JPH028033B2 - - Google Patents
Info
- Publication number
- JPH028033B2 JPH028033B2 JP57058984A JP5898482A JPH028033B2 JP H028033 B2 JPH028033 B2 JP H028033B2 JP 57058984 A JP57058984 A JP 57058984A JP 5898482 A JP5898482 A JP 5898482A JP H028033 B2 JPH028033 B2 JP H028033B2
- Authority
- JP
- Japan
- Prior art keywords
- butyl
- tert
- lower fatty
- fatty acid
- supporting electrolyte
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 23
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 14
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003115 supporting electrolyte Substances 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- 238000002048 anodisation reaction Methods 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 230000005611 electricity Effects 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- -1 acetoxymethyl group Chemical group 0.000 description 6
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DOZRDZLFLOODMB-UHFFFAOYSA-N 3,5-di-tert-Butyl-4-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=CC(C(C)(C)C)=C1O DOZRDZLFLOODMB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LDPXUTOXMVCPSC-UHFFFAOYSA-N (2-hydroxyphenyl)methyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1O LDPXUTOXMVCPSC-UHFFFAOYSA-N 0.000 description 1
- BXCIJCZLZQLUQF-UHFFFAOYSA-N (3,5-ditert-butyl-1-methyl-4-oxocyclohexa-2,5-dien-1-yl) acetate Chemical compound CC(=O)OC1(C)C=C(C(=O)C(=C1)C(C)(C)C)C(C)(C)C BXCIJCZLZQLUQF-UHFFFAOYSA-N 0.000 description 1
- IHHBZEDPSGRLEW-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl propanoate Chemical compound CCC(=O)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 IHHBZEDPSGRLEW-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
Description
本発明は陽極酸化反応を利用して、２，６−ジ
−tert−ブチル−４−アシロキシメチルフエノー
ルを製造する方法に関する。
２，６−ジ−tert−ブチル−４−アシロキシメ
チルフエノールは、フエノール系酸化防止剤の製
造中間体として用いられている。
この化合物の製法としては、２，６−ジ−tert
−ブチルフエノールとパラホルムアルデヒドを酢
酸中で反応させて、４−位置にアセトキシメチル
基を導入する方法（USP 3052715）が公知であ
る。しかしこの方法は、収率が低く、改良が望ま
れていた。
また他の製法として、臭素を触媒に用い、２，
６−ジ−tert−ブチル−４−メチルフエノールと
酢酸を反応させて、４−位置のメチル基をアセト
キシメチル基とする方法（J.Am.Chem.Soc.75巻
734〜736ページ 1953年）が公知である。しか
しこの方法においては、水が共存する場合は、反
応が著しく影響を受け、４−位置がホルミル基の
化合物（後記一般式）が得られ、さらに酢酸銀
を触媒として、２，６−ジ−tert−ブチル−４−
メチルフエノールを酢酸と反応させる方法
（Bull.Chem.Soc.Jpn.631〜２ページ、1979年）が
