CN104592175B - Preparation method of 2,5-dialkoxyl dihydrofuran compound - Google Patents
Preparation method of 2,5-dialkoxyl dihydrofuran compound Download PDFInfo
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- CN104592175B CN104592175B CN201410836951.2A CN201410836951A CN104592175B CN 104592175 B CN104592175 B CN 104592175B CN 201410836951 A CN201410836951 A CN 201410836951A CN 104592175 B CN104592175 B CN 104592175B
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- -1 dihydrofuran compound Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GEVVMWHWTUKSKV-UHFFFAOYSA-M [I-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.[I-] Chemical compound [I-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.[I-] GEVVMWHWTUKSKV-UHFFFAOYSA-M 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- VMFNFNLGPLHBNJ-UHFFFAOYSA-M azanium benzyl(triethyl)azanium diacetate Chemical compound C(C)(=O)[O-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.C(C)(=O)[O-] VMFNFNLGPLHBNJ-UHFFFAOYSA-M 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010980 drying distillation Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000007530 organic bases Chemical group 0.000 claims description 2
- UXRVNHHPRRDXJG-UHFFFAOYSA-M phosphane tetrabutylazanium hydroxide Chemical compound P.[OH-].C(CCC)[N+](CCCC)(CCCC)CCCC UXRVNHHPRRDXJG-UHFFFAOYSA-M 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- HIACZXUUKNSHAN-UHFFFAOYSA-M trimethyl(octadecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C HIACZXUUKNSHAN-UHFFFAOYSA-M 0.000 claims description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 2
- CURCMGVZNYCRNY-UHFFFAOYSA-N trimethylazanium;iodide Chemical compound I.CN(C)C CURCMGVZNYCRNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- QZSJAWGFGAMSNW-UHFFFAOYSA-M P.[OH-].C(C1=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P.[OH-].C(C1=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 QZSJAWGFGAMSNW-UHFFFAOYSA-M 0.000 claims 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims 1
- FTTRLNOPHKYTED-UHFFFAOYSA-M [F-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.[F-] Chemical compound [F-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.[F-] FTTRLNOPHKYTED-UHFFFAOYSA-M 0.000 claims 1
- AUBSNUSTVUZGCC-UHFFFAOYSA-N [NH4+].[Br-].C(C)[PH3+].[Br-] Chemical compound [NH4+].[Br-].C(C)[PH3+].[Br-] AUBSNUSTVUZGCC-UHFFFAOYSA-N 0.000 claims 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims 1
- 150000001649 bromium compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 125000004852 dihydrofuranyl group Chemical class O1C(CC=C1)* 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000003839 salts Chemical group 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 abstract 1
- 125000005233 alkylalcohol group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000008569 process Effects 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- DYOSAFQUIFEGSK-UHFFFAOYSA-N 2,5-dimethoxy-2,3-dihydrofuran Chemical compound COC1CC=C(OC)O1 DYOSAFQUIFEGSK-UHFFFAOYSA-N 0.000 description 4
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- GZYGYLSHLHOMAO-UHFFFAOYSA-N 2,5-dimethoxy-2-methyloxolane Chemical compound COC1CCC(C)(OC)O1 GZYGYLSHLHOMAO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000014102 seafood Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- GFISDBXSWQMOND-UHFFFAOYSA-N 2,5-dimethoxyoxolane Chemical compound COC1CCC(OC)O1 GFISDBXSWQMOND-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KMYQCELRVANQNG-YXGOVGSCSA-N Br.CN1[C@@H]2C[C@H](O)[C@H]1C[C@H](C2)OC(=O)[C@H](CO)c1ccccc1 Chemical compound Br.CN1[C@@H]2C[C@H](O)[C@H]1C[C@H](C2)OC(=O)[C@H](CO)c1ccccc1 KMYQCELRVANQNG-YXGOVGSCSA-N 0.000 description 1
