CN1161323C - 芳香族二胺的磷酸盐 - Google Patents
芳香族二胺的磷酸盐 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 description 8
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- 239000001257 hydrogen Substances 0.000 description 6
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- 229910052763 palladium Inorganic materials 0.000 description 2
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
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- 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
- C07C211/49—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 having at least two amino groups bound to the carbon skeleton
- C07C211/50—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 having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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Abstract
本发明是关于一种N-甲基-邻-苯二胺的新颖盐。
Description
本发明涉及一种N-甲基-邻-苯二胺的新颖盐类。
发明背景
芳香族胺为合成染料、抗氧化剂，特别是制药中的重要中间产物。尤其是芳香族1，2-二胺(特别是具有二个杂氮原子，如苯并咪唑)在生产芳香族杂环化合物中更具有工业重要性。由于这些化合物及其盐类在药理学上的多样性使它们倍受瞩目。
但已知芳香族胺诸如苯胺极易被氧化。这使得在贮存这些化合物时更加困难。这些性质在液态或在芳香族胺溶于液体时特别明显。即使是痕量氧或光存在的情况下，这些溶液在短时间内都会变成深黑色。芳香族胺的高氧化敏感性意味只有当其刚被纯化后(通常为蒸馏后)，才可被用于更进一步的化学反应。这些物质可通过将芳香族胺转化成其盐类，来降低其高氧化敏感性。虽然如此，这些盐类通常仍十分倾向于被氧化，因此必须将其贮存于，例如说，缺氧的状态下，这些盐类亦倾向于吸湿。最常见的盐类为氢卤酸盐(hydrohalides)，特别是盐酸盐。
苯二胺是特别具有氧化倾向。因此，例如O.Fischer在德国化学学会报告，第25卷第2841-2842页中，描述：油性的N-甲基-邻-苯二胺即使在黑暗、封紧的瓶中也会在极短的时间后极迅速地变为黑色。根据O.Fischer的报告，即使是二盐酸盐也是一种对空气及光相当敏感的物质(O.Fischer，德国化学学会报告，25卷2824页)。由现有技术已知，N-甲基-邻-苯二胺的盐、邻-苯二胺本身的盐类及单-、二-和三-N-烷基化的苯二胺的其他盐类也具有相同的性质。
除了它们对氧及光的高敏感性及有时上述苯二胺的卤化氢盐的明显吸湿状况外，这些化合物尚有其他不适用于大规模工业制备的缺点。因为当该盐类进一步反应时，通常必须就地转化为游离碱，因此会生成相应的副产物氢卤酸。当反应混合物处于氢卤酸以气态产生的温度下时，这情形特别不利。因为这些气体具有强侵蚀性及高腐蚀性，因此有毒，所以必须将其自反应物中小心地去除。在某些情况中，这些只能通过可观的技术投入才能完成，这导致高额成本。
苯二胺与氢卤酸的盐类，不仅在使用上遭遇问题，而且在工业规模制备该盐时也有困难。如果将气态形式的氢卤酸供给相应的苯二胺能使产量的损失降到最低则将是适宜的。不过，从技术观点，这法极为费力，且盐必须从氢卤酸水溶液中形成，因而必须忍受产量的高度损失。
发明的说明
本发明的目的是将现有技术所知的关于制备、贮存及使用N-甲基·邻-苯二胺时所遇到的难题减至最小。
本发明另一个目的是将N-甲基-邻-苯二胺转化为易于操作的形式，对氧化和/或光线的敏感度低，和/或不易吸湿且易于贮存，如此该游离碱可迅速地用于下一步的反应。
