CN110483560B - Iron catalysis system for synthesizing alkyl borate through aliphatic olefin hydroboration reaction and application method thereof - Google Patents
Iron catalysis system for synthesizing alkyl borate through aliphatic olefin hydroboration reaction and application method thereof Download PDFInfo
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- CN110483560B CN110483560B CN201910720662.9A CN201910720662A CN110483560B CN 110483560 B CN110483560 B CN 110483560B CN 201910720662 A CN201910720662 A CN 201910720662A CN 110483560 B CN110483560 B CN 110483560B
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- -1 alkyl borate Chemical compound 0.000 title claims abstract description 70
- 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 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 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
- 238000006555 catalytic reaction Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 53
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 20
- 150000002505 iron Chemical class 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 238000001035 drying Methods 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 10
- 239000002585 base Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 238000011049 filling Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 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 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 150000008054 sulfonate salts Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 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
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 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
- 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
- 125000001033 ether group Chemical group 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 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
- 150000007522 mineralic acids Chemical class 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
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 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 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
- 229920001296 polysiloxane Polymers 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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 125000005922 tert-pentoxy group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 5
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 5
- IJLXNUWVHXNGMG-UHFFFAOYSA-N 1-methoxy-4-(3-methylbut-3-enyl)benzene Chemical compound COC1=CC=C(CCC(C)=C)C=C1 IJLXNUWVHXNGMG-UHFFFAOYSA-N 0.000 description 2
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-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
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FWDBZJBJTDRIIY-UHFFFAOYSA-N CC(C)(C)[K] Chemical compound CC(C)(C)[K] FWDBZJBJTDRIIY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel 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
- 230000001737 promoting effect Effects 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
- BBCAQPYJVYMQFB-UHFFFAOYSA-N sodium;2-methylpropane Chemical compound [Na+].C[C-](C)C BBCAQPYJVYMQFB-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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 invention relates to an iron catalysis system for synthesizing alkyl borate through a hydroboration reaction of aliphatic olefin and an application method thereof. Under the condition of the iron catalytic system, the addition conforming to the Ma rule and the addition reflecting the Ma rule can be realized, and the iron catalytic system has the outstanding advantages of high substrate conversion rate, controllable regioselectivity, mild reaction condition, no harm to human bodies and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an iron catalyst system for catalyzing aliphatic olefins to perform hydroboration reaction and an application method thereof.
Background
Alkyl borate is an important organic synthesis intermediate, and at present, a plurality of mature methods can convert C-B bonds into C-O bonds, C-N bonds, C-F bonds, C-C bonds and the like, so that the alkyl borate is widely applied to the fields of medicines, liquid crystal materials, organic functional materials and the like. Besides being widely applied to synthesis, the alkyl borate compounds can also be used as initiators of polymerization reaction, kerosene antioxidants, degerming agents, anticancer drugs, neutron capture and the like. Transition metal catalyzed hydroboration of aliphatic olefins is the most important strategy for the synthesis of alkyl borates, but rhodium, nickel, and the like, expensive or toxic metals have often been used in previous transition metal catalyzed reaction systems and additional ligands have been added to facilitate the reaction. The core of the method is to establish an iron-catalyzed aliphatic olefin hydroboration reaction system, use iron which is abundant in earth reserves, cheap, easy to obtain and nontoxic as a catalyst, do not need to add an additional ligand, and realize the control of regioselectivity through the adjustment of a solvent, so that the addition conforming to the Markov rule can be realized, and the addition of the inverse Markov rule can also be realized. Provides a green sustainable high-efficiency catalytic system for the hydroboration reaction of aliphatic olefin.
Disclosure of Invention
The invention mainly aims to provide an iron catalytic system for promoting aliphatic olefins to carry out hydroboration reaction to synthesize alkyl borate and an application method thereof.
In order to achieve the above object, the present invention provides a catalytic system for synthesizing alkyl borate through hydroboration reaction of aliphatic olefin, wherein the catalytic system comprises an aliphatic olefin compound, an iron salt catalyst, pinacoldiboron ester, an alkoxy base and a solvent; the catalytic system is in an anhydrous and oxygen-free environment; the molar ratio of the iron salt catalyst to the olefin compound is 0.08:1 to 0.12: 1; the molar ratio of the alkoxy base to the iron salt catalyst is from 10:1 to 22: 1.
In a preferred embodiment, the aliphatic olefinic compounds include monoalkyl substituted ethylene and 1, 1-dialkyl substituted ethylene, and have the general formula:
in a preferred embodiment, the alkoxy group in the alkoxy base comprises methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, tert-pentoxy, and the alkoxy base is lithium alkoxide, sodium alkoxide or potassium alkoxide; the solvent is an ether solvent or an amide solvent, the ether solvent comprises diethyl ether, isopropyl ether, N-butyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, and the amide solvent comprises N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide; the iron salt catalyst at least comprises one of the following substances: organic acid iron salt, inorganic acid iron salt, ferric sulfonate salt and heteropoly acid iron salt.
In a preferred embodiment, the organic acid iron salt comprises a ferrous salt and/or a ferric salt; the organic acid comprises at least one of the following: acetic acid, stearic acid, oleic acid, citric acid; the inorganic iron salt comprises ferrous salt and/or ferric salt; the inorganic acid comprises at least one of the following: hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, hydrosulfuric acid, hydrocyanic acid, carbonic acid; the ferric sulfonate salt comprises ferrous salt and/or ferric salt; the sulfonic acid includes at least one of the following: benzenesulfonic acid, p-toluenesulfonic acid, nitrobenzenesulfonic acid, halobenzenesulfonic acid, trifluoromethanesulfonic acid; the heteropolyacid iron salt comprises a ferrous salt and/or a ferric salt; the heteropoly acid comprises at least one of the following substances: phosphomolybdic acid, phosphotungstic acid.
According to the method for synthesizing the alkyl borate through the aliphatic olefin hydroboration reaction, a reaction system comprises an aliphatic olefin compound, an iron salt catalyst, pinacol diboron ester, alkoxy alkali and a solvent, and when an ether solvent is used, the hydroboration reaction shows the anti-Markov regioselectivity; the hydroboration reaction exhibits equilibria regioselectivity when an amide solvent is used. As follows:
in a preferred embodiment, the ether solvent includes diethyl ether, isopropyl ether, N-butyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, and the amide solvent includes N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
The method for synthesizing the alkyl borate through the aliphatic olefin hydroboration reaction is characterized by comprising the following steps of:
s1: adding an iron salt catalyst, alkoxy alkali and pinacol diboron ester into a reactor;
s2: vacuumizing and filling argon;
s3: adding aliphatic olefin compounds and a solvent into the reactor; maintaining a molar ratio of the iron salt catalyst to the olefinic compound of from 0.08:1 to 0.12:1, and a molar ratio of the alkoxy base to the iron salt catalyst of from 10:1 to 22: 1;
s4: heating to a preset temperature, and stirring and refluxing for reaction for several hours;
s5: and carrying out post-treatment to obtain the alkyl borate.
In a preferred scheme, in S2, the sieve is plugged by vacuum silicone grease, the vacuum is pumped and argon is filled for 3 times, and the test tube is sealed;
in S3, under the protection of argon, sequentially injecting the aliphatic olefin compound and the solvent into a reactor by using an injector;
in S4, the reaction tube is put into an oil bath which has been raised to a predetermined temperature, and heated with stirring;
in S5, adding water and ethyl acetate and petroleum ether in a certain proportion for extraction three times, and reserving an organic phase; drying the extract by using anhydrous sodium sulfate, and carrying out rotary drying by using a rotary evaporator to obtain a crude product; and (3) performing fast column chromatography on the crude product by using petroleum ether and ethyl acetate in a certain proportion as developing agents, combining eluent, and evaporating by using a rotary evaporator to obtain the alkyl borate.
The invention has the beneficial effects that: the iron-catalyzed aliphatic olefin hydroboration reaction system designed by the invention uses iron salt which is abundant in earth reserves, cheap and easily available and is biologically nontoxic as a catalyst; no additional catalyst is needed; regioselective control can be achieved by solvent adjustment; the used solvent has low boiling point or is easy to dissolve in water, and the post-treatment is convenient. The catalytic system provides a green, sustainable and efficient tool for selectively synthesizing primary, secondary or tertiary alkyl borate ester.
In addition, the present invention is characterized by high substrate conversion rate and controllable regioselectivity. Catalyzed by the iron catalyst system, with NaOtBu is alkali, and alkyl olefin in N, N-dialkyl amide can realize boration conforming to the Markov rule; when KOiPr is used as base, the alkyl olefin can be boron alkylated in ether solvent according to the inverse Markov's rule.
Detailed Description
The following examples serve to illustrate the invention. The reaction used is carried out under argon and in degassed solvents.
The room temperature in the invention is 25 ℃.
Example 1
This example was carried out using the above chemical reaction formula. Specifically, under the protection of argon, in an ultra-dry 10mL reactor, olefin (3, 3-dimethyl-1-butene, 0.1mmol), pinacoldiboron (0.15mmol) and FeBr are added in sequence2(0.01mmol), KOMe (potassium methoxide, 0.2mmol), evacuation and argon introduction, and Displacement of TrisNext, n-butyl ether (0.5mL) was injected into the reaction tube with a 1mL syringe under argon, and stirred at room temperature for 16 h. Stopping the reaction, heating to room temperature, adding 5mL of water, extracting with a certain proportion of petroleum ether and ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, spin-drying with a rotary evaporator, and separating with silica gel column chromatography (R is petroleum ether, ethyl acetate is 50:1, v: v as eluent)f0.4) gave a colorless liquid in 79% yield.
Nuclear magnetic hydrogen spectrum carbon spectrum 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.
example 2
Under the protection of argon, in an ultra-dry 10ml-Schlenk tube, olefin (2-methyl-4- (p-methoxyphenyl) -1-butene, 0.1mmol), pinacoldiboron (0.25mmol), Fe (OAc) were added in sequence2(0.01mmol)，KOiPr (potassium isopropoxide, 0.2mmol), vacuumizing and filling argon, replacing gas three times, injecting methyl tert-butyl ether (0.5mL) into a reaction tube by using a 1mL syringe under the protection of argon, and stirring for 16h at 30 ℃. Stopping the reaction, heating to room temperature, adding 5mL of water, extracting with a certain proportion of petroleum ether and ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, spin-drying with a rotary evaporator, and separating with silica gel column chromatography (R is petroleum ether, ethyl acetate is 25:1, v: v as eluent)f0.5) gave a colorless liquid in 90% yield.
Nuclear magnetic data:1H NMR(500MHz,Chloroform-d)δ7.09(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)δ156.51,134.26,128.14,112.64,81.85,54.23,40.73,31.79,28.29,23.82(d,J＝8.2Hz),21.24.
example 3
Under argon protection, in an ultra-dry 10ml-Schlenk tube, olefin (vinyl-cyclohexane, 0.1mmol), pinacoldiboron (0.15mmol), Fe (OTf)2(0.01mmol)，LiOtBu (lithium tert-butoxide, 0.15mmol), argon gas was added under vacuum to replace the gas three times, and n-butyl ether (0.5mL) was injected into the reaction tube with a 1mL syringe under argon, and stirred at 80 ℃ for 16 h. Stopping reaction, heating to room temperature, adding 5ml water, extracting with petroleum ether and ethyl acetate for three times, mixing organic phases, drying with anhydrous sodium sulfate, rotary evaporating, and separating with silica gel column chromatography (eluent is petroleum ether: ethyl acetate: 100:1, v: v)f0.4) gave a colorless liquid in 88% yield.
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.
example 4
Under the protection of argon, in an ultra-dry 10ml-Schlenk tube, olefin (0.1mmol), pinacoldiboron (0.15mmol) and Fe [ P (MoO)10)4](0.01mmol)，KOiPr (potassium isopropoxide, 0.2mmol), vacuumizing and filling argon, replacing gas for three times, injecting methyl tert-butyl ether (0.5mL) into a reaction tube by using a 1mL syringe under the protection of argon, and stirring for 16h at 30 ℃. Stopping the reaction, heating to room temperature, adding 5mL of water, extracting with a certain proportion of petroleum ether and ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, spin-drying with a rotary evaporator, and separating with silica gel column chromatography (R is petroleum ether, ethyl acetate is 25:1, v: v as eluent)f0.5) gave a colorless liquid in 78% yield.
Nuclear magnetic data:1H NMR(500MHz,Chloroform-d)δ7.09(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)δ156.51,134.26,128.14,112.64,81.85,54.23,40.73,31.79,28.29,23.82(d,J＝8.2Hz),21.24.
example 5
Under the protection of argon, in an ultra-dry 10ml-Schlenk tube, olefin (3, 3-dimethyl-1-butene, 0.1mmol), pinacoldiboron (0.15mmol) and FeI are added in sequence2(0.01mmol)，KOtBu (tert-butyl potassium alcoholate, 0.2mmol), evacuated and filled with argon, the gas was displaced three times, N-dimethylformamide (0.5mL) was injected into the reaction tube with a 1mL syringe under argon protection, and stirred at 90 ℃ for 16 h. Stopping the reaction, heating to room temperature, adding 5mL of water, extracting with a certain proportion of petroleum ether and ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, spin-drying with a rotary evaporator, and separating with silica gel column chromatography (R is petroleum ether, ethyl acetate is 100:1, v: v as eluent)f0.5) gave a colorless liquid in 78% yield.
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.
example 6
Under the protection of argon, in an ultra-dry 10ml-Schlenk tube, olefin (2-methyl-4- (p-methoxyphenyl) -1-butene, 0.1mmol), pinacol diboron ester (0.15mmol) and FeBr are added in sequence2(0.01mmol)，NaOtBu (tert-butyl sodium alcoholate, 0.2mmol), vacuumizing and filling argon, replacing gas for three times, and adding N under the protection of argonN-dimethylacetamide (0.5mL) was injected into the reaction tube using a 1mL syringe and stirred at 90 ℃ for 16 h. Stopping the reaction, heating to room temperature, adding 5mL of water, extracting with a certain proportion of petroleum ether and ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, spin-drying with a rotary evaporator, and separating with silica gel column chromatography (R is petroleum ether, ethyl acetate is 25:1, v: v as eluent)f0.6) gave a colorless liquid in 78% yield.
Nuclear magnetic data:1H NMR(500MHz,Chloroform-d)δ7.10(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.
it is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (5)
1. A catalytic system for synthesizing alkyl borate by hydroboration reaction of aliphatic olefin,
the catalytic system comprises an aliphatic olefin compound, an iron salt catalyst, pinacol diboron ester, alkoxy base and a solvent;
the catalytic system is in an anhydrous and oxygen-free environment;
the molar ratio of the iron salt catalyst to the olefin compound is 0.08:1 to 0.12: 1;
the molar ratio of the alkoxy alkali to the iron salt catalyst is 10:1 to 22: 1;
the solvent is an ether solvent or an amide solvent, the ether solvent is diethyl ether, isopropyl ether, N-butyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, and the amide solvent is N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide;
the iron salt catalyst at least comprises one of the following substances: organic acid iron salt, inorganic acid iron salt, ferric sulfonate salt and heteropoly acid iron salt;
the ferric salt is ferrous salt and/or ferric salt;
the organic acid is at least one of the following substances: acetic acid, stearic acid, oleic acid, citric acid;
the inorganic acid is at least one of the following substances: hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, hydrosulfuric acid, hydrocyanic acid, carbonic acid;
the sulfonic acid is at least one of the following: benzenesulfonic acid, p-toluenesulfonic acid, nitrobenzenesulfonic acid, halobenzenesulfonic acid, trifluoromethanesulfonic acid;
the heteropoly acid is at least one of the following substances: phosphomolybdic acid, phosphotungstic acid; the aliphatic olefin compounds comprise monoalkyl substituted ethylene and 1, 1-dialkyl substituted ethylene, and the general formula of the aliphatic olefin compounds is shown as follows:
2. the catalytic system for synthesizing alkyl borate ester by hydroboration of aliphatic olefin according to claim 1, wherein,
the alkoxy in the alkoxy base is methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy or tert-pentoxy, and the alkoxy base is lithium alkoxide, sodium alkoxide or potassium alkoxide.
3. A process for the synthesis of alkyl borates using the catalytic system according to claim 1 or 2, characterised in that, when an ethereal solvent is used, the hydroboration reaction exhibits an anti-mahalanobis regioselectivity; the hydroboration reaction exhibits a equinox regioselectivity when an amide solvent is used, as shown below:
4. a method according to claim 3, characterized by the following steps:
s1: adding an iron salt catalyst, alkoxy alkali and pinacol diboron ester into a reactor;
s2: vacuumizing and filling argon;
s3: adding aliphatic olefin compounds and a solvent into the reactor; maintaining a molar ratio of the iron salt catalyst to the olefinic compound of from 0.08:1 to 0.12:1, and a molar ratio of the alkoxy base to the iron salt catalyst of from 10:1 to 22: 1;
s4: heating to a preset temperature, and stirring and refluxing for reaction for several hours;
s5: and carrying out post-treatment to obtain the alkyl borate.
5. The method of claim 4,
in S2, plugging the sieve with vacuum silicone grease, vacuumizing and filling argon gas for 3 times, and sealing the test tube;
in S3, under the protection of argon, sequentially injecting the aliphatic olefin compound and the solvent into a reactor by using an injector;
in S4, the reaction tube is put into an oil bath which has been raised to a predetermined temperature, and heated with stirring;
in S5, adding water and ethyl acetate and petroleum ether in a certain proportion for extraction three times, and reserving an organic phase; drying the extract by using anhydrous sodium sulfate, and carrying out rotary drying by using a rotary evaporator to obtain a crude product; and (3) performing fast column chromatography on the crude product by using petroleum ether and ethyl acetate in a certain proportion as developing agents, combining eluent, and evaporating by using a rotary evaporator to obtain the alkyl borate.
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