CN110885341A - Boron esterification reaction method of alkyl bromide without transition metal catalysis - Google Patents
Boron esterification reaction method of alkyl bromide without transition metal catalysis Download PDFInfo
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- CN110885341A CN110885341A CN201911300453.5A CN201911300453A CN110885341A CN 110885341 A CN110885341 A CN 110885341A CN 201911300453 A CN201911300453 A CN 201911300453A CN 110885341 A CN110885341 A CN 110885341A
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- alkyl
- equivalents
- borate
- silane
- reaction
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 150000001347 alkyl bromides Chemical class 0.000 title claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 title abstract description 13
- 150000003624 transition metals Chemical class 0.000 title abstract description 13
- 229910052796 boron Inorganic materials 0.000 title abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title abstract description 9
- 238000005886 esterification reaction Methods 0.000 title abstract description 8
- -1 alkyl borate Chemical compound 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 150000003254 radicals Chemical class 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- QZEWCQGGAIGUPS-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O.OC1=CC=CC=C1O QZEWCQGGAIGUPS-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 3
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- SGCLBIRCSTXTIU-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SGCLBIRCSTXTIU-UHFFFAOYSA-N 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 229940117969 neopentyl glycol Drugs 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 69
- 239000002904 solvent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 description 1
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- VQHPRVYDKRESCL-UHFFFAOYSA-N 1-bromoadamantane Chemical compound C1C(C2)CC3CC2CC1(Br)C3 VQHPRVYDKRESCL-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- NIDWUZTTXGJFNN-UHFFFAOYSA-N 3-bromopropoxybenzene Chemical compound BrCCCOC1=CC=CC=C1 NIDWUZTTXGJFNN-UHFFFAOYSA-N 0.000 description 1
- XMZQWZJMTBCUFT-UHFFFAOYSA-N 3-bromopropylbenzene Chemical compound BrCCCC1=CC=CC=C1 XMZQWZJMTBCUFT-UHFFFAOYSA-N 0.000 description 1
- XCHSHIAFJZVUSL-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(3-phenoxypropyl)-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1CCCOC1=CC=CC=C1 XCHSHIAFJZVUSL-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- SMTJVGKZVGURTO-UHFFFAOYSA-N B(O)(O)OB(O)O.OCC(C)(CO)C Chemical compound B(O)(O)OB(O)O.OCC(C)(CO)C SMTJVGKZVGURTO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- LOXORFRCPXUORP-UHFFFAOYSA-N bromo-Cycloheptane Chemical compound BrC1CCCCCC1 LOXORFRCPXUORP-UHFFFAOYSA-N 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- RKKDPIDERLAZPQ-UHFFFAOYSA-N cycloheptylboronic acid Chemical compound OB(O)C1CCCCCC1 RKKDPIDERLAZPQ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- KYLVAMSNNZMHSX-UHFFFAOYSA-N methyl 6-bromohexanoate Chemical compound COC(=O)CCCCCBr KYLVAMSNNZMHSX-UHFFFAOYSA-N 0.000 description 1
- AFNBPQGCHQNDRI-UHFFFAOYSA-N methyl 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)heptanoate Chemical compound COC(=O)CCCCCCB1OC(C)(C)C(C)(C)O1 AFNBPQGCHQNDRI-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc 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
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a boron esterification reaction method of alkyl bromide without transition metal catalysis. In the method, under the condition of no metal catalyst, 1 equivalent of alkyl bromide, 1-5 equivalents of diborate, 1-5 equivalents of silane and 1-5 equivalents of free radical initiator are dissolved in an organic solvent, a reaction system is sealed, and the mixture is stirred and reacted at the temperature of 20-150 ℃ to obtain the alkyl borate. The method for synthesizing the alkyl borate by utilizing the alkyl bromide is simple and efficient, does not need transition metal catalysis, only needs the diborate as a boron source, adds the silane and the free radical initiator to react under the heating condition, shows wide functional group compatibility, enables various types of alkyl bromide to be converted into the borate thereof, and has considerable yield. The obtained product alkyl borate can be applied to important reactions in the field of organic synthesis such as Suzuki coupling, and the like, so that the products are converted into a series of compounds with application values.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for boron esterification reaction of alkyl bromide without transition metal catalysis, which can effectively convert carbon-bromine bond into carbon-boron bond.
