CN110711601A - 一种原位转化co2制备喹唑啉-2,4(1h,3h)-二酮及其衍生物的方法及催化剂 - Google Patents
一种原位转化co2制备喹唑啉-2,4(1h,3h)-二酮及其衍生物的方法及催化剂 Download PDFInfo
- Publication number
- CN110711601A CN110711601A CN201911040802.4A CN201911040802A CN110711601A CN 110711601 A CN110711601 A CN 110711601A CN 201911040802 A CN201911040802 A CN 201911040802A CN 110711601 A CN110711601 A CN 110711601A
- Authority
- CN
- China
- Prior art keywords
- quinazoline
- ionic liquid
- derivatives
- situ
- diones
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 150000008516 quinazoline-2,4(1H,3H)-diones Chemical class 0.000 title claims description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003852 triazoles Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 26
- PGLIUCLTXOYQMV-UHFFFAOYSA-N Cetirizine hydrochloride Chemical compound Cl.Cl.C1CN(CCOCC(=O)O)CCN1C(C=1C=CC(Cl)=CC=1)C1=CC=CC=C1 PGLIUCLTXOYQMV-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RHLJLALHBZGAFM-UHFFFAOYSA-N Bunazosinum Chemical compound C1CN(C(=O)CCC)CCCN1C1=NC(N)=C(C=C(OC)C(OC)=C2)C2=N1 RHLJLALHBZGAFM-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- -1 amido rare earth metal amide Chemical class 0.000 description 2
- 229960002467 bunazosin Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- RUZYUOTYCVRMRZ-UHFFFAOYSA-N doxazosin Chemical compound C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 RUZYUOTYCVRMRZ-UHFFFAOYSA-N 0.000 description 2
- 229960001389 doxazosin Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- IENZQIKPVFGBNW-UHFFFAOYSA-N prazosin Chemical compound N=1C(N)=C2C=C(OC)C(OC)=CC2=NC=1N(CC1)CCN1C(=O)C1=CC=CO1 IENZQIKPVFGBNW-UHFFFAOYSA-N 0.000 description 2
- 229960001289 prazosin Drugs 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- SXONDGSPUVNZLO-UHFFFAOYSA-N zenarestat Chemical compound O=C1N(CC(=O)O)C2=CC(Cl)=CC=C2C(=O)N1CC1=CC=C(Br)C=C1F SXONDGSPUVNZLO-UHFFFAOYSA-N 0.000 description 2
- 229950006343 zenarestat Drugs 0.000 description 2
