CN86101095A - 取代苯基脲的制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
- C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
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Abstract
一种制备取代苯基脲的方法。
使一种适当取代的苯胺、对于苯胺的摩尔比至少为1.1的过量的尿素和一种二级胺在不含羟基的有机溶剂中同时反应,反应温度在130℃到250℃之间,并随时移走生成的氨。
所得到的苯基脲可用作除锈剂。
Description
本发明涉及一种制备三取代N-苯基脲的新方法,以及用这种方法制得的产品。
某些苯环上有取代基的N-苯基脲在作为除莠剂-无论是全除莠剂或者是对某些作物有选择性的除莠剂-的使用方面是已知的。具体可以举出N-(4-氯苯基)-N′,N′-二甲基脲(灭草隆)、N-(3,4-二氯苯基)-N′,N′-二甲基脲(敌草隆)、N-(4-异丙基苯基)-N′,N′-二甲基脲(isoproturon)、N-(3,4-二氯苯基)-N′-甲基-N′-正丁基脲(草不隆)、N-(3-氯-4-甲基苯基)-N′,N′-二甲基脲(绿麦隆)、N-(3-氯-4-甲氧基苯基)-N′,N′-二甲基脲(甲氧隆)、N-(3-三氟甲基苯基)-N′,N′-二甲基脲(伏草隆)和N-(3,4-二氯苯基)-N′-甲基-N′-甲氧基脲(利谷隆)。
由于使用量很大,这些化合物必须用工业方法生产。应用最广泛的方法是由适当取代的苯基异氰酸酯与合适的N,N-二取代苯胺起反应。这个方法给出的结果(产率,产物的纯度)一般还是可以接受的。然而,该生产程序涉及相应的苯基异氰酸酯的制造,这经常地是通过光气作用于相应的苯胺而完成的。由于光气的浸蚀性及毒性,此反应要求一种具备许多安全措施的装置和大量的相应投资。另外,甚至在这样的条件下,泄漏的危险也并不等于零,总是在制造场所构成威胁,而且威胁环境。
为了避免这种不利情况,已有人建议在有醇或酚存在时应用相应的苯胺作用于尿素,然后在第二步中,用二甲胺气体反应,并移去形成的氨,这样来制造N-苯基-N′,N′-二甲基脲、灭草隆和敌草隆。
另一已提出的方法是使这三种试剂一起反应,但这需用第四种试剂,即不对称二甲基脲,且该反应要在熔融的介质中完成,从而产率为70%左右。要进行经济上有利的生产,这种产率显然是不够大的。
为了适应对属于此类型的某些除莠剂的日益增长的要求,就需要找到一种具备双重优点-既能提供高产率和高纯度的产品,又对生产人员或环境都没有威胁-的方法。
本申请公司已经肯定地发现,用一种不使用光气的新方法来达到这一双重目的是可能的。
更明确地说,本发明是关于制备三取代N-苯基脲的一种方法,在此方法中,是使相应的苯胺、对于苯胺的摩尔比至少为1.1的尿素以及相应的二级胺一起在非羟基溶剂介质中反应,反应温度在130℃和250℃之间,反应过程中不断移走形成的氨,反应按下式进行:
其中:
X是在3和(或)4位上的囟原子,最好是氯或溴,
n是整数0、1或2,
R是具有1到4个碳原子的烷基,它可以被任意囟代,或是具有1到4个碳原子的烷氧基,R在苯环的3或4位上,
p为整数0或1,最好是满足n+p至多等于2,
R1和R2彼此可以相同或不同,它们各为具有1到4个碳原子的烷基,或者其中一个是具有1到4个碳原子的烷基,另一个是具有1到4个碳原子的烷氧基。
起始的苯胺最好选自如下一组化合物:对氯苯胺、3,4-二氯苯胺、3-氯-4-甲基苯胺、对位枯胺、3-氯-4-甲氧基苯胺和3-三氟甲基苯胺。
尿素的用量是过量的,它对于起始的苯胺的摩尔比至少为1.1,最好是1.25到2。
在N,N-二烷基胺的式子中,基团R1和R2中至少有一个是甲基时是有利的。R1和R2最好均为甲基。
本反应在溶剂介质中进行,它由分子式中不含有羟基的惰性有机溶剂组成,可以使用以下的极性或非极性溶剂,例如:酰胺,如二甲基甲酰胺或二甲基乙酰胺;酮,例如环己酮;脂肪烃,它可以任意地被氯化;或芳香烃,它可以任意地被囟化,如甲苯或氯苯,特别是单氯苯、邻二氯苯和1,3,5-三氯苯。
溶剂中试剂的浓度可以在很宽的比率范围内变动,例如从5到80%。这决定于溶解度,从而决定于试剂和溶剂的性质。已观察到当浓度为15到60%时可以产生较好的效果。
本反应在加热条件下进行,反应温度在130℃和250℃之间,最好在160℃和225℃之间。在较低的温度下反应速率不够大,但若温度过高,则在工业上难于控制各种条件,因而是较为不利的。
本发明的反应过程可在大气压下,在良好的条件下进行。然而由二烷基胺的分压或由内部反应温度的升高所产生的超压而造成的超压能减少反应时间,此超压一般可达10个大气压。
在上述条件下,氨气是在形成时被随时移走的。
连续的操作是可能的,一次操作的母液可用于下次操作。
实施例1:
在装有搅拌器和冷凝器的500cc四颈瓶中,装入蒸馏过的对位一枯胺(54克;0.4摩尔)、按化学计量法相当于过量50%的尿素(36克;0.6摩尔)和邻二氯苯(200克)。使混合物沸腾(180℃),并在60℃用鼓泡法通入二甲胺。让混合物反应约6小时,温度升至185℃。产生的氨在形成时即被移走,然后停止加热并让混合物冷却至100℃,然后停止鼓入二甲胺(通入总量为195克)并在20℃水浴中冷却混合物。得一沉淀,过滤,滴干,用邻二氯苯洗两次。将沉淀放入冷水中,在搅拌、100℃下分出溶剂,并用夹带法将其回收,然后冷却溶液至20℃并过滤,产物用水洗涤,在烘箱中烘干。得到干燥产物(61克),它含有N-(对异丙基苯基)-N′,N′-二甲基脲(59.2克;97%纯度)和二枯基缩二脲(0.43克)。
