JPH0153264B2 - - Google Patents
Info
- Publication number
- JPH0153264B2 JPH0153264B2 JP6526281A JP6526281A JPH0153264B2 JP H0153264 B2 JPH0153264 B2 JP H0153264B2 JP 6526281 A JP6526281 A JP 6526281A JP 6526281 A JP6526281 A JP 6526281A JP H0153264 B2 JPH0153264 B2 JP H0153264B2
- Authority
- JP
- Japan
- Prior art keywords
- trimethylphenol
- reaction
- parts
- cyclohexadien
- trimethyl
- 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
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ULGPAXANYFUWRP-UHFFFAOYSA-N 4-hydroxy-2,4,6-trimethylcyclohexa-2,5-dien-1-one Chemical compound CC1=CC(C)(O)C=C(C)C1=O ULGPAXANYFUWRP-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- -1 phenol compound Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IGWHDMPTQKSDTL-JXOAFFINSA-N TMP Chemical compound O=C1NC(=O)C(C)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(O)=O)O1 IGWHDMPTQKSDTL-JXOAFFINSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- WGHKKEJHRMUKDK-UHFFFAOYSA-N cyclohexa-2,5-dien-1-one Chemical compound O=C1C=CCC=C1 WGHKKEJHRMUKDK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- FINHMKGKINIASC-UHFFFAOYSA-N tetramethyl-pyrazine Natural products CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、2,4,6―トリメチルフエノール
を酸化して4―ヒドロキシ―2,4,6―トリメ
チル―2,5―シクロヘキサジエン―1―オンを
高収率で製造する方法に関する。
4―ヒドロキシ―2,4,6―トリメチル―
2,5―シクロヘキサジエン―1―オンは塩基の
存在下で容易に転位反応を起こし、2,3,6―
トリメチルヒドロキノンを生成する。この2,
3,6―トリメチルヒドロキノンは、酸化防止剤
や重合禁止剤として用いられるばかりでなく、ビ
タミンEの製造原料として非常に有用である。
4―ヒドロキシ―2,4,6―トリメチル―
2,5―シクロヘキサジエン―1―オンの製造方
法としては、種々提案されており、例えばサルコ
ミン触媒を用いて有機溶媒中で2,4,6―トリ
メチルフエノールを分子状酸素で酸化する方法
(例えばGer.Offen.2747497)やアルカリ水溶液中
で2,4,6―トリメチルフエノールを分子状酸
素で酸化する方法(例えば特開昭50―4044号)な
どがあげられる。しかし、いずれの方法において
も、2,4,6―トリメチルフエノールは高純度
のものであることが必要であり、また高価な試剤
が必要であつたり、あるいは目的生成物への選択
性が十分高いとは言い難いという欠点があつた。
本発明者らは、こうした従来の4―ヒドロキシ
―2,4,6―トリメチル―2,5―シクロヘキ
サジエン―1―オンの製造方法の欠点を克服する
ため種々の検討を重ねた結果2,4,6―トリメ
チルフエノールを酸化するに当り、ある種のフエ
ノール化合物を共存させることにより、目的の4
―ヒドロキシ―2,4,6―トリメチル―2,5
―シクロヘキサジエン―1―オンへの選択率が画
期的に向上することを見出し、この知見に基づき
本発明をなすに至つた。
すなわち本発明は、2,4,6―トリメチルフ
エノールを一般式
(式中のR1ないしR5は、水素原子又は低級アル
キル基を示し、それらは互いに同じでも又異なつ
ていてもよい)
で表わされるフエノール化合物(ただし2,4,
6―トリメチルフエノールを除く)の1種又は2
種以上の存在下で酸化することを特徴とする4―
ヒドロキシ―2,4,6―トリメチル―2,5―
シクロヘキサジエン―1―オンの製造方法を提供
するものである。
本発明方法においては、原料として用いられる
2,4,6―トリメチルフエノールは、いかなる
方法で合成されたものでもよい。
本発明の酸化反応は反応方法を問わず、液体媒
体の存在下でも不存在下でも実施することができ
るが、好ましくは、液体媒体中で行なわれる。こ
の液体媒体としては、例えば、水、メタノール、
エタノール、n―プロパノール、i―プロパノー
ル、n―ブタノール、i―ブタノール、t―ブタ
ノール、四塩化炭素、クロロホルム、アセトニト
リル、ジメチルアセトアミド、ジメチルホルムア
ミド、アセトン、メチルエチルケトン、シクロヘ
キサン、ベンゼン、トルエンなどがあり、さらに
水と前記有機液体媒体との溶液も用いられる。
酸化反応は例えば、液体媒体中に溶解又は懸濁
した2,4,6―トリメチルフエノールと分子状
酸素又は、分子状酸素含有ガスを接触せしめる方
法や液体媒体中に溶解又は懸濁した2,4,6―
トリメチルフエノールに過酸化水素を滴下する方
法などにより実施される。この場合、分子状酸素
又は分子状酸素含有ガスは、例えば、常圧〜80
Kg/cm2Gの範囲で、また過酸化水素は例えば、30
重量%程度の過酸化水素水として用いられる。
この酸化反応はアルカリ条件下で行うのが好ま
しい。このアルカリ条件は特に制限はないが、ア
ルカリ金属もしくはその化合物又はアルカリ土類
金属もしくはその化合物の添加により調整するの
が好ましい。
酸化反応の反応温度は、目的の4―ヒドロキシ
―2,4,6―トリメチル―2,5―シクロヘキ
サジエン―1―オンが生成するが、分解又は変化
