JPH0429966A - Production of 2,4-dichloro-3-ethyl-6-nitrophenol - Google Patents
Production of 2,4-dichloro-3-ethyl-6-nitrophenolInfo
- Publication number
- JPH0429966A JPH0429966A JP2227535A JP22753590A JPH0429966A JP H0429966 A JPH0429966 A JP H0429966A JP 2227535 A JP2227535 A JP 2227535A JP 22753590 A JP22753590 A JP 22753590A JP H0429966 A JPH0429966 A JP H0429966A
- Authority
- JP
- Japan
- Prior art keywords
- ethyl
- acid
- chloro
- dichloro
- hydrogen peroxide
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- YTVCECQSAPGJBB-UHFFFAOYSA-N 2,4-dichloro-3-ethyl-6-nitrophenol Chemical compound CCC1=C(Cl)C=C([N+]([O-])=O)C(O)=C1Cl YTVCECQSAPGJBB-UHFFFAOYSA-N 0.000 title description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 12
- MFTBMHRGXBBBOI-UHFFFAOYSA-N 5-chloro-4-ethyl-2-hydroxybenzenesulfonic acid Chemical compound CCC1=CC(O)=C(S(O)(=O)=O)C=C1Cl MFTBMHRGXBBBOI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 6
- DVKVZPIRWWREJC-UHFFFAOYSA-N 4-chloro-3-ethylphenol Chemical compound CCC1=CC(O)=CC=C1Cl DVKVZPIRWWREJC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- AHUIQYHFLOYDGC-UHFFFAOYSA-N 4-ethyl-2-hydroxybenzenesulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C(O)=C1 AHUIQYHFLOYDGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 claims 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims 1
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 6
- RTTKBGCGHTVPGS-UHFFFAOYSA-N 3,5-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid Chemical compound CCC1=C(Cl)C=C(S(O)(=O)=O)C(O)=C1Cl RTTKBGCGHTVPGS-UHFFFAOYSA-N 0.000 abstract description 3
- -1 benzene sulfonic acid compound Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229940092714 benzenesulfonic acid Drugs 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PGVTZHGGFXJPIB-UHFFFAOYSA-N 2,3-dichloro-5-ethylphenol Chemical compound CCC1=CC(O)=C(Cl)C(Cl)=C1 PGVTZHGGFXJPIB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- KXZXZHXQPXXWDR-UHFFFAOYSA-N 1,1-dichloroethane 1,1,2-trichloroethene Chemical group CC(Cl)Cl.ClC=C(Cl)Cl KXZXZHXQPXXWDR-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、カラー写真用シアン発色剤の中間体などとし
て有用な２，４−ジクロロ−３−エチル６−ニトロフェ
ノールの製造法の改良に関する〈従来の技術〉
２、 ４−’）クロロ−３−エチ／１．．−６−ニトロ
フェノールの製造法として、特開昭６１−５７５３６号
公報には、４−クロロ−５−エチルフェノールをハロゲ
ン化炭化水素溶媒中で、無水硫酸錯体を用いるか、ある
いは過剰の濃硫酸中でスルホン化して、２−スルホ−４
−クロロ−５−エチルフェノールとし、これを塩素ガス
又は塩化スルフリルを用いて、塩素化して２−スルホ−
４，６、ジクロロ５−エチルフェノールとし、次に硝酸
を用いてスルホ基をニトロ基て置換して２−エトロー４
，６ジクロルー５−エチル−フェノールを製造する方法
が記載されている。Detailed Description of the Invention <Industrial Application Field> The present invention relates to an improvement in a method for producing 2,4-dichloro-3-ethyl 6-nitrophenol, which is useful as an intermediate for a cyan coloring agent for color photography. <Prior art> 2, 4-') chloro-3-ethyl/1. ．． As a method for producing -6-nitrophenol, JP-A No. 61-57536 discloses that 4-chloro-5-ethylphenol is mixed with a sulfuric anhydride complex in a halogenated hydrocarbon solvent, or with excess concentrated sulfuric acid. 2-sulfo-4
-Chloro-5-ethylphenol is chlorinated using chlorine gas or sulfuryl chloride to produce 2-sulfo-5-ethylphenol.
