JPH0139A - Method for producing 2,4-dichloro-3-methyl-6-tert-butylphenol - Google Patents
Method for producing 2,4-dichloro-3-methyl-6-tert-butylphenolInfo
- Publication number
- JPH0139A JPH0139A JP62-155995A JP15599587A JPH0139A JP H0139 A JPH0139 A JP H0139A JP 15599587 A JP15599587 A JP 15599587A JP H0139 A JPH0139 A JP H0139A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- dichloro
- butylphenol
- tert
- reaction
- 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.)
- Granted
Links
- MXNRALZQWPSLPB-UHFFFAOYSA-N 6-tert-butyl-2,4-dichloro-3-methylphenol Chemical compound CC1=C(Cl)C=C(C(C)(C)C)C(O)=C1Cl MXNRALZQWPSLPB-UHFFFAOYSA-N 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- WYSSJDOPILWQDC-UHFFFAOYSA-N 2,4-ditert-butyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1C(C)(C)C WYSSJDOPILWQDC-UHFFFAOYSA-N 0.000 description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- GIXSFSVVKULPEK-UHFFFAOYSA-N 2,4-dichloro-3-methylphenol Chemical compound CC1=C(Cl)C=CC(O)=C1Cl GIXSFSVVKULPEK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- SXHLRMKATYCFRY-UHFFFAOYSA-N 2,6-dichloro-3-methylphenol Chemical compound CC1=CC=C(Cl)C(O)=C1Cl SXHLRMKATYCFRY-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
- SYZQFPNVWMIJTO-UHFFFAOYSA-N 2-tert-butyl-4,6-dichlorophenol Chemical compound CC(C)(C)C1=CC(Cl)=CC(Cl)=C1O SYZQFPNVWMIJTO-UHFFFAOYSA-N 0.000 description 1
- CIAHODRPDSCRPQ-UHFFFAOYSA-N 4,6-ditert-butyl-2-chloro-3-methylphenol Chemical compound CC1=C(Cl)C(O)=C(C(C)(C)C)C=C1C(C)(C)C CIAHODRPDSCRPQ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 and among these Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 150000002672 m-cresols Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、２．４−ジクロル−３−メチル−６−ターシ
ャリーブチルフェノールの新しい製造法に関するもので
ある。２，４−ジクロル−３−メチル−６−ターシャリ
ーブチルフェノールを脱ターシヤリーブチル化すること
によって得られる２゜４−ジクロル−３−メチルフェノ
ールは、農薬、写真剤等の原料として有用なものである
。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a new method for producing 2,4-dichloro-3-methyl-6-tert-butylphenol. 2゜4-dichloro-3-methylphenol obtained by detertiary-butylation of 2,4-dichloro-3-methyl-6-tert-butylphenol is useful as a raw material for agricultural chemicals, photographic agents, etc. be.
〈従来の技術及びその問題点〉
一般に２．４−ジクロル−３−メチルフェノールの合成
は、例えば特公昭４２−１３８５８号では２，３゜６−
ドリクロルトルエンとメタノールの反応により、２．４
−ジクロル−３−メチルフェノールを得ているが、収率
が低く、しかも大量の苛性ソーダを使用せねばならず工
業的に不利である。<Prior art and its problems> In general, 2,4-dichloro-3-methylphenol is synthesized using 2,3°6-
By the reaction of dolichlortoluene and methanol, 2.4
-Dichloro-3-methylphenol is obtained, but the yield is low and a large amount of caustic soda must be used, which is industrially disadvantageous.
又、Ｊ、 Ａｍ、Ｃｈｅｍ、 Ｓｏｃ ５７．２１７６
（１９３５） にはｍ−クレゾールをスルホン化し
、次いでニトロベンゼン溶媒中で塩素ガスによりクロル
化した後、スルホン基を加水分解して２−クロル−３−
メチルフェノール、２，６−ジクロル−３−メチルフェ
ノールなどの異性体と共に２．４−ジクロル−３−メチ
ルフェノールを得る方法が記述されているが、この方法
の工業的実施には、スルホン化、加水分解という厄介な
プロセスを必要とする上、異性体を分離しなければなら
ないという困難な問題がある。Also, J, Am, Chem, Soc 57.2176
(1935) sulfonated m-cresol, then chlorinated it with chlorine gas in a nitrobenzene solvent, and then hydrolyzed the sulfone group to form 2-chloro-3-
A method for obtaining 2,4-dichloro-3-methylphenol along with isomers such as methylphenol and 2,6-dichloro-3-methylphenol is described, but the industrial implementation of this method requires sulfonation, It requires a cumbersome process of hydrolysis, and the isomers have to be separated, which is a difficult problem.