- SDQJTWBNWQABLE-UHFFFAOYSA-N 1h-quinazoline-2,4-dione Chemical compound C1=CC=C2C(=O)NC(=O)NC2=C1 SDQJTWBNWQABLE-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- 150000003246 quinazolines Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0251—Guanidides (R2N-C(=NR)-NR2)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种原位转化CO2制备喹唑啉‑2,4(1H,3H)‑二酮及其衍生物的方法及催化剂，该方法以不同三氮唑类离子液体为CO2吸收剂与催化剂，以吸收的CO2为原料，直接与不同取代基的邻氨基苯腈底物反应，在邻氨基苯腈/离子液体摩尔比为1:4～8，反应温度为40～100℃，反应时间为2～48h的条件下合成相应的喹唑啉‑2,4(1H,3H)‑二酮。本方法三氮唑类离子液体制备简单、催化性能优异，可以实现在温和条件下将CO2吸收活化并进一步原位催化转化成高附加值喹唑啉‑2,4(1H,3H)‑二酮及其衍生物，且该离子液体与产物易分离，可循环使用。
Description
技术领域
本发明涉及一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法及催化剂，属于CO2清洁资源化利用领域。
背景技术
二氧化碳(CO2)是一种主要的温室气体，近年来，化石燃料的大量消耗直接导致大气中CO2含量不断升高。CO2的捕集与封存技术(CCS)是目前规模化处理CO2的最行之有效的手段之一，但其脱附、压缩、运输和储存过程中，不可避免地消耗能量。同时，CO2还是储量丰富、价廉、无毒、不易燃且可再生的C1资源，可代替传统羰基化试剂合成高附加值的化工产品。因此，CO2的捕集与利用技术(CCU)成为CO2“变废为宝”的有效策略。该策略是利用吸收的CO2为反应起始原料，避免脱附、压缩等耗能过程，使CO2经吸收和预活化后直接原位催化转化为高附加值的化学产品，该原位催化过程不但可以很大程度地节约能耗，而且可避免高压CO2参与反应时对设备的要求，具有重要科学意义及应用价值。
喹唑啉-2,4(1H,3H)-二酮及其衍生物是一类重要的医药中间体，具有广泛的生物与药理活性，可以用于合成并开发治疗高血压、心脑血管及阿尔兹海默症领域的新型高效药物，如布那唑嗪(Bunazosin)、多沙唑嗪(Doxazosin)、哌唑嗪(Prazosin)或折那司他(Zenarestat)。喹唑啉-2,4(1H,3H)-二酮及其衍生物传统合成路线需要使用一氧化碳、光气、氰酸钾或各种异氰酸酯类有毒试剂，不满足绿色生产的要求。利用CO2与不同取代基的2-氨基苯腈通过羧环化反应制备相应的喹唑啉-2,4(1H,3H)-二酮及其衍生物具有较大发展潜力，该反应具有100％原子经济性，属于环境友好型合成工艺。对于该反应，目前报道的催化体系包括酰胺基稀土金属胺化物/DBU(CN 105153048 A)、二乙醇胺水溶液(CN106946800 A)、盐湖卤水(CN 108863952 A)以及不同结构离子液体等。然而，大部分催化体系需要高温、高压条件下进行反应，且需要挥发性有机溶剂参与。此外，需要指出的是在CCU方面，即将吸收的CO2气体作为原料直接原位催化转化合成高附加值化学品，目前主要集中于合成恶唑烷酮(Angew.Chem.Int.Ed.,2012,51,11306–11310)、甲酸甲酯(Inorg.Chem.,2014,53,9849–9854)、甲醇(J.Am.Chem.Soc.,2018,140,1580–1583)、甲酸(Green Chem.,2016,18,5831–5838)或甲酸盐(J.Am.Chem.Soc.,2018,140,16873–16876)以及尿素衍生物(Energy Environ.Sci.,2011,4,3971–3975)，还未发现原位催化转化CO2合成喹唑啉-2,4(1H,3H)-二酮及其衍生物方面的报道。因此，设计合成对CO2具有吸收与催化转化双功能性，且能够实现温和、无溶剂条件下将吸收的CO2原位转化成喹唑啉-2,4(1H,3H)-二酮的新型催化体系具有重要意义。基于此，我们提出本项发明研究。
发明内容
本发明要解决的技术问题是提供一种催化剂合成简单、环境友好、可重复利用，能同时活化CO2与邻氨基苯腈，且能够实现温和、无溶剂条件下原位催化转化CO2合成喹唑啉-2,4(1H,3H)-二酮的方法，对CO2有效资源化利用提供新策略。其中，CO2与邻氨基苯腈经羧环化反应合成喹唑啉-2,4(1H,3H)-二酮反应方程式如下：
为解决上述技术问题，本发明提出一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的三氮唑类离子液体催化剂，所述离子液体催化剂采用一步酸碱中和法合成，其结构为
本发明提出了一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，该方法包含以下步骤：
