WO2010086876A2 - Ether synthesis - Google Patents
Ether synthesis Download PDFInfo
- Publication number
- WO2010086876A2 WO2010086876A2 PCT/IN2010/000007 IN2010000007W WO2010086876A2 WO 2010086876 A2 WO2010086876 A2 WO 2010086876A2 IN 2010000007 W IN2010000007 W IN 2010000007W WO 2010086876 A2 WO2010086876 A2 WO 2010086876A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- nano
- mixture
- group
- fluoro
- Prior art date
Links
- 230000015572 biosynthetic process Effects 0.000 title description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 title description 5
- -1 4-fluoro-3- phenoxy-benzaldehyde acetal Chemical class 0.000 claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 claims abstract description 67
- 239000010949 copper Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- 239000000203 mixture Substances 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 67
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 44
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 34
- 239000002105 nanoparticle Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 150000001879 copper Chemical class 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 claims description 18
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical class [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 11
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019256 formaldehyde Nutrition 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- JDICMOLUAHZVDS-UHFFFAOYSA-N 4-fluoro-3-phenoxybenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1OC1=CC=CC=C1 JDICMOLUAHZVDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002739 cryptand Substances 0.000 claims description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 6
- 239000012433 hydrogen halide Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- 239000011369 resultant mixture Substances 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004072 triols Chemical class 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 239000005750 Copper hydroxide Substances 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- WOLVYCFDDSCRDJ-UHFFFAOYSA-L copper;oxido hydrogen carbonate Chemical compound [Cu+2].OOC([O-])=O.OOC([O-])=O WOLVYCFDDSCRDJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 150000003983 crown ethers Chemical class 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 20
- 238000006887 Ullmann reaction Methods 0.000 description 13
- 239000007858 starting material Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 7
- 150000003935 benzaldehydes Chemical class 0.000 description 5
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000001987 diarylethers Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000005171 halobenzenes Chemical class 0.000 description 2
- 239000011874 heated mixture Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HPRGYUWRGCTBAV-UHFFFAOYSA-N 1-chloro-3-(4-chlorophenoxy)benzene Chemical compound C1=CC(Cl)=CC=C1OC1=CC=CC(Cl)=C1 HPRGYUWRGCTBAV-UHFFFAOYSA-N 0.000 description 1
- JDTMUJBWSGNMGR-UHFFFAOYSA-N 1-nitro-4-phenoxybenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=CC=C1 JDTMUJBWSGNMGR-UHFFFAOYSA-N 0.000 description 1
- XZGIHWAIIZHXKX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-n,n-bis[2-(2-ethoxyethoxy)ethyl]ethanamine Chemical compound CCOCCOCCN(CCOCCOCC)CCOCCOCC XZGIHWAIIZHXKX-UHFFFAOYSA-N 0.000 description 1
- OATOZCSPTSMOIY-UHFFFAOYSA-N 2-(3-bromo-4-fluorophenyl)-1,3-dioxolane Chemical compound C1=C(Br)C(F)=CC=C1C1OCCO1 OATOZCSPTSMOIY-UHFFFAOYSA-N 0.000 description 1
- BOIKPJKVWFRGMY-UHFFFAOYSA-N 2-(4-fluoro-3-phenoxyphenyl)-1,3-dioxolane Chemical compound FC1=CC=C(C2OCCO2)C=C1OC1=CC=CC=C1 BOIKPJKVWFRGMY-UHFFFAOYSA-N 0.000 description 1
- FAHZIKXYYRGSHF-UHFFFAOYSA-N 3-bromo-4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1Br FAHZIKXYYRGSHF-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-M 3-chlorophenolate Chemical compound [O-]C1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-M 0.000 description 1
- QDKIFIYGNKHERN-UHFFFAOYSA-N 4-(bromomethyl)-1-fluoro-2-phenoxybenzene Chemical compound FC1=CC=C(CBr)C=C1OC1=CC=CC=C1 QDKIFIYGNKHERN-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010752 Ullmann ether synthesis reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000007256 debromination reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- C07C41/48—Preparation of compounds having groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/315—Compounds having groups containing oxygen atoms singly bound to carbon atoms not being acetal carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Definitions
- the present invention relates to ether synthesis.
- this invention relates to the use of a novel catalyst in the manufacturing of ethers by the Ullmann reaction.
- this invention relates to a manufacturing of catalyst which is used in the manufacturing of ethers by the Ullmann reaction.
- Ullmann reaction or Ullmann coupling when used in the specification means a reaction which includes copper-catalyzed nucleophilic aromatic substitution between various nucleophiles (e.g. substituted phenoxides) with aryl halides.
- the most common example includes the Ullmann Ether Synthesis wherein phenol is reacted with an aryl halide to obtain a diaryl ether in the presence of a copper compound.
- p-nitrophenol is coupled with bromobenzene in the presence of copper to obtain p-nitrophenyl phenyl ether.
- the Ullmann reaction requires the presence of an activated haloaromatic, such as iodobenzene or bromobenzene.
- an activated haloaromatic such as iodobenzene or bromobenzene.
- Bromine compounds aryl bromides
- the aryl chlorides are said to be sufficiently reactive.
- U.S Patent 3472782 and U.S Patent 3371120 disclose processes carried out using ullmann reaction in which 1,4-dichlorobenzene is reacted with 3-chlorophenolate at 165°C under CuCl/KI catalysis to give 3,4'-dichlorodiphenyl ether.
- European Patent EP0051235 discloses the preparation of diphenyl ethers by Ullmann reaction in which alkali metal phenolates are coupled with halobenzenes in the presence of basic copper carbonate and/or copper salts of lower aliphatic carboxylic acids as catalysts.
- US Patent 4288386 discloses a process for the preparation of a diaryl ether by reacting an unactivated halobenzene with an alkali metal phenolate in the presence of a copper catalyst in the presence of tris-(3,6-dioxaoctyl)-amine (ullmann reaction) .
- WO/1999/038833 discloses the process for the preparation of 4-fiuoro-3-phenoxy benzaldehyde, comprising brominating 4-fluoro-benzaldehyde, acetalizing the crude 3-bromo-4-fluorobenzaldehyde without prior isolation thereof, condensing the 3- bromo-4-fluorophenyldioxolane with potassium phenolate, and hydrolyzing the 4- fluoro-3-phenoxyphenyldioxolane to yield 4-fluoro-3-phenoxybenzaldehyde.
- German Patent DE2709264 discloses the process for preparation of 4-fluoro-3- phenoxy-benzaldehyde by reacting 4-fluoro-3-phenoxy-benzyl bromide with hexamethylehetetramine and then heating with acids. It is clear from the aforementioned processes that they do not provide satisfactory results in respect of yield, reaction control and reaction time. Furthermore, these processes are time consuming and also expensive. The catalysts used in these processes have relatively low selectivity towards the final product.
- Still another object of the present invention is to provide a process for the preparation of substituted benzaldehyde which ensures the easy purification and isolation of the product.
- a process for manufacturing of 4-fluoro-3-phenoxy-benzaldehyde acetal comprises the following steps: a. adding drop-wise 3-bromo-4-fluoro benzaldehyde acetal to a predetermined quantity of dehydrated potassium phenoxide under continuous stirring at a temperature of about 8O 0 C to obtain a resultant mass; b. heating the resultant mass in an environment having a temperature in the range of about 120 to 14O 0 C to obtain a resultant mixture; c.
