CN1017995B - 2-喹喔啉醇-4-氧化物的选择性还原方法 - Google Patents
2-喹喔啉醇-4-氧化物的选择性还原方法Info
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
- C07D241/52—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines 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 carbon atoms of the hetero ring
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Abstract
用氢作还原剂，通过2-喹喔啉醇-4-氧化物与选自硫化的铂、硫化的钯、硫化的铑和硫化的钌的催化剂反应，将某些2-喹喔啉醇-4-氧化物选择性还原为2-喹喔啉醇。
Description
本发明涉及使用选自硫化的铂、硫化的铑、硫化的钌和硫化的钯的一种催化剂和用氢作还原剂，将某些2-喹喔啉醇-4-氧化物选择性还原为2-喹喔啉醇的改进方法。
2-喹喔啉醇化合物如6-氯-2-羟基喹喔啉是人们都熟知的生产药用化学品和农用化学品的中间体。这些化合物一般经2-喹喔啉醇-4-氧化物的选择性还原来制备。选择性还原是必要的，这样可避免导致形成如3，4-二氢-2-喹喔啉醇的过度还原。特别是对于卤化的2-喹喔啉醇化合物，过度氢化会消除卤素取代基。
Ishikura在美国专利No.4，620，003中公开了将2-喹喔啉醇-4-氧化物还原为为2-喹喔啉醇化合物的方法，该方法包括在（ⅰ）兰尼催化剂（特殊的兰尼镍或硫化兰尼镍）和（ⅱ）碱金属氢氧化物，碱土金属氢氧化物或氢氧化铵的存在下，2-喹喔啉醇-4-氧化物与肼反应。尽管该法还原2-喹喔啉醇-4-氧化物的效果合乎要求，但在工业化采用方法的主要缺点是，与其它还原剂特别是氢相比，肼的价格较高。
Davis在美国专利No.4，636，562中公开了从相应的4-4卤-2-硝基苯胺制备2-氯-6-卤喹喔啉化合物的方法。该方法包括用氢作还原剂还原6-氯-2-羟基喹喔啉-2-氧化物为6-氯-2-羟基喹喔啉步骤（在碱金属氢氧化物水溶液和过渡金属氢化催化剂最好是兰尼镍存在下）;但Davis法也不适合于工业化，因为Davis指出：1-4个大气压的氢气压力是有效的，最好是1-2个大气压。熟悉该技术领域的人们都知道，涉及这样低压力气态氢的方法，存在空气渗入体系中的固有危险。如果氢和氧一起接触氢化催化剂，就会以爆炸方式形成水。
Sakata等人在“6-取代的-2-（1H）-喹喔啉酮的费希尔（Facile）一步合成“Heterocycles，Vol.，23，No.1（1985）一文中叙述了用氢作还原剂和钯作催化剂，将6-氯-2-喹喔啉醇-4-氧化物还原成6-氯-2-喹喔啉醇的方法，然而，Sakata等人指出，不要求量的过还原付产物被形成。
因此，需要一种安全地选择性还原2-喹喔啉醇-4-氧化物为2-喹喔啉醇并有效地用氢作还原剂的方法。
本发明的目的是提供一种用氢作还原剂选择性还原2-喹喔啉醇-4-氧化物为2-喹喔啉醇的方
法。
本发明的另一个目的是提供一种用氢作还原剂选择性还原2-喹喔啉醇-4-氧化物为2-喹喔啉醇的高压方法，这样空气渗入反应体系中的危险将大大减小。
从下面的叙述和实施例可更清楚本发明的上述目的和其它的目的。
本发明涉及制备通式如下的2-喹喔啉醇的方法：
式中R为氢，卤素或三卤甲基，
该方法包括在催化有效量的选自硫化的铂、硫化的钯、硫化的铑和硫化的钌的至少一种催化剂存在下，用氢还原通式如下的2-喹喔啉醇-4-氧化物：
式中R的定义同上。
在本发明的方法中，用作原料的2-喹喔啉醇-4-氧化物具有如下通式：
式中R为氢，卤素或三卤甲基。R最好是氢，氯，氟，三氯甲基或三氟甲基。特别好的原料是6-氯-2-羟基喹喔啉-4-氧化物，该化合物接着被还原为6-氯-2-羟基喹喔啉。
这些原料可以是分离出来的化合物或者以反应产物存在。例如，6-氯-2-羟基喹喔啉-4-氧化物可以4-氯-2-硝基-N-乙酰乙酰苯胺与氢氧化物（如氢氧化钠或氢氧化钾）的反应产物存在。
本发明的方法被选自硫化的铂。硫化的钯、硫化的铑和硫化的钌的氢化催化剂催化。最好是使用硫化的铂。这类催化剂的典型用量是每100份重2-喹喔啉醇-4-氧化物用约0.05-100份重的催化剂。
当本发明的方法中所用原料是硝基-N-乙酰乙酰苯胺和氢氧化物的反应产物时，本发明的反应在含有选自碱金属氢氧化物、碱土金属氢氧化物和氢氧化铵的至少一种化合物的溶液中进行。最好是以水作反应溶剂，但是有机溶剂（如醇类或烃类）或水与有机溶剂的混合溶剂也可使用。
本发明的方法典型地在约3-100个大气压下进行，最好是在约6-60个大气压下进行。反应温度可以在较宽的范围内变化，典型的温度范围是约10°-90℃，最好是约20°-75℃。
