CN108358959A - A kind of Hydroboronation process of isocyanide ester - Google Patents
A kind of Hydroboronation process of isocyanide ester Download PDFInfo
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- CN108358959A CN108358959A CN201810079463.XA CN201810079463A CN108358959A CN 108358959 A CN108358959 A CN 108358959A CN 201810079463 A CN201810079463 A CN 201810079463A CN 108358959 A CN108358959 A CN 108358959A
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- China
- Prior art keywords
- beta
- diimine
- magnesium compound
- isocyanide ester
- magnesium
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- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 isocyanide ester Chemical class 0.000 title claims abstract description 27
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 50
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 34
- 229910000085 borane Inorganic materials 0.000 claims abstract description 19
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical group [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- PHSPFUQAZNIVCH-UHFFFAOYSA-M [Mg].[I-].C[N+]1=CC=CC=C1 Chemical compound [Mg].[I-].C[N+]1=CC=CC=C1 PHSPFUQAZNIVCH-UHFFFAOYSA-M 0.000 claims description 6
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical class ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 claims description 4
- MGOLNIXAPIAKFM-UHFFFAOYSA-N 2-isocyanato-2-methylpropane Chemical compound CC(C)(C)N=C=O MGOLNIXAPIAKFM-UHFFFAOYSA-N 0.000 claims description 4
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 claims description 4
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 3
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- HJHZRZFONUPQAA-UHFFFAOYSA-N 2-isocyanato-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C(C)=C1 HJHZRZFONUPQAA-UHFFFAOYSA-N 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- WHULDTBQXVKIHX-UHFFFAOYSA-N propan-2-yl cyanate Chemical compound CC(C)OC#N WHULDTBQXVKIHX-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000006197 hydroboration reaction Methods 0.000 description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GSLTVFIVJMCNBH-UHFFFAOYSA-N 2-isocyanatopropane Chemical compound CC(C)N=C=O GSLTVFIVJMCNBH-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 150000002527 isonitriles Chemical class 0.000 description 3
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/12—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton being acyclic
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of Hydroboronation process of isocyanide ester：Under the conditions of anhydrous and oxygen-free, beta diimine monovalence magnesium compound is dissolved in solvent, pinacol borine is added, adds isocyanide ester, 60 DEG C are reacted 1.5 12 hours.The Hydroboronation process of the isocyanide ester of the present invention, the activity that beta diimine monovalence magnesium compound catalyst isocyanide ester is reacted with pinacol borine is high, and substrate universality is wide.
Description
Technical field
The present invention relates to the hydroboration technical fields of isocyanide ester, and in particular to a kind of Hydroboronation process of isocyanide ester.
Background technology
The reduction of carbonyl important role in organic synthesis and industrial production, hydroboration catalysis receive extensively
Concern because storage is stablized and be easy to borine relatively, it is avoided using highly flammable hydrogen.And the boron ester generated exists
Intermediate [Ruppert A.M., Weinberg K., Palkovits are important in chemicals and material
R.Angew.Chem.,Int.Ed.,2012,51,2564；Bozell J.J.,Petersen G.R.,Green Chem.,
2010,12,539；P.N.R.,Osmundsen C.M.,Christensen C.H.,Taarning
E.Angew.Chem.Int.Ed.,2011,50,10502].In past twoth century, many magnesium-yttrium-transition metals have been catalyzed boron
Hydrogenation [ChongC.C., Kinjo R.ACS Catal.2015,5,3238].In recent years, the hydroboration of main group metal
Receive extensive research, such as magnesium, calcium, germanium, selenium, aluminium, phosphorus, [the Weetman C., AnkerM.D., Arrowsmith such as alkali metal
M.,Hill M.S.,Kociok-KohnG.,Liptrot D.J.,Mahon M.F.Chem.Sci.2016,7,628；
Fohlmeister L.,Stasch A.Chem.Eur.J.2016,22,10235；Mukherjee D.,Osseili H.,
Spaniol T.P.,Okuda J.J.Am.Chem.Soc.2016,138,10790；Yang Z.,Zhong M.,Ma X.,De
S.,Anusha C.,Parameswaran P.,Roesky H.W.Angew.Chem.Int.Ed.2015,54,10225].Although
The report of hydroboration is more, but the hydroboration of isocyanide ester report is less.As far as we know, the isonitrile reported
The hydroboration of acid esters only has two, and all using main group metal magnesium as catalyst.When 2016, the boron of the magnesium such as Okuda
Compound be efficiently catalyzed isocyanide ester hydroboration [Mukherjee D., Shirase S., Spaniol T.P.,
Mashima K.,Okuda J.Chem.Commun.,2016,52,13155].Second is that 2017, the butylation of the magnesium such as Hill
Close the hydroboration that object has been catalyzed a variety of isocyanide esters, effect preferably [Yang Y.；Anker M.D.,Fang J.,Mahon
M.F.,Maron L.,Weetman C.,Hill M.S.Chem.Sci.,2017,8,3529]。
On the other hand, monovalence magnesium compound is widely used [Jones C., Nature in organic and Inorganic synthese
Reviews Chemistry,2017,1,59；Jones C.,Stasch A.Top.Organomet.Chem.2013,45,73].