- the step a optionally comprises addition of at least one solvent selected from a group consisting of dimethoxy ethane, toluene and mixture thereof.
- the step a optionally comprises addition of at least one additive selected from a group consisting of cyclodextrine, crown ether, cryptands containing -OH group and cryptands containing -SH group.
- the nano-copper catalyst system is at least one selected from a group consisting of copper (0) particles, copper (I) oxide particles, copper (II) oxide particles and copper (I) halide particles.
- the nano-copper catalyst system is copper (I) halide particles selected from a group consisting of copper (I)chloride , copper (I) bromide particles and copper (I) iodide particles.
- the amount of nano-copper catalyst system used is in the range of about 0.1 to 1% of the mass of the to 3-bromo-4-fluoro benzaldehyde acetal.
- the ratio of potassium phenoxide to 3-bromo-4-fiuoro benzaldehyde acetal is in the range of about 1 to 2 moles.
- the ratio of dimethoxy ethane to 3-bromo-4-fluoro benzaldehyde acetal is in the range of about 0 to 20 moles.
- the ratio of toluene to 3-bromo-4-fluoro benzaldehyde acetal is in the range of about 0 to 20 moles.
- the yield of 4-fluoro-3-phenoxy-benzaldehyde acetal having purity greater than 80 % is greater than 90 %.
- the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in deionised water by heating at a temperature of about 50 0 C to obtain a solution followed by purging the solution with nitrogen gas to remove dissolved oxygen and adding sodium hydroxide solution drop wise to obtain a mixture; b. adding drop-wise at least one solvent selected from a group consisting of water, methanol and ethanol to the mixture containing copper salt under constant stirring for a period of about 1 hour to obtain a resultant mass; c. heating the resultant mass at a temperature of about 80 0 C for a period of about 2 to 6 hours to obtain copper(I) oxide nano-particles ; d.
- the adsorbing material is selected from a group consisting of silica, TiO 2 , Al 2 O 3 , MgO, SnO 2 , titania and zirconia.
- the ratio of copper salt to adsorbing material is in the range of about 0.1 to 30 % by weight.
- the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues thereof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 195 0 C for a period of about one and half hour to obtain reaction mass; and c. cooling the reaction mass to obtain copper (I) oxide nano particles based nano- copper catalyst system.
- the nano-copper catalyst system is copper (I) halide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 195 0 C for a period of about one and half hour to obtain reaction mass; c. cooling the reaction mass to obtain copper (I) oxide nano particles and d. reacting the copper (I) oxide nano particles with hydrogen halide to form a copper (I) halide particles based nano- copper catalyst system.
- solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain
- the hydrogen halide is at least one selected from a group consisting of hydrogen bromide, hydrogen chloride and hydrogen iodide.
- the copper salt is at least one selected from a group consisting of copper acetate, copper sulphate, copper hydroxide, copper hydroxyl carbonate and copper oxide.
- the particle size of nano copper catalyst is in the range of about 5 nm to 300 nm.
- 4-fluoro-3-phenoxy-benzaldehyde acetal is used as an intermediate product for pesticidally active pyrethroids.
- the conventional methods for manufacturing of 4- fluoro-3-phenoxy-benzaldehyde suffer from disadvantages which includes use of expensive catalysts, comparatively low yield, purity, high temperature reaction conditions and thus economically not feasible methods.
- the first step is drop-wise addition of 3-bromo-4-fluoro benzaldehyde acetal to a predetermined quantity of dehydrated potassium phenoxide under continuous stirring at a temperature of about 8O 0 C to obtain a resultant mass.
- the resultant mass is then heated in an environment having a temperature in the range of about 120 to 14O 0 C to obtain a resultant mixture.
- the next step is addition of nano-copper catalyst system as herein described to the resultant mixture under continuous stirring for a period of about 5 to 6 hours to obtain a reaction product containing 4-fluoro-3-phenoxy-benzaldehyde acetal.
- the obtained reaction product containing 4-fluoro-3-phenoxy-benzaldehyde acetal is then washed with water followed by extracting the product with at least one organic solvent selected from a group consisting of toluene and ethyl acetate and filtering to obtain a filtrate.
- the final step after filtration is evaporation of the filtrate to yield a 4-fluoro-3- phenoxy-benzaldehyde acetal.
- the first step comprises drop- wise addition of 3-bromo-4-fluoro benzaldehyde acetal to a mixture containing predetermined quantities of dehydrated potassium phenoxide and at least one solvent selected from a group consisting of dimethoxy ethane, toluene and mixture thereof under continuous stirring at a temperature of about 8O 0 C to obtain a resultant mass.
- the first step optionally comprises addition of at least one additive selected from a group consisting of cyclodextrine, crown ether, cryptands containing -OH group and cryptands containing -SH group.
- the nano-copper catalyst system used for the synthesis of 4-fluoro-3-phenoxy- benzaldehyde acetal in accordance with the present invention is at least one selected from a group consisting of copper (0) particles, copper (I) oxide particles, copper (II) oxide particles and copper (I) halide particles.
- the nano-copper catalyst system is copper (I) halide particles selected from a group consisting of copper (I) chloride, copper (I) bromide particles and copper (I) iodide particles.
- the amount of nano-copper catalyst system used for the preparation of 4-fluoro-3- phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 0.1 to 1% of the mass of the to 3-bromo-4-fluoro benzaldehyde acetal.
- the ratio of potassium phenoxide to 3-bromo-4-fluoro benzaldehyde acetal used to prepare 4-fluoro-3-phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 1 to 2 moles.
- the ratio of dimethoxy ethane to 3-bromo-4-fiuoro benzaldehyde acetal used to prepare 4-fluoro-3-phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 0 to 20 moles.
- the ratio of toluene to 3-bromo-4-fluoro benzaldehyde acetal used to prepare 4- fluoro-3-phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 0 to 20 moles.
- the yield of 4-fluoro-3-phenoxy- benzaldehyde acetal having purity greater than 80 % is greater than 90 %.
- the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in deionised water by heating at a temperature of about 50 0 C to obtain a solution followed by purging the solution with nitrogen gas to remove dissolved oxygen and adding sodium hydroxide solution drop wise to obtain a mixture; b. adding drop- wise at least one solvent selected from a group consisting of water, methanol and ethanol to the mixture containing copper salt under constant stirring for a period of about 1 hour to obtain a resultant mass; c. heating the resultant mass at a temperature of about 80 0 C for a period of about 2 to 6 hrs to obtain copper(I) oxide nano-particles ; d.
- the adsorbing material used to adsorb the copper nano particles is selected from a group consisting of silica, TiO 2 , Al 2 O 3 , MgO, SnO 2 , titania and zirconia.
- the ratio of copper salt to adsorbing material is in the range of about 0.1 to 30 % by weight.
- the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues thereof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 195 0 C for a period of about one and half hour to obtain reaction mass; and c. cooling the reaction mass to obtain copper (I) oxide nano particles based nano- copper catalyst system.
- the nano-copper catalyst system is copper (I) halide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 195 0 C for a period of about one and half hour to obtain reaction mass; c. cooling the reaction mass to obtain copper (I) oxide nano particles and d. reacting the copper (I) oxide nano particles with hydrogen halide to form a copper (I) halide particles based nano- copper catalyst system.
- solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain
- the hydrogen halide used to prepare copper (I) halide particles based nano- copper catalyst system is at least one selected from a group consisting of hydrogen bromide, hydrogen chloride and hydrogen iodide.
- the copper salt used to prepare nano- copper catalyst system of the present invention is at least one selected from a group consisting of copper acetate, copper sulphate, copper hydroxide, copper hydroxyl carbonate and copper oxide.
- the particle size of nano copper catalyst prepared in accordance with the present invention is in the range of about 5 nm to 300 nm.
- Copper (II) acetate (0.3147g, 0.0015 moles) was taken into 100 ml round bottom flask at a room temperature. To this water (1Og) was added at a room temperature. Then the temperature of the solution was raised to 5O 0 C in order to dissolve copper acetate. To this solution sodium hydroxide solution (prepared by dissolving 0.137 Ig 0.00342 moles of NaOH in 2.9g of water) was added drop wise over a period of one hour during which the colour of the solution began to change to dark brown. Then the solution was heated to 8O 0 C and maintained for 3 hrs.
- silica (based on 1 wt%, 2wt%, 5wt% and 10wt% of CuO) was added and stirred for 2 hrs at 8O 0 C. These copper nano particles were then got adsorbed on the surface of Slica gel.
- the nano copper coated on Silica was recovered by filtration followed by the washing with deionised water (3 xlOO ml) which resulted into residue of catalyst.
- the residue was activated by drying at 250 0 C for 2-3 h.
- the activated catalyst was used for phenoxylation reaction.
- Particle size of the CuO obtained were in the range 5 nm - 40 nm with a mean diameter at 15 nm (measured by TEM.)
- Copper acetate (0.3147g 0.0015 moles) was taken into 100 ml round bottom flask at a room temperature. To this 10 gm of water was added to obtain a mixture. Then this mixture was heated to attain 5O 0 C and the temperature was maintained for 30 min. in order to dissolve copper acetate. To this solution, sodium hydroxide solution prepared in water (0.137 Ig 0.00342 moles NaOH in 2.9g H 2 O) was added drop wise over a period of an hour during which colour of the solution started changing to black. After complete addition of sodium hydroxide, the mixture was heated at 8O 0 C under continuous stirring and kept for 3 hours.
- TiO 2 (based on 5 wt% or 10 wt% CuO) was added and the mixture was stirred for 2 hrs. These copper nano particles were adsorbed on the surface of TiO 2 .
- the nano copper coated on TiO 2 was recovered by filtration followed by washing with de-ionised water (3x100 ml) to obtain residue of catalyst. The residue was then activated by drying at 250-260 0 C for 2-3 hours for. The activated catalyst was used for the further phenoxylation reaction.
- 0.1 M solution of CuSO4 was prepared by dissolving (2.49g) in 100 ml of deionised water and nitrogen was purged to remove the dissolved oxygen. 100 ml 0.5 M sodium citrate was added to it and allowed to stir for 30 minutes under the nitrogen atmosphere. To this 10 ml of 0.1 M aqueous solution of sodium borohydride was added drop wise under constant stirring in N 2 atmosphere. The colour of the solution change to dark brown on complete addition of reducing agent indicated the formation of citrate protected copper nanoparticles. These copper nano particles were adsorbed on the surface by adding Silica gel. The suspension was stirred at 80 0 C 2 hours.
- the nano copper coated Silica was recovered by filtration followed by the washing with deionised water (3x 100 ml) to obtain residual catalyst.
- the residual solid catalyst was activated by dried at 250-260 0 C for 2-3 hours. The activated catalyst was used for the further phenoxylation reaction.
- Copper acetate (0.3147g 0.0015 moles) was taken into the 100 ml round bottom flask at a room temperature. To this water (1Og) was added at a room temperature. The mixture was then heated to 50 0 C with stirring and kept for 30 min. in order to dissolve the copper acetate. To this fixture sodium hydroxide solution (0.137 Ig 0.00342 moles NaOH in 2.9g H2O) was added drop wise over a period of an hour. After addition of NaOH solution, the mixture was heated at 8O 0 C for 5 hours during which black CuO nano particles are formed. Then water was removed from reaction mass on evaporator to get black solids.
- Step-1 Preparation of Cupric Hydroxide [Cu (OH) 2 ]
- Step 2 Preparation of nano copper oxide catalyst from cupric hydroxide
- Cupric hydroxide (3.8g, 38.9mmol, 1.0 MoI Eq) was added to mono ethylene glycol
- Copper Oxide (I) in mono ethylene glycol (63.78 g) was transferred to the three necked 250 ml round bottom flask having one end connected with glass inlet for purging dry HCl gas at a room temperature.
- Sodium chloride powder (20.Og, 1.0 mol eq) was transferred to 100 mL three necked flask to which H 2 SO 4 98% (34.2g, 1.0 MoI Eq.) was added drop wise to generate HCl gas.
- the gas generated was passed through the mixture containg Cu 2 O and methylene glycol for 30 min. After completion of reaction (which is indicated by formation of white material), N 2 gas was purged through the reaction mass to remove trapped HCl.
- Copper Oxide (I) in mono ethylene glycol (63.78g) was taken into the three necked 250 ml round bottom flask having one end connected with glass inlet for purging Dry HBr gas at a room temperature.
- Potassium bromide powder (25.Og, 1.0 mol eq) was taken in 100 mL three necked flask to which H 2 SO 4 (20.58g, 1.0 Mol Eq.) was added drop wise to generate HBr gas.
- the gas generated was passed through methylene glycol containing Cu2O suspension for 30 min. Change in colour from yellowish green to whitish green (in suspension form) was observed. After completion of the reaction, N 2 gas was purged through reaction mass to remove trapped HBr.
- the uniqueness of the present invention lies in the use of novel nano copper coated Cu (I/II) oxide in Ullmann reactions. Furthermore, the process in accordance with the invention provides synthesis of 4-fluoro-3-phenoxy-benzaldehyde using novel nano copper coated Cu (I/II) oxide in high yield, purity and better selectivity.
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Abstract
The present invention relates to processes for preparing novel nano-copper catalyst system. The present invention also relates to manufacturing of 4-fluoro-3- phenoxy-benzaldehyde acetal employing novel nano-copper catalyst system.
Description
ETHER SYNTHESIS
FIELD OF THE INVENTION
The present invention relates to ether synthesis.
Particularly, this invention relates to the use of a novel catalyst in the manufacturing of ethers by the Ullmann reaction.
Still particularly, this invention relates to a manufacturing of catalyst which is used in the manufacturing of ethers by the Ullmann reaction.
BACKGROUND OF THE INVENTION
The expression Ullmann reaction or Ullmann coupling when used in the specification means a reaction which includes copper-catalyzed nucleophilic aromatic substitution between various nucleophiles (e.g. substituted phenoxides) with aryl halides. The most common example includes the Ullmann Ether Synthesis wherein phenol is reacted with an aryl halide to obtain a diaryl ether in the presence of a copper compound. Eg: p-nitrophenol is coupled with bromobenzene in the presence of copper to obtain p-nitrophenyl phenyl ether.
