CN108707162B - Keto hydroboration reaction method under catalyst-free and solvent-free conditions - Google Patents
Keto hydroboration reaction method under catalyst-free and solvent-free conditions Download PDFInfo
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- CN108707162B CN108707162B CN201810456423.2A CN201810456423A CN108707162B CN 108707162 B CN108707162 B CN 108707162B CN 201810456423 A CN201810456423 A CN 201810456423A CN 108707162 B CN108707162 B CN 108707162B
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 27
- 229930194542 Keto Natural products 0.000 title description 2
- 125000000468 ketone group Chemical group 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 150000002576 ketones Chemical class 0.000 claims abstract description 23
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 17
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 8
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 6
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims description 5
- UUWJBXKHMMQDED-UHFFFAOYSA-N 1-(3-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Cl)=C1 UUWJBXKHMMQDED-UHFFFAOYSA-N 0.000 claims description 4
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 4
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 claims description 4
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 claims description 4
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 claims description 4
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims description 4
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 claims description 3
- HEOVGVNITGAUKL-UHFFFAOYSA-N 3-Methyl-1-phenyl-1-butanone Chemical compound CC(C)CC(=O)C1=CC=CC=C1 HEOVGVNITGAUKL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 104
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- -1 aldehyde ketone Chemical class 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 238000004607 11B NMR spectroscopy Methods 0.000 description 17
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 17
- 239000004327 boric acid Substances 0.000 description 16
- 230000002194 synthesizing effect Effects 0.000 description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- ZDQWVKDDJDIVAL-UHFFFAOYSA-N catecholborane Chemical compound C1=CC=C2O[B]OC2=C1 ZDQWVKDDJDIVAL-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004984 proton decoupled 19F NMR spectroscopy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a ketone hydroboration reaction method under the condition of no catalyst and no solvent. The ketone hydroboration reaction is carried out under the condition of no catalyst and no solvent, and is a brand new method. The method is simple and easy to operate, the required articles have low toxicity, the method is safe and environment-friendly, the product yield is high, and the product can be stored at room temperature. The method has the advantages of high reaction activity, high yield and wide substrate universality, and is particularly suitable for hydroboration reaction of ketone.
Description
Technical Field
The invention relates to the technical field of ketohydroboration reaction, in particular to a ketohydroboration reaction method under the condition of no catalyst and no solvent.
Background
The aldehyde ketone hydroboration reaction is an important organic synthesis reaction, not only can synthesize various organic boron compounds, but also can hydrolyze into a plurality of important alcohols [ Chong.C.C.C, Kinjo.R, ACS Catal.2015,5, 3238-3259; Geier.S.J., Vogels.C.M, Westcott.S.A, ACS Symp.Ser.2016,1236,209-225 ]. In addition, boronizing agents such as pinacol borane and catechol borane are very stable and easy to handle, avoiding the use of highly flammable and explosive hydrogen and other metal hydrides. Therefore, the synthesis of new catalysts for catalyzing aldehyde ketone hydroboration reaction is receiving wide attention. Catalysts for the aldoketonic hydroboration reaction to date include transition metal compounds [ das.u.k, highman.c.s, gabidullin.b, hein.j.e, baker.r.t, ACS cat.2018, 8, 1076-1081; wang.w, shen.x, zhao.f, jiang.h, yao.w, pullarkat.s.a, xu.l, ma.m, j.org.chem.2018,83,69-74, main group compounds [ yadav.s, pahar.s, sen.s.s, chem.commu.2017, 53, 4562-; k, china.p, greene.f.x, lin.w, j.am.chem.soc.2016,138,7488-7491, lewis acid-base pairs [ schneider.j, sindlinger.c.p, freitag.s.m, schubert.h, wesemann.l, angelw.chem.int.ed.2017, 56, 333-; Lawson.J.R, Wilkins.L.C, Melen.R.L, chem.Eur.J.2017,23,10997-11000 ]. Although many catalysts are available for catalyzing the aldoketonehydroboration reaction, they contain somewhat metals or organics and are not green chemistries. Moreover, many catalysts are difficult to synthesize and store and are not suitable for large-scale production, which limits their industrial development. Therefore, the method which is green and environment-friendly and can be synthesized in a large scale is imperative to catalyze the aldehyde ketone hydroboration reaction.