Monovalence magnesium can restore many unsaturated substrates, such as Benzophenone, cyclo-octatetraene, phenyl-hexafluoride, azide etc..Monovalence magnesium can be used as
Mild reducing agent, reduction second, 13,14,15 compounds of group etc..Monovalence magnesium can also be reacted with some gas molecules,
Such as sulfur dioxide, carbon dioxide, carbon monoxide etc..
The application of the related monovalence magnesium compound of existing report is all stoichiometry, but monovalence magnesium compound catalytic amount
Application do not report still.
Invention content
Goal of the invention：For the deficiencies in the prior art, the object of the present invention is to provide a kind of boron of isocyanide ester
Method for hydrogenation, catalytic reaction is efficient, and the activity of reaction is high, and substrate universality is wide, and efficiency of pcr product is high.
Technical solution：For achieving the above object, the technical solution adopted by the present invention is：
A kind of Hydroboronation process of isocyanide ester：Catalyst used in reaction is beta-diimine monovalence magnesium compound,
The beta-diimine monovalence magnesium compound, structural formula are as follows：
The Hydroboronation process of the isocyanide ester, it is under the conditions of anhydrous and oxygen-free, beta-diimine monovalence magnesium compound is molten
In solvent, pinacol borine is added, adds isocyanide ester, 60 DEG C are reacted 1.5-12 hours.
The molar ratio of the Hydroboronation process of the isocyanide ester, isocyanide ester and beta-diimine monovalence magnesium compound is
10:1。
The isocyanide ester includes isopropyl isocyanate, ethyl isocyanate, t-butylisocyanate, cyclohexyl isocyanic acid
Ester, 4- chlorophenyl isocyanates, 2,4,6- trimethylbenzene based isocyanates.
A kind of preparation method of the beta-diimine monovalence magnesium compound, includes the following steps：
(1) under the conditions of anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand is dissolved in diethyl ether solution, -80~-40
DEG C, methylpyridinium iodide magnesium is added dropwise above-mentioned solution, and room temperature reaction 8~for 24 hours.Obtain the iodide of beta-diimine magnesium；Wherein β-two
Imine ligand, methylpyridinium iodide magnesium molar ratio be 1:1-1.2；Its reaction equation is as follows：
(2) under the conditions of anhydrous and oxygen-free, in single port reaction tube, the iodide of beta-diimine magnesium are dissolved in toluene solution, transfer
To sodium mirror, 3~5d is reacted, is filtered, concentration, it is beta-diimine monovalence magnesium compound to obtain yellow crystals.Wherein beta-diimine magnesium
Iodide, metallic sodium molar ratio be 1:5-20；Its reaction equation is as follows：
Advantageous effect：Compared with prior art, method of the invention, reaction process is simple to operation, required thing in experiment
Product small toxicity, safety and environmental protection, product is easily purified, yield is high, and can be stored at room temperature, beta-diimine monovalence magnesium compound energy
The hydroboration of enough effective catalysis isocyanide esters, catalytic reaction is efficient, and the activity of reaction is high, and substrate universality is wide, production
Object yield is high.
