CN1043933A - 2-溴-4,6-二硝基苯胺的制备方法 - Google Patents
2-溴-4,6-二硝基苯胺的制备方法 Download PDFInfo
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- CN1043933A CN1043933A CN 89109829 CN89109829A CN1043933A CN 1043933 A CN1043933 A CN 1043933A CN 89109829 CN89109829 CN 89109829 CN 89109829 A CN89109829 A CN 89109829A CN 1043933 A CN1043933 A CN 1043933A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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Abstract
2-溴-4,6-二硝基苯胺的制备是通过用氨的水溶液在有阴离子活性分散存在下,在水或水-有机介质中,在86-90℃温度下进行处理而实施的。
Description
本发明涉及有机合成,更具体地说本发明涉及2-溴-4,6-二硝基苯胺的制备方法。
本发明在分散性染料生产方面有很大的用处。
目前,制备2-溴-4,6-二硝基苯胺的已知方法是通过用溴分子溴化2,4-二硝基苯胺,按照CS,A,152603,在有硫存在时在乙酸中进行;或者,按照DE 3014972,在有过氧化氢存在时在水中进行,或按化学工业杂志(
журалу химической промышленностн,Ⅱ,
1986,399页,在有次氯酸钠存在的稀盐酸中进行。
在全部这些方法中,氨解不是最后的反应阶段,在反应物中都含有杂质2,4-二硝基苯胺。
由2-溴-4,6-二硝基氯苯的氨解制备2-溴-4,6-二硝基苯胺也是已知的,通过以下方法实施:将气态氨通过干的(无水)乙醇并用此溶液处理原料化合物(Journal Chemical Soceity 125,2482-84,1924)。
尽管达到高的目的产品的产率-85%,上述方法不能用于工业而只能用于实验室的实践中,由于必需完成复杂的技术条件-气态氨必须通过有固体KOH的柱以进行干燥,乙醇必须蒸去。这样,使用由瓶中的气态的干燥氨和无水乙醇进行上述方法,类似的生产关系是肯定不赢利的。
由2,4-二硝基氯苯使用氨的水溶液氨解而制备2-溴-4,6-二硝基苯胺也是已知的,此方法在高压釜中100℃下进行,以后就溴化反应物(US,A,4381409)。
完成上述方法的结果是在制得的反应物中含有作为杂质的2,4-二硝基苯胺,树脂状化合物。
本发明的基本任务是通过在保证优选先置换苯环上的氯原子为氨基团的条件下进行反应而制得2-溴-4,6-二硝基苯胺,而且可以得到更纯的产品。
上述任务是这样解决的,通过用氨处理二硝基氯苯的衍生物可以获得目的产物,而实施制备2-溴-4,6-二硝基苯胺的方法,按照本发明作为二硝基氯苯的衍生物使用2-溴-4,6-二硝基氯苯,而其氨处理是在有阴离子活性分散剂存在的水介质中或水-有机介质中,在86-90℃时进行的。
目的产品的产率是理论值的90%。
按照本发明,最好使用亚甲基双萘磺酸二钠作为分散剂。
由以下对2-溴-4,6-二硝基苯胺制备方法的详述和实施本方法的具体实施例,对本发明的其它目的和优点就会更理解。
本发明制备2-溴-4,6-二硝基苯胺的方法是在于氨化2-溴-4,6-二硝基氯苯。
原料化合物2-溴-4,6-二硝基氯苯可以用任何已知方法制备,例如,最好是由予先用硫酸和硝酸混合物处理的氯苯或单一的邻一,对一硝基氯苯或邻一,对一,间一硝基氯苯的低共熔混合物,用溴或碱金属溴化物,硝酸或碱金属硝酸盐和硫酸或发烟硫酸,在试剂的以下摩尔比:所述的芳族化合物卤代衍生物∶溴或碱金属溴化物∶硫酸或发烟硫酸=1.0∶0.5-1.5或1.0-3.0∶2.0-4.0或2.5-5.0∶6.0-70.0,在20-120℃条件下进行处理。
按照本发明,氨化反应是在86-90℃的温度下,在有阴离子活性分散剂存在的水介质或有机溶剂如氯苯中的缓和条件下进行的:
在氨浓度为30%的水溶液中进行氨解。
选择置换氯原子为氨基团,而不是溴原子或氯原子和溴原子同时置换,所以能成功是由于反应是在有任何已知阴离子活性分散剂,如亚甲基双萘磺酸二钠或甲酚甲醛树脂与2,6-萘磺酸钠,甲醛和硫化钠的缩合产物存在时进行所致。
此外,在上述条件下,在有所述分散剂存在时实施氨解过程,避免了在反应物中除了目的产物外还形成树脂杂质和2-溴-4,6-二硝基苯酚。
按本方法实施氨解后,在反应物中仅含有目的产物和大大低于0.5%的溴氯二硝基苯。
为更好地了解本发明,列举了具体实施本发明的下述实施例。
实施例1
将2.8克2-溴-4,6-二硝基氯苯置于100毫升30%氨溶液中,加入0.28克亚甲基双萘磺酸二钠并在86-90℃下搅拌8小时。
反应终点用薄层层析法测定。冷却反应物,过滤沉淀2-溴-4,6-二硝基苯胺,用水洗涤并干燥。得到2.2克2-溴-4,6-二硝基苯胺,其产率为理论值的85%,熔点149-151℃。
实施例2
