CN114195719A - Ionic liquid of iodinated imidazole containing phenolic hydroxyl group, preparation method and application thereof - Google Patents
Ionic liquid of iodinated imidazole containing phenolic hydroxyl group, preparation method and application thereof Download PDFInfo
- Publication number
- CN114195719A CN114195719A CN202111545963.6A CN202111545963A CN114195719A CN 114195719 A CN114195719 A CN 114195719A CN 202111545963 A CN202111545963 A CN 202111545963A CN 114195719 A CN114195719 A CN 114195719A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- iodinated
- phenolic hydroxyl
- compound
- reaction
- 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
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 47
- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 43
- -1 n-octyl Chemical group 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- RCVZGHGQSKMSTP-UHFFFAOYSA-N 2-(1H-imidazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC=CN1 RCVZGHGQSKMSTP-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 23
- 239000002904 solvent Substances 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Chemical group 0.000 description 9
- 229910052739 hydrogen Chemical group 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CYKCUAPYWQDIKR-UHFFFAOYSA-N 4-(1h-imidazol-1-yl)phenol Chemical compound C1=CC(O)=CC=C1N1C=NC=C1 CYKCUAPYWQDIKR-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- POIGXVYPRGOWQD-UHFFFAOYSA-N 2-imidazol-1-ylphenol Chemical compound OC1=CC=CC=C1N1C=NC=C1 POIGXVYPRGOWQD-UHFFFAOYSA-N 0.000 description 1
- BECRMARRTSMUAO-UHFFFAOYSA-N 3-imidazol-1-ylphenol Chemical compound OC1=CC=CC(N2C=NC=C2)=C1 BECRMARRTSMUAO-UHFFFAOYSA-N 0.000 description 1
- HSONPEIWAFGLCA-UHFFFAOYSA-N 4-chloro-1,3-dioxan-2-one Chemical compound ClC1CCOC(=O)O1 HSONPEIWAFGLCA-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen 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
- B01J31/0278—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
- B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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)
Abstract
The invention discloses iodinated imidazole ionic liquid containing phenolic hydroxyl groups, and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving imidazolyl phenol in an organic solvent, adding iodoalkane at room temperature, and heating for reaction to obtain a reaction solution containing a compound I; carrying out rotary evaporation on reaction liquid containing the compound I to remove an organic solvent, and washing with ethyl acetate to obtain a crude product solid of the compound I; and (3) drying the crude product solid of the compound I in a vacuum oven to obtain the iodinated imidazole ionic liquid containing phenolic hydroxyl. The invention also discloses application of the iodinated imidazole ionic liquid containing phenolic hydroxyl groups in catalyzing carbon dioxide cycloaddition reaction. The ionic liquid disclosed by the invention realizes the high-efficiency conversion of the epoxy compound at normal temperature and normal pressure, has good catalytic effect and high conversion efficiency, and is an organic catalyst with great prospect.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to iodinated imidazole ionic liquid containing phenolic hydroxyl groups, and a preparation method and application thereof.
Background
CO2Is a cheap, nontoxic and rich C1 raw material, and is prepared by mixing CO2The conversion into commodity chemicals is the key to relieving the problems of environment and resources, and is beneficial to relieving the greenhouse effect, CO2And an epoxy compound by cycloaddition reaction to fix and utilize CO2Provides an effective way. The cyclic carbonate is not only an organic solvent with excellent performance, high boiling point and high polarity, but also has wide application in the synthesis of medicaments and fine chemicals, is also a key intermediate for synthesizing a green chemical product, namely dimethyl carbonate, and has very high market prospect. But CO2Is a thermodynamically inert molecule whose successful conversion relies on the use of a catalyst and the introduction of a high energy co-reactant to solve the kinetic problem.
For cycloaddition reactions, the source of high catalytic activity of the catalyst is the synergistic effect of a nucleophilic halide (with high nucleophilicity and good leaving ability) and a lewis acid or Hydrogen Bond Donor (HBD). As an advanced organic catalyst consisting of anions and cations, the Ionic Liquids (ILs) not only have the designability, but also have the advantages of low vapor pressure, good solubility, high stability and the like. When ILs are used in cycloaddition reaction, anions and cations of ILs can be designed according to the needs, and in order to realize high catalytic activity, the catalyst must satisfy two conditions: firstly, the anion has good nucleophilic ability and good leaving ability; second, the cation provides a strong HBD to activate the epoxy and stabilize the intermediate.
