JP2024058196A - Method for producing dibromomethylbenzene compounds, method for producing benzoic acid compounds, method for producing benzaldehyde compounds, and method for recycling hydrogen bromide - Google Patents
Method for producing dibromomethylbenzene compounds, method for producing benzoic acid compounds, method for producing benzaldehyde compounds, and method for recycling hydrogen bromide Download PDFInfo
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- JP2024058196A JP2024058196A JP2022165408A JP2022165408A JP2024058196A JP 2024058196 A JP2024058196 A JP 2024058196A JP 2022165408 A JP2022165408 A JP 2022165408A JP 2022165408 A JP2022165408 A JP 2022165408A JP 2024058196 A JP2024058196 A JP 2024058196A
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- Prior art keywords
- compound
- producing
- dibromomethylbenzene
- hydrogen bromide
- photoreaction
- Prior art date
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910000042 hydrogen bromide Inorganic materials 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 150000001558 benzoic acid derivatives Chemical class 0.000 title description 3
- VCJZTATVUDMNLU-UHFFFAOYSA-N dibromomethylbenzene Chemical class BrC(Br)C1=CC=CC=C1 VCJZTATVUDMNLU-UHFFFAOYSA-N 0.000 title description 3
- 150000003935 benzaldehydes Chemical class 0.000 title description 2
- -1 dibromomethylbenzene compound Chemical class 0.000 claims abstract description 201
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 43
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 43
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 33
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 32
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 22
- 230000001678 irradiating effect Effects 0.000 claims abstract description 12
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 18
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 claims description 4
- DVFVNJHIVAPTMS-UHFFFAOYSA-N 1-methyl-2-(trifluoromethyl)benzene Chemical compound CC1=CC=CC=C1C(F)(F)F DVFVNJHIVAPTMS-UHFFFAOYSA-N 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 claims description 3
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 3
- SVQHPJKYUJYLJD-UHFFFAOYSA-N 2,2-difluoroethylbenzene Chemical compound FC(F)CC1=CC=CC=C1 SVQHPJKYUJYLJD-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 44
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 39
- 239000000047 product Substances 0.000 description 31
- 239000006227 byproduct Substances 0.000 description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 20
- 239000011780 sodium chloride Substances 0.000 description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 17
- 239000008346 aqueous phase Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- 229910052794 bromium Inorganic materials 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 229910019093 NaOCl Inorganic materials 0.000 description 11
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- NSNGJCDLAMBUKZ-UHFFFAOYSA-N 1-(dibromomethyl)-2-fluorobenzene Chemical compound FC1=CC=CC=C1C(Br)Br NSNGJCDLAMBUKZ-UHFFFAOYSA-N 0.000 description 6
- GYQNIXGSKFFVIK-UHFFFAOYSA-N 4-(dibromomethyl)benzonitrile Chemical compound BrC(Br)C1=CC=C(C#N)C=C1 GYQNIXGSKFFVIK-UHFFFAOYSA-N 0.000 description 6
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 6
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FFWQLZFIMNTUCZ-UHFFFAOYSA-N 1-(bromomethyl)-2-fluorobenzene Chemical compound FC1=CC=CC=C1CBr FFWQLZFIMNTUCZ-UHFFFAOYSA-N 0.000 description 4
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 4
- BOHCMQZJWOGWTA-UHFFFAOYSA-N 3-methylbenzonitrile Chemical compound CC1=CC=CC(C#N)=C1 BOHCMQZJWOGWTA-UHFFFAOYSA-N 0.000 description 4
- UMLFTCYAQPPZER-UHFFFAOYSA-N 4-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=C(C#N)C=C1 UMLFTCYAQPPZER-UHFFFAOYSA-N 0.000 description 4
- XRDCYWFNXFIPCE-UHFFFAOYSA-N 4-(tribromomethyl)benzonitrile Chemical compound BrC(Br)(Br)C1=CC=C(C#N)C=C1 XRDCYWFNXFIPCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 description 3
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 description 3
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 description 3
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- ZYCMDWDFIQDPLP-UHFFFAOYSA-N hbr bromine Chemical compound Br.Br ZYCMDWDFIQDPLP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000004686 pentahydrates Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LRLRAYMYEXQKID-UHFFFAOYSA-N 1-methyl-4-(trifluoromethyl)benzene Chemical compound CC1=CC=C(C(F)(F)F)C=C1 LRLRAYMYEXQKID-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- FPTRJFGAAHNWEZ-UHFFFAOYSA-N trifluoromethylbenzene Chemical compound FC(F)(F)C1=CC=CC=C1.FC(F)(F)C1=CC=CC=C1 FPTRJFGAAHNWEZ-UHFFFAOYSA-N 0.000 description 2
- HXBMIQJOSHZCFX-UHFFFAOYSA-N 1-(bromomethyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1CBr HXBMIQJOSHZCFX-UHFFFAOYSA-N 0.000 description 1
- IKSNDOVDVVPSMA-UHFFFAOYSA-N 1-(bromomethyl)-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(CBr)C=C1 IKSNDOVDVVPSMA-UHFFFAOYSA-N 0.000 description 1
- KQNBRMUBPRGXSL-UHFFFAOYSA-N 1-(bromomethyl)-4-chlorobenzene Chemical compound ClC1=CC=C(CBr)C=C1 KQNBRMUBPRGXSL-UHFFFAOYSA-N 0.000 description 1
- NVNPLEPBDPJYRZ-UHFFFAOYSA-N 1-(bromomethyl)-4-fluorobenzene Chemical compound FC1=CC=C(CBr)C=C1 NVNPLEPBDPJYRZ-UHFFFAOYSA-N 0.000 description 1
- HETXONIWLNSRGY-UHFFFAOYSA-N 1-(dibromomethyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Br)Br HETXONIWLNSRGY-UHFFFAOYSA-N 0.000 description 1
- DSYDSGAYKSQVOV-UHFFFAOYSA-N 1-(dibromomethyl)-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(Br)Br)C=C1 DSYDSGAYKSQVOV-UHFFFAOYSA-N 0.000 description 1
- ZQNQSIPAAGRZAU-UHFFFAOYSA-N 1-(dibromomethyl)-4-fluorobenzene Chemical compound FC1=CC=C(C(Br)Br)C=C1 ZQNQSIPAAGRZAU-UHFFFAOYSA-N 0.000 description 1
- MKHFRSNFHCJQIQ-UHFFFAOYSA-N 1-(dibromomethyl)-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C(Br)Br)C=C1 MKHFRSNFHCJQIQ-UHFFFAOYSA-N 0.000 description 1
- HZQSOALFSZIQOT-UHFFFAOYSA-N 1-(tribromomethyl)-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(Br)(Br)Br)C=C1 HZQSOALFSZIQOT-UHFFFAOYSA-N 0.000 description 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 1
- YLRBJYMANQKEAW-UHFFFAOYSA-N 1-bromo-4-(bromomethyl)benzene Chemical compound BrCC1=CC=C(Br)C=C1 YLRBJYMANQKEAW-UHFFFAOYSA-N 0.000 description 1
- PGLAXDZKOAPBHY-UHFFFAOYSA-N 1-bromo-4-(dibromomethyl)benzene Chemical compound BrC(Br)C1=CC=C(Br)C=C1 PGLAXDZKOAPBHY-UHFFFAOYSA-N 0.000 description 1
- JYAVJLTUVOJMPZ-UHFFFAOYSA-N 1-bromo-4-(tribromomethyl)benzene Chemical compound BrC1=CC=C(C(Br)(Br)Br)C=C1 JYAVJLTUVOJMPZ-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- JHUHEBLQVJNTOC-UHFFFAOYSA-N 1-chloro-4-(dibromomethyl)benzene Chemical compound ClC1=CC=C(C(Br)Br)C=C1 JHUHEBLQVJNTOC-UHFFFAOYSA-N 0.000 description 1
- ZVMISGZMZBIXTA-UHFFFAOYSA-N 1-chloro-4-(tribromomethyl)benzene Chemical compound ClC1=CC=C(C(Br)(Br)Br)C=C1 ZVMISGZMZBIXTA-UHFFFAOYSA-N 0.000 description 1
- BGVGHYOIWIALFF-UHFFFAOYSA-N 1-fluoro-2-(trifluoromethyl)benzene Chemical compound FC1=CC=CC=C1C(F)(F)F BGVGHYOIWIALFF-UHFFFAOYSA-N 0.000 description 1
- BTQZKHUEUDPRST-UHFFFAOYSA-N 1-fluoro-3-methylbenzene Chemical compound CC1=CC=CC(F)=C1 BTQZKHUEUDPRST-UHFFFAOYSA-N 0.000 description 1
- GHLXPRHSPUOOLQ-UHFFFAOYSA-N 1-fluoro-4-(tribromomethyl)benzene Chemical compound FC1=CC=C(C(Br)(Br)Br)C=C1 GHLXPRHSPUOOLQ-UHFFFAOYSA-N 0.000 description 1
- VJYXZJGDFJJDGF-UHFFFAOYSA-N 1-methyl-3-(trifluoromethyl)benzene Chemical compound CC1=CC=CC(C(F)(F)F)=C1 VJYXZJGDFJJDGF-UHFFFAOYSA-N 0.000 description 1
- XYQBSMKQEYVKAA-UHFFFAOYSA-N 1-nitro-2-(tribromomethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Br)(Br)Br XYQBSMKQEYVKAA-UHFFFAOYSA-N 0.000 description 1
- IXZRLXWDWGAGBH-UHFFFAOYSA-N 1-nitro-4-(tribromomethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(C(Br)(Br)Br)C=C1 IXZRLXWDWGAGBH-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- CVKOOKPNCVYHNY-UHFFFAOYSA-N 3-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=CC(C#N)=C1 CVKOOKPNCVYHNY-UHFFFAOYSA-N 0.000 description 1
- IRWGDVHKYFTVKR-UHFFFAOYSA-N 3-(dibromomethyl)benzonitrile Chemical compound BrC(Br)C1=CC=CC(C#N)=C1 IRWGDVHKYFTVKR-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- VOLRSQPSJGXRNJ-UHFFFAOYSA-N 4-nitrobenzyl bromide Chemical compound [O-][N+](=O)C1=CC=C(CBr)C=C1 VOLRSQPSJGXRNJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DFHPEMDOUTUSEU-UHFFFAOYSA-N C(#N)C=1C=C(C=CC1)C(Br)(Br)Br Chemical compound C(#N)C=1C=C(C=CC1)C(Br)(Br)Br DFHPEMDOUTUSEU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Abstract
【課題】環境負荷の低減、安全性の向上等に配慮した、ジブロモメチルベンゼン化合物の製造方法、安息香酸化合物の製造方法、ベンズアルデヒド化合物の製造方法、及び臭化水素のリサイクル方法の提供。【解決手段】臭化水素と次亜塩素酸ナトリウムの存在下、かつ酸素の非存在下で、式（１）で表されるトルエン化合物に光照射して光反応により式（２）で表されるジブロモメチルベンゼン化合物を得ることを含む、ジブロモメチルベンゼン化合物の製造方法。TIFF2024058196000029.tif29153TIFF2024058196000030.tif27153【選択図】なし[Problem] To provide a method for producing a dibromomethylbenzene compound, a method for producing a benzoic acid compound, a method for producing a benzaldehyde compound, and a method for recycling hydrogen bromide, which are designed to reduce the environmental load and improve safety. [Solution] A method for producing a dibromomethylbenzene compound, which comprises irradiating a toluene compound represented by formula (1) with light in the presence of hydrogen bromide and sodium hypochlorite, and in the absence of oxygen, to obtain a dibromomethylbenzene compound represented by formula (2) by photoreaction. TIFF2024058196000029.tif29153TIFF2024058196000030.tif27153[Selected Figure] None
Description
本発明は、ジブロモメチルベンゼン化合物の製造方法、安息香酸化合物の製造方法、ベンズアルデヒド化合物の製造方法、及び臭化水素のリサイクル方法に関する。 The present invention relates to a method for producing a dibromomethylbenzene compound, a method for producing a benzoic acid compound, a method for producing a benzaldehyde compound, and a method for recycling hydrogen bromide.
