CN110483560A - A kind of the iron catalyst system and its application method of aliphatic olefin hydroboration synthesis of alkyl borate - Google Patents
A kind of the iron catalyst system and its application method of aliphatic olefin hydroboration synthesis of alkyl borate Download PDFInfo
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- CN110483560A CN110483560A CN201910720662.9A CN201910720662A CN110483560A CN 110483560 A CN110483560 A CN 110483560A CN 201910720662 A CN201910720662 A CN 201910720662A CN 110483560 A CN110483560 A CN 110483560A
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- Prior art keywords
- acid
- iron salt
- aliphatic olefin
- solvent
- synthesis
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- -1 aliphatic olefin Chemical class 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910052742 iron Inorganic materials 0.000 title abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 52
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 31
- 150000002505 iron Chemical class 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 25
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000010471 Markovnikov's rule Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000002024 ethyl acetate extract Substances 0.000 description 4
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000707 boryl group Chemical group B* 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- ZOAMZFNAPHWBEN-UHFFFAOYSA-N 2-$l^{1}-oxidanylpropane Chemical compound CC(C)[O] ZOAMZFNAPHWBEN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- FWDBZJBJTDRIIY-UHFFFAOYSA-N CC(C)(C)[K] Chemical compound CC(C)(C)[K] FWDBZJBJTDRIIY-UHFFFAOYSA-N 0.000 description 1
- DFGLZFZXSHRQEA-UHFFFAOYSA-N CC(C)[K] Chemical compound CC(C)[K] DFGLZFZXSHRQEA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910021579 Iron(II) iodide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003005 anticarcinogenic agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the iron catalyst systems and its application method of a kind of aliphatic olefin hydroboration synthesis of alkyl borate, the present invention is using molysite as catalyst, join boron ester as boron source, under the action of certain alkali and solvent, the selectively controllable hydroboration in catalysis aliphatic olefin generation area.Under the conditions of the iron catalyst system, the addition for meeting markovnikov's rule can be realized, can also realize the addition of anti-Markonikov's rule, and there is outstanding advantages of the substrate transformation rate is high, and regioselectivity is controllable, and reaction condition is mildly harmless.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to hydroboration occurs for a kind of catalysis aliphatic olefin
Iron catalyst system and its application method.
Background technique
Boron alkyl acid esters is a kind of important organic synthesis intermediate, and there are many mature methods at present can be by C-B
Key is converted into C-O key, C-N key, C-F key and C-C key etc., is therefore widely used in medicine, liquid crystal material, organic functional material
Equal fields.Alkylboronic acids ester type compound in terms of synthesis in addition to other than being widely used, it may also be used for the initiation of polymerization reaction
Agent, kerosene antioxidant, bacteria remover, anticarcinogen and neutron absorption etc..Transition metal-catalyzed aliphatic olefin hydroboration is
The most important strategy of synthesis of alkyl borate, but it is often of equal value using rhodium, nickel in transition-metal catalysis system before
Lattice valuableness or toxic metal, and need to add additional ligand and promote reaction.Core of the invention is to establish iron catalysis rouge
Fat race alkene hydroboration system uses earth rich reserves, cheap and easy to get and nontoxic iron as catalyst and without adding
Add extra ligand, and can realize the control of regioselectivity by the adjusting of solvent, can be realized and meet markovnikov's rule
Addition can also realize the addition of anti-Markonikov's rule.It is sustainable efficiently that a kind of green is provided for aliphatic olefin hydroboration
Catalyst system.
Summary of the invention
The main object of the present invention is to provide a kind of promotion aliphatic olefin generation hydroboration synthesis of alkyl borate
Iron catalyst system and its application method.
In order to complete above-mentioned purpose, the present invention provides a kind of aliphatic olefin hydroboration synthesis of alkyl borates
Catalyst system, the catalyst system include aliphatic olefin hydro carbons compound, iron salt catalyst, pinacol connection boron ester, alkoxy base and
Solvent；The catalyst system is in anhydrous and oxygen-free environment；The molar ratio of iron salt catalyst and alkenes compounds is 0.08:1
To 0.12:1；The molar ratio of alkoxy base and iron salt catalyst is 10:1 to 22:1.
One Preferable scheme is that, aliphatic olefin hydro carbons compound includes monoalkyl substituted ethylene and 1, and 1- dialkyl group replaces
Ethylene, general formula are as shown:
One Preferable scheme is that, alkoxy includes methoxyl group, ethyoxyl, propoxyl group, isopropyl oxygen in the alkoxy base
Base, tert-butoxy, tertiary amoxy, the alkoxy base are alkoxy lithium, sodium alcoholate or alkoxy potassium；The solvent is ethers
Solvent or amide solvent, ether solvent include ether, isopropyl ether, n-butyl ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, dioxy six
Ring, amide solvent include N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide；The molysite is urged
Agent includes at least one kind of following substance: organic acid molysite, inorganic acid molysite, sulfonic acid molysite, heteropoly acid molysite.