Patent application publication No. US2004/0026666 discloses a structure
Is a substituted imidazolium salt of, wherein R1And R3Are identical or different and are selected from the group consisting of a chiral or achiral alkyl group comprising 10 carbon atoms, preferably up to 6 carbon atoms, a chiral or achiral cycloalkyl group comprising 4 to 10 carbon atoms, a chiral or achiral alkyl group comprising 6 to 10 carbon atoms, and a chiral reactive and achiral tri (C)1～C10) An alkylsilyl group. X-Represents an anion. The ionic liquids are provided for use in solvents for organic reactions requiring catalysis and compositions comprising the ionic liquids and a transition metal compound.
At present, for cycloaddition reaction, especially for a metal-free system, how to develop a faster and more effective ionic liquid as a catalyst to improve the reaction rate is a technical problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel iodinated imidazole ionic liquid containing phenolic hydroxyl groups, a preparation method of the ionic liquid, and application of the ionic liquid.
In one aspect, the invention provides an iodinated imidazole ionic liquid containing phenolic hydroxyl groups, which has the following structural formula:
in the formula: r1Selected from phenol radicals, R2Selected from C1-C16 alkyl.
Preferably, R1Is structured as
Preferably, R2Is a straight-chain alkyl selected from C1-C16, and can be methyl, ethyl, n-butyl, n-octyl or n-hexadecyl.
Further, R2To selectThe straight-chain alkyl from C4 to C8 can be n-butyl or n-octyl.
Further, the specific structural formula is:
in another aspect, the present invention also provides a method for preparing iodinated imidazole ionic liquid containing phenolic hydroxyl groups, wherein the reaction formula is as follows:
in the formula: r1Selected from phenol radicals, R2Selected from C1-C16 alkyl.
Further, R2May be C4-C8 straight chain alkyl.
The preparation method of the ionic liquid comprises the following steps:
a) dissolving a compound II in an organic solvent, adding a compound III at room temperature, and reacting to obtain a reaction solution containing a compound I;
b) carrying out rotary evaporation on reaction liquid containing the compound I to remove an organic solvent, and washing with ethyl acetate to obtain a crude product solid of the compound I;
c) and drying the crude solid of the compound I in a vacuum oven to obtain a pure compound I.
Preferably, the molar ratio of the compound II to the compound III is 1: 0.1-5, and the organic solvent is one of methanol, ethanol, N-propanol, dimethyl sulfoxide or N, N-dimethylformamide.
Further, the reaction temperature is 50-150 ℃, and preferably 60-120 ℃.
The reaction time is 10-120 h.
The invention also provides application of the iodinated imidazole ionic liquid containing the phenolic hydroxyl group in catalyzing cycloaddition reaction of carbon dioxide and epoxy compounds.
The mechanism of ILs in cycloaddition reactions is generally cationicThe hydrogen bond donor activates the epoxide and then the anion nucleophilically attacks the activated epoxide, causing it to ring-open, resulting in high yields of cyclic carbonates. Based on the characteristic that a high catalytic activity source of the catalyst is the synergistic effect of nucleophilic halide with high nucleophilicity and good leaving ability and Lewis acid or a Hydrogen Bond Donor (HBD), the invention adopts quaternary ammonification reaction to successfully graft halogenated alkane to phenol containing imidazolyl to form ionic liquid with high activity, and the ionic liquid is prepared by adding the quaternary ammonification catalyst into CO2In the cycloaddition reaction, the efficient conversion of the substrate under different conditions of normal temperature, normal pressure, high temperature and high pressure is realized. The highest conversion number (TON) and conversion frequency (TOF) of ILs designed by the invention can reach 85234 h and 7438h respectively-1The reaction effect is the best in the reported metal-free system.
Drawings
The following is a brief description of what is presented in the drawings of the specification:
FIG. 1 shows [ p-ArOH-IM ] prepared in example 1 of the present invention]I hydrogen nuclear magnetic spectrum (1H NMR)。
FIG. 2 is [ m-ArOH-IM ] prepared in example 2 of the present invention]I hydrogen nuclear magnetic spectrum (1H NMR)。
FIG. 3 is [ o-ArOH-IM ] prepared in example 4 of the present invention]I hydrogen nuclear magnetic spectrum (1H NMR)。
FIG. 4 shows the results of repeated experiments on the recovery of [ p-ArOH-IM ] I prepared in example 1 of the present invention.