最好的反应温度和压力将依包括特定的催化剂，所用的原料，催化剂浓度等因素而改变。熟悉该技术领域的人们都清楚，反应压力和温度太高会降低反应的选择性，并产生过渡还原的产物。相反地，反应温度和压力太低会降低催化剂的活性。不过，熟悉该技术的人通过例行试验很容易就特定的一组反应剂确定最佳反应条件。
采用熟悉氢化技术的人们都知道的方法，本发明的方法可以连续的或批量的方式进行。
由于本发明的方法使用氢作还原剂，与使用较贵的化学品（如肼）作还原剂的先有技术相比是非常经济的。另外，由于本发明的方法在高压下进行，大大减少了因空气的渗入而发生的爆炸危险。
下面的实施例是要进一步阐明本发明而不是以任何方式限制本发明的范围。
实施例1-5和比较例A及B
在一个装有搅拌的300ml高压釜中加125ml含9.2g6-氯-2-羟基喹喔啉醇-4-氧化物（经482.4g4-氯硝基-N-乙酰乙酰苯胺与813g86.9%的氢氧化钾在3200g水中反应而得）的17.6%（重量）氢氧化钾水溶液的贮备液。按下面表1所给的用量加催化剂并密封高压釜。在这点上要注意，除了比较例B（NiS）外，所有催化剂均是以5%（重量）载于碳上。首先用氮气接着用氢气吹洗高压釜。加氢直至表1所示压力。在搅拌下加热高压釜至给定的反应时间，然后冷却并降压。用水将反应产物移出，经硅藻土过滤（除去催化剂）并干燥。分析反应产物并计算产率。
表1
用氢作还原剂将6-氯-2-羟基喹喔啉醇-4-氧化物
还原为6-氯-2-羟基喹喔啉
表1（续）
用氢作还原剂将6-氯-2-羟基喹喔啉醇-4-氧化物
还原为6-氯-2-羟基喹喔啉
＊这时H2吸收已基本停止。
＊＊基于4-氯硝基-N-乙酰乙酰苯胺转化为6-氯-2-羟基喹喔啉的摩尔转化率。
以上数据表明应用硫化的铂、硫化的钯、硫化的铑或硫化的钌作催化剂的本发明方法与现有技术所用类型催化剂或类似催化剂相比，获得料想不到的选择性还原产物的产率。
应该认识到，在本发明的实践中应避免增加压力和温度的某些结合，例如在60℃反应温度和500-700psig反应压力下，用硫化的钯作催化剂，产生过度还原的产物。
表Ⅰ
用氢作还原剂将6-氯-2-羟基喹喔啉醇-4-氧化物
还原为6-氯-2-羟基喹喔啉
实施例或 催化剂 催化剂量 反应温度 反应压力
比较例 （g） （℃） （psig）
1 硫化的铂 0.125 60 100-200
2 硫化的铂 0.125 60 100-200
3 硫化的钯 1.9 20 100-200
4 硫化的铑 2.0 20 600-700
5 硫化的钌 1.9 60 620-720
A 钯 1.0 30 450-700
B 硫化的镍 3.8 60 660-760
表Ⅰ（续）
用氢作还原剂将6-氯-2-羟基喹喔啉醇-4-氧化物
还原为6-氯-2-羟基喹喔啉
反应时间 H2吸收＊ 产率＊＊
（小时） （%） （%）＊＊
5.0 100 79
4.0 100 78
5.8 117 43
2.0 114 61
5.9 157 24
0.08 232 ＜0.5
5.0 113 19
＊这时H2吸收已基本停止。
＊＊基于4-氯硝基-N-乙酰乙酰苯胺转化为6-氯-2-羟基喹喔啉的摩尔转化率。
Claims (11)
1、制备通式如下的2-喹喔啉醇化合物的方法：
式中R为氢，卤素或三卤甲基，
该方法包括在催化有效量的选自硫化的铂，硫化的钯，硫化的铑和硫化的钌的至少一种催化剂存在下，于10°-90℃和3-100个大气压下，用氢还原通式如下的2-喹喔啉醇-4-氧化物，
式中R的定义同上。
2、权利要求1的方法，其特征在于所述的2-喹喔啉醇-4-氧化物是处于还含有选自碱金属氢氧化物，碱土金属氢氧化物和氢氧化铵的至少一种化合物的溶液中。
3、权利要求2的方法，其特征在于所述的溶液是水溶液。
4、权利要求1的方法，其特征在于通式中的R选自氢，氯，氟，三氯甲基和三氟甲基。
5、权利要求1的方法，其特征在于原料是6-氯-2-羟基喹喔啉-4-氧化物。
6、权利要求1的方法，其特征在于还原反应发生于20°-75℃。
7、权利要求1的方法，其特征在于还原反应发生于6-60个大气压。
8、权利要求1的方法，其特征在于催化剂是硫化的铂。
9、权利要求5的方法，其特征在于该反应在催化剂硫化的铂和碱金属氢氧化物水溶液存在下进行。
10、权利要求5的方法，其特征在于反应发生于20-75℃和6-60个大气压下。
11、权利要求5的方法，其特征在于反应发生于60°和8-15个大气压下。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US064,908 | 1987-06-19 | ||
| US07/064,908 US4814444A (en) | 1987-06-19 | 1987-06-19 | Process for the selective reduction of 2-hydroxyquinoxaline-4-oxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030915A CN1030915A (zh) | 1989-02-08 |
