JPS6111945B2 - - Google Patents
Info
- Publication number
- JPS6111945B2 JPS6111945B2 JP57057484A JP5748482A JPS6111945B2 JP S6111945 B2 JPS6111945 B2 JP S6111945B2 JP 57057484 A JP57057484 A JP 57057484A JP 5748482 A JP5748482 A JP 5748482A JP S6111945 B2 JPS6111945 B2 JP S6111945B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- para
- reaction
- added
- temperature
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 22
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 239000012429 reaction media Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 3
- -1 sulfuric acid ester Chemical class 0.000 description 3
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- VKPQLZPZPYQFOK-UHFFFAOYSA-N 2-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=CC=C1S(Cl)(=O)=O VKPQLZPZPYQFOK-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、パラアミノフエニル−β−ヒドロキ
シエチルスルフイドの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing para-aminophenyl-β-hydroxyethyl sulfide.
更に詳しくは、本発明は、セルロース繊維材料
の染色に多用されているビニルスルホン型反応染
料の重要な中間体である下式（）
で示されるパラアミノフエニル−β−スルフアト
エチルスルホンの中間として有用なパラニトロフ
エニル−β−ヒドロキシエチルスルフイドの新規
な製造方法に関する。 More specifically, the present invention is directed to the following formula ( The present invention relates to a novel method for producing para-nitrophenyl-β-hydroxyethyl sulfide, which is useful as an intermediate for para-aminophenyl-β-sulfatoethyl sulfone.
従来、式（）で示されるパラアミノフエニル
−β−スルフアトエチルスルホンは、アニリンに
無水酢酸を作用させてアセトアニリドとした後、
大過剰のクロルスルホン酸中でスルホニルクロラ
イド化してパラアセチルアミノベンゼンスルホニ
ルクロライドを得、これを亜硫酸ナトリウムで還
元してスルフイン酸とし、次いでエチレンオキサ
イドまたはエチレンクロルヒドリンを作用させて
パラアセチルアミノフエニル−β−ヒドロキシエ
チルスルホンを得、これを硫酸中で加水分解する
と共に硫酸エステル化することにより製造されて
いる。 Conventionally, para-aminophenyl-β-sulfatoethylsulfone represented by the formula () has been prepared by reacting aniline with acetic anhydride to form acetanilide.
Sulfonyl chloride is formed in a large excess of chlorosulfonic acid to obtain paraacetylaminobenzenesulfonyl chloride, which is reduced with sodium sulfite to give sulfinic acid, and then treated with ethylene oxide or ethylene chlorohydrin to give paraacetylaminophenyl. It is produced by obtaining -β-hydroxyethyl sulfone, hydrolyzing it in sulfuric acid, and converting it into sulfuric acid ester.
しかし上記の方法はこれを工業的に実施するに
は以下に列挙する種々の問題があり必ずしも工業
的に有利な方法とはいえない。 However, the above-mentioned method cannot necessarily be said to be an industrially advantageous method due to various problems listed below in implementing it industrially.
クロルスルホン酸中でのスルホニルクロライ
ド化は本質的に平衡反応であり、アセチルアミ
〓〓〓〓〓
ノベンゼンスルホン酸の副生を抑えるため大過
剰のクロルスルホン酸が必要である。 Sulfonyl chloride in chlorosulfonic acid is essentially an equilibrium reaction, with acetylamine
A large excess of chlorosulfonic acid is required to suppress the by-product of nobenzenesulfonic acid.
上述の過剰クロルスルホン酸の回収が困難
で、最終的には酸性廃液として処理することが
必要となる。 It is difficult to recover the above-mentioned excess chlorosulfonic acid, and ultimately it is necessary to treat it as an acidic waste liquid.
アセチルアミノベンゼンスルホニルクロライ
ドは不安定で、収率低下の一因となつている。 Acetylaminobenzenesulfonyl chloride is unstable, which contributes to lower yields.
亜硫酸ナトリウムによるスルフイン酸への還
元は、スルフイン酸の安定性が低く、従つて反
応収率が低い。 Reduction to sulfinic acid with sodium sulfite results in low stability of sulfinic acid and therefore low reaction yield.
最終工程でのアセチル基の加水分解で脱離し
た酢酸とヒドロキシ基との反応により酢酸エス
テル体が副生し純度低下を招き、更には系内に
存在する脱離した酢酸が、反応器材の腐蝕ある
いは廃水問題など大きな障害となる。 In the final step, the acetic acid released by hydrolysis of the acetyl group reacts with the hydroxyl group, producing an acetate as a by-product, leading to a decrease in purity.Furthermore, the released acetic acid present in the system causes corrosion of the reaction equipment. Alternatively, it can become a major obstacle, such as wastewater problems.
