CN115710238A - Beta-carbonyl carbamate compound, preparation method and application thereof - Google Patents
Beta-carbonyl carbamate compound, preparation method and application thereof Download PDFInfo
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- CN115710238A CN115710238A CN202211451330.3A CN202211451330A CN115710238A CN 115710238 A CN115710238 A CN 115710238A CN 202211451330 A CN202211451330 A CN 202211451330A CN 115710238 A CN115710238 A CN 115710238A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005580 one pot reaction Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000002608 ionic liquid Substances 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000002028 Biomass Substances 0.000 claims description 13
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 13
- 229940112669 cuprous oxide Drugs 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000000575 pesticide Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
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- 239000000047 product Substances 0.000 description 63
- 238000005481 NMR spectroscopy Methods 0.000 description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 21
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- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 carbamate compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LQMDOONLLAJAPZ-UHFFFAOYSA-N 1-ethynylcyclopentan-1-ol Chemical compound C#CC1(O)CCCC1 LQMDOONLLAJAPZ-UHFFFAOYSA-N 0.000 description 1
- KSLSOBUAIFEGLT-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C#CC(O)(C)C1=CC=CC=C1 KSLSOBUAIFEGLT-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- PUNRPAWKFTXZIW-UHFFFAOYSA-N 3-ethylpent-1-yn-3-ol Chemical compound CCC(O)(CC)C#C PUNRPAWKFTXZIW-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 201000011510 cancer Diseases 0.000 description 1
- 239000000152 carbamate pesticide Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a beta-carbonyl carbamate compound, a preparation method and an application thereof, wherein the molecular structural formula of the beta-carbonyl carbamate compound is as follows:
mixing alkynol, secondary amine and a catalyst, introducing carbon dioxide, and synthesizing by adopting a one-pot method; the green synthesis method has the advantages of few steps, no need of conventional organic volatile solvents, high atom economy, no toxicity and low price of carbon dioxide as a carbonyl source, environmental friendliness and cyclic utilization of a catalytic system; more importantly, the method realizes that the pure product can be directly extracted without purification for the first time, and the post-treatment is simple, thereby being beneficial to industrial production; the prepared beta-carbonyl carbamate compound has very wide practical value and wide application prospect in various fields of chemical products, medical treatment and health, agricultural production and the like.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a beta-carbonyl carbamate compound, and a preparation method and application thereof.
Background
Carbamate is a compound in which amino or amino is directly connected with carbonyl of formate, and the compound and its derivatives (hereinafter referred to as carbamate compounds) generally have high chemical stability, pharmaceutical activity and biological activity, so that the carbamate is a key skeleton structure of many drugs, is also an important chemical raw material and organic synthesis intermediate, and has very high practical value and wide application prospect in the fields of chemical production, medical treatment and health care and the like. The carbamate compounds also have important application in pesticides, and are called three pesticides in combination with organophosphorus and pyrethroid. The carbamate pesticide has the advantages of high efficiency, low toxicity and low residue, is mostly colorless or white crystal, is slightly soluble in water and organic solvent, is ineffective when hydrolyzed under alkaline conditions, and can stably exist under light, heat and acidic conditions. In conclusion, various carbamate compounds have great development potential in market application.
From literature reports, the synthesis of the carbamate compounds mainly adopts traditional preparation methods such as phosgene method, chloroformate method and isocyanate method, but the synthesis methods all directly or indirectly use virulent phosgene to generate toxic by-products (HCl and the like), thereby causing environmental pollution and potential safety hazards. In recent years, carbon dioxide has been gradually developed as an ideal substitute for conventional carbon sources such as phosgene as a nontoxic, inexpensive, and renewable high-quality C1 carbon source. Therefore, the synthesis of the carbamate compound by using carbon dioxide as a carbonylation reagent has incomparable advantages compared with other approaches.
At present, in various methods for synthesizing carbamate compounds by taking carbon dioxide as a raw material, the adopted catalyst or catalytic system often comprises gold, platinum, silver noble metal, complex organic ligand or strong alkaline additive, the working temperature and pressure of the carbon dioxide are high, and the traditional volatile organic solvent is required to be added in the reaction, so that the problems of low product purity, difficult separation from the reaction system and the like are caused.
Disclosure of Invention
Aiming at least one defect or improvement requirement in the prior art, the invention provides a beta-carbonyl carbamate compound, a preparation method and application thereof.