FIG. 5 is [ p-ArOH-IM ] prepared in example 1 of the present invention]I catalysis of CO at high temperature and normal pressure2And cycloaddition reaction kinetics of epichlorohydrin.
FIG. 6 is [ p-ArOH-IM ] prepared in example 1 of the present invention]I (0.0011 mol%) catalyzes CO under high temperature and high pressure conditions2And 200mmol of epichlorohydrin.
FIG. 7 shows [ p-ArOH-IM ] prepared in example 1 of the present invention]I (0.011 mol%) catalyzes CO under high temperature and high pressure conditions2And 21mmol of epichlorohydrin.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving 2mmol of 4- (imidazole-1-yl) phenol in 10mL of anhydrous methanol, stirring at room temperature for 0.5h to form a uniform mixed solution, weighing 2mmol of n-butyl iodide, dropwise adding the n-butyl iodide into the uniform solution, stirring at room temperature for 0.5h, transferring the uniformly mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting at 80 ℃ for 24h, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent methanol by using a rotary evaporator to obtain a viscous liquid, adding 5 x 20mL of ethyl acetate, washing at room temperature, and stirring for 3 days. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
It can be seen from FIG. 1 that the synthesized sample [ p-ArOH-IM ] I has good purity.
Example 2
Dissolving 2mmol of 3- (imidazole-1-yl) phenol in 10mL of absolute ethyl alcohol, stirring for 0.5h at room temperature to form a uniform mixed solution, weighing 20mmol of n-butyl iodide, dropwise adding the n-butyl iodide into the uniform solution, stirring for 0.5h at room temperature, transferring the uniformly mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting for 24h at 60 ℃, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent ethanol by using a rotary evaporator to obtain a viscous liquid, adding 5 x 20mL of ethyl acetate, washing and stirring for 3 days at room temperature. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
It can be seen from FIG. 2 that the synthesized sample [ m-ArOH-IM ] I has good purity.
Example 3
Dissolving 2mmol of 4- (imidazole-1-yl) phenol in 10mL of anhydrous methanol, stirring for 0.5h at room temperature to form a uniform mixed solution, weighing 5mmol of iodo-n-octane, dropwise adding the iodo-n-octane into the uniform solution, stirring for 0.5h at room temperature, transferring the uniformly mixed solution to a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting for 36h at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent methanol by using a rotary evaporator to obtain a viscous liquid, adding 5 x 20mL of ethyl acetate, washing and stirring for 3 days at room temperature. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
Example 4
Dissolving 2mmol of 2- (imidazole-1-yl) phenol and 10mmol of n-butyl iodide in a flask containing 10mL of n-propanol solvent, stirring and reacting for 24h at 120 ℃ under the protection of nitrogen, cooling to room temperature after the reaction is finished, removing the n-propanol solvent by using a rotary evaporator to obtain viscous liquid, adding 5X 20mL of ethyl acetate for washing, washing at room temperature and stirring for 3 days. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
Comparative example 1
Dissolving 2mmol of 4- (imidazole-1-yl) phenol in 10mL of anhydrous methanol, stirring at room temperature for 0.5h to form a uniform mixed solution, weighing 2mmol of n-butyl chloride, dropwise adding the n-butyl chloride into the uniform solution, stirring at room temperature for 0.5h, transferring the uniformly mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting at 80 ℃ for 24h, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent methanol by using a rotary evaporator to obtain a viscous liquid, adding 5 multiplied by 20mL of ethyl acetate, washing at room temperature, and stirring for 3 days. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
Comparative example 2
Dissolving 2mmol of 4- (imidazole-1-yl) phenol in 10mL of anhydrous methanol, stirring at room temperature for 0.5h to form a uniform mixed solution, weighing 2mmol of n-butyl bromide, dropwise adding the n-butyl bromide into the uniform solution, stirring at room temperature for 0.5h, transferring the uniformly mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting at 80 ℃ for 24h, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent methanol by using a rotary evaporator to obtain viscous liquid, adding 5 multiplied by 20mL of ethyl acetate, washing at room temperature, and stirring for 3 days. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
Comparative example 3
2mmol of reactants:
dissolving in 10mL of anhydrous methanol, stirring for 0.5h at room temperature to form a uniform mixed solution, weighing 2mmol of n-butyl iodide, dropwise adding into the uniform solution, stirring for 0.5h at room temperature, transferring the uniformly mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting for 24h at 80 ℃, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent methanol by using a rotary evaporator to obtain viscous liquid, adding 5 × 20mL of ethyl acetate, washing for washing, and stirring for 3 days at room temperature. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
Comparative example 4
Dissolving 2mmol of 1-phenylimidazole in 10mL of anhydrous methanol, stirring for 0.5h at room temperature to form a uniform mixed solution, weighing 2mmol of n-butyl iodide, dropwise adding the n-butyl iodide into the uniform solution, stirring for 0.5h at room temperature, transferring the uniformly mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, reacting for 24h at 80 ℃, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent methanol by using a rotary evaporator to obtain viscous liquid, adding 5 multiplied by 20mL of ethyl acetate for washing, washing and stirring for 3 days at room temperature. After washing, removing the solvent by filtration, putting the rest powder into a vacuum oven, and drying for 24 hours at 80 ℃ under a vacuum condition to obtain a target product, wherein the structure is as follows:
Testing the reaction performance of the catalyst:
catalyzing cycloaddition reaction under normal temperature and pressure:
epichlorohydrin (5mmol), CO2(0.1MPa, balloon) and the Ionic liquid [ p-ArOH-IM prepared in example 1]A25 mL glass flask reactor was charged with the mixture of I (0.034mg), and the reaction mixture was stirred at room temperature for 24 h. After the reaction was completed, 25mL of ethyl acetate was added to the reactor, and the ionic liquid was removed by centrifugation. Internal standard n-dodecane (0.5g) was added to the liquid phase and further diluted with ethyl acetate. The liquid product was quantitatively analyzed by gas chromatography (Agilent 7890B), flame ionization detector and capillary column (HP-5,30 m.times.0.25 mm.times.0.25 μm). The liquid phase composition was qualitatively identified by gas chromatography-mass spectrometry (Bruker Scion 436 GC-MS). The recovered ionic liquid was washed with ethyl acetate, dried under vacuum, and then charged directly to the next pass to test the recovery performance.
FIG. 4 shows the yield results of five catalytic cycloaddition reaction cycle tests of the catalyst [ p-ArOH-IM ] I at room temperature and normal pressure, and it can be seen that the ionic liquid [ p-ArOH-IM ] I still maintains stable catalytic activity after repeated tests, indicating that the material has good reusability.
Catalyzing cycloaddition reaction under the conditions of normal pressure and high temperature:
epichlorohydrin (5mmol), CO2(0.1MPa, balloon) and the Ionic liquid [ p-ArOH-IM prepared in example 1]A25 mL glass flask reactor was charged with the mixture of I (0.034mg), and the mixture was stirred at 100 ℃ to react.
FIG. 5 is a graph showing CO at 100 ℃ and 0.1MPa when the reaction is carried out2When, [ p-ArOH-IM]I in CO2And cycloaddition reaction kinetics of epichlorohydrin. As can be seen from FIG. 5, when the substrate was used in an amount of 200mmol, [ p-ArOH-IM ]]At an amount of 0.015 mol% I, a conversion of 94% was achieved after a longer reaction, and TONs of 2129 and 6233 were obtained after 48h and 240h, respectively. The best reported to dateThe TON of the organic catalyst is 1000, [ p-ArOH-IM ]]The TON of I is more than six times higher than that of I, which indicates that [ p-ArOH-IM]I is indeed a very efficient, stable and promising organic catalyst.
Catalyzing cycloaddition reaction under high pressure and high temperature conditions:
the high pressure reaction was carried out in a stainless steel autoclave (25mL) equipped with a magnetic stirrer. Epichlorohydrin (5mmol) and the catalyst prepared in example 1[ p-ArOH-IM]A mixture of I (0.034mg) was placed in an autoclave, flushed twice with carbon dioxide and then pressurized to 3 MPa. The reactor was heated to 120 ℃. After the reaction is finished, the reactor is placed in ice water, and excessive CO is slowly discharged2Then 25mL of ethyl acetate was added. The catalyst was separated by centrifugation.
FIGS. 6 and 7 show p-ArOH-IM under high temperature and high pressure conditions (120 ℃ C., 3MPa)]I in CO2And cycloaddition reaction kinetics of epichlorohydrin. As can be seen from FIG. 6, when the amount of the substrate used was 200mmol, [ p-ArOH-IM ]]The highest TON value of 85234 was obtained when I was used at 0.0011 mol%, as can be seen from FIG. 7 when the substrate was used at 21mmol, [ p-ArOH-IM%]When the dosage of I is 0.0110 mol%, the highest TOF value 7438h is obtained at 18h-1In comparison with the prior art, in the presence of epoxide and CO2In the cycloaddition reaction of (A), p-ArOH-IM]I is the highest reaction rate in current single component organic catalyst systems.
