CN1178214A - 胺类的制备方法 - Google Patents
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Classifications
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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
- C07C209/08—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 acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
本发明方法包括两个连续的步骤,其中第一步醇通过与氯化试剂反应被转化为有机氯化物,接着第二步将有机氯化物胺化成相应的胺。在第二步,为便于反应使用了表面活性剂。
Description
本发明涉及用于后续形成生物活性物质的胺类的改进制备方法。
本发明方法包括两个步骤，其中第一步醇通过与氯化试剂反应被转化为有机氯化物，接着第二步胺化有机氯化物为相应的胺。在第二步，为了有利于反应使用表面活性剂。当在第一步形成的有机氯化物是不溶于水而胺化剂是溶于水的时，表面活性剂的存在是特别有价值的。在不受理论限制的情况下，据信表面活性剂在水介质中增加有机氯化物的表面积。这使得氯化物有更大的接触面积与胺化剂反应，结果改进了传质能力；因此减少了反应时间。另外，由于减少了不需要的副产物的形成，使所需胺的选择性和产率提高；结果使该方法经济可行并且能够以更经济的方式为市场提供以后的农药产品。
利用表面活性剂的本发明方法对于从相应的氯代炔和其前体炔醇制备氨基炔类是最有用的，其中氯代炔是不溶于水而胺化剂如氨或甲胺则是溶于水的。氯代炔的胺化方法已经被描述在Michelotti等人的US 5,254,584和Hennion等人的J.Am.Chem.Soc.，75，1653(1953)中；但是在这种方法中使用表面活性剂没有公开或提示。另一种通过氯代炔与氨化钠在液氨中反应制备氨基炔的方法也被描述在J.Org.Chem.，45，4616(1980)中；但是这种方法仅在实验室规模是可行的，不适合作为大规模商业化方法。
本发明方法包括以下步骤：
a.炔醇与HCl反应形成氯代炔，
b.所述氯代炔与水溶性胺化剂在表面活性剂的存在下反应形成氨基炔，并且任选地，
c.通过蒸馏纯化所述氨基炔。
更具体地，本发明方法包括以下步骤：
a.下式炔醇与饱和的HCl水溶液反应形成下式氯代炔，
b.所述氯代炔与式NR3R4的水溶性胺化剂在非离子，阳离子和两性表面活性剂的存在下反应形成下式氨基炔，
并且任选地，
c.通过蒸馏纯化所述氨基炔；其中
R是氢原子，烷基，环烷基，环烷基烷基或芳烷基；
R1和R2各自独立地是烷基，环烷基，环烷基烷基或芳烷基或与连接的碳原子一起形成环烷基；及
R3和R4各自独立地是氢原子或低级烷基。
在本发明中，烷基是直链或支链(C1-C8)烷基并且包括，例如甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基，叔丁基，正戊基，异戊基，正己基和正辛基。低级烷基是直链或支链(C1-C4)烷基。环烷基包括，例如环戊基和环己基。环烷基烷基包括例如环戊基甲基，环己基乙基，3-环戊基丙基，4-环己基丁基等。对于芳烷基的芳基部分被定义为苯基或被一个或两个独立选自卤素和烷基取代基取代的苯基；烷基部分被定义为直链(C1-C4)烷基。芳烷基的实例包括苄基，苯乙基，4-氯苄基，4-甲基苄基和2-氯苯乙基。
在一个本发明优选的实施方案中，R是氢原子或低级烷基，R1和R2独立地是低级烷基，或与连接的碳原子一起形成环戊基或环己基；R3和R4独立地是氢原子或低级烷基，表面活性剂是非离子表面活性剂。在本发明一个更优选的实施方案中，R是氢原子，R1和R2独立地是甲基或乙基，R3和R4均为氢原子，表面活性剂是烷基苯氧基聚乙氧基乙醇。在本发明一个更为优选的实施方案中，R1是甲基及R2是甲基或乙基。
反应步骤1和2最通常在常压和约10℃至约-10℃温度下进行。但是如果需要，该步骤可在高于大气压和较高温度下进行。化学计量相对不重要，但是通常最适宜在第一步使用过量的HCl和在第二步使用过量的胺化剂。在第一步可使用如氯化亚铜(I)的氯化催化剂。通常在第二步使用氯化氢吸收剂，例如强碱如氢氧化钠或氢氧化钾以减少胺化剂的消耗；然而，如果需要，也可使用过量的胺化剂作为HCl吸收剂。两步的反应时间可以变化并且常常取决于反应容器的冷却能力和混合性能；起始原料向所需中间体或产物的转变过程通常用气液色谱(GLC)和高效液相色谱(HPLC)跟踪。第二步中表面活性剂的用量可以变化但通常是所用有机氯化物量的0.01-10％(重量)。优选表面活性剂的用量为所用有机氯化物量的0.1-1.0％(重量)。