このような事情に鑑み、本発明者らは式（）
で示される化合物の工業的有利な製造方法につい
て検討し、パラニトロハロベンゼンにメルカプト
エタノールを作用させてパラニトロフエニル−β
−ヒドロキシエチルスルフイドを得、これを酸化
して得られるパラニトロフエニル−β−ヒドロキ
シエチルスルホン酸を還元し、得られるパラアミ
ノフエニル−β−ヒドロキシエチルスルホンを硫
酸エステル化して目的とする式（）の化合物と
する新規な工程を経る製造方法を見出し、この新
規な製造方法におけるパラニトロハロベンゼンと
メルカプトエタノールとの縮合をより工業的有利
に行う方法について鋭意検討した。 In view of these circumstances, the present inventors developed the formula ()
We investigated an industrially advantageous method for producing the compound represented by
- Obtain hydroxyethyl sulfide, reduce para-nitrophenyl-β-hydroxyethyl sulfonic acid obtained by oxidizing this, and convert the obtained para-aminophenyl-β-hydroxyethyl sulfone into a sulfuric acid ester to obtain the desired product. We found a manufacturing method that involves a new process to produce the compound of formula (), and conducted intensive studies to find a method for conducting the condensation of para-nitrohalobenzene and mercaptoethanol in this new manufacturing method in a more industrially advantageous manner.
ニトロハロベンゼンとメルカプトエタノールと
の反応については、二、三の文献が散見される
が、〔J.Amer.Chem.Soc 55巻4956ページ
（1933）；J.Chem.Soc.（1927）1666〜1676ペー
ジ工業化学雑誌、62巻、825〜28ページなど〕こ
れらの文献にはわずかに０−ニトロクロルベンゼ
ンとメルカプトエタノールを水酸化カリウムの存
在下アルコール溶媒中で実施されている例を見い
出すだけである。しかもこれらの文献中に示され
ている実施例に基づいて実験を試みたところ、ニ
トロ基が反応したと思われるアゾキシ体が多量副
生し、低収率でしか目的のスルフイド誘導体を得
ることができなかつた。 Regarding the reaction between nitrohalobenzene and mercaptoethanol, there are a few references here and there, but [J.Amer.Chem.Soc Vol. 55, p. 4956 (1933); J.Chem.Soc. (1927) 1666~ 1676 pages, Journal of Industrial Chemistry, Volume 62, Pages 825-28, etc.] In these documents, there are only a few examples in which 0-nitrochlorobenzene and mercaptoethanol are treated in an alcoholic solvent in the presence of potassium hydroxide. be. Moreover, when experiments were attempted based on the examples shown in these documents, a large amount of azoxy derivatives, which were thought to have been reacted with nitro groups, were produced as by-products, and the desired sulfide derivatives could only be obtained in low yields. I couldn't do it.
また、パラニトロクロロベンゼンについては他
の合成方法、すなわち、パラニトロチオフエノー
ルとエチレンクロルヒドリンとの反応の方が収率
がよいと推奨されている。 For para-nitrochlorobenzene, another synthesis method, namely, the reaction of para-nitrothiophenol and ethylene chlorohydrin, is recommended as it provides a better yield.
しかし、パラニトロチオフエノールとエチレン
クロルヒドリンとの反応は、たとえば、J.Chem.
Soc.（1927）1666〜1676ページ；J.Chem.Soc
1933 46〜48ページ；Current Sci（India）20巻
155〜156ページ（1951）；J.Org.Chem.24巻
1719〜1722ページ（1959）；工業化学雑誌 62巻
825〜828ページ（1959）などに記載されている
が、原料であるパラニトロチオフエニルの合成は
反応条件の厳密な管理が必要であり、しかも生成
するパラニトロチオフエニルはきわめて不安定で
容易に酸化され、ジスルフイド体が生成する。そ
のため収率が極めて低く、工業的に有利な製造方
法とはなり得ない。 However, the reaction of paranitrothiophenol with ethylene chlorohydrin has been described, for example, in J. Chem.
Soc. (1927) pp. 1666-1676; J.Chem.Soc.