しない温度であれば十分であるが、通常0〜80℃
の範囲が好ましい。反応温度が0℃未満では反応
が、実質的に進まず、また80℃を越えると目的化
合物の選択率が低下する。また反応時間は10分〜
5時間の範囲が好ましい。
本発明方法において添加剤として用いられる、
前記一般式で表わされるフエノール化合物の例と
しては、2,3―キシレノール、2,4―キシレ
ノール、2,5―キシレノール、2,6―キシレ
ノール、2,3,6―トリメチルフエノール、
2,6―ジ―tert―ブチル―4―メチルフエノー
ル、2,4,6―トリ―tert―ブチルフエノール
などをあげることができる。これらの化合物の2
種以上を併用することも可能である。この化合物
は、精製した2,4,6―トリメチルフエノール
を用いて別に添加剤として加える場合ばかりでな
く、2,4,6―トリメチルフエノール中に、そ
れを合成した際の副生物の一つとして含まれてい
る形で用いてもよい。
本発明において、前記一般式で表わされるフエ
ノール化合物の添加量は、2,4,6―トリメチ
ルフエノール1モルに対し、通常0.001〜100モル
の範囲であり、好ましくは0.05〜10.0モル、より
好ましくは0.1〜5.0モルの範囲である。この場
合、その添加量が0.001モル未満では、実質的な
効果が認められず、また100モルより多いと、反
応液量の増加や添加物の酸化による副生物の増加
などによつて経済的な損失が生じるので好ましく
ない。
このように、本発明方法によれば、2,4,6
―トリメチルフエノールの酸化による4―ヒドロ
キシ―2,4,6―トリメチル―2,5―シクロ
ヘキサジエン―1―オンの収率を画期的に向上さ
せることができる。
次に本発明を実施例に基づきさらに詳細に説明
する。なお各例中における部は重量部を示し、ま
た%はモル%を示す。反応生成物の組成分析は、
ガスクロマトグラフイーによつて行つた。
実施例1〜3及び比較例1〜3
ガス導入部を有し、温度計及び撹拌機を装備し
た200ml容ステンレス製オートクレーブに水100
部、水酸化ナトリウム3.5部と下記第1表に示す
量の2,4,6―トリメチルフエノール(以下
TMPと略記する)及び2,6―キシレノールを
仕込み、30Kg/cm2Gの酸素圧をかけ、内温を30℃
に保ち、激しく撹拌しながら4.5時間反応させた。
反応終了後、反応生成物を取り出し分析した結果
を第1表に示した。なお表中HTCDは4―ヒド
ロキシ―2,4,6―トリメチル―2,5―シク
ロヘキサジエン―1―オンを示す。
The present invention relates to a method for producing 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadien-1-one in high yield by oxidizing 2,4,6-trimethylphenol. 4-hydroxy-2,4,6-trimethyl-
2,5-cyclohexadien-1-one easily undergoes a rearrangement reaction in the presence of a base, resulting in 2,3,6-
Produces trimethylhydroquinone. This 2,
3,6-trimethylhydroquinone is not only used as an antioxidant and polymerization inhibitor, but is also very useful as a raw material for producing vitamin E. 4-hydroxy-2,4,6-trimethyl-
Various methods for producing 2,5-cyclohexadien-1-one have been proposed, including a method in which 2,4,6-trimethylphenol is oxidized with molecular oxygen in an organic solvent using a sarcomine catalyst (e.g. Ger. Offen. 2747497) and a method of oxidizing 2,4,6-trimethylphenol with molecular oxygen in an alkaline aqueous solution (for example, JP-A-50-4044). However, in either method, 2,4,6-trimethylphenol must be of high purity, require expensive reagents, or have sufficiently high selectivity to the desired product. The drawback was that it was difficult to say. The present inventors have conducted various studies in order to overcome the shortcomings of the conventional method for producing 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadien-1-one, and as a result2,4 When oxidizing ,6-trimethylphenol, the objective 4
-Hydroxy-2,4,6-trimethyl-2,5
It was discovered that the selectivity to -cyclohexadien-1-one was dramatically improved, and the present invention was completed based on this finding. That is, the present invention provides 2,4,6-trimethylphenol with the general formula (In the formula, R 1 to R 5 represent a hydrogen atom or a lower alkyl group, and they may be the same or different from each other.)