Background
The organic boron compound is an important intermediate for organic synthesis, can convert carbon-boron bonds into various chemical bonds such as carbon-carbon bonds by methods such as Suzuki coupling and the like, and has important significance in the field of organic synthesis. For alkyl borate ester, the traditional method is to use Grignard reagent or organic lithium reagent and other high-activity reagents as raw materials for preparation, but the method has obvious limitations in terms of functional group compatibility and regioselectivity. In this context, transition metal catalyzed boronation of alkyl halides has become a popular method for the synthesis of alkyl borates, and a variety of transition metals, including Cu, Ni, Pd, Fe, Mn, and Zn, have the ability to catalyze boronation of alkyl halides to borates. Although these methods have been widely used, they still have significant disadvantages in the following areas: (1) the metal-ligand combination requires complex and rigorous screening, which is time-consuming and labor-consuming; (2) due to the use of a transition metal catalyst and strong alkali, the reaction is usually very sensitive to air and moisture and has higher cost; (3) stoichiometric amounts of Grignard reagents or organolithium reagents are required for Fe/Mn catalysis and are not easily handled after the reaction. (4) The reaction raw materials are limited, and most of the reaction raw materials are alkyl iodides with higher activity, and the reaction raw materials need artificial synthesis and are high in cost. Therefore, there is an urgent need to develop a transition metal-free boron esterification reaction of alkyl bromides to achieve the following objectives: (1) the use of a transition metal catalyst is avoided, so that the process is simpler, green and environment-friendly; (2) most of the alkyl halide reaction raw materials are expanded from alkyl iodide which is not easy to obtain to alkyl bromide, so that the steps are simplified, and the cost is reduced; thereby overcoming the defects of the traditional preparation method of the alkyl borate.
The boron alkyl esterification reaction has important application in the fields of pharmaceutical chemistry and chemical engineering and the like. With the increasing environmental problems, researchers need to reduce the use of heavy metal ions harmful to the environment during the reaction process and develop a chemical reaction method meeting the requirements of green chemistry. Therefore, the development of a simple, environment-friendly and efficient boron alkyl bromide esterification reaction without transition metal catalysis has important significance.
Disclosure of Invention
The invention aims to provide a simple, environment-friendly and efficient method for preparing alkyl borate, namely, alkyl borate is synthesized by taking alkyl bromide and diborate as raw materials under the condition of heating without a metal catalyst.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
under the condition of no metal catalyst, 1 equivalent of alkyl bromide, 1-5 equivalents of diborate, 1-5 equivalents of silane and 1-5 equivalents of radical initiator are dissolved in an organic solvent, a reaction system is sealed, and the mixture is stirred and reacted at the temperature of 20-150 ℃ for a period of time to obtain the product, namely the alkyl borate.
The method for preparing the alkyl borate has wide functional group compatibility, and primary, secondary and tertiary alkyl bromides can be converted into the alkyl borate under the method. The alkyl bromides may be represented by the following formula I:
in the formula I, R1、R2And R3Independently of each other or forming a ring, selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl or substituted heterocycloalkyl.
The above alkyl group is preferably a C1 to C20 linear or branched alkyl group, including but not limited to methyl, ethyl, propyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like; the cycloalkyl group is preferably a C4-C20 cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, etc.; the heterocycloalkyl group is preferably a heterocycloalkyl group having C4 to C10 as a group containing one or more hetero atoms such as O, N, S, for example, tetrahydropyranyl, piperidinyl, morpholinyl, tetrahydrothienyl, etc.
