CN1184465A - 羧酸衍生物的制备 - Google Patents

羧酸衍生物的制备 Download PDF

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CN1184465A
CN1184465A CN96194035A CN96194035A CN1184465A CN 1184465 A CN1184465 A CN 1184465A CN 96194035 A CN96194035 A CN 96194035A CN 96194035 A CN96194035 A CN 96194035A CN 1184465 A CN1184465 A CN 1184465A
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E·福斯
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
    • C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides

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Abstract

一种制备通式Ⅰ的羧酸衍生物的方法,这里X是OR2或NH2,R1是C1－C20烷基、C1－C20羟基烷基C3－C12环烷基、C4－C12烷基环烷基、C4-C12环烷基烷基、C5-C20烷基环烷基烷基、芳基、C7-C20芳烷基、C7－C20烷基芳基、具有5～8个碳原子的杂脂族或杂芳族环和R2是C1－C20烷基,通式Ⅰ的羧酸衍生物是在50～300℃的温度下,在0.1～350巴的压力下,在多相催化剂的存在下由通式Ⅱ的腈和通式ⅢR1－C≡N(Ⅱ),R2－OH (Ⅲ),的醇制备的,其中该反应在液相中进行,在通式Ⅱ和通式Ⅲ中R1和R2分别具有上述含义。

