JPH0222054B2 - - Google Patents
Info
- Publication number
- JPH0222054B2 JPH0222054B2 JP55133502A JP13350280A JPH0222054B2 JP H0222054 B2 JPH0222054 B2 JP H0222054B2 JP 55133502 A JP55133502 A JP 55133502A JP 13350280 A JP13350280 A JP 13350280A JP H0222054 B2 JPH0222054 B2 JP H0222054B2
- Authority
- JP
- Japan
- Prior art keywords
- ether
- alcohol
- general formula
- butyl
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 16
- 150000002170 ethers Chemical class 0.000 claims description 14
- 150000002366 halogen compounds Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- -1 aralkyl halide Chemical class 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 17
- 239000008346 aqueous phase Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 2
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000002585 base Substances 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
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- VOZVXJVZUMOMPL-UHFFFAOYSA-N 1-butoxy-2-nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1OCCCC VOZVXJVZUMOMPL-UHFFFAOYSA-N 0.000 description 1
- NMMIRFKUKVHGTQ-UHFFFAOYSA-N 1-butoxydodecane Chemical compound CCCCCCCCCCCCOCCCC NMMIRFKUKVHGTQ-UHFFFAOYSA-N 0.000 description 1
- OZQXZXKPJXQTND-UHFFFAOYSA-N 1-butoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCC OZQXZXKPJXQTND-UHFFFAOYSA-N 0.000 description 1
- FVEAPUWITOJHBI-UHFFFAOYSA-N 1-butoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCC FVEAPUWITOJHBI-UHFFFAOYSA-N 0.000 description 1
- HLKBESQBAMRXPZ-UHFFFAOYSA-N 1-butoxyoctane Chemical compound CCCCCCCCOCCCC HLKBESQBAMRXPZ-UHFFFAOYSA-N 0.000 description 1
- POEDHWVTLBLWDA-UHFFFAOYSA-N 1-butylindole-2,3-dione Chemical compound C1=CC=C2N(CCCC)C(=O)C(=O)C2=C1 POEDHWVTLBLWDA-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- LNCKGMDRFWKBHM-UHFFFAOYSA-N 1-ethoxy-2-nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1OCC LNCKGMDRFWKBHM-UHFFFAOYSA-N 0.000 description 1
- HAOXTAJLDMZCQJ-UHFFFAOYSA-N 1-ethoxydodecane Chemical compound CCCCCCCCCCCCOCC HAOXTAJLDMZCQJ-UHFFFAOYSA-N 0.000 description 1
- QGFMFMPFLWUUIH-UHFFFAOYSA-N 1-ethoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCC QGFMFMPFLWUUIH-UHFFFAOYSA-N 0.000 description 1