In general, the Ullmann reaction requires the presence of an activated haloaromatic, such as iodobenzene or bromobenzene. Bromine compounds (aryl bromides) are more reactive than the corresponding chlorine compounds. Only in the case where the aryl nucleus contains further determined activating groups the aryl chlorides are said to be sufficiently reactive.
EXISTING KNOWLEGE
U.S Patent 3472782 and U.S Patent 3371120 disclose processes carried out using ullmann reaction in which 1,4-dichlorobenzene is reacted with 3-chlorophenolate at 165°C under CuCl/KI catalysis to give 3,4'-dichlorodiphenyl ether.
European Patent EP0051235 discloses the preparation of diphenyl ethers by Ullmann reaction in which alkali metal phenolates are coupled with halobenzenes in the presence of basic copper carbonate and/or copper salts of lower aliphatic carboxylic acids as catalysts.
US Patent 4288386 discloses a process for the preparation of a diaryl ether by reacting an unactivated halobenzene with an alkali metal phenolate in the presence of a copper catalyst in the presence of tris-(3,6-dioxaoctyl)-amine (ullmann reaction) .
Published French Application No. 7816746 discloses the Ullmann reaction wherein catalyst used is copper powder or oxide, carbonate, chlorides, bromide or sulfate of copper.
WO/1999/038833 discloses the process for the preparation of 4-fiuoro-3-phenoxy benzaldehyde, comprising brominating 4-fluoro-benzaldehyde, acetalizing the crude 3-bromo-4-fluorobenzaldehyde without prior isolation thereof, condensing the 3- bromo-4-fluorophenyldioxolane with potassium phenolate, and hydrolyzing the 4- fluoro-3-phenoxyphenyldioxolane to yield 4-fluoro-3-phenoxybenzaldehyde.
German Patent DE2709264 discloses the process for preparation of 4-fluoro-3- phenoxy-benzaldehyde by reacting 4-fluoro-3-phenoxy-benzyl bromide with hexamethylehetetramine and then heating with acids.
It is clear from the aforementioned processes that they do not provide satisfactory results in respect of yield, reaction control and reaction time. Furthermore, these processes are time consuming and also expensive. The catalysts used in these processes have relatively low selectivity towards the final product.
Thus, there is felt a need for a process for preparing a catalyst which accelerates the rate of the Ullmann reaction and reduces the debromination of the starting material and which is selective towards the product. There is also a need for a process for manufacture of substituted benzaldehyde in high yield and purity in a cost-effective manner.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a process for preparation of a catalyst.
It is another object of the present invention to provide a process for preparation of a catalyst which accelerates rate of the Ullmann reaction.
It is still another object of the present invention to provide a process for preparation of a catalyst which is tunable.
It is yet another object of the present invention to provide a process for preparation of a catalyst which is used in relatively less quantity.
It is a further object of the present invention to provide a process for preparation of a catalyst which ensures better selectivity towards the product.
According to one aspect of the present invention, there is provided a cost-effective and economically feasible process for the preparation of substituted benzaldehyde by Ullmann reaction.
According to yet another aspect of the present invention there is provided a process for the preparation of substituted benzaldehyde in high yield and high purity.
According to yet another aspect of the present invention there is provided a process for the preparation of substituted benzaldehyde wherein the reaction carried out at low temperature conditions.
Still another object of the present invention is to provide a process for the preparation of substituted benzaldehyde which ensures the easy purification and isolation of the product.
SUMMARY OF THE INVENTION
In accordance with the present invention there is provided a process for manufacturing of 4-fluoro-3-phenoxy-benzaldehyde acetal; said process comprises the following steps: a. adding drop-wise 3-bromo-4-fluoro benzaldehyde acetal to a predetermined quantity of dehydrated potassium phenoxide under continuous stirring at a temperature of about 8O0C to obtain a resultant mass; b. heating the resultant mass in an environment having a temperature in the range of about 120 to 14O0C to obtain a resultant mixture; c. adding nano-copper catalyst system as herein described to the resultant mixture under continuous stirring for a period of about 5 to 6 hours to obtain a reaction product containing 4-fluoro-3-phenoxy-benzaldehyde acetal;
d. washing the reaction product containing 4-fluoro-3-phenoxy- benzaldehyde with water followed by extracting the product with at least one organic solvent selected from a group consisting of toluene and ethyl acetate and filtering to obtain a filtrate; and e. evaporating the filtrate to yield a 4-fluoro-3-phenoxy-benzaldehyde acetal.
Typically, the step a optionally comprises addition of at least one solvent selected from a group consisting of dimethoxy ethane, toluene and mixture thereof.
Typically, the step a optionally comprises addition of at least one additive selected from a group consisting of cyclodextrine, crown ether, cryptands containing -OH group and cryptands containing -SH group.
Typically, the nano-copper catalyst system is at least one selected from a group consisting of copper (0) particles, copper (I) oxide particles, copper (II) oxide particles and copper (I) halide particles.
Typically, the nano-copper catalyst system is copper (I) halide particles selected from a group consisting of copper (I)chloride , copper (I) bromide particles and copper (I) iodide particles.
Typically, the amount of nano-copper catalyst system used is in the range of about 0.1 to 1% of the mass of the to 3-bromo-4-fluoro benzaldehyde acetal.
Typically, the ratio of potassium phenoxide to 3-bromo-4-fiuoro benzaldehyde acetal is in the range of about 1 to 2 moles.
Typically, the ratio of dimethoxy ethane to 3-bromo-4-fluoro benzaldehyde acetal is in the range of about 0 to 20 moles.
Typically, the ratio of toluene to 3-bromo-4-fluoro benzaldehyde acetal is in the range of about 0 to 20 moles.
Typically, the yield of 4-fluoro-3-phenoxy-benzaldehyde acetal having purity greater than 80 % is greater than 90 %.
In accordance with one of the embodiments of the present invention the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in deionised water by heating at a temperature of about 50 0C to obtain a solution followed by purging the solution with nitrogen gas to remove dissolved oxygen and adding sodium hydroxide solution drop wise to obtain a mixture; b. adding drop-wise at least one solvent selected from a group consisting of water, methanol and ethanol to the mixture containing copper salt under constant stirring for a period of about 1 hour to obtain a resultant mass; c. heating the resultant mass at a temperature of about 800C for a period of about 2 to 6 hours to obtain copper(I) oxide nano-particles ; d. adsorbing the copper nanoparticles on the surface of the adsorbing material followed by recovering the adsorbed nano copper by filtration ; e. washing the recovered nano copper with deionised water to obtain a residual nano copper catalyst; and f. drying the residual catalyst at a temperature of about 2500C to 2600C for a period of about 2 to 3 hours to obtain an activated copper (I) oxide particles based nano- copper catalyst system.
Typically, the adsorbing material is selected from a group consisting of silica, TiO2, Al2O3, MgO, SnO2, titania and zirconia.
Typically, the ratio of copper salt to adsorbing material is in the range of about 0.1 to 30 % by weight.
In accordance with another embodiment of the present invention the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues thereof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 1950C for a period of about one and half hour to obtain reaction mass; and c. cooling the reaction mass to obtain copper (I) oxide nano particles based nano- copper catalyst system.
