CN106279084B - 一种芳香酮氧化裂解制备邻苯二甲酸酐及其芳环取代的衍生物的方法 - Google Patents
一种芳香酮氧化裂解制备邻苯二甲酸酐及其芳环取代的衍生物的方法 Download PDFInfo
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- 239000002904 solvent Substances 0.000 claims description 6
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- 229910052751 metal Inorganic materials 0.000 claims description 4
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- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
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- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
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- 235000019441 ethanol Nutrition 0.000 claims description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- KWHUHTFXMNQHAA-UHFFFAOYSA-N 6,7,8,9-tetrahydrobenzo[7]annulen-5-one Chemical compound O=C1CCCCC2=CC=CC=C12 KWHUHTFXMNQHAA-UHFFFAOYSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 230000003213 activating effect Effects 0.000 description 2
- -1 chlorobenzene Vinyl fluoride Chemical compound 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 238000005054 agglomeration Methods 0.000 description 1
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- 150000001555 benzenes Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
本发明提供了一种新的邻苯二甲酸酐及其苯环取代的衍生物的制备方法。该方法以芳香酮为底物，空气或氧气为氧源，在催化剂作用下，液相条件下，芳香酮发生氧化裂解，生成酸酐。此方法条件温和，氧化效率高，产品收率高；以空气或氧气作为氧源，经济、环保，具有很好的应用前景。
Description
技术领域
本发明涉及化学化工领域，具体涉及一种芳香酮氧化裂解制备邻苯二甲酸酐及其芳环取代的衍生物方法。
背景技术
酸酐是一种重要的有机化工原料，广泛应用于有机合成和制药等。酸酐合成主要是采用两个羧酸分子之间脱水的方法。工业邻苯二甲酸酐生产方法一般是采用以五氧化二钒为主的钒系催化剂在400～460℃下进行邻二甲苯的气相氧化。另一种方法也是采用高温气相反应，以萘为原料，氧化制备邻苯二甲酸酐。这些方法都是采用气相氧化法，反应条件苛刻，高能耗。发明人提供了一种新的酸酐的合成方法。以芳香酮为底物分子，液相低温条件下，氧气或者空气为氧源，通过氧化裂解生成邻苯二甲酸酐及其芳环取代的衍生物。
发明内容
本发明提供了一种新的酸酐的合成方法，该方法采用芳香酮为底物，氧气或者空气为氧源，在催化剂作用下，芳香酮被氧化裂解，生成邻苯二甲酸酐及其苯环取代的衍生物；
所述芳香酮为茚酮及其苯环取代衍生物，四氢萘酮及其苯环取代衍生物，苯并环庚酮及其苯环取代衍生物。
所述取代基为OCH3、F、Cl、Br、I、NO2、CH3中的一种或者多种。取代基的个数为1-6个。
按照本发明，采用环境友好的氧气或空气为氧源。三形态的氧气分子不够活波，需要催化剂来活化氧气形成活性氧。本发明采用过渡金属V、Fe、Co、Mn、Cu、Cr、Mo、Ce、Nb、W氧化物或者金属盐中的一种或者两种以上为催化剂来活化氧气分子，实现芳香酮的氧化裂解，制备酸酐。
按照本发明，催化性能与催化剂的用量有关，过低会影响催化反应的活性，用量过高会增加催化剂的成本；因此需要选择适当的用量。为了保证催化剂的活性，同时又能降低催化剂成本，所用催化剂与芳香酮的摩尔比为：0.1-30mol％，优选1-20mol％。
按照本发明，芳香酮氧化效果与氧气压力、反应温度和时间有关，其中氧气分压为0.1-2MPa，反应温度为60-180℃，反应时间为1-48h；优选氧气分压0.4-1MPa，反应温度100-160℃，反应时间6-24h。
按照本发明，该反应需要在溶剂中进行，特别是固体芳香酮底物分子，需要溶解在溶剂里才能够均匀分散，有利于与催化剂的接触。叔胺氧化所用溶剂为甲苯、氯苯、DMF、正辛烷、THF、二氧六环、甲醇、乙醇、乙腈、DMSO中的一种或者两种以上。芳香酮于溶剂中的质量浓度1-80wt％，优选1-40wt％。
