JPH0478633B2 - - Google Patents
Info
- Publication number
- JPH0478633B2 JPH0478633B2 JP62174982A JP17498287A JPH0478633B2 JP H0478633 B2 JPH0478633 B2 JP H0478633B2 JP 62174982 A JP62174982 A JP 62174982A JP 17498287 A JP17498287 A JP 17498287A JP H0478633 B2 JPH0478633 B2 JP H0478633B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- benzotriazole
- formula
- mmol
- solvent
- 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
- 239000004280 Sodium formate Substances 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 23
- 235000019254 sodium formate Nutrition 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- JFEVWPNAOCPRHQ-UHFFFAOYSA-N chembl1316021 Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1O JFEVWPNAOCPRHQ-UHFFFAOYSA-N 0.000 claims description 3
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000012964 benzotriazole Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- -1 polystyene Polymers 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IIHNCIPIAMRRIQ-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(4-chloro-2-nitrophenyl)diazenyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N=NC=2C(=CC(Cl)=CC=2)[N+]([O-])=O)=C1O IIHNCIPIAMRRIQ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 150000001204 N-oxides Chemical class 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- DRPPFIRCBMBJCM-UHFFFAOYSA-N 4-methyl-2-[(2-nitrophenyl)diazenyl]phenol Chemical compound CC1=CC=C(O)C(N=NC=2C(=CC=CC=2)[N+]([O-])=O)=C1 DRPPFIRCBMBJCM-UHFFFAOYSA-N 0.000 description 3
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic 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
- 239000002244 precipitate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 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
- 239000003799 water insoluble solvent Substances 0.000 description 2
- HHUOYYNHGMRSIF-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)-6-[(2-nitrophenyl)diazenyl]phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N=NC=2C(=CC=CC=2)[N+]([O-])=O)=C1O HHUOYYNHGMRSIF-UHFFFAOYSA-N 0.000 description 1
- KKHUPQJJNOFIJV-UHFFFAOYSA-N 2,4-ditert-butyl-6-(5-chloro-1-oxidobenzotriazol-1-ium-2-yl)phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2[N+](=C3C=CC(Cl)=CC3=N2)[O-])=C1O KKHUPQJJNOFIJV-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- YZSBLPWBEDOWSK-UHFFFAOYSA-N C1=CC=CC2=[N+]([O-])NN=C21 Chemical compound C1=CC=CC2=[N+]([O-])NN=C21 YZSBLPWBEDOWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、各種プラスチツク製品の紫外線吸収
剤として有用な2−アリル−2H−ベンゾトリア
ゾール又はそのN−オキシド及びこれらの誘導体
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 2-allyl-2H-benzotriazole or its N-oxide and derivatives thereof, which are useful as ultraviolet absorbers for various plastic products.
[従来の技術]
ベンゾトリアゾール誘導体は、紫外線吸収剤と
して知られており、ポリ塩化ビニル、不飽和ポリ
エステル、ポリスチエン、ポリアミド、ポリメチ
ルタクリレート、セルロールエステル、ABS樹
脂などのプラスチツク製品の紫外線による変色や
劣化などを防止するための添加剤として使用され
ている。したがつて、かかる用途に提供するベン
ゾトリアゾール誘導体は色調が優れ、純度が高い
ことが要求される。[Prior art] Benzotriazole derivatives are known as ultraviolet absorbers, and are effective in discoloring plastic products such as polyvinyl chloride, unsaturated polyester, polystyene, polyamide, polymethyl tacrylate, cellulose ester, and ABS resin due to ultraviolet light. It is used as an additive to prevent corrosion and deterioration. Therefore, benzotriazole derivatives provided for such uses are required to have excellent color tone and high purity.
ベンゾトリアゾール誘導体の公知の製造方法と
して米国特許第2362988号には0−アミノフエニル
アゾフエノールを酸化する方法が開示され;米国
特許第4041044号には0−ニトロアゾフエノール類
を亜鉛粉末で還元する方法が開示され;米国特許
第4141903号には0−ニトロアゾフエノール類を水
素、一酸化炭素又はヒドラジンと共に20〜150℃、
1〜66気圧下で銅化合物とアミン化合物から成る
錯化合物触媒の存在下て還元する方法が開示され
ている。 As a known method for producing benzotriazole derivatives, US Pat. No. 2,362,988 discloses a method of oxidizing 0 -aminophenyl azophenol; US Pat. No. 4,041,044 discloses a method of reducing 0 -nitroazophenols with zinc powder. A process is disclosed; U.S. Pat. No. 4,141,903 discloses the treatment of 0 -nitroazophenols with hydrogen, carbon monoxide or hydrazine at 20-150°C.
A method for reduction in the presence of a complex catalyst consisting of a copper compound and an amine compound under 1 to 66 atmospheres is disclosed.
一方、米国特許第4224451号には一般式()
の0−ニトロアゾフエノール類を水硫化物又は硫
化物の存在下でベンゾトリアゾールN−オキシド
まで還元したのち、さらにこのN−オキシドを亜
鉛又は錯粉末の存在下で還元して2−アリール−
2H−ベンゾトリアゾール誘導体を製造する方法
が開示されている。これは硫化物類がN−オキシ
ドの製造方法としては適当であるが、ベンゾトリ
アゾールの製造方法としては、その還元力が充分
でないことを表わすものである。 On the other hand, U.S. Patent No. 4224451 has the general formula ()
After reducing the 0 -nitroazophenol to benzotriazole N-oxide in the presence of hydrosulfide or sulfide, this N-oxide is further reduced in the presence of zinc or complex powder to form 2-aryl-
A method for making 2H-benzotriazole derivatives is disclosed. This indicates that although sulfides are suitable for the production of N-oxides, their reducing power is not sufficient for the production of benzotriazole.