4,6, dichloro-5-ethylphenol, and then substituted the sulfo group with a nitro group using nitric acid to obtain 2-ethro-4.
, 6 dichloro-5-ethyl-phenol is described.
〈発明が解決しようとする課題〉
特開昭６１−５７５３６号に記載の方法は、塩素化に際
して塩素ガス又は塩化スルフリルを用いる方法であり、
塩素ガスを用いる場合にはその性質上、特殊な安全設備
を必要とすること、又塩化スルフリルを用いる場合には
、試剤が高価であり、かつ有機溶剤中で反応を行なう必
要があり、工業的規模での実施には不利である。<Problem to be solved by the invention> The method described in JP-A-61-57536 uses chlorine gas or sulfuryl chloride during chlorination,
When using chlorine gas, special safety equipment is required due to its nature, and when using sulfuryl chloride, the reagent is expensive and the reaction needs to be carried out in an organic solvent, making it difficult for industrial use. It is disadvantageous for implementation on a large scale.
〈課題を解決するだめの手段〉
本発明は、５−クロロ−４−エチル−２−ヒドロキシベ
ンゼンスルホン酸を、触媒の存在下又は不存在下に、塩
化水素と過酸化水素とによって塩素化して３，５−ジク
ロロ−４−エチル−２−ヒドロキシベンゼンスルホン酸
とし、次いて硝酸を用いてスルホン酸基をニトロ基に置
換することを特徴とする２、４−ジクロロ−３−エチル
−６ニトロフエノールの製造法である。<Means for Solving the Problems> The present invention involves chlorinating 5-chloro-4-ethyl-2-hydroxybenzenesulfonic acid with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst. 2,4-dichloro-3-ethyl-6nitro, which is characterized in that it is made into 3,5-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid, and then the sulfonic acid group is replaced with a nitro group using nitric acid. This is a method for producing phenol.
以下、本発明の方法を詳細に説明する。The method of the present invention will be explained in detail below.
本発明に用いられる５−クロロ−４−エチル２−ヒドロ
キシベンゼンスルホン酸は、４−クロロ−３−エチルフ
ェノールを無水硫酸錯体によってスルホン化する方法、
４−クロロ−３−エチルフェノールを硫酸によりスルホ
ン化する方法、又は４−クロロ−３−エチルフェノール
を溶媒中に於いて、クロロスルホン酸を用いてスルホン
化する方法などによって容易に得られる。5-chloro-4-ethyl 2-hydroxybenzenesulfonic acid used in the present invention can be obtained by sulfonating 4-chloro-3-ethylphenol with a sulfuric anhydride complex.
It can be easily obtained by sulfonating 4-chloro-3-ethylphenol with sulfuric acid, or by sulfonating 4-chloro-3-ethylphenol with chlorosulfonic acid in a solvent.
このスルホン化の溶媒としては、ハロゲン化炭化水素（
例えば、塩化メチレン、クロロホルム、四塩化炭素、ジ
クロロエチレン、ジクロロエタントリクロロエチレン、
トリクロロエタン、テトラクロロエチレン、テトラクロ
ロエタン、ジブロムエタン、クロロベンゼン、０−ジク
ロロベンゼンなど）、ニトロ化炭化水素にトロベンゼン
、０−ニトロトルエンなど）が用いられる。The solvent for this sulfonation is halogenated hydrocarbon (
For example, methylene chloride, chloroform, carbon tetrachloride, dichloroethylene, dichloroethane trichloroethylene,
Trichloroethane, tetrachloroethylene, tetrachloroethane, dibromoethane, chlorobenzene, 0-dichlorobenzene, etc.), nitrated hydrocarbons such as trobenzene, 0-nitrotoluene, etc.) are used.