(1)将三氮唑类离子液体加入反应器中，首先缓慢通入CO2气体以排除反应器内的空气；关闭反应器出气阀，调节CO2进气阀，在反应器内充入CO2至0.1～0.5MPa，在温度为25～50℃条件下对CO2吸收0.5～3h；通过高精度电子天平(±0.1mg)准确称量所述三氮唑类离子液体对CO2气体的吸收量；
(2)将底物邻氨基苯腈加入反应器，邻氨基苯腈与三氮唑离子液体摩尔比为1:4～8；
(3)将反应体系加热至40～100℃，保持2～48h；
(4)反应结束后，将反应器降至室温；
(5)反应器中加蒸馏水洗脱离子液体催化剂，过滤，产物粗品经甲基叔丁基醚洗涤三次、真空干燥后得到高纯度喹唑啉-2,4(1H,3H)-二酮产品；水相中离子液体经旋蒸、真空干燥后回收，测试其重复利用性能。
作为本发明的进一步优化，所述步骤(1)离子液体结构为
作为本发明的进一步优化，所述步骤(1)CO2吸收温度为40℃，吸收时间为1h。
作为本发明的进一步优化，所述步骤(2)底物邻氨基苯腈结构式如下：
作为本发明的进一步优化，所述步骤(2)底物邻氨基苯腈与三氮唑离子液体摩尔比为1:6。
作为本发明的进一步优化，所述步骤(3)反应温度为80～90℃，反应时间为6h。
采用上述技术方案所产生的有益效果在于：本发明提出的原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的催化剂为三氮唑类离子液体，该离子液体简单易得，采用一步酸碱中和法即可合成；该三氮唑类离子液体具有活化CO2与邻氨基苯腈的双功能性，能够实现温和、无溶剂条件下喹唑啉-2,4(1H,3H)-二酮及其衍生物的清洁合成；向反应体系中加水即可实现离子液体与产品的分离，易于实现离子液体的循环使用；以三氮唑类离子液体为反应介质，可以按照摩尔比1:1对CO2进行高效吸收并活化，同时可以实现将吸收的CO2直接原位催化转化成不同喹唑啉-2,4(1H,3H)-二酮及其衍生物；本发明实现了CO2吸收与催化转化的集成，采用该方法可以将CO2脱附所需的能量直接应用于后续催化转化，大大降低过程所需能耗，展现出广阔的工业化应用前景。
附图说明
图1是本发明回收前后离子液体[HTMG][Triz]红外谱图对比；
图2是本发明回收离子液体[HTMG][Triz]核磁氢谱图。
具体实施方式
本发明将结合具体实施方式作进一步详细的说明，以下实施例只用于说明本发明，并不是本发明的限定。
实施例1
将离子液体[HTMG][Triz]3mmol加入100mL连接CO2气球的Schlenk(施伦克)反应瓶中，首先缓慢通入CO2气体以排除瓶内的空气；关闭反应瓶出气阀，打开CO2进气阀，通入0.1MPa CO2气体，在温度为25℃条件下对CO2吸收1h；之后移除CO2气球，向瓶内加入2-氨基苯腈0.5mmol，2-氨基苯腈与[HTMG][Triz]摩尔比为1:6，在50℃条件下反应6h；反应结束后，将反应瓶降至室温；反应瓶中混合物用蒸馏水洗涤3次分离[HTMG][Triz]与产品，产物粗品再经甲基叔丁基醚洗涤3次、真空干燥后得到喹唑啉-2,4(1H,3H)-二酮，收率81％。
实施例2
将离子液体[HTMG][Triz]3mmol加入25mL带聚四氟乙烯内衬的不锈钢高压反应釜中，首先缓慢通入CO2气体以排除反应釜内的空气；关闭反应釜出气阀，打开CO2进气阀，通入0.5MPa CO2气体，在温度为40℃条件下对CO2吸收1h；打开反应釜，向釜内加入2-氨基苯腈0.5mmol，2-氨基苯腈与[HTMG][Triz]摩尔比为1:6，在90℃条件下反应6h；反应结束后，将反应釜降至室温；釜内混合物用蒸馏水洗涤3次分离[HTMG][Triz]与产品，产物粗品再经甲基叔丁基醚洗涤3次、真空干燥后得到喹唑啉-2,4(1H,3H)-二酮，收率94％。
实施例3
具体实验过程与后处理方法同实施例2，与实施例2不同的是离子液体选择[HDBU][Triz]，反应温度为100℃，喹唑啉-2,4(1H,3H)-二酮收率89％。
实施例4
具体实验过程与后处理方法同实施例2，与实施例2不同的是2-氨基苯腈与[HTMG][Triz]摩尔比为1:4，CO2吸收时间为3h，反应温度为40℃，反应时间为48h，喹唑啉-2,4(1H,3H)-二酮收率90％。
实施例5
具体实验过程与后处理方法同实施例1，与实施例1不同的是选用的离子液体为[HTBD][Triz]，CO2吸收时间为2h，反应温度为90℃，喹唑啉-2,4(1H,3H)-二酮收率93％。
实施例6
具体实验过程与后处理方法同实施例2，选择不同取代基邻氨基苯腈底物与吸收活化的CO2反应，所得结果见表1：
表1原位催化转化CO2合成不同取代基喹唑啉-2,4(1H,3H)-二酮
实施例7-11
具体实验条件与步骤同实施例2，只是将离子液体[HTMG][Triz]改为实施例2中回收的离子液体，附图1和附图2表征了回收的离子液体结构，表明回收前后离子液体结构没有发生改变，在相同条件下进行5次循环实验，所得结果见表2：
表2实施例7-11催化剂回用实验结果
Claims (7)
1.一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的催化剂，其特征在于所述催化剂为三氮唑类离子液体，其结构为 