これと関連してAust.J.Chem.1984.37、2489に
は0−ニトロアゾールフエノールをエタノール中
で亜二イオン酸ナトリウムの存在下で還元して直
接2−アリール−2H−ベンゾトリアゾール誘導
体を製造する方法が開示されている。 In this connection, Aust.J.Chem.1984.37, 2489 describes the reduction of 0 -nitroazolephenols in ethanol in the presence of sodium diionite to directly prepare 2-aryl-2H-benzotriazole derivatives. A method is disclosed.
しかしながら、このように還元剤として亜二チ
オン酸ナトリウムを用いる場合には、反応途中に
おいて亜二チオン酸ナトリウムが分解してコロイ
ド状イオウを生成するという問題、さらにはこの
コロイド状イオウ生成による亜二チオン酸ナトリ
ウムの損失を補うために、理論量の約5倍モル量
もの亜二チオン酸ナトリウムを使用しなければな
らないという問題がある。また、得られる2−ア
リール−2H−ベンゾトリアゾール誘導体の収率
や純度も一定しないという問題がある。 However, when sodium dithionite is used as a reducing agent in this way, there is the problem that sodium dithionite decomposes during the reaction and produces colloidal sulfur, and furthermore, the production of colloidal sulfur causes the production of colloidal sulfur. The problem is that approximately five times the theoretical amount of sodium dithionite must be used to compensate for the loss of sodium thionate. Further, there is a problem that the yield and purity of the obtained 2-aryl-2H-benzotriazole derivatives are not constant.
[発明が解決しようとする問題点]
上記の従来技術において、水素、一酸化炭素又
はヒドラジンなどを用いる方法は安全性の点で問
題があり、亜二チオン酸ナトリウムのみを用いる
方法もコロイド状イオウの生成により起こる問題
がある。[Problems to be Solved by the Invention] In the above-mentioned conventional techniques, the method using hydrogen, carbon monoxide, hydrazine, etc. has a problem in terms of safety, and the method using only sodium dithionite also has problems with colloidal sulfur. There are problems caused by the generation of
したがつて本発明は、上記問題点を解決し、高
収率で色調のよい2−アリール−2H−ベンゾト
リアゾール及びその誘導体を製造する方法を提供
することを目的とする。 Therefore, an object of the present invention is to solve the above problems and provide a method for producing 2-aryl-2H-benzotriazole and its derivatives with high yield and good color tone.
[問題点を解決するための手段]
本発明者らは上記目的を達成するべく研究の結
果、0−ニトロアゾフエノールを還元して2−アリ
ール−2H−ベンゾトリアゾールを製造する場合
に、亜二チアン酸ナトリウムと共に蟻酸ナトリウ
ムを共存させることによつて、亜二チオン酸ナト
リウムによる還元反応を行いがら、同時に亜二チ
オン酸ナトリウムの分解により生じた二酸化イオ
ウを蟻酸ナトリウムにより亜二チオン酸ナトリウ
ムに変化させる反応を行うことにより、還元剤と
して少量の亜二チオン酸ナトリムムの使用でも高
い収率で2−アリール−2H−ベンゾトリアゾー
ルを得られることを見出し、また、亜二チオン酸
ナトリウムの代わりに亜硫酸水素ナトリウムを用
いた場合にも同様の結果が得られることを合わせ
て見出し、本発明を完成するに至つた。[Means for Solving the Problems] As a result of research to achieve the above object, the present inventors found that when producing 2 -aryl-2H-benzotriazole by reducing 0-nitroazophenol, By allowing sodium formate to coexist with sodium thianate, the reduction reaction by sodium dithionite is carried out, and at the same time, the sulfur dioxide generated by the decomposition of sodium dithionite is converted to sodium dithionite by the sodium formate. We found that 2-aryl-2H-benzotriazole can be obtained in high yield even when using a small amount of sodium dithionite as a reducing agent by carrying out a reaction in which 2-aryl-2H-benzotriazole is used as a reducing agent. They also discovered that similar results can be obtained when sodium hydrogen is used, leading to the completion of the present invention.
すなわち本発明は、一般式():
(式中、R1は水素又は塩素を表し、R2及びR3は
水素、炭素数1〜5と低級アルキル基又は炭素数
7〜9のフエニルアルキル基を表す)
で示される0−ニトロアゾフエノールを、溶媒中
において亜二チオン酸ナトリウム及び蟻酸ナトリ
ウム又は亜硫酸水素ナトリウム及び蟻酸ナトリウ
ムの存在下で、前記溶媒の還流温度まで加熱して
還元せしめることにより生成した一般式():
(式中、R1、R2及びR3の意味は上記と同じであ
る)
で示される2−アリール−2H−ベンゾトリアゾ
ール及びその誘導体又は一般式():
(式中、R1、R2及びR3の意味は上記と同じであ
る)
で示される2−アリール−2H−ベンゾトリアゾ
ール−N−オキシド及びその誘導体を分離するこ
とを特徴とする前記一般式()又は()で示
される化合物の製造方法に関する。 That is, the present invention is based on the general formula (): (In the formula, R 1 represents hydrogen or chlorine, R 2 and R 3 represent hydrogen, a lower alkyl group having 1 to 5 carbon atoms, or a phenyl alkyl group having 7 to 9 carbon atoms) General formula () produced by reducing azophenol by heating it to the reflux temperature of the solvent in the presence of sodium dithionite and sodium formate or sodium bisulfite and sodium formate in a solvent: (In the formula, the meanings of R 1 , R 2 and R 3 are the same as above.) 2-Aryl-2H-benzotriazole and derivatives thereof or general formula (): (wherein the meanings of R 1 , R 2 and R 3 are the same as above) The present invention relates to a method for producing a compound represented by () or ().
出発原料となる0−ニトロアゾフエノールを示
す式()中のR1、R2及びR3の意味は上記のと
おりであるが、ここでR2において炭素数1〜5
とアルキル基はメチル基、エチル基、n−プロピ
ル基、イソプロピル基、n−ブチル基、iso−ブ
チル基、sec−ブチル基、tert−ブチル基、n−
アミル基、イソアミル基、sec−アミル基、活性
アミル基、tert−アミル基である。 The meanings of R 1 , R 2 and R 3 in the formula () representing 0 -nitroazophenol, which is the starting material, are as described above, but here, R 2 has 1 to 5 carbon atoms.
and alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-
They are amyl group, isoamyl group, sec-amyl group, activated amyl group, and tert-amyl group.