On the other hand, hydroboration reaction under the condition of no catalyst and no solvent is only reported. In the last century, Knochel and Piers reported hydroboration of alkenes and alkynes without catalyst [ Tucker. C.E, Davidson. J, Knochel, P, J.org. chem.1992,57, 3482-; parks.D.J., Piers.W.E, Yap.G.P.A, organometallics.1998,17, 5492-5503; parks.D.J., Piers.W.E, Tetrahedron,1998,54,15469-]. Recently, Bertrand et al reported the dehydrocoupling of amines, alcohols, thiols, etc. with pinacolborane and 9-borabicyclo (3,3,1) -nonane [ Romero. E.A, Peltier. J.L, Jazzar. R, Bertrand. G, chem. Commun.2016,52,10563-]. Shortly before, Hreczycho et al reported hydroboration of aldehydes in the absence of catalysts and solvents [ Stachylowiak. H,
J,Kuciński.K,Hreczycho.G,Green Chem.2018,ahead of print.DOI:10.1039/C8GC00042E]。
generally, the hydroboration reaction of ketone is more difficult than that of aldehyde, and the hydroboration reaction of ketone requires more severe conditions mainly because the steric hindrance of ketone is larger than that of aldehyde. The catalyst is reported to catalyze hydroboration of aldehyde ketone and hydroboration reaction of aldehyde under the condition of no catalyst and no solvent, but the hydroboration reaction of ketone under the condition of no catalyst and no solvent is not reported.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a hydroboration reaction of ketone under the condition of no catalyst and no solvent, which has the advantages of simple operation, high reaction activity, high yield, wide substrate universality and the like.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the technical scheme that:
a ketone hydroboration reaction method under the condition of no catalyst and no solvent is characterized in that ketone and pinacol borane are sequentially added into a nuclear magnetic tube in a glove box, then the nuclear magnetic tube is removed from the glove box to react, and the ketone hydroboration reaction can be realized under the condition of no catalyst and no solvent.
According to the ketone hydroboration reaction method under the catalyst-free and solvent-free conditions, the molar ratio of the ketone to the pinacol borane is 1: 2.
The ketone is selected from acetophenone, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methoxyacetophenone, benzophenone, isobutyl phenyl ketone, 4-fluoroacetophenone, 4-chloroacetophenone, 4-bromoacetophenone, 3-chloroacetophenone, 2-chloroacetophenone, 4-nitroacetophenone, 2-acetylfuran, 2-acetylthiophene, cycloheptanone and 1-adamantane ketone.
The ketone hydroboration reaction method under the catalyst-free and solvent-free conditions is characterized in that the reaction is carried out after the reaction is carried out in a glove box at the reaction temperature of 140 ℃.
According to the ketone hydroboration reaction method under the catalyst-free and solvent-free conditions, the reaction is carried out after the reaction is carried out in a glove box, and the reaction time is 0.8-9 h.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1) the ketone hydroboration reaction is carried out under the condition of no catalyst and no solvent, and is a brand new method.
2) The method of the invention is simple and easy to operate, the toxicity of the required articles is low, the method is safe and environment-friendly, the product yield is high, and the product can be stored at room temperature.
3) The method has the advantages of high reaction activity, high yield and wide substrate universality, and is particularly suitable for the hydroboration reaction of ketone.