To achieve the above object, according to a first aspect of the present invention, there is provided a β -carbonyl carbamate compound having the following structural formula:
wherein R is 1 、R 2 Respectively is any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy, heteroatom and hydrogen atom, R 1 、R 2 May be the same or different;
R 3 、R 4 respectively is any one of alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy and heteroatom; r is 3 、R 4 May be the same or different.
Further, in the above β -carbonyl carbamate compound, the aryl group may have one or more substituents; when there are a plurality of substituents, the substituents may be the same or different;
further, the beta-carbonyl carbamate compound has 1-20 carbon atoms in the alkyl group, and is in a linear chain structure, a cyclic structure or a branched chain structure; the alkyl group may have one or more substituents, and when a plurality of substituents are present, the substituents may be the same or different, and the positions may be the same or different.
According to the second aspect of the present invention, there is also provided a process for producing a β -carbonyl carbamate compound, comprising the steps of:
mixing alkynol, secondary amine and a catalyst, introducing carbon dioxide, and synthesizing the beta-carbonyl carbamate compound by adopting a one-pot method;
the molecular structural formula of the alkynol is shown in the specification
The molecular structural formula of the secondary amine is as follows:
the chemical structural formula of the beta-carbonyl carbamate compound is as follows:
wherein R is 1 、R 2 Respectively is any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy, heteroatom and hydrogen atom, R 1 、R 2 May be the same or different;
R 3 、R 4 respectively is any one of alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy and heteroatom; r 3 、R 4 May be the same or different.
The reaction equation is as follows:
further, in the method for preparing the beta-carbonyl carbamate compound, the molar ratio of the alkynol to the secondary amine is 1.
Further, in the preparation method of the beta-carbonyl carbamate compound, the catalyst comprises biomass-based ionic liquid, and the using amount of the biomass-based ionic liquid accounts for 20-40 mol% of the total amount of the alkynol;
the biomass-based ionic liquid is [ DBUH ]][Lev]、[DBUH] 2 [Sa]、[DBUH] 2 [ITa]、[DBUH] 2 [FDCa]、[DBUH] 2 [Ma]、[Emim][Lev]、[Bmim][Lev]、[DBNH][Lev]、[P 4444 ][Lev]、[N 4444 ][Lev]One or more of (a).
The molecular structural formula of the biomass-based ionic liquid is shown as follows:
further, in the preparation method of the beta-carbonyl carbamate compound, the catalyst comprises copper salt, and the using amount of the copper salt accounts for 0.5-4 mol% of the total amount of the alkynol;
the cupric salt is one or more of cupric chloride, cuprous chloride, cupric sulfate, cupric acetate, copper trifluoromethanesulfonate, cuprous iodide, cuprous bromide, cuprous sulfide, cuprous oxide and cuprous thiocyanate.
The method adopts a double-catalyst system of copper salt and biomass-based ionic liquid, the metal copper salt is cheap and easy to obtain, the introduced biomass-based ionic liquid is not only a catalyst, but also a solvent of a reaction system, the reaction does not need to add any traditional organic volatile solvent, the steps are simple, the atom economy is high, and the method is green and environment-friendly. Experiments show that the double-catalyst system formed by cuprous oxide and [ DBUH ] [ Lev ] is the optimal catalyst system, so that the yield of the product is maximum.
Further, in the preparation method of the beta-carbonyl carbamate compound, the reaction time of the one-pot synthesis is 6-36 h; the reaction temperature is 25-100 ℃. More preferably, the reaction time is 24h; the reaction temperature was 60 ℃.
Further, the preparation method of the beta-carbonyl carbamate compound further comprises the following steps:
after the reaction is finished, cooling to room temperature, releasing unreacted carbon dioxide, and adding an extracting agent into the mixed solution for multiple times of extraction;
combining the upper organic phases, and removing the extractant under reduced pressure to obtain a target product beta-carbonyl carbamate compound;
and combining the lower water phases, drying in vacuum to remove the extractant, and recovering the catalyst.
In the application, the ionic liquid and the copper salt in the synthesis method of the 'one-pot method' can be recovered and recycled: after the reaction is finished, adding an extraction liquid for extraction, and dividing the system into two phases, wherein the lower phase is a catalyst; after extraction, separating and separating the catalyst in the lower layer, and drying the catalyst in vacuum at 60 ℃ for 6h to remove the residual extract, wherein the obtained catalytic system can be directly used for the next reaction.
