CN111470954A - 一种原羧酸酯的合成方法 - Google Patents
一种原羧酸酯的合成方法 Download PDFInfo
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- CN111470954A CN111470954A CN202010282325.9A CN202010282325A CN111470954A CN 111470954 A CN111470954 A CN 111470954A CN 202010282325 A CN202010282325 A CN 202010282325A CN 111470954 A CN111470954 A CN 111470954A
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000002148 esters Chemical class 0.000 title claims description 13
- 230000002194 synthesizing effect Effects 0.000 title claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 150000007942 carboxylates Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 27
- -1 C3-C8Cycloalkyl radical Chemical class 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 9
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 239000003930 superacid Substances 0.000 claims description 6
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 4
- 229910021630 Antimony pentafluoride Inorganic materials 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
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910004770 HSO3F Inorganic materials 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000006644 (C2-C6) haloalkynyl group Chemical group 0.000 claims description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910017049 AsF5 Inorganic materials 0.000 claims description 2
- 229910015844 BCl3 Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 229910019787 NbF5 Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910004546 TaF5 Inorganic materials 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- QLYSAMSIXPXFDZ-UHFFFAOYSA-I gold pentafluoride Chemical compound F[Au](F)(F)(F)F QLYSAMSIXPXFDZ-UHFFFAOYSA-I 0.000 claims description 2
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 2
- SWLJJEFSPJCUBD-UHFFFAOYSA-N tellurium tetrachloride Chemical compound Cl[Te](Cl)(Cl)Cl SWLJJEFSPJCUBD-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- HPICRATUQFHULE-UHFFFAOYSA-J uranium(4+);tetrachloride Chemical compound Cl[U](Cl)(Cl)Cl HPICRATUQFHULE-UHFFFAOYSA-J 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- FPIVAWNGRDHRSQ-UHFFFAOYSA-N 2-[di(propan-2-yloxy)methoxy]propane Chemical compound CC(C)OC(OC(C)C)OC(C)C FPIVAWNGRDHRSQ-UHFFFAOYSA-N 0.000 description 2