将2.8克2-溴-4,6-二硝基氯苯置于30毫升氯苯中,搅拌直到完全溶解,加入100毫升30%氨溶液,0.28克亚甲基双萘磺酸二钠并在88-90℃温度下搅拌8小时。在反应结束时(用薄层层析法测定)在反应物中再加入30毫升水,加热并将氯苯和水一起蒸馏掉。滤出析出的沉淀并干燥。制得2.35克2-溴-4,6-二硝基苯胺,其产率是理论值的90%,熔点为150-151℃。
将28克2-溴-4,6-二硝基氯苯置于300毫升30%氨的水溶液中,加入3克亚甲基双萘磺酸二钠并在86-90℃下搅拌8小时。
反应终点用薄层层析法测定。
冷却反应物,滤出沉淀2-溴-4,6-二硝基苯胺,用水洗涤并干燥。产品产额22.5克(理论值的85.3%)。
实施例4
将28克2-溴-4,6-二硝基氯苯置于300毫升30%氨的水溶液,加入3克甲酚甲醛树脂与2,6-萘磺酸钠,甲醛和硫化钠的缩合产物,以下反应按实施例3的所述相同方法进行。
得到32克2-溴-4,6-二硝基苯胺,其产率为理论值的85%。
Claims (2)
1、通过用氨的水溶液处理二硝氯苯衍生物以获得目的产物的2-溴-4,6-二硝基苯胺的制备方法,其特征在于使用2-溴-4,6-二硝基氯苯作为二硝基氯苯衍生物,其氨处理是在有阴离子活性分散剂存在下,在水介质或水-有机介质中,在86-90℃温度下进行的。
2、根据权利要求1的方法,其特征在于使用亚甲基双萘磺酸二钠作为阴离子活性分散剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU4622747 | 1988-12-30 | ||
SU4622747 RU2007385C1 (ru) | 1988-12-30 | 1988-12-30 | Способ получения 2-бром-4,6-динитроанилина |
Publications (1)
Publication Number | Publication Date |
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CN1043933A true CN1043933A (zh) | 1990-07-18 |
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CN 89109829 Pending CN1043933A (zh) | 1988-12-30 | 1989-12-29 | 2-溴-4,6-二硝基苯胺的制备方法 |
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Country | Link |
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EP (1) | EP0402486A4 (zh) |
JP (1) | JPH03503173A (zh) |
CN (1) | CN1043933A (zh) |
CS (1) | CS759089A3 (zh) |
RU (1) | RU2007385C1 (zh) |
WO (1) | WO1990007489A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5292899A (en) * | 1991-11-27 | 1994-03-08 | Synthetic Technology Corporation | Synthesis of 11-nor-Δ-9-tetrahydrocannabinol-9-carboxylic acid glucuronide |
-
1988
- 1988-12-30 RU SU4622747 patent/RU2007385C1/ru active
-
1989
- 1989-12-22 WO PCT/SU1989/000332 patent/WO1990007489A1/ru not_active Application Discontinuation
- 1989-12-22 EP EP19900901096 patent/EP0402486A4/de not_active Withdrawn
- 1989-12-22 JP JP90501831A patent/JPH03503173A/ja active Pending
- 1989-12-29 CN CN 89109829 patent/CN1043933A/zh active Pending
- 1989-12-29 CS CS897590A patent/CS759089A3/cs unknown
Also Published As
Publication number | Publication date |
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RU2007385C1 (ru) | 1994-02-15 |
EP0402486A4 (en) | 1991-06-05 |
CS759089A3 (en) | 1992-01-15 |
JPH03503173A (ja) | 1991-07-18 |
WO1990007489A1 (en) | 1990-07-12 |
EP0402486A1 (de) | 1990-12-19 |
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