具体实施方式
下列实施例将有助于理解本发明，但本发明内容并不局限于此。
实施例1：
将0.01g MnO2催化剂、1mmol 1-茚酮和2g氯苯加入不锈钢高压反应釜，内附聚四氟乙烯内衬。采用自动控温仪程序升温至反应温度100℃，加入0.6MPa氧气，反应4h，反应过程中保持压力不变。反应产物使用GC-MS进行分析，邻苯二甲酸酐收率为80％。
实施例2-23：
除了催化剂及用量、压力、反应时间不同，催化剂活性评价与实施例1相同。反应条件和催化反应结果见表1。从表1可以看出催化剂及用量、氧气压力、反应温度和反应时间对催化效果有影响。随着反应温度(实施例2和3)、催化剂用量(实施例2和5)、氧气压力(实施例3和5)和反应时间的(实施例5和6)增加，收率增加。催化剂用量增加氧气压力增加，酸酐收率也随之增加。过渡金属V、Fe、Co、Mn、Cu、Cr、Mo、Ce、Nb、W氧化物或者金属盐，都表现出较好的效果。
表1 1-茚酮氧化裂解制备邻苯二甲酸酐
实施例24-36：
除了底物不同，催化剂活性评价与实施例1相同。反应条件和催化反应结果见表2。不同芳环取代的1-茚酮都可以发生氧化裂解，生成相应的酸酐化合物。
表2不同芳香酮的氧化裂解
本发明氧化效率高，产品收率高；以空气或氧气作为氧源，经济、环保，具有很好的应用前景。
Claims (1)
1.一种芳香酮氧化裂解制备邻苯二甲酸酐及其苯环被取代的衍生物的方法，其特征在于：以空气或氧气中的一种或者两种为氧源，在催化剂作用下，芳香酮发生氧化裂解，生成邻苯二甲酸酐或其苯环被取代的衍生物；
催化剂为过渡金属V、Fe、Co、Mn、Cu、Cr、Mo、Ce、Nb、W的氧化物或者金属盐中的一种或者两种以上；
所述芳香酮为茚酮或其苯环被取代衍生物，四氢萘酮或其苯环被取代的衍生物，苯并环庚酮或其苯环被取代的衍生物；
上述苯环被取代的衍生物中的取代基均选自OCH3、F、Cl、Br、I、NO2、CH3中的一种或者两种以上；
其中氧气分压为0.1-2MPa，反应温度为60-180℃，反应时间为1-48h；
以金属计，所用催化剂用量为芳香酮的0.1-30mol％；
芳香酮氧化裂解所用溶剂为甲苯、氯苯、DMF、正辛烷、四氢呋喃、二氧六环、甲醇、乙醇、二甲基亚砜中的一种或者两种以上，芳香酮于溶剂中的质量浓度1-80wt％。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671470A (zh) * | 2002-06-19 | 2005-09-21 | 隆萨公开有限公司 | 包含钛－钒－锡的催化剂和邻苯二甲酸酐的制造工艺 |
| CN101448810A (zh) * | 2006-05-19 | 2009-06-03 | 巴斯夫欧洲公司 | 通过邻二甲苯气相氧化制备邻苯二甲酸酐 |
| WO2011051102A1 (en) * | 2009-10-26 | 2011-05-05 | Exxonmobil Chemical Patents Inc. | Improved phthalic anhydride process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1671470A (zh) * | 2002-06-19 | 2005-09-21 | 隆萨公开有限公司 | 包含钛－钒－锡的催化剂和邻苯二甲酸酐的制造工艺 |
| CN101448810A (zh) * | 2006-05-19 | 2009-06-03 | 巴斯夫欧洲公司 | 通过邻二甲苯气相氧化制备邻苯二甲酸酐 |
| WO2011051102A1 (en) * | 2009-10-26 | 2011-05-05 | Exxonmobil Chemical Patents Inc. | Improved phthalic anhydride process |
Non-Patent Citations (3)
| Title |
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| Cuprous Oxide Catalyzed Oxidative C-CBond Cleavage for C-N Bond Formation:Synthesis of Cyclic Imides from Ketones and Amines;Min Wang et al;《Angew.Chem. Int.Ed.》;20151023;第54卷;第14061-14065页 * |
| Nermin Sımsek Kus.One-step synthesis of substituted isobenzofuran-1(3H)-ones and isobenzofuran-1,3-diones from indane derivatives in subcritical media.《Monatsh Chem》.2013,第144卷第1183-1186页. * |
| 催化氧化制备生物基有机二元酸研究进展;刘俊霞等;《中国科学：化学》;20150312;第45卷(第5期);第526-532页 * |
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