CN111635364A - 一种脯氨酸离子液体及其催化尼泊金酯的合成 - Google Patents
一种脯氨酸离子液体及其催化尼泊金酯的合成 Download PDFInfo
- Publication number
- CN111635364A CN111635364A CN202010548048.1A CN202010548048A CN111635364A CN 111635364 A CN111635364 A CN 111635364A CN 202010548048 A CN202010548048 A CN 202010548048A CN 111635364 A CN111635364 A CN 111635364A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- proline
- solvent
- reaction
- synthesis
- 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.)
- Granted
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 52
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 title claims abstract description 51
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- -1 nipagin ester Chemical class 0.000 title claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 68
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000012544 monitoring process Methods 0.000 claims abstract description 17
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims abstract description 11
- SHPPDRZENGVOOR-UHFFFAOYSA-N 1-butylbenzimidazole Chemical compound C1=CC=C2N(CCCC)C=NC2=C1 SHPPDRZENGVOOR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 4
- CMHMMKSPYOOVGI-UHFFFAOYSA-N Isopropylparaben Chemical compound CC(C)OC(=O)C1=CC=C(O)C=C1 CMHMMKSPYOOVGI-UHFFFAOYSA-N 0.000 description 3
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 description 3
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 3
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 3
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 3
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 3
- 229960002216 methylparaben Drugs 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229940113094 isopropylparaben Drugs 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KSHVDKDQYBNSAN-UHFFFAOYSA-N 3-methylbutyl 4-hydroxybenzoate Chemical compound CC(C)CCOC(=O)C1=CC=C(O)C=C1 KSHVDKDQYBNSAN-UHFFFAOYSA-N 0.000 description 1
- XPJVKCRENWUEJH-UHFFFAOYSA-N Isobutylparaben Chemical compound CC(C)COC(=O)C1=CC=C(O)C=C1 XPJVKCRENWUEJH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BAYSQTBAJQRACX-UHFFFAOYSA-N dodecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 BAYSQTBAJQRACX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- LZFIOSVZIQOVFW-UHFFFAOYSA-N propyl 2-hydroxybenzoate Chemical compound CCCOC(=O)C1=CC=CC=C1O LZFIOSVZIQOVFW-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
-
- 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
- B01J31/0284—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 aromatic ring, e.g. pyridinium
