对作物有选择性的氨磺酰脲除草剂1-{[邻-(环丙基羰基)苯基]氨磺酰基}-3-(4,6-二甲氧基-2-嘧啶基)脲。该氨磺酰脲化合物对作物,特别是稻具有超级的安全性范围但同时可以控制阔叶杂草及莎草。
4-卤代-2′-硝基丁酰苯化合物是制备氨磺酰脲除草剂的关键的中间产物。美国专利第4,075,346和待批美国申请第08/161,382号(1993年12月2日提交)揭示了从乙酰基丁内酯的镁烯醇型盐经多步反应制得4-卤代-2′-硝基丁酰苯化合物。但是,这些方法需要多步化学反应,这会增加化学废物并降低成本效率。
本发明的一个目的是提供有效的4-卤代-2′-硝基丁酰苯化合物单步聚制备方法,这能避免使用卤化氢反应试剂,可减少废物并提高成本效率。
本发明涉及从2-硝基苯甲酰卤化合物及乙酰基丁内酯的镁烯醇型盐制备4-卤代-2′-硝基丁酰苯的单步方法。
4-卤代-2′-硝基丁酰苯化合物是制备氨磺酰脲化合物中的重要中间产物。
本发明涉及具有结构式Ⅰ的4-卤代-2′-硝基丁酰苯化合物制备方法。
其中
X是Cl或Br;
R是氢、卤素、C1~C4烷基或C1~C4卤代烷基,该方法包括在溶剂存在下使结构式Ⅱ的2-硝基苯甲酰卤化合物其中X和R的定义同上,与至少一摩尔当量的乙酰基丁内酯的镁烯醇盐于升高的温度下反应,通过蒸发去溶剂以任意地浓缩所得的反应混合物以形成所需的式Ⅰ化合物。
上述的卤素例子是氟、氯、溴和碘。术语“C1~C4卤代烷基”定义为被一个或多个卤素原子取代的C1~C4烷基。
独特的是,业已发现从2-硝基苯甲酰卤化合物和乙酰基丁内酯的镁烯醇盐反应可以直接制备4-卤代-2′-硝基丁酰苯。反应式如流程Ⅰ所示。
有利的是,本发明的方法可以避免如脱乙酰化作用和氢卤化作用的多步过程的操作方法。此外,本发明的方法减少了废物并避免了卤化氢的使用。
然后,4-卤代-2′-硝基丁酰苯化合物如流程Ⅱ所示,容易地转变成2-氨基苯基环丙基酮化合物。
再如流程Ⅲ所示,2-氨基苯基环丙基酮化合物然后被转化成氨磺酰脲化合物。
由本发明的方法制备的较好的4-卤代-2′-硝基丁酰苯化合物是这些,其中X是Cl或Br;R是氢或卤素。
由本发明的方法制备的更好的式Ⅰ化合物是这些,其中X是Cl或Br;R是氢或5′-氟代。
本发明的方法在制备4-氯-2′-硝基丁酰苯及4-氯-5′-氟代-2′-硝基丁酰苯中尤为有用。
适用于本发明的溶剂包括芳烃及氯代芳烃,如甲苯、邻-二甲苯、对-二甲苯、间-二甲苯、苯、氯苯之类,以甲苯较为优选。
本发明的方法在升高的温度下,较好在75~155℃,最好在约100~130℃下进行。
美国专利4,075,346号及Chem.Pharm.bull.,9719~721页(1961)中揭示了起始物乙酰基丁内酯镁烯醇盐及其制备方法。
下列实施例用来进一步理解本发明,本发明不被这些实施例所限定,其范围由权利要求书限定。
实施例14-氯-2′-硝基丁酰苯的制备
将邻-硝基苯甲酰氯(0.050摩尔,在20%的甲苯溶液中)加至乙酰基丁内酯的镁烯醇盐中[系从乙醇镁(3.1克,0.027摩尔)及乙酰基丁内酯(7.1g,0.055摩尔)在甲苯(25ml)中的混合物中制得]。将反应混合物加热,并在110~123℃下保持约两小时,此时蒸去了大部分甲苯。然后冷却反应混合物并用乙酸乙酯/小混合物稀释,分离出有机相,真空浓缩得到油状的标题产物(9.0克,45%纯度,35%得率)。
将5-氟-2-硝基苯甲酰氯(37.5mmol,在甲苯溶液中)加至乙酰基丁内酯的镁烯醇盐中[从乙醇镁(2.32g,20.3mmol)及乙酰基丁内酯(5.33g,41.3mmol)在甲苯中的混合物中制得]。加热反应混合物,在110~125℃下保持约2.5小时,此时大部分甲苯被蒸去。然后将反应混合物冷却并用乙酸乙酯/水混合物烯释。分离出有机相,真空浓缩以得到油状的标题产物。
将4-氯-2′-硝基丁酰苯(2.96g,0.013摩尔)及氢氧化钠(0.76g,0.019摩尔)在水中的搅拌混合物加热回流,直至用薄层层析分析显示反应完全为止,使混合物冷却至室温,并用二乙醚萃取,合并有机层,用无水硫酸钠干燥,真空浓缩得到残留物。将该残留物置于二乙醚中用硅胶过滤,真空浓缩以得到黄色油状的标题化合物。
将搅拌着的4-氯-5′-氟-2′-硝基丁酰苯(2.65g,10.8mmol)及氢氧化钠(0.63g,15.8mmol)在水中的混合物于回流下加热,冷却并用二乙醚萃取。合并有机萃取物,用无水硫酸钠干燥,真空浓缩得到油状的标题产物。
在氢气大气压下搅拌邻-硝基丁酰苯(100mg,0.52mmol)及催化量10%钯碳在甲醇中的混合物,直至由TLC分析指示反应完全为止。过滤反应混合物,真空浓缩滤液以得到浅黄色油状物。经快速色谱层析得到米色的晶体的标题产物。
在氢气及大气压下搅拌5-氟-2-硝基丁酰苯(98mg,0.47mmol)及催化量的钯碳在甲醇中的溶液。然后过滤反应混合物,真空浓缩滤液得到油状的标题产物。
Claims (8)
2.根据权利要求1所述的方法,其中的温度是100~130℃。
3.根据权利要求1所述的方法,其中的溶剂系选自由芳烃及氯代芳烃所组成的组。
4.根据权利要求3所述的方法,其中的溶剂选自由甲苯、邻-二甲苯、间-二甲苯、对-二甲苯、苯及氯苯所组成的组。
5.根据权利要求4所述的方法,其中的溶剂是甲苯。
6.根据权利要求1所述的方法,其中
X是Cl或Br;
R是氢或5′-氟。
7.根据权利要求6所述的方法,其中
X是Cl;
R是氢。
8.根据权利要求1所述的方法,其中所得的反应混合物通过蒸去溶剂来浓缩。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/235,579 | 1994-04-29 | ||
US08/235,579 US5414136A (en) | 1994-04-29 | 1994-04-29 | Method for the preparation of 4-halo-2'-nitrobutyrophenone compounds |