实施例2:
操作方法如实施例1所述,只是反应是这样进行的:苯基脲的最后理论浓度按重量计为15%,反应在180℃进行4小时,尿素的过量程度也改变了。每一单元操作后所得产品的产率和纯度记录在下面的表1中:
上表清楚地说明,无论从所得产品的产率还是从其纯度来看,按化学计算的条件都不是令人满意的,为了得到工业上可接受的条件,尿素需要足够过量。
实施例3:
操作方法如实施例1所述,只不过反应是这样进行的:N-(4-异丙基苯基)脲的最后理论浓度按重量计为45%,反应在185~188℃进行10小时,尿素的过量程度改变了。在单元操作中得到的产品的产率及其纯度记录在下面的表2中。
实施例4:
操作方法如实施例1所述,环己烷及二甲基甲酰胺代替了邻二氯苯作溶剂。就isproturn的产率及纯度而言,得到相似的结果。
实施例5:
操作方法如实施例1所述,反应分别在180℃,在邻二氯苯中,以及在205℃,在1,3,5-三氯苯中进行,原料是枯胺(27,克;0.2摩尔)和尿素(18克;0.3摩尔),反应介质中试剂的浓度为15%。在这些条件下观察到,在205℃及180℃,分别在5及7小时后,得到的产率是定量的。
实施例6:
操作方法如实施例1所述,对位枯胺分别为等摩尔量的3,4-二氯苯胺、3-氯-4-甲基苯胺、3-氯-4-甲氧基苯胺、3-三氟甲基苯胺所代替,在一个情况下,二甲基胺为N-甲基-N-丁基胺所代替。
在这些条件下,分别得到以下各化合物:
N-(3,4-二氯苯基)-N′,N′-二甲基脲,
N-(3,4-二氯苯基)-N′-甲基-N′-正丁基脲,
N-(3-氯-4-甲基苯基)-N′,N′-二甲基脲,
N-(3-氯-4-甲基苯基)-N′,N′-二甲基脲,
N-(3-三氯甲基苯基)-N′,N′-二甲基脲。
下面的表3列出了每个实例的起始的取代苯胺及二烷基胺,也列出了反应时间及相应取代苯脲的实际产率(TY)及其纯度。
由液相色谱法红外光谱及核磁共振谱证实了所得苯基脲的结构。
*通过除去邻二氯苯并用己烷处理沉淀出产品。
此表清楚地说明,本发明的方法适合于在工业条件下制造各种主要的有除莠性质的商品苯基脲。
Claims (9)
2、根据权利要求1的方法,反应是在160℃和225℃之间的温度下进行的。
3、根据权利要求1的方法,反应在氯苯中进行。
4、根据权利要求1的方法,其中尿素的用量,按对苯胺的摩尔比计,在1.25和2之间。
5、根据权利要求1到4中之一的方法,其中X是氯原子。
6、根据权利要求1至5中之一的方法,其中R是具有1至3个碳原子的烷基,并且p等于1。
7、根据权利要求1至6中之一的方法,其中R1和R2中至少有一个是甲基。
8、根据权利要求5和7中之一的方法,其中X是氯原子,R1和R2均为甲基。
9、根据权利要求1至7中之一的方法,其中n等于0,R是一个在4位上的异丙基,p等于1。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8502079A FR2577221B1 (fr) | 1985-02-11 | 1985-02-11 | Procede de preparation d'une phenyluree substituee |
FR8502079 | 1985-02-11 |
Publications (2)
Publication Number | Publication Date |
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CN86101095A true CN86101095A (zh) | 1986-08-06 |
CN1009274B CN1009274B (zh) | 1990-08-22 |
Family
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Application Number | Title | Priority Date | Filing Date |
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CN86101095A Expired CN1009274B (zh) | 1985-02-11 | 1986-02-06 | 取代苯基脲的制备方法 |
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Country | Link |
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US (1) | US4814499A (zh) |
JP (1) | JPS61183258A (zh) |
KR (1) | KR940003067B1 (zh) |
CN (1) | CN1009274B (zh) |
AT (1) | AT395848B (zh) |
AU (1) | AU577178B2 (zh) |
BE (1) | BE904217A (zh) |
BR (1) | BR8600539A (zh) |