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members 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
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyrrole Compounds (AREA)
Abstract
本发明公开了一种脯氨酸离子液体及其催化尼泊金酯的合成。于干燥的三口烧瓶中加入N‑丁基苯并咪唑、溶剂和脯氨酸，回流反应至反应完全（TLC监测）。蒸除溶剂，得淡黄色油状液体即脯氨酸离子液体。向干燥的三口瓶中加入对羟基苯甲酸，醇及脯氨酸离子液体，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金甲酯，产率可达88%以上；剩余物即离子液体，经水洗、干燥后可循环使用多次。本发明方法高效、绿色环保、安全、催化剂可回收利用、降低了成本、对设备的要求低，是一种高效合成尼泊金酯的方法。
Description
技术领域
本发明属于化学合成技术领域，特别涉及一种脯氨酸离子液体及其催化尼泊金酯的合成。
背景技术
尼泊金酯，又称对羟基苯甲酸酯，通常是由对羟基苯甲酸和醇发生酯化而得到目标产物。尼泊金酯系列产品有非常广泛的应用，可应用于食品、饮料、化妆品和医药等行业。目前尼泊金酯类的工业合成方法大都采用浓硫酸催化对羟基苯甲酸和醇发生酯化反应来合成，这种方法成本低廉，但是不仅反应时间过长，腐蚀设备，产生大量废酸，对环境会造成危害。因此探索绿色、高效、环保的催化剂成了研究尼铂金酯合成的热点。该工艺首先制备用有机酸脯氨酸与N-丁基苯并咪唑反应合成离子液体，避免了使用无机酸，合成的离子液体绿色环保。将其应用于催化尼泊金酯的合成，其优势是高效、可回收利用、绿色环保、降低了成本、对设备的要求低。
发明内容
本发明的目的是提供一种脯氨酸离子液体及其催化尼泊金酯的合成。
为了实现上述目的，本发明采用如下技术方案：
1)脯氨酸离子液体的合成：于干燥的三口烧瓶中加入A mol N-丁基苯并咪唑、溶剂和Bmol脯氨酸，回流反应至反应完全(TLC监测)。蒸除溶剂，得淡黄色油状液体即脯氨酸离子液体。
2)尼泊金酯的合成：向干燥的三口瓶中加入对羟基苯甲酸(Cmol)，醇(Dmol)及脯氨酸离子液体(Emol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金酯，产率可达88％以上；剩余物即离子液体，经水洗、干燥后可循环使用多次。
所述的脯氨酸离子液体的合成方法，N-丁基苯并咪唑与脯氨酸的摩尔比为A：B为1：(1-1.2)。
所述的脯氨酸离子液体的合成方法，溶剂为无水乙醇或无水甲醇。
所述的尼泊金酯的合成方法，对羟基苯甲酸、醇、离子液体的摩尔比为1：(1～1.5):(0.05～0.15)。
所述的脯氨酸离子液体的结构为：
所述尼泊金酯类化合物的结构式为：
其中R为：甲基，乙基、正丙基、异丙基、正丁基、正戊基、异戊基、十二烷基、十四烷基、十六烷基、十八烷基。
与现有技术相比，本发明用制备的脯氨酸离子液体催化合成尼泊金酯，具有以下优点：催化剂可回收利用、绿色环保、是一种高效、低成本合成尼泊金酯的方法。
附图说明
图1脯氨酸离子液体的FT-IR谱图；
图2脯氨酸离子液体的1HNMR谱图；
图3脯氨酸离子液体的13CNMR谱图；
图4尼泊金甲酯的FT-IR谱图；
图5尼泊金乙酯的FT-IR谱图；
图6尼泊金正丙酯的FT-IR谱图；
图7尼泊金异丙酯的FT-IR谱图；
图8尼泊金正丁酯的FT-IR谱图；
图9尼泊金异丁酯的FT-IR谱图；
图10尼泊金异戊酯的FT-IR谱图；
图11尼泊金十二醇酯的FT-IR谱图；
图12尼泊金十六醇酯的FT-IR谱图；
图13尼泊金十八醇酯的FT-IR谱图。
具体实施方式
本发明一种脯氨酸离子液体的合成：于干燥的三口烧瓶中加入AmolN-丁基苯并咪唑、溶剂和Bmol脯氨酸，回流反应至反应完全(TLC监测)。蒸除溶剂，得淡黄色油状液体即脯氨酸离子液体。
其反应式如下：
尼泊金酯的合成：向干燥的三口瓶中加入对羟基苯甲酸(Cmol)，醇(Dmol)及脯氨酸离子液体(Emol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金酯。其反应式如下：
其中R为：甲基，乙基、正丙基、异丙基、正丁基、正戊基、异戊基、十二烷基、十四烷基、十六烷基、十八烷基。
下面结合本发明的具体实例对本发明作进一步详细说明，但本发明的实施方式不限于此。
实施例1脯氨酸离子液体的合成
于干燥的三口烧瓶中加入1m molN-丁基苯并咪唑、10mL无水乙醇溶剂和1mmol脯氨酸，回流反应至反应完全(TLC监测)。蒸除溶剂，得淡黄色油状液体即脯氨酸离子液体，产率83％。
IR(KBr)ν:3071(νPh-H),1612(νC＝N),1505,1447(ν苯环骨架),1378(νC-N),718(γ1,2-Ph-H)；
1H NMR(400MHz,DMSO-d6)δ:8.22(s,1H,CH),7.64(m,2H,Ar-H),7.22(m,2H,Ar-H),4.20(t,J＝2.4Hz,2H,N-CH2),3.59(m,6H,Pr o-CH2-CH2-CH2),3.15(m,1H,Pro-NH),3.02(s,1H,Pro-CH),1.81(m,2H,-CH2),1.11(m,2H,-CH2),0.87(t,J＝1.6Hz,3H,-CH3)；
13CNMR(101MHz,DMSO-d6)δ:144.09,143.45,133.86,122.33,121.50,119.47,110.54,43.89,38.88,31.52,23.88,19.42,13.48.
