CN1100755C - 氨基苯基酮衍生物及其制备方法 - Google Patents
氨基苯基酮衍生物及其制备方法 Download PDFInfo
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- C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C307/04—Diamides of sulfuric acids
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
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- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/21—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- 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
本发明提供了邻-氨基苯基酮衍生物，它们是制备除草的氨磺酰脲化合物，包括对作物有特异性的除草剂1-{[邻-(环丙基羰基)苯基]氨磺酰基}-3-(4，6-二甲氧基-嘧啶基)脲中有用的中间体。本发明也提供了所述中间体的制备方法。
Description
本发明提供了式I的邻-氨基苯基酮衍生物。
其中R、R1和X的定义于下。
在制备各种除草的氨磺酰脲衍生物，特别是在制备对作物有选择性的除草剂1-{[邻-(环丙基羰基)苯基]氨磺酰基}-3-(4，6-二甲氧基-2-嘧啶基)脲中式I化合物氨基苯基酮衍生物是有用的中间体。这里也提供了制备所述式I中间体的方法。
本发明提供了式I化合物或其酸加成盐：其中
R是直链或支链C1-C6烷基，或是任意被C1-C3烷基、C1-C3烷氧基、氯或溴取代的苯基；
R1是氢，氰基，硝基，卤素，甲酰基，任意被一个或多个卤素、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基取代的C1-C4烷基，
任意被一个或多个卤素、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基取代的C1-C4烷氧基，
任意被一个或多个卤素、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基取代的C1-C4烷硫基，
任意被一个或多个卤素、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基取代的C1-C4烷基亚磺酰基，
任意被一个或多个卤素、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基取代的C1-C4烷基磺酰基，
任意被一个或多个卤素、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基取代的C1-C4烷基羰基，
任意被一个或多个卤素或C1-C3烷氧基取代的C1-C4烷氧基羰基，
任意被一个或多个卤素或C1-C3烷氧基取代的二(C1-C4烷基)氨基，
任意被一个或多个卤素或C1-C3烷氧基取代的二(C1-C4烷基)氨基羰基，
任意被一个或多个卤素或C1-C3烷氧基取代的二(C1-C4烷基)氨基磺酰基，
有2-6个碳原子和1-3个氮、氧或硫原子的杂环，碳原子上被一个或多个卤素、C1-C4烷基或C1-C4卤代烷基任意取代；
X是-(CH2)3-Y，环丙基或四氢-2-氧基-3-糠酰基；
Y是氯、溴或羟基。
本发明也提供了制备式A化合物的方法其中R1的定义同上，该方法包括下列步骤：
i)使式B化合物其中R和R1的定义同上，与式C化合物
在碱和有机溶剂存在下反应形成式D和式E化合物的混合物：
ii)通过水解或结晶分离化合物E；
iii)使式E化合物与浓HCl在有机溶剂存在下反应以形成式F的化合物；
iv)在升高的温度下用碱水溶液处理化合物F；
v)分离式G化合物；
vi)用强酸处理化合物G；
vii)分离式H化合物；
viii)使化合物H与HCl反应以形成式A化合物。
R1是氢的化合物A，即1-(邻-氨基苯基)-4-氯-1-丁酮盐酸盐，被用来制备除草的中间体邻-(氨基苯基)环丙基酮。现有技术中揭示了邻-(氨基苯基)环丙基酮和其在制备1-{[邻-(环丙基羰基)苯基]氨磺酰基}-3-(4，6-二甲氧基-2-嘧啶基)脲除草剂中的应用。本发明也避免使用爆炸性的邻-硝基苯甲酰氯作为中间体。
用于步骤1的碱可为C1-C4醇化镁，优选的是容易得到的，如甲醇镁或乙醇镁。用于步骤1的有机溶剂可为芳烃或二烷基醚，如甲苯、二甲苯或四氢呋喃。用于制备化合物F的步骤3的有机溶剂可为惰性有机溶剂，如甲苯或二甲苯，用于步骤3的酸可为无机酸，如浓HCl。用于制备化合物G的步骤4的碱可为碱金属氢氧化物，如氢氧化钠或氢氧化钾。步骤4中升高的温度可为25℃以上的任何温度，较好的约是90-130℃。用于制备化合物H的步骤6中的强酸可为硫酸。用于制备化合物A的步骤8中的酸可为诸如浓HCl的无机酸。
本发明的化合物可这样用来制备除草的氨磺酰脲化合物(K)：用本发明的方法制备式A化合物，用现有技术揭示的常规方法将所述的式A化合物转化为相应的邻-(氨基苯基)环丙基酮(J)，将所述的苯基酮转化为所需的氨磺酰脲除草剂产物，较好的是对谷类植物有选择性的除草的氨磺酰脲，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。可用已知方法将苯基酮衍生物转化为氨磺酰脲除草剂。
制备方法如流程I所示。流程I
根据本发明的方法，如上所述制备式A化合物，并通过常规的脱卤化氢技术转化为式J的邻-(氨基苯基)环丙基酮化合物，在三乙胺和溶剂存在下使式J化合物与式L的2-氨基芳基化合物及氯磺酰基异氰酸酯反应得到所需式K的氨磺酰脲除草剂。
本发明在下列实施例中作了进一步的揭示，但不为其所限制。术语NMR和MS各自指质子核磁共振和质谱。
实施例1