Drawings
FIG. 1 is a drawing of the product of example 11H NMR chart;
FIG. 2 is a photograph of the product of example 113C NMR chart;
FIG. 3 is a photograph of the product of example 111B NMR chart;
FIG. 4 is a photograph of the product of example 21H NMR chart;
FIG. 5 is a photograph of the product of example 213C NMR chart;
FIG. 6 is a graph of a product of example 2Of an object11B NMR chart;
FIG. 7 is a photograph of the product of example 31H NMR chart;
FIG. 8 is a photograph of the product of example 313C NMR chart;
FIG. 9 is a photograph of the product of example 311B NMR chart;
FIG. 10 is a photograph of the product of example 41H NMR chart;
FIG. 11 is a photograph of the product of example 413C NMR chart;
FIG. 12 is a photograph of the product of example 411B NMR chart;
FIG. 13 is a photograph of the product of example 51H NMR chart;
FIG. 14 is a photograph of the product of example 513C NMR chart;
FIG. 15 is a photograph of the product of example 511B NMR chart;
FIG. 16 is a photograph of the product of example 61H NMR chart;
FIG. 17 is a photograph of the product of example 613C NMR chart;
FIG. 18 is a photograph of the product of example 611B NMR chart;
FIG. 19 is a photograph of the product of example 71H NMR chart;
FIG. 20 is a photograph of the product of example 713C NMR chart;
FIG. 21 is a photograph of the product of example 711B NMR chart;
FIG. 22 is a photograph of the product of example 81H NMR chart;
FIG. 23 is a photograph of the product of example 813C NMR chart;
FIG. 24 is a photograph of the product of example 811B NMR chart;
FIG. 25 is a photograph of the product of example 819F NMR chart;
FIG. 26 is the product of example 91H NMR chart;
FIG. 27 is a photograph of the product of example 913C NMR chart;
FIG. 28 is the product of example 911B NMR chart;
FIG. 29 is a photograph of the product of example 101H NMR chart;
FIG. 30 is a photograph of the product of example 1013C NMR chart;
FIG. 31 is a photograph of the product of example 1011B NMR chart;
FIG. 32 is the product of example 111H NMR chart;
FIG. 33 is the product of example 1113C NMR chart;
FIG. 34 is a photograph of the product of example 1111B NMR chart;
FIG. 35 is a photograph of the product of example 121H NMR chart;
FIG. 36 is a photograph of the product of example 1213C NMR chart;
FIG. 37 is a photograph of the product of example 1211B NMR chart;
FIG. 38 is a depiction of the product of example 1313C NMR chart;
FIG. 39 is the product of example 1313C NMR chart;
FIG. 40 is the product of example 1311B NMR chart;
FIG. 41 is a photograph of the product of example 141H NMR chart;
FIG. 42 is a graph of the product of example 1413C NMR chart;
FIG. 43 is a photograph of the product of example 1411B NMR chart;
FIG. 44 is a graphic representation of the product of example 151H NMR chart;
FIG. 45 is a photograph of the product of example 1513C NMR chart;
FIG. 46 is a photograph of the product of example 1511B NMR chart;
FIG. 47 is a photograph of the product of example 161H NMR chart;
FIG. 48 is a photograph of the product of example 1613C NMR chart;
FIG. 49 is a photograph of the product of example 1611B NMR chart;
FIG. 50 is a graph of the product of example 171H NMR chart;
FIG. 51 is a photograph of the product of example 1713C NMR chart;