Publications (2)
Publication Number | Publication Date |
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CN1113227A CN1113227A (zh) | 1995-12-13 |
CN1070170C true CN1070170C (zh) | 2001-08-29 |
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Application Number | Title | Priority Date | Filing Date |
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CN95114849A Expired - Fee Related CN1070170C (zh) | 1994-04-29 | 1995-04-06 | 4-卤代-2'-硝基丁酰苯化合物的制备方法 |
Country Status (14)
Country | Link |
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US (1) | US5414136A (zh) |
EP (1) | EP0682007B1 (zh) |
JP (1) | JP3663229B2 (zh) |
KR (1) | KR100343658B1 (zh) |
CN (1) | CN1070170C (zh) |
AT (1) | ATE171932T1 (zh) |
AU (1) | AU697345B2 (zh) |
DE (1) | DE69505183T2 (zh) |
DK (1) | DK0682007T3 (zh) |
ES (1) | ES2123175T3 (zh) |
HK (1) | HK1009962A1 (zh) |
LV (1) | LV12185B (zh) |
MY (1) | MY130190A (zh) |
SI (1) | SI0682007T1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US5492884A (en) * | 1994-04-29 | 1996-02-20 | American Cyanamid Company | 1-[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl)-3-(4,6-dimethoxy-2-pyrimidinyl) urea and its herbicidal method of use |
US5847140A (en) * | 1995-06-06 | 1998-12-08 | American Cyanamid Company | Intermediates for the manufacture of herbicidal 1-{ 2-(cyclopropylcarbonyl) Phenyl! Sulfamoyl}-3-(4,6-dialkoxy-2-pyrimidinyl) urea compounds |
DE19527577A1 (de) * | 1995-07-28 | 1997-01-30 | Basf Ag | Schlagzähe thermoplastische Formmasse |
US6127576A (en) * | 1996-12-20 | 2000-10-03 | American Cyanamid Company | Aminophenyl ketone derivatives and a method for the preparation thereof |
US5856576A (en) * | 1997-02-04 | 1999-01-05 | American Cyanamid Company | Aryne intermediates and a process for the preparation thereof |
DE60136187D1 (de) * | 2000-08-11 | 2008-11-27 | Japan Tobacco Inc | Calciumrezeptor-antagonisten |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0577945A1 (en) * | 1992-07-06 | 1994-01-12 | American Cyanamid Company | Herbicide intermediate o-nitrophenyl cyclopropyl ketone and a method for the preparation thereof |
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FI60559C (fi) * | 1975-07-17 | 1982-02-10 | Sumitomo Chemical Co | Foerfarande foer framstaellning av ny-(tertiaer amino)-orto-aminobutyrofenonfoereningar |
US4622065A (en) * | 1984-11-01 | 1986-11-11 | Ppg Industries, Inc. | Sulfamoyl urea derivatives |