1933 pages 46-48; Current Sci (India) vol. 20
Pages 155-156 (1951); J.Org.Chem.24 volumes
Pages 1719-1722 (1959); Industrial Chemistry Magazine Volume 62
As described in pages 825-828 (1959), the synthesis of the raw material para-nitrothiophenyl requires strict control of reaction conditions, and the produced para-nitrothiophenyl is extremely unstable. Easily oxidized to form disulfides. Therefore, the yield is extremely low and it cannot be an industrially advantageous production method.
このような事情の下で、本発明者らはパラニト
ロハロベンゼンとメルカプトエタノールとの反応
により、簡単な操作でパラニトロフエニル−β−
ヒドロキシエチルスルフイドを高純度、高収率で
製造する方法について鋭意研究の結果、該縮合反
応を特定の反応条件下で行うことによりその目的
が達成されることを見出し本発明を完成するに至
つた。 Under these circumstances, the present inventors produced para-nitrophenyl-β-by a simple operation by reacting para-nitrohalobenzene with mercaptoethanol.
As a result of intensive research into a method for producing hydroxyethyl sulfide with high purity and high yield, it was discovered that the purpose could be achieved by carrying out the condensation reaction under specific reaction conditions, and the present invention was completed. I've reached it.
即ち、本発明は、Ｎ−アルキル置換アミド類お
よびスルホキサイド類から選ばれる少なくとも１
種の有機溶媒と水との混合溶媒を反応媒体とし、
パラニトロハロベンゼンとメルカプトエタノール
とを30゜乃至50℃の温度範囲でアルカリ金属水酸
化物を添加しながら反応させることを特徴とする
パラニトロフエニル−β−ヒドロキシエチルスル
フイドの製造方法を提供する。 That is, the present invention provides at least one compound selected from N-alkyl substituted amides and sulfoxides.
A mixed solvent of a seed organic solvent and water is used as a reaction medium,
A method for producing para-nitrophenyl-β-hydroxyethyl sulfide, which comprises reacting para-nitrohalobenzene and mercaptoethanol in a temperature range of 30° to 50°C while adding an alkali metal hydroxide. provide.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明方法で用いられるパラニトロハロベンゼ
ンとはたとえば、パラニトロクロロベンゼン、パ
ラニトロブロモベンゼンなどである。 Examples of para-nitrohalobenzene used in the method of the present invention include para-nitrochlorobenzene and para-nitrobromobenzene.
このうちパラニトロクロロベンゼンが好まし
い。 Among these, para-nitrochlorobenzene is preferred.
使用されるメルカプトエタノールの量はパラニ
トロハロベンゼンに対して、化学理論量以上、３
モル倍以下が好ましく用いられる。より好ましい
量は1.05モル倍〜2.0モル倍である。 The amount of mercaptoethanol used is more than the stoichiometric amount, based on para-nitrohalobenzene,
A mole ratio or less is preferably used. A more preferable amount is 1.05 times to 2.0 times by mole.
本発明の方法に使用される有機溶媒は、ジメチ
ルホルムアミド、Ｎ−メチル−２−ピロリドン、
ジメチルアセトアミドなどのＮ−アルキル置換ア
ミド類、スルホラン、ジメチルスルホキサイドな
〓〓〓〓〓
どのスルホキサイド類である。これらの溶媒は、
単独または二種類以上を混合して用いることがで
きる。特に好ましい有機溶媒はジメチルスルホキ
シドおよびジメチルホルムアミド、ジメチルアセ
トアミド、Ｎ−メチル−２−ピロリドンである。 The organic solvents used in the method of the present invention include dimethylformamide, N-methyl-2-pyrrolidone,
N-alkyl substituted amides such as dimethylacetamide, sulfolane, dimethyl sulfoxide, etc.
Which sulfoxides? These solvents are
They can be used alone or in combination of two or more. Particularly preferred organic solvents are dimethylsulfoxide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone.
とりわけ、ジメチルホルムアミドが好ましい。 Particularly preferred is dimethylformamide.