クロロスルホン酸を用いてスルホン化する方法の場合に
は、スルホン化後水に投入し、水層を用いることによっ
て、スルホン酸を単離することなく、水溶媒中でり四ツ
化を実施することができるという利点を有する。In the case of the method of sulfonation using chlorosulfonic acid, the sulfonate is poured into water after sulfonation, and the aqueous layer is used to perform tetrateration in the water solvent without isolating the sulfonic acid. It has the advantage of being able to
本発明の塩素化に用いられる塩化水素は、工業的に入手
し得る塩酸溶液（５〜３８％）の形態が最も好ましく用
いられる。しかしながら、この塩素化反応の技術分野に
おいて常用されている気体状の塩化水素でもよく、この
場合反応混合物中に適当な分配装置を経て導入される。Hydrogen chloride used in the chlorination of the present invention is most preferably used in the form of an industrially available hydrochloric acid solution (5 to 38%). However, gaseous hydrogen chloride, which is customary in the art of chlorination reactions, may also be used, which is introduced into the reaction mixture via a suitable distribution device.
この塩化水素は、５−クロロ−４−エチル−２ヒドロキ
シベンゼンスルホン酸１モルに対して０．９モル以上、
好ましくは１〜１０モル、更に好ましくは１〜４．０モ
ルの範囲である。This hydrogen chloride is 0.9 mol or more per 1 mol of 5-chloro-4-ethyl-2hydroxybenzenesulfonic acid,
Preferably it is in the range of 1 to 10 mol, more preferably 1 to 4.0 mol.
本発明で使用される過酸化水素は、塩化水素と同様に過
酸化水素水溶液（５〜６０％）の形態か最も好ましく用
いられる。また、この過酸化水素は、高濃度の、例えば
９８％Ｈ２０□を用いることもてきる。The hydrogen peroxide used in the present invention is most preferably used in the form of an aqueous hydrogen peroxide solution (5 to 60%), similar to hydrogen chloride. Moreover, this hydrogen peroxide can also be used at a high concentration, for example, 98% H20□.
この過酸化水素は、前記塩化水素に対して通常化学量論
量か用いられるが、やや過剰の使用がより好ましい。従
って過酸化水素の使用量は、塩化水素１モルに対して０
．５〜２モル、好ましくは１〜１，２モルの範囲である
。This hydrogen peroxide is usually used in a stoichiometric amount relative to the hydrogen chloride, but it is more preferable to use a slight excess. Therefore, the amount of hydrogen peroxide used is 0 per mole of hydrogen chloride.
．． It ranges from 5 to 2 mol, preferably from 1 to 1.2 mol.
本発明の塩素化において、触媒を用いることができる。A catalyst can be used in the chlorination of the present invention.
用いられる触媒とは、具体的には塩化アルミニウム、塩
化第二鉄などが挙げられる。Specific examples of the catalyst used include aluminum chloride and ferric chloride.
この触媒の使用量は５−クロロ−４−エチル２−ヒドロ
キシベンゼンスルホン酸に対して０．０１〜１０重量％
、好ましくは０．１〜３重量％の範囲である。The amount of this catalyst used is 0.01 to 10% by weight based on 5-chloro-4-ethyl 2-hydroxybenzenesulfonic acid.
, preferably in the range of 0.1 to 3% by weight.
本発明の塩素化反応は水を溶媒として実施することかで
きる点において、工業的にすぐれている。The chlorination reaction of the present invention is industrially superior in that it can be carried out using water as a solvent.
次に、ニトロ化は塩素化反応によって得られた３、４−
ジクロロ−４−エチル−２−ヒドロキシベンゼンスルホ
ン酸の水溶液に、硝酸を滴下し、或いは硝酸水溶液に３
，４−ジクロロ−４−エチル−２−ヒドロキシベンゼン
スルホン酸の水溶液を滴下することにより、スルホン酸
基を二１・口塞に置換する。特に後者、すなわち硝酸水
溶液に３４−ジクロロ−４−エチル−２−ヒドロキシベ
ンゼンスルホン酸の水溶液を滴下することによりニトロ
化の収率を格段に向上させることができることを見出し
た。Next, nitration is performed on the 3,4-
Add nitric acid dropwise to an aqueous solution of dichloro-4-ethyl-2-hydroxybenzenesulfonic acid, or add nitric acid to an aqueous solution of nitric acid.