The substituted alkyl, substituted cycloalkyl and substituted heterocycloalkyl groups may have one or more substituent groups selected from alkyl, aryl, halogen, aryloxy, alkoxy, ester, amide, sulfonyl and the like and combinations thereof, and more preferably, C1 to C20 alkyl, phenyl, C5 to C20 aryloxy, C1 to C20 alkoxy, C2 to C20 ester, C2 to C20 amide, sulfonyl and combinations thereof.
Throughout the specification, the term "aryl" denotes an aromatic cyclic functional group having 5 to 12 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, o-methylphenyl, p-methoxyphenyl, and the like.
Throughout the specification, the term "alkoxy" denotes an alkyl group attached to an oxygen atom and may have 1 to 20 carbon atoms. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, and the like.
Throughout the specification, the term "aryloxy" denotes an alkyl aromatic cyclic functional group attached to an oxygen atom and may have 5 to 12 carbon atoms. Exemplary aryloxy groups include, but are not limited to, phenoxy, p-methylphenoxy, 1-naphthyloxy, and the like.
In the method for preparing the alkyl borate, the raw materials of the alkyl bromide, the diborate, the silane and the free radical initiator can be fed in batches and can also be reacted by a one-pot method, and good yield can be obtained. Any manner of feeding method is within the scope of the present invention.
In the above method for preparing the alkyl borate, the diboronate is preferably a bis-catechol borate, but the scope of the present invention is not limited to the class of diboronates. Exemplary diboronates include, but are not limited to, bis catechol borate, bis pinacol borate, bis neopentyl glycol diborate. Bisochthalateoborate abbreviated as B2cat2The structure is as follows:
in the above process for preparing an alkyl borate ester, the "silane" is a silicon-substituted analog of a carbon alkane. Silane generates silicon free radicals under the action of free radicals generated by a free radical initiator, and can break carbon-bromine bonds, so that the carbon-bromine bonds are subsequently converted to generate carbon-boron bonds. Exemplary silanes include, but are not limited to, tris (trimethylsilyl) silane, trimethylsilane, diphenylsilane. In the above-described process for preparing an alkyl borate ester, the silane used is preferably tris (trimethylsilyl) silane, abbreviated to TTMSS, having the structure shown below:
in the above-mentioned method for producing an alkyl borate ester, the "radical initiator" is a substance that can generate a radical under certain conditions and promote a radical reaction, and a commonly used radical initiator includes an azo compound (R-N ═ N-R ', R, R' may be an aryl group or an alkyl group), an organic peroxide (R-O-R ', R, R' may be an aryl group or an alkyl group), and the like. Exemplary free radical initiators include, but are not limited to, Azobisisobutyronitrile (AIBN), azobiscyclohexylcarbonitrile, benzoyl peroxide, t-butyl peroxide.
In the above method for preparing an alkyl borate, the radical initiator is preferably azo compound azobisisobutyronitrile, abbreviated as AIBN, having the following structure:
in the above-mentioned method for producing an alkylboronic ester, when a bis-catechol borate is used as a diboronic ester, the produced product alkylboronic catechol ester is unstable in air, and therefore, it is necessary to convert it into an alkylboronic acid pinacol ester for separation. One specific example of a transformation method is: to the reacted solution, 1 to 8 equivalents of pinacol and 10 to 100 equivalents of excess triethylamine are added, and the reaction is stirred at room temperature for a certain period of time (e.g., 1 to 5 hours). The reaction is shown below:
in the above-mentioned method for converting an alkyl borate ester, the scope of the present invention is not limited by any difference in the method for converting the product alkyl borate ester.
In the above-described process for producing an alkyl borate ester, the organic solvent is preferably an aprotic polar solvent, and the proton autodelivery reaction of such a solvent is extremely weak or has no tendency to autodeliver. Commonly used solvents include, but are not limited to, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), dimethylsulfoxide, acetone, 1, 3-dimethyl-2-imidazolidinone (DMI), and the like. The preferred reaction solvent is N, N-Dimethylacetamide (DMA).