かかる式()で示される化合物は、例えば米
国特許第3773751号明細書に記載の方法により製
造することができる。 The compound represented by the formula () can be produced, for example, by the method described in US Pat. No. 3,773,751.
式()又は式()で示される化合物は、上
記の式()で示される化合物を所定条件下で還
元せしめることにより得ることができる。 The compound represented by formula () or formula () can be obtained by reducing the compound represented by formula () above under predetermined conditions.
本発明で用いる溶媒としては、水、N,N′−
ジメチルホルムアミド、トルエン、クロロベンセ
ン、ベンゼン、キシレン、リグロインなどを挙げ
ることができ、これらは1種を用いることがで
き、2種以上を混合して用いることができる。こ
こで、溶媒として水及び水に不溶な溶媒との混合
溶媒を用いた場合には、反応は2相状態で行われ
ることになる。 The solvent used in the present invention includes water, N,N'-
Dimethylformamide, toluene, chlorobenzene, benzene, xylene, ligroin, etc. can be mentioned, and one type of these can be used, or two or more types can be used as a mixture. Here, when a mixed solvent of water and a water-insoluble solvent is used as the solvent, the reaction will be carried out in a two-phase state.
本発明で用いる亜二チオン酸ナトリウム又は亜
硫酸水素ナトリウムは還元剤として作用するもの
であり、蟻酸ナトリウムは還元反応中に亜二チオ
ン酸ナトリウム又は亜硫酸水素ナトリウムが分解
して生じたイオウ酸化物を亜二チオン酸ナトリウ
ム又は亜硫酸水素ナトリウムに変化される働きを
するものである。 Sodium dithionite or sodium hydrogen sulfite used in the present invention acts as a reducing agent, and sodium formate reduces the sulfur oxide produced by the decomposition of sodium dithionite or sodium hydrogen sulfite during the reduction reaction. It works by being converted into sodium dithionate or sodium bisulfite.
亜二チオン酸ナトリウムと蟻酸ナトリウムの使
用量は、式()で示される化合物1モルに対し
て亜二チオン酸ナトリウムウは1.12〜4モル倍量
を用い、蟻酸ナトリウムは3〜4.5モル倍量を用
いる。亜硫酸水素ナトリウムと蟻酸ナトリウムを
用いる場合の使用量も同様である。亜二チオン酸
ナトリウム又は亜硫酸水素ナトリウムと蟻酸ナト
リウムは、一度にもしくは分割して使用すること
ができる。 The amounts of sodium dithionite and sodium formate to be used are 1.12 to 4 times the amount of sodium dithionite and 3 to 4.5 times the amount of sodium formate per 1 mole of the compound represented by formula (). Use. The amounts used when using sodium bisulfite and sodium formate are also similar. Sodium dithionite or sodium bisulfite and sodium formate can be used at once or in parts.
本発明においては、必要に応じて水酸化ナトリ
ウム、炭酸ナトリウム、水酸化カリウム、炭酸カ
リウムなどの塩基を反応系に共存させることがで
き、また、反応を上記のとおり2相状態で行う場
合には相転移触媒として例えば、2−アントラキ
ノンスルホンナトリウムなどのキノン又は1,4
−ナフトキノンとパラトルエンスルホン酸ナトリ
ウムとの混合物を反応系に共存させることが還元
反応をより効率的に進行させることができるため
に好ましい。 In the present invention, a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, etc. can be allowed to coexist in the reaction system if necessary. As a phase transfer catalyst, for example, a quinone such as sodium 2-anthraquinone sulfone or 1,4
- It is preferable to coexist a mixture of naphthoquinone and sodium p-toluenesulfonate in the reaction system because the reduction reaction can proceed more efficiently.
還元反応は、式()で示される化合物を上記
溶媒に溶解させたのち、この溶媒の還流温度まで
加熱することにより行う。加熱温度は使用する溶
媒により異なるが、通常は80℃以上であり、好ま
しくは100〜104℃の範囲である。また、反応時間
は通常4時間以内である。 The reduction reaction is carried out by dissolving the compound represented by formula () in the above solvent and then heating it to the reflux temperature of the solvent. The heating temperature varies depending on the solvent used, but is usually 80°C or higher, preferably in the range of 100 to 104°C. Further, the reaction time is usually within 4 hours.
反応液のPHは特に調節する必要がないが、9.5
〜10の範囲が好ましく、反応は窒素雰囲気下で行
うことが好ましい。 There is no need to particularly adjust the pH of the reaction solution, but it is 9.5.
The range is preferably from 10 to 10, and the reaction is preferably carried out under a nitrogen atmosphere.
反応液から目的とする式()又は式()で
示される化合物を分離する方法は、使用した溶倍
が単独溶媒であるか又は水と水に不溶の溶媒の混
合溶液であるかによつて異なる。以下、その一例
を掲げる。 The method for separating the target compound represented by formula () or formula () from the reaction solution depends on whether the solubility used is a single solvent or a mixed solution of water and a water-insoluble solvent. different. An example is given below.
単独溶媒の場合には、まず、反応液に例えばイ
ソプロパノールなどの溶媒を添加し、生成物の溶
解度を減少させたのち、高温で加熱し、熱いまま
過して主に硫酸ナトリウムと亜硫酸ナトリウム
から構成されている不純物を除去する。その後、
液を約5℃まで冷却して式()又は式()
で示されうる化合物の結晶を析出させたのち、こ
れを過する。 In the case of a single solvent, first, a solvent such as isopropanol is added to the reaction solution to reduce the solubility of the product, and then heated at a high temperature and filtered while still hot to dissolve the product, which is mainly composed of sodium sulfate and sodium sulfite. Remove impurities that have been after that,
Cool the liquid to about 5℃ and use formula () or formula ()
After precipitating crystals of a compound that can be represented by:
溶媒とて例えば水とトルエンを用い2相反応を
行つた場合には、反応液から水層を分離し、残り
のトルエン溶液を必要に応じて蒸留・濃縮したの
ちに、イソプロパノールなどの溶媒を添加し、以
下単独溶媒を用いた場合と同様にして式()又
は()で示される化合物を得ることができる。 When performing a two-phase reaction using water and toluene as solvents, for example, separate the aqueous layer from the reaction solution, distill and concentrate the remaining toluene solution as necessary, and then add a solvent such as isopropanol. However, the compound represented by formula () or () can be obtained in the same manner as when using a single solvent.