实施例2脯氨酸离子液体的合成
于干燥的三口烧瓶中加入1m molN-丁基苯并咪唑、10mL无水乙醇溶剂和1.2mmol脯氨酸，回流反应至反应完全(TLC监测)。蒸除溶剂，得淡黄色油状液体即脯氨酸离子液体，产率88％。
实施例3尼泊金甲酯的合成
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，甲醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金甲酯产率90％，m.p.122～123.6℃。
IR(KBr)ν:3292(νO-H),3037(νPh-H),2958(νC-H),1679(νC＝O),1593,1514,1438(ν-苯环),1278(νC-O-C),850(γ1,4-Ph-H).
实施例4尼泊金乙酯的制备：
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，无水乙醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金乙酯产率88％，m.p.112～114℃。
IR(KBr)ν:3212(νO-H),3023(νPh-H),2977(νC-H),1680(νC＝O),1582,1526,1421(ν-苯环),1259(νC-O-C),844(γ1,4-Ph-H).
实施例5尼泊金正丙酯的制备：
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，正丙醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金正丙酯产率89％，m.p.96～97℃。
IR(KBr)ν:3321(νO-H),3016(νPh-H),2967(νC-H),1672(νC＝O),1589,1522,1423(ν-苯环),1278(νC-O-C),849(γ1,4-Ph-H).
实施例6尼泊金异丙酯的制备：
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，异丙醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂得到尼泊金异丙酯产率88％，m.p.101～104℃。
IR(KBr)ν:3400(νO-H),3028(νPh-H),2987(νC-H),1690(νC＝O),1591,1508,1432(ν-苯环),1285(νC-O-C),853(γ1,4-Ph-H).
实施例7尼泊金正丁酯的制备：
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，正丁醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂得到尼泊金正丁酯产率89％，m.p.68-69℃。
IR(KBr)ν:3381(νO-H),2949(νPh-H),2875(νC-H),1681(νC＝O),1589,1545,1429(ν-苯环),1285(νC-O-C),844(γ1,4-Ph-H).
实施例8尼泊金十二醇酯的制备：
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，月桂醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂得到尼泊金十二醇酯产率90％，m.p.37～38℃。
IR(KBr)ν:3390(νO-H),2911(νPh-H),2845(νC-H),1688(νC＝O),1595,1532,1411(ν-苯环),1275(νC-O-C),852(γ1,4-Ph-H).
实施例9尼泊金十八醇酯的制备：
向干燥的三口瓶中加入对羟基苯甲酸(1mmol)，十八醇(1.1mol)及脯氨酸离子液体(0.1mmol)，升温至回流反应，TLC监测至反应结束；减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂得到尼泊金十八醇酯产率89％，m.p.63-65℃。
IR(KBr)ν:3332(νO-H),3001(νPh-H),2915(νC-H),1705(νC＝O),1613,1551,1447(ν-苯环),1296(νC-O-C),859(γ1,4-Ph-H)。
实施例10脯氨酸离子液体的重复使用性
本发明制备的脯氨酸离子液体，使用氨基酸-脯氨酸代替无机酸，制备及使用时对设备的要求低，未引入无机离子，避免了其他类型离子液体使用中存在大量无机阴离子的弊端，更加绿色，安全、更加契合现代的环保及绿色合成理念，为打造绿水青山做出贡献。除此之外，催化剂可以重复使用多次仍具有较好的催化效果，降低了成本。