The method for preparing the alkyl borate has wide applicable temperature range. The reaction yield is assisted by suitable reaction temperatures which are dependent on the type of diboronic ester, the type of silane and the type of free radical initiator. For example, when using bis-pyrocatechol borate as the boron source, TTMSS as the silane, and AIBN as the free radical initiator, the reaction temperature under the preferred conditions is 80 ℃.
In the method for preparing the alkyl borate, the reaction time range is wide, usually 1-72 hours, and the prolonged time basically has no influence on the reaction. The optimum reaction time is dependent on the type of silane, the type of free radical initiator and is not intended to limit the scope of the invention in any way. For example, in the case of using a bis-catechol borate as a boron source, TTMSS as a silane, and AIBN as a radical initiator, the reaction temperature is 80 ℃ and the preferred reaction time is 6 hours. At lower temperatures, the reaction times are correspondingly longer.
The invention discloses a method for carrying out boron esterification reaction without transition metal catalysis on alkyl bromide and diborate under the heating condition, which does not need a transition metal catalyst, mixes reactants and a solvent in an inert atmosphere, then stirs and reacts under a closed condition, washes off an aprotic polar solvent by water after the reaction, extracts a water phase by ethyl acetate, removes the ethyl acetate by rotary evaporation, can separate by column chromatography and other methods to obtain a product, and is simple and easy to implement.
The possible principle of the invention is as follows: the reaction process may be via a free radical mechanism. (1) The free radical initiator generates free radicals under the heating condition; (2) reacting the free radical with silane to generate a silicon free radical; (3) the silicon free radical reacts with alkyl bromide to break the carbon-bromine bond and generate alkyl free radical; (4) the alkyl free radical reacts with the diboronate to form an alkyl boronate. As shown in the following legend:
the invention discloses a simple and efficient boronizing method for synthesizing alkyl borate by using alkyl bromide. The method does not need transition metal catalysis, only needs diborate as a boron source, adds silane and a free radical initiator to react under the heating condition, shows wide functional group compatibility, enables various types of alkyl bromide to be converted into the borate thereof, and has considerable yield. The obtained product alkyl borate can be applied to important reactions in the field of organic synthesis such as Suzuki coupling, and the like, so that the products are converted into a series of compounds with application values.
Detailed Description
The present invention is described in further detail below by way of specific embodiments, but the scope of the present invention is not limited in any way.
Example 1
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.45mmol, 1.5 equiv., 107.0mg), AIBN (0.33mmol,1.1 equiv., 54.2mg), 2mL of solvent N, N-dimethylacetamide, TTMSS (0.33mmol,1.1 equiv., 101.8. mu.L) and bromo-N-octane (0.3mmol, 52.3. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, pinacol (141.8mg, 4.0 equivalents) was added to the reaction flask, and 1.0mL of triethylamine was added thereto and stirred at room temperature for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, to which was then added 3After washing with 0mL of water and extracting the aqueous phase 3 times with 30mL of ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL of saturated brine, dried over anhydrous sodium sulfate and filtered, followed by the addition of 2.0mL of TBAF (1mol/L in THF) for the removal of the silicon-containing by-products of the reaction. Adding a small spoon of 200-mesh silica gel with 300 meshes, removing the solvent under reduced pressure, adsorbing the mixture on the silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 50: 1-30: 1 to obtain 58.4mg of the required n-octyl boronic acid pinacol ester with the yield of 81%.
Example 2
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.75mmol, 1.5 equiv., 178.4mg), AIBN (0.55mmol,1.1 equiv., 90.3mg), 3mL of solvent N, N-dimethylacetamide, TTMSS (0.55mmol,1.1 equiv., 169.7. mu.L) and methyl 6-bromohexanoate (0.5mmol, 79.4. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, pinacol (236.3mg, 4.0 equivalents) was added to the reaction flask, 1.5mL triethylamine was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, then washed with water by adding 30mL water, the aqueous phase was extracted 3 times with 30mL ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL saturated brine, and after the organic phase was dried over anhydrous sodium sulfate and filtered, 2.5mL TBAF (1mol/L in THF) was added for removal of the silicon-containing by-product of the reaction. Adding a small spoon of 200-mesh silica gel with 300 meshes, removing the solvent under reduced pressure, adsorbing the mixture on the silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 30: 1-20: 1 to obtain 55.2mg of the desired 6-methoxycarbonylhexylboronic acid pinacol ester with the yield of 43%.
