CN110003261A - A kind of Hydroboronation process of organic carbon hydrochlorate - Google Patents
A kind of Hydroboronation process of organic carbon hydrochlorate Download PDFInfo
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- CN110003261A CN110003261A CN201910301524.7A CN201910301524A CN110003261A CN 110003261 A CN110003261 A CN 110003261A CN 201910301524 A CN201910301524 A CN 201910301524A CN 110003261 A CN110003261 A CN 110003261A
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- organic carbon
- carbonate
- beta
- carbon hydrochlorate
- ketone
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 22
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 41
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 41
- 229910000085 borane Inorganic materials 0.000 claims abstract description 30
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000006197 hydroboration reaction Methods 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- PIZLBWGMERQCOC-UHFFFAOYSA-N dibenzyl carbonate Chemical compound C=1C=CC=CC=1COC(=O)OCC1=CC=CC=C1 PIZLBWGMERQCOC-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 5
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- BHPXLRFSKUSDNN-UHFFFAOYSA-N 4-ethyl-1,3-dioxane Chemical class CCC1CCOCO1 BHPXLRFSKUSDNN-UHFFFAOYSA-N 0.000 claims description 4
- -1 hexamethylene Alkane Chemical class 0.000 claims description 4
- MHLPUDQXLUBKRS-UHFFFAOYSA-N 5-methyl-5-propyl-1,3-dioxane Chemical class CCCC1(C)COCOC1 MHLPUDQXLUBKRS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 72
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- FWDBZJBJTDRIIY-UHFFFAOYSA-N CC(C)(C)[K] Chemical compound CC(C)(C)[K] FWDBZJBJTDRIIY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 244000274906 Quercus alba Species 0.000 description 1
- 235000009137 Quercus alba Nutrition 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C07F5/04—Esters of boric acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of Hydroboronation process of organic carbon hydrochlorate, belong to organic synthesis technical field.This method are as follows: under the conditions of anhydrous and oxygen-free, beta-diimine monovalence magnesium compound is added in the mixture of pinacol borine and organic carbon hydrochlorate, reaction is stirred at room temperature.The Hydroboronation process of organic carbon hydrochlorate of the invention, the activity that catalyst beta-diimine monovalence magnesium compound catalysis organic carbon hydrochlorate is reacted with pinacol borine is high, and substrate universality is wide, and catalytic reaction is high-efficient, and efficiency of pcr product is high, has good practicability.
Description
Technical field
The present invention relates to hydroboration technical fields, and in particular to a kind of Hydroboronation process of organic carbon hydrochlorate.
Background technique
Organic carbon hydrochlorate is widely used in synthesis and catalysis frequently as a kind of green solvent
[Schaffner.B, Schaffner.F, Verevkin.S.P, Borner.A, Chem.Rev.2010,110,4554-4581].
In recent years, the reduction of organic carbon hydrochlorate has received widespread attention, because these compounds are easy to from carbon dioxide or an oxygen
Change and generated in carbon, and can further hydrolyze generation carbinol derivatives etc. [Balaraman.E, Gunanathan.C,
Zhang.J, Shimon.L.J, Milstein.D, Nat.Chem.2011,3,609-614；Han.Z, Rong.L, Wu.J,
Zhang.L, Wang.Z, Ding.K, Angew.Chem.Int. Ed.2012,51,13041-13045].On the other hand, pass through two
The cyclic organic carbonates that carbonoxide is synthesized with ethylene oxide or the direct coupling reaction of oxetanes can be used as blocking group
Or the precursor of the corresponding glycol of synthesis, can be used in multi-chemical and material [Crich.D, Vinod.A.U, Picione.J,
J.Org.Chem. 2003,68,8453-8458；Laserna.V, Fiorani.G, Whiteoak.C.J, Martin.E,
Escudero.E. A, Kleij.A.W, Angew.Chem.Int.Ed.2014,53,1-5].Catalytic hydrogenation method is a kind of good
Restore the method that cyclic annular organic carbon hydrochlorate generates various dihydric alcohols.But hydrogen and higher reaction temperature that it needs high pressure inflammable