In accordance with still another embodiment of the present invention the nano-copper catalyst system is copper (I) halide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 1950C for a period of about one and half hour to obtain reaction mass; c. cooling the reaction mass to obtain copper (I) oxide nano particles and d. reacting the copper (I) oxide nano particles with hydrogen halide to form a copper (I) halide particles based nano- copper catalyst system.
Typically, the hydrogen halide is at least one selected from a group consisting of hydrogen bromide, hydrogen chloride and hydrogen iodide.
Typically, the copper salt is at least one selected from a group consisting of copper acetate, copper sulphate, copper hydroxide, copper hydroxyl carbonate and copper oxide.
Typically, the particle size of nano copper catalyst is in the range of about 5 nm to 300 nm.
DETAILED DESCRIPTION OF THE INVENTION
4-fluoro-3-phenoxy-benzaldehyde acetal is used as an intermediate product for pesticidally active pyrethroids. The conventional methods for manufacturing of 4- fluoro-3-phenoxy-benzaldehyde suffer from disadvantages which includes use of expensive catalysts, comparatively low yield, purity, high temperature reaction conditions and thus economically not feasible methods.
In accordance with the present invention there is provided a process for manufacturing of 4-fluoro-3-phenoxy-benzaldehyde acetal; said process comprises the following steps:
The first step is drop-wise addition of 3-bromo-4-fluoro benzaldehyde acetal to a predetermined quantity of dehydrated potassium phenoxide under continuous stirring at a temperature of about 8O0C to obtain a resultant mass.
The resultant mass is then heated in an environment having a temperature in the range of about 120 to 14O0C to obtain a resultant mixture.
The next step is addition of nano-copper catalyst system as herein described to the resultant mixture under continuous stirring for a period of about 5 to 6 hours to obtain a reaction product containing 4-fluoro-3-phenoxy-benzaldehyde acetal.
The obtained reaction product containing 4-fluoro-3-phenoxy-benzaldehyde acetal is then washed with water followed by extracting the product with at least one organic solvent selected from a group consisting of toluene and ethyl acetate and filtering to obtain a filtrate.
The final step after filtration is evaporation of the filtrate to yield a 4-fluoro-3- phenoxy-benzaldehyde acetal.
In accordance with another embodiment of the present invention, the first step comprises drop- wise addition of 3-bromo-4-fluoro benzaldehyde acetal to a mixture containing predetermined quantities of dehydrated potassium phenoxide and at least one solvent selected from a group consisting of dimethoxy ethane, toluene and mixture thereof under continuous stirring at a temperature of about 8O0C to obtain a resultant mass. ■
In accordance with still another embodiment of the present invention, the first step optionally comprises addition of at least one additive selected from a group consisting of cyclodextrine, crown ether, cryptands containing -OH group and cryptands containing -SH group.
The nano-copper catalyst system used for the synthesis of 4-fluoro-3-phenoxy- benzaldehyde acetal in accordance with the present invention is at least one selected from a group consisting of copper (0) particles, copper (I) oxide particles, copper (II) oxide particles and copper (I) halide particles.
In accordance with one of the embodiments the nano-copper catalyst system is copper (I) halide particles selected from a group consisting of copper (I) chloride, copper (I) bromide particles and copper (I) iodide particles.
The amount of nano-copper catalyst system used for the preparation of 4-fluoro-3- phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 0.1 to 1% of the mass of the to 3-bromo-4-fluoro benzaldehyde acetal.
The ratio of potassium phenoxide to 3-bromo-4-fluoro benzaldehyde acetal used to prepare 4-fluoro-3-phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 1 to 2 moles.
The ratio of dimethoxy ethane to 3-bromo-4-fiuoro benzaldehyde acetal used to prepare 4-fluoro-3-phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 0 to 20 moles.
The ratio of toluene to 3-bromo-4-fluoro benzaldehyde acetal used to prepare 4- fluoro-3-phenoxy-benzaldehyde acetal in accordance with the present invention is in the range of about 0 to 20 moles.
In accordance with the present invention the yield of 4-fluoro-3-phenoxy- benzaldehyde acetal having purity greater than 80 % is greater than 90 %.
In accordance with one of the embodiments of the present invention the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in deionised water by heating at a temperature of about 50 0C to obtain a solution followed by purging the solution with nitrogen gas to remove dissolved oxygen and adding sodium hydroxide solution drop wise to obtain a mixture; b. adding drop- wise at least one solvent selected from a group consisting of water, methanol and ethanol to the mixture containing copper salt under constant stirring for a period of about 1 hour to obtain a resultant mass;
c. heating the resultant mass at a temperature of about 800C for a period of about 2 to 6 hrs to obtain copper(I) oxide nano-particles ; d. adsorbing the copper nanoparticles on the surface of the adsorbing material followed by recovering the adsorbed nano copper by filtration ; e. washing the recovered nano copper with deionised water to obtain a residual nano copper catalyst; and f. drying the residual catalyst at a temperature of about 2500C to 2600C for a period of about 2 to 3 hours to obtain an activated copper (I) oxide particles based nano- copper catalyst system.
In accordance with the present invention the adsorbing material used to adsorb the copper nano particles is selected from a group consisting of silica, TiO2, Al2O3, MgO, SnO2, titania and zirconia.
In accordance with the present invention the ratio of copper salt to adsorbing material is in the range of about 0.1 to 30 % by weight.
In accordance with another embodiment of the present invention the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues thereof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 1950C for a period of about one and half hour to obtain reaction mass; and c. cooling the reaction mass to obtain copper (I) oxide nano particles based nano- copper catalyst system.
In accordance with still another embodiment of the present invention the nano-copper catalyst system is copper (I) halide particles prepared by:
a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 1950C for a period of about one and half hour to obtain reaction mass; c. cooling the reaction mass to obtain copper (I) oxide nano particles and d. reacting the copper (I) oxide nano particles with hydrogen halide to form a copper (I) halide particles based nano- copper catalyst system.
In accordance with the present invention, the hydrogen halide used to prepare copper (I) halide particles based nano- copper catalyst system is at least one selected from a group consisting of hydrogen bromide, hydrogen chloride and hydrogen iodide.
In accordance with the present invention the copper salt used to prepare nano- copper catalyst system of the present invention is at least one selected from a group consisting of copper acetate, copper sulphate, copper hydroxide, copper hydroxyl carbonate and copper oxide.
The particle size of nano copper catalyst prepared in accordance with the present invention is in the range of about 5 nm to 300 nm.
The invention will now be described with respect to the following examples which do not limit the invention in any way and only exemplify the invention.
Example 1:
Preparation of nano copper (I) oxide catalyst:
Methylene glycol (1.0 mol) was taken into a round bottom flask at a room temperature and nitrogen was purged to remove the dissolved oxygen. To this 0.038 mol of copper
acetate was added and the mixture was heated to reflux at 1950C for one and half hour. Then the mixture was allowed to cool to room temperature. The copper (I) oxide nano particle thus obtained was used as master batch for phenoxylation reactions. The particle size of the nano particles was in the range 5 nm-300 nm with a mean size of 70-80 nm.