- DGLWHXRTXWIDEE-UHFFFAOYSA-N 1-ethoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCC DGLWHXRTXWIDEE-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- BCXIOLDAECLTCX-UHFFFAOYSA-N 1-methoxy-2-nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1OC BCXIOLDAECLTCX-UHFFFAOYSA-N 0.000 description 1
- JWCACDSKXWPOFF-UHFFFAOYSA-N 1-methoxydodecane Chemical compound CCCCCCCCCCCCOC JWCACDSKXWPOFF-UHFFFAOYSA-N 0.000 description 1
- YOTHBMSACCHRLC-UHFFFAOYSA-N 1-methoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC YOTHBMSACCHRLC-UHFFFAOYSA-N 0.000 description 1
- RVJIJWSQYZTQBW-UHFFFAOYSA-N 1-methoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC RVJIJWSQYZTQBW-UHFFFAOYSA-N 0.000 description 1
- DKZRLCHWDNEKRH-UHFFFAOYSA-N 1-nonoxynonane Chemical compound CCCCCCCCCOCCCCCCCCC DKZRLCHWDNEKRH-UHFFFAOYSA-N 0.000 description 1
- PZXWWFHJHJPDTN-UHFFFAOYSA-N 1-nonyl-2-propoxybenzene Chemical compound CCCCCCCCCC1=CC=CC=C1OCCC PZXWWFHJHJPDTN-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- PIIRYSWVJSPXMW-UHFFFAOYSA-N 1-octyl-4-(4-octylphenoxy)benzene Chemical compound C1=CC(CCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCC)C=C1 PIIRYSWVJSPXMW-UHFFFAOYSA-N 0.000 description 1
- SOOBJWBRPWEOMW-UHFFFAOYSA-N 1-propoxydodecane Chemical compound CCCCCCCCCCCCOCCC SOOBJWBRPWEOMW-UHFFFAOYSA-N 0.000 description 1
- OUDWNTLJRZDXFC-UHFFFAOYSA-N 1-propoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCC OUDWNTLJRZDXFC-UHFFFAOYSA-N 0.000 description 1
- XIHDFPHFJXUOQA-UHFFFAOYSA-N 1-propoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCC XIHDFPHFJXUOQA-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- AMOYMEBHYUTMKJ-UHFFFAOYSA-N 2-(2-phenylethoxy)ethylbenzene Chemical compound C=1C=CC=CC=1CCOCCC1=CC=CC=C1 AMOYMEBHYUTMKJ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- XZBXAYCCBFTQHH-UHFFFAOYSA-N 3-chloropropylbenzene Chemical compound ClCCCC1=CC=CC=C1 XZBXAYCCBFTQHH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940028820 didecyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はエーテル類の新規な製造方法に関す
る。
従来エーテル類の製造方法としては例えば過剰
のアルコール中金属ナトリウムを作用させてアル