本発明の方法で用いる反応媒体は、これらの有
機溶媒と水との混合溶媒である。一般に、これら
有機溶媒は、いずれも強い吸湿性を有し、乾燥状
態に保持するのは、容易でないが、本発明の方法
においては、水を含んだ溶媒を使用するためにこ
れらの有機溶媒を乾燥する必要がなく、従つて回
収溶媒の再使用が容易であり、且つ反応温度のコ
ントロールが容易である。有機溶媒中の水分含有
率は、２重量％以上30重量％以下が好ましく30重
量％を越えると反応原料であるパラニトロハロベ
ンゼンの溶解度が低下して反応の進行が阻害され
るだけでなく、好ましくない副反応が増加する。 The reaction medium used in the method of the present invention is a mixed solvent of these organic solvents and water. In general, all of these organic solvents have strong hygroscopicity and are difficult to maintain in a dry state. However, in the method of the present invention, these organic solvents are used because they contain water. There is no need for drying, so the recovered solvent can be easily reused and the reaction temperature can be easily controlled. The water content in the organic solvent is preferably 2% by weight or more and 30% by weight or less, and if it exceeds 30% by weight, the solubility of para-nitrohalobenzene, which is a reaction raw material, will not only decrease, but also inhibit the progress of the reaction. Undesirable side reactions increase.
反応系内に含まれる水は、使用される有機溶媒
中にあらかじめ含有されていてもよいし、あるい
は、反応に使用されるアルカリ金属水酸化物と同
伴されて反応系内に入つてもよい。 The water contained in the reaction system may be contained in advance in the organic solvent used, or may enter the reaction system together with the alkali metal hydroxide used in the reaction.
有機溶媒の使用量は、溶媒の種類、原料パラニ
トロハロベンゼンの溶媒への溶解度などにより、
多少変動があるが、原料パラニトロハロベンゼン
に対して0.2〜15重量倍の範囲で十分で良好な結
果が得られる。好ましい量は0.5〜10重量倍、よ
り好ましい量は0.5〜５重量倍である。 The amount of organic solvent used depends on the type of solvent, the solubility of the raw material p-nitrohalobenzene in the solvent, etc.
Although there is some variation, a range of 0.2 to 15 times the weight of the raw material p-nitrohalobenzene is sufficient and good results can be obtained. A preferable amount is 0.5 to 10 times by weight, and a more preferable amount is 0.5 to 5 times by weight.
本発明の方法に用いられるアルカリ金属水酸化
物としては水酸化ナトリウム、水酸化カリウム等
が例示される。 Examples of the alkali metal hydroxide used in the method of the present invention include sodium hydroxide and potassium hydroxide.
これらアルカリ金属水酸化物の使用量は、パラ
ニトロハロベンゼンに対して、化学理論量以上
1.1モル倍末満が用いられ、好ましくは1.0乃至
1.03モルが用いられる。 The amount of these alkali metal hydroxides used is more than the stoichiometric amount for para-nitrohalobenzene.
More than 1.1 molar amount is used, preferably 1.0 to 1.0 molar.
1.03 mol is used.
アルカリ金属水酸化物の使用量がパラニトロベ
ンゼンに対して1.1モル倍以上であると、ニトロ
基が反応したアゾキシ体等が多数副生し、目的物
の収率、純度が低下する。 If the amount of alkali metal hydroxide used is 1.1 times or more moles or more relative to paranitrobenzene, a large number of azoxy compounds with reacted nitro groups will be produced as by-products, resulting in a decrease in the yield and purity of the target product.
反応温度は、収用するパラニトロハロベンゼン
および有機溶媒の種類により異なるが、30゜乃至
50℃の範囲である。反応温度が30℃未満のときは
反応速度が低下し、一方50℃を越えると好ましく
ない副反応が増加する。 The reaction temperature varies depending on the type of p-nitrohalobenzene and organic solvent used, but is between 30° and
It is in the range of 50℃. When the reaction temperature is less than 30°C, the reaction rate decreases, while when it exceeds 50°C, undesirable side reactions increase.
反応時間は、反応温度、反応原料の種類などに
より異なるが通常１〜15時間の範囲内であり、好
ましくは２〜８時間の範囲である。不必要な反応
時間の延長は副反応が増加し、収率、純度を低下
させるので好ましくない。 The reaction time varies depending on the reaction temperature, the type of reaction raw materials, etc., but is usually in the range of 1 to 15 hours, preferably in the range of 2 to 8 hours. Unnecessary prolongation of reaction time is undesirable because it increases side reactions and reduces yield and purity.
本発明の実施形態としては、原料パラニトロハ
ロベンゼンとメルカプトエタノールの所定量を反
応媒体中に添加し、所望の温度に昇温後、所定量
のアルカリ金属水酸化物を反応系内に添加しなが
ら反応を進行させることができる。この場合、ア
ルカリ金属水酸化物を一挙に添加すると発熱反応
のため系内温度が急激に上昇し好ましくない副反
応を増加させるので徐々に添加する。 In an embodiment of the present invention, predetermined amounts of raw material p-nitrohalobenzene and mercaptoethanol are added to a reaction medium, and after the temperature is raised to a desired temperature, a predetermined amount of alkali metal hydroxide is added into the reaction system. The reaction can proceed while In this case, if the alkali metal hydroxide is added all at once, the temperature inside the system will rise rapidly due to the exothermic reaction, increasing undesirable side reactions, so it should be added gradually.