| CN1017995B true CN1017995B (zh) | 1992-08-26 |
Family
ID=22059048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88103659A Expired CN1017995B (zh) | 1987-06-19 | 1988-06-17 | 2-喹喔啉醇-4-氧化物的选择性还原方法 |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4814444A (zh) |
| EP (1) | EP0295797B1 (zh) |
| JP (1) | JPH0629267B2 (zh) |
| KR (1) | KR900004416B1 (zh) |
| CN (1) | CN1017995B (zh) |
| AT (1) | ATE161832T1 (zh) |
| AU (1) | AU609489B2 (zh) |
| BR (1) | BR8802783A (zh) |
| CA (1) | CA1321202C (zh) |
| DE (1) | DE3856098T2 (zh) |
| ES (1) | ES2110396T3 (zh) |
| FI (1) | FI99204C (zh) |
| IL (1) | IL86415A (zh) |
| MX (1) | MX168769B (zh) |
| PH (1) | PH25129A (zh) |
| ZA (1) | ZA883784B (zh) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL86416A (en) * | 1987-06-19 | 1993-07-08 | Uniroyal Chem Co Inc | Process for the preparation of 2-quinoxalinol derivatives |
| DE3925969A1 (de) * | 1989-08-05 | 1991-02-07 | Hoechst Ag | Verfahren zur herstellung von 2,6-dichlorchinoxalin |
| US5169955A (en) * | 1990-03-01 | 1992-12-08 | Nippon Kayaku Kabushiki Kaisha | Process for producing 2-hydroxyquinoxaline derivatives |
| CZ279488B6 (cs) * | 1990-09-25 | 1995-05-17 | Lonza A.G. | Způsob mikrobiologické výroby hydroxylovaných heterocyklů |
| US5786479A (en) * | 1994-02-17 | 1998-07-28 | Nissan Chemical Industries, Ltd. | Process for producing a 6-subsitituted 2(1H)-quinoxalinone |
| CN101941947B (zh) * | 2010-08-27 | 2012-06-27 | 山东京博控股股份有限公司 | 一种6-氯-2-羟基喹喔啉的合成方法 |
| CN102180840A (zh) * | 2011-03-15 | 2011-09-14 | 安徽丰乐农化有限责任公司 | 6-氯-2-羟基喹喔啉的制备新工艺 |
| CN111239125A (zh) * | 2020-03-06 | 2020-06-05 | 中国药科大学 | 一种利用二硫化铂的葡萄糖比色检测法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3350450A (en) * | 1963-08-12 | 1967-10-31 | Uniroyal Inc | Process of preparing aromatic amines by the catalytic hydrogenation of aromatic nitro compounds |
| JPS48973A (zh) * | 1971-05-28 | 1973-01-09 | ||
| US4636562A (en) * | 1982-05-07 | 1987-01-13 | E. I. Du Pont De Nemours And Company | Process for preparing 6-halo-2-chloroquinoxaline |
| JPS59216878A (ja) * | 1983-05-25 | 1984-12-06 | Nippon Kayaku Co Ltd | ２−キノキサリノ−ル類の製法 |