コキシドを生成させ、これはハロゲン化アルキル
もしくはハロゲン化アラルキルを反応させる方法
が知られている。またこの方法の変法としてアル
コールとハロゲン化アルキルもしくはハロゲン化
アラルキルとを種々の塩基の存在下有機溶媒中に
て反応させる方法がある。この場合、ナトリウム
アミド、水酸化ナトリウム、炭酸カリウム、水素
化ナトリウム等を塩基とし、ジメチルホルムアミ
ド、ジメチルアセトアミド、テトラメチル尿素、
ジメチルスルホキシド、モノグライム、テトラヒ
ドロフラン等を溶媒として使用している。しかし
ながら前者の方法は、高価で取り扱いが困難な金
属ナトリウムを使用しており、作業面、経済面で
の難点を有し、それ故エーテル類の工業的生産に
は不適当である。また後者の方法は、比較的高価
な溶媒を使用しており、しかも斯かる溶媒殊にジ
メチルホルムアミド、ジメチルアセトアミド、テ
トラメチル尿素等は反応時に加水分解を受け易く
反応系内が汚染されることになり、その結果反応
終了後目的とするエーテル類の分離が困難とな
り、得られるエーテル類の純度が低下するという
難点を有する。従つて後者の方法もエーテル類の
工業的生産には不適当である。
本発明の目的は特に有機溶媒を使用することな
く簡便な操作で目的とするエーテル類を好収率、
好純度にて製造し得る工業的にも極めて有利な方
法を提供することにある。
即ち本発明は、一般式
R1OH (1)
〔式中R1はアルキル基、アルコキシアルキル
基またはアラルキル基を示す。〕で表わされるア
ルコールと一般式
R2X (2)
〔式中R2はアルキル基またはアラルキル基を、
Ｘはハロゲン原子をそれぞれ示す。〕で表わされ
るハロゲン化合物とを反応させて一般式
R1OR2 (3)
〔式中R1及びR2は前記に同じ。〕で表わされる
エーテル類を得るに当り、上記アルコール及びハ
ロゲン化合物を含有する有機相とアルカリ水溶液
からなる水相との２相間でこれらを反応させ且つ
反応系内に一般式
R3O（C2H4O）nR4 (4)
［式中R3及びR4は同一又は相異なつて水素原
子、アルキル基、アルケニル基、アリール基また
はアラルキル基を、ｍは４〜90の整数をそれぞれ
示す。］で表わされる化合物を存在させることを
特徴とするエーテル類の製造方法に係る。
本発明に於て出発原料として用いられる一般式
(1)のアルコール及び一般式(2)のハロゲン化合物は
いずれも公知の化合物である。一般式(1)及び一般
式(2)に於てR1乃至R2で示されるアルキル基には
メチル、エチル、ｎ―プロピル、iso―プロピル、
ｎ―ブチル、tert―ブチル、ｎ―アミル、iso―
アミル、ｎ―ヘキシル、ｎ―ヘプチル、ｎ―オク
チル、ｎ―デシル、ｎ―ドデシル、ｎ―テトラデ
シル、ｎ―ヘキサデシル、ｎ―オクタデシル、ｎ
―エイコシル基等が包含され、またアルコキシア
ルキル基にはメトキシエチル、エトキシエチル、
ｎ―ブトキシエチル、メトキシエトキシエチル、
エトキシエトキシエチル、ｎ―ブトキシエトキシ
エチル等が包含され、またアラルキル基にはベン
ジル、２―フエニルエチル、ｐ―メチルベンジ
ル、３―フエニルプロピル、ナフチルメチル基等
が包含される。一般式(1)のアルコールとしては具
体的にはメチルアルコール、エチルアルコール、
ｎ―プロピルアルコール、iso―プロピルアルコ
ール、ｎ―ブチルアルコール、iso―ブチルアル
コール、sec―ブチルアルコール、tert―ブチル
アルコール、ｎ―アミルアルコール、iso―アミ
ルアルコール、ｎ―ヘキシルアルコール、ｎ―ペ
プチルアルコール、ｎ―オクチルアルコール、２
―オクチルアルコール、２―エチルヘキシルアル
コール、ｎ―デシルアルコール、ラウリルアルコ
ール、ミリスチルアルコール、パルミチルアルコ
ール、ステアリルアルコール、メチルセロソル
ブ、エチルセロソルブ、ｎ―ブチルセロソルブ、
メチルカルビトール、エチルカルビトール、ｎ―
ブチルカルビトール等を例示できる。一般式(2)の
ハロゲン化合物としては具体的には塩化メチル、
塩化エチル、塩化ｎ―プロピル、塩化iso―プロ
ピル、塩化ｎ―ブチル、塩化ｎ―アミル、塩化
iso―アミル、塩化ｎ―ヘキシル、塩化ｎ―ヘプ
チル、塩化ｎ―ペンチル、塩化ｎ―オクチル、塩
化ベンジル、塩化ｐ―メチルベンジル、塩化２―
フエニルエチル、塩化３―フエニルプロピル、塩
化ナフチルメチル等の塩化物やこれらの化合物の
塩素原子を弗素原子、臭素原子または沃素原子で
置き換えた化合物を例示できる。
本発明では一般式(1)のアルコールと一般式(2)の
ハロゲン化合物とを反応させるに当り、一般式(1)
のアルコール及び一般式(2)のハロゲン化合物を含
有する有機相とアルカリ水溶液からなる水相とを
２相間にて反応させ且つ反応系内に一般式(4)で表
わされる化合物を存在させることを必須とする。
一般式(4)に於てR3及びR4で示されるアルキル基
にはメチル、エチル、ｎ―プロピル、iso―プロ
ピル、ｎ―ブチル、tert―ブチル、ｎ―アミル、