, 4-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid is added dropwise to replace the sulfonic acid group with 21. In particular, it has been found that the yield of nitration can be significantly improved by dropping an aqueous solution of 34-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid into an aqueous nitric acid solution.
ニトロ化の反応温度は８０°Ｃ以下、好ましくは６０℃
以下で実施するのが有利である。The reaction temperature for nitration is 80°C or less, preferably 60°C.
It is advantageous to carry out:
目的物である２、４−ジクロロ−３−エチル６−ニトロ
フェノールは、反応後、結晶をろ過することによって得
ることができる。必要ならばろ過前にベンゼン、トルエ
ン、キシレン、モノクロロベンゼン、オルトジクロロベ
ンゼンなどの芳香族炭化水素によって抽出し、水溶性の
不純物を除くことができる。また、メタノール、イソプ
ロパツール、などを用いて洗浄あるいは再結晶すること
も可能である。The target product, 2,4-dichloro-3-ethyl 6-nitrophenol, can be obtained by filtering the crystals after the reaction. If necessary, water-soluble impurities can be removed by extraction with an aromatic hydrocarbon such as benzene, toluene, xylene, monochlorobenzene, orthodichlorobenzene before filtration. It is also possible to wash or recrystallize using methanol, isopropanol, or the like.
〈発明の効果〉
本発明の方法によれば、５−クロロ−４−エチル−２−
ヒドロキシベンゼンスルホン酸から目的とする２、４−
ジクロロ−３−エチル−６−ニトロフェノールを高純度
、高収率で、工業的に有利に製造することが出来る。<Effects of the Invention> According to the method of the present invention, 5-chloro-4-ethyl-2-
From hydroxybenzenesulfonic acid to the desired 2,4-
Dichloro-3-ethyl-6-nitrophenol can be industrially advantageously produced with high purity and high yield.
〈実施例〉
以下、本発明を実施例によって、更に詳細に説明するが
、本発明はそれら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 these Examples.
実施例１
５００ｍｌのガラス製４ツロのフラスコに、４−クロロ
−３−エチルフェノール１００ｇ、モノクロロベンゼン
２００ｇを入れて、溶解する。２５〜３０’Ｃに保ちな
がら、クロロスルホン酸８０ｇを滴下する。同温度で３
時間保温した後、水２００ｇを入れた１１のガラス製４
ツロフラスコにジスチャージする。Example 1 100 g of 4-chloro-3-ethylphenol and 200 g of monochlorobenzene were placed in a 500 ml glass 4-volume flask and dissolved. 80 g of chlorosulfonic acid is added dropwise while maintaining the temperature at 25-30'C. 3 at the same temperature
After keeping warm for an hour, add 200g of water to 11 glass 4
Discharge the Turo flask.
次に３５％塩酸溶液１３３ｇを加え、温度を３０°Ｃに
保って、３５％過酸化水素水９３ｇを滴下する。同温度
に３時間保った後、２０°Ｃまで冷却する。油層を分離
後、水層に７０％硝酸３１９ｇを２０〜２５°Ｃに保ち
ながら滴下する。滴下終了後４５°Ｃに昇温し、その温
度で４時間保温する。５°Ｃ迄冷却してろ過する。水で
洗浄して、乾燥することにより、２，４−ジクロロ−３
−エチル−６−ニトロフェノールが得られる。収量１３
４．５ｇ（収率：４−クロロ−３−エチルフェノールに
対して８９％）
実施例２
触媒として塩化アルミニウム１．３ｇを用い、実施例１
と同様にして反応を行った結果、２，４ジクロロ−３−
エチル−６−ニトロフェノール１３６．０ｇ（収率９０
％）を得た。Next, 133 g of 35% hydrochloric acid solution is added, and while maintaining the temperature at 30° C., 93 g of 35% hydrogen peroxide solution is added dropwise. After keeping at the same temperature for 3 hours, cool to 20°C. After separating the oil layer, 319 g of 70% nitric acid is added dropwise to the water layer while maintaining the temperature at 20 to 25°C. After completion of the dropping, the temperature was raised to 45°C and kept at that temperature for 4 hours. Cool to 5°C and filter. By washing with water and drying, 2,4-dichloro-3
-Ethyl-6-nitrophenol is obtained. Yield 13
4.5 g (Yield: 89% based on 4-chloro-3-ethylphenol) Example 2 Using 1.3 g of aluminum chloride as a catalyst, Example 1
As a result of carrying out the reaction in the same manner as above, 2,4dichloro-3-
Ethyl-6-nitrophenol 136.0g (yield 90
%) was obtained.