- 239000005730 Azoxystrobin Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 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 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BQFPCTXLBRVFJL-UHFFFAOYSA-N triethoxymethylbenzene Chemical compound CCOC(OCC)(OCC)C1=CC=CC=C1 BQFPCTXLBRVFJL-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/60—Preparation of compounds having groups or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种原羧酸酯的合成方法，其特征在于用羧酸酯与醚在催化剂催化下在一定的温度下，一定的压力下反应一定的时间制备：
Description
技术领域
本发明属于精细化学品绿色合成领域，具体地涉及到一种原羧酸酯的合成方法。
背景技术
原羧酸酯在精细化学品的合成中有着广泛的应用，其中比较有代表性的产品为原甲酸三甲酯、原甲酸三乙酯、原甲酸三异丙酯等等。
传统的原羧酸酯的合成是通过如下几条反应路线制备：
1、腈类与醇类在通入氯化氢气体条件下反应是目前世界上常用的原羧酸酯的生产方法，比较有代表性的产品为原甲酸三甲酯、原甲酸三乙酯。该方法是通过腈与甲醇(或者乙醇)、氯化氢反应，生成氢卤酸亚胺盐，然后醇解、纯化得到原羧酸酯产品；其中的纯化步骤是对醇解反应液进行纯化，具体是分别进行一级蒸馏、纯化处理及二级蒸馏，其中一级蒸馏主要包括初馏、一级精馏、溶剂回收步骤。但是，这种方法得到的产品液中，含有三氮杂苯(三嗪)等含氮杂质是不可避免的。极少量该杂质的存在，会严重干扰和限制了原羧酸酯的应用，比如，以原甲酸三甲酯为原料生产嘧菌酯时，即使原料中含有0.1％的三嗪，也将大大降低嘧菌酯收率。
2、同原子的三氯烷烃与醇钠反应缩合制备。如原甲酸三甲酯的合成，用氯仿与甲醇钠缩合制备。这种反应首先制备醇钠，而醇钠的制备往往是通过钠与甲醇反应制备。在制备甲醇钠的过程中，会产生大量的氢气，对于生产安全产生巨大威胁。
2、酯交换法
如用原甲酸三甲酯与乙醇反应制备原甲酸三乙酯，或者原甲酸三甲酯与异丙醇制备原甲酸三异丙酯。
3、酰氯法
如原甲酸三乙酯的制备，用苯甲酰氯与甲酰胺和乙醇制备原甲酸三乙酯。
4、二烷氧基醇钠法
这种方法通过羧酸酯与醇钠反应后与卤代烷缩合制备。
发明内容
为了满足绿色生产的需要，为了更好地减少化工生产对于自然界产生的污染和危害，本发明提供了一种原羧酸酯的合成方法。其优点为，用羧酸酯与醚在催化剂催化下一步合成出原羧酸酯。
其反应式如下，
其反应过程如下：用催化剂催化羧酸酯与醚在一定的反应温度、一定的反应压力下反应一定的时间直接制得原羧酸酯。
在反应式中：
R选自C1-C6烷基，C2-C6炔基，C3-C8环烷基，每个可用以下基团任意选择取代：(卤素，CN，NO2，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基；C3-C6三烷基甲硅烷基，或苯基，苯氧基或5元或6元杂芳环，每个环可用以下的基团任意选择取代：(C1-C6烷基，，C2-C6炔基，C3-C8环烷基，C1-C6卤烷基，C2-C6卤炔基；C3-C8卤环烷基，卤素，CN，NO2，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C2-C6烷基羰基))；或为苯基，苄基，五元或六元杂环，每个可用以下基团任意选择取代：(C1-C6烷基，C2-C6炔基，C3-C8环烷基，C1-C6卤烷基，C2-C6卤炔基，C3-C8卤环烷基，卤素，CN，NO2，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C2-C6烷基羰基，或C1-C6三烷基甲硅烷基)。
R1、R2和R3分别独立地选自：C1-C6烷基，C2-C6烯基，C2-C6炔基，C3-C8环烷基。
在上述的反应中，所述的催化剂为酸性催化剂，选自：1)路易斯酸，包括BF3、BCl3、AlBr3、CbCl3、TiCl4、ZrCl4、FeCl3、FeBr3、SbCl5、SbF5、AsF5、MbCl3、BeCl3、UCl4、WCl4、ZnCl2、CuCl2、HgCl2、SnCl4、TeCl4、AuF5、TaF5、NbF5；2)质子酸，包括氯化氢、氟化氢、发烟硫酸、硫酸、磷酸、过磷酸、三氟乙酸、高氯酸；3)液体超强酸，包括HSO3Cl、HSO3F、HSO3CF3；4)无机固体超强酸，包括TiO2·H2SO4、SbF5-SiO2-Al2O3、SbF5-TiO2-SiO2、SO4 -/Fe2O3、SO4 -/TiO2、SO4 -/ZnO2、SO4 -/SnO2、SO4 -/Al2O3、SO4 -/Al2O3-ZnO2、SO4 -/TiO2-ZnO2、SO4 -/WO3-ZnO2；5)有机高分子超强酸，包括DSFB(制备方法见《离子交换与吸附》1995,11(4),363-367)6)无机杂多酸，包括H3PW12O40、H4SiW12O40-H4GeW12O40、H5BW12O40、H6P2W18O62、H6CoW12O40；其中的任意一种或者两种以上。
在上述反应中，所述的羧酸酯和醚的比例在1:100-100：1(摩尔比)；优选范围在1:1-1:10；