公知であるが、反応温度が118℃と高温を必要と
する。
一方、電解酸化を利用して、芳香族化合物の側
鎖メチルを酢酸中でアセトキシ化することも、従
来から試みられており、２，６−ジ−tert−ブチ
ル−４−メチルフエノールを陽極酸化することに
関しては、J.Chem.Soc.(C)3214ページ（1971年）
が報告されている。しかし、この文献には、２，
６−ジ−tert−ブチル−４−メチルフエノールを
酢酸ナトリウムの存在下に陽極酸化すると、４−
アセトキシ−２，６−ジ−tert−ブチル−４−メ
チル−シクロヘキサ−２，５−ジエノンが主成分
として得られ、２，６−ジ−tert−ブチル−４−
アセトキシメチルフエノールの収量はわずかであ
ることが開示されているだけである。
これに対し、本発明者らは、２，６−ジ−tert
−ブチル−４−メチルフエノールの電解反応の条
件について更に検討を行ない、酢酸等の低級脂肪
酸の存在下に、下記の陽極酸化反応を行なうにあ
たり、支持電解質として酸性または中性の化合物
を用いることにより、ジエノン化合物（）およ
びアルデヒド化合物（）の副生を抑制し、目的
化合物（）が高収率、高選択率、高電流効率で
得られることを見出
し、本発明を完成するに至つた。
すなわち本発明は、２，６−ジ−tert−ブチル
−４−メチルフエノールを一般式
RCOOH （）
（Ｒは、メチル、エチルまたはプロピル基）で示
される低級脂肪酸を含有する溶媒中で、酸性また
は中性の化合物から選ばれる支持電解質の存在下
に、陽極酸化することを特徴とする一般式
（Ｒは前記同様）で示される２，６−ジ−tert−
ブチル−４−アシロキシメチルフエノールの製法
に関する。
本発明に使用される低級脂肪酸は、前記一般式
（）で示される酢酸、プロピオン酸および酪酸
から選ばれる化合物である。これらの低級脂肪酸
は、更に他の溶媒と併用してもよい。原料や支持
電解質等の各成分の溶解度を向上させ、また電解
効率を向上させ、さらには目的化合物（）の選
択率を向上させ、あるいは端子電圧を低下させる
ために、これら低級脂肪酸に他の溶媒を添加併用
することは有効である。
この目的で用いられる他の溶媒としては、塩化
メチレン、ジクロロエタンどのハロゲン化炭化水
素類、アセトニトリルなどの非プロトン性有機溶
媒、ターシヤリーブタノールなどの第三アルコー
ルがある。これらの中では、とくに塩化メチレン
が好ましい。
使用される支持電解質は、酸性または中性の化
合物から選ばれる少なくとも１種類以上の化合物
である。これらの化合物を使用することにより、
ジエノン化合物（）の副生が抑制され、目的化
合物（）が選択的に得られる。
酸性または中性の化合物のうちでは、とくに硫
酸、硫酸アンモニウムなどの硫酸類、ベンゼンス
ルホン酸、パラトルエンスルホン酸などのスルホ
ン酸類、過塩素酸リチウム、過塩素酸ナトリウム
などの過塩素酸類、臭化リチウム、臭化カリウム
などのアルカリ金属ハロゲン化物、臭化テトラエ
チルアンモニウム、過塩素酸テトラエチルアンモ
ニウム、パラトルエンスルホン酸テトラエチルア
ンモニウムなどのアンモニウム塩類が好適であ
り、必要に応じて１種または２種以上が併用され
る。中でもアンモニウム塩類は、目的化合物
（）の選択率を向上させる点において好適であ
る。
本発明において、２，６−ジ−tert−４−メチ
ルフエノールの仕込濃度は通常約0.01ないし約
2.0M／であり、とくに約0.1ないし約1.0M／
の範囲が好適である。
また低級脂肪酸に添加される第二溶媒の仕込割
合は、通常０〜90容積％の範囲で、溶質の溶解度
および端子電圧を考慮して好適な割合に設定する
ことができる。
さらに支持電解質の仕込割合は、その濃度とし
て、通常0.01ないし3M／、好ましくは0.1ない
し1.5M／の範囲である。
電解セル様式としては、陽陰両極を同一セル中
に対峙させた非分離型セルが使用されるが、各種
多孔質膜、イオン交換膜等で陽陰両極を分離する
分離型セルを使用することもできる。
電極には、白金、ニツケル、鉛あるいは黒鉛な
どの炭素が好適に用いられ、中でも白金または炭
素が好適である。
電解温度は、種々変えることができるが、一般
には低級脂肪酸などの電解液の融点、支持電解質
の溶解性、原料である被電解質あるいは電解によ
つて生成される目的化合物（）の溶解性を考慮
して決定される。本発明では、電解温度をとくに
約10ないし約70℃の範囲とすることが好ましい。
さらに付言すれば、常温常圧下での実施でも十分
な効果が得られる。
電解反応の電流密度は、通常約１〜100ｍＡ／
cm2（約0.1〜10A／ｄm2）の範囲内から選択され、
とくに約５〜50ｍＡ／cm2（約0.5〜5A／ｄm2）の
範囲内が好適である。
通電する電気量は、電流効率を決定する重要な
因子であり、本発明では、理論的必要電気量（原
料２，６−ジ−tert−ブチル−４−メチルフエノ
ール１モル当り、２フアラデー）で充分である
が、必要に応じて更に多量の電気量とすることが
できる。しかしながらこの場合は、前記のアルデ
ヒド化合物（）の生成を抑制するために、上記
理論的電気量の約1.5倍以下に留めることが望ま
しい。