按照实施例2的方法合成尼泊金甲酯，反应结束后，减压蒸除溶剂，剩余物用乙醚萃取，乙醚相蒸除溶剂即得尼泊金甲酯。剩余物即离子液体，经水洗、干燥后再重复使用于下一批尼泊金甲酯的合成。离子液体重复使用5次的结果见附表1。
表1脯氨酸离子液体的重复使用
由附表数据可以看出，离子液体重复使用5次，仍然具有较好的催化活性。
Claims (9)
1.一种脯氨酸离子液体，其特征在于，具有式(1)结构：
2.权利要求1所述离子液体的制备方法，其特征在于，包括以下步骤：
N-丁基苯并咪唑与脯氨酸在甲醇或乙醇中回流反应，反应完全后去除溶剂，得到脯氨酸离子液体。
3.如权利要求2所述的方法，其特征在于，N-丁基苯并咪唑与脯氨酸的摩尔比为1：(1-1.2)。
4.如权利要求2所述的方法，其特征在于，包括以下步骤：于干燥的三口烧瓶中加入Amol N-丁基苯并咪唑、溶剂和B mol脯氨酸，回流反应，TLC监测至反应完全；蒸除溶剂，得淡黄色油状液体即脯氨酸离子液体；
所述A：B为1：(1-1.2)；
所述溶剂为无水乙醇或无水甲醇。
5.权利要求1所述的脯氨酸离子液体在尼泊金酯合成中的应用。
6.如权利要求5所述的应用，其特征在于，包括以下步骤：
对羟基苯甲酸与醇类化合物在权利要求1所述的脯氨酸离子液体中回流反应，得到尼泊金酯。
7.如权利要求6所述的应用，其特征在于，对羟基苯甲酸、醇类化合物、脯氨酸离子液体的摩尔比为1：(1～1.5)：(0.05～0.15)。
8.如权利要求6所述的应用，其特征在于，所述醇类化合物为甲醇、乙醇、正丙醇、异丙醇、正丁醇、正戊醇、异戊醇、十二醇、十四醇、十六醇或十八醇。
9.如权利要求6所述的应用，其特征在于，包括以下步骤：
向干燥的三口瓶中加入对羟基苯甲酸、醇类化合物及权利要求1所述的脯氨酸离子液体，升温至回流反应，TLC监测至反应结束；减压蒸除低沸点组分；剩余物用乙醚萃取，乙醚相蒸除低沸点组分即得尼泊金甲酯；非乙醚相即离子液体，经水洗、干燥后可循环使用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010548048.1A CN111635364B (zh) | 2020-06-16 | 2020-06-16 | 一种脯氨酸离子液体及其催化尼泊金酯的合成 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010548048.1A CN111635364B (zh) | 2020-06-16 | 2020-06-16 | 一种脯氨酸离子液体及其催化尼泊金酯的合成 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111635364A true CN111635364A (zh) | 2020-09-08 |
| CN111635364B CN111635364B (zh) | 2022-01-25 |
Family
ID=72327984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010548048.1A Active CN111635364B (zh) | 2020-06-16 | 2020-06-16 | 一种脯氨酸离子液体及其催化尼泊金酯的合成 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111635364B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115974728A (zh) * | 2022-12-29 | 2023-04-18 | 陕西科技大学 | 一种苯基缩氨基脲的合成及其对六价铬离子的识别 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010371A (zh) * | 2010-10-27 | 2011-04-13 | 华南理工大学 | 一种脯氨酸离子液体及其制备方法和应用 |
| CN103709032A (zh) * | 2013-12-26 | 2014-04-09 | 江西师范大学 | 一种脯氨酸类离子液体催化合成碳酸二丁酯的制备方法 |
| CN109879753A (zh) * | 2019-03-05 | 2019-06-14 | 陕西科技大学 | 一种制备尼泊金酯的方法 |
| CN110759955A (zh) * | 2019-11-19 | 2020-02-07 | 陕西科技大学 | 一种含二茂铁基噻二唑或噁二唑基Mannich碱的制备方法 |
| CN110878018A (zh) * | 2019-11-19 | 2020-03-13 | 陕西科技大学 | 一种制备尼泊金酯的方法 |
-
2020
- 2020-06-16 CN CN202010548048.1A patent/CN111635364B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010371A (zh) * | 2010-10-27 | 2011-04-13 | 华南理工大学 | 一种脯氨酸离子液体及其制备方法和应用 |