ここで式()で示される化合物は、式()
で示される化合物を還元せしめて式()で示さ
れる化合物を製造する過程で得られる中間体であ
る。したがつて、還元反応の進行を反応途中の適
当な段階で中断させることにより式()で示さ
れる化合物を得ることができ、還元反応を反応途
中で中断させずに完結されることにより式()
で示される化合物を得ることができる。すなわ
ち、式()で示される化合物を製造したのち、
これを還元することにより式()で示される化
合物を得ることができる。還元反応の進行度は、
薄層クロマトグラフイー(展開溶媒;n−ヘキサ
ン:酢酸エチル=4:1)により容易に確認する
ことができ、生成物の確認は、赤外線吸収スペク
トルによる一般式()におけるニトロ基の変化
の確認により可能である。 Here, the compound represented by the formula () is the compound represented by the formula ()
It is an intermediate obtained in the process of reducing the compound represented by formula () to produce the compound represented by formula (). Therefore, by interrupting the progress of the reduction reaction at an appropriate stage during the reaction, the compound represented by the formula () can be obtained, and by completing the reduction reaction without interrupting the reaction, the compound represented by the formula ( )
A compound represented by can be obtained. That is, after producing the compound represented by formula (),
By reducing this, a compound represented by formula () can be obtained. The progress of the reduction reaction is
It can be easily confirmed by thin layer chromatography (developing solvent: n-hexane: ethyl acetate = 4:1), and the product can be confirmed by infrared absorption spectroscopy to confirm the change in the nitro group in general formula (). This is possible.
このようにして得られる()で示される化合
物はほぼ白色であり、式()で示される化合物
はわずかに淡黄色である。 The compound represented by () thus obtained is almost white, and the compound represented by formula () is slightly pale yellow.
[実施例]
5−クロロ−2−(2′−ヒドロキシ−3′,5′−ジ
−tert−ブチルフエニル)2Hベンゾトリアゾ
ールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。ここにDMF
(12ml)、2−ニトロ−4−クロロ−2′−ヒドロキ
シ−3′,5′−ジ−tert−ブチルアゾベンゼン
(3.89g、10ミリモル)、蟻酸ナトリウム(2.53
g、37.2ミリモル)及び亜二チオン酸ナトリウム
(2g、11.5ミリモル)を添加した。窒素雰囲気
下で、攪拌を始めて還流が始まる時まで加熱し、
さらに1時間の間100〜105℃で反応させた。この
後亜二チオン酸ナトリウム(1g、5.7ミリモル)
を追加し、さらに1.5時間100〜105℃で反応を継
続させた。次にイソプロピルアルコール(40ml)
を加え、80〜85℃で加熱して20分間維持した後、
熱い状態で過した。主に硫酸ナトリウムから構
成された白い固体は捨てた。過した母液を5℃
まで冷却させて生成した沈澱物をさらに化し
て、最少量のイソプロピルアルコールで洗浄し、
殆ど白色の目的とするベンゾトリアゾールを得た
(2.10g)。また、残りの母液から減圧蒸溜し溶媒
を除去し、残留物から10mlイソプロピルアルコー
ルで再結晶させることにより、さらに0.9gの目
的とするベンゾトリアゾールを得た。総収率は
(理論値の84%):融点153.5−155.5℃。[Example] Production of 5-chloro-2-(2'-hydroxy-3',5'-di-tert-butylphenyl)2H benzotriazole First, a 100 ml three-necked flask was equipped with a stirrer, a reflux condenser, and nitrogen injection. The device was attached. DMF here
(12 ml), 2-nitro-4-chloro-2'-hydroxy-3',5'-di-tert-butylazobenzene (3.89 g, 10 mmol), sodium formate (2.53
g, 37.2 mmol) and sodium dithionite (2 g, 11.5 mmol) were added. Under a nitrogen atmosphere, start stirring and heat until reflux begins.
The reaction was continued at 100-105°C for an additional hour. After this sodium dithionite (1 g, 5.7 mmol)
was added and the reaction was continued at 100-105°C for an additional 1.5 hours. Then isopropyl alcohol (40ml)
After heating at 80-85℃ and maintaining for 20 minutes,
I was in a hot state. The white solid, consisting primarily of sodium sulfate, was discarded. The filtered mother liquor was heated to 5°C.
The precipitate formed is further evaporated and washed with a minimum amount of isopropyl alcohol.
The desired benzotriazole, almost white in color, was obtained (2.10 g). Further, the remaining mother liquor was distilled under reduced pressure to remove the solvent, and the residue was recrystallized from 10 ml of isopropyl alcohol to obtain an additional 0.9 g of the desired benzotriazole. Total yield (84% of theory): mp 153.5-155.5°C.
実施例 2
2−(2′−ヒドロキシ−5′メチルフエニル)−2H
−ベンゾトリアゾールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これにDMF
(10ml)、2−ニトロ−2′−ヒドロキシ−5′−メチ
ルアゾベンゼン(2.57g、10ミリモル)、蟻酸ナ
トリウム(3.00g、44ミリモル)及び亜硫酸水素
ナトリウム(3.57g、34ミリモル)の添加した。
窒素雰囲気で攪拌を始め、還流が始まる時まで加
熱し、さらに、一時間の間100〜105℃で反応させ
た。次にイソプロピルアルコール(20ml)を添加
し実施例1と同様に処理して殆ど白色の目的とす
るベンゾトリアゾールを得た。Example 2 2-(2'-hydroxy-5'methylphenyl)-2H
-Production of benzotriazole First, a stirrer, a reflux condenser, and a nitrogen injection device were attached to a 100 ml three-necked flask. DMF for this
(10 ml), 2-nitro-2'-hydroxy-5'-methylazobenzene (2.57 g, 10 mmol), sodium formate (3.00 g, 44 mmol) and sodium bisulfite (3.57 g, 34 mmol) were added.