CH (1) | CH666681A5 (zh) |
DD (1) | DD242803A5 (zh) |
DE (1) | DE3602657A1 (zh) |
DK (1) | DK169030B1 (zh) |
ES (1) | ES8702347A1 (zh) |
FI (1) | FI84597C (zh) |
FR (1) | FR2577221B1 (zh) |
GB (1) | GB2170808B (zh) |
HU (1) | HU199111B (zh) |
IE (1) | IE58978B1 (zh) |
IN (1) | IN166514B (zh) |
IT (1) | IT1190483B (zh) |
LU (1) | LU86296A1 (zh) |
NL (1) | NL8600189A (zh) |
NZ (1) | NZ215067A (zh) |
PH (1) | PH20993A (zh) |
PL (1) | PL257891A1 (zh) |
SE (1) | SE465927B (zh) |
ZA (1) | ZA86931B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1045002C (zh) * | 1995-03-28 | 1999-09-08 | 天津大学 | 2,6-二氯苯胺的制备方法 |
CN106008276A (zh) * | 2016-05-20 | 2016-10-12 | 湖北出入境检验检疫局检验检疫技术中心 | 苯脲类除草剂或氘代标记的苯脲类除草剂的合成方法 |
CN110938019A (zh) * | 2019-12-10 | 2020-03-31 | 江苏快达农化股份有限公司 | 连续化合成异丙隆方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK0427963T3 (da) * | 1989-11-10 | 1994-05-02 | Agrolinz Agrarchemikalien | Fremgangsmåde til fremstilling af rene, asymmetrisk disubstituerede urinstoffer |
AT397384B (de) * | 1991-08-16 | 1994-03-25 | Chemie Linz Gmbh | Verfahren zur herstellung reiner n,n'-unsymmetrisch substituierter phenylharnstoffe |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2878284A (en) * | 1945-06-09 | 1959-03-17 | Du Pont | Process for preparing symmetrical hexachlorodiphenyl urea |
US2673877A (en) * | 1951-10-26 | 1954-03-30 | Du Pont | Preparation of chlorphenyldimethyl-ureas |
US2729677A (en) * | 1954-03-16 | 1956-01-03 | Allied Chem & Dye Corp | Process for the manufacture of substituted ureas |
US2768971A (en) * | 1954-05-26 | 1956-10-30 | Ici Ltd | Preparation of alkyl-aryl-ureas |
DE1064051B (de) * | 1958-04-09 | 1959-08-27 | Basf Ag | Verfahren zur Herstellung von substituierten Harnstoffen |
NL255093A (zh) * | 1959-08-21 | |||
CA1201725A (en) * | 1979-12-06 | 1986-03-11 | Terence Gilkerson | Urea derivative, process for its preparation, herbicidal compositions containing it, and method of combating weeds using it |
AT379146B (de) * | 1980-01-25 | 1985-11-25 | Reanal Finomvegyszergyar | Verfahren zur herstellung von n'-(mono- oder disubstituierten)-n-aryl-harnstoff-derivaten |
CH652391A5 (de) * | 1982-01-15 | 1985-11-15 | Sandoz Ag | Harnstoff-derivate. |
IT1152510B (it) * | 1982-08-25 | 1987-01-07 | Anic Spa | Procedimento per la produzione di uree asimmetriche sostituite |