下列实施例是要进一步说明本发明而不是限定权利要求定义的范围。
实施例1：形成3-氯-3-甲基-1-戊炔
在一个由1L装有温度计的树脂锅、气体扩散管、具有精制搅拌叶片的顶部机动搅拌器、Lauda型循环浴、碱洗气器和具有慢速氮气吹气装置的均压加料漏斗组成的反应器中与1.58g(16mol)氯化亚铜(I)一起加入300mL(3.6mol)浓盐酸。将冷却浴设置在0℃，并引入氯化氢气体。HCl的溶解是放热的；由于溶液接近饱和，因此将浴温进一步调低直到锅温达到约-5℃。将3-甲基-1-戊炔-3-醇(250g，2.5mol)装入加料漏斗。开始慢速吹过氮气，使HCl蒸汽不能通过侧臂进入醇。以保持反应在0℃或更低温度的速度滴加醇2-3小时。在滴加期间继续加入氯化氢气体以保持饱和。加完后，停止加入氯化氢气体并将扩散管升高至液面以上。允许将反应混合物在0℃搅拌30分钟，然后停止搅拌并分离两相。放掉下面的水相并先后用水和饱和盐水与碳酸氢钠溶液的混合物洗涤有机相。将有机相储存在冰箱中直到用于下一步。该步骤得到约280-290g黄色至棕色液体，用GLC分析发现其纯度介于90-96％之间。
实施例2：形成3-氨基-3-甲基-1-戊炔
在一个由1L装有顶部搅拌器的树脂锅、Lauda型冷却浴，气体扩散管，两个均压加料漏斗，温度计，氮气吹气管和装有适当夹子的进气口和排气口组成的反应器中加入350mL(2.6mol)浓氢氧化铵溶液和1.00g TritonX-100(Footnotel)。将冷却浴设置在大约0℃并引入氨气。氨的溶解是颇为放热的。由于溶液接近饱和，因此将浴温进一步调低到锅温达到约-5℃。在一个加料漏斗中装入250g(2.0mol)3-氯-3-甲基-1-戊炔，在另一个加料漏斗中装入172g(2.2mol)50％的氢氧化钠。将慢速氮气吹气管放在有氯化物的加料漏斗中以防止氨蒸汽通过侧臂进入漏斗。以保持反应在0℃或更低温度的速度同时滴加氯化物和苛性(物质)3-4小时。在滴加期间继续加入氨气以保持饱和。加完后，停止加入氨气并将扩散管升高至液面以上。在0℃搅拌反应混合物直到用GLC发现未反应的氯化物少于1％。停止搅拌并分离两相。放掉下面的水相并弃去，将上面的有机相转移至有75mL水的蒸馏烧瓶中。用15cm包裹的Vigreues柱蒸馏该混合物。收集沸点在85-92℃之间的馏分，得到174.3g无色液体。主要馏分为与水的共沸物。该物质中含有约28％的水。GLC分析表明，在剩下的有机物质中90％为3-氨基-3-甲基-1-戊炔，其余主要是3-甲基-1-戊炔-3-醇和丁酮。以3-氯-3-甲基-1-戊炔起始原料为基准3-氨基-3-甲基-1-戊炔的产率为60％。
比较实施例：形成3-氨基-3-甲基-1-戊炔
所用方法基本上类似于实施例2的方法，只是在反应器系统中没有加入表面活性剂。在这种情况下以3氯-3-甲基1-戊炔起始原料为基准3-氨基-3-甲基-1-戊炔的产率为39％。
应当理解本说明书利用非限定性实例进行说明，在不背离本发明精神和所附权利要求定义的范围的情况下可进行各种改变和变化。
Claims (22)
1.一种合成氨基炔的方法，该方法包括以下步骤：
a.炔醇与HCl反应形成氯代炔，
b.所述氯代炔与水溶性胺化剂在表面活性剂的存在下反应形成氨基炔，并且任选地，
c.通过蒸馏纯化所述氨基炔。
2.权利要求1的方法，包括以下步骤：
a.下式炔醇与饱和的HCl水溶液反应
形成下式氯代炔，
b.所述氯代炔与式NR3R4水溶性胺化剂在非离子，阳离子和两性表面活性剂的存在下反应形成下式氨基炔，
并且任选地，
c.通过蒸馏纯化所述氨基炔；其中：
R是氢原子，烷基，环烷基，环烷基烷基或芳烷基；
R1和R2各自独立地是烷基，环烷基，环烷基烷基，芳烷基或与连接的碳原子一起形成环烷基；及
R3和R4各自独立地是氢原子或低级烷基。
3.权利要求2的方法，其中R是氢原子或低级烷基。
4.权利要求2的方法，其中R1和R2独立地是低级烷基，或与其连接的碳原子一起形成环戊基或环己基。
5.权利要求2的方法，其中R3和R4独立地是氢原子或低级烷基。
6.权利要求2的方法，其中表面活性剂是非离子表面活性剂。
7.权利要求3的方法，其中R是氢原子。
8.权利要求4的方法，其中R1和R2独立地是甲基或乙基。
9.权利要求5的方法，其中R3和R4均为氢原子。
10.权利要求8的方法，其中R1是甲基及R2是甲基或乙基。
11.一种从氯代炔合成氨基炔的方法，包括所述氯代炔与水溶性胺化剂在表面活性剂的存在下反应。
12.权利要求11的方法，其中下式氯代炔，
与式NR3R4水溶性胺化剂在非离子，阳离子和两性表面活性剂的存在下反应形成下式氨基炔，其中