実施例３
５００ｍ Ｉ！のガラス製４ツロのフラスコに、４−り
コロ−３−エチルフェノール１００ｇ、モノクロロベン
ゼン２００ｇを入れて、溶解する。２５〜３０°Ｃに保
ちながら、クロロスルホン酸８０ｇを滴下する。同温度
で３時間保温した後、水２００ｇを入れた１１のガラス
製４ツロフラスコにジスチャージする。Example 3 500m I! 100 g of 4-licorro-3-ethylphenol and 200 g of monochlorobenzene were placed in a 4-meter glass flask and dissolved. 80 g of chlorosulfonic acid is added dropwise while maintaining the temperature at 25-30°C. After incubating at the same temperature for 3 hours, the mixture was charged into 11 glass 4-tube flasks containing 200 g of water.
油層を分離後、水層に３５％塩酸溶液１３３ｇを加え、
温度を３０°Ｃに保って、３５％過酸化水素水９３ｇを
滴下する。同温度に３時間保った後、２０°Ｃまで冷却
する。７０％硝酸３１９ｇを２０〜２５°Ｃに保ちなが
ら滴下する。滴下終了後４５°Ｃに昇温し、その温度で
４時間保温する。５°Ｃ迄冷却してろ過する。水て洗浄
して、乾燥することにより、２，４−ジクロロ３−エチ
ル−６−ニトロフェノールか得られる。収量１２８．４
ｇ （収率、４−クロロ−３−エチルフェノールに対し
て８５％）
実施例４
５００ｍ Ｒのガラス製４ツロのフラスコに、４−クロ
ロ−３−エチルフェノール１００ｇ、二塩化エタン３５
０ｇを入れて、溶解する。２５〜３０’Ｃに保ちながら
クロロスルホン酸８０ｇを滴下する。同温度で３時間保
温した後、水２００ｇを入れた１１のガラス製４ツロフ
ラスコにジスチャージする。After separating the oil layer, 133 g of 35% hydrochloric acid solution was added to the aqueous layer.
While maintaining the temperature at 30°C, 93g of 35% hydrogen peroxide solution was added dropwise. After keeping at the same temperature for 3 hours, cool to 20°C. Add 319 g of 70% nitric acid dropwise while maintaining the temperature at 20-25°C. After completion of the dropping, the temperature was raised to 45°C and kept at that temperature for 4 hours. Cool to 5°C and filter. By washing with water and drying, 2,4-dichloro3-ethyl-6-nitrophenol is obtained. Yield 128.4
g (Yield, 85% based on 4-chloro-3-ethylphenol) Example 4 In a 500 m R glass 4-ton flask, 100 g of 4-chloro-3-ethylphenol and 35 ml of ethane dichloride were added.
Add 0g and dissolve. 80 g of chlorosulfonic acid is added dropwise while maintaining the temperature at 25-30'C. After incubating at the same temperature for 3 hours, the mixture was charged into 11 glass 4-tube flasks containing 200 g of water.
次に３５％塩酸溶液１３３ｇおよび塩化アルミニウム１
、３ｇを加え、温度を３０°Ｃに保って、１８％過酸化
水素水１８１ ｇを滴下する。同温度に３時間保った後
、２０°Ｃまて冷却する。油層を分離後、水層に７０％
硝酸３１９ｇを２０〜２５°Ｃに保ちなから滴下する。Next, 133 g of 35% hydrochloric acid solution and 1 aluminum chloride
, and 181 g of 18% hydrogen peroxide solution was added dropwise while maintaining the temperature at 30°C. After keeping at the same temperature for 3 hours, cool to 20°C. After separating the oil layer, 70% is transferred to the water layer.