发明的详细说明
令人惊讶的是，已发现N-甲基-邻-苯二胺与磷酸的盐类并没有其他这种盐类在现有技术中所提及的缺点及因而导致的问题，或使这种缺点及问题有明显的减低。
本发明通过转化N-甲基-邻-苯二胺为下列通式(I)的磷酸盐而解决了该问题：
其中n为0.5至1之间的数字。
“磷酸盐”一词表示N-甲基-邻-苯二胺与正磷酸(H3PO4)的盐。根据化学式I，1分子的H3PO4对1分子的N-甲基-邻-苯二胺的比例以在统计上的平均值n表示。
上述盐中，n以0.7至0.8为优选：以0.75至0.78为最佳。
在一特佳的实施方案中，本发明的N-甲基-邻-苯二胺的磷酸盐为无水的或只含有非常少量的水。该盐的含水量一般为1.0％至1.5重量％之间。
根据本发明的N-甲基-邻-苯二胺的磷酸盐的优点在于其本身的氧化稳定性、光不敏感性及不吸湿的特性。因此易于贮存而不需任何大的花费，以及视情况有时需将其转化为游离碱外，可于无另外处置下用于后续反应。另外，可惊人地以简便方式大量制造，所用磷酸可以以晶体的方式加入。再者，当该磷酸盐本身在高温下被进一步使用时，在该反应条件下，不会生产具有强侵蚀性及高腐蚀的气体。
再一方面，本发明是关于上述N-甲基-邻-苯二胺-磷酸盐的工业规模制造。
该盐易于通过下法以高产量获得：将N-甲基-邻-苯二胺溶于和水可互溶的或与醇可互溶的溶剂(诸如C1-C5的醇类，优选为乙醇、丙醇或异丙醇)中。然后将此混合物与结晶磷酸或磷酸溶液(75至100摩尔百分比的量)反应。磷酸可溶于或悬浮于水、C1-C5醇类(如甲醇、乙醇、丙醇、异丙醇)或其混合物中。优选以乙醇、丙醇或异丙醇作为溶剂。
N-甲基-邻-苯二胺-磷酸盐可从溶剂中析出，或视情况通过加入非极性溶剂如脂肪族或芳香族烃或醚而使其析出。
在优选的制备方法中，使用无水磷酸。
本发明的另一实施方案是通过邻-硝基-N-甲苯胺的还原而就地制备N-甲基-邻-苯二胺的制备方法。
邻-硝基-N-甲苯胺的还原可用现有技术已知的方法进行。优选的还原剂为氢，并在作为溶剂的醇类(以乙醇、丙醇或异丙醇为较佳)中使用氢化催化剂。当除去此催化剂后，将所得的溶液与磷酸或磷酸溶液进行反应。进行氢化时优选使用结晶性无水磷酸悬浮于氢化所使用的醇的悬浮液。
实施例1
将190公斤的邻-硝基-N-甲苯胺、0.95公斤的钯/碳催化剂(10％的钯)及570升的乙醇的混合物在1200升-VA-氢化器中氢化直到氢的吸收已停止，氢化条件为在氢气压2至6巴u、温度60℃，最高为85℃。将99公斤的磷酸晶体与238升的乙醇置于另一1200升的装置中，使氢化装置中的内容物于搅拌下流入装置中，同时滤除催化剂。
用95升的乙醇洗涤过滤器和所过滤的催化剂后，冷却至10至20℃并搅拌30至60分钟后。离心该产物、以238升的乙醇清洗并在40至60℃下真空干燥。
产量：230公斤的N-甲基苯二胺、0.77公斤的磷酸盐(92％的理论回收率)。
该产物一般含有1.0至1.5％的水。
根据滴定的结果，计算出内容物为61.0％的N-甲基苯二胺及37.7％的磷酸。
元素分析：碳：42.00％氢：6.34％氮：14.00％磷：11.92％
实施例2
将190公斤的邻-硝基-N-甲苯胺、0.95公斤的钯/碳催化剂(10％的钯)及570升的异丙醇的混合物在1200升-VA-氢化作用器中还原直到氢的吸收已停止，氢化条件为在氢气压2至6巴u、温度60℃，最高为85℃。将99公斤的磷酸晶体与238升的异丙醇置于一1200公升的装置中，使氢化装置中的内容物于搅拌下流入装置中，同时滤除催化剂。
用95升的异丙醇洗涤过滤器和所过滤的催化剂，冷却至10至20℃并搅拌30至60分钟后。离心该产物、以238升的异丙醇清洗并在40至60℃下真空干燥。
产量：225公斤的N-甲基苯二胺、0.77公斤的磷酸盐(90％的理论回收率)。
根据滴定的结果，计算出内容物为61.1％的N-甲基苯二胺及37.6％的磷酸。
元素分析：碳：41.98％氢：6.35％氮：14.04％磷：11.93％。
Claims (10)
1.一种N-甲基-邻苯二胺的磷酸盐，其通式I为
其中n为0.5至1之间的数字。
2.根据权利要求1的N-甲基-邻苯二胺的磷酸盐，其中，n为0.7至0.8之间的数字。
3.根据权利要求1或2中之一的N-甲基-邻苯二胺的磷酸盐，其中，n为0.75至0.78之间的数字。
4.一种制备通式I的N-甲基-邻苯二胺的磷酸盐的方法，
其中n为0.5至1之间的数字，其中，将N-甲基-邻苯二胺溶于溶剂中并与结晶的或被溶解的磷酸混合。