在上述反应中，可以选用非质子有机溶剂作为溶剂，选自1)芳香烃如苯、甲苯、氯苯、二甲苯，2)烷烃或者环烷烃如环己烷、正庚烷、正辛烷；3)氯代烃如二氯甲烷、二氯乙烷、氯仿、四氯化碳中的一种或两种以上。
在上述反应中，所述的溶剂可以用反应物本身。
在上述反应中，所述的反应时间从0.1小时-144小时。
在上述反应中，所述的反应压力在0.01Mpa-100Mpa之间。
在上述反应中，所述的反应温度在0-200℃之间。
具体实施方式：
下面结合实施例来说明本发明的内容，但是本发明保护范围绝对不仅仅局限在实施例的范围。
实施例1、原苯甲酸三乙酯制备
在50ml带有磁力搅拌子的不锈钢高压釜里，加入1.50g(10mmol)苯甲酸乙酯，0.1g正十六烷(内标)以及含有0.068g(1mmol)三氟化硼的7.40g(100mmol)乙醚溶液中，升温到110℃反应6.0小时，待反应结束后，降温到0-5℃。样品用气相分析，得到苯甲酸乙酯的转化率98％，原苯酸三乙酯收率95％。
实施例2-40
根据实施例-1的反应条件，选用不同的羧酸酯和醚类化合物，以及不同的反应条件，可以得到相应的原羧酸酯类。实施例1-40的结果见表1
表1
实施例41-60
根据实施例1的反应过程，把催化剂调整为三氯化铝、三溴化铝、SO4 -/TiO2、SbF5、HSO3F、DSFB、SO4 -/Al2O3-ZnO2、H3PW12O40、HF-SbF5等催化剂(其中催化剂当量和三氟化硼相同)。其结果见表2
表2
Claims (8)
1.一种原羧酸酯的合成方法，其特征在于用羧酸酯与醚在催化剂催化下在一定的温度下，一定的压力下反应一定的时间制备：
式中：
R选自C1-C6烷基，C2-C6炔基，C3-C8环烷基，每个可用以下基团任意选择取代：（卤素，CN，NO2，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基；C3-C6三烷基甲硅烷基，或苯基，苯氧基或5元或6元杂芳环，每个环可用以下的基团任意选择取代：（C1-C6烷基，C2-C6炔基，C3-C8环烷基，C1-C6 卤烷基，C2-C6卤炔基；C3-C8卤环烷基，卤素，CN，NO2，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6 烷基磺酰基，C2-C6烷基羰基））；或为苯基，苄基，五元或六元杂环，每个可用以下基团任意选择取代：（C1-C6烷基，C2-C6炔基，C3-C8环烷基，C1-C6卤烷基，C2-C6卤炔基，C3-C8卤环烷基，卤素，CN，NO2，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C2-C6烷基羰基，或C1-C6三烷基甲硅烷基）；
R1、R2和R3分别独立地选自：C1-C6烷基，C2-C6烯基，C2-C6炔基，C3-C8环烷基。
2.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于所述的催化剂选自：1）路易斯酸，包括BF3、BCl3、AlBr3、CbCl3、TiCl4、ZrCl4、FeCl3、FeBr3、SbCl5、SbF5、AsF5、MbCl3、BeCl3、UCl4、WCl4、ZnCl2、CuCl2、HgCl2、SnCl4、TeCl4、AuF5、TaF5、NbF5；2）质子酸，包括氯化氢、氟化氢、发烟硫酸、硫酸、磷酸、过磷酸、三氟乙酸、高氯酸；3）液体超强酸，包括HSO3Cl、HSO3F、HSO3CF3；4）无机固体超强酸，包括 TiO2·H2SO4、SbF5-SiO2-Al2O3、SbF5-TiO2-SiO2、SO4 -/Fe2O3、SO4 -/TiO2、SO4 -/ZnO2、SO4 -/SnO2、SO4 -/Al2O3、SO4 -/Al2O3-ZnO2、SO4 -/TiO2-ZnO2、SO4 -/WO3-ZnO2；5）有机高分子超强酸，包括DSFB（制备方法见《离子交换与吸附》1995,11(4),363-367）6）无机杂多酸，包括H3PW12O40、H4SiW12O40-H4GeW12O40、H5BW12O40、H6P2W18O62、H6CoW12O40；其中的任意一种或者两种以上。
3.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于所述的羧酸酯和醚的比例在1:100-100：1（摩尔比）；优选范围在1:1-1:10。
4.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于可以选用非质子有机溶剂，选自1)芳香烃如苯、 甲苯、氯苯、二甲苯，2）烷烃或者环烷烃如环己烷、正庚烷、正辛烷；3）氯代烃如二氯甲烷、二氯乙烷、氯仿、四氯化碳中的一种或两种以上。
5.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于所述的溶剂可以用反应物本身。
6.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于所述的反应时间从0.1小时-144小时。
7.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于所述的反应压力在0.01Mpa-100Mpa之间。
8.根据权利要求1所述的一种原羧酸酯的合成方法，其特征在于所述的反应温度在0-200℃之间。
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