CN113234099A - Photochemical synthesis method of alkyl borate compound - Google Patents
Photochemical synthesis method of alkyl borate compound Download PDFInfo
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- CN113234099A CN113234099A CN202110555459.8A CN202110555459A CN113234099A CN 113234099 A CN113234099 A CN 113234099A CN 202110555459 A CN202110555459 A CN 202110555459A CN 113234099 A CN113234099 A CN 113234099A
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- photochemical synthesis
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- ultraviolet light
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- -1 alkyl borate compound Chemical class 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 230000008878 coupling Effects 0.000 claims abstract description 3
- 238000010168 coupling process Methods 0.000 claims abstract description 3
- 238000005859 coupling reaction Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- QZEWCQGGAIGUPS-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O.OC1=CC=CC=C1O QZEWCQGGAIGUPS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims 1
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 238000004607 11B NMR spectroscopy Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012036 alkyl zinc reagent Substances 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AYESKMWPTSCYSJ-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol;hydrochloride Chemical compound [Cl-].OC[PH+](CO)CO AYESKMWPTSCYSJ-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GXJABQQUPOEUTA-RDJZCZTQSA-N bortezomib Chemical compound C([C@@H](C(=O)N[C@@H](CC(C)C)B(O)O)NC(=O)C=1N=CC=NC=1)C1=CC=CC=C1 GXJABQQUPOEUTA-RDJZCZTQSA-N 0.000 description 1
- 229960001467 bortezomib Drugs 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photochemical synthesis method of alkyl borate compounds, which comprises the steps of taking alkane and duplex catechol borate as raw materials, realizing coupling of carbon-boron bonds under the illumination of ultraviolet light in the presence of an additive, and separating and purifying to obtain the alkyl borate compounds. The method has the characteristics of high atom economy, greenness, high efficiency, no use of oxidant, simple process and the like, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a photochemical synthesis method of an alkyl borate compound, belonging to the field of organic compound synthesis.
Background
Alkylboronic acid derivatives are compounds of interest in pharmaceutical chemistry (e.g. bortezomib)[1]. The alkylboronic acid derivatives can be easily purified before use and have excellent storage stability, compared to other organometallic compounds (e.g., alkylmagnesium, alkylzinc reagents). Their cross-coupling reactions also show excellent compatibility with various functional groups. The direct reaction of organic metal reagent (such as Grignard reagent, organic lithium reagent, etc.) and boric acid triester is the traditional carbon-boron bond construction method[2]. The method has the advantages of low reaction temperature, high yield and the like. However, the sensitivity of organometallic reagents has resulted in a large limitation in the range of substrates and functional group compatibility of the process.
In recent years, in the synthesis process using a transition metal catalyst, the synthesis of organoboron derivatives has been remarkably advanced. For example, the development of Miyaura boronation over palladium catalysts allows efficient synthesis of organoboron compounds from aryl iodides, bromides and chlorides[3]. However, these methods require high temperature and high costA noble metal reagent. These drawbacks limit the utility of these synthetic methods.
[ REFERENCE ] to
[1]Beenen M A,An C,Ellman J A.J.Am.Chem.Soc.2008,130,6910.
[2](a)Han,F.-S.Chem.Soc.Rev.2013,42,5270.(b)Xu,L.；Zhang,S.；Li,P.Chem.Soc.Rev.2015,44,8848.
[3]Ishiyama,T.；Murata,M.；Miyaura,N.J.Org.Chem.1995,60,7508.
Disclosure of Invention
Aiming at the defects of the existing synthetic route, the invention provides a photochemical synthesis method of alkyl borate compounds, which has the advantages of simple process, convenient operation and the like.
The photochemical synthesis method of the alkyl borate compound takes alkane and double pyrocatechol borate as raw materials, copper chloride as an additive, realizes the coupling of carbon-boron bonds by the illumination of ultraviolet light with the wavelength of 365-. When copper chloride is not added, the reaction cannot be carried out; in the absence of ultraviolet light irradiation, the reaction cannot proceed; when the reaction wavelength is not 365-.