iso―アミル、ｎ―ヘキシル、ｎ―ヘプチル、ｎ
―オクチル、ｎ―ノニル、ｎ―デシル、ｎ―ラウ
リル、ｎ―セチル、ｎ―ステアリル基等が、アル
ケニル基にはｎ―オレイル基等が、アリール基に
はフエニル、ｎ―オクチルフエニル、ｎ―ノニル
フエニル、ナフチル基等が、またアラルキル基に
はベンジル、２―フエニルエチル、３―フエニル
プロピル基等がそれぞれ包含される。一般式(4)で
表わされる化合物としては具体的にはポリエチレ
ングリコール―200，―300，―400，―600，―
1000，これらのモノまたはジメチルエーテル、モ
ノまたはジエチルエーテル、モノまたはジプロピ
ルエーテル、モノまたはジブチルエーテル、モノ
またはペンチルエーテル、モノまたはヘキシルエ
ーテル、モノまたはジヘプチルエーテル、モノま
たはジオクチルエーテル、モノまたはジノニルエ
ーテル、モノまたはジデシルエーテル、モノラウ
リルエーテル、モノセチルエーテル、モノステア
リルエーテル、モノオレイルエーテル、モノオク
チルフエニルエーテル、モノノニルフエニルエー
テル、モノフエニルエーテル、モノナフチルエー
テル、モノベンジルエーテル、モノフエニルエチ
ルエーテル、ラウリルメチルエーテル、ラウリル
エチルエーテル、ラウリルプロピルエーテル、ラ
ウリルブチルエーテル、セチルメチルエーテル、
セチルエチルエーテル、セチルプロピルエーテ
ル、セチルブチルエーテル、ステアリルメチルエ
ーテル、ステアリルエチルエーテル、ステアリル
プロピルエーテル、ステアリルブチルエーテル、
オレイルメチルエーテル、オレイルエチルエーテ
ル、オレイルプロピルエーテル、オレイルブチル
エーテル、オクチルフエニル・メチルエーテル、
オクチルフエニル・エチルエーテル、オクチルフ
エニル・プロピルエーテル、オクチルフエニル・
ブチルエーエル、ノニルフエニル・メチルエーテ
ル、ノニルフエニル・エチルエーテル、ノニルフ
エニル・プロピルエーテル、ノニルフエニル・ブ
チルエーテル、ジフエニルエーテル、ジナフチル
エーテル、ジベンジルエーテル、ジフエニルエチ
ルエーテル等を例示できる。これらのうちでポリ
エチレングリコール（PEG）―400―ジメチルエ
ーテル、PEG―400―ジエチルエーテル、PEG―
400―ジ―ｎ―プロピルエーテル、PEG―400―
ジ―ｎ―ブチルエーテル、PEG―600―ジメチル
エーテル、PEG―600―ジエチルエーテル、PEG
―600―ジ―ｎ―プロピルエーテル、PEG―600
―ジ―ｎ―ブチルエーテル、PEG―1000―ジメ
チルエーテル、PEG―1000―ジエチルエーテル、
PEG―1000―ジ―ｎ―ブチルエーテル、PEG―
600及びPEG―1000が特に好適である。反応系内
に存在させるべき一般式(4)の化合物の量としては
特に限定されないが、一般式(1)のアルコール１モ
ルに対し通常0.01〜0.2モル、好ましくは0.01〜
0.05モル程度存在させればよい。
本発明で用いられる有機相には一般式(1)のアル
コール及び一般式(2)のハロゲン化化合物が含有さ
れている。これらの含有割合としては特に限定が
なく広い範囲内で適宜選択できるが、一般式(2)の
ハロゲン化合物を一般式(1)のアルコール１モルに
対して通常0.1〜10モル、好ましくは３〜４モル
となるように有機相中に含有させればよい。
また本発明で用いられる水相はアルカリ水溶液
からなるものである。アルカリとしては公知のも
のを広く使用でき、例えば水酸化カリウム、水酸
化ナトリウム、水酸化リチウム等のアルカリ金属
の水酸化物、水酸化カルシウム、水酸化バリウ
ム、水酸化マグネシウム等のアルカリ土類金属の
水酸化物等を挙げることができる。これらのアル
カリのうちで水酸化カリウムが特に好適である。
アルカリ水溶液中のアルカリ濃度は特に限定され
ないが、通常40％以上、好ましくは60％以上であ
るのがよい。
本発明では斯かる有機相、水相及び一般式(4)の
化合物の混合物を加熱する。有機相と水相との混
合割合としては特に限定されないが、混合した際
のアルカリの量が一般式(1)のアルコール１モルに
対して通常３〜10モル、好ましくは５モル〜10モ
ルとなるように混合すればよい。加熱温度は通常
30〜100℃、好ましくは30〜70℃とするのがよく、
加熱時間は２〜10時間の範囲内で充分である。
斯くして生成する本発明の目的化合物は慣用の
分離手段により容易に反応混合物から単離、精製
される。例えば反応終了後析出する金属ハロゲン
化物を去し、水相と有機相とを分離した後、予
機相を蒸留して目的とする一般式(3)のエーテル
類、未反応のハロゲン化合物等を分離すればよ
い。一般式(4)の化合物は有機相の蒸留残渣として
回収でき、これを再使用することができる。また
回収される水相はアルカリ濃度が減少しているの
でさらに適量のアルカリを加え、再使用すること
ができる。
本発明の方法は従来法の難点を全て解消したも
のである。即ち本発明の方法は、アルコール及び
ハロゲン化合物を含有する有機相とアルカリ水溶