319 g of nitric acid is added dropwise while maintaining the temperature at 20-25°C.
滴下終了後４５°Ｃに昇温し、その温度で４時間保温す
る。After completion of the dropping, the temperature was raised to 45°C and kept at that temperature for 4 hours.
５°Ｃ迄冷却してろ過する。水で洗浄して、乾燥するこ
とにより、２，４−ジクロロ−３−エチル６−ニトロフ
ェノールが得られる。収量１２６．８ｇ（収率；４−ク
ロロ−３−エチルフェノールに対しして８４％）
実施例５
１１のガラス製４ツロのフラスコに、４−クロロ−３−
エチルフェノール１００ｇ、二塩化エタン３５０ｇを入
れて、溶解する。３５〜４５°Ｃに保ちながら、クロロ
スルホン酸８０ｇを滴下した後、４０〜４５°Ｃて１時
間保温する。Cool to 5°C and filter. By washing with water and drying, 2,4-dichloro-3-ethyl 6-nitrophenol is obtained. Yield: 126.8 g (Yield: 84% based on 4-chloro-3-ethylphenol) Example 5 Into 11 glass 4-wall flasks, 4-chloro-3-
Add 100 g of ethylphenol and 350 g of ethane dichloride and dissolve. After dropping 80 g of chlorosulfonic acid while maintaining the temperature at 35-45°C, the mixture is kept at 40-45°C for 1 hour.
次に１４．３％塩酸３２６ｇを加え、温度を４０〜４５
°Ｃに保って、３５％過酸化水素水６８ ｇを滴下する
。同温度に８時間保った後、２０°Ｃまで冷却する。Next, add 326g of 14.3% hydrochloric acid and adjust the temperature to 40-45%.
While keeping the temperature at °C, 68 g of 35% hydrogen peroxide solution was added dropwise. After keeping at the same temperature for 8 hours, cool to 20°C.
油層を分離後、水層を滴下濾斗に入れ、予め仕込んでお
いた３５％硝酸水溶液２３０ｇ中に、３０〜４０’Ｃ保
ちながら滴下する。滴下終了後、同温度で２時間保温す
る。５°Ｃまで冷却して濾過する。水で洗浄して乾燥す
ることにより、２，４−ジクロロ−３−エチル−６−ニ
トロフェノールが得られる。After separating the oil layer, the aqueous layer is placed in a dropping funnel and added dropwise into 230 g of a 35% nitric acid aqueous solution charged in advance while maintaining the temperature at 30 to 40'C. After finishing dropping, keep warm at the same temperature for 2 hours. Cool to 5°C and filter. By washing with water and drying, 2,4-dichloro-3-ethyl-6-nitrophenol is obtained.
収量１４３ｇ
（収率：４−クロロ−３−エチルフェノールに対して９
５％）
（以下 余白）Yield: 143g (yield: 9% based on 4-chloro-3-ethylphenol)
5%) (hereinafter referred to as margin)
Claims (9)
ンスルホン酸を、触媒の存在下又は不存在下に、塩化水
素と過酸化水素とによって塩素化することを特徴とする
３，５−ジクロロ−４−エチル−２−ヒドロキシベンゼ
ンスルホン酸の製造法。(1) 3,5-dichloro, characterized by chlorinating 5-chloro-4-ethyl-2-hydroxybenzenesulfonic acid with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst. -Production method of 4-ethyl-2-hydroxybenzenesulfonic acid.
の形態で用いる請求項（１）に記載の方法。(2) Hydrogen chloride, hydrochloric acid solution (5% to 38% hydrochloric acid solution)
The method according to claim (1), which is used in the form of
＿２Ｏ＿２溶液）の形態で用いる請求項（１）又は（２
）に記載の方法。(3) Add hydrogen peroxide to a hydrogen peroxide aqueous solution (5-60% H
Claim (1) or (2) used in the form of __2O_2 solution)
).
第二鉄を用いる請求項（１）〜（３）のいずれかに記載
の方法。(4) The method according to any one of claims (1) to (3), wherein aluminum chloride or ferric chloride is used as the chlorination catalyst.