1 or 2 of (excluding 6-trimethylphenol)
4-, which is characterized by being oxidized in the presence of more than one species.
Hydroxy-2,4,6-trimethyl-2,5-
A method for producing cyclohexadien-1-one is provided. In the method of the present invention, 2,4,6-trimethylphenol used as a raw material may be synthesized by any method. The oxidation reaction of the present invention can be carried out in the presence or absence of a liquid medium, regardless of the reaction method, but is preferably carried out in a liquid medium. Examples of this liquid medium include water, methanol,
Ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, carbon tetrachloride, chloroform, acetonitrile, dimethylacetamide, dimethylformamide, acetone, methyl ethyl ketone, cyclohexane, benzene, toluene, etc. Solutions of water and the organic liquid medium described above may also be used. The oxidation reaction can be carried out, for example, by contacting 2,4,6-trimethylphenol dissolved or suspended in a liquid medium with molecular oxygen or a molecular oxygen-containing gas, or by contacting 2,4,6-trimethylphenol dissolved or suspended in a liquid medium. ,6-
This is carried out by dropping hydrogen peroxide into trimethylphenol. In this case, the molecular oxygen or molecular oxygen-containing gas is, for example, at normal pressure to 80
Kg/cm 2 G and hydrogen peroxide e.g.
It is used as a hydrogen peroxide solution of about % by weight. This oxidation reaction is preferably carried out under alkaline conditions. The alkaline conditions are not particularly limited, but are preferably adjusted by adding an alkali metal or a compound thereof, or an alkaline earth metal or a compound thereof. The reaction temperature for the oxidation reaction is sufficient if the target 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadien-1-one is produced but does not decompose or change. 0~80℃
A range of is preferred. If the reaction temperature is less than 0°C, the reaction will not substantially proceed, and if it exceeds 80°C, the selectivity of the target compound will decrease. Also, the reaction time is 10 minutes ~
A range of 5 hours is preferred. used as an additive in the method of the present invention,
Examples of the phenol compound represented by the above general formula include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol,
Examples include 2,6-di-tert-butyl-4-methylphenol and 2,4,6-tri-tert-butylphenol. 2 of these compounds
It is also possible to use more than one species in combination. This compound is added not only as a separate additive using purified 2,4,6-trimethylphenol, but also as one of the by-products when it is synthesized into 2,4,6-trimethylphenol. It may also be used in a contained form. In the present invention, the amount of the phenol compound represented by the above general formula added is generally in the range of 0.001 to 100 mol, preferably 0.05 to 10.0 mol, more preferably 0.05 to 10.0 mol, per 1 mol of 2,4,6-trimethylphenol. It ranges from 0.1 to 5.0 moles. In this case, if the amount added is less than 0.001 mol, no substantial effect will be observed, and if it is more than 100 mol, it will not be economical due to an increase in the amount of reaction liquid and an increase in by-products due to oxidation of the additive. This is not preferable because it causes loss. Thus, according to the method of the present invention, 2, 4, 6
- The yield of 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadien-1-one by oxidation of trimethylphenol can be dramatically improved. Next, the present invention will be explained in more detail based on examples. In each example, parts indicate parts by weight, and % indicates mol%. Compositional analysis of reaction products
This was done by gas chromatography. Examples 1 to 3 and Comparative Examples 1 to 3 100ml of water was placed in a 200ml stainless steel autoclave equipped with a gas inlet, a thermometer, and a stirrer.
part, 3.5 parts of sodium hydroxide and the amounts of 2,4,6-trimethylphenol (hereinafter referred to as
(abbreviated as TMP) and 2,6-xylenol, an oxygen pressure of 30 kg/cm 2 G was applied, and the internal temperature was kept at 30°C.
The reaction was carried out for 4.5 hours while stirring vigorously.
After the reaction was completed, the reaction product was taken out and analyzed. The results are shown in Table 1. Note that HTCD in the table indicates 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadien-1-one.
【表】
実施例 4
実施例1と同様のオートクレーブにTMP7.5
部、水100部、水酸化ナトリウム3.5部及び2,6
―ジ―tert―ブチル―4―メチルフエノール7.5部
を仕込み30Kg/cm2Gの酸素圧をかけ、内温を30℃
に保ち、激しく撹拌しながら4.5時間反応させた。
反応生成物を取り出し分析したところ、TMP転
化率72.2%、HTCD選択率64.5%であつた。
実施例 5及び6
実施例1と同様のオートクレーブに水100部、
水酸化ナトリウム3.5部と下記第2表に示した量
のTMP、2,6―キシレノール及び2,6―ジ
―tert―ブチルフエノールを仕込み、30Kg/cm2G
の酸素圧をかけ内温を30℃に保ち、激しく撹拌し
ながら、4.5時間反応させた。反応生成物を取り
出し分析した結果を第2表に示す。[Table] Example 4 TMP7.5 in the same autoclave as Example 1
parts, 100 parts of water, 3.5 parts of sodium hydroxide and 2.6 parts
- 7.5 parts of di-tert-butyl-4-methylphenol was added, an oxygen pressure of 30 kg/cm 2 G was applied, and the internal temperature was raised to 30°C.