Degree, usually also need noble ruthenium compound as catalyst [Kim.S.H, Hong.S.H, ACS Catal.2014,4,3630-
3636；Stein.T.V, Meuresch.M, Limper.D, Schmitz.M,M, Coetzee.J, Cole-
Hamilton.D.J, Klankermayer.J, Leitner.W, J.Am. Chem.Soc.2014,136,13217-13225].Mesh
Before, only one report is to use cheap magnesium-yttrium-transition metal manganese compound as catalyst, but the reaction condition is more severe
It carves, needs 1mol% Mn catalyst and 2.5 mol% tert-butyl potassium alcoholates are alkali, in the case where Isosorbide-5-Nitrae-dioxane is solvent, 50 air pressures
Lower hydrogen, 140 DEG C react 16 hours [Zuba., V, Lebedev.Y, Azofra.L.M, Cavallo.L, El-Sepelgy.O,
Ruepin.M, Angew.Chem.Int.Ed.2018,57,13439-13443].It the shortcomings that due to above-mentioned catalytic hydrogenation method, urges
The hydroboration for changing organic carbon hydrochlorate is a kind of important alternative, and only an example report is about catalysis organic carbon at present
The hydroboration of hydrochlorate.Leitner et al. uses magnesium-yttrium-transition metal manganese compound Mn (Ph2PCH2SiMe2)2NH(CO)2Br makees
For catalyst, tert-butyl sodium alkoxide is alkali, reacted at solvent-free lower 90 DEG C 8 hours [Erken.C, Kaithal.A, Sen.S,
Weyherm ü ller.T,M, Werl é .C, Leitner.W, Nat.Commun.2018,9,4521-4529].According to me
It is known, so far, rich content, cheap, environmental protection main group metal catalyst is also never explored in the reaction.For
Further other potential catalysis uses for exploring monovalence magnesium compound, we attempt to be catalyzed organic carbon with monovalence magnesium compound
The hydroboration of hydrochlorate.
Summary of the invention
Goal of the invention: the deficiencies in the prior art are directed to, the object of the present invention is to provide a kind of organic carbon hydrochlorates
Hydroboronation process, catalytic reaction is high-efficient, and the activity of reaction is high, and substrate universality is wide, and efficiency of pcr product is high.Of the invention is another
Purpose is to provide application of the beta-diimine monovalence magnesium compound in organic carbon hydrochlorate hydroboration.
Technical solution: for achieving the above object, the technical solution adopted by the present invention is that:
A kind of Hydroboronation process of organic carbon hydrochlorate adds beta-diimine monovalence magnesium compound under the conditions of anhydrous and oxygen-free
In the mixture for entering pinacol borine and organic carbon hydrochlorate, room temperature reaction；The structure of the beta-diimine monovalence magnesium compound
Formula is as follows:
The Hydroboronation process of the organic carbon hydrochlorate, mole of organic carbon hydrochlorate and beta-diimine monovalence magnesium compound
Than being 100: 1.
The organic carbon hydrochlorate is selected from: ethylene carbonate, propene carbonate, 4- ethyl -1,3- dioxanes -2- ketone, carbon
Sour vinylethylene, 1,3- dioxane -2- ketone, 5,5- diformazan -1,3- dioxanes -2- ketone, propyl -1 5- methyl -5-,
3- dioxanes -2- ketone, dibenzyl carbonate, diphenyl carbonate, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate.
Application of the beta-diimine monovalence magnesium compound in the hydroboration of organic carbon hydrochlorate, the beta-diimine
The structural formula of monovalence magnesium compound is as follows:
Beta-diimine monovalence magnesium compound is added pinacol borine and had by the application under the conditions of anhydrous and oxygen-free
In the mixture of machine carbonate, 6h is reacted at room temperature.
The molar ratio of the application, organic carbon hydrochlorate and beta-diimine monovalence magnesium compound is 100: 1.
The application, the organic carbon hydrochlorate are selected from: ethylene carbonate, propene carbonate, 4- ethyl -1,3- bis-
Oxane -2- ketone, vinylethylene carbonate, 1,3- dioxane -2- ketone, 5,5- diformazan -1,3- dioxanes -2- ketone, 5- first
Base -5- propyl -1,3- dioxanes -2- ketone, dibenzyl carbonate, diphenyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid
Dimethyl ester.