FIG. 52 is of the product of example 1711B NMR chart.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The reaction method for synthesizing the boric acid ester by the acetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of acetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is moved out of the glove box and reacts for 3 hours at 140 ℃, and the nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nuclear magnetic pattern as shown in fig. 1, 2 and 3, and the specific nuclear magnetic data:1H NMR(400MHz,CDCl3):7.36(d,3JHH＝7.2Hz,2H,Ar-H),7.30(t,3JHH＝7.2Hz,2H,Ar-H),7.22(t,3JHH＝7.2Hz,1H,Ar-H),5.24(q,3JHH＝6.4Hz,1H,OCH),1.48(d,3JHH＝6.4Hz,3H,OCHCH3),1.23(s,6H,BOCMe2),1.20(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):144.71,128.30,127.21,125.46(Ar-C),82.85(BOCMe2),72.70(OCH),25.55(CH3CHO),24.68,24.64(BOCMe2).11B{1H}NMR(128MHz,CDCl3):21.96。
example 2
The reaction method for synthesizing the boric acid ester by the 4-methylacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 4-methylacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed out of the glove box, reacted for 1.6h at 140 ℃, and nuclear magnetism is detected, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 4, 5 and 6, with specific nmr data: nuclear magnetic data:1HNMR(400MHz,CDCl3):7.25(d,3JHH＝8.0Hz,2H,Ar-H),7.11(d,3JHH＝8.0Hz,2H,Ar-H),5.21(q,3JHH＝6.4Hz,1H,OCH),2.31(s,3H,CH3),1.47(d,3JHH＝6.4Hz,3H,OCHCH3),1.23(s,6H,BOCMe2),1.20(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):141.67,136.59,128.85,125.29(Ar-C),82.65(BOCMe2),72.42(OCH),25.45(CH3CHO),24.57,24.53(BOCMe2),21.06(CH3).11B{1H}NMR(128MHz,CDCl3):22.08。
example 3
The reaction method for synthesizing the boric acid ester by using the 3-methylacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of p-3-methylacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed out of the glove box, reacted for 3 hours at 140 ℃, and nuclear magnetism is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 7, 8 and 9, with specific nmr data: nuclear magnetic data:1HNMR(400MHz,CDCl3):7.20-7.12(m,3H,Ar-H),7.03(d,3JHH＝7.2Hz,1H,Ar-H),5.21(q,3JHH＝6.4Hz,1H,OCH),2.33(s,3H,CH3),1.47(d,3JHH＝6.4Hz,3H,OCHCH3),1.23(s,6H,BOCMe2),1.21(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):144.52,137.72,128.08,127.82,125.98,122.41(Ar-C),82.68(BOCMe2),72.55(OCH),25.50(CH3CHO),24.57,24.53(BOCMe2),21.43(CH3).11B{1H}NMR(128MHz,CDCl3):22.08。
example 4
The reaction of 2-methylacetophenone and pinacol borane to synthesize borate without catalyst and solvent comprises the following steps:
in a glove box, 0.5mmol of p-2-methylacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed out of the glove box, reacted for 2 hours at 140 ℃, and nuclear magnetism is measured, so that the yield is calculated to be 98%.
The product was characterized by its nuclear magnetic patterns as shown in FIGS. 10, 11 and 12, the specific nucleiMagnetic data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.52(d,3JHH＝7.6Hz,1H,Ar-H),7.21-7.08(m,3H,Ar-H),5.43(q,3JHH＝6.4Hz,1H,OCH),2.34(s,3H,CH3),1.45(d,3JHH＝6.4Hz,3H,OCHCH3),1.23(s,6H,BOCMe2),1.19(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):142.93,133.79,130.10,126.99,126.27,125.21(Ar-C),82.77(BOCMe2),69.59(OCH),24.66,24.61(BOCMe2),24.30(CH3CHO),19.13(CH3).11B{1H}NMR(128MHz,CDCl3):21.97。
example 5
The reaction method for synthesizing the boric acid ester by the 4-methoxyacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of p-4-methoxyacetophenone and 1mmol of pinacol borane are sequentially added into a nuclear magnetic tube, then the mixture is removed from the glove box, reacted for 0.8h at the temperature of 140 ℃, and nuclear magnetism is detected, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 13, 14 and 15, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.29(d,3JHH＝8.4Hz,2H,Ar-H),6.85(d,3JHH＝8.8Hz,2H,Ar-H),5.20(q,3JHH＝6.4Hz,1H,OCH),3.79(OCH3),1.47(d,3JHH＝6.4Hz,3H,OCHCH3),1.24(s,6H,BOCMe2),1.21(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):158.87,136.97,126.77,113.68(Ar-C),82.81(BOCMe2),72.36(OCH),55.37(OCH3),25.46(CH3CHO),24.71,24.65(BOCMe2).11B{1H}NMR(128MHz,CDCl3):22.00。