5.根据权利要求4的方法，其中，由邻-硝基-N-甲基苯胺就地制备N-甲基-邻-苯二胺。
6.根据权利要求5的方法，其中n为0.7至0.8之间的数字。
7.根据权利要求5的方法，其中n为0.75至0.78之间的数字。
8.根据权利要求4至7中之一的制备方法，其特征在于，溶剂为C1至C5醇类。
9.根据权利要求8的方法，其特征在于，溶剂为乙醇、丙醇或异丙醇。
10.根据权利要求9的方法，其特征在于，N-甲基-邻-苯二胺及磷酸的溶剂为乙醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19917526A DE19917526C1 (de) | 1999-04-17 | 1999-04-17 | Phosphorsäuresalz von N-Methyl-o-phenylendiamin und Verfahren zu seiner Herstellung |
| DE19917526.8 | 1999-04-17 |
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| CN1347402A CN1347402A (zh) | 2002-05-01 |
| CN1161323C true CN1161323C (zh) | 2004-08-11 |
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| CNB00806301XA Expired - Fee Related CN1161323C (zh) | 1999-04-17 | 2000-04-12 | 芳香族二胺的磷酸盐 |
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| DE (2) | DE19917526C1 (zh) |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102004040647B4 (de) * | 2004-08-20 | 2013-01-03 | Dhw Deutsche Hydrierwerke Gmbh Rodleben | Verfahren zur Herstellung von hellfarbenen, primären Fettaminen |
| KR20070061583A (ko) * | 2004-10-15 | 2007-06-13 | 테바 파마슈티컬 인더스트리즈 리미티드 | 텔미사르탄의 제조 방법 |
| US9977667B2 (en) | 2015-09-09 | 2018-05-22 | Red Hat, Inc. | Updating software utilizing domain name system (DNS) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2142585A1 (de) * | 1971-08-20 | 1973-02-22 | Schering Ag | 2-(5-nitro-2-thiazolyl)-benzimidazole |
| CH774974A4 (zh) * | 1974-06-06 | 1976-02-13 | ||
| HU186018B (en) * | 1982-05-12 | 1985-05-28 | Magyar Asvanyolaj Es Foeldgaz | Process for preparing o-phenylene-diamine |
| US5149700A (en) * | 1990-05-30 | 1992-09-22 | American Home Products Corporation | Substituted arylsulfonamides and benzamides |
| IL98599A (en) * | 1990-06-28 | 1995-06-29 | Merck & Co Inc | Stable salts of "4-deoxy-" 4-epi-methylamino abramectin and insecticides containing them |
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