また本発明の実施形態として半回分式または連
続式の形態もとることができる。 Further, as an embodiment of the present invention, a semi-batch type or a continuous type can be adopted.
また反応雰囲気は空気のほかに不活性ガスの雰
囲気中または気流中に反応を行なうことができ
る。不活性ガスとしては窒素などが用いられる。 In addition to air, the reaction can be carried out in an inert gas atmosphere or in an air stream. Nitrogen or the like is used as the inert gas.
本発明方法により生成したパラニトロフエニル
−β−ヒドロキシエチルスルフイドを含む反応液
中には、反応の結果生成する無機塩が析出してい
るためいつたん過により、この無機塩を除いた
後、続いて、有機溶媒を蒸留等の操作により回収
し、最終的に目的のパラニトロフエニル−β−ヒ
ドロキシエチルスルフイドを高純度、高収率で得
ることができる。 In the reaction solution containing para-nitrophenyl-β-hydroxyethyl sulfide produced by the method of the present invention, inorganic salts produced as a result of the reaction were precipitated, so this inorganic salt was removed by filtration. Subsequently, the organic solvent is recovered by operations such as distillation, and the desired para-nitrophenyl-β-hydroxyethyl sulfide can finally be obtained with high purity and high yield.
あるいは、反応液から有機溶媒を蒸留などの操
作により回収した後多量の水に注加し、目的のパ
ラニトロフエニル−β−ヒドロキシエチルスルフ
イドを、過あるいは分液操作により得ることが
できる。 Alternatively, the organic solvent can be recovered from the reaction solution by an operation such as distillation, then poured into a large amount of water, and the desired para-nitrophenyl-β-hydroxyethyl sulfide can be obtained by filtration or separation. .
本発明方法によれば、パラニトロフエニル−β
−ヒドロキシエチルスルフイドは高純度、高収率
で得られ、また、これを酸化し、続いて還元する
ことによつて得られるパラアミノフエニル−β−
ヒドロキシエチルスルホンに硫酸化剤を作用させ
ることによつて式（）で表わされる染料中間体
を高品質で得ることができる。 According to the method of the present invention, paranitrophenyl-β
-Hydroxyethyl sulfide can be obtained with high purity and yield, and para-aminophenyl-β- can be obtained by oxidizing it and then reducing it.
A high quality dye intermediate represented by the formula () can be obtained by treating hydroxyethyl sulfone with a sulfating agent.
以下本発明を実施例をもつて詳細に説明する
が、本発明はこれら実施例に限定されるものでは
ない。尚、実施例中部および％は夫々重量部、重
量％を表わす。 EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited to these Examples. Incidentally, in the examples, % and % represent parts by weight and % by weight, respectively.
実施例 １
パラニトロクロロベンゼン158部をジメチルホ
〓〓〓〓〓
ルムアミド160部と水８部に添加しメルカプトエ
タノール94部（1.2モル倍）を加え、50℃に昇温
した。続いて水酸化ナトリウムの粉体41部（1.01
モル倍）を４時間で添加した。添加終了後、更に
１時間、同温度で保温した。反応終了後反応マス
を中和し、析出している塩化ナトリウムを別し
た後、液をフラツシユ蒸留し、ジメチルホルム
アミドを留去した。Example 1 158 parts of para-nitrochlorobenzene was dissolved in dimethylphos
160 parts of lumamide and 8 parts of water were added, 94 parts of mercaptoethanol (1.2 times the mole) was added, and the temperature was raised to 50°C. Next, 41 parts of sodium hydroxide powder (1.01
molar) was added over 4 hours. After the addition was completed, the mixture was kept at the same temperature for an additional hour. After the reaction was completed, the reaction mass was neutralized and the precipitated sodium chloride was separated, and then the liquid was flash distilled to remove dimethylformamide.
パラニトロフエニル−β−ヒドロキシエチルス
ルフイドを193部得た。収率は97％である。 193 parts of para-nitrophenyl-β-hydroxyethyl sulfide were obtained. Yield is 97%.