US5009699A (en) * | 1990-06-22 | 1991-04-23 | American Cyanamid Company | 1-{[O-(cyclopropylcarbonyl)phenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea herbicidal composition and use |
US5280007A (en) * | 1991-12-18 | 1994-01-18 | American Cyanamid Company | Method for safening rice against the phytotoxic effects of a sulfamoyl urea herbicide |
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1994
- 1994-04-29 US US08/235,579 patent/US5414136A/en not_active Expired - Lifetime
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1995
- 1995-03-09 MY MYPI95000592A patent/MY130190A/en unknown
- 1995-04-06 CN CN95114849A patent/CN1070170C/zh not_active Expired - Fee Related
- 1995-04-24 AU AU17626/95A patent/AU697345B2/en not_active Ceased
- 1995-04-25 SI SI9530085T patent/SI0682007T1/xx unknown
- 1995-04-25 JP JP12304795A patent/JP3663229B2/ja not_active Expired - Fee Related
- 1995-04-25 AT AT95106165T patent/ATE171932T1/de not_active IP Right Cessation
- 1995-04-25 DK DK95106165T patent/DK0682007T3/da active
- 1995-04-25 DE DE69505183T patent/DE69505183T2/de not_active Expired - Lifetime
- 1995-04-25 ES ES95106165T patent/ES2123175T3/es not_active Expired - Lifetime
- 1995-04-25 EP EP95106165A patent/EP0682007B1/en not_active Expired - Lifetime
- 1995-04-26 KR KR1019950009935A patent/KR100343658B1/ko not_active IP Right Cessation
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1998
- 1998-09-17 HK HK98110698A patent/HK1009962A1/xx not_active IP Right Cessation
- 1998-11-03 LV LVP-98-267A patent/LV12185B/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0577945A1 (en) * | 1992-07-06 | 1994-01-12 | American Cyanamid Company | Herbicide intermediate o-nitrophenyl cyclopropyl ketone and a method for the preparation thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1113227A (zh) | 1995-12-13 |
EP0682007A1 (en) | 1995-11-15 |
EP0682007B1 (en) | 1998-10-07 |
HK1009962A1 (en) | 1999-06-11 |
ES2123175T3 (es) | 1999-01-01 |
AU697345B2 (en) | 1998-10-01 |
DE69505183D1 (de) | 1998-11-12 |
JP3663229B2 (ja) | 2005-06-22 |
LV12185B (en) | 1999-02-20 |
LV12185A (lv) | 1998-12-20 |
ATE171932T1 (de) | 1998-10-15 |
US5414136A (en) | 1995-05-09 |
AU1762695A (en) | 1995-11-02 |
KR100343658B1 (ko) | 2002-10-31 |
SI0682007T1 (en) | 1999-04-30 |
DE69505183T2 (de) | 1999-03-25 |
DK0682007T3 (da) | 1999-02-15 |
MY130190A (en) | 2007-06-29 |
JPH07300445A (ja) | 1995-11-14 |
KR950032071A (ko) | 1995-12-20 |
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