Example 2:
Preparation of nano copper(II) oxide coated on Silica
Copper (II) acetate (0.3147g, 0.0015 moles) was taken into 100 ml round bottom flask at a room temperature. To this water (1Og) was added at a room temperature. Then the temperature of the solution was raised to 5O0C in order to dissolve copper acetate. To this solution sodium hydroxide solution (prepared by dissolving 0.137 Ig 0.00342 moles of NaOH in 2.9g of water) was added drop wise over a period of one hour during which the colour of the solution began to change to dark brown. Then the solution was heated to 8O0C and maintained for 3 hrs. Then silica (based on 1 wt%, 2wt%, 5wt% and 10wt% of CuO) was added and stirred for 2 hrs at 8O0C. These copper nano particles were then got adsorbed on the surface of Slica gel. The nano copper coated on Silica was recovered by filtration followed by the washing with deionised water (3 xlOO ml) which resulted into residue of catalyst. The residue was activated by drying at 250 0C for 2-3 h. The activated catalyst was used for phenoxylation reaction. Particle size of the CuO obtained were in the range 5 nm - 40 nm with a mean diameter at 15 nm (measured by TEM.)
Example 3:
Preparation of nano copper (II) oxide coated on Titanium oxide
Copper acetate (0.3147g 0.0015 moles) was taken into 100 ml round bottom flask at a room temperature. To this 10 gm of water was added to obtain a mixture. Then this mixture was heated to attain 5O0C and the temperature was maintained for 30 min. in
order to dissolve copper acetate. To this solution, sodium hydroxide solution prepared in water (0.137 Ig 0.00342 moles NaOH in 2.9g H2O) was added drop wise over a period of an hour during which colour of the solution started changing to black. After complete addition of sodium hydroxide, the mixture was heated at 8O0C under continuous stirring and kept for 3 hours. Then TiO2 (based on 5 wt% or 10 wt% CuO) was added and the mixture was stirred for 2 hrs. These copper nano particles were adsorbed on the surface of TiO2. The nano copper coated on TiO2 was recovered by filtration followed by washing with de-ionised water (3x100 ml) to obtain residue of catalyst. The residue was then activated by drying at 250-2600C for 2-3 hours for. The activated catalyst was used for the further phenoxylation reaction.
Example 4:
Preparation of nano copper (0) coated on Slica
0.1 M solution of CuSO4 was prepared by dissolving (2.49g) in 100 ml of deionised water and nitrogen was purged to remove the dissolved oxygen. 100 ml 0.5 M sodium citrate was added to it and allowed to stir for 30 minutes under the nitrogen atmosphere. To this 10 ml of 0.1 M aqueous solution of sodium borohydride was added drop wise under constant stirring in N2 atmosphere. The colour of the solution change to dark brown on complete addition of reducing agent indicated the formation of citrate protected copper nanoparticles. These copper nano particles were adsorbed on the surface by adding Silica gel. The suspension was stirred at 80 0C 2 hours. The nano copper coated Silica was recovered by filtration followed by the washing with deionised water (3x 100 ml) to obtain residual catalyst. The residual solid catalyst was activated by dried at 250-260 0C for 2-3 hours. The activated catalyst was used for the further phenoxylation reaction.
Example 5:
Preparation of nano copper(II) oxide particles
Copper acetate (0.3147g 0.0015 moles) was taken into the 100 ml round bottom flask at a room temperature. To this water (1Og) was added at a room temperature. The mixture was then heated to 50 0C with stirring and kept for 30 min. in order to dissolve the copper acetate. To this fixture sodium hydroxide solution (0.137 Ig 0.00342 moles NaOH in 2.9g H2O) was added drop wise over a period of an hour. After addition of NaOH solution, the mixture was heated at 8O0C for 5 hours during which black CuO nano particles are formed. Then water was removed from reaction mass on evaporator to get black solids.
Example 6:
Preparation of nano Copper (I)oxide particles
Step-1 : Preparation of Cupric Hydroxide [Cu (OH) 2]
5 gm of Copper (II) Chloride (37.1 mmol) was dissolved in 10.OmL of water to get clear blue solution. To this 14.OmL of 4M NaOH solution was added to give thick viscous blue colour precipitate. The reaction mass was then filtered and vacuum dried till constant weight is obtained. Solid Cupric hydroxide formed was further used for preparation of copper oxide.
Step 2: Preparation of nano copper oxide catalyst from cupric hydroxide
Cupric hydroxide (3.8g, 38.9mmol, 1.0 MoI Eq) was added to mono ethylene glycol
(64.22g, 1.03 mol, 36.6 MoI Eq.) in 250 mL round bottom flask under N2 atmosphere and heated to reflux at 1950C for 1.5 hours. During the reaction the colour began to change from bluish green to yellowish green in suspension form. The heating was then stopped and the mixture was allowed to cool to room temperature. The copper (I) oxide nano particle formed was used directly for further phenoxylation reaction.
Example 7:
Preparation of nano Copper (I) chloride from Cu2O
Copper Oxide (I) in mono ethylene glycol (63.78 g) was transferred to the three necked 250 ml round bottom flask having one end connected with glass inlet for purging dry HCl gas at a room temperature.
Sodium chloride powder (20.Og, 1.0 mol eq) was transferred to 100 mL three necked flask to which H2SO4 98% (34.2g, 1.0 MoI Eq.) was added drop wise to generate HCl gas.
The gas generated was passed through the mixture containg Cu2O and methylene glycol for 30 min. After completion of reaction (which is indicated by formation of white material), N2 gas was purged through the reaction mass to remove trapped HCl.
The suspension as such was used for the phenoxylation reaction.
Example 8:
Preparation of nano Copper (I) bromide:
Copper Oxide (I) in mono ethylene glycol (63.78g) was taken into the three necked 250 ml round bottom flask having one end connected with glass inlet for purging Dry HBr gas at a room temperature.
Potassium bromide powder (25.Og, 1.0 mol eq) was taken in 100 mL three necked flask to which H2SO4 (20.58g, 1.0 Mol Eq.) was added drop wise to generate HBr gas. The gas generated was passed through methylene glycol containing Cu2O suspension for 30 min. Change in colour from yellowish green to whitish green (in suspension form) was observed. After completion of the reaction, N2 gas was purged through reaction mass to remove trapped HBr.
Example 9:
Preparation of nano Copper (I) iodide
Copper Oxide (I) in mono ethylene glycol (50.0 g) was taken into the three necked
100 ml round bottom flask at a room temperature and under N2 atmosphere. To this 57% HI (2.65g) was added drop wise till the colour changes from yellow to pale bluish green (in suspension form) was observed. After completion of the reaction, N2 gas was purged through reaction mass to remove trapped HI.
Example 10:
Preparation of 3-phenoxy 4-fluoro benzaldehyde Acetal from 3-bromo-4- fluorobenzaldehyde acetal
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and dimethoxy ethane (5g ,0.055mol), 3-bromo 4-fluoro benzaldehyde acetal(30g, 0.1209 moles) was added drop wise at 800C. Then the mixture was heated to 125 to 140 0C. To this heated mixture 0.9g of nano CuO coated SiO2 was added and the mixture was stirred for 5-6 hours to complete the conversion of starting material. The progress of the reaction was monitored by GC at every hour. The GC sample was prepared by extracting the sample with a toluene/ ethyl acetate mixture. The inorganics were separated by water wash and the isolated organic phase was evaporated to get syrupy liquid showing 90% conversion with >80% selectivity.