）のいずれかに記載の方法。(5) Claims (1) to (4) wherein the chlorination is carried out in an aqueous solvent.
).
ンスルホン酸を、触媒の存在下又は不存在下に、塩化水
素と過酸化水素とによって塩素化して３，５−ジクロロ
−４−エチル−２−ヒドロキシベンゼンスルホン酸とし
、次いで硝酸を用いてスルホン酸基をニトロ基に置換す
ることを特徴とする２，４−ジクロロ−３−エチル−６
−ニトロフェノールの製造法。(6) 5-chloro-4-ethyl-2-hydroxybenzenesulfonic acid is chlorinated with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst to produce 3,5-dichloro-4-ethyl- 2,4-dichloro-3-ethyl-6, characterized in that it is made into 2-hydroxybenzenesulfonic acid and then the sulfonic acid group is replaced with a nitro group using nitric acid.
- A method for producing nitrophenol.
−ヒドロキシベンゼンスルホン酸水溶液を滴下して、ス
ルホン酸基をニトロ基に置換することを特徴とする請求
項（６）に記載の方法。(7) 3,5-dichloro-4-ethyl-2 in nitric acid aqueous solution
7. The method according to claim 6, wherein the sulfonic acid group is replaced with a nitro group by dropping an aqueous solution of -hydroxybenzenesulfonic acid.
して得られる５−クロロ−４−エチル−２−ヒドロキシ
ベンゼンスルホン酸を用いる請求項（１）〜（７）のい
ずれかに記載の方法。(8) The method according to any one of claims (1) to (7), wherein 5-chloro-4-ethyl-2-hydroxybenzenesulfonic acid obtained by sulfonating 4-chloro-3-ethylphenol is used.
求項（８）に記載の方法。(9) The method according to claim (8), wherein the sulfonation is carried out using chlorosulfonic acid.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2227535A JP2883179B2 (en) | 1990-04-06 | 1990-08-28 | Method for producing 3,5-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid |
| US07/707,097 US5136109A (en) | 1990-08-28 | 1991-05-29 | Process for preparing 2,4-dichloro-3-alkyl-6-nitrophenols |
| EP91401381A EP0473464B1 (en) | 1990-08-28 | 1991-05-29 | Process for preparing 2-4-dichloro-3-alkyl-6-nitrophenols |
| DE69110377T DE69110377T2 (en) | 1990-08-28 | 1991-05-29 | Process for the preparation of 2,4-dichloro-3-alkyl-6-nitrophenol. |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-92769 | 1990-04-06 | ||
| JP9276990 | 1990-04-06 | ||
| JP2227535A JP2883179B2 (en) | 1990-04-06 | 1990-08-28 | Method for producing 3,5-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0429966A true JPH0429966A (en) | 1992-01-31 |
| JP2883179B2 JP2883179B2 (en) | 1999-04-19 |
Family
ID=26434144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2227535A Expired - Fee Related JP2883179B2 (en) | 1990-04-06 | 1990-08-28 | Method for producing 3,5-dichloro-4-ethyl-2-hydroxybenzenesulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2883179B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990430A (en) * | 2014-04-25 | 2014-08-20 | 重庆文理学院 | Pecan shell/sorghum straw bio-char and preparation method thereof |
| WO2021015263A1 (en) * | 2019-07-24 | 2021-01-28 | 王子ホールディングス株式会社 | Base paper for product packaged with base paper, product packaged with base paper, device for manufacturing product packaged with base paper, and method for manufacturing product packaged with base paper. |
-
1990
- 1990-08-28 JP JP2227535A patent/JP2883179B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990430A (en) * | 2014-04-25 | 2014-08-20 | 重庆文理学院 | Pecan shell/sorghum straw bio-char and preparation method thereof |
| WO2021015263A1 (en) * | 2019-07-24 | 2021-01-28 | 王子ホールディングス株式会社 | Base paper for product packaged with base paper, product packaged with base paper, device for manufacturing product packaged with base paper, and method for manufacturing product packaged with base paper. |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2883179B2 (en) | 1999-04-19 |
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