Dissolving alkane, bis-catechol borate and an additive in a solvent at room temperature under the protection of inert gas, reacting under the illumination of ultraviolet light, and separating and purifying after the reaction to obtain the target compound.
The alkane has a structural formula of R-H, wherein R is alkyl.
The structural formula of the bi-pyrocatechol borate is as follows:
the additive is copper chloride.
The molar ratio of the alkane to the bis-catechol borate to the copper chloride is 10:1: 2.
The solvent is acetonitrile.
The reaction temperature of the synthetic method is 25 ℃, and the reaction time is 20-24 h.
The wavelength of the ultraviolet light is 365-.
And the separation and purification comprises the steps of adding a proper amount of water into the reaction solution, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, and purifying by column chromatography (petroleum ether: ethyl acetate: 10: 1-100: 1, v/v) to obtain the target product.
The reaction process of the invention is as follows:
the 365nm means that ultraviolet light with the wavelength of 365nm is used for irradiation.
The invention has the beneficial effects that:
1. the synthesis method has mild conditions and is carried out at room temperature and normal pressure; the operation is simple, convenient and safe, and the environment is protected;
2. the synthetic method has wide applicability of the substrate, can be compatible with various alkanes, and can prepare various alkyl borate compounds.
Detailed Description
To further illustrate the features and advantages of the present invention, the following description of the embodiments of the present invention is provided in conjunction with the accompanying drawings. However, the following examples are intended to further illustrate the invention, but not to limit it.
Example 1:
adding cyclohexane (5mmol), bis-catechol borate (0.5mmol) and copper chloride (1mmol) into a 25mL Schlenk reaction tube equipped with a magnetic stirrer, and then adding 4.0mL acetonitrile; fixing the reaction tube on a magnetic stirrer, adding an ultraviolet lamp with the wavelength of 365nm for irradiation, and uniformly stirring the reaction liquid; the mixture was reacted at room temperature (25 ℃ C.) for 24 hours, and pinacol (2mmol) and tris (hydroxymethyl) phosphonium chloride were added theretoEthylamine (5.0mL) is evenly stirred for 2 hours, and the reaction is finished; adding a proper amount of water into the reaction solution, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by using a rotary evaporator, and separating and purifying the crude product by column chromatography (petroleum ether: ethyl acetate: 15:1) to obtain the target product (3a) with the yield of 80%. The nuclear magnetic data for this compound are:1H NMR(600MHz,CDCl3)δ1.66–1.52(m,5H),1.36–1.23(m,5H),1.20(s,12H),0.94(m,1H).13C NMR(151MHz,CDCl3)δ82.83,77.37,77.16,76.95,28.09,27.26,26.90,24.87.11B NMR(193MHz,CDCl3)δ33.03.
example 2:
the procedure of example 1 was repeated, except that cyclopentane (1b) was used in place of cyclohexane (1 a). Column chromatography (petroleum ether: ethyl acetate: 20:1) afforded the desired product (3b) in 64% yield. The nuclear magnetic data for this compound are:1H NMR(600MHz,CDCl3)δ1.88–1.69(m,2H),1.68–1.26(m,6H),1.23(s,12H),1.16(s,1H).13C NMR(151MHz,CDCl3)δ83.00,28.74,27.07,24.97.11B NMR(193MHz,CDCl3)δ33.67.
example 3:
the procedure of example 1 was repeated except that cycloheptane (1c) was used in place of cyclohexane (1 a). Column chromatography (petroleum ether: ethyl acetate: 20:1) afforded the desired product (3c) in 49% yield. The nuclear magnetic data for this compound are:1H NMR(600MHz,CDCl3)δ1.77–1.63(m,4H),1.58–1.39(m,8H),1.23(s,12H),1.08–1.04(m,1H).13C NMR(151MHz,CDCl3)δ82.89,29.75,29.11,28.50,24.87.11B NMR(193MHz)δ33.48.
example 4:
example 1 was repeated except that cyclooctane (1d) was used in place of cyclohexane (1 a). Column chromatography (petroleum ether: ethyl acetate: 20:1) gave the desired compound (3d) in 37% yield. The nuclear magnetic data for this compound are:1H NMR(600MHz,CDCl3)δ2.11–1.67(m,14H),1.59(s,12H),1.48–1.44(m,1H).13C NMR(151MHz,CDCl3)δ82.88,27.71,27.15,26.99,26.79,24.87.11B NMR(193MHz,CDCl3)δ33.59.