次に実施例により説明する。
実施例 １
50mlの枝付試験管反応器に温度計および２cm×
３cmの黒鉛陽極および２cm×３cmの白金陰極を５
mm隔てて取り付けた。これに２，６−ジ−ｔ−ブ
チル−４−メチルフエノール（以下BHTと略称
する）0.88ｇ、パラトルエンスルホン酸テトラエ
チルアンモニウム1.0ｇ、酢酸30mlを加えて均一
に溶解した。反応器を水浴下に25〜27℃に保ちつ
つ端子電圧19〜20Volt、電流密度10ｍＡ／cm2で
8.0×10-3フアラデーの電気量を通電した。電解
終了後、少量の水で水洗したのち油層をガスクロ
マトグラフイーおよび高速液体クロマトグラフイ
ーで分析したところBHTの転化率は91％、２，
６−ジ−ｔ−ブチル−４−アセトキシメチルフエ
ノール（）の収率は79％（選択率87％、電流効
率79％）で、副生成物は２，６−ジ−ｔ−ブチル
−４−アセトキシ−４−メチル−シクロヘキサ−
２，５−ジエノン（）2.7％および３，５−ジ
−ｔ−ブチル−４−ヒドロキシベンズアルデヒド
（、Ｒ＝CH3）0.7％であつた。
実施例 ２
実施例１において陽極に２cm×３cmの白金を使
用し、パラトルエンスルホン酸テトラエチルアン
モニウムのかわりに臭化テトラエチルアンモニウ
ム0.84ｇを用いた他は全く同様に実施したところ
BHT転化率は70％、目的化合物（、Ｒ＝CH3）
の収率は65％（選択率93％、電流効率46％）であ
つた。
実施例３〜８、比較例１〜２
実施例１において電極、支持電解質および電気
量をそれぞれ変えて行つた実施例３〜８を比較例
１〜２と合わせて表１にまとめて示す。変更した
項目以外は実施例１と同様に行つた。
The present invention relates to a method for producing 2,6-di-tert-butyl-4-acyloxymethylphenol using an anodic oxidation reaction. 2,6-di-tert-butyl-4-acyloxymethylphenol is used as an intermediate in the production of phenolic antioxidants. The method for producing this compound is 2,6-di-tert
A method is known in which an acetoxymethyl group is introduced at the 4-position by reacting -butylphenol and paraformaldehyde in acetic acid (USP 3052715). However, this method had a low yield, and improvements were desired. In addition, as another production method, bromine is used as a catalyst, 2,
A method of converting the methyl group at the 4-position into an acetoxymethyl group by reacting 6-di-tert-butyl-4-methylphenol with acetic acid (J.Am.Chem.Soc. Vol. 75)
734-736, 1953) is publicly known. However, in this method, when water coexists, the reaction is significantly affected and a compound with a formyl group at the 4-position (general formula described later) is obtained. tert-butyl-4-
A method of reacting methylphenol with acetic acid (Bull. Chem. Soc. Jpn. 631-2 pages, 1979) is known, but requires a high reaction temperature of 118°C. On the other hand, attempts have been made to acetoxylate the side chain methyl of aromatic compounds in acetic acid using electrolytic oxidation. Regarding what to do, J.Chem.Soc.(C) page 3214 (1971)
has been reported. However, this document contains 2,
Anodizing 6-di-tert-butyl-4-methylphenol in the presence of sodium acetate gives 4-di-tert-butyl-4-methylphenol.