And removing the extract liquor from the upper organic phase under reduced pressure to obtain the target product beta-carbonyl carbamate compound, and directly extracting the beta-carbonyl carbamate compound by using the extract liquor without any purification steps such as column chromatography or recrystallization and the like to obtain a pure product.
According to the third aspect of the present invention, there is also provided the use of a β -carbonyl carbamate compound as an intermediate for organic synthesis or for the preparation of pesticides, chemical materials and biomedical materials.
The beta-carbonyl carbamate compound prepared by the method is an important intermediate for organic synthesis, can be used in the field of medicine, can be applied to treatment of diseases such as cancer and Alzheimer's disease, can be used for preparing pesticides such as herbicides and insecticides, and can also be used in the fields of synthetic resin modification and the like.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) According to the invention, carbon dioxide, alkynol and secondary amine are used as raw materials, and under the action of a copper salt and a biomass-based ionic liquid double catalyst, carbamate is generated through a one-pot reaction, and the raw materials are non-toxic, low in price, easy to obtain, and safe and simple to operate;
(2) The invention adopts a double-catalyst system of copper salt and biomass-based ionic liquid, the metal copper salt is cheap and easy to obtain, the introduced biomass-based ionic liquid is not only a catalyst, but also is used as a solvent of a reaction system, the synthetic method has few steps, does not need conventional organic volatile solvents, has high atom economy, takes nontoxic and cheap carbon dioxide as a carbonyl source, is environment-friendly, and the catalytic system can also be recycled; more importantly, the biomass-based ionic liquid used in the method has higher polarity, is not easy to mix with organic products, is not easy to remain in the products, and has higher purity of the obtained products, so that the method can directly extract and obtain pure carbamate products without purification for the first time.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a target product 1 obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a target product 1 obtained in example 1 of the present invention;
FIG. 3 is a NMR spectrum of a target product 2 obtained in example 2 of the present invention;
FIG. 4 is a NMR spectrum of a target product 2 obtained in example 2 of the present invention;
FIG. 5 is a NMR spectrum of a target product 3 obtained in example 3 of the present invention;
FIG. 6 is a NMR carbon spectrum of a target product 3 obtained in example 3 of the present invention;
FIG. 7 is a NMR spectrum of a target product 4 obtained in example 4 of the present invention;
FIG. 8 is a NMR spectrum of a target product 4 obtained in example 4 of the present invention;
FIG. 9 is a NMR spectrum of a target product 5 obtained in example 5 of the present invention;
FIG. 10 is a NMR spectrum of a target product 5 obtained in example 5 of the present invention;
FIG. 11 is a NMR chart of the objective product 6 obtained in example 6 of the present invention;
FIG. 12 is a NMR spectrum of a target product 6 obtained in example 6 of the present invention;
FIG. 13 is a NMR spectrum of a target product 7 obtained in example 7 of the present invention;
FIG. 14 is a NMR C spectrum of a target product 7 obtained in example 7 of the present invention;
FIG. 15 is a NMR spectrum of a target product 8 obtained in example 8 of the present invention;
FIG. 16 is a NMR spectrum of a target product 8 obtained in example 8 of the present invention;
FIG. 17 is a NMR spectrum of a target product 9 obtained in example 9 of the present invention;
FIG. 18 is a NMR C spectrum of a target product 9 obtained in example 9 of the present invention;
FIG. 19 is a NMR spectrum of a target product 10 obtained in example 10 of the present invention;
FIG. 20 is a NMR spectrum of a target product 10 obtained in example 10 of the present invention;
FIG. 21 is a NMR chart of a target product 11 obtained in example 11 of the present invention;
FIG. 22 is a NMR carbon spectrum of the objective product 11 obtained in example 11 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. The experimental methods in the present invention are conventional methods unless otherwise specified. The experimental materials used in the present invention were all purchased from the market unless otherwise specified.