又、特公昭６１−６００５６号では３−メチル−６−タ
ーシャリーブチルフェノールを出発原料として２゜４−
ジクロル−３−メチル−６−ターシャリーブチルフェノ
ールを合成した後、脱ターンヤリブチル化シて２．４−
ジクロル−３−メチルフェノールを得ているが、原料の
３−メチル−６−ターシャリーブチルフェノールは、−
船釣には３−メチル−４，６−ジターシャリーブチルフ
ェノールを部分的に脱アルキル化した後、精留等の分離
手段によって得るため、工業的には煩雑な工程を行わね
ばならないという不利がある。In addition, in Japanese Patent Publication No. 61-60056, 2゜4-
After synthesizing dichloro-3-methyl-6-tert-butylphenol, de-turning butylation was performed to obtain 2.4-tert-butylphenol.
Dichloro-3-methylphenol is obtained, but the raw material 3-methyl-6-tert-butylphenol is -
Boat fishing has the disadvantage that 3-methyl-4,6-ditertiarybutylphenol is partially dealkylated and then obtained by separation means such as rectification, which is a complicated process from an industrial perspective. .
更にＪ、 Ａｍ、 Ｃｈｅｍ、 Ｓｏｃ ７６、４９７
７ （１９５４） には３−メチル−４，６−ジター
ンヤリープチルフエノールを塩素化すると、最初に２−
クロル−３−メチル−４，６−ジターシャリーブチルフ
ェノールが得られ、更に塩素化すると２．４−ジクロル
−３−メチル−６−ターシャリーブチルフェノールと新
規化合物である２、４−ジクロル−３−メチル−４，６
−ジターシャリ−ブチル２，５−シクロヘキサジエン（
Ａ） が得られるとの記載がある。Further J, Am, Chem, Soc 76, 497
7 (1954), when 3-methyl-4,6-diternarybutylphenol is chlorinated, 2-
Chloro-3-methyl-4,6-ditertiarybutylphenol is obtained, and further chlorination produces 2,4-dichloro-3-methyl-6-tertiarybutylphenol and a new compound, 2,4-dichloro-3-methyl. -4,6
-ditert-butyl 2,5-cyclohexadiene (
A) It is stated that the following can be obtained.
しかしながら、本発明者等が上記記述を追試するべく、
その類似化合物である２、４−ジブロム−３−メチル−
６−ターシャリーブチルフェノールの合成について具体
的に記載された方法（同文献第４９７８頁、右欄下から
１２行〜同第４９７９頁左欄第７行目）に準じて、目的
とする２゜４−ジクロル−３−メチル−６−ターンヤリ
−ブチルフェノールを合成したところ、同文献の当初に
記載の通り、新規化合物（Ａ） が相当量生成し、目
的とする２、４−ジクロル−３−メチル−６−ターシャ
リーブチルフェノールの収率は、約３０％にとどまった
。However, in order to retest the above description, the present inventors
Its similar compound 2,4-dibromo-3-methyl-
The desired 2°4 -Dichloro-3-methyl-6-ternary-butylphenol was synthesized, and as described at the beginning of the same document, a considerable amount of the new compound (A) was produced, and the desired 2,4-dichloro-3-methyl- The yield of 6-tert-butylphenol remained at about 30%.
本発明者らは、上記実情に鑑み、３−メチル−４，６−
ジターシャリーブチルフェノールを出発原料とし、高収
率で目的とする２、４−ジクロル−６−ターシャリーブ
チルフェノールを選択的に製造する方法について、鋭意
研究・検討を重ねた結果、本発明を完成するに至ったの
である。In view of the above circumstances, the present inventors have determined that 3-methyl-4,6-
As a result of extensive research and consideration on a method for selectively producing the desired 2,4-dichloro-6-tert-butylphenol in high yield using di-tert-butylphenol as a starting material, we have completed the present invention. It has come to this.
く問題を解決するための手段〉
本発明は、３−メチル−４，６−ジターシャリーブチル
フェノールに、好ましくは１５〜５０℃の温度範囲で、
有機溶媒中、鉄系触媒の存在下、塩素ガスを作用させる
ことを特徴とする２、４−ジクロル−３−メチル−６−
ターシャリーブチルフェノールの製造方法である。Means for Solving the Problems> The present invention provides 3-methyl-4,6-ditertiarybutylphenol, preferably at a temperature range of 15 to 50°C.
2,4-dichloro-3-methyl-6-, characterized in that it is treated with chlorine gas in an organic solvent in the presence of an iron-based catalyst.