Stirring was started under a nitrogen atmosphere, heating was continued until reflux started, and the reaction was continued at 100-105° C. for one hour. Next, isopropyl alcohol (20 ml) was added and treated in the same manner as in Example 1 to obtain an almost white benzotriazole.
総収率(理論値の74.2%):融点129−130℃。 Total yield (74.2% of theory): mp 129-130°C.
実施例 3
2−(2′−ヒドロキシ−3′,5′−ジ−tert−アミ
ルフエニル)−2H−ベンゾトリアゾールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これにDMF
(10ml)、2−ニトロ−2′−ヒドロキシ−3′,5′−
ジ−tert−アミルアゾベンゼン(3.83g、10ミリ
モル)蟻酸ナトリウム(2.53g、37ミリモル)及
び亜硫酸水素ナトリウム(3.24g、31ミリモル)
を添加した。窒素雰囲気下で攪拌を始めて還流が
始まる時まで加熱し、さらに一時間の間10〜105
℃で反応をさせた。次にイソプロピルアルコール
(35ml)を添加して実施例1と同様に処理して殆
ど白色の目的とするベンゾトリアゾールを得た。
総収率(理論値の80.9%):融点80−81℃。Example 3 Production of 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-2H-benzotriazole First, a 100 ml three-necked flask was equipped with a stirrer, a reflux condenser, and a nitrogen injection device. I let it happen. DMF for this
(10ml), 2-nitro-2'-hydroxy-3',5'-
Di-tert-amyl azobenzene (3.83 g, 10 mmol) Sodium formate (2.53 g, 37 mmol) and Sodium bisulfite (3.24 g, 31 mmol)
was added. Begin stirring under nitrogen atmosphere and heat until reflux begins, then heat at 10 to 105 °C for another hour.
The reaction was carried out at ℃. Next, isopropyl alcohol (35 ml) was added and the mixture was treated in the same manner as in Example 1 to obtain the desired benzotriazole, which was almost white in color.
Total yield (80.9% of theory): mp 80-81°C.
実施例 4
2−(2′−ヒドロキシ−3′,5′−ジ(1″,1″ジメ
チルベンジル)フエニル)−2H−ベンゾトリア
ゾールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これにDMF
(5ml)、2−ニトロ−(2′−ヒドロキシ−3′,5′
ジ
(a,a−ジメチルベンジル)フエニル)アゾベ
ンゼン(2.4g、5ミリモル)、蟻酸ナトリウム
(1.5g、22.0ミリモル)及び亜硫酸水素ナトリウ
ム(1.5g、14ミリモル)を添加した。窒素雰囲
気下で攪拌を始めて還流が始まる時まで加熱し、
さらに1時間の間100〜105℃で反応をさせた。次
にイソプロピルアルコール(20ml)を添加して実
施例1と同様に処理して殆ど白色の目的とするベ
ンゾトリアゾールを得た。総収率(理論値の55.4
%):融点138−138.5℃。Example 4 Production of 2-(2′-hydroxy-3′,5′-di(1″,1″dimethylbenzyl)phenyl)-2H-benzotriazole First, place a 100 ml three-necked flask with a stirrer and a reflux condenser. and a nitrogen injection device was attached. DMF for this
(5 ml), 2-nitro-(2'-hydroxy-3',5'
Di(a,a-dimethylbenzyl)phenyl)azobenzene (2.4 g, 5 mmol), sodium formate (1.5 g, 22.0 mmol) and sodium bisulfite (1.5 g, 14 mmol) were added. Start stirring under nitrogen atmosphere and heat until reflux begins.
The reaction was allowed to proceed for an additional hour at 100-105°C. Next, isopropyl alcohol (20 ml) was added and treated in the same manner as in Example 1 to obtain the desired benzotriazole, which was almost white in color. Total yield (theoretical value of 55.4
%): Melting point 138-138.5℃.
実施例 5
5−クロロ−2−(2′−ヒドロキシ−3′,5′−ジ
−tert−ブチルフエニル)−2H−ベンゾトリア
ゾールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これにDMF
(6ml)、クロロベンゼン(4ml)、2−ニトロ−
4−クロロ−2′−ヒドロキシ−3′,5′−ジ−tert
−ブチルアゾベンゼン(3.89g、10ミリモル)、
蟻酸ナトリウム(3.0g、44ミリモル)及び亜硫
酸水素ナトリウム(3.5g、33.7ミリモル)を添
加した。窒素雰囲気下で攪拌を始め還流が始まる
時まで加熱し、さらに1時間半の間100〜105℃で
反応をさせた。Example 5 Production of 5-chloro-2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole First, a 100 ml three-necked flask was equipped with a stirrer, a reflux condenser, and nitrogen. An injection device was attached. DMF for this
(6 ml), chlorobenzene (4 ml), 2-nitro-
4-chloro-2'-hydroxy-3',5'-di-tert
-butylazobenzene (3.89 g, 10 mmol),
Sodium formate (3.0 g, 44 mmol) and sodium bisulfite (3.5 g, 33.7 mmol) were added. Stirring was started under a nitrogen atmosphere, heating was continued until reflux began, and the reaction was continued at 100 to 105°C for an additional hour and a half.
次にイソプロピルアルコール(50ml)を添加
し、実施例1と同様に処理して目的とするベンゾ
トリアゾールを得た。総収率(理論値の75%)。 Next, isopropyl alcohol (50 ml) was added and treated in the same manner as in Example 1 to obtain the desired benzotriazole. Total yield (75% of theory).
