CN1191234C - 哌啶化合物的制备方法 - Google Patents

哌啶化合物的制备方法 Download PDF

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CN1191234C
CN1191234C CNB011179406A CN01117940A CN1191234C CN 1191234 C CN1191234 C CN 1191234C CN B011179406 A CNB011179406 A CN B011179406A CN 01117940 A CN01117940 A CN 01117940A CN 1191234 C CN1191234 C CN 1191234C
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G·吉菲尔斯
H·迪尔
G·马丁
L·弗洛恩
E·哈默施米德特
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Abstract

在钯催化剂存在下，通过活性吡啶化合物催化氢化以有益的方式制备派啶化合物，所用催化剂是钯/炭和所用溶剂是芳烃。

Description

哌啶化合物的制备方法
本发明涉及通过相应的吡啶环氢化制备哌啶化合物的改进方法。
哌啶化合物是制备药物活性化合物的中间体(参见例如，EP-A603887和EP-A 350733，特别是第2和17页)。因此，它们必须以尽可能纯的形式获得。
活性吡啶化合物通常在醇溶剂如甲醇、乙醇、异丙醇或乙二醇甲醚中，用钯催化剂氢化成相应的哌啶化合物(参见HeterogenousCatalysis for the Synthetics Chemist，New York 1996，17章421一424页和EP-A 350733，特别是65-66页)。反应混合物一般通过除去催化剂和溶剂进行后处理。所得哌啶化合物须经进一步提纯，例如通过结晶，蒸馏或经色谱提纯。以此除去哌啶化合物中所的不需要的副产物。除了与提纯有关的费用外，在进一步提纯期间发生的产物损失也是不利的，特别是由于溶剂中含有杂质而难以循环使用。
因此，仍然需要一种不必进一步提纯从反应混合物中分离出的产物的制备哌啶化合物的方法。
本发明提供一种在钯催化剂存在下催化氢化活性吡啶化合物制备哌啶化合物的方法，其特征在于所用钯催化剂是钯/炭和所用溶剂是芳烃。
用于本发明方法中的适合的活性吡啶化合物是，例如通式(I)的化合物，
Figure C0111794000041
其中
R1代表COOR3、CONH2、CO-NH-COR3或COOH基或两个相邻的R1基一起代表CO-NR4-CO基，
R2代表直链或支链C1-C20烷基，
R3代表直链或支链C1-C6烷基、苯基或苄基，
R4代表氢、直链或支链C1-C6烷基、苯基或苄基，
n代表1或2，和
m代表0、1或2。
如果n代表2，可以存在两个相同或两个不同的R1；同样地，
如果m代表2，可以存在两个相同或两个不同的R2。
优选R1代表COO-C1-C4烷基或两个相邻的R1一起代表CO-N(苄基)-CO基，R2代表C1-C4烷基，n代表1或2和m代表0或1。
如果在本发明方法中使用通式(I)的活性吡啶化合物，那么得到相应于通式(II)的派啶化合物，
其中所有符号的含义与通式(I)的相同。
本发明使用的钯/炭催化剂可以是，例如在任何炭上含1-10％(重量)钯的催化剂。优选的催化剂含2-8％(重量)钯。适合的催化剂是市场上可买到的。
催化剂的用量例如每摩尔活性吡啶0.5-30mmol钯。该量优选为2-15mmol。
适合的芳烃是例如苯、甲苯、二甲苯和其它烷基芳烃，优选甲苯。基于1mol活性吡啶，使用例如50-5000g芳烃(可以是混合物形式)。
本发明的催化氢化反应可以于例如20-200℃进行，优选50-150℃，特别优选60-100℃。适合的压力是例如1-200巴，优选3-150巴，特别优选5-60巴。
温度和压力应避免同时选用上限，因为会有溶剂共还原的危险。
催化氢化进行后，待处理的反应混合物通过例如过滤除去催化剂，然后通过例如蒸馏除去芳烃，如果合适的话在减压下。除去的催化剂和除去的芳烃可以循环使用。如果合适的话，新鲜的催化剂和新鲜的芳烃可以分别加到循环的催化剂和循环的芳烃中。
除去催化剂和芳烃后，制得的哌啶化合物的纯度一般大于98％，因此，不必进一步提纯。如在比较例中显示的，应用醇溶剂的常规方法，不进一步提纯的话，只给出约94％纯度的哌啶化合物。为了哌啶化合物作为药物中间体的进一步应用，按照本发明获得的纯度是决定性的重要。
令人惊奇的是，本发明找到了一种不能从先有技术文献预料的有益的方法，其在非极性溶剂中以钯/炭催化剂的多相催化获得高产率和选择性。另外，预料不仅所用的吡啶化合物而且作为溶剂使用的芳烃会被氢化，结果不仅污染了产物而且损失了溶剂；然而，这种现象没有发生。
实施例1
在装有搅拌器、温度传感器和升气管的0.7升搅拌着的高压釜中，将163.7g吡啶-2，3-二甲酸N-苄基酰亚胺和6.6g 5％(重量)钯/炭悬浮于256.7g甲苯中。用氮气吹洗高压釜两次，然后，用氢气吹洗两次。在5巴氢气压下加热高压釜至80℃，氢气压逐渐增加至50巴，反应温度维持于80℃。达到50巴后，于80℃下继续搅拌10小时，然后冷却高压釜。经过滤从反应混合物中除去催化剂并用旋转蒸发器在减压下除去甲苯，得到170g哌啶-2，3-二甲酸N-苄基酰亚胺，纯度为98.8％(GC面积百分数)。
实施例2
重复实施例1，使用181.7g吡啶-2，3-二甲酸N-苄基酰亚胺在10巴压力下氢化，得到183.2g哌啶-2，3-二甲酸N-苄基酰亚胺，纯度为98.2％(GC面积百分数)。
实施例3
在装有搅拌器、温度传感器和升气管的搅拌着的1.3升高压釜中，将666g吡啶-2，3-二甲酸N-苄基酰亚胺和28.2g 5％(重量)钯/炭悬浮于959g甲苯中。然后，如实施例1那样，分别以氮气并以氢气吹洗高压釜，在80℃下反应。如实施例1那样后处理反应混合物，得到618g哌啶-2，3-二甲酸N-苄基酰亚胺，纯度为98.7％(GC面积百分数)。
实施例4
在装有搅拌器和温度传感器的0.3升搅拌着的高压釜中，将19.52g吡啶-2，3-二甲酸二甲酯和2.25g 5％(重量)钯/炭最初加入131g甲苯中。高压釜以氮气吹洗两次后以氢气吹洗两次。加热高压釜至80℃并在达此温度后，施用10巴氢气压和在这些条件下氢化混合物4小时。反应混合物冷却后，过滤分出催化剂和以旋转蒸发器在减压下除去甲苯，得到19.13g顺-哌啶-2，3-二甲酸二甲酯，纯度为98.7％(GC面积百分数)。
比较例1(溶剂：异丙醇)
重复实施例2，但使用261.7g异丙醇代替甲苯，得到185.7g哌啶-2，3-二甲酸N-苄基酰亚胺，纯度为94％(GC面积百分数)。
比较例2(溶剂：乙二醇单甲醚)
重复实施例1，但是用同样量的乙二醇单甲醚代替甲苯，得到171.1g哌啶-2，3-二甲酸N-苄基酰亚胺，纯度为94.8％(GC面积百分数)。