| CN103709032A (zh) * | 2013-12-26 | 2014-04-09 | 江西师范大学 | 一种脯氨酸类离子液体催化合成碳酸二丁酯的制备方法 |
| CN109879753A (zh) * | 2019-03-05 | 2019-06-14 | 陕西科技大学 | 一种制备尼泊金酯的方法 |
| CN110759955A (zh) * | 2019-11-19 | 2020-02-07 | 陕西科技大学 | 一种含二茂铁基噻二唑或噁二唑基Mannich碱的制备方法 |
| CN110878018A (zh) * | 2019-11-19 | 2020-03-13 | 陕西科技大学 | 一种制备尼泊金酯的方法 |
Non-Patent Citations (1)
| Title |
|---|
| 姜小英，等: "氨基酸离子液体催化合成乳酸乙酯乙酸酯", 《湖南师范大学自然科学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115974728A (zh) * | 2022-12-29 | 2023-04-18 | 陕西科技大学 | 一种苯基缩氨基脲的合成及其对六价铬离子的识别 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111635364B (zh) | 2022-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3260441A1 (en) | Method for preparing formamide compound | |
| CN111635364B (zh) | 一种脯氨酸离子液体及其催化尼泊金酯的合成 | |
| CN101723771A (zh) | 新型功能离子液体催化制备β-氨基酮、酯、腈和酰胺衍生物的方法 | |
| CN110878018A (zh) | 一种制备尼泊金酯的方法 | |
| CN105367535B (zh) | 一种绿色催化合成1，8‑二氧代‑十氢吖啶衍生物的方法 | |
| CN109305912B (zh) | 由异丁醛缩合制备2,2,4-三甲基-1,3-戊二醇单异丁酸酯的方法 | |
| CN103553931A (zh) | 合成手性二酮类化合物的方法 | |
| CN111701618A (zh) | 一种离子液体催化剂及其制备方法和用途 | |
| CN110655497B (zh) | 一种有机-金属催化剂一锅法制备γ-戊内酯的方法 | |
| Zhou et al. | HSO 3-functionalized Brønsted acidic ionic liquids promote esterification of aromatic acid | |
| CN107602516B (zh) | 氨基酸类离子液体催化合成δ-环戊内酯的方法 | |
| CN110590550A (zh) | 一种异戊酸烯丙酯的合成方法 | |
| CN112295600A (zh) | 一种用于制备叔烷基酯的催化剂 | |
| CN112403522B (zh) | 介孔槲皮素锆催化剂及其在制备α，β-不饱和醇中的应用 | |
| CN110790651A (zh) | 一种微通道反应器连续生产3-甲基-3-戊烯-2-酮的方法 | |
| CN201372256Y (zh) | 一种合成二元羧酸酯的釜式高效酯化反应装置 | |
| CN104151283A (zh) | 一种催化合成12-芳基-8，9，10，12-四氢苯并[α]氧杂蒽-11-酮衍生物的方法 | |
| CN109081817A (zh) | CuI/离子液体常温常压催化转化CO2合成1,3-恶唑烷-2-酮类化合物的方法 | |
| CN117886692A (zh) | 一种三苯基膦离子液体催化合成尼泊金酯的方法 | |
| CN115536494B (zh) | 1-(4-溴苯基)-1,4-丁二醇的合成方法 | |
| CN113957114B (zh) | 一种酶法合成维生素a棕榈酸酯的方法 | |
| CN107827916A (zh) | 一种(r)‑（1‑氨基‑3‑甲基）丁基‑1‑硼酸蒎烷二醇酯的合成方法 | |
| CN110590555A (zh) | 双(2-羟基乙基)对苯二甲酸酯的制法 | |
| CN101092358B (zh) | 丁二酸二异丙酯的间歇制备方法 | |
| CN110294768B (zh) | 一种通过2,6-二乙基-4-甲基苯丙二酸酯合成唑啉草酯的方法 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |