CN106946682B - A kind of preparation method of propine acid compounds - Google Patents
A kind of preparation method of propine acid compounds Download PDFInfo
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- CN106946682B CN106946682B CN201710203363.9A CN201710203363A CN106946682B CN 106946682 B CN106946682 B CN 106946682B CN 201710203363 A CN201710203363 A CN 201710203363A CN 106946682 B CN106946682 B CN 106946682B
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- terminal acetylenes
- acid
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- alkali
- additive
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- 239000002253 acid Substances 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 7
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 propiolic acid salt compounds Chemical class 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 3
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical class Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- AGJLZAWPAODMHX-UHFFFAOYSA-N C(C)(C)(C)P(C(C)(C)C)C(C)(C)C.B(O)(O)O Chemical compound C(C)(C)(C)P(C(C)(C)C)C(C)(C)C.B(O)(O)O AGJLZAWPAODMHX-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical group CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 claims description 2
- VKFAUCPBMAGVRG-UHFFFAOYSA-N dipivefrin hydrochloride Chemical compound [Cl-].C[NH2+]CC(O)C1=CC=C(OC(=O)C(C)(C)C)C(OC(=O)C(C)(C)C)=C1 VKFAUCPBMAGVRG-UHFFFAOYSA-N 0.000 claims 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 239000012043 crude product Substances 0.000 claims 2
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical group [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims 1
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 239000003480 eluent Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- ITCMXBVIXVDAKR-UHFFFAOYSA-M azanium tetrabutylazanium diacetate Chemical compound C(C)(=O)[O-].[NH4+].C(CCC)[N+](CCCC)(CCCC)CCCC.C(C)(=O)[O-] ITCMXBVIXVDAKR-UHFFFAOYSA-M 0.000 description 6
- 150000000475 acetylene derivatives Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- JATGRGIILZTUIT-UHFFFAOYSA-N C(C#C)(=O)O.BrC1=CC=CC=C1 Chemical compound C(C#C)(=O)O.BrC1=CC=CC=C1 JATGRGIILZTUIT-UHFFFAOYSA-N 0.000 description 4
- XNERWVPQCYSMLC-UHFFFAOYSA-N phenylpropiolic acid Chemical compound OC(=O)C#CC1=CC=CC=C1 XNERWVPQCYSMLC-UHFFFAOYSA-N 0.000 description 4
- HAXWPFGDNUPJJM-UHFFFAOYSA-N 3-(4-ethylphenyl)prop-2-ynoic acid Chemical compound CCC1=CC=C(C#CC(O)=O)C=C1 HAXWPFGDNUPJJM-UHFFFAOYSA-N 0.000 description 3
- RGJNIEUQOSFVKJ-UHFFFAOYSA-N 3-(4-propylphenyl)prop-2-ynoic acid Chemical compound CCCC1=CC=C(C#CC(O)=O)C=C1 RGJNIEUQOSFVKJ-UHFFFAOYSA-N 0.000 description 3
- XJEQEPGQSHBCSG-UHFFFAOYSA-N C(C#C)(=O)O.C1(=CC=CC=C1)OC Chemical compound C(C#C)(=O)O.C1(=CC=CC=C1)OC XJEQEPGQSHBCSG-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- HXUUKDJAFBRYMD-UHFFFAOYSA-N 3-(4-chlorophenyl)prop-2-ynoic acid Chemical compound OC(=O)C#CC1=CC=C(Cl)C=C1 HXUUKDJAFBRYMD-UHFFFAOYSA-N 0.000 description 2
- DVXIRBTZXZKOPP-UHFFFAOYSA-N 3-(4-methylphenyl)prop-2-ynoic acid Chemical compound CC1=CC=C(C#CC(O)=O)C=C1 DVXIRBTZXZKOPP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- ZNTJVJSUNSUMPP-UHFFFAOYSA-N 1-ethyl-4-ethynylbenzene Chemical group CCC1=CC=C(C#C)C=C1 ZNTJVJSUNSUMPP-UHFFFAOYSA-N 0.000 description 1
- UFOVULIWACVAAC-UHFFFAOYSA-N 1-ethynyl-2-methoxybenzene Chemical group COC1=CC=CC=C1C#C UFOVULIWACVAAC-UHFFFAOYSA-N 0.000 description 1
- UVFFOABHOIMLNB-UHFFFAOYSA-N 1-ethynyl-4-propylbenzene Chemical group CCCC1=CC=C(C#C)C=C1 UVFFOABHOIMLNB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- VRKGBSGNFQZBLU-UHFFFAOYSA-N 3-(2-methylphenyl)prop-2-ynoic acid Chemical compound CC1=CC=CC=C1C#CC(O)=O VRKGBSGNFQZBLU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- QBXYYIGKBUSLQJ-UHFFFAOYSA-N CC(OCOC(C)=O)=O.N Chemical group CC(OCOC(C)=O)=O.N QBXYYIGKBUSLQJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- XQFARSXVMYNQRL-UHFFFAOYSA-N acetylene chlorobenzene Chemical group C#C.ClC1=CC=CC=C1 XQFARSXVMYNQRL-UHFFFAOYSA-N 0.000 description 1
- QDJZBFLFHUMZBE-UHFFFAOYSA-N acetylene;bromobenzene Chemical group C#C.BrC1=CC=CC=C1 QDJZBFLFHUMZBE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical group CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to CO2Activating conversion and related chemistry technical field, be related to it is a kind of synthesize propine acid compounds method.It is characterized by: realizing Terminal Acetylenes and CO in the presence of outer doping and alkali2Directly reaction generates propine acid compounds.The Terminal Acetylenes class substrate that the present invention is applicable in is related to phenylacetylene, substitutedphenylethynyl, heterocycle aryne or aliphatic Terminal Acetylenes etc..Compared with prior art, the present invention is mainly to provide a kind of new simple reaction system.Reaction as additive and facilitates the acetonitrile of post-processing as solvent using potassium carbonate as alkali, quaternary ammonium salt, and still belong to the first time report.The reaction system has the characteristics that without transition-metal catalyst, experimental implementation is simple, raw material is cheap and easily-available, environmental-friendly, has biggish application value and economic results in society.
Description
Technical field
The present invention relates to CO2Activating conversion and related chemistry technical field, be related to a kind of propine acid compounds
Preparation method.
Background technique
Carbon dioxide is rich reserves, cheap and easy to get and reproducible C1Its activating conversion is generated high added value by resource
The research of fine chemicals caused the extensive concern of people.In the past few decades, many passes are reported
In carbon dioxide fixation and the method for conversion [referring to (a) Sakakura, T.；Choi,J.-C.；Yasuda,
H.Chem.Rev.2007,107,2365.(b)Q.Liu；L.Wu；R.Jackstell；M.Beller,Nat.Commun.2015,
6,5933.].Propine acid compounds are important synthetic intermediate, are widely used in synthesis fine chemicals, pharmaceutical molecules etc..
So the synthesis of propine acid compounds is constantly subjected to widely pay close attention to.In the prior art, the side of propine acid compounds is synthesized
Method is mainly the oxidation carboxylation reaction of alkynes, and using formaldehyde or carbon monoxide as carboxylated reagent, but there are CO for this method
The problems such as toxicity is big.There is document report to promote CO using transition metal-catalyzed or cesium carbonate in the recent period2Preparation third is reacted with Terminal Acetylenes
Alkynes acid compounds, but that there are transition-metal catalysts is expensive, ligand is huge and synthesis is difficult, high boiling solvent used
The problems such as difficulty are post-processed [referring to (a) Dingyi Yu；Yugen Zhang,PNAS,2010,47,20189.(b)Hao
Cheng；Bei Zhao；Yingming Yao；Chengrong Lu.Green Chem.,2015,17,1675；(c)Manoj
Trivedi；a Abhinav Kumarb；Nigam P.Rath.Dalton Trans.,2015,44,20874；(d)Seung
Hyo Kim；Kwang Hee Kim；Soon Hyeok Hong.Angew.Chem.Int.Ed.2014,53,771；(e)Xiao-
Huan Liu；Jian-Gong Ma；Zheng Niu；Guang-Ming Yang；Peng
Cheng.Angew.Chem.Int.Ed.2015,54,988].Also once had been reported that using carbon dioxide and Terminal Acetylenes be raw material in no metal
Propine acid compounds are generated in catalyst system, but alkali TBD used and cesium carbonate are more expensive, and the DMF etc. used
Solvent post-processing it is difficult [referring to document (a) Yu Dingyi, Zhang Yugen, Green Chem., 2011,13,1275；(b)
X.Wang,Y.N.Lim,C.Lee,H.-Y.Jang,B.Y.Lee,Eur.J.Org.Chem.2013,1867].Therefore it is urged without metal
Agent, the new method of propine acid compounds at low cost and being easy to post-processing have a good application prospect.
Summary of the invention
The present invention provides a kind of non-metal catalyst, the system without ligand promote CO2It is reacted with Terminal Acetylenes and generates propiolic acid
The method of class compound.This method has many advantages, such as that reaction cost is low, experimental implementation is simple, easily realizes industrialization.
The present invention is one kind with Terminal Acetylenes and CO2For raw material, in the case where additive and alkali promote, Terminal Acetylenes and carbon dioxide are organic
It is reacted in solvent, generates propine acid compounds, reaction equation is as follows:
This method the technical solution adopted is as follows:
The synthesis of propiolic acid: after additive, alkali, solvent and Terminal Acetylenes are added sequentially to autoclave in glove box,
CO is filled with outside glove box2.Autoclave is closed, is put into and starts to react in oil bath pan.
It is characterized in that, organic solvent includes: toluene, n-hexane, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, methylene chloride, three
Chloromethanes, acetonitrile.Preferential tetrahydrofuran, acetonitrile, 1,4- dioxane.
Range of reaction temperature is 20 DEG C~150 DEG C, preferably 75 DEG C~100 DEG C.
Reaction time range is 4~36 hours, preferably 15~24 hours.
Alkali is selected from potassium carbonate, sodium carbonate, sodium acetate, potassium acetate etc..It is preferred that potassium carbonate.
Additive is selected from methylene diacetate ammonium, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutyl vinegar
Sour ammonium, four n-octyl ammonium bromides, cetyl trimethylammonium bromide, ten alkyl trimethyl ammonium bromides, tetrabutyl ammonium nitrate, tetramethyl
Base ammonium iodide, sodium trifluoroacetate, sodium sulphate, ammonium acetate, methyltriphenylphosphonium bromide, tetrafluoro boric acid tri-tert-butylphosphine, ammonium nitrate,
Sodium nitrate, potassium nitrate, sodium sulfite etc..It is preferred that tetrabutylammonium acetate ammonium and tetrabutyl ammonium nitrate.
The amount of organic solvent is 3~10mL.
The molar ratio of terminal alkyne compound and alkali is 1:0.5~10, preferably 1:4.
The molar ratio of terminal alkyne compound and additive is 1:0.1~5, preferably 1:1.5.
CO2Pressure is 0.1MPa~6MPa, preferably 1MPa.
Detailed description of the invention
Fig. 1 is phenylpropiolic acid in embodiment 11H nuclear magnetic spectrogram.
Fig. 2 is phenylpropiolic acid in embodiment 113C nuclear magnetic spectrogram.
Fig. 3 is 2- methoxybenzene propiolic acid in embodiment 21H nuclear magnetic spectrogram.
Fig. 4 is 2- methoxybenzene propiolic acid in embodiment 213C nuclear magnetic spectrogram.
Fig. 5 is this propiolic acid of 4- chlorine in embodiment 31H nuclear magnetic spectrogram.
Fig. 6 is this propiolic acid of 4- chlorine in embodiment 313C nuclear magnetic spectrogram.
Fig. 7 is 4- methyl phenylpropiolic acid in embodiment 41H nuclear magnetic spectrogram.
Fig. 8 is 4- methyl phenylpropiolic acid in embodiment 413C nuclear magnetic spectrogram.
Fig. 9 is in embodiment 5 to bromobenzene propiolic acid1H nuclear magnetic spectrogram.
Figure 10 is in embodiment 5 to bromobenzene propiolic acid13C nuclear magnetic spectrogram.
Figure 11 is 3- fluorobenzene propiolic acid in embodiment 61H nuclear magnetic spectrogram.
Figure 12 is 3- fluorobenzene propiolic acid in embodiment 613C nuclear magnetic spectrogram.
Figure 13 is 4- ethyl phenylpropiolic acid in embodiment 71H nuclear magnetic spectrogram.
Figure 14 is 4- ethyl phenylpropiolic acid in embodiment 713C nuclear magnetic spectrogram.
Figure 15 is 2- propiolic acid thiophene in embodiment 81H nuclear magnetic spectrogram.
Figure 16 is 2- propiolic acid thiophene in embodiment 813C nuclear magnetic spectrogram.
Figure 17 is 4- propyl phenylpropiolic acid in embodiment 91H nuclear magnetic spectrogram.
Figure 18 is 4- propyl phenylpropiolic acid in embodiment 913C nuclear magnetic spectrogram.
Figure 19 is in embodiment 10 to fluorobenzene propiolic acid1H nuclear magnetic spectrogram.
Figure 20 is in embodiment 10 to fluorobenzene propiolic acid13C nuclear magnetic spectrogram.
Specific embodiment
The present invention provides one kind, and propiolic acid method is generated under alkali promotion, and this method has reaction green, experimental implementation
Simply, it easily realizes the advantages that industrialization, shows good application prospect.
Present invention will be further explained below with reference to specific examples.Embodiment is merely to illustrate the present invention rather than limit
The scope of the present invention processed.Technical staff in the art belongs to institute of the present invention to the simple replacement of the invention done or improvement
Within the technical solution of protection.
Embodiment 1: the synthesis of phenylpropiolic acid
Accurately measured in glove box potassium carbonate (552mg, 4mmol, 400mol%), tetrabutylammonium acetate ammonium (451.5mg,
1.5mmol, 150mol%), refined acetonitrile (5.0mL), phenylacetylene (102mg, 1mmol), be added sequentially to the anti-of 25mL
It answers in kettle, CO is filled with outside glove box2(0.1MPa).Capping kettle is placed in 90 DEG C of oil baths and reacts 4h.After reaction, will
Reaction kettle is slowly cooled to room temperature, and then slowly releases remaining gas.Remaining reaction solution is transferred to single port bottle in reaction kettle,
1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, solvent is removed in vacuum, (is washed through silica gel post separation
De- agent: petrol ether/ethyl acetate=6/1) obtain phenylpropiolic acid 124mg, yield 85%.1H NMR(400MHz,CDCl3)δ
11.03(s,1H),7.65–7.57(m,2H),7.53–7.34(m,1H),7.22(d,2H).13C NMR(101MHz,CDCl3)δ
159.00,133.34,131.22,128.70,119.06,89.20,80.13.
The synthesis of embodiment 2:2- methoxybenzene propiolic acid
Accurately measured in glove box sodium carbonate (312mg, 3mmol, 300mol%), tetrabutyl ammonium nitrate (304mg,
1mmol, 100mol%), refined THF (5.0mL), 2- Methoxy-phenylacetylene (132mg, 1mmol), be added sequentially to 25mL
Reaction kettle in, CO is filled with outside glove box2(4MPa).Capping kettle is placed in 30 DEG C of oil baths and reacts 36h.After reaction,
Reaction kettle is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution is transferred to single port in reaction kettle
Bottle is added 1M hydrochloric acid and is acidified to PH=1, be extracted with ethyl acetate, collects organic phase, solvent is removed in vacuum, through silica gel post separation
(eluant, eluent: petrol ether/ethyl acetate=6/1) obtains 2- methoxybenzene propiolic acid 158mg, yield 90%.1H NMR
(400MHz,CDCl3)δ10.42(s,1H),7.65(d,1H),7.54(t,1H),7.04(dd,2H),4.01(s,3H).13C
NMR(101MHz,CDCl3)δ161.90,158.72,135.22,132.87,120.60,110.91,108.40,86.20,
84.07,55.88.
The synthesis of embodiment 3:4- chlorobenzene propiolic acid
Potassium carbonate (552mg, 4mmol, 400mol%), positive tetrabutylammonium bromide are accurately measured in glove box
(644.6mg, 2mmol, 200mol%), refined methylene chloride (5.0mL), 4- chlorobenzene acetylene (136.5mg, 1mmol), according to
It is secondary to be added in the reaction kettle of 25mL, CO is filled with outside glove box2(2MPa).Capping kettle is placed in 60 DEG C of oil baths and reacts
18h.After reaction, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.It is remaining anti-in reaction kettle
It answers liquid to be transferred to single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, is removed in vacuum molten
Agent obtains 4- chlorobenzene propiolic acid 145mg, yield 80% through silica gel post separation (eluant, eluent: petrol ether/ethyl acetate=6/1).1H
NMR(400MHz,MeOD)δ7.56(d,2H),7.44(d,2H)；13C NMR(101MHz,MeOD)δ155.02,136.63,
133.91,128.85,118.28,83.73,81.37.
The synthesis of embodiment 4:4- methyl phenylpropiolic acid
Sodium acetate (123mg, 1.5mmol, 150mol%), tetrabutylammonium acetate ammonium are accurately measured in glove box
(451.5mg, 1.5mmol, 150mol%), refined n-hexane (5.0mL), to methyl phenylacetylene (116mg, 1mmol), according to
It is secondary to be added in the reaction kettle of 25mL, CO is filled with outside glove box2(0.5MPa).Capping kettle is placed in 100 DEG C of oil baths and reacts
24h.After reaction, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.It is remaining anti-in reaction kettle
It answers liquid to be transferred to single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, is removed in vacuum molten
Agent is obtained through silica gel post separation (eluant, eluent: petrol ether/ethyl acetate=6/1) to methyl phenylpropiolic acid 147mg, and yield is
92%.1H NMR(400MHz,CDCl3)δ7.44(d,2H),7.30(d,2H),2.37(s,3H).13C NMR(101MHz,
CDCl3)δ159.10,142.01,133.36,129.49,115.97,89.86,79.84,21.78.
Embodiment 5: the synthesis to bromobenzene propiolic acid
Potassium carbonate (552mg, 4mmol, 400mol%), four n-octyl ammonium bromides are accurately measured in glove box
(2734.0mg, 5mmol, 500mol%), refined acetonitrile (5.0mL), to bromobenzene acetylene (181mg, 1mmol), successively plus
Enter into the reaction kettle of 25mL, CO is filled with outside glove box2(1.5MPa).Capping kettle is placed in 110 DEG C of oil baths and reacts 28h.
After reaction, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.Remaining reaction solution in reaction kettle
It is transferred to single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, solvent is removed in vacuum, passes through
Silica gel post separation (eluant, eluent: petrol ether/ethyl acetate=6/1) is obtained to bromobenzene propiolic acid 178mg, yield 79%.1H
NMR(400MHz,MeOD)δ7.57(d,2H),7.46(d,2H)；13C NMR(101MHz,MeOD)δ154.98,134.00,
131.86,124.91,118.69,83.78,81.49.
The synthesis of embodiment 6:3- fluorobenzene propiolic acid
Potassium carbonate (345.5mg, 2.5mmol, 250mol%), tetramethyl ammonium acetate are accurately measured in glove box
(226.4mg, 2mmol, 200mol%), refined Isosorbide-5-Nitrae-dioxane (5.0mL), 3- fluorobenzene acetylene (120mg, 1mmol),
It is added sequentially in the reaction kettle of 25mL, CO is filled with outside glove box2(3MPa).Capping kettle is placed in 100 DEG C of oil baths and reacts
18h.After reaction, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.It is remaining anti-in reaction kettle
It answers liquid to be transferred to single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, is removed in vacuum molten
Agent obtains 3- fluorobenzene propiolic acid 137mg, yield 84% through silica gel post separation (eluant, eluent: petrol ether/ethyl acetate=6/1).1H
NMR (400MHz, MeOD) δ 7.49-7.38 (m, 2H), 7.33 (d, J=9.2Hz, 1H), 7.25 (t, J=8.4Hz, 1H)13C
NMR(101MHz,MeOD)δ161.11,154.89,130.57,128.56,121.47,119.00,117.79,83.30,
81.10.
The synthesis of embodiment 7:4- ethyl phenylpropiolic acid
Potassium carbonate (221mg, 1.6mmol, 160mol%), tetrabutylammonium acetate ammonium are accurately measured in glove box
(451.5mg, 1.5mmol, 150mol%), refined THF (5.0mL), 4- Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene (130mg, 1mmol), successively
It is added in the reaction kettle of 25mL, CO is filled with outside glove box2(2MPa).Capping kettle is placed in 80 DEG C of oil baths and reacts 20h.
After reaction, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.Remaining reaction solution in reaction kettle
It is transferred to single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, solvent is removed in vacuum, passes through
Silica gel post separation (eluant, eluent: petrol ether/ethyl acetate=6/1) obtains 4- ethyl phenylpropiolic acid 149mg, yield 86%.1H
NMR(400MHz,CDCl3)δ9.62(s,1H),7.55(d,2H),7.25(t,2H),2.70(q,2H),1.26(t,3H).13C
NMR(101MHz,CDCl3)δ158.79,148.15,133.47,128.30,116.18,89.75,79.80,29.05,15.14.
The synthesis of embodiment 8:2- propiolic acid thiophene
Potassium carbonate (552mg, 4mmol, 400mol%), methyltriphenylphosphonium bromide are accurately measured in glove box
(1074.7mg, 3mmol, 300mol%), refined acetonitrile (5.0mL), 2- thiophene acetylene (108mg, 1mmol), successively
It is added in the reaction kettle of 25mL, CO is filled with outside glove box2(1MPa).Capping kettle is placed in 120 DEG C of oil baths and reacts 12h.
After reaction, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.Remaining reaction solution in reaction kettle
It is transferred to single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, solvent is removed in vacuum, passes through
Silica gel post separation (eluant, eluent: petrol ether/ethyl acetate=6/1) obtains 2- propiolic acid thiophene 118.6mg, yield 78%.1H
NMR(400MHz,MeOD)δ7.69(d 1H),7.60–7.55(m,1H),7.15(t,1H)；13C NMR(101MHz,MeOD)δ
155.08,136.21,131.26,127.48,119.04,84.63,79.00.。
The synthesis of embodiment 9:4- propyl phenylpropiolic acid
Accurately measured in glove box potassium carbonate (552mg, 4mmol, 400mol%), tetrabutylammonium acetate ammonium (451.5mg,
1.5mmol, 150mol%), refined acetonitrile (5.0mL), 4- propyl phenylacetylene (144mg, 1mmol), be added sequentially to
In the reaction kettle of 25mL, CO is filled with outside glove box2(1.3MPa).Capping kettle is placed in 50 DEG C of oil baths and reacts for 24 hours.Reaction
After, reaction kettle is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution transfer in reaction kettle
To single port bottle, 1M hydrochloric acid is added and is acidified to PH=1, is extracted with ethyl acetate, collects organic phase, solvent is removed in vacuum, through silica gel
Post separation (eluant, eluent: petrol ether/ethyl acetate=6/1) obtains 4- propyl phenylpropiolic acid 165mg, yield 88%.1H NMR
(400MHz,CDCl3)δ10.81(s,1H),7.56(d,2H),7.23(d,2H),2.64(t,2H),1.67(dd,2H),0.96
(t,3H).13C NMR(101MHz,CDCl3)δ158.91,146.65,133.37,128.87,116.22,89.77,79.86,
38.13,24.16,13.72.