液からなる水相とを混合し有機相と水相との２相
間でアルコールとハロゲン化合物とを一般式(4)の
化合物の存在下に反応させるものであつて、従来
法のような有機溶媒や取り扱いが困難な金属ナト
リウムは全く不必要であり、作業性は極めて良好
であり、しかも目的とするエーテル類を好収率、
好純度で得ることができる。また本発明に於て触
媒的に作用する一般式(4)の化合物は、反応終了後
反応混合物から容易に単離、回収でき、繰り返し
て使用できる。さらにまた未反応のアルコール及
びハロゲン化合物やアルカリ水溶液も反応混合物
から容易に回収して再使用できる。それ故本発明
の方法はエーテル類の工業的な製造方法として極
めて好適な方法であると言うことができる。
以下に本発明の実施例を挙げる。
実施例 １
一般式(1)のアルコール0.1モル及び一般式(2)の
ハロゲン化合物0.3モルを混合して有機相を調製
する。一方、85％水酸化カリウム33ｇ（0.5モル）
に水10ｇを加えて水相を調製する。有機相、水相
及びPEG―600―ジ―ｎ―ブチルエーテル0.005モ
ルを混合し、激しく撹拌しながら30℃または70℃
にて２〜６時間反応させる。反応終了後析出する
ハロゲン化カリウムを去し、水相と有機相とを
分離し、有機相を精留して目的とするエーテルを
得る。結果を第１表に示す。尚第１表中の収率は
一般式(1)のアルコールを基準にして算出したもの
である。
The present invention relates to a novel method for producing ethers. As a conventional method for producing ethers, for example, an alkoxide is produced by reacting an excess amount of sodium metal in an alcohol, and this is reacted with an alkyl halide or an aralkyl halide. Further, as a modification of this method, there is a method in which an alcohol and an alkyl halide or an aralkyl halide are reacted in an organic solvent in the presence of various bases. In this case, sodium amide, sodium hydroxide, potassium carbonate, sodium hydride, etc. are used as a base, and dimethylformamide, dimethylacetamide, tetramethylurea,
Dimethyl sulfoxide, monoglyme, tetrahydrofuran, etc. are used as solvents. However, the former method uses metallic sodium, which is expensive and difficult to handle, and has operational and economical difficulties, and is therefore unsuitable for industrial production of ethers. In addition, the latter method uses relatively expensive solvents, and such solvents, especially dimethylformamide, dimethylacetamide, tetramethylurea, etc., are easily hydrolyzed during the reaction, resulting in contamination of the reaction system. As a result, it becomes difficult to separate the desired ethers after the reaction is completed, and the purity of the obtained ethers decreases. Therefore, the latter method is also unsuitable for industrial production of ethers. The purpose of the present invention is to produce target ethers in good yields through simple operations without using any organic solvents.