安息香酸化合物及びベンズアルデヒド化合物は、医薬、農薬及び材料科学の分野で広く用いられている。これらの化合物は、一般的にはトルエン化合物を酸化することにより合成される。例えば、トルエン化合物を酸化して安息香酸化合物を得る反応では、マンガン又はクロムを含む重金属酸化剤を使用する方法（例えば、特許文献１）が古くから知られている。しかし、重金属酸化物は有害で環境負荷が大きく、大量合成には向いていない。したがって、工業的な生産においては、重金属酸化剤の使用に代えて、トルエン化合物等を高温高圧下で空気酸化する方法（例えば、特許文献２、及び非特許文献１、２）や、塩素化して加水分解する方法（例えば、特許文献３、４、及び非特許文献３）が提案されている。しかし、このような方法も、試薬の毒性、環境負荷、及びプロセスの危険性等の問題が指摘されている。
上記の問題に対処すべく、上記の酸化反応をより安全に、また環境負荷をより抑えて行う方法が提案されている。例えば、臭化水素酸（ＨＢｒ）、臭化カリウム（ＫＢｒ）、及び四臭化炭素（ＣＢｒ４）等の臭素化合物と、過酸化水素、オキソン、及び酸素等を用いて、光照射下で、トルエン化合物やキシレン化合物の酸化反応を生じさせることが提案されている（例えば、非特許文献４～６）。
Benzoic acid compounds and benzaldehyde compounds are widely used in the fields of medicine, agricultural chemicals, and material science. These compounds are generally synthesized by oxidizing a toluene compound. For example, in the reaction of oxidizing a toluene compound to obtain a benzoic acid compound, a method using a heavy metal oxidizing agent containing manganese or chromium (e.g., Patent Document 1) has long been known. However, heavy metal oxides are harmful and have a large environmental load, and are not suitable for mass synthesis. Therefore, in industrial production, instead of using heavy metal oxidizing agents, a method of air-oxidizing a toluene compound or the like under high temperature and pressure (e.g., Patent Document 2, and Non-Patent Documents 1 and 2) and a method of chlorinating and hydrolyzing (e.g., Patent Documents 3, 4, and Non-Patent Document 3) have been proposed. However, problems such as the toxicity of the reagent, the environmental load, and the danger of the process have also been pointed out in such methods.
To address the above problems, methods have been proposed for carrying out the above oxidation reaction more safely and with less environmental impact, such as the use of bromine compounds such as hydrobromic acid (HBr), potassium bromide (KBr), and carbon tetrabromide (CBr 4 ), hydrogen peroxide, oxone, oxygen, and the like under light irradiation to cause the oxidation reaction of toluene compounds and xylene compounds (e.g., Non-Patent Documents 4 to 6).
昨今、持続可能な開発目標（ＳＤＧｓ）への地球規模での取り組みが加速しており、その一環として、化学合成反応による化合物の工業的な生産においても、環境負荷の低減、安全性の向上への一層の取り組みが求められている。例えば、安全性の高い原料ないし試薬を使用すること、原料ないし試薬の無駄を抑えてより高い収率で目的化合物を得ること、有害な副生物を生じないこと、副生物を有効利用（例えばリサイクル）できること、低エネルギーコスト化を実現すること等は、サステイナブル社会の構築に貢献する技術要素として社会的にも価値が高まっている。 Recently, efforts to achieve the Sustainable Development Goals (SDGs) have been accelerating on a global scale, and as part of this, there is a demand for greater efforts to reduce the environmental burden and improve safety even in the industrial production of compounds through chemical synthesis reactions. For example, the use of safe raw materials or reagents, the production of target compounds in higher yields with reduced waste of raw materials or reagents, the absence of harmful by-products, the effective use of by-products (e.g. recycling), and the realization of low energy costs are all technological elements that contribute to the creation of a sustainable society and are therefore of increasing social value.
このような状況下、本発明者は、臭素（Ｂｒ２）と水（Ｈ２Ｏ）と空気（酸素、Ｏ２）の存在下で、トルエン化合物に光照射すると、ＬＥＤ等の低エネルギー光源を用いた場合でも、無触媒で、安息香酸化合物が高効率に得られることを見出している。この光反応では、トルエン化合物が臭素化されてジブロモメチルベンゼン化合物を生じ、このジブロモメチルベンゼン化合物を経由して安息香酸化合物が生成する。トルエン化合物が電子求引性基を有する場合には、トルエン化合物の臭素化効率が低下するというのが一般的な知見であるが、上記光反応を採用すると、電子求引性基を有するトルエン化合物であっても、目的の安息香酸化合物を高効率に得ることができる。 Under such circumstances, the present inventor has found that when a toluene compound is irradiated with light in the presence of bromine (Br 2 ), water (H 2 O), and air (oxygen, O 2 ), a benzoic acid compound can be obtained with high efficiency without a catalyst, even when a low-energy light source such as an LED is used. In this photoreaction, the toluene compound is brominated to produce a dibromomethylbenzene compound, and a benzoic acid compound is produced via this dibromomethylbenzene compound. It is a common knowledge that when a toluene compound has an electron-withdrawing group, the bromination efficiency of the toluene compound decreases, but when the above photoreaction is adopted, the target benzoic acid compound can be obtained with high efficiency even when the toluene compound has an electron-withdrawing group.
また、本発明者は、上記光反応において、臭素に代えて、臭化水素酸と次亜塩素酸ナトリウムを用いて反応系内で臭素を発生させる方法でも、安息香酸化合物が高効率に得られることを見出している。この光反応は、副生物として臭化水素を含む水溶液を生じるため、この水溶液を回収すれば、当該光反応の臭素源として再利用できる。
他方、この光反応では副生物として、臭化水素に加えて食塩（塩化ナトリウム、ＮａＣｌ）も生成する。塩化ナトリウムそれ自体は有害ではないものの、回収した臭化水素を含む水溶液の再利用を繰り返すと、回収溶液には塩化ナトリウムが蓄積してしまう問題がある。
臭化水素酸を臭素源として用いる上記光反応スキームを以下に示す。Ｘは水素原子又は置換基を示す。
The present inventors have also found that a benzoic acid compound can be obtained with high efficiency by using hydrobromic acid and sodium hypochlorite instead of bromine in the above photoreaction to generate bromine in the reaction system. This photoreaction generates an aqueous solution containing hydrogen bromide as a by-product, and if this aqueous solution is recovered, it can be reused as a bromine source for the photoreaction.
On the other hand, this photoreaction also produces salt (sodium chloride, NaCl) as a by-product in addition to hydrogen bromide. Although sodium chloride itself is not harmful, repeated reuse of the recovered aqueous solution containing hydrogen bromide causes the problem of sodium chloride accumulating in the recovered solution.
The photoreaction scheme using hydrobromic acid as the bromine source is shown below: X represents a hydrogen atom or a substituent.
本発明は、臭素と水と酸素の存在下で、置換基として電子求引性基を有するトルエン化合物に光照射して、光反応により、電子求引性基を有する安息香酸化合物を得るに当たり、前記臭素源として臭化水素酸を、次亜塩素酸ナトリウムとともに供給し、この臭化水素酸と次亜塩素酸ナトリウムとの反応により生じる臭素を、前記光反応における前記臭素として用いる、電子求引性基を有する安息香酸化合物の製造方法を基礎とする技術である（当該「光反応」を「一体的光反応方法」とも称する）。そのなかで本発明は、当該製造方法で生じる、副生物の臭化水素を含む水溶液中への塩化ナトリウムの混入を回避する技術に関する。 The present invention is based on a method for producing a benzoic acid compound having an electron-withdrawing group, in which a toluene compound having an electron-withdrawing group as a substituent is irradiated with light in the presence of bromine, water, and oxygen to produce a benzoic acid compound having an electron-withdrawing group by photoreaction, in which hydrobromic acid is supplied as the bromine source together with sodium hypochlorite, and the bromine produced by the reaction between this hydrobromic acid and sodium hypochlorite is used as the bromine in the photoreaction (this "photoreaction" is also referred to as an "integrated photoreaction method"). Among these, the present invention relates to a technology for avoiding the contamination of sodium chloride in an aqueous solution containing hydrogen bromide as a by-product produced by the production method.
本発明者らは鋭意検討を重ねた結果、上記の一体的光反応方法は、電子求引性基を有するトルエン化合物からジブロモメチルベンゼン化合物を生じる第１段階反応と、このジブロモメチルベンゼン化合物から安息香酸化合物を生じる第２段階反応とに整理できること、上記の一体的光反応方法を、酸素を遮断した条件で行うと、第１段階反応で反応を止めることができ（第１段階反応と第２段階反応とを、工程として明確に分離でき）、しかも、トルエン化合物が電子求引性基を有するにもかかわらず、第１段階反応の生成物である目的のジブロモメチルベンゼン化合物が高い収率で、高効率に得られることがわかってきた。これらの知見を踏まえ、酸素遮断下の第１段階反応後に、塩化ナトリウムを除去して上記ジブロモメチルベンゼン化合物を第２段階反応に供すれば、第２段階反応後に塩化ナトリウムを含まない臭化水素酸を回収でき、これを第１段階反応の臭素源として、繰り返し再利用できるとの着想に至った。
本発明は、これらの知見に基づきさらに検討を重ねて完成されるに至ったものである。
As a result of intensive research, the present inventors have found that the above-mentioned integrated photoreaction method can be divided into a first-stage reaction in which a dibromomethylbenzene compound is produced from a toluene compound having an electron-withdrawing group, and a second-stage reaction in which a benzoic acid compound is produced from the dibromomethylbenzene compound, and that when the above-mentioned integrated photoreaction method is carried out under conditions in which oxygen is blocked, the reaction can be stopped at the first-stage reaction (the first-stage reaction and the second-stage reaction can be clearly separated as steps), and further, the target dibromomethylbenzene compound, which is the product of the first-stage reaction, can be obtained in high yield and with high efficiency, even though the toluene compound has an electron-withdrawing group. Based on these findings, the inventors have come up with the idea that if sodium chloride is removed after the first-stage reaction under oxygen blocking and the above-mentioned dibromomethylbenzene compound is subjected to the second-stage reaction, hydrobromic acid not containing sodium chloride can be recovered after the second-stage reaction, and this can be repeatedly reused as a bromine source for the first-stage reaction.