Acetoxy-2,6-di-tert-butyl-4-methyl-cyclohexa-2,5-dienone was obtained as the main component, and 2,6-di-tert-butyl-4-
Only a small yield of acetoxymethylphenol is disclosed. In contrast, the present inventors have discovered that 2,6-di-tert
- We further investigated the conditions for the electrolytic reaction of butyl-4-methylphenol, and found that when carrying out the following anodic oxidation reaction in the presence of lower fatty acids such as acetic acid, we found that by using an acidic or neutral compound as a supporting electrolyte. It was discovered that the by-products of dienone compounds () and aldehyde compounds () could be suppressed, and the target compound () could be obtained with high yield, high selectivity, and high current efficiency. This led to the completion of the present invention. That is, the present invention deals with the treatment of 2,6-di-tert-butyl-4-methylphenol in an acidic or A general formula characterized by anodization in the presence of a supporting electrolyte selected from neutral compounds. (R is the same as above) 2,6-di-tert-
The present invention relates to a method for producing butyl-4-acyloxymethylphenol. The lower fatty acid used in the present invention is a compound selected from acetic acid, propionic acid, and butyric acid represented by the above general formula (). These lower fatty acids may be further used in combination with other solvents. In order to improve the solubility of each component such as raw materials and supporting electrolytes, improve electrolytic efficiency, further improve the selectivity of the target compound (), or lower the terminal voltage, other solvents may be added to these lower fatty acids. It is effective to use them together. Other solvents used for this purpose include halogenated hydrocarbons such as methylene chloride and dichloroethane, aprotic organic solvents such as acetonitrile, and tertiary alcohols such as tertiary butanol. Among these, methylene chloride is particularly preferred. The supporting electrolyte used is at least one compound selected from acidic or neutral compounds. By using these compounds,
The by-product of the dienone compound () is suppressed, and the target compound () can be selectively obtained. Among acidic or neutral compounds, especially sulfuric acids such as sulfuric acid and ammonium sulfate, sulfonic acids such as benzenesulfonic acid and paratoluenesulfonic acid, perchloric acids such as lithium perchlorate and sodium perchlorate, and lithium bromide. , alkali metal halides such as potassium bromide, ammonium salts such as tetraethylammonium bromide, tetraethylammonium perchlorate, and tetraethylammonium paratoluenesulfonate, and one or more of them may be used in combination as necessary. Ru. Among these, ammonium salts are suitable in that they improve the selectivity of the target compound (). In the present invention, the feed concentration of 2,6-di-tert-4-methylphenol is usually about 0.01 to about
2.0M/, especially about 0.1 to about 1.0M/
A range of is suitable. Further, the charging ratio of the second solvent added to the lower fatty acid is usually in the range of 0 to 90% by volume, and can be set to a suitable ratio in consideration of the solubility of the solute and the terminal voltage. Further, the charging ratio of the supporting electrolyte is generally in the range of 0.01 to 3 M/, preferably 0.1 to 1.5 M/ in terms of its concentration. As for the electrolytic cell format, a non-separated type cell is used in which the positive and negative poles face each other in the same cell, but it is also possible to use a separated type cell in which the positive and negative poles are separated using various porous membranes, ion exchange membranes, etc. You can also do it. Platinum, nickel, lead, or carbon such as graphite is preferably used for the electrode, with platinum or carbon being particularly preferred. The electrolysis temperature can be changed in various ways, but generally it takes into account the melting point of the electrolyte such as lower fatty acids, the solubility of the supporting electrolyte, the solubility of the raw material electrolyte or the target compound produced by electrolysis. Determined by In the present invention, it is particularly preferred that the electrolysis temperature be in the range of about 10 to about 70°C.