Example 11:
Preparation of 3-phenoxy 4-fluoro benzaldehyde Acetal
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and toluene (5g ,0.0543mol), 3-bromo 4-fluoro benzaldehyde acetal (30g, 0.1209 moles) was added drop wise. Then the mixture was heated to 8O0C. The mixture was further heated to attain 125 to 1400C. To this heated mixture 0.9 g of nano CuO coated SiO2 was added. The resulting mixture was heated with continuous stirring for 5-6 hours to complete the conversion of starting material. The reaction was monitored by GC at every hour by taking a sample. After completion of the reaction, the product was washed with water and extracted by a toluene/ ethyl acetate mixture. The filtrate was
then evaporated to yield the product as syrupy liquid containing 90% product with the selectivity of 78%
Example 12:
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and toluene (5g ,0.0543mol), 3-bromo 4-fluoro benzaldehyde acetal (3Og, 0.1209 moles) was added drop wise at 8O0C. The resulting mixture was heated to 125 to 140 0C. To this 0.9g of nano copper coated TiO2 was added with stirring. After completion of addition, the mixture was stirred for 5-6 hours by maintaining the same temperature. The reaction was monitored by GC at time intervals of one hour. After completion of the reaction the mixture was cooled to room temperature and washed with water. The organic layer was extracted with toluene/ethyl acetate mixture and evaporated to get syrupy liquid showing 80% product in the crude by GC area %.
Example 13:
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and toluene (5g ,0.0543mol), 3-bromo 4-fluoro benzaldehyde acetal (3Og, 0.1209 moles) was added drop wise at 8O0C. The resulting mixture was heated to 125 to 140 0C. To this 0.3 mole % of nano Cu2O with respect to acetal was added. The resulting mixture was stirred for 5-6 hr to complete the conversion of starting material. The reaction was monitored by GC analysis of the sample at every hour. After completion of the reaction, the product was washed with water and extracted with a mixture of toluene/ ethyl acetate (50 ml). The isolated organic phase was evaporated to get syrupy liquid showing 99% conversion of the starting material and >82% selectivity.
Example 14:
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and dimethoxy ethane (5g ,0.055mol), 3-bromo 4-fluoro benzaldehyde acetal (30g, 0.1209 moles) was added drop wise at 8O0C. The resulting mixture was heated to 125
to 140 0C Then 0.3 mole% of nano Cu2O was added and the suspension was stirred for 5-6 hours to complete the conversion of starting material. Reaction was monitored by GC at time intervals of one hour. The reaction mixture was then cooled to room temperature and washed with water. The organic layer was extracted with a toluene/ ethyl acetate mixture (50 ml). The organic layer containing the product was evaporated to get syrupy liquid showing complete conversion of starting material. The GC area% shows >85% selectivity of the product.
Example 15:
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and toluene (5g ,0.0543mol), 3-bromo 4-fluoro benzaldehyde acetal (3Og, 0.1209 moles) was added drop wise at 8O0C. The resulting mixture was heated to 125 to 140 0C. To this 0.9 g of nano Cu2O was added and the heating was continued for 5-6 hours to complete the conversion of startingmaterial. The reaction was monitored by GC at time intervals of one hour. After completion of the reaction the product was cooled to room temperature and washed with water. The organic layer was extracted with toluene/ ethyl acetate(50 ml) and then evaporated to get brown liquid. The GC area % of the crude shows >98% conversion and 81% selectivity.
Example 16:
To the mixture containing dehydrated potassium phenoxide (2Og, 0.1515 mol) and toluene (5g ,0.0543mol), 3-bromo 4-fluoro benzaldehyde acetal (3Og, 0.1209 moles) was added drop wise. The resulting mixture was heated to 125 to 140 0C. To the resulting mixture 0.3 wt % of nano Cu2O with respect to starting material was added with stirring and the mixture was kept for 5-6 hr to complete the conversion of starting material. The reaction was monitored by GC at time interval of one hour. After
completion of the reaction, the crude was cooled to room temperature and washed with water. The product was extracted by adding a mixture of toluene/ ethyl acetate (50 ml) and evaporated to get brown liquid. The GC area% showed >99% conversion and >84% product selectivity.
Example 17:
To the mixture containing dehydrated potassium phenoxide 33.33g (0.2525mol) and toluene 16.3g (0.1771mol), 3-bromo 4-fluoro benzaldehyde acetal (50g, 0.2016 mol.) was added drop wise. The resulting mixture was heated to 125 to 140 0C. To the resulting mixture 0.3wt% of nano CuCl with respect to starting material was added and the suspension was stirred for 5-6 hr to complete the conversion of starting material. The reaction was monitored by GC at time intervals of one hour. After completion of the reaction, the reaction mass was cooled to room temperature. The mixture was then washed with water and the product was extracted with a mixture of toluene/ ethyl acetate (50 ml). The organic layer was evaporated to get brown liquid showing 98% conversion and 77% selectivity.
Example 18:
To the mixture containing dehydrated potassium phenoxide 33.33g (0.2525mol) and toluene 16.3g (0.1771 mol), 3-bromo 4-fluoro benzaldehyde acetal (50g, 0.2016 mol.) was added drop wise. The resulting mixture was heated to 125 to 140 0C. Under this condition 0.3 wt% of nano CuI was added and the suspension was stirred for 5-6 hr to complete the conversion of starting molecule. The reaction was monitored by GC at time intervals of one hour. After completion of the reaction the reaction mixture was cooled to room temperature. The product was then washed with water and extracted with a mixture of toluene/ ethyl acetate, 50 ml. The organic layer thus obtained was evaporated to get brown liquid. The GC result shows 99% conversion and 82% selectivity.
Example 19:
To the mixture containing dehydrated potassium phenoxide 33.33g (0.2525mol) and dimethoxy ethane 16.3g (0.1881mol), 3-bromo 4-fluoro benzaldehyde acetal (5Og, 0.2016 mol.) was added drop wise. The resulting mixture was heated to 125 to 140 0C. To this 0.3% of nano CuCI was added with continuous stirring. The suspension was then heated for 5-6 hr to complete the conversion of starting molecule. The reaction was monitored by GC at time intervals of one hour. After completion of the reaction the reaction mixture was cooled to room temperature. The crude thus obtained was washed with water and extracted with a mixture of toluene/ ethyl acetate (50 ml). The final organic layer was separated and evaporated to get brown liquid. GC results show the conversion of 99% and the selectivity of the product > 84% based on area %.
Technical Advancement:
The uniqueness of the present invention lies in the use of novel nano copper coated Cu (I/II) oxide in Ullmann reactions. Furthermore, the process in accordance with the invention provides synthesis of 4-fluoro-3-phenoxy-benzaldehyde using novel nano copper coated Cu (I/II) oxide in high yield, purity and better selectivity.
While considerable emphasis has been placed herein on the specific steps of the preferred process, it will be appreciated that many steps can be made and that many changes can be made in the preferred steps without departing from the principles of the invention. These and other changes in the preferred steps of the invention will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation.