Application of the ionic liquid catalyst prepared in example 1 to catalysis of CO of different substrates2In the cycloaddition reaction, the reaction conditions are as follows: epoxide 5mmol, [ p-ArOH-IM]I20 mol%, room temperature (where c has a reaction temperature of 90 ℃). The test results are shown in table 1.
TABLE 1[ p-ArOH-IM]I in CO2Substrate examination results of cycloaddition reaction
As can be seen from Table 1, the ionic liquid prepared according to the scheme of example 1 has a relatively ideal catalytic effect in cycloaddition reactions of different substrates. Taking epichlorohydrin as an example, when the dosage of the substrate is 5mmol under normal temperature and normal pressure, 20 mol% of catalyst is added, and after reaction for 4 hours, the yield of the epichlorohydrin carbonate can reach 96%.
The ionic liquid catalysts prepared in the above examples and comparative examples and the existing catalysts are applied to Epichlorohydrin (ECH) and CO2In the reaction of (1), conditions: ECH 5mmol, catalyst 2 mol%, CO 21 bar. The test results are shown in table 2.
Table 2 comparison of the reactivity of different ionic liquid catalysts
As can be seen from the results in Table 2, the ionic liquid obtained by the scheme of the invention is remarkably improved in catalytic effect in the cycloaddition reaction compared with ionic liquids with other structures.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The iodinated imidazole ionic liquid containing phenolic hydroxyl is characterized by having the following structural formula:
in the formula: r1Selected from phenol radicals, R2Selected from C1-C16 alkyl.
2. The iodinated imidazole ionic liquid containing a phenolic hydroxyl group according to claim 1, wherein R is1Has the structure of
3. The iodinated imidazole ionic liquid containing a phenolic hydroxyl group according to claim 1, wherein R is2Is a straight-chain alkyl selected from C1-C16.
4. The iodinated imidazole ionic liquid containing a phenolic hydroxyl group according to claim 3, wherein R is2Is one of methyl, ethyl, n-butyl, n-octyl or n-hexadecyl.
5. The iodinated imidazole ionic liquid containing a phenolic hydroxyl group according to claim 2 or 4, wherein the ionic liquid has a structural formula:
6. a process for preparing iodinated imidazole ionic liquids containing phenolic hydroxyl groups according to any of claims 1-5, characterized by the following reaction formula:
7. the method for preparing iodinated imidazole ionic liquids containing phenolic hydroxyl groups according to claim 6, characterized by comprising the following steps:
a) dissolving a compound II in an organic solvent, adding a compound III at room temperature, and reacting to obtain a reaction solution containing a compound I;
b) carrying out rotary evaporation on the reaction liquid containing the compound I to remove the organic solvent, and washing with ethyl acetate to obtain a crude product solid of the compound I;
c) and drying the crude solid of the compound I in a vacuum oven to obtain a pure compound I.
8. The method for preparing iodinated imidazole ionic liquid containing phenolic hydroxyl groups according to claim 7, wherein the molar ratio of the compound II to the compound III is 1: 0.1-5; the organic solvent is any one of methanol, ethanol, N-propanol, dimethyl sulfoxide or N, N-dimethylformamide.
9. The method for preparing iodinated imidazole ionic liquid containing phenolic hydroxyl groups according to claim 7, wherein the reaction temperature is 50-150 ℃ and the reaction time is 10-120 h.