Furthermore, sufficient effects can be obtained even when carried out at room temperature and pressure. The current density of electrolytic reaction is usually about 1 to 100 mA/
cm 2 (approximately 0.1 to 10 A/dm 2 ),
In particular, a range of approximately 5 to 50 mA/cm 2 (approximately 0.5 to 5 A/dm 2 ) is suitable. The amount of electricity to be applied is an important factor that determines the current efficiency, and in the present invention, the theoretically required amount of electricity (2 Faradays per mole of raw material 2,6-di-tert-butyl-4-methylphenol) Although this is sufficient, a larger amount of electricity can be used if necessary. However, in this case, in order to suppress the formation of the above-mentioned aldehyde compound (), it is desirable to keep the amount of electricity to about 1.5 times or less of the above-mentioned theoretical amount of electricity. Next, an example will be explained. Example 1 A thermometer and a 2 cm x 50 ml test tube reactor with
3cm graphite anode and 2cm x 3cm platinum cathode
Installed at a distance of mm. To this were added 0.88 g of 2,6-di-t-butyl-4-methylphenol (hereinafter abbreviated as BHT), 1.0 g of tetraethylammonium p-toluenesulfonate, and 30 ml of acetic acid, and the mixture was uniformly dissolved. The reactor was kept in a water bath at 25-27°C with a terminal voltage of 19-20 Volt and a current density of 10 mA/ cm2.
An amount of electricity of 8.0×10 -3 Huaday was applied. After the electrolysis was completed, the oil layer was washed with a small amount of water and analyzed by gas chromatography and high performance liquid chromatography, and the conversion rate of BHT was 91%.
The yield of 6-di-t-butyl-4-acetoxymethylphenol () was 79% (selectivity 87%, current efficiency 79%), and the by-product was 2,6-di-t-butyl-4- Acetoxy-4-methyl-cyclohexa-
2,5-dienone (2.7%) and 3,5-di-t-butyl-4-hydroxybenzaldehyde (,R= CH3 ) 0.7%. Example 2 The same procedure as in Example 1 was carried out except that 2 cm x 3 cm of platinum was used for the anode and 0.84 g of tetraethylammonium bromide was used instead of tetraethylammonium paratoluenesulfonate.
BHT conversion rate is 70%, target compound (,R=CH 3 )
The yield was 65% (selectivity 93%, current efficiency 46%). Examples 3 to 8, Comparative Examples 1 to 2 Examples 3 to 8, which were carried out in Example 1 by changing the electrode, supporting electrolyte, and quantity of electricity, are summarized in Table 1 together with Comparative Examples 1 to 2. The same procedure as in Example 1 was carried out except for the changed items.