example 6
The reaction method for synthesizing the boric acid ester by the benzophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of p-benzophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is moved out of the glove box and reacts for 0.8h at the temperature of 140 ℃, and the nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 16, 17 and 18, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.37(d,3JHH＝7.6Hz,4H,Ar-H),7.26(t,3JHH＝7.2Hz,4H,Ar-H),7.18(t,3JHH＝7.2Hz,2H,Ar-H),6.18(s,1H,OCH),1.17(s,12H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):143.11,128.19,127.25,126.46(Ar-C),82.89(BOCMe2),77.88(OCH),24.48(BOCMe2).11B{1H}NMR(128MHz,CDCl3):22.45。
example 7
The reaction method for synthesizing the boric acid ester by the isobutyl phenyl ketone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of p-isobutyl phenyl ketone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed from the glove box and reacts for 2.5 hours at the temperature of 140 ℃, and nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 19, 20 and 21, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.31-7.26(m,4H,Ar-H),7.22-7.19(m,1H,Ar-H),4.81(d,3JHH＝6.4Hz,1H,OCH),1.97(sept,3JHH＝6.4Hz,1H,CH(CH3)2),1.20(s,6H,BOCMe2),1.62(s,6H,BOCMe2),0.90(d,3JHH＝6.8Hz,3H,CH3),0.83(d,3JHH＝6.8Hz,3H,CH3).13C{1H}NMR(101MHz,CDCl3):142.42,127.76,126.95,126.44(Ar-C),82.52(BOCMe2),81.40(OCH),35.26(CH(CH3)2),24.44(BOCMe2),18.80,17.48(CH(CH3)2).11B{1H}NMR(128MHz,CDCl3):22.09。
example 8
The reaction method for synthesizing the boric acid ester by the 4-fluoroacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 4-fluoro acetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed from the glove box, reacted for 7 hours at 140 ℃, and nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 22, 23, 24 and 25, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.33(q,3JHH＝5.2Hz,2H,Ar-H),6.99(t,3JHH＝8.4Hz,2H,Ar-H),5.22(q,3JHH＝6.4Hz,1H,OCH),1.47(d,3JHH＝6.4Hz,3H,OCHCH3),1.24(s,6H,BOCMe2),1.21(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):162.06(d,3JC-F＝245.43Hz),140.46(d,3JC-F＝3.03Hz),127.13(d,3JC-F＝8.08Hz),115.04(d,3JC-F＝21.21Hz)(Ar-C),82.89(BOCMe2),72.10(OCH),25.49(CH3CHO),24.65,24.59(BOCMe2).11B{1H}NMR(128MHz,CDCl3):21.92.19F{1H}NMR(376MHz,CDCl3):-115.97。
example 9
The reaction method for synthesizing the boric acid ester by the 4-chloroacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 4-chloroacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed out of the glove box, reacted for 7 hours at 140 ℃, and nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 26, 27 and 28, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.28(s,4H,Ar-H),5.21(q,3JHH＝6.4Hz,1H,OCH),1.46(d,3JHH＝6.4Hz,3H,OCHCH3),1.24(s,6H,BOCMe2),1.21(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):143.20,132.83,128.40,126.87(Ar-C),82.93(BOCMe2),72.02(OCH),25.42(CH3CHO),24.63,24.59(BOCMe2).11B{1H}NMR(128MHz,CDCl3):22.02。
example 10
The reaction method for synthesizing the boric acid ester by the 4-bromoacetophenone and the pinacol borane without the catalyst and the solvent comprises the following steps:
in a glove box, 0.5mmol of 4-bromoacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed from the glove box and reacted for 6 hours at 140 ℃, nuclear magnetism is measured, and the yield is calculated to be 99%.