The present invention has been completed through further investigation based on these findings.
本発明によれば、次のジブロモメチルベンゼン化合物の製造方法、安息香酸化合物の製造方法、ベンズアルデヒド化合物の製造方法、及び臭化水素のリサイクル方法が提供される。
［１］
臭化水素と次亜塩素酸ナトリウムの存在下、かつ酸素の非存在下で、下記式（１）で表されるトルエン化合物に光照射して光反応により下記式（２）で表されるジブロモメチルベンゼン化合物を得ることを含む、ジブロモメチルベンゼン化合物の製造方法。
［２］
前記Ｘが、ニトロ基、シアノ基、ハロゲノメチル基、又はハロゲン原子である、［１］に記載のジブロモメチルベンゼン化合物の製造方法。
［３］
前記式（１）で表される化合物が、シアノトルエン、ニトロトルエン、フルオロトルエン、クロロトルエン、ブロモトルエン、ジフルオロメチルトルエン、又はトリフルオロメチルトルエンである、［１］に記載のジブロモメチルベンゼン化合物の製造方法。
［４］
水と酸素の存在下、下記式（２）で表される化合物に光照射して光反応により下記式（３）で表される安息香酸化合物を生成し、副生した臭化水素を、［１］～［３］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法における前記臭化水素として用いる、［１］～［３］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法。
［５］
下記式（２）で表される化合物を加水分解して下記式（４）で表されるベンズアルデヒド化合物を生成し、副生した臭化水素を、［１］～［３］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法における前記臭化水素として用いる、［１］～［３］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法。
［６］
水と酸素の存在下、［１］～［５］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物に光照射して光反応により下記式（３）で表される安息香酸化合物を得ることを含む、安息香酸化合物の製造方法。
［１］～［５］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物を加水分解して下記式（４）で表されるベンズアルデヒド化合物を得ることを含む、ベンズアルデヒド化合物の製造方法。
水と酸素の存在下、［１］～［５］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物に光照射して光反応により下記式（３）で表される安息香酸化合物を得て、副生した臭化水素を、［１］～［５］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法における前記臭化水素として用いることを含む、臭化水素のリサイクル方法。
［１］～［５］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物を加水分解して下記式（４）で表されるベンズアルデヒド化合物を得て、副生した臭化水素を、［１］～［５］のいずれか１つに記載のジブロモメチルベンゼン化合物の製造方法における前記臭化水素として用いることを含む、臭化水素のリサイクル方法。
[1]
A method for producing a dibromomethylbenzene compound, comprising irradiating a toluene compound represented by the following formula (1) with light in the presence of hydrogen bromide and sodium hypochlorite, and in the absence of oxygen, to obtain a dibromomethylbenzene compound represented by the following formula (2) by a photoreaction:
[2]
The method for producing a dibromomethylbenzene compound according to [1], wherein X is a nitro group, a cyano group, a halogenomethyl group, or a halogen atom.
[3]
The method for producing a dibromomethylbenzene compound according to [1], wherein the compound represented by formula (1) is cyanotoluene, nitrotoluene, fluorotoluene, chlorotoluene, bromotoluene, difluoromethyltoluene, or trifluoromethyltoluene.
[4]
The method for producing a dibromomethylbenzene compound according to any one of [1] to [3], comprising irradiating a compound represented by the following formula (2) with light in the presence of water and oxygen to produce a benzoic acid compound represented by the following formula (3) through a photoreaction, and using the by-produced hydrogen bromide as the hydrogen bromide in the method for producing a dibromomethylbenzene compound according to any one of [1] to [3].
[5]
The method for producing a dibromomethylbenzene compound according to any one of [1] to [3], comprising hydrolyzing a compound represented by the following formula (2) to produce a benzaldehyde compound represented by the following formula (4), and using the by-produced hydrogen bromide as the hydrogen bromide in the method for producing a dibromomethylbenzene compound according to any one of [1] to [3].
[6]
A method for producing a benzoic acid compound, comprising irradiating a dibromomethylbenzene compound obtained by the method for producing a dibromomethylbenzene compound according to any one of [1] to [5] with light in the presence of water and oxygen to obtain a benzoic acid compound represented by the following formula (3) by a photoreaction.
A method for producing a benzaldehyde compound, comprising hydrolyzing a dibromomethylbenzene compound obtained by the method for producing a dibromomethylbenzene compound according to any one of [1] to [5] to obtain a benzaldehyde compound represented by the following formula (4):
A method for recycling hydrogen bromide, comprising: irradiating a dibromomethylbenzene compound obtained by the method for producing a dibromomethylbenzene compound according to any one of [1] to [5] with light in the presence of water and oxygen to obtain a benzoic acid compound represented by the following formula (3) by a photoreaction; and using the by-produced hydrogen bromide as the hydrogen bromide in the method for producing a dibromomethylbenzene compound according to any one of [1] to [5].
A method for recycling hydrogen bromide, comprising: hydrolyzing a dibromomethylbenzene compound obtained by the method for producing a dibromomethylbenzene compound according to any one of [1] to [5] to obtain a benzaldehyde compound represented by the following formula (4); and using the by-produced hydrogen bromide as the hydrogen bromide in the method for producing a dibromomethylbenzene compound according to any one of [1] to [5].
本発明において、「～」を用いて表される数値範囲は、その数値を下限値及び上限値として含む範囲を意味する。例えば、「ａ～ｂ」と記載されている場合、その数値範囲は、「ａ以上ｂ以下」である。 In the present invention, a numerical range expressed using "~" means a range that includes the numerical value as the lower limit and upper limit. For example, when it is written as "a~b", the numerical range is "a or more and b or less".
本発明のジブロモメチルベンゼン化合物の製造方法によれば、電子求引性基を有する安息香酸化合物や電子求引性基を有するベンズアルデヒド化合物の合成中間体として有用な電子求引性基を有するジブロモメチルベンゼン化合物を、電子求引性基を有するトルエン化合物を出発原料として、少ないエネルギー量で、安全に、簡単に、高効率に得ることができる。また、副生物は実質的に塩化ナトリウムのみであり、この塩化ナトリウムは排水によって簡単に除去できる。
本発明の安息香酸化合物の製造方法及びベンズアルデヒドの製造方法によれば、電子求引性基を有するジブロモメチルベンゼン化合物を出発原料として、目的の電子求引性基を有する安息香酸化合物や電子求引性基を有するベンズアルデヒド化合物を、少ないエネルギー量で、安全に、簡単に、高効率に得ることができる。また、副生物を実質的に臭化水素のみとすることが可能であり、この臭化水素は本発明のジブロモメチルベンゼン化合物の製造方法の臭素源として無駄なく再利用することができる。
According to the method for producing a dibromomethylbenzene compound of the present invention, a dibromomethylbenzene compound having an electron-withdrawing group, which is useful as a synthetic intermediate for a benzoic acid compound having an electron-withdrawing group or a benzaldehyde compound having an electron-withdrawing group, can be obtained safely, simply, and highly efficiently with a small amount of energy from a toluene compound having an electron-withdrawing group as a starting material. In addition, the by-product is essentially only sodium chloride, which can be easily removed by wastewater.
According to the method for producing a benzoic acid compound and the method for producing a benzaldehyde of the present invention, a dibromomethylbenzene compound having an electron-withdrawing group can be used as a starting material to safely, simply, and efficiently produce a target benzoic acid compound having an electron-withdrawing group or a benzaldehyde compound having an electron-withdrawing group with a small amount of energy. In addition, the by-product can be substantially only hydrogen bromide, and this hydrogen bromide can be reused without waste as a bromine source in the method for producing a dibromomethylbenzene compound of the present invention.
本発明の好ましい実施形態を以下に説明する。
以降の説明において、単に「トルエン化合物」、「ジブロモメチルベンゼン化合物」、「安息香酸化合物」又は「ベンズアルデヒド化合物」という場合、特段の断りの無い限り、それぞれ「電子求引性基を有するトルエン化合物」、「電子求引性基を有するジブロモメチルベンゼン化合物」、「電子求引性基を有する安息香酸化合物」又は「電子求引性基を有するベンズアルデヒド化合物」を意味する。
Preferred embodiments of the present invention are described below.
In the following description, unless otherwise specified, when the term "toluene compound", "dibromomethylbenzene compound", "benzoic acid compound", or "benzaldehyde compound" is used, it means "toluene compound having an electron-withdrawing group", "dibromomethylbenzene compound having an electron-withdrawing group", "benzoic acid compound having an electron-withdrawing group", or "benzaldehyde compound having an electron-withdrawing group", respectively.
［ジブロモメチルベンゼン化合物の製造方法］
本発明のジブロモメチルベンゼン化合物の製造方法では、臭化水素と次亜塩素酸ナトリウムの存在下、かつ酸素の非存在下で、下記式（１）で表されるトルエン化合物に光照射して光反応により下記式（２）で表されるジブロモメチルベンゼン化合物を得ることを含む。
[Method of producing dibromomethylbenzene compound]
The method for producing a dibromomethylbenzene compound of the present invention includes irradiating a toluene compound represented by the following formula (1) with light in the presence of hydrogen bromide and sodium hypochlorite, and in the absence of oxygen, to obtain a dibromomethylbenzene compound represented by the following formula (2) by photoreaction.