Specific implementation mode
With reference to embodiment, the invention will be further described.In following embodiment, filter, drain, extracting, concentrating,
The operating procedures such as freezing and crystallizing, separation belong to the prior art, and those skilled in the art can give according to the property of actual product
Selection.
Embodiment 1
The preparation of the iodide of beta-diimine magnesium, process are as follows：
Under anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand 3.28mmol is dissolved in 25mL diethyl ether solutions, and -80
DEG C, above-mentioned solution is added dropwise in methylpyridinium iodide magnesium 3.92mmol, and room temperature reaction is for 24 hours.Filtering, solid are drained, and filtrate is concentrated into
5mL, obtains clear crystal, and solid and crystal quality are 1.63g, yield 94%.M.p.271-273℃.Nuclear magnetic resoance spectrum：1H
NMR(600MHz,C6D6):δ6.99-6.91(m,6H,Ar-H),4.88(s,1H,CH),3.12(s,4H,OCH2CH3),2.65
(s,6H,CH3),2.08(s,6H,CH3),1.55(s,6H,NCCH3),0.48(s,6H,OCH2CH3)ppm.13C{1H}NMR
(151MHz,C6D6):δ168.87(NCCH3), 147.75,131.57,129.56,124.76 (Ar-C), 95.31 (=CH),
65.96(OCH2CH3),23.52(OCH2CH3),21.09(NCCH3),18.89,13.15(CH3)ppm.
Embodiment 2
The preparation of the iodide of beta-diimine magnesium, process are as follows：
Under anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand 3.28mmol is dissolved in 25mL diethyl ether solutions, and -60
DEG C, above-mentioned solution is added dropwise in methylpyridinium iodide magnesium 3.60mmol, reacts at room temperature 15h.Filtering, solid are drained, and filtrate is concentrated into
5mL, obtains clear crystal, and solid and crystal quality are 1.61g, yield 92%.M.p.271-273℃.Nuclear magnetic resoance spectrum：1H
NMR(600MHz,C6D6):δ6.99-6.91(m,6H,Ar-H),4.88(s,1H,CH),3.12(s,4H,OCH2CH3),2.65
(s,6H,CH3),2.08(s,6H,CH3),1.55(s,6H,NCCH3),0.48(s,6H,OCH2CH3)ppm.13C{1H}NMR
(151MHz,C6D6):δ168.87(NCCH3), 147.75,131.57,129.56,124.76 (Ar-C), 95.31 (=CH),
65.96(OCH2CH3),23.52(OCH2CH3),21.09(NCCH3),18.89,13.15(CH3)ppm.
Embodiment 3
The preparation of the iodide of beta-diimine magnesium, process are as follows：
Under anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand 3.28mmol is dissolved in 25mL diethyl ether solutions, and -40
DEG C, above-mentioned solution is added dropwise in methylpyridinium iodide magnesium 3.27mmol, reacts at room temperature 15h.Filtering, solid are drained, and filtrate is concentrated into
5mL, obtains clear crystal, and solid and crystal quality are 1.63g, yield 94%.M.p.271-273℃.Nuclear magnetic resoance spectrum：1H
NMR(600MHz,C6D6):δ6.99-6.91(m,6H,Ar-H),4.88(s,1H,CH),3.12(s,4H,OCH2CH3),2.65
(s,6H,CH3),2.08(s,6H,CH3),1.55(s,6H,NCCH3),0.48(s,6H,OCH2CH3)ppm.13C{1H}NMR
(151MHz,C6D6):δ168.87(NCCH3), 147.75,131.57,129.56,124.76 (Ar-C), 95.31 (=CH),
65.96(OCH2CH3),23.52(OCH2CH3),21.09(NCCH3),18.89,13.15(CH3)ppm.