- RFTPGNDRKDYXJO-UHFFFAOYSA-N CC1(OC(CC1)(OCC)C)OCC Chemical compound CC1(OC(CC1)(OCC)C)OCC RFTPGNDRKDYXJO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940121948 Muscarinic receptor antagonist Drugs 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- HOBWAPHTEJGALG-JKCMADFCSA-N [(1r,5s)-8-methyl-8-azoniabicyclo[3.2.1]octan-3-yl] 3-hydroxy-2-phenylpropanoate;sulfate Chemical compound [O-]S([O-])(=O)=O.C([C@H]1CC[C@@H](C2)[NH+]1C)C2OC(=O)C(CO)C1=CC=CC=C1.C([C@H]1CC[C@@H](C2)[NH+]1C)C2OC(=O)C(CO)C1=CC=CC=C1 HOBWAPHTEJGALG-JKCMADFCSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229960002028 atropine sulfate Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000812 cholinergic antagonist Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GRVPDGGTLNKOBZ-UHFFFAOYSA-M triethyl(methyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(CC)CC GRVPDGGTLNKOBZ-UHFFFAOYSA-M 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of a 2,5-dialkoxyl dihydrofuran compound. The preparation method comprises the following steps: adding a furan compound shown by a formula I, alkyl alcohol shown by a formula III and an acid-binding agent into a reactor, stirring to react with chlorine, keeping the reaction temperature to be (-25)-25 DEG C, and reacting to obtain a 2,5-dialkoxyl dihydrofuran compound shown by a formula II, wherein in the formulas, R1, R2, R3 and R4 are independent hydrogen, halogen and C1-C5 alkyl, and R1 is a C1-C12 alkyl. The method provided by the invention is less in investment, low in energy consumption and high in efficiency; the reaction method is simple, and the operation is convenient and easy to implement; the raw materials are low in price, easy to obtain, and low in production cost; a byproduct is salt and can meet requirements on environmental protection; and the preparation method is suitable for performing industrial large-scale production of the 2,5-dialkoxyl dihydrofuran compound. Particularly, when a phase transfer catalyst is added into the method provided by the invention, the method also has the advantage that the yield of a target product is obviously improved.
Description
Technical field
The present invention relates to organic synthesis field is and in particular to a kind of preparation of 2,5- dialkoxy dihydrofuran class compound
Method.
Background technology
2,5- dialkoxy dihydrofuran class compound is the important medicine intermediate of a class and fragrance intermediates.As 2,5- bis-
Melonia furan is the intermediate of synthesis anticholinergic agent atropine sulfate and anisodamine hydrobromide, and it is acceptable
For taking a picture, post bake reagent uses it is also possible to directly be used as sterilization reagent, may also pass through hydrochloric acid hydrolysis and hydrogenation and prepares weight
Want Speciality Petrochemicals intermediate butanedial, in addition it can obtain 2,5- dimethoxy-tetrahydrofuran with catalytic hydrogenation.As 2-
Methyl -2,5- dimethoxy dihydrofuran is then the indispensable raw material of preparing essence, spice, in seafood, seafood taste using fragrant
It is widely used in essence.
There is in 2,5- dialkoxy dihydrofuran class compound the synthesis of the 2,5- dimethoxy dihydrofuran of typicality
Technique mainly has following two.1st, electrochemical oxidation process: reaction is carried out in a cell, and anode can use graphite and dsa net, anode
Liquid is furan+methanol+sodium bromide (amine bromide), is barrier film with asbestos, catholyte sodium bromide and methanol solution, and negative electrode is filling
Graphite, product directly generates on anode.The method investment is big, high energy consumption, efficiency are low, is not suitable for large-scale production.2nd, chemistry
Synthetic method: having document report to adopt furan is raw material, to synthesize 2,5- diformazan in the mixed solution and dripping bromine of methanol and benzene
Epoxide dihydrofuran.The bromine that the method uses has extremely strong strong toxic and corrosivity, and solvent benzol is poisonous, is the iarc first kind
Carcinogen；The furan utilization rate of the method is not also high, and product yield is low.
Content of the invention
For the deficiency preparing 2,5- dialkoxy dihydrofuran class compound method in prior art, the invention discloses
A kind of new method preparing 2,5- dialkoxy dihydrofuran class compound.
Therefore, the present invention provides a kind of preparation method of 2,5- dialkoxy dihydrofuran class compound, including by such as formula i
Alkylol shown in shown furfuran compound, formula iii and acid binding agent add in reactor, stirring and and chlorine reaction, keep anti-
Answer temperature at -25 DEG C～25 DEG C, reaction obtains 2, the 5- dialkoxy dihydrofuran class compound as shown in formula ii；
In formula, r1, r2, r3, r4For each independent hydrogen, halogen, c1-c5Alkyl, r1For c1-c12Alkyl.