上記式中、Ｘは電子求引性基を示す。この電子求引性基としては、例えば、ニトロ基、
シアノ基、ハロゲノメチル基（好ましくはジハロゲノメチル基又はトリハロゲノメチル基）、ハロゲン原子、アシル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１０、さらに好ましくは炭素数２～５）、アルコシキカルボニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１０、さらに好ましくは炭素数２～５）、アリールオキシカルボニル基（好ましくは炭素数７～２０、より好ましくは炭素数７～１０）、カルバモイル基、アルキルスルホニル基（好ましくは炭素数１～２０、より好ましくは炭素数１～１０、さらに好ましくは炭素数２～５）、アリールスルホニル基（好ましくは炭素数６～２０、より好ましくは炭素数６～１０）、及びスルファモイル基が挙げられるが、これらの基に限定されない。上記電子求引性基として採り得るハロゲノメチル基におけるハロゲン原子、及び上記電子求引性基として採り得るハロゲン原子としては、フッ素原子、塩素原子、臭素原子又はヨウ素原子が好ましく、フッ素原子、塩素原子又は臭素原子がより好ましい。
上記電子求引性基は、なかでも、ニトロ基、シアノ基、ハロゲノメチル基、又はハロゲン原子が好ましく、ニトロ基、シアノ基、フルオロメチル基（好ましくはジフルオロメチル基又はトリフルオロメチル基）、又はフッ素原子がより好ましい。
上記式（１）において、上記Ｘは、メチル基が結合する環構成炭素原子に対して、オルト位、メタ位及びパラ位のいずれに位置してもよく、立体的に嵩高い置換基を有する場合にはメタ位又はパラ位に位置することが好ましい。
In the above formula, X represents an electron-withdrawing group. Examples of the electron-withdrawing group include a nitro group,
Examples of the halogenomethyl group include, but are not limited to, a cyano group, a halogenomethyl group (preferably a dihalogenomethyl group or a trihalogenomethyl group), a halogen atom, an acyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 2 to 5 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 2 to 5 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 10 carbon atoms), a carbamoyl group, an alkylsulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, and even more preferably having 2 to 5 carbon atoms), an arylsulfonyl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 10 carbon atoms), and a sulfamoyl group. The halogen atom in the halogenomethyl group that can be taken as the electron-withdrawing group and the halogen atom that can be taken as the electron-withdrawing group are preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom.
Of these, the electron-withdrawing group is preferably a nitro group, a cyano group, a halogenomethyl group, or a halogen atom, and more preferably a nitro group, a cyano group, a fluoromethyl group (preferably a difluoromethyl group or a trifluoromethyl group), or a fluorine atom.
In the above formula (1), the above X may be located at any of the ortho, meta, and para positions relative to the ring-constituting carbon atom to which the methyl group is bonded, and when the X has a sterically bulky substituent, it is preferably located at the meta or para position.
上記式（１）で表される化合物は、上記式（１）の規定を満たせば特に制限されない。上記式（１）で表される化合物として、例えば、シアノトルエン、ニトロトルエン、フルオロトルエン、クロロトルエン、ブロモトルエン、又はトリフルオロメチルトルエンが挙げられる。これらの化合物が有する２つ置換基の位置関係は特に制限されず、互いにオルト位でもよく、メタ位でもよく、パラ位でもよい。収率の観点からは、互いにメタ位又はパラ位の位置関係であることが好ましい。
上記式（１）で表される化合物は、好ましくは、３－シアノトルエン、４－シアノトルエン、３－ニトロトルエン、４－ニトロトルエン、２－フルオロトルエン、３－フルオロトルエン、４－フルオロトルエン、２－クロロトルエン、３－クロロトルエン、４－クロロトルエン、２－ブロモトルエン、３－ブロモトルエン、４－ブロモトルエン、３－トリフルオロメチルトルエン、又は４－トリフルオロメチルトルエンであり、３－シアノトルエン又は４－シアノトルエンがより好ましい。
The compound represented by the above formula (1) is not particularly limited as long as it satisfies the requirements of the above formula (1). Examples of the compound represented by the above formula (1) include cyanotoluene, nitrotoluene, fluorotoluene, chlorotoluene, bromotoluene, and trifluoromethyltoluene. The positional relationship of the two substituents of these compounds is not particularly limited, and may be ortho-position, meta-position, or para-position. From the viewpoint of yield, it is preferable that the positional relationship is meta-position or para-position.
The compound represented by the above formula (1) is preferably 3-cyanotoluene, 4-cyanotoluene, 3-nitrotoluene, 4-nitrotoluene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2-bromotoluene, 3-bromotoluene, 4-bromotoluene, 3-trifluoromethyltoluene, or 4-trifluoromethyltoluene, and 3-cyanotoluene or 4-cyanotoluene is more preferable.
本発明のジブロモメチルベンゼン化合物の製造方法は、上記の光反応を酸素の非存在下で行う。酸素の非存在下とは、例えば不活性ガス雰囲気中である。不活性ガスとしては、窒素原子や希ガスが挙げられ、窒素ガス雰囲気中又はアルゴン雰囲気中で光反応を行うことが好ましい。窒素ガス雰囲気を採用した場合の反応式を以下に示す。下記反応式における副生物である塩化ナトリウムは、水相中に分離して廃棄することができる。 In the method for producing a dibromomethylbenzene compound of the present invention, the above-mentioned photoreaction is carried out in the absence of oxygen. In the absence of oxygen, for example, in an inert gas atmosphere. Examples of inert gases include nitrogen atoms and rare gases, and the photoreaction is preferably carried out in a nitrogen gas atmosphere or an argon atmosphere. The reaction formula when a nitrogen gas atmosphere is used is shown below. Sodium chloride, which is a by-product in the following reaction formula, can be separated into the aqueous phase and discarded.
上記反応は無溶媒またはハロゲン化されにくい溶媒中で行うことができる。溶媒としては、ベンゾトリフルオリド（トリフルオロメチルベンゼン）、又はパラクロロベンゾトリフルオリド等が好ましい。四塩化炭素はハロゲン化に昔から汎用されてきたが、環境への影響とその毒性のために避けられる傾向にある。溶媒量はトルエン化合物が溶解すればよい。 The above reaction can be carried out without a solvent or in a solvent that is difficult to halogenate. Preferred solvents include benzotrifluoride (trifluoromethylbenzene) and parachlorobenzotrifluoride. Carbon tetrachloride has long been widely used for halogenation, but is being avoided due to its environmental impact and toxicity. The amount of solvent should be sufficient to dissolve the toluene compound.
上記反応では、下記の通り、２当量の臭化水素酸（ＨＢｒ）と１当量の次亜塩素酸ナトリウム（ＮａＯＣｌ）との反応により１当量の臭素（Ｂｒ２）が生じる。
２ＨＢｒ＋ＮａＯＣｌ→Ｂｒ２＋ＮａＣｌ＋Ｈ２Ｏ
In the above reaction, two equivalents of hydrobromic acid (HBr) react with one equivalent of sodium hypochlorite (NaOCl) to produce one equivalent of bromine (Br 2 ), as shown below.
2HBr+NaOCl-> Br2 +NaCl+ H2O
次いで、臭素は光エネルギーによるラジカル開裂により臭素ラジカル（２Ｂｒ・）となり、トルエン化合物のメチル基を臭素置換することで、ブロモメチル体を生成する。この際、１当量の臭化水素（ＨＢｒ）が副生するが、もう０．５当量の次亜塩素酸ナトリウム（ＮａＯＣｌ）により酸化されて０．５当量の臭素（Ｂｒ２）に再生され、この繰り返しにより上記ブロモメチル体の臭素化反応に使用されて目的のジブロモメチル体を生じる。 Next, bromine is cleaved by light energy to become a bromine radical (2Br.), which substitutes the methyl group of the toluene compound with bromine to produce a bromomethyl compound. During this process, one equivalent of hydrogen bromide (HBr) is produced as a by-product, but this is oxidized with another 0.5 equivalent of sodium hypochlorite (NaOCl) to regenerate 0.5 equivalent of bromine (Br 2 ), which is then used in the bromination reaction of the bromomethyl compound to produce the desired dibromomethyl compound.
本発明のジブロモメチルベンゼン化合物の製造方法では、臭化水素酸の酸化剤として次亜塩素酸ナトリウムを用いる。これにより、副生物を無害な塩化ナトリウムのみとすることができる。また、光反応後に水相を分離するだけで、塩化ナトリウムを簡単に除去することができる。したがって、本発明のジブロモメチルベンゼン化合物の製造方法は、好ましくは、上記光反応後の反応液から塩化ナトリウムを除去することを含む。例えば、上記光反応後の反応液を有機相と水相に分離して、塩化ナトリウムを水相中に分離して除去することが好ましい。例えば、上記光反応後の反応液に水性成分（例えば重曹水）と有機性成分（例えば酢酸エチル）を加えてからの抽出操作（分液操作）によって塩化ナトリウムが水相、ジブロモメチルベンゼン化合物が有機相に溶解し、この水相と有機相とを分離することで塩化ナトリウムフリーのジブロモメチルベンゼン化合物が得られる。 In the method for producing a dibromomethylbenzene compound of the present invention, sodium hypochlorite is used as an oxidizing agent for hydrobromic acid. This allows the by-product to be only harmless sodium chloride. In addition, sodium chloride can be easily removed by simply separating the aqueous phase after the photoreaction. Therefore, the method for producing a dibromomethylbenzene compound of the present invention preferably includes removing sodium chloride from the reaction solution after the photoreaction. For example, it is preferable to separate the reaction solution after the photoreaction into an organic phase and an aqueous phase, and separate and remove sodium chloride in the aqueous phase. For example, an aqueous component (e.g., sodium bicarbonate water) and an organic component (e.g., ethyl acetate) are added to the reaction solution after the photoreaction, and then an extraction operation (liquid separation operation) is performed to dissolve sodium chloride in the aqueous phase and the dibromomethylbenzene compound in the organic phase, and the aqueous phase and the organic phase are separated to obtain a sodium chloride-free dibromomethylbenzene compound.
上記光反応に用いる次亜塩素酸ナトリウムは、市販の次亜塩素酸ナトリウム水溶液を用いることができる。また、次亜塩素酸ナトリウム結晶を固体のまま、又は任意の濃度の水溶液として用いることができる。次亜塩素酸ナトリウム結晶として、ＮａＯＣｌ・５水和物結晶（商品名：ニッケイジアソー（登録商標）５水塩、日本軽金属社製）が挙げられる。また、次亜塩素酸ナトリウムの使用量はトルエン化合物のメチル基（１当量）に対して１．０～１０．０当量とすることが好ましく、１．５～８．０当量とすることがより好ましく、２．０～６．０当量とすることがさらに好ましく、２．０～５．０当量であることがさらに好ましく、２．０～４．０当量であることがさらに好ましい。さらに、臭化水素の使用量はトルエン化合物のメチル基に対して０．５～５．０当量であることが好ましく、０．８～４．０当量であることがより好ましく、１．０～３．０当量であることがさらに好ましく、１．５～３．０当量であることがさらに好ましく、２．０～２．６当量とすることがさらに好ましい。 The sodium hypochlorite used in the photoreaction may be a commercially available aqueous solution of sodium hypochlorite. Sodium hypochlorite crystals may be used as a solid or as an aqueous solution of any concentration. Examples of sodium hypochlorite crystals include NaOCl. pentahydrate crystals (trade name: Nikkei Diazo (registered trademark) pentahydrate, manufactured by Nippon Light Metals Co., Ltd.). The amount of sodium hypochlorite used is preferably 1.0 to 10.0 equivalents relative to the methyl group (1 equivalent) of the toluene compound, more preferably 1.5 to 8.0 equivalents, even more preferably 2.0 to 6.0 equivalents, even more preferably 2.0 to 5.0 equivalents, and even more preferably 2.0 to 4.0 equivalents. The amount of hydrogen bromide used is preferably 0.5 to 5.0 equivalents relative to the methyl group of the toluene compound, more preferably 0.8 to 4.0 equivalents, even more preferably 1.0 to 3.0 equivalents, even more preferably 1.5 to 3.0 equivalents, and even more preferably 2.0 to 2.6 equivalents.