Example 1:
0.05mmol of cuprous oxide, 5mmol of 2-methyl-3-butyn-2-ol, 5mmol of pyrrolidine and 2mmol of 2 DBUH ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24h under the environment of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed by rotary evaporator under reduced pressure to 100mbar to give the desired product 1 (4.65 mmol) in a calculated yield of 93% and 97% purity of the desired product 1.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500MHz, chloroform-d) delta 3.44-3.27 (m, 4H), 2.14 (s, 3H), 1.87 (s, 4H), 1.46 (s, 6H), specific NMR spectrum shown in FIG. 1; 13 c NMR (126MHz, chloroform-d) delta 207.99,153.86,82.86,46.09,46.04,25.76,24.95,23.84, and specific NMR spectra are shown in FIG. 2.
From the above structural characterization data, the structure of the obtained product is shown below:
example 2:
0.05mmol of cuprous oxide, 5mmol of 2-methyl-3-butyn-2-ol, 5mmol of morpholine and 2mmol of Emim ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, carbon dioxide is used for degassing three times, the mixture reacts for 24h under the environment of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed by rotary evaporator under reduced pressure to 100mbar to give pure target product 2 (3.6 mmol) in a calculated yield of 72% and purity of 95% of target product 2.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500MHz, chloroform-d) delta 3.69-3.63 (m, 4H), 3.47 (s, 4H), 2.13 (s, 3H), 1.46 (s, 6H), specific NMR spectrum shown in figure 3; 13 c NMR (126MHz, chloroform-d) delta 207.33,154.32,83.64,66.78,43.94,23.84,23.73, and specific NMR spectra are shown in FIG. 4.
From the above structural characterization data, the structure of the obtained product is shown below:
example 3:
0.05mmol of copper chloride, 5mmol of 2-methyl-3-butyn-2-ol, 5mmol of diethylamine and 2mmol of DBUH ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24h under the environment of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed by rotary evaporator to 100mbar to give the desired product 3 (3.8 mmol) in a calculated yield of 76% and a purity of 96% for the desired product 3.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 3.24 (s, 4H), 2.07 (s, 3H), 1.40 (s, 6H), 1.09 (d, J =22.4hz, 6H), specific NMR spectrogram of NMR is shown in fig. 5. 13 C NMR (126MHz, chloroform-d) delta 207.97,155.00,83.19,42.13,41.93,23.95,23.67,14.46,13.81, and a specific NMR spectrum is shown in FIG. 6.
From the above structural characterization data, the structure of the obtained product is shown below:
example 4:
0.05mmol of cuprous oxide, 5mmol of 2-methyl-3-butyn-2-ol, 5mmol of di-n-butylamine and 2mmol of 2 [ DBUH ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to the room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed by rotary evaporator to a reduced pressure of 100mbar to give the desired product 4 (4.4 mmol) in a calculated yield of 88% and 97% purity of the desired product 4.
The obtained material was subjected to nuclear magnetic resonance analysis using a nuclear magnetic resonance apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 3.26-3.14 (m, 4H), 2.10 (s, 3H), 1.56-1.46 (m, 4H), 1.43 (s, 6H), 1.29 (dq, J =22.3,7.1hz, 4H), 0.91 (dt, J =19.0,7.1hz, 6H), specific nuclear magnetic resonance hydrogen spectrum see fig. 7; 13 C NMR(126MHz，Chloroform-d)δ207.81,155.17,83.02,47.17,46.84,30.92,30.29,23.72,23.46,20.06,20.02,13.92, see FIG. 8 for specific NMR spectra.
From the above structural characterization data, the structure of the obtained product is shown below:
example 5:
0.05mmol of cuprous oxide, 5mmol of 2-methyl-3-butyn-2-ol, 5mmol of N-methylbenzylamine and 2mmol of DBUH (diethylene glycol dimethyl ether) Lev are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in a bottle for extraction for 3 times. The organic phases were combined and the solvent dry ether was removed by rotary evaporator under reduced pressure to 100mbar to give target product 5 (4.25 mmol) calculated to yield 85% target product 5 and 98% purity.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 7.40-7.20 (m, 5H), 4.48 (d, J =22.8hz, 2h), 2.89 (d, J =5.8hz, 3h), 2.16 (d, J =19.4hz, 3h), 1.48 (d, J =20.7hz, 6h), and a specific nuclear magnetic resonance hydrogen spectrum is shown in fig. 9. 13 C NMR(126MHz，Chloroform-d)δ207.71,137.35,128.82,128.77,127.91,127.63,127.31,83.56,83.52,52.82,52.49,34.54,33.92,23.81,23.70 . The specific nuclear magnetic resonance carbon spectrum is shown in figure 10.