2.一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，其特征在于：该方法包含以下步骤：
(1)将权利要求1所述的三氮唑类离子液体加入反应器中，首先缓慢通入CO2气体以排除反应器内的空气；关闭反应器出气阀，调节CO2进气阀，在反应器内充入CO2至0.1～0.5MPa，在温度为25～50℃条件下对CO2吸收0.5～3h；
(2)将底物邻氨基苯腈加入反应器，邻氨基苯腈与三氮唑离子液体摩尔比为1:4～8；
(3)将反应体系加热至40～100℃，保持2～48h；
(4)反应结束后，将反应器降至室温；
(5)反应器中加蒸馏水洗脱离子液体催化剂，产物粗品经甲基叔丁基醚洗涤三次、真空干燥得到高纯度喹唑啉-2,4(1H,3H)-二酮产品。
3.根据权利要求2所述的一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，其特征在于：所述离子液体结构为
4.根据权利要求2或3所述的一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，其特征在于：所述步骤(1)CO2吸收温度为40℃，吸收时间为1h。
5.根据权利要求2或3所述的一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，其特征在于：所述步骤(2)底物邻氨基苯腈结构式如下：
6.根据权利要求2或3所述的一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，其特征在于：所述步骤(2)底物邻氨基苯腈与三氮唑离子液体摩尔比为1:6。
7.根据权利要求2或3所述的一种原位转化CO2制备喹唑啉-2,4(1H,3H)-二酮及其衍生物的方法，其特征在于：步骤(3)反应温度为80～90℃，反应时间为6h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911040802.4A CN110711601A (zh) | 2019-10-30 | 2019-10-30 | 一种原位转化co2制备喹唑啉-2,4(1h,3h)-二酮及其衍生物的方法及催化剂 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911040802.4A CN110711601A (zh) | 2019-10-30 | 2019-10-30 | 一种原位转化co2制备喹唑啉-2,4(1h,3h)-二酮及其衍生物的方法及催化剂 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110711601A true CN110711601A (zh) | 2020-01-21 |
Family
ID=69213463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911040802.4A Pending CN110711601A (zh) | 2019-10-30 | 2019-10-30 | 一种原位转化co2制备喹唑啉-2,4(1h,3h)-二酮及其衍生物的方法及催化剂 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110711601A (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778219A (zh) * | 2021-01-27 | 2021-05-11 | 浙江外国语学院 | 一种制备 2,4-（1h, 3h）-喹唑啉二酮类化合物的方法 |
| CN113666933A (zh) * | 2021-07-21 | 2021-11-19 | 厦门大学 | 质子型离子液体[HDBN][2-PyOH]及其制备和应用 |
| CN114082442A (zh) * | 2021-11-18 | 2022-02-25 | 河南大学 | 丁二酰亚胺基离子液体及用其催化合成喹唑啉-2,4(1h,3h)-二酮的方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896952A (zh) * | 2014-04-09 | 2014-07-02 | 中国科学院化学研究所 | 离子液体催化剂及其制备方法与应用 |
| CN106946800A (zh) * | 2017-03-21 | 2017-07-14 | 华东师范大学 | 一种喹唑啉‑2,4(1h,3h)‑二酮及其衍生物的合成方法 |
-
2019
- 2019-10-30 CN CN201911040802.4A patent/CN110711601A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896952A (zh) * | 2014-04-09 | 2014-07-02 | 中国科学院化学研究所 | 离子液体催化剂及其制备方法与应用 |