R是氢原子，烷基，环烷基，环烷基烷基或芳烷基；
R1和R2各自独立地是烷基，环烷基，环烷基烷基，芳烷基或与其连接的碳原子一起形成环烷基；及
R3和R4各自独立地是氢原子或低级烷基。
13.权利要求12的方法，其中R是氢原子或低级烷基。
14.权利要求12的方法，其中R1和R2独立地是低级烷基，或与其连接的碳原子一起形成环戊基或环己基。
15.权利要求12的方法，其中R3和R4独立地是氢原子或低级烷基。
16.权利要求12的方法，其中表面活性剂是非离子表面活性剂。
17.权利要求13的方法，其中R是氢原子。
18.权利要求14的方法，其中R1和R2独立地是甲基或乙基。
19.权利要求15的方法，其中R3和R4均为氢原子。
20.权利要求18的方法，其中R1是甲基及R2是甲基或乙基。
21.权利要求6的方法，其中表面活性剂是烷基苯氧基聚乙氧基乙醇。
22.权利要求16的方法，其中表面活性剂是烷基苯氧基聚乙氧基乙醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2686496P | 1996-10-01 | 1996-10-01 | |
| US60/026,864 | 1996-10-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178214A true CN1178214A (zh) | 1998-04-08 |
| CN1124253C CN1124253C (zh) | 2003-10-15 |
Family
ID=21834227
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116937A Expired - Lifetime CN1124253C (zh) | 1996-10-01 | 1997-09-26 | 胺类的制备方法 |
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| Country | Link |
|---|---|
| EP (1) | EP0834498B1 (zh) |
| JP (1) | JPH10114727A (zh) |
| KR (1) | KR19980032426A (zh) |
| CN (1) | CN1124253C (zh) |
| AT (1) | ATE193520T1 (zh) |
| AU (1) | AU3759697A (zh) |
| BR (1) | BR9704945A (zh) |
| CA (1) | CA2215813A1 (zh) |
| DE (1) | DE69702171T2 (zh) |
| HU (1) | HUP9701594A3 (zh) |
| IL (1) | IL121799A (zh) |
| MX (1) | MX9707345A (zh) |
| TR (1) | TR199701087A2 (zh) |
| ZA (1) | ZA978492B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180798A (zh) * | 2011-03-18 | 2011-09-14 | 湖北汉星化工新材料有限公司 | 一步法催化合成n,n-二乙基丙炔胺的方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0312863D0 (en) | 2003-06-04 | 2003-07-09 | Syngenta Ltd | Fungicides |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1927528C3 (de) * | 1969-05-30 | 1978-01-19 | Basf Ag | Verfahren zur herstellung von alpha- aethinylaminen |
| HU187775B (en) * | 1982-07-14 | 1986-02-28 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt,Hu | New process for producing propargile-amines of pharmaceutical activity |
| US5254584A (en) * | 1992-12-18 | 1993-10-19 | Rohm And Haas Company | N-acetonylbenzamides and their use as fungicides |