This is a method for producing tert-butylphenol.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
原料の３−メチル−４，６−ジターシャリーブチルフェ
ノールは公知の方法で製造される。たとえば、３−メチ
ルフェノールを硫酸等の酸性触媒の存在下、インブチレ
ンとの反応により容易に得ることができる。The raw material 3-methyl-4,6-ditertiarybutylphenol is produced by a known method. For example, 3-methylphenol can be easily obtained by reaction with imbutylene in the presence of an acidic catalyst such as sulfuric acid.
本発明の方法の特徴は、特定の反応試剤と触媒の組合せ
を選択することにより、目的物を選択的に効率よく製造
することである。A feature of the method of the present invention is that the desired product can be selectively and efficiently produced by selecting a specific combination of reaction reagent and catalyst.
本発明の方法にふいて、塩素化は塩素ガスを用いること
によって行うことが重要であり、かつこの塩素化は１０
〜５０℃の温度範囲内、好ましくは１５〜４０℃の温度
範囲で行うことが好ましい。すなわち、反応を５０℃以
上で実施すると２゜４．６−）リクロルー３−メチルフ
ェノールが多量に副生する傾向を示し、目的物の収率を
下げるだけでなく、目的物からの分離が困難な為、純度
の低下、品質の悪化を招くことになる。In the method of the present invention, it is important to carry out chlorination using chlorine gas, and this chlorination
It is preferred to carry out in the temperature range of -50 °C, preferably in the temperature range of 15-40 °C. In other words, when the reaction is carried out at 50°C or higher, a large amount of 2゜4.6-)lichloro-3-methylphenol tends to be produced as a by-product, which not only lowers the yield of the target product but also makes it difficult to separate it from the target product. This results in a decrease in purity and deterioration in quality.
一方、１０℃以下で実施することもできるが、この場合
反応が遅くなるだけでなく、新規化合物（Ａ） が生
成し７、目的物の収率、純度が低くなる傾向を示す。On the other hand, the reaction can be carried out at a temperature of 10° C. or lower, but in this case, not only does the reaction slow down, but also a new compound (A) is produced, 7 which tends to lower the yield and purity of the target product.
本発明の方法において、原料の３−メチル−４，６−ジ
ターシャリーブチルフェノールの融点が約６０〜６２℃
であるので、反応は有機溶媒の存在下で行われるのが好
ましい。ここで使用する有機溶媒としては、塩素化反応
で用いられる一般的な溶媒が用いられる。In the method of the present invention, the melting point of the raw material 3-methyl-4,6-ditertiarybutylphenol is about 60 to 62°C.
Therefore, the reaction is preferably carried out in the presence of an organic solvent. As the organic solvent used here, a general solvent used in a chlorination reaction is used.
具体的には、クロロホルム、四塩化炭素、ジクロルエタ
ン、テトラクロルエチレン、塩化メチレンもしくはトリ
クロルエチレン等のハロケン化炭化水素、ニトロベンゼ
ンまたはモノクロルベンゼンなどである。Specifically, they include chloroform, carbon tetrachloride, dichloroethane, tetrachloroethylene, halokenated hydrocarbons such as methylene chloride or trichloroethylene, nitrobenzene, and monochlorobenzene.
ここで溶媒の使用量は、原料３−メチル−４，６−ジタ
ーシャリーブチルフェノールの０．５〜１０倍量、より
好ましくは１〜５倍量である。The amount of the solvent used here is 0.5 to 10 times, more preferably 1 to 5 times the amount of the raw material 3-methyl-4,6-ditertiarybutylphenol.
必要以上の使用は容積効率等から考え、工業的でない。Using more than necessary is not industrially practical in terms of volumetric efficiency.
本発明の方法において、最も重要な点は、塩素ガスの作
用を鉄系の触媒の存在下に行うことである。The most important point in the method of the present invention is that the action of chlorine gas is carried out in the presence of an iron-based catalyst.
本発明に用いられる鉄系の触媒としては鉄、塩化鉄、硫
酸鉄などが挙げられ、これらの中でも鉄もしくは鉄粉が
特に好適である。Examples of the iron-based catalyst used in the present invention include iron, iron chloride, and iron sulfate, and among these, iron or iron powder is particularly preferred.
該触媒の使用量は、原料３−メチル−４，６−リターン
ヤリ−ブチルフェノ−９１モル当り０．００１〜０．２
モル、好ましくは０．００５〜０．０５モル、更に好ま
しくは０．０１〜０．０３モルである。The amount of the catalyst used is 0.001 to 0.2 per 91 mol of raw material 3-methyl-4,6-return-butylphenol.
mol, preferably 0.005 to 0.05 mol, more preferably 0.01 to 0.03 mol.