Claims (7)

1.在钯催化剂存在下，通过将通式(I)的活性吡啶化合物催化氢化制备哌啶化合物的方法，
Figure C011179400002C1
其中
R1代表COOR3、CONH2、CO-NH-COR3或COOH基或两个相邻的R1基一起代表CO-NR4-CO基，
R2代表直链或支链C1-C20烷基，
R3代表直链或支链C1-C6烷基、苯基或苄基，
R4代表氢、直链或支链C1-C6烷基、苯基或苄基，
n代表1或2，和
m代表0、1或2，
得到相应的通式(II)的哌啶化合物，
其中所用符号的含义与通式(I)中的相同，该方法的特征在于所用的钯催化剂是钯/炭和所用溶剂是芳烃。
2.权利要求1的方法，其特征在于在通式(I)和(II)中，R1代表COO-C1-C4烷基或两个相邻的R1一起代表CO-N(苄基)-CO基，R2代表C1-C4烷基，n代表1或2和m代表0或1。
3.权利要求1的方法，其特征在于所用钯/炭催化剂含有1-10％(重量)的钯。
4.权利要求1的方法，其特征在于所用催化剂的量是每摩尔吡啶存在0.5-30mmol钯。
5.权利要求1的方法，其特征在于所用芳烃是苯、甲苯或二甲苯或者其它烷基芳烃。
6.权利要求1的方法，其特征在于该反应在20-200℃温度范围内进行。
7.权利要求1的方法，其特征在于该反应在1-200巴压力范围内进行。
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HUP0101875A3 (en) 2002-11-28
JP2002003474A (ja) 2002-01-09
CN1322715A (zh) 2001-11-21
US20010056186A1 (en) 2001-12-27
ES2225336T3 (es) 2005-03-16
MXPA01004645A (es) 2002-06-04
EP1153918B1 (de) 2004-09-08
US6458954B2 (en) 2002-10-01
DK1153918T3 (da) 2005-01-10
JP4817527B2 (ja) 2011-11-16
ATE275547T1 (de) 2004-09-15
PL347387A1 (en) 2001-11-19
DE50103506D1 (de) 2004-10-14
DE10022369A1 (de) 2001-11-15
KR20010102934A (ko) 2001-11-17
IL142973A0 (en) 2002-04-21
EP1153918A1 (de) 2001-11-14
HU0101875D0 (en) 2001-07-30
CZ20011587A3 (cs) 2001-12-12
HUP0101875A2 (hu) 2002-04-29

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