example 5:
the same procedure as in example 1 was repeated, except that cyclododecane (1e) was used in place of cyclohexane (1 a). Column chromatography (petroleum ether: ethyl acetate: 20:1) afforded the desired product (3e) in 45% yield. The nuclear magnetic data for this compound are:1H NMR(600MHz,CDCl3)δ1.50–1.22(m,22H),1.21(s,12H),1.04–1.01(m,1H).13C NMR(151MHz,CDCl3)δ83.32,25.51,25.35,24.87,24.71,24.07,24.03,23.99.11B NMR(193MHz,CDCl3)δ33.63.
the method for synthesizing the alkyl borate compound provided by the invention is described in detail above. The above description is only an example of the present invention, and is not intended to limit the scope of the present invention. Without departing from the principle of the invention, the invention can be modified and modified, and the modification and modification are also included in the protection scope of the invention.
Claims (8)
1. A photochemical synthesis method of alkyl borate compounds is characterized in that:
the alkane and the double catechol borate ester are used as raw materials, the coupling of carbon-boron bonds is realized through ultraviolet light illumination, and the alkyl borate ester compound is obtained after separation and purification;
the alkane has a structural formula of R-H, wherein R is alkyl.
The structural formula of the bi-pyrocatechol borate is as follows:
2. the photochemical synthesis process of claim 1, wherein:
dissolving alkane, bis-catechol borate and an additive in a solvent at room temperature under the protection of inert gas, reacting under the illumination of ultraviolet light, and separating and purifying after the reaction to obtain the target compound.
3. The photochemical synthesis process of claim 2, wherein:
the additive is copper chloride.
4. The photochemical synthesis process of claim 2, wherein:
the solvent is acetonitrile.
5. The photochemical synthesis process of claim 2, wherein:
the reaction temperature is 25 ℃, and the reaction time is 20-24 h.
6. The photochemical synthesis process of claim 2, wherein:
the wavelength of the ultraviolet light is 365-.
7. The photochemical synthesis process of claim 2, wherein:
and the separation and purification comprises the steps of adding a proper amount of water into the reaction solution, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, and purifying by column chromatography to obtain the target product.
8. The photochemical synthesis process of claim 7, wherein:
the eluent used in the column chromatography purification is petroleum ether and ethyl acetate which are 10: 1-100: 1, v/v.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819232A (en) * | 2022-10-24 | 2023-03-21 | 山东大学 | Synthetic method of naphthenic acrylate compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150191493A1 (en) * | 2012-07-13 | 2015-07-09 | Universite de Bordeaux | New process for preparing arylboranes by arylation of organoboron compounds |
| CN112746289A (en) * | 2021-01-21 | 2021-05-04 | 合肥工业大学 | Synthesis method of alkyl borate compound |
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- 2021-05-21 CN CN202110555459.8A patent/CN113234099B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150191493A1 (en) * | 2012-07-13 | 2015-07-09 | Universite de Bordeaux | New process for preparing arylboranes by arylation of organoboron compounds |
| CN112746289A (en) * | 2021-01-21 | 2021-05-04 | 合肥工业大学 | Synthesis method of alkyl borate compound |
Non-Patent Citations (3)
| Title |
|---|
| CHAO SHU等: "Metal-free photoinduced C(sp3)-H borylation of alkanes", 《NATURE》, vol. 586, pages 715 * |
| PENGCHENG LIAN等: "Visible-Light-Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2", 《ANGEW. CHEM. INT. ED.》, vol. 59, pages 23605 * |
| 徐玉良 等: "芳基硼酸类化合物合成研究进展", 《有机化学》, vol. 38, pages 738 - 751 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819232A (en) * | 2022-10-24 | 2023-03-21 | 山东大学 | Synthetic method of naphthenic acrylate compound |
| CN115819232B (en) * | 2022-10-24 | 2024-05-10 | 山东大学 | Synthesis method of cycloalkyl acrylate compound |
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