Claims
1. A process for manufacturing of 4-fluoro-3-phenoxy-benzaldehyde acetal; said process comprises the following steps: a. adding drop-wise 3-bromo-4-fluoro benzaldehyde acetal to a predetermined quantity of dehydrated potassium phenoxide under continuous stirring at a temperature of about 8O0C to obtain a resultant mass; b. heating the resultant mass in an environment having a temperature in the range of about 120 to 14O0C to obtain a resultant mixture; c. adding nano-copper catalyst system as herein described to the resultant mixture under continuous stirring for a period of about 5 to 6 hours to obtain a reaction product containing 4-fluoro-3-phenoxy-benzaldehyde acetal; d. washing the reaction product containing 4-fluoro-3-phenoxy- benzaldehyde with water followed by extracting the product with at least one organic solvent selected from a group consisting of toluene and ethyl acetate and filtering to obtain a filtrate; and e. evaporating the filtrate to yield a 4-fluoro-3-phenoxy-benzaldehyde acetal.
2. The process as claimed in claim 1, wherein the step a optionally comprises addition of at least one solvent selected from a group consisting of dimethoxy ethane, toluene and mixture thereof.
3. The process as claimed in claim 1, wherein the step a optionally comprises addition of at least one additive selected from a group consisting of cyclodextrine, crown ether, cryptands containing -OH group and cryptands containing -SH group.
4. The process as claimed in claim 1, wherein the nano-copper catalyst system is at least one selected from a group consisting of copper (0) particles, copper (I) oxide particles, copper (II) oxide particles and copper (I) halide particles.
5. The process as claimed in claim 4, wherein the nano-copper catalyst system is copper (I) halide particles selected from a group consisting of copper (I)chloride , copper (I) bromide particles and copper (I) iodide particles.
6. The process as claimed in claim 1, wherein the amount of nano-copper catalyst system used is in the range of about 0.1 to 1% of the mass of the to 3-bromo-4- fluoro benzaldehyde acetal.
7. The process as claimed in claim 1, wherein the ratio of potassium phenoxide to 3- bromo-4-fluoro benzaldehyde acetal is in the range of about 1 to 2 moles.
8. The process as claimed in any of the preceding claims, wherein the ratio of dimethoxy ethane to 3-bromo-4-fluoro benzaldehyde acetal is in the range of about 0 to 20 moles.
9. The process as claimed in any of the preceding claims, wherein the ratio of toluene to 3-bromo-4-fluoro benzaldehyde acetal is in the range of about 0 to 20 moles.
10. The process as claimed in claim 1, wherein the yield of 4-fluoro-3-phenoxy- benzaldehyde acetal having purity greater than 80 % is greater than 90 %.
11. The process as claimed in claim 1 and 4, wherein the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in deionised water by heating at a temperature of about 50 0C to obtain a solution followed by purging the solution with nitrogen gas to remove dissolved oxygen and adding sodium hydroxide solution drop wise to obtain a mixture; b. adding drop- wise at least one solvent selected from a group consisting of water, methanol and ethanol to the mixture containing copper salt under constant stirring for a period of about 1 hour to obtain a resultant mass; c. heating the resultant mass at a temperature of about 800C for a period of about 2 to 6 hours to obtain copper(I) oxide nano-particles ; d. adsorbing the copper nanoparticles on the surface of the adsorbing material followed by recovering the adsorbed nano copper by filtration ; e. washing the recovered nano copper with deionised water to obtain a residual nano copper catalyst; and f. drying the residual catalyst at a temperature of about 2500C to 2600C for a period of about 2 to 3 hours to obtain an activated copper (I) oxide particles based nano- copper catalyst system.
12. The process as claimed in claim 1 and 4, wherein the nano-copper catalyst system is copper (I) oxide particles prepared by: a. dissolving a copper salt in at least, one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues thereof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 1950C for a period of about one and half hour to obtain reaction mass; and c. cooling the reaction mass to obtain copper (I) oxide nano particles based nano- copper catalyst system.
13. The process as claimed in claim 1 and 4, wherein the nano-copper catalyst system is copper (I) halide particles prepared by: a. dissolving a copper salt in at least one solvent selected from a group consisting of methylene glycol, diethyelene glycol, triethylene glycol and higher homologues therof, ethoxylated triol based on glycerol and triethylol propane to obtain a mixture; b. heating the mixture to reflux at a temperature of about 1950C for a period of about one and half hour to obtain a reaction mass; c. cooling the reaction mass to obtain copper (I) oxide nano particles; and d. reacting the copper (I) oxide nano particles with hydrogen halide to form a copper (I) halide particles based nano- copper catalyst system.
14. The process as claimed in claim 13, wherein the hydrogen halide is at least one selected from a group consisting of hydrogen bromide, hydrogen chloride, and hydrogen iodide.
15. The process as claimed in claim 11, 12 and 13, wherein the copper salt is at least one selected from a group consisting of copper acetate, copper sulphate, copper hydroxide, copper hydroxyl carbonate and copper oxide.
16. The process as claimed in claim 11, wherein the adsorbing material is selected from a group consisting of silica, TiO2, Al2O3, MgO, SnO2, titania and zirconia.
17. The process as claimed in claim 11, wherein the ratio of copper salt to adsorbing material is in the range of about 0.1 to 30 % by weight.
8. The process as claimed in any of the preceding claims, wherein the particle size of nano copper catalyst is in the range of about 5 nm to 300 run.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118702656A (en) * | 2024-08-28 | 2024-09-27 | 安徽秀朗新材料科技有限公司 | Environment-friendly polyimide monomer preparation process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044002A1 (en) * | 1980-07-16 | 1982-01-20 | Bayer Ag | Process for preparing 3-bromo-4-fluorobenzaldehyde (-acetals),3-bromo- 4-fluoro-benzoic acid nitrile and its preparation |
| EP0061004A1 (en) * | 1979-08-22 | 1982-09-29 | Bayer Ag | 3-Bromo-4-fluorobenzaldehyde and its acetals, and process for their preparation |
| CN1255481A (en) * | 1999-11-12 | 2000-06-07 | 广东省化州市农药厂 | Process for preparing 3-phenoxy-4-fluorophenyl formaldehyde by p-fluorophenyl formaldehyde method |
| CN1508124A (en) * | 2002-12-18 | 2004-06-30 | 颜汉新 | Method for synthesizing lambda-cyhalothrin from p-fluorobenzoic aldehyde |
-
2010
- 2010-01-06 WO PCT/IN2010/000007 patent/WO2010086876A2/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0061004A1 (en) * | 1979-08-22 | 1982-09-29 | Bayer Ag | 3-Bromo-4-fluorobenzaldehyde and its acetals, and process for their preparation |
| EP0044002A1 (en) * | 1980-07-16 | 1982-01-20 | Bayer Ag | Process for preparing 3-bromo-4-fluorobenzaldehyde (-acetals),3-bromo- 4-fluoro-benzoic acid nitrile and its preparation |
| CN1255481A (en) * | 1999-11-12 | 2000-06-07 | 广东省化州市农药厂 | Process for preparing 3-phenoxy-4-fluorophenyl formaldehyde by p-fluorophenyl formaldehyde method |
| CN1508124A (en) * | 2002-12-18 | 2004-06-30 | 颜汉新 | Method for synthesizing lambda-cyhalothrin from p-fluorobenzoic aldehyde |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118702656A (en) * | 2024-08-28 | 2024-09-27 | 安徽秀朗新材料科技有限公司 | Environment-friendly polyimide monomer preparation process |
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