トルエン化合物のメチル基に対し、使用する次亜塩素酸ナトリウムの当量は、使用する臭化水素の当量以上であることが好ましく、１０≧［次亜塩素酸ナトリウムの当量］／［臭化水素の当量］≧１が好ましく、８≧［次亜塩素酸ナトリウムの当量］／［臭化水素の当量］≧１がより好ましく、６≧［次亜塩素酸ナトリウムの当量］／［臭化水素の当量］≧１がさらに好ましく、５≧［次亜塩素酸ナトリウムの当量］／［臭化水素の当量］≧１がさらに好ましく、４≧［次亜塩素酸ナトリウムの当量］／［臭化水素の当量］≧１がさらに好ましい。
一例として、臭化水素及び次亜塩素酸ナトリウムの使用量はトルエン化合物のメチル基に対して典型的には約２当量とすることができ、また、過剰量使用してもよい。
The equivalent of sodium hypochlorite used relative to the methyl group of the toluene compound is preferably equal to or greater than the equivalent of hydrogen bromide used, and is preferably 10≧[equivalent of sodium hypochlorite]/[equivalent of hydrogen bromide]≧1, more preferably 8≧[equivalent of sodium hypochlorite]/[equivalent of hydrogen bromide]≧1, even more preferably 6≧[equivalent of sodium hypochlorite]/[equivalent of hydrogen bromide]≧1, even more preferably 5≧[equivalent of sodium hypochlorite]/[equivalent of hydrogen bromide]≧1, and even more preferably 4≧[equivalent of sodium hypochlorite]/[equivalent of hydrogen bromide]≧1.
As an example, the amount of hydrogen bromide and sodium hypochlorite used may typically be about 2 equivalents relative to the methyl group of the toluene compound, and may also be used in excess.
上記反応に用いる臭化水素酸において、臭化水素の濃度は特に制限されず、例えば、市販の４８％ＨＢｒ水溶液を用いることができる。 There are no particular limitations on the concentration of hydrogen bromide in the hydrobromic acid used in the above reaction, and for example, a commercially available 48% HBr aqueous solution can be used.
また、水と酸素の存在下、上記式（２）で表される化合物に光照射して光反応により下記式（３）で表される安息香酸化合物を生成したとき、副生した臭化水素（臭化水素酸）を回収し、上記光反応における臭化水素源として用いることも好ましい。下記式（３）中のＸは上記式（１）中のＸと同義である。こうすることで、目的の安息香酸化合物を製造しながら、その副生物を、安息香酸化合物の合成中間体であるジブロモメチルベンゼン化合物の製造に用いることができ、原料ないし試薬のリサイクル系を作り出すことができる。 In addition, when the compound represented by formula (2) above is irradiated with light in the presence of water and oxygen to produce a benzoic acid compound represented by formula (3) below through a photoreaction, it is also preferable to recover the by-product hydrogen bromide (hydrobromic acid) and use it as a hydrogen bromide source in the photoreaction. X in formula (3) below has the same meaning as X in formula (1) above. In this way, while producing the target benzoic acid compound, the by-product can be used to produce a dibromomethylbenzene compound, which is a synthetic intermediate for the benzoic acid compound, creating a recycling system for raw materials and reagents.
なお、この安息香酸化合物を生成する反応で用いる上記式（２）で表される化合物は、本発明のジブロモメチルベンゼン化合物の製造方法で得られるものに限定されない。この安息香酸化合物の生成反応の詳細は後述する。 The compound represented by the above formula (2) used in the reaction to produce this benzoic acid compound is not limited to the compound obtained by the method for producing a dibromomethylbenzene compound of the present invention. The details of the reaction to produce this benzoic acid compound will be described later.
また、上記式（２）で表される化合物を加水分解して下記式（４）で表されるベンズアルデヒド化合物を生成したとき、副生した臭化水素（臭化水素酸）を回収し、上記光反応における臭化水素源として用いることも好ましい。下記式（４）中のＸは上記式（１）中のＸと同義である。こうすることで、目的のベンズアルデヒド化合物を製造しながら、その副生物を、ベンズアルデヒド化合物の合成中間体であるジブロモメチルベンゼン化合物の製造に用いることができ、原料ないし試薬のリサイクル系を作り出すことができる。 When the compound represented by formula (2) above is hydrolyzed to produce the benzaldehyde compound represented by formula (4) below, it is also preferable to recover the by-product hydrogen bromide (hydrobromic acid) and use it as a hydrogen bromide source in the photoreaction. X in formula (4) below has the same meaning as X in formula (1) above. In this way, while producing the target benzaldehyde compound, the by-product can be used to produce a dibromomethylbenzene compound, which is a synthetic intermediate of the benzaldehyde compound, creating a recycling system for raw materials and reagents.
なお、このベンズアルデヒド化合物を生成する反応で用いる上記式（２）で表される化合物は、本発明のジブロモメチルベンゼン化合物の製造方法で得られるものに限定されない。このベンズアルデヒド化合物の生成反応の詳細は後述する。 The compound represented by the above formula (2) used in the reaction to produce this benzaldehyde compound is not limited to the compound obtained by the method for producing a dibromomethylbenzene compound of the present invention. The details of the reaction to produce this benzaldehyde compound will be described later.
上記光反応における光照射の波長は、例えば、波長３６０～５００ｎｍとすることが好ましい。光源としては、水銀灯、紫外光（３６０ｎｍ以上４００ｎｍ未満）、可視光（４００ｎｍ以上５００ｎｍ未満）、蛍光灯、又はブラックライトなどを用いることができる。光源として、単一波長のＬＥＤ（発光ダイオード：Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）光源（例えば、波長３６５～４５４ｎｍ）を用いると、無駄な熱が発生せず、エネルギーロスを抑えることができる。 The wavelength of the light irradiation in the above photoreaction is preferably, for example, 360 to 500 nm. As the light source, a mercury lamp, ultraviolet light (360 nm or more and less than 400 nm), visible light (400 nm or more and less than 500 nm), fluorescent lamp, black light, or the like can be used. If a single-wavelength LED (Light Emitting Diode) light source (for example, wavelength 365 to 454 nm) is used as the light source, no unnecessary heat is generated and energy loss can be suppressed.
上記光反応の温度は５～１００℃が好ましい。低エネルギーコスト、作業安全性の観点からは１０～７０℃で行うことが好ましく、１５～５０℃で行うことがより好ましく、室温（２５℃程度）で行うことがさらに好ましい。 The temperature of the photoreaction is preferably 5 to 100°C. From the viewpoint of low energy costs and work safety, it is preferable to carry out the reaction at 10 to 70°C, more preferably at 15 to 50°C, and even more preferably at room temperature (about 25°C).
［安息香酸化合物の製造方法］
本発明の安息香酸化合物の製造方法は、水と酸素の存在下、上記のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物（上記式（２）で表されるジブロモメチルベンゼン化合物）に光照射して光反応により上記式（３）で表される安息香酸化合物を得ることを含む。
[Method for producing benzoic acid compound]
The method for producing a benzoic acid compound of the present invention includes irradiating a dibromomethylbenzene compound (the dibromomethylbenzene compound represented by the above formula (2)) obtained by the above method for producing a dibromomethylbenzene compound with light in the presence of water and oxygen to obtain a benzoic acid compound represented by the above formula (3) by a photoreaction.
本発明の安息香酸化合物の製造方法では、本発明のジブロモメチルベンゼン化合物の製造方法を経由するため、ジブロモメチルベンゼン化合物を得る光反応で生じる副生物である塩化ナトリウムは簡単に除去できる。したがって、塩化ナトリウムフリーのジブロメチルモベンゼン化合物から安息香酸化合物を得ることが可能となる。また、ジブロモメチルベンゼン化合物から安息香酸化合物を得る光反応で生じる副生物の臭化水素は、本発明のジブロモメチルベンゼン化合物の製造方法の原料としてリサイクルすることができ、原料ないし試薬の無駄を削減することが可能になる。これらの利点を含めて、本発明の安息香酸化合物の製造方法の反応スキームの一例を示すと次の通りである。 The method for producing a benzoic acid compound of the present invention uses the method for producing a dibromomethylbenzene compound of the present invention, so sodium chloride, a by-product produced in the photoreaction to obtain a dibromomethylbenzene compound, can be easily removed. Therefore, it is possible to obtain a benzoic acid compound from a sodium chloride-free dibromomethylbenzene compound. In addition, hydrogen bromide, a by-product produced in the photoreaction to obtain a benzoic acid compound from a dibromomethylbenzene compound, can be recycled as a raw material for the method for producing a dibromomethylbenzene compound of the present invention, making it possible to reduce waste of raw materials or reagents. An example of a reaction scheme for the method for producing a benzoic acid compound of the present invention, including these advantages, is shown below.
上記反応スキームの下段に示すように、水と酸素の存在下でジブロモメチルベンゼン化合物に光照射すると、空気中の活性化された酸素による反応と、加水分解とにより安息香酸化合物が得られる。この反応過程では、２当量の臭化水素（ＨＢｒ）が副生し、この臭化水素を回収すれば、副生した臭化水素を、上記反応スキームの上段に示すジブロモメチルベンゼン化合物の合成反応に無駄なく再利用（リサイクル）することができる。 As shown in the lower part of the above reaction scheme, when dibromomethylbenzene compounds are irradiated with light in the presence of water and oxygen, benzoic acid compounds are obtained through a reaction with activated oxygen in the air and hydrolysis. In this reaction process, two equivalents of hydrogen bromide (HBr) are produced as a by-product. If this hydrogen bromide is recovered, it can be reused (recycled) without waste in the synthesis reaction of dibromomethylbenzene compounds shown in the upper part of the above reaction scheme.