実施例 6
5−クロロ−2−(2′−ビトロキシ−3′,5′−ジ
−tert−ブチルフエニル)−2H−ベンゾトリア
ゾールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これにDMF
(6ml)、トルエン(4ml)、2−ニトロ−4−ク
ロロ−2′−ヒドロキシ−3′,5′−ジ−tert−ブチ
ルアゾベンゼン(3.89g、10ミリモル)、蟻酸ナ
トリウム(3.09g、44ミリモル)及び亜硫酸水素
ナトリウム(3.5g、34ミリモル)を添加した。Example 6 Production of 5-chloro-2-(2'-bitroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole First, place a stirrer, a reflux condenser, and nitrogen into a 100 ml three-necked flask. An injection device was attached. DMF for this
(6 ml), toluene (4 ml), 2-nitro-4-chloro-2'-hydroxy-3',5'-di-tert-butylazobenzene (3.89 g, 10 mmol), sodium formate (3.09 g, 44 mmol). ) and sodium bisulfite (3.5 g, 34 mmol) were added.
窒素雰囲気下で攪拌を始めて還流が始まる時ま
で加熱し、さらに1時間半の間100〜105℃を反応
をさせた。次にイソプロピルアルコール(50ml)
を添加した実施例1と同様に処理して目的とする
ベンゾトリアゾールを得た。総収率(理論値の75
%)。 Stirring was started under a nitrogen atmosphere and heating was continued until reflux began, and the reaction was continued at 100 to 105°C for an additional hour and a half. Then isopropyl alcohol (50ml)
The desired benzotriazole was obtained by processing in the same manner as in Example 1 in which . Total yield (theoretical 75
%).
実施例 7
2−(2′−ヒドロキシ−5′−メチルフエニル)−
2H−ベンゾトリアゾール−N−オキシトの製
造
まず、250mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これに100ml
の水、水酸化ナトリウム(1.5g)、2−ニトロ−
2′−ヒドロキシ−5′−メチル−アゾベンゼン
(2.57g、10ミリモル)及び蟻酸ナトリウム
(3.00g、44ミリモル)を添加した。窒素雰囲気
下で攪拌を始めて70〜75℃まで加熱し、さらに次
に亜二チオン酸ナトリウム(2.2g、12.6ミリモ
ル)を水20mlに溶かした水溶液を、亜二チオン酸
イオンを余り過量に存在しないように少しずつ必
要に応じて添加した。この添加に際しては初期
に、パラコートの25%水溶液1滴を入れてこれと
亜二チオン酸イオンが反応して生じる青色が消え
てから少しずつ添加した。追加時間は約3.5時間
であつた。継続してさらに30分間反応をさせた。
次に50℃まで冷却して生成させた反応物を過さ
れた溶液を5mlの農塩酸で酸性にすることにより
約25℃で生成した生成物を過して淡い黄色の目
的とするベンゾトリアゾール−N−オキシドを得
た。さらに母液に13mlのイソプロピルアルコール
を加えたのち再結晶させて1.8gの淡い黄色の目
的とするベンゾトリアゾール−N−オキシドの結
晶を得た。収率(理論値の74.7%):融点138−
139℃。Example 7 2-(2'-hydroxy-5'-methylphenyl)-
Production of 2H-benzotriazole-N-oxyto First, a 250 ml three-necked flask was equipped with a stirrer, a reflux condenser, and a nitrogen injection device. 100ml of this
of water, sodium hydroxide (1.5 g), 2-nitro-
2'-Hydroxy-5'-methyl-azobenzene (2.57 g, 10 mmol) and sodium formate (3.00 g, 44 mmol) were added. Start stirring under a nitrogen atmosphere and heat to 70-75°C, and then add an aqueous solution of sodium dithionite (2.2 g, 12.6 mmol) dissolved in 20 ml of water so that the dithionite ions are not present in excess. It was added little by little as needed. At the time of this addition, one drop of a 25% aqueous solution of paraquat was added at the beginning, and after the blue color produced by the reaction between paraquat and dithionite ions disappeared, it was added little by little. The additional time was approximately 3.5 hours. The reaction was continued for an additional 30 minutes.
Next, the reaction product was cooled to 50°C, and the resulting solution was acidified with 5 ml of agricultural hydrochloric acid. N-oxide was obtained. Further, 13 ml of isopropyl alcohol was added to the mother liquor and recrystallized to obtain 1.8 g of pale yellow crystals of the desired benzotriazole-N-oxide. Yield (74.7% of theory): melting point 138−
139℃.