Description

羧酸衍生物的制备
本发明涉及一种在二氧化钛催化剂上在升温的条件下由腈和醇制备羧酸衍生物的方法。
DE-A 2714767公开了一种通过腈与醇类和水在含金属的固体催化剂例如在载体如Al2O3、SiO2、ZrO2或TiO2上的铜、锌、铬、铋、锰、铁、镍、镉上的气相反应制备羧酸衍生物的方法。发现了作为副反应的脱水作用和醚化作用。
例如，EP-A 412310公开了一种通过在含锰的催化剂上用水水合腈来制备羧酰胺的方法，例如正如在US-A 4,613,684中公开的一样，在金属盐的存在下，或正如在EP-A 561614中公开的一样，在气相中在固体催化剂上，或正如在EP-A 392361中公开的一样在金属氧化物上，羧酰胺随后通过酸性催化可以与醇类反应得到羧酸衍生物。
工业应用中的缺陷是二步骤和副产物的形成，例如盐的产生或甲酰胺的生成。
DE-A 4339648公开了一种在二氧化钛催化剂上，在乙醇溶液中，通过氨基己腈与水反应制备己内酰胺(一种环状酰胺)的方法。
本发明的目的是消除上述缺陷。
我们已经发现可以这样实现本发明的目的，即通过一种制备通式I的羧酸衍生物的新的和改进的方法，
Figure A9619403500041
这里X是OR2或NH2，R1是C1-C20烷基、C1-C20羟基烷基、C3-C12环烷基、C4-C12烷基环烷基、C4-C12环烷基烷基、C5-C20烷基环烷基烷基、芳基、C7-C20芳烷基、C7-C20烷基芳基、具有5～8个碳原子的杂脂族或杂芳族环和R2是C1-C20烷基,通式I的羧酸衍生物是在50～300℃的温度下，在0.1～350巴的压力下，在多相催化剂的存在下由通式II
R1-C≡N    (II)，的腈和通式III
R2-OH      (III)，的醇制备的，其中该反应在液相中进行，在通式II和通式III中R1和R2分别具有上述含义。
本发明的方法可以以下面的方式进行
通常在压力稳定的设备例如高压釜和管式反应器、优选管式反应器中，在具有二氧化钛催化剂的液相中，在50～300℃、优选100～290℃、特别优选140～270℃的温度下，在0.1～350巴、优选1～200巴、特别优选30～140巴的压力下，将腈II与醇III接触，优选溶解在醇III中。通常结果是得到一种羧酸酯和羧酰胺I的醇溶液，通过常规的方法例如蒸馏、萃取或结晶方法可以从该溶液中得到羧酸酯和羧酰胺I。
羧酰胺可以与新的腈II一起返回反应器中。
固体腈II或固体醇III的反应可以在惰性溶剂中进行，例如在醚类中，优选在具有2～20个碳原子的醚中，特别优选在具有4～12个碳原子的醚中，例如在二乙醚、甲基叔丁基醚或四氢呋喃中，在烃中，优选在具有5～30个碳原子的烃中，特别优选在具有5～12个碳原子的烃例如甲苯和二甲苯中，或有利地在合适的羧酸酯I中进行。
合适的多相催化剂的例子是元素周期表第IIA、IIIA和IVA族元素的酸性、碱性或两性氧化物，例如氧化钙、氧化镁、氧化硼、氧化铝、氧化锡或二氧化硅，热解的二氧化硅，硅胶形式的二氧化硅，硅藻土，石英，以及元素周期表第IIB、IIIB、IVB、VB、VIB和VIIB族金属的氧化物例如氧化钛、特别是二氧化钛例如无定形的，金红石或锐钛矿形式的二氧化钛，氧化锆，氧化锌，氧化锰，氧化钒，氧化铌，氧化铁，氧化铬，氧化钼，氧化钨，镧系和锕系的氧化物例如氧化铈、氧化钍、氧化镨、氧化钐，混合稀土元素的氧化物或它们的混合物。也可以使用一些硫化物、硒化物和碲化物例如碲化锌、硒化锡、硫化钼、硫化钨、镍、锌或铬的硫化物。
上述化合物可以被元素周期表IA、IIA、IIIA、IVA、VA、VIA和VIIA族的化合物掺杂或包含它们。
其它适合的催化剂是沸石、磷酸盐和杂多酸、和酸性和碱性离子交换剂例如Naphion(原文如此)
如果合适的话，在各种情况下这些催化剂可以包含达50重量％的铜、锡、锌、锰、铁、钴、镍、钌、钯、铂、银或铑。
根据催化剂的组成，可以将催化剂作为非担载或担载催化剂使用。因此，例如，二氧化钛可以作为二氧化钛丸使用或以涂覆在载体上的二氧化钛薄层的形式使用。在载体例如二氧化硅、氧化铝和二氧化锆上涂覆二氧化钛的方法可以是文献中描述的所有方法。因此，可以通过水解有机钛化合物例如异丙氧化钛或丁氧化钛或通过水解TiCl4或其它无机含钛的化合物来涂覆二氧化钛薄层。还可以使用含氧化钛的盐水。
例如可以在悬浮液中，优选在固定床中进行该反应。反应优选在固定床中进行，因为这可以使反应的连续进行变得容易，通常在固定床中产率和选择性是非常高的，因此导致短的停留时间和非常高的物料通过量。因为，根据迄今为止的观察，所使用的多相催化剂具有长的使用寿命，所以催化剂的消耗是非常低的。
在化合物I、II、III中取代基X、R1和R2具有下述含义：X-OR2-NH2R1，R2-C1-C20烷基、优选C1-C12烷基、特别优选C1-C8烷基例如甲基、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、异己基、正庚基、异庚基、正辛基和异辛基，特别是C1-C4烷基例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基。-C1-C20羟基烷基、优选C1-C8羟基烷基、特别优选C1-C4羟基烷基例如羟基甲基、1-羟基乙基、2-羟基乙基和1-甲基-1-羟基乙基。-C3-C12环烷基、优选C5-C8环烷基例如环戊基、环己基、环庚基和环辛基，特别优选环戊基和环己基。-C4-C12烷基环烷基、优选C5-C10烷基环烷基和特别优选C5-C8烷基环烷基，-C4-C12环烷基烷基、优选C5-C10环烷基烷基和特别优选C5-C8环烷基烷基，-C5-C20烷基环烷基烷基、优选C6-C16烷基环烷基烷基和特别优选C7-C12烷基环烷基烷基，-芳基例如苯基、1-萘基和2-萘基，优选苯基，-C7-C20烷基芳基、优选C7-C16烷基芳基、优选C7-C12烷基苯基例如2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、3-乙基苯基和4-乙基苯基-C7-C20芳烷基、优选C7-C16芳烷基、优选C7-C12苯烷基例如苯基甲基、1-苯基乙基和2-苯基乙基、-具有5～8个碳原子的杂脂族环例如2-吗啉基、3-吗啉基、2-哌啶基、3-哌啶基和4-哌啶基-具有5～8个碳原子的杂芳族环例如2-吡啶基、3-吡啶基、4-吡啶基、2-吡唑基、2-咪唑基、4(5)-咪唑基，优选3-吡啶基。
羧酸酯和羧酰胺I适合作为中间产物、塑料前体和适用于农作物保护和药物学。
实施例实施例1
在220℃和80巴下，使20重量％的烟腈乙醇溶液流过填充有氧化钛(1.5mm的丸状)的管，同时加入1摩尔的水(以溶液的重量计为3.5％)。通过流速可变地调节停留时间。
来自反应的排出物的组成总结在表1中。
                     表1
  停留时间     烟腈   烟酸乙酯   烟酰胺     其它
    [分钟]     [％]     [％]     [％]     [％]
    15     5.1     5.4     9.4     0.1
    30     1.9     8.6     9.1     0.4
    60     0.6     11.3     7.4     0.7
实施例2
如实施例1一样，在220℃和80巴下，在1摩尔水的存在下，泵送20重量％的烟腈乙醇溶液流过空管。没有反应发生。