One Preferable scheme is that, the organic acid molysite includes divalent iron salt and/or trivalent iron salt；The organic acid packet
Include at least one of following substance: acetic acid, stearic acid, oleic acid, citric acid；Inorganic acid molysite includes divalent iron salt and/or three
Valence molysite；Inorganic acid includes at least one of following substance: hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid,
Phosphoric acid, pyrophosphoric acid, hydrosulphuric acid, hydrogen cyanide, carbonic acid；The sulfonic acid molysite includes divalent iron salt and/or trivalent iron salt；The sulfonic acid
Including at least one of following substance: benzene sulfonic acid, p-methyl benzenesulfonic acid, nitrobenzene-sulfonic acid, halogenated benzene sulfonic acid, trifluoromethanesulfonic acid；
The heteropoly acid molysite includes divalent iron salt and/or trivalent iron salt；The heteropoly acid includes at least one of following substance: phosphorus
Molybdic acid, phosphotungstic acid.
The method of aliphatic olefin hydroboration synthesis of alkyl borate provided by the invention, reaction system include fat
Race's alkenes compounds, iron salt catalyst, pinacol connection boron ester, alkoxy base and solvent, and when use ether solvent, hydroboration
Reaction shows anti-geneva regioselectivity；When using amide solvent, hydroboration shows geneva regioselectivity.Such as
Shown in lower:
It is a kind of Preferable scheme is that, ether solvent includes ether, isopropyl ether, n-butyl ether, methyl tertiary butyl ether(MTBE), tetrahydro furan
It mutters, dioxane, amide solvent includes N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide.
The method of aliphatic olefin hydroboration synthesis of alkyl borate provided by the invention, which is characterized in that including
Following step:
S1: iron salt catalyst, alkoxy base and pinacol connection boron ester is added into reactor；
S2: applying argon gas is vacuumized；
S3: aliphatic olefin hydro carbons compound, solvent is added into the reactor；Keep iron salt catalyst and olefines
The molar ratio for closing object is 0.08:1 to 0.12:1, and the molar ratio of alkoxy base and iron salt catalyst is 10:1 to 22:1；
S4: being heated to predetermined temperature, is stirred at reflux reaction a few hours；
S5: post-processing obtains boron alkyl acid esters.
One Preferable scheme is that, in S2, sieve is stoppered with vacuum estersil, applying argon gas is vacuumized and is repeated 3 times, will try
The seal of tube；
In S3, under protection of argon gas, aliphatic olefin hydro carbons compound, solvent are successively injected into reactor with syringe
In；
In S4, reaction tube is put into the oil bath pan for having risen to predetermined temperature, heating stirring；
In S5, water and certain ratio ethyl acetate and petroleum ether extraction is added three times, leaves and takes organic phase；By extract liquor
Dry with anhydrous sodium sulfate, Rotary Evaporators are spin-dried for, and obtain crude product；Crude product is used into a certain proportion of petroleum ether and acetic acid
Ethyl ester carries out rapid column chromatography as solvent, and eluent merges, and Rotary Evaporators are evaporated, and obtains boron alkyl acid esters.
The invention has the benefit that the iron catalysis aliphatic olefin hydroboration system that the present invention designs, uses ground
Ball rich reserves, molysite cheap and easy to get and biological nontoxic are as catalyst；It is not required to add additional catalyst；Pass through solvent
Adjust the control that can be realized regioselectivity；Solvent for use low boiling point is soluble easily in water, convenient post-treatment.The catalyst system is
It selectively synthesizes level-one, second level or three-level boron alkyl acid esters and provides the sustainable efficient tool of green.
In addition, of the invention be further characterized in that, the substrate transformation rate is high, and regioselectivity is controllable.It is urged with the iron catalyst system
Change, with NaOtBu is alkali, and alkyl alkene is able to achieve the boryl for meeting markovnikov's rule in N, N- dialkyl amide；And works as and use
KOiPr is alkali, and then alkyl alkene is able to achieve the boryl for meeting anti-Markonikov's rule again in ether solvent.
Specific embodiment
Following embodiment is used to explain the present invention.Reaction used carries out in argon gas and the solvent of degassing.
Meaning room temperature of the invention is 25 DEG C.
Embodiment 1
The present embodiment is carried out using chemical equation above.Specifically, under argon gas protection, in super dry 10mL reactor
In, it sequentially adds alkene (3,3- dimethyl -1- butylene, 0.1mmol), pinacol joins boron ester (0.15mmol), FeBr2
(0.01mmol), KOMe (potassium methoxide, 0.2mmol) vacuumize applying argon gas, gas three times are replaced, under protection of argon gas by positive fourth
Ether (0.5mL) is injected in reaction tube with 1mL syringe, stirs 16h at room temperature.Reaction is stopped heating restoring to room temperature, is added
Enter 5mL water, a certain proportion of petroleum ether and ethyl acetate extract three times, merge organic phase, and dry with anhydrous sodium sulfate, rotation is steamed
Hair instrument is spin-dried for, and silica gel column chromatography (eluant, eluent is petroleum ether: ethyl acetate=50:1, v:v) separates (Rf=0.4) colourless liquid is obtained
Body, yield 79%.
Nucleus magnetic hydrogen spectrum carbon modal data:1H NMR(500MHz,Chloroform-d)δ1.25(m,14H),0.85(s,9H),
0.76–0.66(m,2H).13C NMR(126MHz,Chloroform-d)δ82.85,37.75,30.82,28.85,24.82.
Embodiment 2
Under argon gas protection, in super dry 10ml-Schlenk pipe, sequentially adding alkene, (2- methyl -4- is (to methoxybenzene
Base) -1- butylene, 0.1mmol), pinacol joins boron ester (0.25mmol), Fe (OAc)2(0.01mmol), KOiPr (potassium isopropoxide,
0.2mmol), applying argon gas is vacuumized, gas three times is replaced, under protection of argon gas injects methyl tertiary butyl ether(MTBE) (0.5mL) with 1mL
Device injects in reaction tube, stirs 16h at 30 DEG C.Reaction is stopped heating restoring to room temperature, 5mL water is added, it is a certain proportion of
Petroleum ether and ethyl acetate extract three times, merge organic phase, dry with anhydrous sodium sulfate, and Rotary Evaporators are spin-dried for, silica gel column layer
It analyses (eluant, eluent is petroleum ether: ethyl acetate=25:1, v:v) and separates (Rf=0.5) colourless liquid, yield 90% are obtained.
Nuclear magnetic data:1H NMR (500MHz, Chloroform-d) δ 7.09 (d, J=8.4Hz, 2H), 6.81 (d, J=
8.6Hz, 2H), 3.78 (s, 3H), 2.63-2.40 (m, 2H), 1.75 (dt, J=13.6,6.8Hz, 1H), 1.64-1.40 (m,
3H), 1.25 (s, 12H), 0.97 (d, J=6.6Hz, 3H), 0.94-0.61 (m, 2H)13C NMR(126MHz,Chloroform-
D) 9,23.82 (d, J=of δ 156.51,134.26,128.14,112.64,81.85,54.23,40.73,31.79,28.2
8.2Hz),21.24.
Embodiment 3
Argon gas protection under, in super dry 10ml-Schlenk pipe, sequentially add alkene (vinyl-cyclohexane,
0.1mmol), pinacol connection boron ester (0.15mmol), Fe (OTf)2(0.01mmol), LiOtBu (tert-butyl lithium alkoxide,
0.15mmol), applying argon gas is vacuumized, gas three times is replaced, under protection of argon gas infuses n-butyl ether (0.5mL) with 1mL syringe
Enter in reaction tube, stirs 16h at 80 DEG C.Reaction is stopped heating restoring to room temperature, 5ml water, a certain proportion of petroleum is added
Ether and ethyl acetate extract three times, merge organic phase, dry with anhydrous sodium sulfate, and Rotary Evaporators are spin-dried for, and silica gel column chromatography (is washed
De- agent is petroleum ether: ethyl acetate=100:1, v:v) separation (Rf=0.4) colourless liquid, yield 88% are obtained.
Nuclear magnetic data:1H NMR(500MHz,Chloroform-d)δ1.76–1.52(m,5H),1.35–1.06(m,
18H),0.89–0.77(m,2H),0.79–0.72(m,2H).13C NMR(126MHz,Chloroform-d)δ82.83,39.96,
32.99,31.38,26.78,26.46,24.82.
Embodiment 4
It under argon gas protection, in super dry 10ml-Schlenk pipe, sequentially adds alkene (0.1mmol), pinacol joins boron
Ester (0.15mmol), Fe [P (MoO10)4] (0.01mmol), KOiPr (isopropyl potassium alcoholate, 0.2mmol), vacuumizes applying argon gas, sets
Gas three times is changed, is under protection of argon gas injected methyl tertiary butyl ether(MTBE) (0.5mL) in reaction tube with 1mL syringe, at 30 DEG C
Stir 16h.Reaction is stopped heating restoring to room temperature, 5mL water, a certain proportion of petroleum ether and ethyl acetate extraction three is added
It is secondary, merge organic phase, dry with anhydrous sodium sulfate, Rotary Evaporators are spin-dried for, and (eluant, eluent is petroleum ether to silica gel column chromatography: acetic acid
Ethyl ester=25:1, v:v) separation (Rf=0.5) colourless liquid, yield 78% are obtained.
Nuclear magnetic data:1H NMR (500MHz, Chloroform-d) δ 7.09 (d, J=8.4Hz, 2H), 6.81 (d, J=
8.6Hz, 2H), 3.78 (s, 3H), 2.63-2.40 (m, 2H), 1.75 (dt, J=13.6,6.8Hz, 1H), 1.64-1.40 (m,
3H), 1.25 (s, 12H), 0.97 (d, J=6.6Hz, 3H), 0.94-0.61 (m, 2H)13C NMR(126MHz,Chloroform-
D) 9,23.82 (d, J=of δ 156.51,134.26,128.14,112.64,81.85,54.23,40.73,31.79,28.2
8.2Hz),21.24.
Embodiment 5
Argon gas protection under, in super dry 10ml-Schlenk pipe, sequentially add alkene (3,3- dimethyl -1- butylene,
0.1mmol), pinacol connection boron ester (0.15mmol), FeI2(0.01mmol), KOtBu (tert-butyl potassium alcoholate, 0.2mmol) takes out true
Empty applying argon gas replaces gas three times, under protection of argon gas injects n,N-Dimethylformamide (0.5mL) with 1mL syringe anti-
It answers in test tube, stirs 16h at 90 DEG C.Reaction is stopped heating restoring to room temperature, is added 5mL water, a certain proportion of petroleum ether with
Ethyl acetate extracts three times, merges organic phase, dry with anhydrous sodium sulfate, and Rotary Evaporators are spin-dried for, silica gel column chromatography (eluant, eluent
For petroleum ether: ethyl acetate=100:1, v:v) separation (Rf=0.5) colourless liquid, yield 78% are obtained.
Nuclear magnetic data:1H NMR(500MHz,Chloroform-d)δ1.24(s,12H),0.93(s,9H),0.88(m,
4H).13C NMR(126MHz,Chloroform-d)δ82.60,29.03,24.80,24.76,11.00.
Embodiment 6
Under argon gas protection, in super dry 10ml-Schlenk pipe, sequentially adding alkene, (2- methyl -4- is (to methoxybenzene
Base) -1- butylene, 0.1mmol), pinacol joins boron ester (0.15mmol), FeBr2(0.01mmol), NaOtBu (tert-butyl sodium alkoxide,
0.2mmol), applying argon gas is vacuumized, gas three times is replaced, n,N-dimethylacetamide (0.5mL) is used into 1mL under protection of argon gas
Syringe injects in reaction tube, stirs 16h at 90 DEG C.Reaction is stopped heating restoring to room temperature, 5mL water is added, it is certain to compare
The petroleum ether and ethyl acetate of example extract three times, merge organic phase, dry with anhydrous sodium sulfate, and Rotary Evaporators are spin-dried for, silica gel
Column chromatographs (eluant, eluent is petroleum ether: ethyl acetate=25:1, v:v) and separates (Rf=0.6) colourless liquid, yield 78% are obtained.
Nuclear magnetic data:1H NMR (500MHz, Chloroform-d) δ 7.10 (d, J=8.5Hz, 2H), 6.81 (d, J=
8.6Hz,2H),3.78(s,3H),2.74–2.21(m,2H),1.82–1.39(m,2H),1.25(s,12H),0.99(s,6H)
.13C NMR(126MHz,Chloroform-d)δ157.53,135.77,129.15,113.67,82.97,55.26,43.77,
32.12,24.78,24.75.
Obviously, described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of catalyst system of aliphatic olefin hydroboration synthesis of alkyl borate, which is characterized in that
The catalyst system includes aliphatic olefin hydro carbons compound, iron salt catalyst, pinacol connection boron ester, alkoxy base and solvent；
The catalyst system is in anhydrous and oxygen-free environment；
The molar ratio of iron salt catalyst and alkenes compounds is 0.08:1 to 0.12:1；
The molar ratio of alkoxy base and iron salt catalyst is 10:1 to 22:1.
2. the catalyst system of aliphatic olefin hydroboration synthesis of alkyl borate according to claim 1, feature
It is,
The aliphatic olefin hydro carbons compound includes monoalkyl substituted ethylene and 1,1- dialkyl group substituted ethylene, the following institute of general formula
Show:
3. the catalyst system of aliphatic olefin hydroboration synthesis of alkyl borate according to claim 1, feature
It is,
Alkoxy includes methoxyl group, ethyoxyl, propoxyl group, isopropoxy, tert-butoxy, tertiary amoxy in the alkoxy base,
The alkoxy base is alkoxy lithium, sodium alcoholate or alkoxy potassium.
4. the catalyst system of aliphatic olefin hydroboration synthesis of alkyl borate according to claim 1, feature
It is,
The solvent is ether solvent or amide solvent, and ether solvent includes ether, isopropyl ether, n-butyl ether, methyl tertbutyl
Ether, tetrahydrofuran, dioxane, amide solvent include N-Methyl pyrrolidone, n,N-Dimethylformamide, N, N- dimethyl
Acetamide.
5. the catalyst system of aliphatic olefin hydroboration synthesis of alkyl borate according to claim 1, feature
It is,
The iron salt catalyst includes at least one kind of following substance: organic acid molysite, inorganic acid molysite, sulfonic acid molysite, miscellaneous more
Sour molysite.
6. the catalyst system of aliphatic olefin hydroboration synthesis of alkyl borate according to claim 5, feature
It is,
The organic acid molysite includes divalent iron salt and/or trivalent iron salt；
The organic acid includes at least one of following substance: acetic acid, stearic acid, oleic acid, citric acid；
Inorganic acid molysite includes divalent iron salt and/or trivalent iron salt；
Inorganic acid includes at least one of following substance: hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid, phosphorus
Acid, pyrophosphoric acid, hydrosulphuric acid, hydrogen cyanide, carbonic acid；
The sulfonic acid molysite includes divalent iron salt and/or trivalent iron salt；
The sulfonic acid includes at least one of following substance: benzene sulfonic acid, p-methyl benzenesulfonic acid, nitrobenzene-sulfonic acid, halogenated benzene sulfonic acid,
Trifluoromethanesulfonic acid；
The heteropoly acid molysite includes divalent iron salt and/or trivalent iron salt；
The heteropoly acid includes at least one of following substance: phosphomolybdic acid, phosphotungstic acid.
7. a kind of method of aliphatic olefin hydroboration synthesis of alkyl borate, which is characterized in that reaction system includes rouge
Fat race alkenes compounds, iron salt catalyst, pinacol connection boron ester, alkoxy base and solvent, and when use ether solvent, boron hydrogen
Change reaction and shows anti-geneva regioselectivity；When using amide solvent, hydroboration shows geneva regioselectivity,
It is as follows:
8. the method for aliphatic olefin hydroboration synthesis of alkyl borate according to claim 7, which is characterized in that
Ether solvent includes ether, isopropyl ether, n-butyl ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, dioxane, and amide solvent includes
N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide.
9. a kind of method of aliphatic olefin hydroboration synthesis of alkyl borate, which is characterized in that include the steps that following:
S1: iron salt catalyst, alkoxy base and pinacol connection boron ester is added into reactor；
S2: applying argon gas is vacuumized；
S3: aliphatic olefin hydro carbons compound, solvent is added into the reactor；Keep iron salt catalyst and alkenes compounds
Molar ratio be 0.08:1 to 0.12:1, and the molar ratio of alkoxy base and iron salt catalyst be 10:1 to 22:1；
S4: being heated to predetermined temperature, is stirred at reflux reaction a few hours；
S5: post-processing obtains boron alkyl acid esters.
10. the method for aliphatic olefin hydroboration synthesis of alkyl borate according to claim 9, feature exist
In,
In S2, sieve is stoppered with vacuum estersil, applying argon gas is vacuumized and is repeated 3 times, test tube is sealed；
In S3, under protection of argon gas, aliphatic olefin hydro carbons compound, solvent are successively injected into reactor with syringe；
In S4, reaction tube is put into the oil bath pan for having risen to predetermined temperature, heating stirring；
In S5, water and certain ratio ethyl acetate and petroleum ether extraction is added three times, leaves and takes organic phase；By extract liquor nothing
Aqueous sodium persulfate is dry, and Rotary Evaporators are spin-dried for, and obtains crude product；Crude product is used into a certain proportion of petroleum ether and ethyl acetate
Rapid column chromatography is carried out as solvent, eluent merges, and Rotary Evaporators are evaporated, and obtains boron alkyl acid esters.
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