【表】
実施例 ９
実施例１において溶媒として酢酸7.5mlおよび
塩化メチレン22.5mlの混合溶媒を用いた以外は全
く同様に電解反応を行つた。電解終了時まで端子
電圧は７〜8Voltに維持され、分析の結果BHT
転化率は91％、目的化合物（）の収率は88％
（選択率97％、電流効率88％）であつた。このと
きの副生物として（）1.0％および３，５−ジ
−ｔ−ブチル−４−ヒドロキシベンズアルデヒド
（）1.3％を確認した。
実施例 10
実施例９において支持電解質としてパラトルエ
ンスルホン酸テトラエチルアンモニウム1.0ｇお
よびパラトルエンスルホン酸0.3ｇを用いた以外
は同様に実施した。電解終了時まで端子電圧は５
〜6Voltに維持されBHT転化率は92％、目的化
合物の収率は88％（選択率95％、電流効率88％）
であつた。
実施例 11
実施例１において溶媒を酢酸7.5mlおよびアセ
トニトリル22.5mlの混合溶媒にかえて実施したと
ころ、端子電圧は2.3〜2.5Voltに維持されBHT
転化率は92％、目的化合物（）の収率は73％
（選択率80％、電流効率73％）であつた。
実施例 12
実施例１において溶媒を酢酸27mlおよび第３級
ブチルアルコール３mlの混合溶媒にかえて実施し
た（端子電圧は21〜22Volt）。反応液を分折した
結果BHTの転化率は86％、目的化合物の収率は
76％（選択率85％、電流効率76％）であつた。
実施例 13
実施例１と同じ反応器および電極を使用して
BHT6.17ｇ、酢酸7.5ml、塩化メチレン22.5mlお
よびパラトルエンスルホン酸テトラエチルアンモ
ニウム3.0ｇを均一に溶解したのち、端子電圧
15Volt、電流密度35ｍＡ／cm2で5.6×10-2フアラ
デーの電気量を通電した。電解終了後の反応液を
分折した結果、BHTの転化率は89％、目的化合
物（）の収率は79％（選択率89％、電流効率79
％）であつた。
実施例 14
実施例９において溶媒をプロピオン酸10mlおよ
び塩化メチレン20mlの混合溶媒に変えた以外は全
く同様に電解した。その結果BHTの転化率は94
％、２，６−ジ−ｔ−ブチル−４−プロピオニル
オキシメチルフエノールの収率は82％（選択率88
％、電流効率82％）であつた。
実施例 15
実施例９において溶媒を酪酸10mlおよび塩化メ
チレン20mlの混合溶媒に変えた以外は全く同様に
電解した。その結果BHTの転化率は90％、２，
６−ジ−ｔ−ブチル−４−ブチリルオキシメチル
フエノールの収率は79％（選択率88％、電流効率
79％）であつた。[Table] Example 9 An electrolytic reaction was carried out in exactly the same manner as in Example 1 except that a mixed solvent of 7.5 ml of acetic acid and 22.5 ml of methylene chloride was used as the solvent. The terminal voltage was maintained at 7 to 8 Volt until the end of electrolysis, and as a result of analysis BHT
Conversion rate is 91%, yield of target compound () is 88%
(selectivity 97%, current efficiency 88%). At this time, 1.0% of () and 1.3% of 3,5-di-t-butyl-4-hydroxybenzaldehyde () were confirmed as by-products. Example 10 The same procedure as in Example 9 was carried out except that 1.0 g of tetraethylammonium para-toluenesulfonate and 0.3 g of para-toluenesulfonic acid were used as the supporting electrolyte. The terminal voltage is 5 until the end of electrolysis.
Maintained at ~6 Volt, BHT conversion rate is 92%, target compound yield is 88% (selectivity 95%, current efficiency 88%)
It was hot. Example 11 When the solvent in Example 1 was changed to a mixed solvent of 7.5 ml of acetic acid and 22.5 ml of acetonitrile, the terminal voltage was maintained at 2.3 to 2.5 Volt and BHT
Conversion rate is 92%, yield of target compound () is 73%
(selectivity 80%, current efficiency 73%). Example 12 Example 1 was carried out except that the solvent was changed to a mixed solvent of 27 ml of acetic acid and 3 ml of tertiary butyl alcohol (terminal voltage was 21 to 22 Volt). As a result of fractionating the reaction solution, the conversion rate of BHT was 86%, and the yield of the target compound was
76% (selectivity 85%, current efficiency 76%). Example 13 Using the same reactor and electrodes as Example 1
After uniformly dissolving 6.17 g of BHT, 7.5 ml of acetic acid, 22.5 ml of methylene chloride, and 3.0 g of tetraethylammonium paratoluenesulfonate, the terminal voltage
Electricity of 5.6×10 −2 faradays was applied at 15 Volt and a current density of 35 mA/cm 2 . As a result of fractionating the reaction solution after the completion of electrolysis, the conversion rate of BHT was 89%, and the yield of the target compound () was 79% (selectivity 89%, current efficiency 79%).