The product was characterized by its nmr charts as shown in fig. 29, 30 and 31, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.43(d,3JHH＝6.8Hz,2H,Ar-H),7.23(d,3JHH＝6.8Hz,2H,Ar-H),5.19(q,3JHH＝6.4Hz,1H,OCH),1.45(d,3JHH＝6.4Hz,3H,OCHCH3),1.23(s,6H,BOCMe2),1.21(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):143.67,131.29,127.16,120.86(Ar-C),82.85(BOCMe2),71.97(OCH),25.34(CH3CHO),24.58,24.54(BOCMe2).11B{1H}NMR(128MHz,CDCl3):22.03。
example 11
The reaction method for synthesizing the boric acid ester by using the 3-chloroacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 3-chloroacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is moved out of the glove box and reacts for 5 hours at the temperature of 140 ℃, and the nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 32, 33 and 34, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.37(s,1H,Ar-H),7.26-7.19(m,3H,Ar-H),5.20(q,3JHH＝6.4Hz,1H,OCH),1.47(d,3JHH＝6.4Hz,3H,OCHCH3),1.24(s,6H,BOCMe2),1.22(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):146.69,134.15,129.55,127.25,125.64,123.54(Ar-C),82.91(BOCMe2),71.96(OCH),25.34(CH3CHO),24.59,24.54(BOCMe2).11B{1H}NMR(128MHz,CDCl3):22.04。
example 12
The reaction method for synthesizing the boric acid ester by using the 2-chloroacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 2-chloroacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is moved out of the glove box and reacts for 9 hours at the temperature of 140 ℃, and the nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 35, 36 and 37, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.63(d,3JHH＝8.0Hz,1H,Ar-H),7.31-7.24(m,2H,Ar-H),7.19-7.15(m,1H,Ar-H),5.58(q,3JHH＝6.4Hz,1H,OCH),1.48(d,3JHH＝6.4Hz,3H,OCHCH3),1.25(s,6H,BOCMe2),1.22(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):142.32,131.17,129.19,128.22,127.11,126.72(Ar-C),82.96(BOCMe2),69.61(OCH),24.62(BOCMe2),23.96(CH3CHO).11B{1H}NMR(128MHz,CDCl3):21.99.
example 13
The reaction method for synthesizing the boric acid ester by the 4-nitroacetophenone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 4-nitroacetophenone and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed out of the glove box, reacted for 1h at 140 ℃, and nuclear magnetic resonance is detected, so that the yield is calculated to be 98%.
The product was characterized by its nmr charts as shown in fig. 38, 39 and 40, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):8.18(d,3JHH＝8.8Hz,2H,Ar-H),7.55(d,3JHH＝8.8Hz,2H,Ar-H),5.35(q,3JHH＝6.4Hz,1H,OCH),1.52(d,3JHH＝6.4Hz,3H,OCHCH3),1.26(s,6H,BOCMe2),1.23(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):151.81,147.00,126.06,123.46(Ar-C),83.00(BOCMe2),71.66(OCH),25.16(CH3CHO),24.44(BOCMe2).11B{1H}NMR(128MHz,CDCl3):21.13.
example 14
The reaction method for synthesizing the boric acid ester by using the 2-acetylfuran and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 2-acetylfuran and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is removed out of the glove box and reacts for 2.5 hours at the temperature of 140 ℃, nuclear magnetic property is measured, and the yield is calculated to be 98%.
The product was characterized with nmr charts as shown in fig. 41, 42 and 43, and specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.34-7.33(m,1H,Ar-H),6.30-6.28(m,1H,Ar-H),6.23(d,3JHH＝3.2Hz,1H,Ar-H),5.24(q,3JHH＝6.4Hz,1H,OCH),1.54(d,3JHH＝6.4Hz,3H,OCHCH3),1.25(s,12H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):156.37,141.72,110.03,105.57(Ar-C),82.90(BOCMe2),66.11(OCH),24.60(BOCMe2),21.02(CH3CHO).11B{1H}NMR(128MHz,CDCl3):22.11.
example 15
The reaction method for synthesizing the boric acid ester by using the 2-acetylthiophene and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 2-acetylthiophene and 1mmol of pinacolborane are sequentially added into a nuclear magnetic tube, then the mixture is moved out of the glove box and reacts for 3 hours at the temperature of 140 ℃, and the nuclear magnetic property is measured, so that the yield is calculated to be 97%.