Embodiment 4
Prepared by beta-diimine monovalence magnesium compound, process is as follows：
Under anhydrous and oxygen-free, in single port reaction tube, the iodide 2.83mmol of beta-diimine magnesium is dissolved in 30mL toluene solutions
In, it is transferred in 14.15mmol sodium mirrors, reacts 5d.Filtering, filtrate is concentrated into 2mL, obtain yellow crystals [(XylNacnac)
Mg}2], quality 0.56g, yield 60%.M.p.177-179℃.Nuclear magnetic resoance spectrum：1H NMR(600MHz,C6D6):δ
7.03(d,JH-H=7.2Hz, 8H, Ar-H), 6.97 (t, JH-H=7.2Hz, 4H, Ar-H), 4.77 (s, 2H, CH), 1.91 (s,
24H,CH3),1.50(s,12H,NCCH3)ppm.13C{1H}NMR(151MHz,C6D6):166.31(NCCH3),148.04,
(131.81,128.46,124.15 Ar-C), 95.36 (=CH), 23.13 (NCCH3),19.31(CH3)ppm.
Embodiment 5
Prepared by beta-diimine monovalence compound magnesium, process is as follows：
Under anhydrous and oxygen-free, in single port reaction tube, the iodide 2.83mmol of beta-diimine magnesium is dissolved in 30mL toluene solutions
In, it is transferred in 28.3mmol sodium mirrors, reacts 4d.Filtering, filtrate is concentrated into 2mL, obtain yellow crystals [(XylNacnac)
Mg}2], quality 0.54g, yield 59%.M.p.177-179℃.Nuclear magnetic resoance spectrum：1H NMR(600MHz,C6D6):δ
7.03(d,JH-H=7.2Hz, 8H, Ar-H), 6.97 (t, JH-H=7.2Hz, 4H, Ar-H), 4.77 (s, 2H, CH), 1.91 (s,
24H,CH3),1.50(s,12H,NCCH3)ppm.13C{1H}NMR(151MHz,C6D6):166.31(NCCH3),148.04,
(131.81,128.46,124.15 Ar-C), 95.36 (=CH), 23.13 (NCCH3),19.31(CH3)ppm.
Embodiment 6
Prepared by beta-diimine monovalence magnesium compound, process is as follows：
Under anhydrous and oxygen-free, in single port reaction tube, the iodide 2.83mmol of beta-diimine magnesium is dissolved in 30mL toluene solutions
In, it is transferred in 56.6mmol sodium mirrors, reacts 3d.Filtering, filtrate is concentrated into 2mL, obtain yellow crystals [(XylNacnac)
Mg}2], quality 0.56g, yield 60%.M.p.177-179℃.Nuclear magnetic resoance spectrum：1H NMR(600MHz,C6D6):δ
7.03(d,JH-H=7.2Hz, 8H, Ar-H), 6.97 (t, JH-H=7.2Hz, 4H, Ar-H), 4.77 (s, 2H, CH), 1.91 (s,
24H,CH3),1.50(s,12H,NCCH3)ppm.13C{1H}NMR(151MHz,C6D6):166.31(NCCH3),148.04,
(131.81,128.46,124.15 Ar-C), 95.36 (=CH), 23.13 (NCCH3),19.31(CH3)ppm.
Embodiment 7
Beta-diimine monovalence magnesium compound catalysis isopropyl isocyanate is reacted with pinacol borine, and process is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.1mmol, isopropyl isocyanate 1mmol and pinacol borine 3mmol, are then moved out glove box, and 60 DEG C of reaction 1.5h lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 90%.
Embodiment 8
Beta-diimine monovalence magnesium compound catalysis ethyl isocyanate is reacted with pinacol borine, and process is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.1mmol, ethyl isocyanate 1mmol and pinacol borine 3mmol, are then moved out glove box, and 60 DEG C of reaction 12h pass through
Nuclear magnetic spectrogram obtains the rate of output 88%.
Embodiment 9
Beta-diimine monovalence magnesium compound catalysis propyl isocyanate is reacted with pinacol borine, and process is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.1mmol, propyl isocyanate 1mmol and pinacol borine 3mmol, are then moved out glove box, and 60 DEG C of reaction 12h pass through
Nuclear magnetic spectrogram obtains the rate of output 85%.
Embodiment 10
Beta-diimine monovalence magnesium compound catalysis t-butylisocyanate is reacted with pinacol borine, and process is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.1mmol, t-butylisocyanate 1mmol and pinacol borine 3mmol, are then moved out glove box, and 60 DEG C of reaction 3h lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 89%.