Embodiment 10: the synthesis to fluorobenzene propiolic acid
Accurately measured in glove box potassium carbonate (552mg, 4mmol, 400mol%), tetrabutylammonium acetate ammonium (451.5mg,
1.5mmol, 150mol%), refined toluene (5.0mL), to fluorobenzene acetylene (120mg, 1mmol), be added sequentially to 25mL
Reaction kettle in, CO is filled with outside glove box2(0.7MPa).Capping kettle is placed in 75 DEG C of oil baths and reacts 16h.Reaction terminates
Afterwards, reaction kettle is slowly cooled to room temperature, then slowly releases remaining gas.Remaining reaction solution is transferred to list in reaction kettle
Mouth bottle is added 1M hydrochloric acid and is acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, through silicagel column point
It obtains from (eluant, eluent: petrol ether/ethyl acetate=6/1) to fluorobenzene propiolic acid 126mg, yield 77%.1H NMR(400
MHz,MeOD)δ7.71(dd,2H),7.32(t,2H)；13C NMR(101 MHz,MeOD)δ165.18,162.68,155.16,
135.05,134.96,115.93,115.70,84.09,80.43.
Claims (3)
1. a kind of preparation method of propine acid compounds, which is characterized in that in the case where additive and alkali promote, Terminal Acetylenes and titanium dioxide
Carbon reacts in organic solvent, generates propine acid compounds, and synthetic route is as follows:
The following steps are included:
(1) autoclave is added in additive, alkali, Terminal Acetylenes, organic solvent, is then charged with carbon dioxide and closes autoclave, in oil
It is reacted under magnetic agitation in bath；
(2) the propiolic acid salt compounds crude product that step (1) obtains is added into water, is acidified, is then extracted with ethyl acetate, obtains
Propiolic acid crude product purified by silica gel column is separated, and propine acid product is finally separating to obtain；
Reaction temperature is 20 DEG C~150 DEG C；Reaction pressure is 0.1MPa~6MPa；Reaction time 4~36 hours；
The Terminal Acetylenes general structure isWherein it is miscellaneous to be selected from substituted or unsubstituted aliphatic group, aryl radical, fragrance by R
Ring group；
The additive is selected from tetramethyl ammonium acetate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, the tetrabutyl
Ammonium acetate, four n-octyl ammonium bromides, cetyl trimethylammonium bromide, ten alkyl trimethyl ammonium bromides, tetrabutyl ammonium nitrate, four
The mixing of one or both of methylpyridinium iodide ammonium, methyltriphenylphosphonium bromide, tetrafluoro boric acid tri-tert-butylphosphine；Terminal Acetylenes and additive
Molar ratio be 1:0.1~5；The alkali is selected from one of potassium carbonate, sodium carbonate, sodium acetate, potassium acetate；The organic solvent
It is at least one of toluene, n-hexane, tetrahydrofuran, 1,4- dioxane, methylene chloride, chloroform, acetonitrile solvent.
2. preparation method as described in claim 1, which is characterized in that the molar ratio of Terminal Acetylenes and alkali used is 1:0.5~10.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the molar concentration of Terminal Acetylenes is 0.01~2mmol/mL.
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