本発明の安息香酸化合物の製造方法では、ジブロモメチルベンゼン化合物への光照射を、上記の通り、水に加え、酸素も存在する条件下で行われる。例えば、オープンエアーで反応させることができる。また、酸素又は空気の吹込みにより反応が加速される。この光反応は、５～１００℃の温度範囲で行うことが好ましい。低エネルギーコスト、作業安全性の観点からは１０～７０℃の温度範囲で行うことが好ましく、１５～５０℃の温度範囲で行うことがより好ましく、室温（２５℃程度）で行うことがさらに好ましい。 In the method for producing a benzoic acid compound of the present invention, the dibromomethylbenzene compound is irradiated with light under conditions in which oxygen is also present in addition to water, as described above. For example, the reaction can be carried out in the open air. The reaction can also be accelerated by blowing in oxygen or air. This photoreaction is preferably carried out at a temperature range of 5 to 100°C. From the standpoint of low energy costs and work safety, it is preferable to carry out the reaction at a temperature range of 10 to 70°C, more preferably at a temperature range of 15 to 50°C, and even more preferably at room temperature (about 25°C).
上記反応の終了後、反応液をアルカリ性し、目的の安息香酸化合物を水相に溶解させることができるので、有機相を簡単に取り除くことができる。この際、その後の分液操作を円滑にするために別途有機溶媒を添加してもよい。通常は、酢酸エチルの添加が好ましい。分液したアルカリ性水溶液を塩酸などで酸性にすると、目的の安息香酸化合物の固体が析出する。これをろ過又は溶媒抽出により単離すれば、目的の安息香酸化合物を、高純度且つ高収率に得ることができる。なお、本発明の安息香酸化合物の製造方法では、必要に応じて再結晶などの精製工程が行われてもよい。 After the reaction is completed, the reaction solution is made alkaline, and the target benzoic acid compound can be dissolved in the aqueous phase, so that the organic phase can be easily removed. In this case, an organic solvent may be added separately with hydrochloric acid to facilitate the subsequent separation operation. Usually, the addition of ethyl acetate is preferred. When the separated alkaline aqueous solution is acidified with hydrochloric acid or the like, the target benzoic acid compound is precipitated as a solid. If this is isolated by filtration or solvent extraction, the target benzoic acid compound can be obtained in high purity and high yield. In addition, in the method for producing a benzoic acid compound of the present invention, a purification step such as recrystallization may be performed as necessary.
［ベンズアルデヒド化合物の製造方法］
本発明のベンズアルデヒド化合物の製造方法は、上記のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物（上記式（２）で表されるジブロモメチルベンゼン化合物）を加水分解して上記式（４）で表されるベンズアルデヒド化合物を得ることを含む。
[Method for producing benzaldehyde compound]
The method for producing a benzaldehyde compound of the present invention includes hydrolyzing a dibromomethylbenzene compound (a dibromomethylbenzene compound represented by the above formula (2)) obtained by the above method for producing a dibromomethylbenzene compound to obtain a benzaldehyde compound represented by the above formula (4).
本発明のベンズアルデヒド化合物の製造方法では、本発明のジブロモメチルベンゼン化合物の製造方法を経由するため、ジブロモメチルベンゼン化合物を得る光反応で生じる副生物である塩化ナトリウムは簡単に除去できる。したがって、塩化ナトリウムフリーのジブロモメチルベンゼン化合物からベンズアルデヒド化合物を得ることが可能となる。また、ジブロモメチルベンゼン化合物からベンズアルデヒド化合物を得る反応で生じる副生物の臭化水素は、本発明のジブロモメチルベンゼン化合物の製造方法の原料としてリサイクルすることができ、原料ないし試薬の無駄を削減することが可能になる。これらの利点を含めて、本発明のベンズアルデヒド化合物の製造方法の反応スキームの一例を示すと次の通りである。 The method for producing a benzaldehyde compound of the present invention uses the method for producing a dibromomethylbenzene compound of the present invention, so sodium chloride, a by-product produced in the photoreaction to obtain a dibromomethylbenzene compound, can be easily removed. Therefore, it is possible to obtain a benzaldehyde compound from a sodium chloride-free dibromomethylbenzene compound. In addition, hydrogen bromide, a by-product produced in the reaction to obtain a benzaldehyde compound from a dibromomethylbenzene compound, can be recycled as a raw material for the method for producing a dibromomethylbenzene compound of the present invention, making it possible to reduce waste of raw materials or reagents. An example of a reaction scheme for the method for producing a benzaldehyde compound of the present invention, including these advantages, is shown below.
上記反応スキームの下段に示すように、ジブロモメチルベンゼン化合物を加水分解することによりベンズアルデヒド化合物が得られる。この反応過程では、２当量の臭化水素（ＨＢｒ）が副生し、この臭化水素を回収すれば、副生した臭化水素を、上記反応スキームの上段に示すジブロモメチルベンゼン化合物の合成反応に無駄なく再利用（リサイクル）することができる。 As shown in the lower part of the above reaction scheme, a benzaldehyde compound is obtained by hydrolyzing a dibromomethylbenzene compound. In this reaction process, two equivalents of hydrogen bromide (HBr) are produced as a by-product. If this hydrogen bromide is recovered, it can be reused (recycled) without waste in the synthesis reaction of the dibromomethylbenzene compound shown in the upper part of the above reaction scheme.
本発明のベンズアルデヒド化合物の製造方法では、ジブロモメチルベンゼン化合物の加水分解反応は、例えば９０～１１０℃とすることができる。なお、この反応温度は圧力に応じて適宜に調整することができる。 In the method for producing a benzaldehyde compound of the present invention, the hydrolysis reaction of the dibromomethylbenzene compound can be carried out at, for example, 90 to 110°C. This reaction temperature can be adjusted appropriately depending on the pressure.
［臭化水素のリサイクル方法］
上述した実施形態に関し、本発明は、一実施形態において、次の臭化水素のリサイクル方法を提供するものである。
[Method of recycling hydrogen bromide]
In relation to the above-mentioned embodiment, the present invention provides the following method for recycling hydrogen bromide in one embodiment.
水と酸素の存在下、上述した本発明のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物に光照射して光反応により上記式（３）で表される安息香酸化合物を得て、副生した臭化水素を、上述した本発明のジブロモメチルベンゼン化合物の製造方法における前記臭化水素として用いることを含む、臭化水素のリサイクル方法。 A method for recycling hydrogen bromide, comprising irradiating a dibromomethylbenzene compound obtained by the above-mentioned method for producing a dibromomethylbenzene compound of the present invention with light in the presence of water and oxygen to obtain a benzoic acid compound represented by the above formula (3) through a photoreaction, and using the by-produced hydrogen bromide as the hydrogen bromide in the above-mentioned method for producing a dibromomethylbenzene compound of the present invention.
上述した本発明のジブロモメチルベンゼン化合物の製造方法により得られたジブロモメチルベンゼン化合物を加水分解して上記式（４）で表されるベンズアルデヒド化合物を得て、副生した臭化水素を、上述した本発明のジブロモメチルベンゼン化合物の製造方法における前記臭化水素として用いることを含む、臭化水素のリサイクル方法。 A method for recycling hydrogen bromide, comprising hydrolyzing a dibromomethylbenzene compound obtained by the above-mentioned method for producing a dibromomethylbenzene compound of the present invention to obtain a benzaldehyde compound represented by the above-mentioned formula (4), and using the by-produced hydrogen bromide as the hydrogen bromide in the above-mentioned method for producing a dibromomethylbenzene compound of the present invention.
以下に、本発明を、実施例に基づき、さらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
［実施例１］
４－シアノトルエン１．７６ｇ（１５ｍｍｏｌ）と、溶媒としてトリフルオロメチルベンゼン（以下、ＢＴＦと記す。）６０ｍｌを、撹拌子を入れた２００ｍｌの４つ口フラスコ内に投入した。続いて、４８％ＨＢｒ水溶液３．７３ｍｌ（ＨＢｒとして３３ｍｍｏｌ）、ＮａＯＣｌ・５水和物結晶６．６７ｇ（ＮａＯＣｌとして４０．５ｍｍｏｌ）及び水２１ｍＬをフラスコ内に投入した。フラスコを氷浴（０℃）に浸し、フラスコ内を窒素置換し、窒素雰囲気下（酸素の非存在下）、フラスコ内の溶液を撹拌しながらこの溶液に４時間光照射した。光照射は、青色ＬＥＤ光源（ワット数：１０Ｗ、波長：４５４ｎｍ）をフラスコから５ｃｍの距離に配して行った。フラスコ内に亜硫酸ナトリウム水溶液を数滴滴下して溶液の臭素の色を消した後、フラスコ内に重曹水と酢酸エチルを投入して振り混ぜて水相と有機相を分離した。この操作により溶液中のＮａＣｌが水相に溶解し、ＮａＣｌが除去される。次いで、得られた有機相を飽和食塩水で洗浄した後、洗浄された有機相を硫酸ナトリウムで乾燥した。硫酸ナトリウムを濾別した後、乾燥後の有機相を減圧濃縮することで、黄色の固体（光反応生成物）３．６３ｇ（粗収率：８８％）を得た。ＧＣ-ＭＳ測定の結果、この固体は、４－ブロモメチルベンゾニトリルを４．５％、４－ジブロモメチルベンゾニトリルを９０．８％、４－トリブロモメチルベンゾニトリルを２．３％含有していた（ＧＣ純度が９０．８％の４－ジブロモメチルベンゾニトリルとも称す）。
なお、上記の「粗収率」とは、上記固体のすべてがジブロモメチル体と仮定した場合の収率（トルエン化合物（出発原料）のモル量（Ｍ１）に対するジブロモメチル体のモル量（Ｍ２）の百分率（（Ｍ２／Ｍ１）×１００）の値）であり、以降の説明でも同様である。また、上記の光反応生成物中のモノブロモ体、ジブロモ体、及びトリブロモ体の含有割合は、ＧＣ-ＭＳ測定の結果から得られる面積％であり、以降の説明でも同様である。
４－ジブロモメチルベンゾニトリルのＧＣ-ＭＳ：ｍ/ｚ＝２７７（Ｍ＋４；相対強度０．６０％）、２７５（Ｍ＋２；相対強度１．１６％）、２７３（Ｍ＋；相対強度０．６０％）、１９６（Ｍ－Ｂｒ＋２，９４％）、１９４（Ｍ－Ｂｒ，１００％）、１１５（Ｍ－２Ｂｒ、４８％）、１１４（Ｍ－ＣＨＢｒ２，２３％）
[Example 1]
1.76 g (15 mmol) of 4-cyanotoluene and 60 ml of trifluoromethylbenzene (hereinafter referred to as BTF) as a solvent were placed in a 200 ml four-neck flask containing a stirrer. Then, 3.73 ml of 48% HBr aqueous solution (33 mmol as HBr), 6.67 g of NaOCl-pentahydrate crystals (40.5 mmol as NaOCl) and 21 mL of water were placed in the flask. The flask was immersed in an ice bath (0°C), the flask was replaced with nitrogen, and the solution in the flask was irradiated with light for 4 hours under a nitrogen atmosphere (absence of oxygen) while stirring. The light irradiation was performed by placing a blue LED light source (wattage: 10 W, wavelength: 454 nm) at a distance of 5 cm from the flask. A few drops of sodium sulfite aqueous solution were dropped into the flask to remove the color of bromine in the solution, and then sodium bicarbonate water and ethyl acetate were placed in the flask and shaken to separate the aqueous phase and the organic phase. This operation dissolves NaCl in the solution into the aqueous phase, and NaCl is removed. The organic phase obtained was then washed with saturated saline, and the washed organic phase was then dried over sodium sulfate. The sodium sulfate was filtered off, and the dried organic phase was concentrated under reduced pressure to obtain 3.63 g (crude yield: 88%) of a yellow solid (photoreaction product). As a result of GC-MS measurement, this solid contained 4.5% 4-bromomethylbenzonitrile, 90.8% 4-dibromomethylbenzonitrile, and 2.3% 4-tribromomethylbenzonitrile (also referred to as 4-dibromomethylbenzonitrile with a GC purity of 90.8%).