From the above structural characterization data, the structure of the obtained product is shown below:
example 6:
0.05mmol of cuprous oxide, 5mmol of 3-methyl-1-pentyn-3-ol, 5mmol of pyrrolidine and 2mmol of [ DBUH ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24h under the environment of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent dry ether was removed by rotary evaporator under reduced pressure to 100mbar to give target product 6 (3.55 mmol) which was calculated to give target product 6 in 71% yield and 98% purity.
The obtained material was subjected to nuclear magnetic resonance analysis using a nuclear magnetic resonance apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 3.37 (dd, J =15.6,5.5hz, 4H), 2.13 (s, 3H), 1.88 (dt, J =15.5,7.8hz, 5h), 1.70 (dt, J =14.1,7.4hz, 1h), 1.46 (s, 3H), 0.89 (t, J =7.5hz, 3h), and a specific nuclear magnetic resonance hydrogen spectrum is shown in fig. 11. 13 C NMR (126MHz, chloroform-d) delta 208.27,153.92,85.58,46.15,29.84,25.88,25.06,24.42,20.24,7.74, and specific NMR C-spectrum is shown in FIG. 12.
From the above structural characterization data, the structure of the obtained product is shown below:
example 7:
0.05mmol of cuprous oxide, 5mmol of 3-ethyl-1-pentyn-3-ol, 5mmol of pyrrolidine and 2mmol of [ DBUH ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24h under the environment of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed by rotary evaporator to a reduced pressure of 100mbar to give the desired product 7 (4.15 mmol) in a calculated yield of 83% and purity of 98% of the desired product 7.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 3.53-3.27 (m, 4H), 2.11 (s, 3H), 1.97 (dt, J =14.8,7.4hz, 2h), 1.91-1.80 (m, 6H), 0.77 (t, J =7.5hz, 6H), and the specific nuclear magnetic resonance hydrogen spectrum is shown in fig. 13. 13 C NMR (126MHz, chloroform-d) delta 208.44,153.67,88.58,46.12,46.10,25.83,25.41,25.32,25.01,7.46, and specific NMR C spectra are shown in FIG. 14.
From the above structural characterization data, the structure of the obtained product is shown below:
example 8:
0.05mmol of cuprous oxide, 5mmol of 3, 5-dimethyl-1-hexyne-3-ol, 5mmol of pyrrolidine and 2mmol of DBUH (Lev) are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24 hours at the temperature of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in a bottle for extraction for 3 times. The organic phases were combined and the solvent dry ether was removed by rotary evaporator under reduced pressure to 100mbar to give target 8 (2.5 mmol) which was calculated to give target 8 in 50% yield and 98% purity.
The obtained material was subjected to nuclear magnetic resonance analysis using a nuclear magnetic resonance apparatus, and the results were as follows: 1 H NMR(500MHz，Chloroform-d)δ3.44–3.33(m,4H),2.14(s,3H),1.88(dp,J＝18.0,6.6Hz,4H),1.80(dd,J＝6.8,5.4Hz,1H),1.75–1.69(m,1H),1.60(dd, J =14.3,4.9Hz, 1H), 1.52 (s, 3H), 0.94 (dd, J =10.4,6.6Hz, 6H), and the specific NMR spectrum is shown in FIG. 15. 13 C NMR (126MHz, chloroform-d) delta 208.34,153.96,85.82,46.22,46.20,45.06,25.92,25.06,24.74,24.30,24.14,23.87,20.95, and specific NMR C-spectrum is shown in FIG. 16.
From the above structural characterization data, the structure of the obtained product is shown below:
example 9:
adding 0.05mmol of cuprous oxide, 5mmol of 1-ethynylcyclopentanol, 5mmol of pyrrolidine and 2mmol of DBUH ] [ Lev ] into a 15ml Schlenk test tube in sequence, ventilating with carbon dioxide for three times, reacting for 24h under the environment of 60 ℃, cooling to room temperature after the reaction is finished, slowly releasing unreacted carbon dioxide, and adding 15ml of anhydrous ether into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent dry ether was removed by rotary evaporator under reduced pressure to 100mbar to give the desired product 9 (1.5 mmol) in a calculated yield of 30% and purity of 98% of the desired product 9.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 3.38 (dt, J =12.6,6.5hz, 4H), 2.26-2.07 (m, 5H), 1.89 (ddt, J =17.0,13.1,6.6hz, 6H), 1.78-1.66 (m, 4H), specific nuclear magnetic resonance hydrogen spectrum is shown in fig. 17. 13 C NMR (126MHz, chloroform-d) delta 207.08,154.33,93.40,46.19,35.91,25.89,25.09,25.03,24.78, and specific NMR C spectra are shown in FIG. 18.