The utility model has the advantages that compared with prior art, preparation method of the invention, reaction process is simple to operation, institute in reaction
Article small toxicity, safety and environmental protection are needed, product is easily purified, yield is high, and can be stored at room temperature.Beta-diimine monovalence magnesium
The hydroboration that object can effectively be catalyzed organic carbon hydrochlorate is closed, catalytic reaction is high-efficient, and the activity of reaction is high, and substrate is general
Adaptive is wide, and efficiency of pcr product is high.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
Beta-diimine monovalence magnesium compound catalysis ethylene carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, ethylene carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): 63.86 (s, 4H, OCH2), 1.18 (s,
24H, BOCMe2).13C{1H } NMR (151MHz, CDCl3): 82.65 (BOCMe of δ2), 64.98 (OCH2), 24.53 (BOCMe2)
.11B{1H } NMR (193MHz, CDCl3): δ 22.24.
It can obtain, product structure formula are as follows:
Embodiment 2
Beta-diimine monovalence magnesium compound catalysis propene carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, propene carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 4.23-4.18 (m, 1H, CH), 3.67
(d,3JHH=4.2Hz, 2H, OCH2), 1.17 (s, 24H, BOCMe2), 1.09 (d,3JHH=6.0 Hz, 3H, Me)13C{1H}NMR
(151MHz, CDCl3): 82.70,82.67 (BOCMe of δ2), 70.32 (OCH2), 69.12 (CH), 24.54,24.53
(BOCMe2), 18.46 (Me)11B{1H } NMR (193MHz, CDCl3): δ 22.19.
It can obtain, product structure formula are as follows:
Embodiment 3
Beta-diimine monovalence magnesium compound catalysis 4- ethyl -1,3- dioxanes -2- ketone is reacted with pinacol borine, mistake
Journey is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, 4- ethyl -1,3- is sequentially added in reaction flask
Then dioxanes -2- ketone 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, pass through nuclear magnetic spectrogram
Obtain the rate of output 99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 4.01-3.97 (m, 1H, CH), 3.75-
3.65 (m, 2H, OCH2), 1.49-1.36 (m, 2H, CH2), 1.17 (s, 24H, BOCMe2), 0.84 (t,3JHH=7.2Hz, 3H,
Me).13C{1H } NMR (151MHz, CDCl3): 82.58,82.44 (BOCMe of δ2), 75.31 (CH), 67.64 (OCH2), 25.21
(CH2), 24.51,24.48 (BOCMe2), 9.40 (Me)11B{1H } NMR (193MHz, CDCl3): 622.24.
It can obtain, product structure formula are as follows:
Embodiment 4
Beta-diimine monovalence magnesium compound catalysis vinylethylene carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, ethylene carbonate Asia second are sequentially added in reaction flask
Then ester 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 5.77-5.71 (m, 1H, CH=CH2),
5.28-5.25 (m, 1H, CH=CH2), 5.09-5.07 (m, 1H, CH=CH2), 4.57-4.55 (m, 1H, CH), 3.77-3.67
(m, 2H, OCH2), 1.17 (s, 24H, BOCMe2).13C{1H } NMR (151MHz, CDCl3): 135.37 (CH=CH of δ2),
116.35 (CH=CH2), 82.66,82.65 (BOCMe2), 74.80 (CH), 67.80 (OCH2), 24.56,24.51
(BOCMe2).11B{1H } NMR (193MHz, CDCl3): δ 22.24.
It can obtain, product structure formula are as follows:
Embodiment 5
Beta-diimine monovalence magnesium compound catalysis 1,3- dioxane -2- ketone is reacted with pinacol borine, process
It is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, 1,3- dioxane are sequentially added in reaction flask
Then hexane-2-one 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtained by nuclear magnetic spectrogram
The rate of output 98%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): 63.85 (t,3JHH=6.6Hz, 4H,
OCH2), 1.78-1.73 (m, 2H, CH2), 1.17 (s, 24H, BOCMe2).13C{1H } NMR (151 MHz, CDCl3): δ 82.59
(BOCMe2), 61.47 (OCH2), 33.26 (CH2), 24.55 (BOCMe2). 11B{1H } NMR (193MHz, CDCl3): δ 22.18.