2′-(四氢-2-氧基-3-糠酰基)-对-甲苯-N-磺酰苯胺的制备
在氮气和5-10℃下向在烧瓶中的40毫升甲苯和2.03克(178毫摩尔)乙醇镁混合物中在2分钟内加入4.6克(36毫摩尔)2-乙酰基丁内酯。所得的浆状物在5-10℃下搅拌10分钟，在20℃下搅拌约1.5小时。反应混合物用10.0克(32毫摩尔)N-对-甲苯基磺酰基邻氨基苯甲酰氯在20毫升甲苯中的溶液处理，在室温下搅拌数小时，在45-50℃下搅拌约2小时。加入水(120毫升)，使灰色浆状物在65-70℃下搅拌约4小时。用浓硫酸将pH调节到1。分离各相，过滤有机层得到7.6克2’-(四氢-2-氧基-3-糠酰基)-对-甲苯-N-磺酰苯胺。剩余的产物通过真空浓缩从有机层滤液中分离出来，得到另外的2.1克产物，总得率为83％(熔点138-141℃)。产物用NMR和MS分析鉴别。
实施例2
2′-(环丙基羰基)-对-甲苯-N-磺酰苯胺的制备
使3.56克(1.0毫摩尔)实施例1产物、25毫升甲苯和20毫升37％HCl的两相浆状混合物回流约12小时，冷却并过滤所得的浆状物得到1.98克4-氯-1-(2-N-甲苯磺酰基氨基苯基)-1-丁酮。分离滤液相，水相用甲苯萃取。合并有机相，真空浓缩得到剩余的4-氯-1-(2-N-甲苯磺酰基氨基苯基)-1-丁酮产物(1.15克)，总得率为90％(熔点108-113℃)。产物经NMR和MS鉴别。
向1.62克(4.6毫摩尔)4-氯-1-(2-N-甲苯磺酰基氨基苯基)-1-丁酮在10毫升甲苯中的溶液加入17.3克(28.7毫摩尔)的6.6％氢氧化钠溶液。所得的两相混合物回流约1小时，冷却并用浓硫酸调节pH到1。分离有机层，真空浓缩得到1.50克2’-(环丙基羰基)-对-甲苯-N-磺酰苯胺，得率100％(熔点92-100℃)。产物经NMR和MS分析鉴别。
实施例3
1-(邻-氨基苯基)-4-氯-1-丁酮盐酸盐的制备
用96％硫酸处理实施例2产物(1.5克，4.7毫摩尔)，在90℃下加热15分钟。冷却溶液，用氢氧化胺将溶液调节到pH9，用二氯甲烷萃取。合并的萃取物经真空浓缩得到1-(邻-氨基苯基)-4-羟基-1-丁酮(80％得率，熔点58-61℃)。产物经NMR和MS分析来鉴别。
使9.3克(5.1毫摩尔)1-(邻-氨基苯基)-4-羟基-丁酮、26毫升水和90毫升37％ HC1的混合物回流约6.5小时，冷却并过滤得到8.0克1-(邻-氨基苯基)-4-氯-1-丁酮盐酸盐。用二氯甲烷萃取水性的母液得到另外的1.10克标题产物，总得率73％(熔点142-145℃)。产物经NMR和MS分析鉴别。
实施例4
邻-氨基苯基环丙基酮的制备
0.30克(1.3毫摩尔)1-(邻-氨基苯基)-4-氯-1-丁酮盐酸盐在3毫升二氯甲烷和3毫升二氯乙烷中的溶液用1.2克(3毫摩尔)10％氢氧化钠溶液和0.05克(0.2毫摩尔)75％甲基三丁基氯化铵水溶液处理，在50℃下加热约5小时。冷却到室温后，分离各相。水层用二氯甲烷萃取。合并的有机萃取用水洗涤，真空浓缩得到0.14克(70％得率)的邻-氨基苯基环丙基酮(熔点46-48℃)。产物经NMR和MS分析鉴别。
Claims (7)
1.一种式I化合物或其酸加成盐，其中
R是直链或支链C1-C6烷基，或是任意被C1-C3烷基、C1-C3烷氧基、氯或溴取代的苯基；
R1是氢；
X是-(CH2)3-Y，环丙基或四氢-2-氧基-3-糠酰基；
Y是氯或溴。
2.根据权利要求1所述的化合物，其中R是甲基或对-甲苯基。
3.一种制备式A化合物的方法，其特征在于：
i)使式B化合物
与式C化合物
在碱和有机溶剂存在下反应形成式D和式E化合物的混合物；
ii)通过水解或结晶分离化合物E；
iii)使式E化合物与浓HCl在有机溶剂存在下反应以形成式F化合物；
iv)在25℃以上到回流的温度下用碱水溶液处理化合物F；
v)分离式G化合物；
在式E-G化合物中R和R1的定义见权利要求1；
vi)用硫酸处理化合物G；
vii)分离式H化合物；
viii)使化合物H与HCl反应以形成式A化合物。
4.根据权利要求3所述的方法，其中步骤1中的碱是乙醇镁，有机溶剂是甲苯；步骤3中的有机溶剂是甲苯；步骤5中的碱是NaOH。
5.根据权利要求4所述的方法，式B化合物中的R1是氢。
6.根据权利要求4所述的方法，式B化合物中的R是对-甲苯基或甲基。
7.根据权利要求5所述的方法，它进一步包括使式A化合物与碱反应制备邻-氨基苯基环丙基酮。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US771318 | 1985-08-30 | ||
| US77131896A | 1996-12-20 | 1996-12-20 | |
| US771,318 | 1996-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185430A CN1185430A (zh) | 1998-06-24 |
| CN1100755C true CN1100755C (zh) | 2003-02-05 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97108762A Expired - Fee Related CN1100755C (zh) | 1996-12-20 | 1997-12-19 | 氨基苯基酮衍生物及其制备方法 |
Country Status (29)
| Country | Link |
|---|---|
| EP (1) | EP0849262B1 (zh) |
| JP (1) | JP3958851B2 (zh) |
| KR (1) | KR100555052B1 (zh) |
| CN (1) | CN1100755C (zh) |
| AR (1) | AR011771A1 (zh) |
| AT (1) | ATE207066T1 (zh) |
| AU (1) | AU721862B2 (zh) |
| BG (1) | BG63390B1 (zh) |
| BR (1) | BR9706365A (zh) |