From the above structural characterization data, the structure of the obtained product is shown below:
example 10:
adding 0.05mmol of cuprous oxide, 5mmol of ethynl cyclohexanol, 5mmol of pyrrolidine and 2mmol of DBUH ] [ Lev ] in a 15ml Schlenk test tube in sequence, ventilating with carbon dioxide for three times, reacting at 60 ℃ for 24h, cooling to room temperature after the reaction is finished, slowly releasing unreacted carbon dioxide, and adding 15ml of anhydrous ether into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed by rotary evaporator under reduced pressure to 100mbar to give the desired product 10 (3 mmol) in a calculated yield of 60% and purity of 98% of the desired product 10.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 3.45 (s, 2H), 3.36 (s, 2H), 2.12 (s, 3H), 2.04 (d, J =13.8hz, 2h), 1.88 (dq, J =20.0,6.6hz, 4h), 1.62 (td, J =18.3,16.5,9.8hz, 5h), 1.55-1.46 (m, 2H), 1.26-1.19 (m, 1H), and a specific nuclear magnetic resonance hydrogen spectrum is shown in fig. 19. 13 C NMR (126MHz, chloroform-d) delta 208.58,153.69,84.21,46.21,46.13,31.18,25.88,25.30,25.04,23.80,21.56, and specific NMR spectrum is shown in FIG. 20.
From the above structural characterization data, the structure of the obtained product is shown below:
example 11:
0.05mmol of cuprous oxide, 5mmol of 2-phenyl-3-butyn-2-ol, 5mmol of pyrrolidine and 2mmol of 2 DBUH ] [ Lev ] are sequentially added into a 15ml Schlenk test tube, gas is pumped by carbon dioxide for three times, the mixture reacts for 24h under the environment of 60 ℃, the temperature is cooled to room temperature after the reaction is finished, unreacted carbon dioxide is slowly released, and 15ml of anhydrous ether is added into the mixed solution in the bottle for extraction for 3 times. The organic phases were combined and the solvent, anhydrous ether, was removed using a rotary evaporator under reduced pressure to 100mbar to give the desired product 11 (3.55 mmol) in a calculated yield of 71% and 98% purity of desired product 11.
The obtained material was subjected to nmr analysis using an nmr apparatus, and the results were as follows: 1 h NMR (500mhz, chloroform-d) δ 7.37 (d, J =7.5hz, 2h), 7.26 (t, J =7.5hz, 2h), 7.20 (t, J =7.3hz, 1h), 3.60-3.48 (m, 2H), 3.35 (t, J =6.7hz, 2h), 1.89 (s, 5H), 1.82 (q, J =6.6hz, 2h), 1.77 (s, 3H), specific nuclear magnetic resonance hydrogen spectrum see fig. 21. 13 C NMR (126MHz, chloroform-d) delta 204.18,152.98,139.34,128.31,127.53,124.42,86.45,45.95,45.91,25.47,24.59,23.52,23.33, and specific NMR spectra are shown in FIG. 22.
From the above structural characterization data, the structure of the obtained product is shown below:
it should be noted that, the above examples all use the optimal reaction temperature and reaction time, and most of the examples also use the optimal catalytic system, so as to verify the yield and purity results of the optimal reaction and/or the optimal catalytic conditions for the products of different reaction raw materials with the least variables; however, other catalytic systems and reaction conditions listed herein are also within the scope of the present invention, and are not specifically limited.
The above embodiments only express the implementation manner of the present invention, and the description is specific and detailed, but it should not be understood that the invention scope is limited. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. A beta-carbonyl carbamate compound, characterized in that it has the following structural formula:
wherein R is 1 、R 2 Respectively is any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy, heteroatom and hydrogen atom, R 1 、R 2 May be the same or different;
R 3 、R 4 respectively is any one of alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy and heteroatom; r 3 、R 4 May be the same or different.