The reaction was carried out for 4.5 hours while stirring vigorously.
When the reaction product was taken out and analyzed, it was found that the TMP conversion rate was 72.2% and the HTCD selectivity was 64.5%. Examples 5 and 6 100 parts of water was added to the same autoclave as in Example 1.
3.5 parts of sodium hydroxide and the amounts of TMP, 2,6-xylenol and 2,6-di-tert-butylphenol shown in Table 2 below were charged, and 30Kg/cm 2 G
of oxygen pressure was applied, the internal temperature was maintained at 30°C, and the mixture was reacted for 4.5 hours with vigorous stirring. The reaction products were extracted and analyzed, and the results are shown in Table 2.
【表】
実施例 7
実施例1と同様のオートクレーブにTMP10.5
部、2,6―キシレノール3.0部、2,6―ジ―
tert―ブチルフエノール1.5部、水100部及び水酸
化ナトリウム3.5部を仕込み80Kg/cm2Gの酸素圧
をかけ内温を30℃に保ち、激しく撹拌しながら
3.5時間反応させた。反応生成物を取り出し分析
したところTMP転化率99.0%、HTCD選択率
67.7%であつた。
実施例8、9及び比較例4、5
TMP1.5部、NaOH0.35部、水30部、及び下記
第3表に示した添加剤を0.2〜0.3部仕込み、反応
液を50℃に保ち、常圧で3時間酸素をバブリング
した。反応生成物を取り出し分析した結果を第3
表に示した。[Table] Example 7 TMP10.5 in the same autoclave as Example 1
part, 2,6-xylenol 3.0 parts, 2,6-di-
Add 1.5 parts of tert-butylphenol, 100 parts of water, and 3.5 parts of sodium hydroxide, apply oxygen pressure of 80 kg/cm 2 G, keep the internal temperature at 30°C, and stir vigorously.
The reaction was allowed to proceed for 3.5 hours. When the reaction product was taken out and analyzed, the TMP conversion rate was 99.0% and the HTCD selectivity was found to be 99.0%.
It was 67.7%. Examples 8 and 9 and Comparative Examples 4 and 5 1.5 parts of TMP, 0.35 parts of NaOH, 30 parts of water, and 0.2 to 0.3 parts of the additives shown in Table 3 below were charged, and the reaction solution was kept at 50°C. Oxygen was bubbled for 3 hours at normal pressure. The results of extracting and analyzing the reaction products are shown in the third column.
Shown in the table.
Claims (1)
キル基を示し、それらは互いに同じでも又、異な
つていてもよい。) で表わされるフエノール化合物(ただし2,4,
6―トリメチルフエノールを除く)の1種又は2
種以上の存在下で酸化することを特徴とする4―
ヒドロキシ―2,4,6―トリメチル―2,5―
シクロヘキサジエン―1―オンの製造方法。[Claims] 1 2,4,6-trimethylphenol expressed by the general formula (In the formula, R 1 to R 5 represent a hydrogen atom or a lower alkyl group, and they may be the same or different from each other.)
1 or 2 of (excluding 6-trimethylphenol)
4-, which is characterized by being oxidized in the presence of more than one species.
Hydroxy-2,4,6-trimethyl-2,5-
A method for producing cyclohexadien-1-one.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6526281A JPS57183734A (en) | 1981-05-01 | 1981-05-01 | Production of 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadiene- 1-one |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6526281A JPS57183734A (en) | 1981-05-01 | 1981-05-01 | Production of 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadiene- 1-one |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57183734A JPS57183734A (en) | 1982-11-12 |
JPH0153264B2 true JPH0153264B2 (en) | 1989-11-13 |
Family
ID=13281819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6526281A Granted JPS57183734A (en) | 1981-05-01 | 1981-05-01 | Production of 4-hydroxy-2,4,6-trimethyl-2,5-cyclohexadiene- 1-one |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57183734A (en) |
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JP6118733B2 (en) * | 2011-02-07 | 2017-04-19 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Method for oxidation of mesitol |
-
1981
- 1981-05-01 JP JP6526281A patent/JPS57183734A/en active Granted
Cited By (1)
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Also Published As
Publication number | Publication date |
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JPS57183734A (en) | 1982-11-12 |
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