-
1987
- 1987-06-19 US US07/064,908 patent/US4814444A/en not_active Expired - Lifetime
-
1988
- 1988-05-18 IL IL86415A patent/IL86415A/xx not_active IP Right Cessation
- 1988-05-25 ES ES88304755T patent/ES2110396T3/es not_active Expired - Lifetime
- 1988-05-25 EP EP88304755A patent/EP0295797B1/en not_active Expired - Lifetime
- 1988-05-25 DE DE3856098T patent/DE3856098T2/de not_active Expired - Lifetime
- 1988-05-25 AT AT88304755T patent/ATE161832T1/de not_active IP Right Cessation
- 1988-05-26 ZA ZA883784A patent/ZA883784B/xx unknown
- 1988-05-26 CA CA000567838A patent/CA1321202C/en not_active Expired - Lifetime
- 1988-06-08 AU AU17497/88A patent/AU609489B2/en not_active Expired
- 1988-06-08 BR BR8802783A patent/BR8802783A/pt not_active IP Right Cessation
- 1988-06-10 PH PH37047A patent/PH25129A/en unknown
- 1988-06-14 KR KR1019880007107A patent/KR900004416B1/ko not_active Expired
- 1988-06-16 FI FI882894A patent/FI99204C/fi active IP Right Grant
- 1988-06-16 JP JP63149242A patent/JPH0629267B2/ja not_active Expired - Fee Related
- 1988-06-17 MX MX011942A patent/MX168769B/es unknown
- 1988-06-17 CN CN88103659A patent/CN1017995B/zh not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| MX168769B (es) | 1993-06-07 |
| ZA883784B (en) | 1989-11-29 |
| EP0295797B1 (en) | 1998-01-07 |
| PH25129A (en) | 1991-02-19 |
| ATE161832T1 (de) | 1998-01-15 |
| JPS6416772A (en) | 1989-01-20 |
| DE3856098D1 (de) | 1998-02-12 |
| DE3856098T2 (de) | 1998-05-07 |
| FI99204B (fi) | 1997-07-15 |
| IL86415A (en) | 1993-02-21 |
| JPH0629267B2 (ja) | 1994-04-20 |
| KR900004416B1 (ko) | 1990-06-25 |
| BR8802783A (pt) | 1988-12-27 |
| KR890000439A (ko) | 1989-03-14 |
| AU609489B2 (en) | 1991-05-02 |
| CA1321202C (en) | 1993-08-10 |
| EP0295797A3 (en) | 1989-11-15 |
| ES2110396T3 (es) | 1998-02-16 |
| EP0295797A2 (en) | 1988-12-21 |
| FI99204C (fi) | 1997-10-27 |
| FI882894L (fi) | 1988-12-20 |
| AU1749788A (en) | 1988-12-22 |
| FI882894A0 (fi) | 1988-06-16 |
| US4814444A (en) | 1989-03-21 |
| CN1030915A (zh) | 1989-02-08 |
| IL86415A0 (en) | 1988-11-15 |
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