Chemical equation in the inventive method is as follows:
From aforesaid equation as can be seen that furfuran compound is with chlorine reaction, first Isosorbide-5-Nitrae-addition generates 2,5- dichloro-dihydro
Furans intermediate, then replace compound shown in production ii through alkoxyl.Alkylol was both former as reaction in the reaction
Material (second step reaction), and as solvent (first step reaction).In a kind of specific embodiment, described alkylol is anhydrous
Alcohol.
The method that the present invention provides is suitable for preparing 2,5- dialkoxy dihydrofuran class compound, in particular for closing
Become important medicine intermediate 2,5- dimethoxy dihydrofuran and fragrance intermediates 2- methyl -2,5- dimethoxy dihydrofuran.
The present invention is compared to electrochemical oxidation process of the prior art and chemical synthesiss although excellent in terms of product yield
Gesture is inconspicuous；But small investment of the present invention, energy consumption is low, and efficiency is higher；Reaction method is simple, easy to operate；Raw material is inexpensively easy
, low production cost；By-product is salt (such as sodium chloride), meets the requirement of environmental protection；It is applied to industrialization large-scale production
2,5- dialkoxy dihydrofuran class compound.
In the present invention, the amount of the material of chlorine is, for example, 1～10 times of described furfuran compound.
Preferably, using Catalyzed By Phase-transfer Catalyst shown in formula i 2, the 5- bis- shown in furfuran compound formula ii
The reaction of alkoxyl dihydrofuran class compound.In the present invention, when being occurred using this reaction of Catalyzed By Phase-transfer Catalyst, protecting
Under conditions of holding aforementioned preparation process items advantage in the present invention, the yield of purpose product in the program is also made to be greatly improved
(under the conditions of same reaction temperature, yield can improve nearly 30%), this also make in the present invention the method compared to existing technology in
Electrochemical oxidation process and chemical synthesiss for, yield sharp rises.The quality of phase transfer catalyst of the present invention and formula i
The mass ratio of shown furfuran compound is 0.002～0.2:1, preferably 0.02～0.1:1.Phase transfer catalyst of the present invention
Can be the catalyst of commercially available acquisition, the phase transfer catalyst that for example, Zhejiang Kent Chemical Co., Ltd. produces.
Operation is simple for the present invention, in system add acid binding agent can effectively absorbing reaction generation hydrogen chloride, make
React and move to positive direction, improve the utilization rate of raw material.Especially in the preferred embodiment adding phase transfer catalyst, phase
The addition of transfer catalyst can accelerate acid binding agent to sour absorption, prevents acid system from the side reactions such as furan open loop occurring, thus
The quality of product and yield are improved significantly.
In a kind of specific embodiment, described phase transfer catalyst is selected from quaternary amine and season phosphine alkali, and described quaternary amine
Salt is selected from methyl triethyl ammonium chloride, methyl triethylammonium bromide, methyl triethyl group ammonium iodide, methyl triethyl group ammonium acetate, benzyl
Base triethyl group ammonium fluoride, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium iodide, benzyl triethyl ammonium
Ammonium acetate, Dodecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, trimethyl ammonium iodide, octadecane
One or more of base trimethyl ammonium chloride, 18 protective embankment base trimethylammonium bromides and octadecyl trimethyl ammonium iodide, described
Season, phosphine alkali was selected from tetramethyl hydroxide phosphine, tetraethyl hydroxide phosphine, tetrapropyl hydroxide phosphine, tetrabutylammonium hydroxide phosphine, benzyl
In triphenyl hydroxide phosphine, methyl triphenyl hydroxide phosphine, ethyl triphenyl hydroxide phosphine and propyl group triphenyl hydroxide phosphine
One or more.
In a kind of specific embodiment, the response time of described reaction is 1～15h, preferably 8～12h.And anti-
First remove residual chlorine after the completion of answering, then obtain described 2,5- dialkoxy dihydro after solid-liquid separation, drying and vacuum distillation
Furfuran compound.