本発明の方法における反応時間は特に限定的ではなく、
１〜２０時間と許容範囲は広い。The reaction time in the method of the present invention is not particularly limited,
The allowable range is 1 to 20 hours.
本発明の方法において、塩素化剤として、塩素ガスを用
いることが重要である。In the method of the present invention, it is important to use chlorine gas as the chlorinating agent.
この塩素化における塩素ガスの使用量は、理論量の若干
過剰、たとえば理論量の１．０３〜１．５倍程度にして
おけば未反応の３−メチル−４，６−ジターシャリーブ
チルフェノール、２−クロル−３−メチル４．６−ジタ
ーシャリーブチルフェノールの残存は見られない。反応
終了後は、通常の塩素化の後処理方法、すなわち、窒素
ガスを通すことにより塩素を除去したり、あるいは亜硫
酸ソーダ等の水溶液で洗浄した後、溶媒を除去し、残分
として目的とする２、４−ジクロル−３−メチル−６−
ターンヤリ−ブチルフェノールを高純度、高収率で得る
ことができる。If the amount of chlorine gas used in this chlorination is slightly in excess of the theoretical amount, for example, about 1.03 to 1.5 times the theoretical amount, unreacted 3-methyl-4,6-ditertiarybutylphenol, 2 No residual -chloro-3-methyl 4,6-ditertiarybutylphenol was observed. After the reaction is completed, use the usual chlorination post-treatment method, that is, remove the chlorine by passing nitrogen gas through it, or wash it with an aqueous solution such as sodium sulfite, remove the solvent, and use the residue as the desired product. 2,4-dichloro-3-methyl-6-
Tertiary butylphenol can be obtained with high purity and high yield.
本発明の反応様式は実施例に記載のものだけに限定され
るものではなく、常圧・加圧の回分式、連続式いずれで
も実施可能であることは言うまでもない。It goes without saying that the reaction mode of the present invention is not limited to that described in the examples, and can be carried out either in a batchwise manner or a continuous manner under normal pressure or pressurization.
〈発明の効果〉
本発明によれば、３−メチル−４，６−ジターシャリー
ブチルフェノールを原料として、高収率かつ高純度で、
目的とする２、４−ジクロル−３−メチル−６−ターシ
ャリーブチルフェノールを工業的に有利に製造すること
ができる。<Effects of the Invention> According to the present invention, using 3-methyl-4,6-ditertiarybutylphenol as a raw material, high yield and high purity,
The desired 2,4-dichloro-3-methyl-6-tert-butylphenol can be produced industrially and advantageously.
〈実施例〉
以下、本発明を実施例により更に詳細に説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
尚、実施例中の部及び％はそれぞれ重量部または重量％
を意味する。In addition, parts and % in the examples are parts by weight or % by weight, respectively.
means.
実施例１
３−メチル−４，６−ジターシャリーブチルフェノール
１１０部（純度９５％）と、四塩化炭素３８０部をフラ
スコに加え、更に鉄粉０１部を加えた後、撹拌上温度２
８〜３２℃に加温し、塩素ガス７４部を５時間で吹込む
。反応後、窒素ガスを通じて溶存する未反応の塩素ガス
を除去する。四塩化炭素を留去後、得られた反応液の組
成はガスクロマトグラフィーで分析の結果、２．４−ジ
クロル−３−メチル−６−ターシャリーブチルフェノー
ルの含量８９％、収率９３ｍｏ１％であった。Example 1 110 parts of 3-methyl-4,6-ditertiarybutylphenol (purity 95%) and 380 parts of carbon tetrachloride were added to a flask, and 01 part of iron powder was added thereto, followed by stirring at an upper temperature of 2
It is heated to 8-32°C and 74 parts of chlorine gas is blown in for 5 hours. After the reaction, dissolved unreacted chlorine gas is removed by passing nitrogen gas. After distilling off carbon tetrachloride, the composition of the resulting reaction solution was analyzed by gas chromatography, and the content of 2,4-dichloro-3-methyl-6-tert-butylphenol was 89%, yield 93mol1%. Ta.
実施例２〜５
実施例１の四塩化炭素の代わりに、下記溶媒を用い、同
条件で反応させて下記純度、収率で２゜４−ジクロル−
３−メチル−６−ターシャリーブチルフェノールを得た
。Examples 2 to 5 In place of carbon tetrachloride in Example 1, the following solvent was used and the reaction was carried out under the same conditions to produce 2°4-dichloro-
3-Methyl-6-tert-butylphenol was obtained.