-
1997
- 1997-09-17 AU AU37596/97A patent/AU3759697A/en not_active Abandoned
- 1997-09-18 IL IL12179997A patent/IL121799A/en not_active IP Right Cessation
- 1997-09-18 CA CA002215813A patent/CA2215813A1/en not_active Abandoned
- 1997-09-22 ZA ZA9708492A patent/ZA978492B/xx unknown
- 1997-09-25 MX MX9707345A patent/MX9707345A/es not_active Application Discontinuation
- 1997-09-26 CN CN97116937A patent/CN1124253C/zh not_active Expired - Lifetime
- 1997-09-29 JP JP9279317A patent/JPH10114727A/ja not_active Withdrawn
- 1997-09-29 KR KR1019970049657A patent/KR19980032426A/ko not_active Application Discontinuation
- 1997-09-30 DE DE69702171T patent/DE69702171T2/de not_active Expired - Lifetime
- 1997-09-30 EP EP97307688A patent/EP0834498B1/en not_active Expired - Lifetime
- 1997-09-30 BR BR9704945A patent/BR9704945A/pt not_active Application Discontinuation
- 1997-09-30 HU HU9701594A patent/HUP9701594A3/hu unknown
- 1997-09-30 AT AT97307688T patent/ATE193520T1/de not_active IP Right Cessation
- 1997-10-01 TR TR97/01087A patent/TR199701087A2/xx unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180798A (zh) * | 2011-03-18 | 2011-09-14 | 湖北汉星化工新材料有限公司 | 一步法催化合成n,n-二乙基丙炔胺的方法 |
| CN102180798B (zh) * | 2011-03-18 | 2013-11-06 | 湖北汉星化工新材料有限公司 | 一步法催化合成n,n-二乙基丙炔胺的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19980032426A (ko) | 1998-07-25 |
| BR9704945A (pt) | 1999-05-18 |
| HU9701594D0 (en) | 1997-11-28 |
| DE69702171T2 (de) | 2000-12-14 |
| EP0834498A1 (en) | 1998-04-08 |
| HUP9701594A3 (en) | 1999-04-28 |
| DE69702171D1 (de) | 2000-07-06 |
| CA2215813A1 (en) | 1998-04-01 |
| HUP9701594A2 (hu) | 1998-07-28 |
| AU3759697A (en) | 1998-04-09 |
| IL121799A (en) | 2001-04-30 |
| EP0834498B1 (en) | 2000-05-31 |
| CN1124253C (zh) | 2003-10-15 |
| ZA978492B (en) | 1998-03-23 |
| TR199701087A2 (xx) | 1998-04-21 |
| MX9707345A (es) | 1998-04-30 |
| ATE193520T1 (de) | 2000-06-15 |
| IL121799A0 (en) | 1998-02-22 |
| JPH10114727A (ja) | 1998-05-06 |
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