Example 3
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.75mmol, 1.5 equiv., 178.4mg), AIBN (0.55mmol,1.1 equiv., 90.3mg), 3mL of solvent N, N-dimethylacetamide, TTMSS (0.55mmol,1.1 equiv., 169.7. mu.L) and bromocycloheptane (0.5mmol, 68.7. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, pinacol (236.3mg, 4.0 equivalents) was added to the reaction flask, 1.5mL triethylamine was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, then washed with water by adding 30mL water, the aqueous phase was extracted 3 times with 30mL ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL saturated brine, and after the organic phase was dried over anhydrous sodium sulfate and filtered, 2.0mL TBAF (1mol/L in THF) was added for removal of the silicon-containing by-product of the reaction. Adding a small spoon of 200-mesh silica gel with 300 meshes, removing the solvent under reduced pressure, adsorbing the mixture on the silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 40: 1-30: 1 to obtain 73.6mg of the desired product pinacol cycloheptylboronate with a yield of 66%.
Example 4
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.75mmol, 1.5 equiv., 178.4mg), AIBN (0.55mmol,1.1 equiv., 90.3mg), 3mL of solvent N, N-dimethylacetamide, TTMSS (0.55mmol,1.1 equiv., 169.7. mu.L) and bromocyclohexane (0.5mmol, 61.0. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, pinacol (236.3mg, 4.0 equivalents) was added to the reaction flask, 1.5mL triethylamine was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, then washed with water by adding 30mL water, the aqueous phase was extracted 3 times with 30mL ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL saturated brine, and after the organic phase was dried over anhydrous sodium sulfate and filtered, 1.5mL TBAF (1mol/L in THF) was added subsequently for removing the silicon-containing by-product of the reaction. Adding a small spoon of 200-mesh silica gel of 300 meshes, and removing the solvent under reduced pressureAnd adsorbing the mixture on silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 50: 1-30: 1, so as to obtain 75.8mg of the required product, namely the cyclohexyl boronic acid pinacol ester, and the yield is 72%.
Example 5
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.75mmol, 1.5 equiv., 178.4mg), AIBN (0.55mmol,1.1 equiv., 90.3mg), 1-bromoadamantane (0.5mmol, 107.6mg), 3mL solvent N, N-dimethylacetamide, TTMSS (0.55mmol,1.1 equiv., 169.7. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, pinacol (236.3mg, 4.0 equivalents) was added to the reaction flask, 1.5mL triethylamine was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, then washed with water by adding 30mL water, the aqueous phase was extracted 3 times with 30mL ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL saturated brine, and after the organic phase was dried over anhydrous sodium sulfate and filtered, 1.5mL TBAF (1mol/L in THF) was added for removal of the silicon-containing by-product of the reaction. Adding a small spoon of 200-mesh silica gel with 300 meshes, removing the solvent under reduced pressure, adsorbing the mixture on the silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 40: 1-30: 1 to obtain 80.8mg of the required product 1-adamantyl boronic acid pinacol ester with a yield of 62%.
Example 6
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.75mmol, 1.5 equiv., 178.4mg), AIBN (0.55mmol,1.1 equiv., 90.3mg), 1-bromo 3-phenylpropane (0.5mmol, 76.0. mu.L), 3mL solvent N, N-dimethylacetamide, TTMSS (0.55mmol,1.1 equiv., 169.7. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, the reaction flask was charged with pinacol (236.3mg, 4.0 equivalents), and 1.5mL of triethylamine was added at room temperatureStirred for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, then washed with water by adding 30mL water, the aqueous phase was extracted 3 times with 30mL ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL saturated brine, and after the organic phase was dried over anhydrous sodium sulfate and filtered, 1.5mL TBAF (1mol/L in THF) was added for removal of the silicon-containing by-product of the reaction. Adding a small spoon of 200-mesh silica gel with 300 meshes, removing the solvent under reduced pressure, adsorbing the mixture on the silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 40: 1-30: 1 to obtain 52.4mg of the required product of the 3-phenylpropyl boronic acid pinacol ester with the yield of 43%.