The object of the present invention is to provide an industrially extremely advantageous method that can be produced with good purity. That is, the present invention provides a compound having the general formula R 1 OH (1) [wherein R 1 represents an alkyl group, an alkoxyalkyl group, or an aralkyl group]. ] and the general formula R 2 X (2) [wherein R 2 is an alkyl group or an aralkyl group,
Each X represents a halogen atom. ] and a halogen compound represented by the general formula R 1 OR 2 (3) [wherein R 1 and R 2 are the same as above. ] In order to obtain the ethers represented by the formula R 3 O H 4 O) n R 4 (4) [In the formula, R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and m represents an integer from 4 to 90, respectively. . The present invention relates to a method for producing ethers, characterized by the presence of a compound represented by the following. General formula used as starting material in the present invention
The alcohol in (1) and the halogen compound in general formula (2) are both known compounds. In the general formulas (1) and (2), the alkyl groups represented by R 1 to R 2 include methyl, ethyl, n-propyl, iso-propyl,
n-butyl, tert-butyl, n-amyl, iso-
amyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n
-Eicosyl group etc. are included, and alkoxyalkyl group includes methoxyethyl, ethoxyethyl,
n-butoxyethyl, methoxyethoxyethyl,
Ethoxyethoxyethyl, n-butoxyethoxyethyl and the like are included, and the aralkyl group includes benzyl, 2-phenylethyl, p-methylbenzyl, 3-phenylpropyl, naphthylmethyl and the like. Specifically, the alcohol of general formula (1) is methyl alcohol, ethyl alcohol,
n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, iso-amyl alcohol, n-hexyl alcohol, n-peptyl alcohol , n-octyl alcohol, 2
-Octyl alcohol, 2-ethylhexyl alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve,
Methyl carbitol, ethyl carbitol, n-
Examples include butyl carbitol. Specifically, the halogen compound of general formula (2) is methyl chloride,
Ethyl chloride, n-propyl chloride, iso-propyl chloride, n-butyl chloride, n-amyl chloride, chloride
iso-amyl, n-hexyl chloride, n-heptyl chloride, n-pentyl chloride, n-octyl chloride, benzyl chloride, p-methylbenzyl chloride, 2- chloride
Examples include chlorides such as phenylethyl, 3-phenylpropyl chloride, and naphthylmethyl chloride, and compounds in which the chlorine atom of these compounds is replaced with a fluorine atom, a bromine atom, or an iodine atom. In the present invention, when reacting the alcohol of general formula (1) with the halogen compound of general formula (2),
An organic phase containing an alcohol and a halogen compound of general formula (2) and an aqueous phase consisting of an aqueous alkali solution are reacted between the two phases, and a compound represented by general formula (4) is present in the reaction system. Required.
In the general formula (4), the alkyl groups represented by R 3 and R 4 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-amyl,
iso-amyl, n-hexyl, n-heptyl, n
-Octyl, n-nonyl, n-decyl, n-lauryl, n-cetyl, n-stearyl groups, etc., alkenyl groups include n-oleyl groups, and aryl groups include phenyl, n-octylphenyl, n-stearyl groups, etc. -nonylphenyl, naphthyl groups, etc., and aralkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl groups, etc., respectively. Specifically, the compounds represented by the general formula (4) include polyethylene glycol-200, -300, -400, -600, -
1000, mono or dimethyl ether, mono or diethyl ether, mono or dipropyl ether, mono or dibutyl ether, mono or pentyl ether, mono or hexyl ether, mono or diheptyl ether, mono or dioctyl ether, mono or dinonyl ether , mono- or didecyl ether, monolauryl ether, monocetyl ether, monostearyl ether, monooleyl ether, monooctyl phenyl ether, monononyl phenyl ether, monophenyl ether, mononaphthyl ether, monobenzyl ether, monophenylethyl Ether, lauryl methyl ether, lauryl ethyl ether, lauryl propyl ether, lauryl butyl ether, cetyl methyl ether,
Cetyl ethyl ether, cetyl propyl ether, cetyl butyl ether, stearyl methyl ether, stearyl ethyl ether, stearyl propyl ether, stearyl butyl ether,
Oleyl methyl ether, oleyl ethyl ether, oleyl propyl ether, oleyl butyl ether, octylphenyl methyl ether,
octylphenyl ethyl ether, octylphenyl propyl ether, octylphenyl
Examples include butyl ether, nonylphenyl methyl ether, nonylphenyl ethyl ether, nonylphenyl propyl ether, nonylphenyl butyl ether, diphenyl ether, dinaphthyl ether, dibenzyl ether, diphenyl ethyl ether, and the like. Among these, polyethylene glycol (PEG)-400-dimethyl ether, PEG-400-diethyl ether, PEG-
400-G-n-propyl ether, PEG-400-
Di-n-butyl ether, PEG-600-dimethyl ether, PEG-600-diethyl ether, PEG
-600-G-n-propyl ether, PEG-600
-di-n-butyl ether, PEG-1000-dimethyl ether, PEG-1000-diethyl ether,
PEG-1000-d-n-butyl ether, PEG-
600 and PEG-1000 are particularly preferred. The amount of the compound of general formula (4) to be present in the reaction system is not particularly limited, but is usually 0.01 to 0.2 mol, preferably 0.01 to 0.2 mol, per 1 mol of alcohol of general formula (1).