10. Use of the iodinated imidazole ionic liquid containing phenolic hydroxyl groups of claim 1 for catalyzing the cycloaddition reaction of carbon dioxide and epoxy compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111545963.6A CN114195719A (en) | 2021-12-16 | 2021-12-16 | Ionic liquid of iodinated imidazole containing phenolic hydroxyl group, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111545963.6A CN114195719A (en) | 2021-12-16 | 2021-12-16 | Ionic liquid of iodinated imidazole containing phenolic hydroxyl group, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114195719A true CN114195719A (en) | 2022-03-18 |
Family
ID=80654710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111545963.6A Pending CN114195719A (en) | 2021-12-16 | 2021-12-16 | Ionic liquid of iodinated imidazole containing phenolic hydroxyl group, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114195719A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250052A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Process for continuously preparing cyclic carbonate |
| CN109280063A (en) * | 2017-07-21 | 2019-01-29 | 三星显示有限公司 | Organo-metallic compound and organic luminescent device including it |
| CN111362901A (en) * | 2020-03-17 | 2020-07-03 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide with fluoroalcohol functionalized ionic liquid |
-
2021
- 2021-12-16 CN CN202111545963.6A patent/CN114195719A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250052A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Process for continuously preparing cyclic carbonate |
| CN109280063A (en) * | 2017-07-21 | 2019-01-29 | 三星显示有限公司 | Organo-metallic compound and organic luminescent device including it |
| CN111362901A (en) * | 2020-03-17 | 2020-07-03 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide with fluoroalcohol functionalized ionic liquid |
Non-Patent Citations (3)
| Title |
|---|
| MATTHIEU RAYNAL等: ""Unprecedented cubane-type silver cluster with a novel phosphinite functionalized N-heterocyclic carbene ligand"", 《DALTON TRANSACTIONS》, no. 35, pages 7288 * |
| SHI WU等: "Phenolic hydroxyl-functionalized imidazolium ionic liquids: Highly efficient catalysts for the fixation of CO2 to cyclic carbonates"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 418, pages 1 - 8, XP029524241, DOI: 10.1016/j.molcata.2016.03.002 * |
| XIANGHAO LIU等: ""Complexes with Hybrid Phosphorus-NHC Ligands: Pincer-Type Ir Hydrides, Dinuclear Ag and Ir and Tetranuclear Cu and Ag Complexes"", 《INORGANIC CHEMISTRY》, vol. 52, no. 13, pages 7367 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tharun et al. | A novel approach of utilizing quaternized chitosan as a catalyst for the eco-friendly cycloaddition of epoxides with CO 2 | |
| CN110105321B (en) | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide through eutectic ionic liquid | |
| EP1080084B1 (en) | Process for epoxidation of aryl allyl ethers | |
| US6087513A (en) | Epoxidation process for aryl allyl ethers | |
| Yue et al. | Amino acid-based ionic liquids for CO2 conversion to form cyclic carbonate under solvent-free conditions | |
| CN112778533B (en) | Porphyrin-based porous organic polymer, preparation method thereof and synthesis method of cyclic carbonate | |
| CN108772102B (en) | High-efficiency catalyst of heteropolymetal for synthesizing cyclic carbonate by high-efficiency catalysis of carbon dioxide | |
| CN111362901B (en) | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide with fluoroalcohol functionalized ionic liquid | |
| CN102491862B (en) | Method for preparing biaryl compound in pure water | |
| Deng et al. | Bis-ammonium immobilized polystyrenes with co-catalyzing functional end groups as efficient and reusable heterogeneous catalysts for synthesis of cyclic carbonate from CO 2 and epoxides | |
| CN114716371B (en) | N-containing active center metal organic catalyst for synthesizing cyclic carbonate, and preparation method and application thereof | |
| CN110872254B (en) | Pyrazole salt diionic liquid and method for catalytic synthesis of cyclic carbonate by using same | |
| CN105521825A (en) | Catalyst for preparing phenol by benzene oxidation, and preparation method and application thereof | |
| CN112316978A (en) | Organic catalyst for synthesizing cyclic carbonate, preparation method and catalytic reaction method thereof | |
| CN112409190A (en) | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst | |
| Yue et al. | Novel hydroxyl-functionalized ionic liquids as efficient catalysts for the conversion of CO 2 into cyclic carbonates under metal/halogen/cocatalyst/solvent-free conditions | |
| WO2016081685A1 (en) | Zirconium- and hafnium-based metal-organic frameworks as epoxide ring-opening catalysts | |
| CN109810091A (en) | The method for preparing alkylene carbonates for epoxyalkane and carbon dioxide | |
| CN112409317B (en) | Synthesis method of cyclic carbonate and derivatives thereof | |
| CN111233816B (en) | Preparation method of cyclic carbonate | |
| CN114195719A (en) | Ionic liquid of iodinated imidazole containing phenolic hydroxyl group, preparation method and application thereof | |
| EP3805208A1 (en) | Method for preparing alkylene carbonate from epoxyalkane and carbon dioxide | |
| CN115108912A (en) | Strongly alkaline ionic liquid catalyzed CO 2 Method for synthesizing dimethyl carbonate catalyst | |
| Bao et al. | Ionic liquid post-modified carboxylate-rich MOFs for efficient catalytic CO 2 cycloaddition under solvent-free conditions | |
| CN113045533A (en) | Synthetic method of cyclic carbonate |
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: 20220318 |