%). Example 14 Electrolysis was carried out in exactly the same manner as in Example 9 except that the solvent was changed to a mixed solvent of 10 ml of propionic acid and 20 ml of methylene chloride. As a result, the conversion rate of BHT was 94
%, the yield of 2,6-di-t-butyl-4-propionyloxymethylphenol was 82% (selectivity 88
%, current efficiency 82%). Example 15 Electrolysis was carried out in exactly the same manner as in Example 9 except that the solvent was changed to a mixed solvent of 10 ml of butyric acid and 20 ml of methylene chloride. As a result, the conversion rate of BHT was 90%, 2.
The yield of 6-di-t-butyl-4-butyryloxymethylphenol was 79% (selectivity 88%, current efficiency
79%).
Claims (1)
ノールを一般式 RCOOH （） （Ｒは、メチル、エチルまたはプロピル基）で示
される低級脂肪酸を含有する溶媒中で、酸性また
は中性の化合物から選ばれる支持電解質の存在下
に陽極酸化することを特徴とする一般式 （Ｒは前記同様）で示される２，６−ジ−tert−
ブチル−４−アシロキシメチルフエノールの製
法。 ２ 支持電解質が、硫酸類、スルホン酸類、過塩
素酸類、アルカリ金属ハロゲン化物、アンモニウ
ム塩類から選ばれることを特徴とする特許請求の
範囲第１項に記載の製法。 ３ 陽極が、白金または炭素であることを特徴と
する特許請求の範囲第１項または第２項に記載の
方法。 ４ 該低級脂肪酸を含有する溶媒が、該低級脂肪
酸の他にさらにハロゲン化炭化水素、非プロトン
性有機溶媒および第三アルコールから選ばれる溶
媒を含有することを特徴とする特許請求の範囲第
１項記載の製法。[Claims] 1 2,6-di-tert-butyl-4-methylphenol in a solvent containing a lower fatty acid represented by the general formula RCOOH (R is a methyl, ethyl or propyl group), A general formula characterized by anodization in the presence of a supporting electrolyte selected from acidic or neutral compounds. (R is the same as above) 2,6-di-tert-
Method for producing butyl-4-acyloxymethylphenol. 2. The production method according to claim 1, wherein the supporting electrolyte is selected from sulfuric acids, sulfonic acids, perchloric acids, alkali metal halides, and ammonium salts. 3. The method according to claim 1 or 2, wherein the anode is platinum or carbon. 4. Claim 1, wherein the solvent containing the lower fatty acid further contains, in addition to the lower fatty acid, a solvent selected from halogenated hydrocarbons, aprotic organic solvents, and tertiary alcohols. Manufacturing method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57058984A JPS58177482A (en) | 1982-04-10 | 1982-04-10 | Production of 2,6-di-tert-butyl-4-acyloxymethylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57058984A JPS58177482A (en) | 1982-04-10 | 1982-04-10 | Production of 2,6-di-tert-butyl-4-acyloxymethylphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58177482A JPS58177482A (en) | 1983-10-18 |
| JPH028033B2 true JPH028033B2 (en) | 1990-02-22 |
Family
ID=13100109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57058984A Granted JPS58177482A (en) | 1982-04-10 | 1982-04-10 | Production of 2,6-di-tert-butyl-4-acyloxymethylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58177482A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017009651A1 (en) * | 2015-07-14 | 2017-01-19 | F2G Limited | 2-amino-1,3,4-thiadiazine and 2-amino-1,3,4-oxadiazine based antifungal agents |
-
1982
- 1982-04-10 JP JP57058984A patent/JPS58177482A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017009651A1 (en) * | 2015-07-14 | 2017-01-19 | F2G Limited | 2-amino-1,3,4-thiadiazine and 2-amino-1,3,4-oxadiazine based antifungal agents |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58177482A (en) | 1983-10-18 |
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