| CN106946800A (zh) * | 2017-03-21 | 2017-07-14 | 华东师范大学 | 一种喹唑啉‑2,4(1h,3h)‑二酮及其衍生物的合成方法 |
Non-Patent Citations (8)
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778219A (zh) * | 2021-01-27 | 2021-05-11 | 浙江外国语学院 | 一种制备 2,4-（1h, 3h）-喹唑啉二酮类化合物的方法 |
| CN113666933A (zh) * | 2021-07-21 | 2021-11-19 | 厦门大学 | 质子型离子液体[HDBN][2-PyOH]及其制备和应用 |
| CN114082442A (zh) * | 2021-11-18 | 2022-02-25 | 河南大学 | 丁二酰亚胺基离子液体及用其催化合成喹唑啉-2,4(1h,3h)-二酮的方法 |
| CN114082442B (zh) * | 2021-11-18 | 2024-01-19 | 河南大学 | 丁二酰亚胺基离子液体及用其催化合成喹唑啉-2,4(1h,3h)-二酮的方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110711601A (zh) | 一种原位转化co2制备喹唑啉-2,4(1h,3h)-二酮及其衍生物的方法及催化剂 | |
| Ji et al. | Conversion of CO 2 into cyclic carbonates by a Co (ii) metal–organic framework and the improvement of catalytic activity via nanocrystallization | |
| RU2446152C2 (ru) | Способ получения мочевины и установка для его осуществления | |
| CN103755588A (zh) | 一种共价有机框架材料的合成方法及应用 | |
| CN104829494A (zh) | 一种节能型尿素生产系统及其生产工艺 | |
| CN104321305A (zh) | 由氨和二氧化碳制备尿素的方法和装置 | |
| CN102267921A (zh) | 一种合成草酰胺连续工艺 | |
| CN108435255A (zh) | 一种铱单原子催化剂及其制备方法与应用 | |
| WO2021253370A1 (zh) | 一种制取甲醇的系统及方法 | |
| CN114437364B (zh) | 金属耦合三嗪多孔有机框架及其构筑方法和催化co2与环氧化物耦合制备环状碳酸酯应用 | |
| CN204661587U (zh) | 一种节能型尿素生产系统 | |
| CN104610087B (zh) | 一种黄磷尾气经净化连续合成草酰胺的装置和方法 | |
| CN101560160B (zh) | 一种1-氨基-2,3-丙二醇的催化合成方法 | |
| CN105367439B (zh) | 一种酯氨交换法联产草酰胺和氨基甲酸酯的工艺方法 | |
| CN106345525A (zh) | 一种铁基金属有机骨架材料水氧化反应催化剂及其制备方法 | |
| CN107540660A (zh) | 一种以三联吡啶衍生物为配体的铁配合物及其合成方法和应用 | |
| CN101993381B (zh) | 3-氨基-1，2-丙二醇的合成方法 | |
| CN115505135B (zh) | 一种Fe-Zr MOFs及其制备方法和应用 | |
| CN109095438B (zh) | 一种生物质多级转换联合制氢装置及其工作方法 | |
| RU2289566C1 (ru) | Способ производства метанола | |
| CN107488133A (zh) | 一种氮化碳光催化合成氨基甲酸酯类化合物的方法 | |
| CN103864597A (zh) | 一种负载型Ru基催化剂的应用 | |
| CN110804004B (zh) | 一种尿素生产低压分解气热利用、三段吸收工艺 | |
| CN106380374A (zh) | 碳酸盐煅烧烟气中二氧化碳利用及制备甲醇的方法 | |
| CN207478574U (zh) | 一种硫代卡巴肼的生产装置 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200121 |
|
| RJ01 | Rejection of invention patent application after publication |