-
1985
- 1985-02-11 FR FR8502079A patent/FR2577221B1/fr not_active Expired
-
1986
- 1986-01-28 IN IN79/DEL/86A patent/IN166514B/en unknown
- 1986-01-28 NL NL8600189A patent/NL8600189A/nl not_active Application Discontinuation
- 1986-01-29 DE DE19863602657 patent/DE3602657A1/de not_active Ceased
- 1986-01-30 PH PH33351A patent/PH20993A/en unknown
- 1986-02-06 CN CN86101095A patent/CN1009274B/zh not_active Expired
- 1986-02-06 LU LU86296A patent/LU86296A1/fr unknown
- 1986-02-07 AU AU53299/86A patent/AU577178B2/en not_active Ceased
- 1986-02-07 BR BR8600539A patent/BR8600539A/pt not_active IP Right Cessation
- 1986-02-07 DD DD86286892A patent/DD242803A5/de unknown
- 1986-02-07 ZA ZA86931A patent/ZA86931B/xx unknown
- 1986-02-07 IT IT47634/86A patent/IT1190483B/it active
- 1986-02-07 IE IE35286A patent/IE58978B1/en not_active IP Right Cessation
- 1986-02-07 US US06/827,782 patent/US4814499A/en not_active Expired - Fee Related
- 1986-02-07 NZ NZ215067A patent/NZ215067A/xx unknown
- 1986-02-07 JP JP61025684A patent/JPS61183258A/ja active Pending
- 1986-02-10 KR KR1019860000901A patent/KR940003067B1/ko not_active IP Right Cessation
- 1986-02-10 DK DK063186A patent/DK169030B1/da not_active IP Right Cessation
- 1986-02-10 FI FI860597A patent/FI84597C/fi not_active IP Right Cessation
- 1986-02-10 AT AT0032586A patent/AT395848B/de not_active IP Right Cessation
- 1986-02-10 PL PL25789186A patent/PL257891A1/xx unknown
- 1986-02-10 ES ES551790A patent/ES8702347A1/es not_active Expired
- 1986-02-10 GB GB08603223A patent/GB2170808B/en not_active Expired
- 1986-02-10 HU HU86542A patent/HU199111B/hu not_active IP Right Cessation
- 1986-02-11 BE BE0/216258A patent/BE904217A/fr not_active IP Right Cessation
- 1986-02-11 CH CH545/86A patent/CH666681A5/fr unknown
- 1986-02-11 SE SE8600596A patent/SE465927B/sv not_active IP Right Cessation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1045002C (zh) * | 1995-03-28 | 1999-09-08 | 天津大学 | 2,6-二氯苯胺的制备方法 |
CN106008276A (zh) * | 2016-05-20 | 2016-10-12 | 湖北出入境检验检疫局检验检疫技术中心 | 苯脲类除草剂或氘代标记的苯脲类除草剂的合成方法 |
CN110938019A (zh) * | 2019-12-10 | 2020-03-31 | 江苏快达农化股份有限公司 | 连续化合成异丙隆方法 |
CN110938019B (zh) * | 2019-12-10 | 2022-06-24 | 江苏快达农化股份有限公司 | 连续化合成异丙隆方法 |
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