実施例 8
2−(2′−ビドロキシ−5′−メチルフエニル)−
2H−ベンゾトリアゾールの製造
まず、250mlの3口フラスコに攪拌器、還流冷
却器と窒素注入装置を付着させた。これに100ml
の水、水酸化ナトリウム(1.5g)、2−ニトロ−
2′−ヒドロキシ−5′−メチル−アゾベンゼン
(2.57g、10ミリモル)と蟻酸ナトリウム(3.00
g、44ミリモル)を添加し、窒素雰囲気下で攪拌
を始めて70〜75℃まで加熱した。次に亜二チオン
酸ナトリウム(6.68g、38ミリモル)を水60mlに
溶かした水溶液を実施例4と同様に11時間に亘つ
て添加し、さらに1時間反応を継続させた。その
後反応物を室温まで冷却して生成した沈澱物を
過した。過した溶液をクロロホルム10mlで3回
抽出したのち低圧で溶液を除去して残留物を12ml
のイソピロピルアルコールで再結晶させて1.6g
の目的とするトリアゾールを得た。収率(71%の
理論値)
実施例 9
6−クロロ−2−(2′−ヒドロキシ−3′,5′−ジ
−tert−ブチルフエニル)−2H−ベンゾトリア
ゾール−1−オキシドの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器及び窒素注入装置を付着させた。これに水
(30ml)、2−ニトロ−4−クロロ−2′−ヒドロキ
シ−3′,5′−tert−ブチルアゾベンゼン(3.89g、
10ミリモル)、水酸化ナトリウム(5.2g)、クロ
ロベンゼン(20ml)、蟻酸ナトリウム(2.04g、
30ミリモル)、パラトルエンスルホン酸ナトリウ
ム(3.0g)及び1,4ナフトキノン(0.2g)を
添加した。窒素雰囲気下で攪拌を始めて還流が始
まる時まで加熱した(95〜100℃)。次に亜二チオ
ン酸ナトリウム(3.6g、20ミリモルを20mlの水
に溶かした)水溶液を4時間に亘つて、出来限り
均等に添加したのち、さらに3分間100−105℃で
反応をさせた。その後、常温まで冷却したのち、
水層を分離除去した残つた有機物層を、水30mlで
2回洗浄した。次に溶媒を減圧蒸溜して回収し、
残留物を40mlのイソプロピルアルコールで結晶さ
せて3.55gの目的とするベンゾトリアゾール1−
オキシドを得た。収率(理論値の95.2%):融点
190−192℃。Example 8 2-(2'-hydroxy-5'-methylphenyl)-
Production of 2H-benzotriazole First, a 250 ml three-necked flask was equipped with a stirrer, a reflux condenser, and a nitrogen injection device. 100ml of this
of water, sodium hydroxide (1.5 g), 2-nitro-
2'-Hydroxy-5'-methyl-azobenzene (2.57 g, 10 mmol) and sodium formate (3.00
g, 44 mmol) was added and stirring was started under a nitrogen atmosphere and heated to 70-75°C. Next, an aqueous solution of sodium dithionite (6.68 g, 38 mmol) dissolved in 60 ml of water was added over 11 hours in the same manner as in Example 4, and the reaction was continued for an additional hour. The reaction mixture was then cooled to room temperature and the precipitate formed was filtered off. The filtered solution was extracted three times with 10 ml of chloroform, and then the solution was removed under low pressure to obtain 12 ml of the residue.
Recrystallize with isopropyl alcohol to give 1.6g
The desired triazole was obtained. Yield (71% of theory) Example 9 Production of 6-chloro-2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole-1-oxide First, 100 ml A three-necked flask was equipped with a stirrer, a reflux condenser, and a nitrogen injection device. To this was added water (30 ml), 2-nitro-4-chloro-2'-hydroxy-3',5'-tert-butylazobenzene (3.89 g,
10 mmol), sodium hydroxide (5.2 g), chlorobenzene (20 ml), sodium formate (2.04 g,
30 mmol), sodium p-toluenesulfonate (3.0 g) and 1,4 naphthoquinone (0.2 g). Stirring was started under a nitrogen atmosphere and heated (95-100°C) until reflux began. Next, an aqueous solution of sodium dithionite (3.6 g, 20 mmol dissolved in 20 ml of water) was added as evenly as possible over a period of 4 hours, followed by a further 3 minutes of reaction at 100-105°C. Then, after cooling to room temperature,
The aqueous layer was separated and removed, and the remaining organic layer was washed twice with 30 ml of water. The solvent is then recovered by distillation under reduced pressure,
The residue was crystallized from 40 ml of isopropyl alcohol to give 3.55 g of the desired benzotriazole 1-
Obtained oxide. Yield (95.2% of theory): Melting point
190−192℃.
実施例 9
6−クロロ−2−(2′−ヒドロキシ−3′,5′−ジ
−tert−ブチルフエニル)−2H−ベンゾトリア
ゾール−1−オキシドの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器及び窒素注入装置を付着させた。これに水
(30ml)、2−ニトロ−4−クロロ−2′−ヒドロキ
シ−3′,5′−ジ−tert−ブチルアゾベンゼン
(8.89g、10ミリモル)、水酸化ナトリウム(5.1
g)、クロロベンゼン(20ml)、蟻酸ナトリウム
(2.04g、30ミリモル)及び2−アントラキノン
スルホン酸ナトリウム(0.02g)を添加した。窒
素雰囲気下で攪拌を始めて還流が始まる時まで加
熱した(95〜100℃)。亜二チオン酸ナトリウム
(3.4g、19.5ミリモルを20mlの水に溶かした)水
溶液を4時間に亘つて出来得る限り均等に添加し
たのち、さらに30分間95−100℃で反応を継続さ
せた。その後、常温まで冷却したのちに水層を分
離除去し、残つた有機物層は30mlの水で2回洗浄
した。溶媒を減圧蒸溜して回収し、残留物を40ml
のイソプロピルアルコールで結晶させることに
3.6gの目的とするベンゾトリアゾール−1−オ
キシドを得た。収率(理論値の96.5%)
実施例 11
5−クロロ−2−(2′−ヒドロキシ−3′,5′−ジ
−tert−ブチルフエニル)−2H−ベンゾトリア
ゾールの製造
まず、100mlの3口フラスコに攪拌器、還流冷
却器及び窒素注入装置を付着させた。これに
DMF(6ml)、クロロベンゼン(4ml)、5−クロ
ロ−2−(2′−ヒドロキシ−3′,5′−ジ−tert−ブ
チルフエニル)−2H−ベンゾトリアゾール−N−
オキシド(2.39g、6.4ミリモル)、炭酸ナトリウ
ム(5.5g)、蟻酸ナトリウム(2.10g、3ミリモ
ル)及び亜硫酸水素ナトリウム(2.03g、20ミリ
モル)を添加した。窒素雰囲気下で攪拌を始めて
還流が始まる時まで加熱した(100−105℃)。反
応をこの温度で1.5時間継続させたのちに50mlの
イソプロピルアルコールを添加して実施例1と同
様に処理して1.49gの目的とするベンゾトリアゾ
ールを得た。収率(理論値の65.1%)
[発明の効果]
本発明によれば、高収率で、色調のよい2−ア
リール−2H−ベンゾトリアゾール及びそのN−
オキシド又はこれらの誘導体を得ることができ
る。また、蟻酸ナトリウムを使用することによ
り、還元剤の使用量を大幅に減少させることがで
きる。Example 9 Production of 6-chloro-2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole-1-oxide First, place a stirrer in a 100 ml three-necked flask and reflux. A cooler and nitrogen injection system were attached. To this was added water (30 ml), 2-nitro-4-chloro-2'-hydroxy-3',5'-di-tert-butylazobenzene (8.89 g, 10 mmol), sodium hydroxide (5.1
g), chlorobenzene (20ml), sodium formate (2.04g, 30mmol) and sodium 2-anthraquinonesulfonate (0.02g) were added. Stirring was started under a nitrogen atmosphere and heated (95-100°C) until reflux began. An aqueous solution of sodium dithionite (3.4 g, 19.5 mmol dissolved in 20 ml of water) was added as evenly as possible over a period of 4 hours, after which the reaction was continued for an additional 30 minutes at 95-100°C. Thereafter, after cooling to room temperature, the aqueous layer was separated and removed, and the remaining organic layer was washed twice with 30 ml of water. Collect the solvent by distillation under reduced pressure and collect 40ml of the residue.