2. A β -carbonyl carbamate according to claim 1, wherein said aryl group has one or more substituents; when there are a plurality of substituents, the substituents may be the same or different.
3. The β -carbonyl carbamate compound according to claim 1, wherein the alkyl group has 1 to 20 carbon atoms and has a linear structure, a cyclic structure, or a branched structure; the alkyl group may have one or more substituents, and when a plurality of substituents are present, the substituents may be the same or different, and the positions may be the same or different.
4. A preparation method of beta-carbonyl carbamate compounds is characterized by comprising the following steps:
mixing alkynol, secondary amine and a catalyst, introducing carbon dioxide, and synthesizing the beta-carbonyl carbamate compound by adopting a one-pot method;
the molecular structural formula of the alkynol is shown as
The molecular structural formula of the secondary amine is as follows:
the chemical structural formula of the beta-carbonyl carbamate compound is as follows:
wherein R is 1 、R 2 Respectively is any one of aryl, heteroaryl, alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy, heteroatom and hydrogen atom, R 1 、R 2 May be the same or different;
R 3 、R 4 respectively is any one of alkyl, alkenyl, alkynyl, ester group, cyano, nitro, alkoxy and heteroatom; r 3 、R 4 May be the same or different.
5. The method for producing a β -carbonyl carbamate compound according to claim 4, wherein the molar ratio of the alkynol to the secondary amine is 1.
6. The method for preparing beta-carbonyl carbamate compounds according to claim 4, wherein the catalyst comprises biomass-based ionic liquid, and the amount of the biomass-based ionic liquid is 20mol% to 40mol% of the total amount of the alkynol;
the biomass-based ionic liquid is [ DBUH ]][Lev]、[DBUH] 2 [Sa]、[DBUH] 2 [ITa]、[DBUH] 2 [FDCa]、[DBUH] 2 [Ma]、[Emim][Lev]、[Bmim][Lev]、[DBNH][Lev]、[P 4444 ][Lev]、[N 4444 ][Lev]One or more of (a).
7. The method for preparing beta-carbonyl carbamate compounds according to claim 4 or 6, wherein the catalyst comprises copper salt, and the amount of the copper salt is 0.5mol% to 4mol% of the total amount of the alkynol;
the copper salt is one or more of cupric chloride, cuprous chloride, cupric sulfate, cupric acetate, copper trifluoromethanesulfonate, cuprous iodide, cuprous bromide, cuprous sulfide, cuprous oxide and cuprous thiocyanate.
8. The method for preparing beta-carbonyl carbamates compound according to claim 4 wherein the reaction time of the one-pot synthesis is 6 to 36 hours; the reaction temperature is 25-100 ℃.
9. The method for producing a β -carbonyl carbamate compound according to claim 4, further comprising the steps of:
after the reaction is finished, cooling to room temperature, releasing unreacted carbon dioxide, and adding an extracting agent into the mixed solution for multiple times of extraction;
combining the upper organic phases, and removing the extractant under reduced pressure to obtain a target product beta-carbonyl carbamate compound;
and combining the lower aqueous phases, vacuum drying to remove the extractant, and recovering the catalyst.
10. Use of the beta-carbonyl carbamate compound according to any one of claims 1 to 3 or the beta-carbonyl carbamate compound prepared by the preparation method according to any one of claims 4 to 9 as an intermediate for organic synthesis or for preparing pesticides, chemical materials and biomedical materials.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1122937B (en) * | 1960-09-28 | 1962-02-01 | Basf Ag | Process for the production of ketourethanes |
| DE1130803B (en) * | 1960-12-23 | 1962-06-07 | Basf Ag | Process for the production of ketourethanes |
| DE1177335B (en) * | 1962-01-23 | 1964-09-03 | Basf Ag | Polyester molding compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1122937B (en) * | 1960-09-28 | 1962-02-01 | Basf Ag | Process for the production of ketourethanes |
| DE1130803B (en) * | 1960-12-23 | 1962-06-07 | Basf Ag | Process for the production of ketourethanes |
| DE1177335B (en) * | 1962-01-23 | 1964-09-03 | Basf Ag | Polyester molding compounds |
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