Preferably, r1For c1-c3Alkyl；r1, r2, r3, r4For each independent hydrogen and c1-c3Alkyl.
In a kind of specific embodiment, described alkylol consumption is the amount of the material of furfuran compound shown in formula i
3～20 times, chlorine consumption is 1～3 times of the amount of the material of furfuran compound shown in formula i.
Preferably, reaction temperature of the present invention is -10 DEG C～5 DEG C, more preferably -5 DEG C～0 DEG C.
In the present invention, described acid binding agent is organic base or inorganic base, is preferably selected from triethylamine, pyridine, liquefied ammonia, hydroxide
One or more of sodium, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, Sodium Acetate Trihydrate and potassium acetate.In the present invention, institute
State acid binding agent consumption and be 1～5 times of the amount of the material of furfuran compound shown in formula i, preferably 1～3 times.
Specific embodiment
The present invention is illustrated by following examples, but following examples are not intended to limit the present invention.
Embodiment 1
Furan 60g, sodium carbonate 110g, phase transfer catalyst methyl triethyl ammonium chloride 2g, methanol is put into in reactor
300g, stirring, when opening low temperature thermostat bath and being cooled to -5 DEG C～5 DEG C, logical chlorine 80g simultaneously keeps this reaction temperature, anti-after reaction 10h
Should terminate.Remaining chlorine in reactant liquor is taken out in decompression, and standing (makes solid-liquid be layered), filters and (remove the phase transfer catalysis of solid-state
Agent and salt), terminate backward reactant liquor and add appropriate anhydrous sodium sulfate drying, after standing a period of time, sucking filtration (removes sulphuric acid
Sodium), filtrate decompression is distilled, and obtains product 2,5- dimethoxy dihydrofuran 97.6g, yield 85.3%.
Embodiment 2
2- methylfuran 73g, sodium bicarbonate 170g, phase transfer catalyst methyl triethyl ammonium chloride is put into in reactor
With tetraethyl hydroxide phosphine (mass ratio is 1:1) common 2g, methanol 350g, stirring, open low temperature thermostat bath and be cooled to -5 DEG C～5 DEG C
When, logical chlorine 80g simultaneously keeps this reaction temperature, reacts and terminate after reaction 10h.Last handling process, with embodiment 1, obtains product 2-
Methyl -2,5- dimethoxy dihydrofuran 107.3g, yield 83.7%.
Embodiment 3
2,5- dimethyl furan 85g, pyridine 160g, phase transfer catalyst trimethyl chlorine is put into in reactor
Change ammonium 2g, ethanol 400g, stirring, when opening low temperature thermostat bath and being cooled to -5 DEG C～5 DEG C, logical chlorine 80g simultaneously keeps this reaction temperature,
React after reaction 10h and terminate.Last handling process, with embodiment 1, obtains product 2,5- dimethyl -2,5- diethoxy dihydrofuran
130.6g, yield 79.3%.
Embodiment 4
Furan 60g, sodium carbonate 110g, phase transfer catalyst methyl triethyl ammonium chloride 2g, methanol is put into in reactor
600g, stirring, when opening low temperature thermostat bath and being cooled to 5 DEG C～15 DEG C, logical chlorine 80g simultaneously keeps this reaction temperature, after reaction about 15h
Reaction terminates.Last handling process, with embodiment 1, obtains product 2,5- dimethoxy dihydrofuran 84.4g, yield 73.6%.
Embodiment 5
Put into 2- methylfuran 73g, sodium bicarbonate 170g, methanol 350g, stirring in reactor, open low temperature thermostat bath fall
When temperature is to -5 DEG C～5 DEG C, logical chlorine 80g simultaneously keeps this reaction temperature, reacts and terminate after reaction 10h.Last handling process is with enforcement
Example 1, obtains producing 2- first -2,5- dimethoxy dihydrofuran 69.5g, yield 54.2%.
Knowable to the results contrast of embodiment 1 and embodiment 4, reaction temperature is bright on the product yield impact in the present invention
Aobvious.Reaction in the present invention is strong exothermal reaction, keeps reaction temperature that reaction can be made under -5 DEG C～5 DEG C of low temperature state to receive
Rate reaches optimal value.