It is sufficient if it is present in an amount of about 0.05 mol. The organic phase used in the present invention contains an alcohol of general formula (1) and a halogenated compound of general formula (2). The content ratio of these is not particularly limited and can be appropriately selected within a wide range, but the halogen compound of general formula (2) is usually 0.1 to 10 mol, preferably 3 to 10 mol, per 1 mol of alcohol of general formula (1). It may be contained in the organic phase in an amount of 4 mol. Further, the aqueous phase used in the present invention consists of an alkaline aqueous solution. As the alkali, a wide variety of known alkalis can be used, such as alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide, and magnesium hydroxide. Examples include hydroxides. Among these alkalis, potassium hydroxide is particularly preferred.
The alkaline concentration in the alkaline aqueous solution is not particularly limited, but it is usually 40% or more, preferably 60% or more. In the present invention, the mixture of the organic phase, aqueous phase and the compound of general formula (4) is heated. The mixing ratio of the organic phase and the aqueous phase is not particularly limited, but the amount of alkali when mixed is usually 3 to 10 mol, preferably 5 mol to 10 mol, per mol of the alcohol of general formula (1). All you have to do is mix it up. Heating temperature is normal
The temperature is preferably 30 to 100°C, preferably 30 to 70°C,
A heating time of 2 to 10 hours is sufficient. The target compound of the present invention thus produced can be easily isolated and purified from the reaction mixture by conventional separation means. For example, after the metal halide precipitated after the reaction is completed and the aqueous phase and organic phase are separated, the preliminary phase is distilled to remove the desired ether of general formula (3), unreacted halogen compounds, etc. Just separate it. The compound of general formula (4) can be recovered as a distillation residue of the organic phase, and this can be reused. Furthermore, since the aqueous phase recovered has a reduced alkali concentration, it can be reused by adding an appropriate amount of alkali. The method of the present invention overcomes all the drawbacks of conventional methods. That is, in the method of the present invention, an organic phase containing an alcohol and a halogen compound and an aqueous phase consisting of an aqueous alkali solution are mixed, and the alcohol and the halogen compound are mixed into a compound of general formula (4) between the organic phase and the aqueous phase. Since the reaction is carried out in the presence of ethers, there is no need for organic solvents or metallic sodium, which is difficult to handle, as in the conventional method, and the workability is extremely good.Moreover, the desired ethers can be produced in good yields. ,
It can be obtained with good purity. Further, in the present invention, the compound of general formula (4) that acts catalytically can be easily isolated and recovered from the reaction mixture after the completion of the reaction, and can be used repeatedly. Furthermore, unreacted alcohols, halogen compounds, and alkaline aqueous solutions can be easily recovered from the reaction mixture and reused. Therefore, it can be said that the method of the present invention is an extremely suitable method for industrially producing ethers. Examples of the present invention are listed below. Example 1 An organic phase is prepared by mixing 0.1 mol of alcohol of general formula (1) and 0.3 mol of halogen compound of general formula (2). Meanwhile, 33 g (0.5 mol) of 85% potassium hydroxide
Add 10g of water to prepare the aqueous phase. Mix the organic phase, aqueous phase and 0.005 mol of PEG-600-d-n-butyl ether and heat at 30°C or 70°C with vigorous stirring.
to react for 2 to 6 hours. After the reaction is complete, the precipitated potassium halide is removed, an aqueous phase and an organic phase are separated, and the organic phase is rectified to obtain the desired ether. The results are shown in Table 1. The yields in Table 1 were calculated based on the alcohol of general formula (1).