The above-mentioned "crude yield" refers to the yield (the percentage ((M2/M1)×100) of the molar amount (M2) of the dibromomethyl body relative to the molar amount (M1) of the toluene compound (starting material)) when it is assumed that all of the solid is the dibromomethyl body, and this also applies to the following explanation. The contents of the monobromo body, dibromo body, and tribromo body in the above-mentioned photoreaction product are area % obtained from the results of GC-MS measurement, and this also applies to the following explanation.
GC-MS of 4-dibromomethylbenzonitrile: m/z = 277 (M+4; rel. intensity 0.60%), 275 (M+2; rel. intensity 1.16%), 273 (M + ; rel. intensity 0.60%), 196 (M-Br+2, 94%), 194 (M-Br, 100%), 115 (M-2Br, 48%), 114 (M-CHBr 2 , 23%).
［実施例２］
４－シアノトルエン、ＢＴＦ、４８％ＨＢｒ水溶液、ＮａＯＣｌ・５水和物結晶、水の投入量を、それぞれ、０．５９ｇ（５ｍｍｏｌ）、２０ｍｌ、１．２４ｍｌ（ＨＢｒとして１１ｍｍｏｌ）、１．９７ｇ（ＮａＯＣｌとして１２ｍｍｏｌ）、７ｍｌに変更したこと以外は、実施例１と同様にして光反応生成物を得た（粗収率７９％）。この光反応生成物は、４－ブロモメチルベンゾニトリルを８．０％、４－ジブロモメチルベンゾニトリルを８９．０％、４－トリブロモメチルベンゾニトリルを３．０％含んでいた。
[Example 2]
A photoreaction product was obtained in the same manner as in Example 1 (crude yield 79%), except that the amounts of 4-cyanotoluene, BTF, 48% HBr aqueous solution, NaOCl pentahydrate crystals, and water added were changed to 0.59 g (5 mmol), 20 ml, 1.24 ml (11 mmol as HBr), 1.97 g (12 mmol as NaOCl), and 7 ml, respectively. This photoreaction product contained 8.0% 4-bromomethylbenzonitrile, 89.0% 4-dibromomethylbenzonitrile, and 3.0% 4-tribromomethylbenzonitrile.
［実施例３］
４－シアノトルエンを３－シアノトルエン（５ｍｍｏｌ）に変更し、光照射時間を６時間に変更したこと以外は、実施例２と同様にして光反応生成物を得た（粗収率９３％）。この光反応生成物は、３－ブロモメチルベンゾニトリルを３．０％、３－ジブロモメチルベンゾニトリルを９３．０％、３－トリブロモメチルベンゾニトリルを２．０％含んでいた。
[Example 3]
A photoreaction product was obtained (crude yield 93%) in the same manner as in Example 2, except that 4-cyanotoluene was changed to 3-cyanotoluene (5 mmol) and the light irradiation time was changed to 6 hours. This photoreaction product contained 3.0% 3-bromomethylbenzonitrile, 93.0% 3-dibromomethylbenzonitrile, and 2.0% 3-tribromomethylbenzonitrile.
［実施例４］
３－シアノトルエンを４－ニトロトルエン（５ｍｍｏｌ）に変更し、青色ＬＥＤ光源のワット数を５Ｗに変更したこと以外は、実施例３と同様にして光反応生成物を得た（粗収率８２％）。この光反応生成物は、１－ブロモメチル－４－ニトロベンゼンを１．０％未満、１－ジブロモメチル－４－ニトロベンゼンを９４．０％、１－トリブロモメチル－４－ニトロベンゼンを１．０％未満含んでいた。
[Example 4]
A photoreaction product was obtained in the same manner as in Example 3 (crude yield 82%), except that 3-cyanotoluene was changed to 4-nitrotoluene (5 mmol) and the wattage of the blue LED light source was changed to 5 W. This photoreaction product contained less than 1.0% 1-bromomethyl-4-nitrobenzene, 94.0% 1-dibromomethyl-4-nitrobenzene, and less than 1.0% 1-tribromomethyl-4-nitrobenzene.
［実施例５］
４－シアノトルエンを２－ニトロトルエン（５ｍｍｏｌ）に変更し、光照射時間を２４時間に変更したこと以外は、実施例２と同様にして光反応を行った。この光反応生成物は１－ブロモメチル－２－ニトロベンゼンを２８．０％、１－ジブロモメチル－２－ニトロベンゼンを５８．０％含み、１－トリブロモメチル－２－ニトロベンゼンは検出されなかった。
[Example 5]
Except for changing 4-cyanotoluene to 2-nitrotoluene (5 mmol) and changing the light irradiation time to 24 hours, the photoreaction was carried out in the same manner as in Example 2. The photoreaction product contained 28.0% 1-bromomethyl-2-nitrobenzene and 58.0% 1-dibromomethyl-2-nitrobenzene, and no 1-tribromomethyl-2-nitrobenzene was detected.
［実施例６］
４－ニトロトルエンを４－ブロモトルエン（５ｍｍｏｌ）に変更し、光照射時間を２時間に変更したこと以外は、実施例４と同様にして光反応生成物を得た（粗収率８６％）。この光反応生成物からは、１－ブロモメチル－４－ブロモベンゼンは検出されず、１－ジブロモメチル－４－ブロモベンゼンを９１．０％、１－トリブロモメチル－４－ブロモベンゼンを５．０％含んでいた。
[Example 6]
A photoreaction product was obtained (crude yield 86%) in the same manner as in Example 4, except that 4-nitrotoluene was changed to 4-bromotoluene (5 mmol) and the light irradiation time was changed to 2 hours. No 1-bromomethyl-4-bromobenzene was detected from this photoreaction product, and it contained 91.0% 1-dibromomethyl-4-bromobenzene and 5.0% 1-tribromomethyl-4-bromobenzene.
［実施例７］
４－ブロモトルエンを４－クロロトルエン（５ｍｍｏｌ）に変更し、光照射時間を５時間に変更したこと以外は、実施例６と同様にして光反応生成物を得た（粗収率６７％）。この光反応生成物からは、１－ブロモメチル－４－クロロベンゼンは検出されず、１－ジブロモメチル－４－クロロベンゼンを９１．０％、１－トリブロモメチル－４－クロロベンゼンを６．０％含んでいた。
[Example 7]
A photoreaction product was obtained (crude yield 67%) in the same manner as in Example 6, except that 4-bromotoluene was changed to 4-chlorotoluene (5 mmol) and the light irradiation time was changed to 5 hours. No 1-bromomethyl-4-chlorobenzene was detected from this photoreaction product, and it contained 91.0% 1-dibromomethyl-4-chlorobenzene and 6.0% 1-tribromomethyl-4-chlorobenzene.
［実施例８］
４－ブロモトルエンを４－フルオロトルエン（５ｍｍｏｌ）に変更したこと以外は、実施例６と同様にして光反応生成物を得た（粗収率８４％）。この光反応生成物は、１－ブロモメチル－４－フルオロベンゼンを１．０％未満、１－ジブロモメチル－４－フルオロベンゼンを９５．０％、１－トリブロモメチル－４－フルオロベンゼンを４．０％含んでいた。
[Example 8]
A photoreaction product was obtained (crude yield 84%) in the same manner as in Example 6, except that 4-bromotoluene was replaced with 4-fluorotoluene (5 mmol). This photoreaction product contained less than 1.0% 1-bromomethyl-4-fluorobenzene, 95.0% 1-dibromomethyl-4-fluorobenzene, and 4.0% 1-tribromomethyl-4-fluorobenzene.
［実施例９］
４－フルオロトルエンを２－フルオロトルエン（５ｍｍｏｌ）に変更し、光照射時間を４時間に変更したこと以外は、実施例８と同様にして光反応生成物を得た（粗収率８９％）。この光反応生成物は、１－ブロモメチル－２－フルオロベンゼンを１．０％未満、１－ジブロモメチル－２－フルオロベンゼンを９７．０％含み、１－トリフルオロメチル－２－フルオロベンゼンは検出されなかった。
[Example 9]
A photoreaction product was obtained (crude yield 89%) in the same manner as in Example 8, except that 4-fluorotoluene was changed to 2-fluorotoluene (5 mmol) and the light irradiation time was changed to 4 hours. This photoreaction product contained less than 1.0% 1-bromomethyl-2-fluorobenzene and 97.0% 1-dibromomethyl-2-fluorobenzene, and 1-trifluoromethyl-2-fluorobenzene was not detected.
［実施例１０］
４－クロロトルエンを４－トリフルオロメチルトルエン（５ｍｍｏｌ）に変更したこと以外は、実施例７と同様にして光反応生成物を得た（粗収率８４％）。この光反応生成物は、１－ブロモメチル－４－トリフルオロメチルベンゼンを１．０％未満、１－ジブロモメチル－４－トリフルオロメチルベンゼンを８７．０％、１－トリブロモメチル－４－トリフルオロメチルベンゼンを８．０％含んでいた。
[Example 10]
A photoreaction product was obtained (crude yield 84%) in the same manner as in Example 7, except that 4-chlorotoluene was replaced with 4-trifluoromethyltoluene (5 mmol). This photoreaction product contained less than 1.0% 1-bromomethyl-4-trifluoromethylbenzene, 87.0% 1-dibromomethyl-4-trifluoromethylbenzene, and 8.0% 1-tribromomethyl-4-trifluoromethylbenzene.
［実施例１１］
青色ＬＥＤ光源をＵＶ－ＬＥＤ光源（ワット数：１０Ｗ、波長３６５ｎｍ）に変更し、ＮａＯＣｌ・５水和物結晶をＮａＯＣｌとして１４ｍｍｏｌとなるように用いたこと以外は、実施例２と同様にして光反応生成物を得た（粗収率９７％）。この光反応生成物は、４－ブロモメチルベンゾニトリルを３．０％、４－ジブロモメチルベンゾニトリルを９５．０％含み、４－トリブロモメチルベンゾニトリルは検出されなかった。
[Example 11]
A photoreaction product was obtained in the same manner as in Example 2 (crude yield 97%), except that the blue LED light source was changed to a UV-LED light source (wattage: 10 W, wavelength 365 nm) and NaOCl.pentahydrate crystals were used in an amount of 14 mmol as NaOCl. This photoreaction product contained 3.0% 4-bromomethylbenzonitrile and 95.0% 4-dibromomethylbenzonitrile, and no 4-tribromomethylbenzonitrile was detected.