| CA (1) | CA2225206C (zh) |
| CO (1) | CO5021225A1 (zh) |
| CZ (1) | CZ393797A3 (zh) |
| DE (1) | DE69707408T2 (zh) |
| EG (1) | EG21392A (zh) |
| ES (1) | ES2166052T3 (zh) |
| HK (1) | HK1012504A1 (zh) |
| HR (1) | HRP970613B1 (zh) |
| HU (1) | HU219612B (zh) |
| IL (1) | IL122672A (zh) |
| NO (1) | NO309934B1 (zh) |
| NZ (1) | NZ329428A (zh) |
| PL (1) | PL190620B1 (zh) |
| RU (1) | RU2201418C2 (zh) |
| SG (1) | SG64466A1 (zh) |
| SK (1) | SK169397A3 (zh) |
| TR (1) | TR199701597A2 (zh) |
| UA (1) | UA43896C2 (zh) |
| YU (1) | YU48897A (zh) |
| ZA (1) | ZA9711397B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0184122A2 (en) * | 1984-12-03 | 1986-06-11 | Ppg Industries, Inc. | Sulfamoyl urea derivatives |
| EP0264467A1 (en) * | 1984-12-03 | 1988-04-27 | Ppg Industries, Inc. | Sulfamoyl urea derivates |
| EP0463287A1 (en) * | 1990-06-22 | 1992-01-02 | American Cyanamid Company | 1-((O-(cyclopropylcarbonyl)phenyl)sulfamoyl)-3-(4,6-dimethoxy-2-pyrimidinyl)urea and method for the preparation thereof |
| EP0655436A1 (en) * | 1993-11-30 | 1995-05-31 | American Cyanamid Company | Improved process for the manufacture of cycloalkyl and haloalkyl o-aminophenyl ketones |
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- 1997-12-15 EP EP97310120A patent/EP0849262B1/en not_active Expired - Lifetime
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- 1997-12-19 CN CN97108762A patent/CN1100755C/zh not_active Expired - Fee Related
- 1997-12-19 KR KR1019970070780A patent/KR100555052B1/ko not_active IP Right Cessation
- 1997-12-19 PL PL97323892A patent/PL190620B1/pl not_active IP Right Cessation
- 1997-12-19 NO NO975983A patent/NO309934B1/no not_active IP Right Cessation
- 1997-12-19 AR ARP970106066A patent/AR011771A1/es active IP Right Grant
- 1997-12-19 HU HU9702511A patent/HU219612B/hu not_active IP Right Cessation
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1998
- 1998-12-15 HK HK98113419A patent/HK1012504A1/xx not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0184122A2 (en) * | 1984-12-03 | 1986-06-11 | Ppg Industries, Inc. | Sulfamoyl urea derivatives |
| EP0264467A1 (en) * | 1984-12-03 | 1988-04-27 | Ppg Industries, Inc. | Sulfamoyl urea derivates |
| EP0463287A1 (en) * | 1990-06-22 | 1992-01-02 | American Cyanamid Company | 1-((O-(cyclopropylcarbonyl)phenyl)sulfamoyl)-3-(4,6-dimethoxy-2-pyrimidinyl)urea and method for the preparation thereof |
| EP0655436A1 (en) * | 1993-11-30 | 1995-05-31 | American Cyanamid Company | Improved process for the manufacture of cycloalkyl and haloalkyl o-aminophenyl ketones |
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