to crystallize it with isopropyl alcohol.
3.6 g of the desired benzotriazole-1-oxide was obtained. Yield (96.5% of theory) Example 11 Production of 5-chloro-2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole First, a 100 ml three-necked flask was fitted with a stirrer, reflux condenser and nitrogen injection device. to this
DMF (6 ml), chlorobenzene (4 ml), 5-chloro-2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole-N-
Oxide (2.39 g, 6.4 mmol), sodium carbonate (5.5 g), sodium formate (2.10 g, 3 mmol) and sodium bisulfite (2.03 g, 20 mmol) were added. Stirring was started under a nitrogen atmosphere and heated (100-105°C) until reflux began. After the reaction was continued at this temperature for 1.5 hours, 50 ml of isopropyl alcohol was added and the mixture was treated as in Example 1 to obtain 1.49 g of the desired benzotriazole. Yield (65.1% of theoretical value) [Effect of the invention] According to the present invention, 2-aryl-2H-benzotriazole and its N-
Oxides or derivatives thereof can be obtained. Furthermore, by using sodium formate, the amount of reducing agent used can be significantly reduced.
Claims (1)
水素、炭素数1〜5の低級アルキル基又は炭素数
7〜9のフエニルアルキル基を表す) で示されるo−ニトロアゾフエノールを、溶媒中
において亜二チオン酸ナトリウム及び蟻酸ナトリ
ウム又は亜硫酸水素ナトリウム及び蟻酸ナトリウ
ムの存在下で、前記溶媒の還流温度まで加熱して
還元せしめることにより生成した一般式(): (式中、R1、R2及びR3の意味は上記と同じであ
る) で示される2−アリール−2H−ベンゾトリアゾ
ール及びその誘導体又は一般式(): (式中、R1、R2及びR3の意味は上記と同じであ
る) で示される2−アリール−2H−ベンゾトリアゾ
ール−N−オキシド及びその誘導体を分離するこ
とを特徴とする前記の一般式()又は()で
示される化合物の製造方法。 2 溶媒が水、N,N′−ジメチルホルムアミド、
トルエン及びクロロベンゼンからなる群から選ば
れる少なくとも1種である特許請求の範囲第1項
記載の製造方法。 3 2−アントラキノンスルホン酸ナトリウム又
は1,4−ナフトキノン及びp−トルエンスルホ
ン酸ナトリウムの混合物を溶媒中に存在させる特
許請求の範囲第1項記載の製造方法。[Claims] 1 General formula (): (In the formula, R 1 represents hydrogen or chlorine, R 2 and R 3 represent hydrogen, a lower alkyl group having 1 to 5 carbon atoms, or a phenyl alkyl group having 7 to 9 carbon atoms) General formula () produced by reducing azophenol by heating it to the reflux temperature of the solvent in the presence of sodium dithionite and sodium formate or sodium bisulfite and sodium formate in a solvent: (In the formula, the meanings of R 1 , R 2 and R 3 are the same as above.) 2-Aryl-2H-benzotriazole and derivatives thereof or general formula (): (wherein the meanings of R 1 , R 2 and R 3 are the same as above) A method for producing a compound represented by formula () or (). 2 The solvent is water, N,N'-dimethylformamide,
The manufacturing method according to claim 1, wherein at least one kind is selected from the group consisting of toluene and chlorobenzene. 3. The manufacturing method according to claim 1, wherein sodium 2-anthraquinonesulfonate or a mixture of 1,4-naphthoquinone and sodium p-toluenesulfonate is present in the solvent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR870003887A KR880012569A (en) | 1987-04-22 | 1987-04-22 | Method for preparing benzotriazole derivatives |
KR3887/1987 | 1987-04-22 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63267766A JPS63267766A (en) | 1988-11-04 |
JPH0478633B2 true JPH0478633B2 (en) | 1992-12-11 |
Family
ID=19260904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62174982A Granted JPS63267766A (en) | 1987-04-22 | 1987-07-15 | Manufacture of 2-aryl-2h-benzotriazole or n-oxide of same and derivatives |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPS63267766A (en) |
KR (1) | KR880012569A (en) |
DE (1) | DE3731860A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02202879A (en) * | 1989-01-31 | 1990-08-10 | Kemipuro Kasei Kk | Production of 2-phenylbenzotriazoles |
US6566507B2 (en) | 2000-08-03 | 2003-05-20 | Ciba Specialty Chemicals Corporation | Processes for the preparation of benzotriazole UV absorbers |
-
1987
- 1987-04-22 KR KR870003887A patent/KR880012569A/en not_active Application Discontinuation
- 1987-07-15 JP JP62174982A patent/JPS63267766A/en active Granted
- 1987-09-22 DE DE19873731860 patent/DE3731860A1/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
JPS63267766A (en) | 1988-11-04 |
KR880012569A (en) | 1988-11-28 |
DE3731860A1 (en) | 1988-11-10 |
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