It can obtain, product structure formula are as follows:
Embodiment 6
Beta-diimine monovalence magnesium compound catalysis 5,5- diformazan -1,3- dioxanes -2- ketone is reacted with pinacol borine,
Process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol% is sequentially added in reaction flask, 5,5- diformazan -1,
Then 3- dioxanes -2- ketone 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, composed by nuclear-magnetism
Scheme to obtain the rate of output 96%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 3.56 (s, 4H, OCH2), 1.17 (s,
24H, BOCMe2), 0.80 (s, 6H, Me)13C{1H } NMR (151MHz, CDCl3): 82.62 (BOCMe of δ2), 70.32 (OCH2),
36.70(C(Me)2), 24.60 (BOCMe2), 20.87 (Me)11B{1H } NMR (193MHz, CDCl3): δ 22.23.
It can obtain, product structure formula are as follows:
Embodiment 7
Beta-diimine monovalence magnesium compound is catalyzed 5- methyl -5- propyl -1,3- dioxanes -2- ketone and pinacol borine
Reaction, process are as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, 5- methyl -5- third is sequentially added in reaction flask
Then base -1,3- dioxanes -2- ketone 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, pass through core
Magnetic spectrum figure obtains the rate of output 99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): 63.58 (d,3JHH=8.4Hz, 4H,
OCH2), 1.18-1.15 (overlap, 28H, BOCMe2, CH2), 0.79 (t,3JHH=6.6Hz, 3H, CH2Me), 0.75 (s,
3H, CMe)13C{1H } NMR (151MHz, CDCl3): 82.46 (BOCMe of δ2), 68.71 (OCH2), 39.00 (CMe), 35.94,
(CCH2), 24.49 (BOCMe2), 18.22 (CMe), 16.32 (CH2Me), 14.84 (CH2Me).11B{1H } NMR (193MHz,
CDCl3): δ 22.18.
It can obtain, product structure formula are as follows:
Embodiment 8
Beta-diimine monovalence magnesium compound catalysis dibenzyl carbonate is reacted with pinacol borine, and process is as follows:
In glove box, p- diimine monovalence magnesium compound 1mol%, dibenzyl carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 7.23-7.12 (m, 5H, Ar-H), 4.81
(s, 2H, OCH2), 1.14 (s, 12H, BOCMe2).13C{1H } NMR (151MHz, CDCl3): δ 139.14,128.11,127.20,
126.56 (Ar-C), 82.70 (BOCMe2), 66.49 (OCH2), 24.45 (BOCMe2).11B{1H } NMR (193MHz, CDCl3):
622.33.
It can obtain, product structure formula are as follows:
Embodiment 9
Beta-diimine monovalence magnesium compound catalysis diphenyl carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, diphenyl carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
97%.
Product is characterized, data are as follows:1HNMR (600MHz, CDCl3): δ 7.18-7.15 (m, 2H, Ar-H), 7.00-
6.92 (m, 3H, Ar-H), 1.15 (s, 12H, BOCMe2).13C{1H } NMR (151 MHz, CDCl3): δ 153.46,129.24,
123.01,119.48 (Ar-C), 83.43 (BOCMe2), 24.58 (BOCMe2).11B{1H } NMR (193MHz, CDCl3): δ
22.32.
It can obtain, product structure formula are as follows:
Embodiment 10
Beta-diimine monovalence magnesium compound catalysis diethyl carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, diethyl carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
99%.
Product is characterized, data are as follows:1HNMR (600MHz, CDCl3): δ 3.81 (q,3JHH=7.2Hz, 2H,
OCH2), 1.17 (s, 12H, BOCMe2), 1.13 (t,3JHH=7.2Hz, 3H, Me)13C{1H } NMR (151MHz, CDCl3): δ
82.44(BOCMe2), 60.49 (OCH2), 24.50 (BOCMe2), 17.11 (Me)11B{1H } NMR (193MHz, CDCl3):
622.04.