Claims (10)

1、一种制备通式I的羧酸衍生物的方法，
Figure A9619403500021
这里X是OR2或NH2，R1是C1-C20烷基、C1-C20羟基烷基、C3-C12环烷基、C4-C12烷基环烷基、C4-C12环烷基烷基、C5-C20烷基环烷基烷基、芳基、C7-C20芳烷基、C7-C20烷基芳基、具有5～8个碳原子的杂脂族或杂芳族环和R2是C1-C20烷基，通式I的羧酸衍生物是在50～300℃的温度下，在0.1～350巴压力下，在多相催化剂的存在下由通式II
R1-C≡N   (II)，的腈和通式III
R2-OH     (III)，的醇制备的，其中该反应在液相中进行，在通式II和通式III中R1和R2分别具有上述含义。
2、根据权利要求1的制备羧酸衍生物的方法，其中多相催化剂是元素周期表第IIA、IIIA、IVA、IIB、IIIB、IVB、VB、VIB和VIIB族元素的酸性、碱性或两性氧化物、镧系和锕系的氧化物、混合稀土元素的氧化物或它们的混合物，或沸石、磷酸盐、杂多酸、酸性和碱性离子交换剂，它们可以被元素周期表IA、IIA、IIIA、IVA、VA、VIA和VIIA族的化合物掺杂或包含它们，也可以包含0.001-50重量％的铜、锡、锌、锰、铁、钴、镍、钌、钯、铂、银或铑或其混合物。
3、根据权利要求1和2之一的制备羧酸衍生物的方法，其中作为多相催化剂的是氧化钙、氧化镁、氧化硼、氧化铝、氧化锡、二氧化硅、硅胶、硅藻土、石英、二氧化钛、氧化锆、氧化锌、氧化锰、氧化钒、氧化铌、氧化铁、氧化铬、氧化钼、氧化钨、氧化铈、氧化钍、氧化镨、氧化钐和它们的混合物。
4、根据权利要求1～3之一的制备羧酸衍生物的方法，其中多相催化剂是氧化铝、氧化钛、氧化锆和它们的混合物。
5、根据权利要求1～4之一的制备羧酸衍生物的方法，其中将金红石、锐钛矿或它们的混合物作为二氧化钛使用。
6、根据权利要求1～5之一的制备羧酸衍生物的方法。其中反应在100～290℃的温度下进行。
7、根据权利要求1～6之一的制备羧酸衍生物的方法，其中反应在140～270℃的温度下进行。
8、根据权利要求1～7之一的制备羧酸衍生物的方法，其中反应在1～200巴的压力下在液相中进行。
9、根据权利要求1～8之一的制备羧酸衍生物的方法，其中反应在30～140巴的压力下进行。
10、根据权利要求1的制备羧酸衍生物的方法，其中R1是3-吡啶基、1-甲基-1-羟基乙基、1-羟基乙基或2-羟基乙基。
CN96194035A 1995-05-19 1996-05-07 羧酸衍生物的制备 Expired - Fee Related CN1081622C (zh)