The product was characterized by its nmr charts shown in fig. 44, 45 and 46, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):7.19(d,3JHH＝5.2Hz,1H,Ar-H),6.96-6.91(m,2H,Ar-H),5.48(q,3JHH＝6.4Hz,1H,OCH),1.59(d,3JHH＝6.4Hz,3H,OCHCH3),1.25(s,6H,BOCMe2),1.24(s,6H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):148.25,126.43,124.16,123.32(Ar-C),82.95(BOCMe2),68.67(OCH),25.11(CH3CHO),24.67,24.58(BOCMe2).11B{1H}NMR(128MHz,CDCl3):22.06.
example 16
The reaction method for synthesizing the boric acid ester by the cycloheptanone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, sequentially adding 0.5mmol of cycloheptanone and 1mmol of pinacol borane into a nuclear magnetic tube, then removing the cycloheptanone and the pinacol borane out of the glove box, reacting for 2.5h at 140 ℃, and measuring nuclear magnetism to obtain the yield of 99 percent by calculation.
The product was characterized by its nuclear magnetic patterns as shown in fig. 47, 48 and 49, with specific nuclear magnetic data: nuclear magnetic data:1H NMR(400MHz,CDCl3):4.21(sept,3JHH＝4.8Hz,1H,OCH),1.89-1.82(m,2H,CH2),1.69-1.60(m,4H,CH2),1.55-1.52(m,4H,CH2),1.43-1.37(m,2H,CH2),1.24(s,12H,BOCMe2).13C{1H}NMR(101MHz,CDCl3):82.32(BOCMe2),74.96(OCH),36.39,28.26(CH2),24.55(BOCMe2),22.35(CH2).11B{1H}NMR(128MHz,CDCl3):21.74.
example 17
The reaction method for synthesizing the boric acid ester by the 1-adamantane ketone and the pinacol borane under the conditions of no catalyst and no solvent comprises the following steps:
in a glove box, 0.5mmol of 1-adamantane ketone and 1mmol of pinacol borane are sequentially added into a nuclear magnetic tube, then the mixture is moved out of the glove box and reacts for 2.5h at the temperature of 140 ℃, and nuclear magnetic property is measured, so that the yield is 99 percent by calculation.
The product was characterized by its nmr charts as shown in fig. 50, 51 and 52, with specific nmr data: nuclear magnetic data:1H NMR(400MHz,CDCl3):3.69(q,3JHH＝6.4Hz,1H,OCH),1.96(s,3H,CH(CH2)3),1.70-1.49(m,12H,CH2),1.253(s,6H,BOCMe2),1.248(s,6H,BOCMe2),1.09(d,3JHH＝6.4Hz,3H,OCHCH3).13C{1H}NMR(101MHz,CDCl3):82.48(BOCMe2),78.47(OCH),37.72,37.36,36.51,28.47(C10H15),24.73,24.54(BOCMe2),15.99(CH3CHO).11B{1H}NMR(128MHz,CDCl3):21.89。
Claims (1)
1. a ketone hydroboration reaction method under the condition of no catalyst and no solvent is characterized in that ketone and pinacol borane are sequentially added into a nuclear magnetic tube in a glove box, then the glove box is removed for reaction, and the ketone hydroboration reaction can be realized under the condition of no catalyst and no solvent; wherein the molar ratio of the ketone to the pinacolborane is 1:2, the mixture is removed from a glove box and reacted for 0.8 to 9 hours, and the reaction temperature is 140 ℃; the ketone is selected from acetophenone, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methoxyacetophenone, benzophenone, isobutyl phenyl ketone, 4-fluoroacetophenone, 4-chloroacetophenone, 4-bromoacetophenone, 3-chloroacetophenone, 2-chloroacetophenone, 4-nitroacetophenone, 2-acetylfuran, 2-acetylthiophene, cycloheptanone and 1-adamantane ketone.
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