It can obtain, product structure formula are as follows:
Embodiment 11
Beta-diimine monovalence magnesium compound catalysis methyl ethyl carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, methyl ethyl carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
98%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 3.81 (q,3JHH=7.2Hz, 2H,
OCH2), 1.17 (s, 12H, BOCMe2), 1.13 (t,3JHH=7.2Hz, 3H, Me)13C{1H } NMR (151MHz, CDCl3): δ
82.44(BOCMe2), 60.49 (OCH2), 24.50 (BOCMe2), 17.11 (Me)11B{1H } NMR (193MHz, CDCl3): δ
22.04.
It can obtain, product structure formula are as follows:
Embodiment 12
Beta-diimine monovalence magnesium compound catalysis dimethyl carbonate is reacted with pinacol borine, and process is as follows:
In glove box, beta-diimine monovalence magnesium compound 1mol%, dimethyl carbonate are sequentially added in reaction flask
Then 0.4mmol, pinacol borine 1.6mmol are moved out glove box, stir 6h, obtain the rate of output by nuclear magnetic spectrogram
99%.
Product is characterized, data are as follows:1H NMR (600MHz, CDCl3): δ 3.51 (s, 3H, Me), 1.18 (s, 12H,
BOCMe2).13C{1H } NMR (151MHz, CDCl3): 82.63 (BOCMe of δ2), 52.43 (Me), 24.53 (BOCMe2).11B{1H}
NMR (193MHz, CDCl3): δ 22.20.
It can obtain, product structure formula are as follows:
Claims (7)
1. a kind of Hydroboronation process of organic carbon hydrochlorate, which is characterized in that under the conditions of anhydrous and oxygen-free, by beta-diimine monovalence magnesium
Compound is added in the mixture of pinacol borine and organic carbon hydrochlorate, room temperature reaction；The beta-diimine monovalence magnesium chemical combination
The structural formula of object is as follows:
2. the Hydroboronation process of organic carbon hydrochlorate according to claim 1, which is characterized in that organic carbon hydrochlorate and β-two are sub-
The molar ratio of amine monovalence magnesium compound is 100: 1.
3. the Hydroboronation process of organic carbon hydrochlorate according to claim 1, which is characterized in that the organic carbon hydrochlorate choosing
From: ethylene carbonate, propene carbonate, 4- ethyl -1,3- dioxanes -2- ketone, vinylethylene carbonate, 1,3- dioxa hexamethylene
Alkane -2- ketone, 5,5- diformazan -1,3- dioxanes -2- ketone, 5- methyl -5- propyl -1,3- dioxanes -2- ketone, dibenzyl carbonate,
Diphenyl carbonate, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate.
4. application of the beta-diimine monovalence magnesium compound in the hydroboration of organic carbon hydrochlorate, the beta-diimine monovalence
The structural formula of magnesium compound is as follows:
5. application according to claim 4, which is characterized in that under the conditions of anhydrous and oxygen-free, by beta-diimine monovalence magnesium
It closes object to be added in the mixture of pinacol borine and organic carbon hydrochlorate, reacts at room temperature 6h.
6. application according to claim 5, which is characterized in that organic carbon hydrochlorate rubs with beta-diimine monovalence magnesium compound
You are than being 100: 1.
7. application according to claim 5, which is characterized in that the organic carbon hydrochlorate is selected from: ethylene carbonate, carbonic acid
Acrylic ester, 4- ethyl -1,3- dioxanes -2- ketone, vinylethylene carbonate, 1,3- dioxane -2- ketone, 5,5- diformazans -
1,3- dioxanes -2- ketone, 5- methyl -5- propyl -1,3- dioxanes -2- ketone, dibenzyl carbonate, diphenyl carbonate, carbonic acid two
Ethyl ester, methyl ethyl carbonate, dimethyl carbonate.
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Non-Patent Citations (3)
| Title |
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| CHEE KOON NG ET AL: "A binary catalyst system of a cationic Ru–CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide", 《CHEM. COMMUN.》 * |
| DAFYDD D. L. JONES ET AL: "The complex reactivity of β-diketiminato magnesium(I) dimers towards pinacolborane: implications for catalysis", 《DALTON TRANS.》 * |
| XU CAO ET AL: "Magnesium-catalyzed hydroboration of organic carbonates, carbon dioxide and esters", 《DALTON TRANS.》 * |
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