Example 7
In a glove box under nitrogen atmosphere, B was sequentially added to a 10mL Schlenk flask equipped with a stirrer2cat2(0.75mmol, 1.5 equiv., 178.4mg), AIBN (0.55mmol,1.1 equiv., 90.3mg), 3-phenoxybromopropane (0.5mmol, 78.8. mu.L), 3mL solvent N, N-dimethylacetamide, TTMSS (0.55mmol,1.1 equiv., 169.7. mu.L). The capped Schlenk flask was removed from the glove box and the reaction mixture was stirred at 80 ℃ for 6 hours. After cooling to room temperature, pinacol (236.3mg, 4.0 equivalents) was added to the reaction flask, 1.5mL triethylamine was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then transferred to a 125mL separatory funnel via 30mL ethyl acetate, then washed with water by adding 30mL water, the aqueous phase was extracted 3 times with 30mL ethyl acetate, the organic phases were combined and transferred to a 250mL separatory funnel, washed with 100mL saturated brine, and after the organic phase was dried over anhydrous sodium sulfate and filtered, 1.5mL TBAF (1mol/L in THF) was added for removal of the silicon-containing by-product of the reaction. Adding a small spoon of 200-mesh silica gel with 300 meshes, removing the solvent under reduced pressure, adsorbing the mixture on the silica gel, and purifying by column chromatography, wherein the developing agent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 50: 1-30: 1 to obtain 79.5mg of the required product of the 3-phenoxypropylboronic acid pinacol ester with a yield of 61%.
Claims (10)
1. A method for preparing alkyl borate comprises the steps of dissolving 1 equivalent of alkyl bromide, 1-5 equivalents of diborate, 1-5 equivalents of silane and 1-5 equivalents of free radical initiator in an organic solvent in the absence of a metal catalyst, sealing a reaction system, and stirring and reacting at 20-150 ℃ for a period of time to obtain the alkyl borate.
2. The method of claim 1, wherein the alkyl bromide has the structure of formula I:
in the formula I, R1、R2And R3Independently of each other or forming a ring, selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl or substituted heterocycloalkyl.
3. The method of claim 2, wherein the substituted alkyl, cycloalkyl and heterocycloalkyl have one or more substituents selected from the group consisting of alkyl, aryl, halo, aryloxy, alkoxy, ester, amide, sulfonyl and combinations thereof.
4. The method of claim 1, wherein the diboronate is selected from the group consisting of a bis-catechol borate, a bis-pinacol borate, and a bis-neopentylglycol diborate.
5. The method of claim 1, wherein the silane is selected from the group consisting of tris (trimethylsilyl) silane, trimethylsilane, and diphenylsilane.
6. The method of claim 1, wherein the free radical initiator is an azo compound or an organic peroxide.
7. The method of claim 6, wherein the free radical initiator is azobisisobutyronitrile, azobiscyclohexylcarbonitrile, benzoyl peroxide, or t-butyl peroxide.
8. The method of claim 1, wherein in the absence of a metal catalyst, 1 equivalent of alkyl bromide, 1-5 equivalents of bis-catechol borate, 1-5 equivalents of silane, and 1-5 equivalents of a radical initiator are dissolved in an organic solvent, the reaction system is sealed, stirring reaction is performed at 20-150 ℃ to obtain alkyl boronic acid catechol ester, then 1-8 equivalents of pinacol and 10-100 equivalents of triethylamine are added, and stirring reaction is performed at room temperature for a period of time to obtain alkyl boronic acid pinacol ester.
9. The method of claim 1, wherein the organic solvent is an aprotic polar solvent.
10. The method of claim 9, wherein the organic solvent is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, 1, 3-dimethyl-2-imidazolidinone.
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