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CN102260185A (zh) * 2011-06-13 2011-11-30 昆山市亚香日用香料有限公司 一种n-乙基-2，2-二异丙基丁酰胺的合成方法
CN102911057A (zh) * 2011-08-04 2013-02-06 浙江九洲药业股份有限公司 一种酮洛芬乙酯的制备方法
CN103351306A (zh) * 2013-07-24 2013-10-16 重庆紫光化工股份有限公司 一种一锅法制备n,n-二甲基甘氨酸酯的方法
CN109225191A (zh) * 2018-11-05 2019-01-18 河南省农村科学技术开发中心有限责任公司 一种制备呋虫胺中间体3-羟甲基四氢呋喃的方法及其催化剂
CN116199625A (zh) * 2023-01-19 2023-06-02 上海昱菘医药科技有限公司 一种烟酸酯类化合物的制备方法

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GB0616053D0 (en) 2006-08-11 2006-09-20 Bhp Billiton Petroleum Pty Ltd Improvements relating to hose
US9441766B2 (en) 2009-06-02 2016-09-13 Bhp Billiton Petroleum Pty Ltd. Reinforced hose
US11358927B2 (en) * 2018-04-27 2022-06-14 Showa Denko K.K. Method of producing N,N-disubstituted amide and catalyst for producing N,N-disubstituted amide

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260185A (zh) * 2011-06-13 2011-11-30 昆山市亚香日用香料有限公司 一种n-乙基-2，2-二异丙基丁酰胺的合成方法
CN102911057A (zh) * 2011-08-04 2013-02-06 浙江九洲药业股份有限公司 一种酮洛芬乙酯的制备方法
CN103351306A (zh) * 2013-07-24 2013-10-16 重庆紫光化工股份有限公司 一种一锅法制备n,n-二甲基甘氨酸酯的方法
CN109225191A (zh) * 2018-11-05 2019-01-18 河南省农村科学技术开发中心有限责任公司 一种制备呋虫胺中间体3-羟甲基四氢呋喃的方法及其催化剂
CN116199625A (zh) * 2023-01-19 2023-06-02 上海昱菘医药科技有限公司 一种烟酸酯类化合物的制备方法

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WO1996036592A2 (de) 1996-11-21
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SK155097A3 (en) 1998-07-08
CA2218134C (en) 2005-01-04
BG63869B1 (bg) 2003-04-30
AU5814696A (en) 1996-11-29
MX9708580A (es) 1998-02-28
US6002010A (en) 1999-12-14
KR19990014911A (ko) 1999-02-25
NO975296D0 (no) 1997-11-18
WO1996036592A3 (de) 1997-01-09
DE59604459D1 (de) 2000-03-23
EA199700391A1 (ru) 1998-06-25
NO975296L (no) 1997-11-18
KR100384095B1 (ko) 2003-08-21
EP0825977B1 (de) 2000-02-16
DE19518474A1 (de) 1996-11-21
CN1081622C (zh) 2002-03-27
HUP9801403A2 (hu) 1998-09-28
NO308465B1 (no) 2000-09-18
CZ290156B6 (cs) 2002-06-12
PL323388A1 (en) 1998-03-30
TW347385B (en) 1998-12-11
AU713436B2 (en) 1999-12-02
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PL183753B1 (pl) 2002-07-31
CZ358097A3 (cs) 1998-04-15
HUP9801403A3 (en) 1998-10-28
TR199701393T1 (xx) 1998-03-21
EP0825977A2 (de) 1998-03-04
EA000799B1 (ru) 2000-04-24
MY117672A (en) 2004-07-31
BG102026A (en) 1998-08-31
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UA50739C2 (uk) 2002-11-15

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