【表】
実施例 ２
ｎ―オクチルアルコール0.1モル及び塩化ｎ―
ブチル0.3モルを混合して有機相を調製する。一
方、85％水酸化カリウム33ｇ（0.5モル）水10ｇ
を加えて水相を調製する。有機相、水相及び下記
第２表記載の一般式(4)の化合物所定量を混合し、
激しく撹拌しながら70℃にて５〜８時間反応させ
る。反応終了後析出する塩化カリウムを去し、
水相と有機相とを分離し、有機相を精留して目的
とするエーテル（ｎ―ブチルｎ―オクチルエーテ
ル）を得る。結果を第２表に示す。尚第２表中の
収率はｎ―オクチルアルコールを基準にして算出
したものである。[Table] Example 2 0.1 mol of n-octyl alcohol and n-chloride
The organic phase is prepared by mixing 0.3 mol of butyl. Meanwhile, 85% potassium hydroxide 33g (0.5 mol) water 10g
Prepare the aqueous phase by adding Mixing an organic phase, an aqueous phase, and a predetermined amount of the compound of general formula (4) listed in Table 2 below,
React for 5-8 hours at 70°C with vigorous stirring. After the reaction is complete, remove the precipitated potassium chloride,
An aqueous phase and an organic phase are separated, and the organic phase is rectified to obtain the desired ether (n-butyl n-octyl ether). The results are shown in Table 2. The yields in Table 2 are calculated based on n-octyl alcohol.
Claims (1)
基またはアラルキル基を示す。］で表わされるア
ルコールと一般式 R2X ［式中R2はアルキル基またはアラルキル基を、
Ｘはハロゲン原子をそれぞれ示す。］で表わされ
るハロゲン化合物とを反応させて一般式 R1OR2 ［式中R1及びR2は前記に同じ。］で表わされる
エーテル類を得るに当り、上記アルコール及びハ
ロゲン化合物を含有する有機相とアルカリ水溶液
からなる水相との２相間でこれらを反応させ且つ
反応系内に一般式 R3O（C2H4O）nR4 (4) ［式中R3及びR4は同一又は相異なつて水素原
子、アルキル基、アルケニル基、アリール基また
はアラルキル基を、ｍは４〜90の整数をそれぞれ
示す。］で表わされる化合物を存在させることを
特徴とするエーテル類の製造方法。[Claims] 1 General formula R 1 OH [wherein R 1 represents an alkyl group, an alkoxyalkyl group or an aralkyl group]. ] and the general formula R 2 X [wherein R 2 is an alkyl group or an aralkyl group,
Each X represents a halogen atom. ] is reacted with a halogen compound represented by the general formula R 1 OR 2 [wherein R 1 and R 2 are the same as above. ] To obtain the ethers represented by the formula R 3 O(C 2 H 4 O) n R 4 (4) [In the formula, R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and m represents an integer from 4 to 90, respectively. . ] A method for producing ethers, characterized by the presence of a compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55133502A JPS5758637A (en) | 1980-09-24 | 1980-09-24 | Preparation of ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55133502A JPS5758637A (en) | 1980-09-24 | 1980-09-24 | Preparation of ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5758637A JPS5758637A (en) | 1982-04-08 |
| JPH0222054B2 true JPH0222054B2 (en) | 1990-05-17 |
Family
ID=15106261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55133502A Granted JPS5758637A (en) | 1980-09-24 | 1980-09-24 | Preparation of ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5758637A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH089564B2 (en) * | 1985-12-24 | 1996-01-31 | 広栄化学工業株式会社 | Method for producing partial ether of polyol |
| JP2003335764A (en) * | 2002-03-12 | 2003-11-28 | Toagosei Co Ltd | Method for producing oxetane compound using polyalkyl ether |
| JP2009280566A (en) * | 2008-04-25 | 2009-12-03 | Sanyo Chem Ind Ltd | 2,2-bis(4-hydroxycyclohexyl)propanedi(meth)allyl ether compound |
-
1980
- 1980-09-24 JP JP55133502A patent/JPS5758637A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5758637A (en) | 1982-04-08 |
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