Knowable to the results contrast of embodiment 1 and embodiment 5, if using phase transfer catalyst, product in the present invention is received
The impact of rate is extremely notable, the yield difference nearly 30% of the purpose product in this two embodiments.That is, adding in the present invention
Technical scheme with phase transfer catalyst has compared with electrochemical oxidation process of the prior art that equipment investment is little and high income
Advantage, and have compared with chemical synthesiss of the prior art avoid using molecular weight is larger, Atom economy is poor and
The costly bromine atoms of post processing, by-product is the salt of environmental protection, and the advantage that yield is considerably higher.
Claims (13)
1. one kind 2, the preparation method of 5- dialkoxy dihydrofuran class compound, including by furfuran compound as shown in formula i,
Alkylol shown in formula iii and acid binding agent add in reactor, stirring and and chlorine reaction, keep reaction temperature -25 DEG C～25
DEG C, reaction under the catalytic action of phase transfer catalyst obtains 2, the 5- dialkoxy dihydrofuran class chemical combination as shown in formula ii
Thing；
In formula, r1, r2, r3, r4For each independent hydrogen, halogen, c1-c5Alkyl, r1For c1-c12Alkyl.
2. according to claim 1 method it is characterised in that described phase transfer catalyst be selected from quaternary amine and season phosphine alkali.
3. according to claim 2 method it is characterised in that described quaternary amine be selected from methyl triethyl ammonium chloride, methyl three
Ethyl phosphonium bromide ammonium, methyl triethyl group ammonium iodide, methyl triethyl group ammonium acetate, benzyl triethyl ammonium ammonium fluoride, benzyl triethyl ammonium chlorination
Ammonium, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium iodide, benzyl triethyl ammonium ammonium acetate, Dodecyl trimethyl ammonium chloride, ten
Dialkyl group trimethylammonium bromide, trimethyl ammonium iodide, octadecyl trimethyl ammonium chloride, 18 protective embankment base front three bromides
Change one or more of ammonium and octadecyl trimethyl ammonium iodide, described season phosphine alkali be selected from tetramethyl hydroxide phosphine, tetrem
Base hydroxide phosphine, tetrapropyl hydroxide phosphine, tetrabutylammonium hydroxide phosphine, benzyltriphenyl phosphonium hydroxide phosphine, methyl triphenyl hydroxide
One or more of phosphine, ethyl triphenyl hydroxide phosphine and propyl group triphenyl hydroxide phosphine.
4. according to any one methods described in claims 1 to 3 it is characterised in that the response time of described reaction be 1～
15h, and first remove residual chlorine after completion of the reaction, then obtain described 2,5- bis- after solid-liquid separation, drying and vacuum distillation
Alkoxyl dihydrofuran class compound.
5. according to any one methods described in claims 1 to 3 it is characterised in that r1For c1-c3Alkyl；r1, r2, r3, r4
For each independent hydrogen and c1-c3Alkyl.
6. according to any one methods described in claims 1 to 3 it is characterised in that described alkylol consumption is furan shown in formula i
3～20 times of the amount of material of class of muttering compound, chlorine consumption is 1～3 of the amount of the material of furfuran compound shown in formula i
Times.
7. according to any one methods described in claims 1 to 3 it is characterised in that described reaction temperature is -10 DEG C～5 DEG C.
8. according to claim 7 method it is characterised in that described reaction temperature be -5 DEG C～0 DEG C.
9. according to any one methods described in claims 1 to 3 it is characterised in that described acid binding agent is organic base or inorganic
Alkali.
10. according to claim 9 method it is characterised in that described acid binding agent is selected from triethylamine, pyridine, liquefied ammonia, hydrogen-oxygen
Change one or more of sodium, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, Sodium Acetate Trihydrate and potassium acetate.
11. according to any one methods described in claims 1 to 3 it is characterised in that described acid binding agent consumption be formula i shown in
1～3 times of the amount of the material of furfuran compound.
12. according to any one methods described in claims 1 to 3 it is characterised in that the quality of described phase transfer catalyst with
The mass ratio of furfuran compound shown in formula i is 0.002～0.2:1.
13. according to claim 12 methods described it is characterised in that the quality of described phase transfer catalyst and furan shown in formula i
The mass ratio of class compound is 0.02～0.1:1.
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