実施例６
３−メチル−４，６−ジターシャリーブチルフェノール
１２０部（純度９２％）とジクロルエタン６００部をフ
ラスコに加え、更に無水塩化第二鉄１．０部を加えた後
、撹拌下３０〜３５℃で塩素ガス８８部を６時間で吹込
んだ。反応後、窒素ガスを通じて溶存する塩素および塩
化水素を除去する。ジクロルエタンを留去後、得られた
反応液の組成は、ガスクロマトグラフィーで分析の結果
、２．４−ジクロル−３−メチル−６−ターシャリーブ
チルフェノールの含量９２％、収率９４ｍｏ１％であっ
た。Example 6 120 parts of 3-methyl-4,6-ditertiarybutylphenol (purity 92%) and 600 parts of dichloroethane were added to a flask, and then 1.0 part of anhydrous ferric chloride was added, and the mixture was heated for 30 to 35 minutes with stirring. 88 parts of chlorine gas was blown in at 6 hours. After the reaction, dissolved chlorine and hydrogen chloride are removed by passing nitrogen gas. After distilling off dichloroethane, the composition of the reaction solution obtained was analyzed by gas chromatography, and the content of 2.4-dichloro-3-methyl-6-tert-butylphenol was 92% and the yield was 94 mo1%. .
実施例７〜９
実施例６のジクロルエタンの代わりに下記溶媒を用い、
同条件で反応させて、下記純度、収率で２．４−ジクロ
ル−３−メチル−６−ターシャリーブチルフェノールを
得た。Examples 7 to 9 Using the following solvent instead of dichloroethane in Example 6,
The reaction was carried out under the same conditions to obtain 2,4-dichloro-3-methyl-6-tert-butylphenol with the following purity and yield.
実施例１０〜１２
実施例１の反応温度２８〜３２℃の代わりに下記温度条
件下で反応させて、下記純度、収率で２．４−ジクロル
−３−メチル−６−ターンヤリ−ブチルフェノールを得
た。（他の条件は、実施例１と同じ）Examples 10 to 12 Instead of the reaction temperature of 28 to 32°C in Example 1, the reaction was carried out under the following temperature conditions to obtain 2,4-dichloro-3-methyl-6-ternary-butylphenol with the following purity and yield. Ta. (Other conditions are the same as Example 1)
Claims (1)
ールに、鉄系触媒の存在下、塩素ガスを作用させること
を特徴とする２，４−ジクロル−３−メチル−６−ター
シャリーブチルフェノールの製造方法 ２、塩素ガスの作用を、１０〜５０℃の温度範囲で行う
特許請求の範囲第１項に記載の方法。 ３、塩素ガスの作用を、有機溶媒中で行う特許請求の範
囲第１項又は第２項に記載の方法[Claims] 2,4-dichloro-3-methyl-6-, which is characterized in that 1,3-methyl-4,6-ditertiarybutylphenol is treated with chlorine gas in the presence of an iron-based catalyst. Method 2 for producing tertiary-butylphenol: The method according to claim 1, wherein the action of chlorine gas is carried out at a temperature range of 10 to 50°C. 3. The method according to claim 1 or 2, in which the action of chlorine gas is carried out in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155995A JPH07108874B2 (en) | 1987-06-22 | 1987-06-22 | Method for producing 2,4-dichloro-3-methyl-6-tert-butylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155995A JPH07108874B2 (en) | 1987-06-22 | 1987-06-22 | Method for producing 2,4-dichloro-3-methyl-6-tert-butylphenol |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPS6439A JPS6439A (en) | 1989-01-05 |
| JPH0139A true JPH0139A (en) | 1989-01-05 |
| JPH07108874B2 JPH07108874B2 (en) | 1995-11-22 |
Family
ID=15618044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62155995A Expired - Lifetime JPH07108874B2 (en) | 1987-06-22 | 1987-06-22 | Method for producing 2,4-dichloro-3-methyl-6-tert-butylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07108874B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003225228A1 (en) | 2002-05-03 | 2003-11-17 | Donnelly Corporation | Object detection system for vehicle |
| JP4929746B2 (en) * | 2006-02-13 | 2012-05-09 | 株式会社明電舎 | Engine test equipment |
| JP6270849B2 (en) * | 2013-08-09 | 2018-01-31 | 株式会社小糸製作所 | Vehicle lamp |
-
1987
- 1987-06-22 JP JP62155995A patent/JPH07108874B2/en not_active Expired - Lifetime
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