［実施例１２］
青色ＬＥＤ光源をＵＶ－ＬＥＤ光源（ワット数：１０Ｗ、波長３９５ｎｍ）に変更し、光照射時間を５時間としたこと以外は、実施例２と同様にして光反応生成物を得た（粗収率７３％）。この光反応生成物は、４－ブロモメチルベンゾニトリルを１．０％、４－ジブロモメチルベンゾニトリルを９５．０％含み、４－トリブロモメチルベンゾニトリルは検出されなかった。
[Example 12]
A photoreaction product was obtained in the same manner as in Example 2, except that the blue LED light source was changed to a UV-LED light source (wattage: 10 W, wavelength: 395 nm) and the light irradiation time was changed to 5 hours (crude yield: 73%). This photoreaction product contained 1.0% 4-bromomethylbenzonitrile and 95.0% 4-dibromomethylbenzonitrile, and no 4-tribromomethylbenzonitrile was detected.
［実施例１３］
実施例９と同様にして光反応生成物（１－ジブロモメチル－２－フルオロベンゼン：ＧＣ純度９３．０％）を得た。この光反応生成物をフラスコ中でＢＴＦ２０ｍｌに溶解し、さらに水８ｍｌを加えた。大気開放下（室温（２５℃））で、フラスコ内の溶液を撹拌しながらこの溶液にＵＶ－ＬＥＤ光源（ワット数：１０Ｗ、波長：３９５ｎｍ）の光を１６時間照射した。ＧＣ－ＭＳ測定すると、光反応生成物は２－フルオロ安息香酸を９７．７％（面積％）含んでいた。次いで、２－フルオロ安息香酸を含む有機相と、ＨＢｒを含む水相とを分離し、この水相を水酸化ナトリウムで滴定した。水相には７．５ｍｍｏｌ（回収率７５％）のＨＢｒが含まれていた。
２－フルオロ安息香酸のＧＣ－ＭＳ：ｍ/ｚ＝１４０（Ｍ＋、６０％）、１２３（Ｍ―ＯＨ，１００％）、９５（Ｍ－ＣＯ２Ｈ，４８％）
[Example 13]
A photoreaction product (1-dibromomethyl-2-fluorobenzene: GC purity 93.0%) was obtained in the same manner as in Example 9. This photoreaction product was dissolved in 20 ml of BTF in a flask, and 8 ml of water was added. The solution in the flask was irradiated with light from a UV-LED light source (wattage: 10 W, wavelength: 395 nm) for 16 hours while stirring the solution in the flask in an open atmosphere (room temperature (25°C)). When measured by GC-MS, the photoreaction product contained 97.7% (area%) of 2-fluorobenzoic acid. Next, an organic phase containing 2-fluorobenzoic acid and an aqueous phase containing HBr were separated, and the aqueous phase was titrated with sodium hydroxide. The aqueous phase contained 7.5 mmol of HBr (recovery rate 75%).
GC-MS of 2-fluorobenzoic acid: m/z = 140 (M+, 60%), 123 (M-OH, 100%), 95 (M-CO 2 H, 48%)
［実施例１４］
実施例１３で得られた水相に４８％ＨＢｒ水溶液を加えてＨＢｒを１１ｍｍｏｌ含むＨＢｒ水溶液とした。そこに２－フルオロトルエン０．５５ｇ（５ｍｍｏｌ）と、ＮａＯＣｌ・５水和物結晶１．９７ｇ（ＮａＯＣｌとして１２ｍｍｏｌ）と、ＢＴＦ２０ｍｌとを加え、フラスコを氷浴（０℃）に浸し、フラスコ内を窒素置換し、窒素雰囲気下、撹拌しながら青色ＬＥＤ光源（ワット数：５Ｗ、波長：４５４ｎｍ）の光を２時間照射した。ＧＣ－ＭＳ測定すると、光反応生成物は１－ブロモメチル－２－フルオロベンゼンを２２．８％、１－ジブロモメチル－２－フルオロベンゼンを７４．８％含んでいた。続いて、４８％ＨＢｒ水溶液０．２７ｍｌ（ＨＢｒとして２．４ｍｍｏｌ）と、ＮａＯＣｌ・５水和物結晶０．４３ｇ（ＮａＯＣｌとして２．６ｍｍoｌ）とをフラスコ内に投入し、引き続き窒素雰囲気下で１時間光反応を行った。ＧＣ－ＭＳ測定すると、光反応生成物は１－ブロモメチル－２－フルオロベンゼンを４．９％、１－ジブロモメチル－２－フルオロベンゼンを９３．９％含んでいた。
[Example 14]
A 48% HBr aqueous solution was added to the aqueous phase obtained in Example 13 to obtain an HBr aqueous solution containing 11 mmol of HBr. 0.55 g (5 mmol) of 2-fluorotoluene, 1.97 g of NaOCl-pentahydrate crystals (12 mmol as NaOCl), and 20 ml of BTF were added thereto, the flask was immersed in an ice bath (0°C), the flask was replaced with nitrogen, and the mixture was irradiated with light from a blue LED light source (wattage: 5 W, wavelength: 454 nm) for 2 hours while stirring under a nitrogen atmosphere. When measured by GC-MS, the photoreaction product contained 22.8% 1-bromomethyl-2-fluorobenzene and 74.8% 1-dibromomethyl-2-fluorobenzene. Next, 0.27 ml of a 48% HBr aqueous solution (2.4 mmol as HBr) and 0.43 g of NaOCl-pentahydrate crystals (2.6 mmol as NaOCl) were added to the flask, and the photoreaction was continued for 1 hour under a nitrogen atmosphere. GC-MS measurement revealed that the photoreaction products contained 4.9% 1-bromomethyl-2-fluorobenzene and 93.9% 1-dibromomethyl-2-fluorobenzene.
[実施例１５]
実施例９と同様にして、光反応生成物（１－ジブロモメチル－２－フルオロベンゼン：ＧＣ純度９６．０％）を得た。この光反応生成物と、水１０ｍｌをフラスコに投入し、フラスコ内の溶液を２時間還流した。ＧＣ－ＭＳ測定すると、２－フルオロベンズアルデヒドを９７．７％（面積％）含んでいた。次いで、フラスコにジクロロメタン５ｍｌを加え、２－フルオロベンズアルデヒドを含む有機相と、ＨＢｒを含む水相とを分離した。この水相を水酸化ナトリウムで滴定すると、水相には８．８ｍｍｏｌ（回収率８８％）のＨＢｒが含まれていた。
２－フルオロベンズアルデヒドのＧＣ－ＭＳ；ｍ/ｚ＝１２４（Ｍ＋、８５％）、１２３（Ｍ－１，１００％）、９５（Ｍ－ＣＨＯ，５７％）
[Example 15]
A photoreaction product (1-dibromomethyl-2-fluorobenzene: GC purity 96.0%) was obtained in the same manner as in Example 9. This photoreaction product and 10 ml of water were placed in a flask, and the solution in the flask was refluxed for 2 hours. GC-MS measurement revealed that the solution contained 97.7% (area %) of 2-fluorobenzaldehyde. Next, 5 ml of dichloromethane was added to the flask, and an organic phase containing 2-fluorobenzaldehyde and an aqueous phase containing HBr were separated. When this aqueous phase was titrated with sodium hydroxide, it was found to contain 8.8 mmol (recovery rate 88%) of HBr.
GC-MS of 2-fluorobenzaldehyde; m/z=124 (M + , 85%), 123 (M-1, 100%), 95 (M-CHO, 57%)
［実施例１６］
実施例１５で得られた水相に４８％ＨＢｒ水溶液を加えてＨＢｒを１１ｍｍｏｌ含むＨＢｒ水溶液とした。そこに２－フルオロトルエン０．５５ｇ（５．０ｍｍｏｌ）と、ＮａＯＣｌ・５水和物結晶１．９７ｇ（ＮａＯＣｌとして１２ｍｍｏｌ）と、ＢＴＦ２０ｍｌとを加え、フラスコを氷浴（０℃）に浸し、フラスコ内を窒素置換し、窒素雰囲気下、撹拌しながら青色ＬＥＤ光源（ワット数：１０Ｗ、波長：４５４ｎｍ）の光を２時間照射した。ＧＣ－ＭＳ測定すると、１－ジブロモメチル－２－フルオロベンゼンを９２．８％含み、１－ブロモメチル－２－フルオロベンゼンは検出されなかった。
[Example 16]
A 48% HBr aqueous solution was added to the aqueous phase obtained in Example 15 to obtain an HBr aqueous solution containing 11 mmol of HBr. 0.55 g (5.0 mmol) of 2-fluorotoluene, 1.97 g of NaOCl-pentahydrate crystals (12 mmol as NaOCl), and 20 ml of BTF were added thereto, the flask was immersed in an ice bath (0°C), the flask was replaced with nitrogen, and the mixture was irradiated with light from a blue LED light source (wattage: 10 W, wavelength: 454 nm) for 2 hours while stirring under a nitrogen atmosphere. GC-MS measurement showed that the mixture contained 92.8% 1-dibromomethyl-2-fluorobenzene, and no 1-bromomethyl-2-fluorobenzene was detected.
上記の結果から、本発明で規定する光反応によって、電子求引基を有するトルエン化合物を出発原料として、ジブロモメチル体を、食塩を含まない状態で、安全に、収率よく得られることがわかった。さらに、当該ジブロモメチル体から安息香酸化合物又はベンズアルデヒド化合物を光反応によって効率的に得られること、この光反応で副生する臭化水素酸をジブロモメチル体の生成に再利用できることもわかった。
From the above results, it was found that the dibromomethyl compound can be obtained safely and in good yield without containing salt by the photoreaction defined in the present invention, using a toluene compound having an electron-withdrawing group as a starting material. Furthermore, it was also found that a benzoic acid compound or a benzaldehyde compound can be efficiently obtained from the dibromomethyl compound by the photoreaction, and that the hydrobromic acid by-product of this photoreaction can be reused for the production of the dibromomethyl compound.
Claims (9)
A method for recycling hydrogen bromide, comprising hydrolyzing a dibromomethylbenzene compound obtained by the method for producing a dibromomethylbenzene compound according to any one of claims 1 to 5 to obtain a benzaldehyde compound represented by the following formula (4), and using the by-produced hydrogen bromide as the hydrogen bromide in the method for producing a dibromomethylbenzene compound according to any one of claims 1 to 5.
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