Embodiment 11
Beta-diimine monovalence magnesium compound catalysis cyclohexyl isocyanate is reacted with pinacol borine, and process is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.1mmol, cyclohexyl isocyanate 1mmol and pinacol borine 3mmol are moved out glove box, 60 DEG C are reacted 3.5h,
The rate of output 80% is obtained by nuclear magnetic spectrogram.
Embodiment 12
Beta-diimine monovalence magnesium compound catalysis 4- chlorophenyl isocyanates are reacted with pinacol borine, and process is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.1mmol, 4- chlorophenyl isocyanate 1mmol and pinacol borine 3mmol are moved out glove box, 60 DEG C are reacted 2h,
The rate of output 93% is obtained by nuclear magnetic spectrogram.
Embodiment 13
Beta-diimine monovalence magnesium compound 2,4,6- trimethylbenzene based isocyanates of catalysis are reacted with pinacol borine, mistake
Journey is as follows：
In glove box, equipped with 0.5mL C6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.1mmol, 2,4,6- trimethylbenzene based isocyanate 1mmol and pinacol borine 3mmol, are then moved out glove box, and 60
DEG C reaction 3h, the rate of output 91% is obtained by nuclear magnetic spectrogram.
Claims (6)
1. a kind of Hydroboronation process of isocyanide ester, it is characterised in that：Catalyst used in reaction is beta-diimine monovalence
Magnesium compound, the beta-diimine monovalence magnesium compound, structural formula are as follows：
2. the Hydroboronation process of isocyanide ester according to claim 1, it is characterised in that：It, will under the conditions of anhydrous and oxygen-free
Beta-diimine monovalence magnesium compound is dissolved in solvent, and pinacol borine is added, and adds isocyanide ester, and 60 DEG C of reaction 1.5-12 are small
When.
3. the Hydroboronation process of isocyanide ester according to claim 2, it is characterised in that：Isocyanide ester and beta-diimine one
The molar ratio of valence magnesium compound is 10:1.
4. the Hydroboronation process of isocyanide ester according to claim 2, it is characterised in that：The isocyanide ester includes different
Cyanic acid isopropyl ester, ethyl isocyanate, t-butylisocyanate, cyclohexyl isocyanate, 4- chlorophenyl isocyanates, 2,4,6- tri-
Methylphenyl isocyanate.
5. the Hydroboronation process of isocyanide ester according to claim 2, it is characterised in that：The solvent is C6D6。
6. a kind of method preparing beta-diimine monovalence magnesium compound described in claim 1, which is characterized in that including following step
Suddenly：
(1) under the conditions of anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand is dissolved in diethyl ether solution, -80~-40 DEG C, first
Base magnesium iodide is added dropwise above-mentioned solution, and room temperature reaction 8~for 24 hours；Obtain the iodide of beta-diimine magnesium；Wherein, beta-diimine
Ligand, methylpyridinium iodide magnesium molar ratio be 1:1~1.2；
(2) under the conditions of anhydrous and oxygen-free, in single port reaction tube, the iodide of beta-diimine magnesium are dissolved in toluene solution, are transferred to sodium
Mirror reacts 3~5d, filters, concentration, and it is beta-diimine monovalence magnesium compound to obtain yellow crystals；Wherein, the iodine of beta-diimine magnesium
Compound, metallic sodium molar ratio are 1:5~20.
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| CN111410668A (en) * | 2019-11-19 | 2020-07-14 | 南京林业大学 | β -diimine zinc-lithium bimetallic compound, preparation method thereof and application thereof in hydroboration of isocyanate |
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| CN111410668A (en) * | 2019-11-19 | 2020-07-14 | 南京林业大学 | β -diimine zinc-lithium bimetallic compound, preparation method thereof and application thereof in hydroboration of isocyanate |
| CN111410668B (en) * | 2019-11-19 | 2022-02-25 | 南京林业大学 | Beta-diimine zinc lithium bimetallic compound, preparation method thereof and application thereof in hydroboration of isocyanate |
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