実施例 ２
パラニトロクロロベンゼン158部をジメチルス
ルホキシド160部と水16部に添加し、メルカプト
エタノール150部（1.9モル倍）を加え、50℃に昇
温した。水酸化ナトリウムの粉体41部（1.01モル
倍）を５時間にわたつて添加した。添加終了後更
に１時間同温度で保温した。Example 2 158 parts of para-nitrochlorobenzene was added to 160 parts of dimethyl sulfoxide and 16 parts of water, 150 parts of mercaptoethanol (1.9 times the mole) was added, and the temperature was raised to 50°C. 41 parts (1.01 mole times) of sodium hydroxide powder was added over 5 hours. After the addition was completed, the mixture was kept at the same temperature for an additional hour.
反応終了後、約1000容量部の水に反応マスをチ
ヤージし、オイル層を分液により取り出した。 After the reaction was completed, the reaction mass was charged in about 1000 parts by volume of water, and the oil layer was taken out by liquid separation.
オイル層中のパラニトロフエニル−β−ヒドロ
キシエチルスルフイドの含量を分析したところ、
原料パラニトロクロロベンゼンにより収率96％で
パラニトロフエニル−β−ヒドロキシエチルスル
フイドが得られている事がわかつた。 Analysis of the content of paranitrophenyl-β-hydroxyethyl sulfide in the oil layer revealed that
It was found that para-nitrophenyl-β-hydroxyethyl sulfide was obtained with a yield of 96% using the raw material para-nitrochlorobenzene.
実施例 ３
パラニトロクロロベンゼン158部をジメチルホ
ルムアミド150部に添加し、メルカプトエタノー
ル94部（1.2モル倍）を加え、50℃に昇温した。Example 3 158 parts of para-nitrochlorobenzene was added to 150 parts of dimethylformamide, 94 parts of mercaptoethanol (1.2 times the mole) was added, and the temperature was raised to 50°C.
続いて、49％水酸化ナトリウム水溶液83部
（1.02モル倍）を５時間で添加した。 Subsequently, 83 parts (1.02 mol) of a 49% aqueous sodium hydroxide solution was added over 5 hours.
添加終了後、反応マスを中和した後、水を留去
した。析出する塩化ナトリウムを別した。ジメ
チルホルムアミドに溶解しているパラニトロフエ
ニル−β−ヒドロキシエチルスルフイドは190部
であつた。収率は95％である。 After the addition was completed, the reaction mass was neutralized and water was distilled off. The precipitated sodium chloride was separated. The amount of paranitrophenyl-β-hydroxyethyl sulfide dissolved in dimethylformamide was 190 parts. Yield is 95%.
実施例 ４
パラニトロクロロベンゼン300部をジメチルホ
ルムアミド300部と水15部に添加し、メルカプト
エタノール171部（1.15モル倍）を加え、窒素雰
囲気下、40℃に昇温した。Example 4 300 parts of para-nitrochlorobenzene was added to 300 parts of dimethylformamide and 15 parts of water, 171 parts of mercaptoethanol (1.15 times the mole) was added, and the temperature was raised to 40°C under a nitrogen atmosphere.
水酸化ナトリウムの粉体77部（1.01モル倍）を
４時間で添加した。添加後更に２時間、同温度に
て保温した。反応終了後反応マスを中和し、70
℃、60mmHgの減圧下水を留去し、更に減圧度を
高めながらジメチルホルムアミドを留去した。最
後に140℃、10mmHgで１時間保つた。系内を常圧
にもどした後80℃まで冷却し、水600部を加え70
℃で30分間撹拌し、下層のオイル層410部を分液
にて取り出した。パラニトロフエニル−β−ヒド
ロキシエチルスルフイドの含量89％であつた。収
率は96％である。 77 parts (1.01 mol) of sodium hydroxide powder was added over 4 hours. After the addition, the mixture was kept at the same temperature for an additional 2 hours. After the reaction is complete, neutralize the reaction mass and
The water was distilled off under reduced pressure of 60 mmHg at ℃, and dimethylformamide was further distilled off while increasing the degree of vacuum. Finally, it was kept at 140°C and 10mmHg for 1 hour. After returning the pressure inside the system to normal pressure, it was cooled to 80℃, and 600 parts of water was added to
After stirring at ℃ for 30 minutes, 410 parts of the lower oil layer was separated. The content of paranitrophenyl-β-hydroxyethyl sulfide was 89%. Yield is 96%.
実施例 ５
パラニトロクロロベンゼン300部をジメチルホ
ルムアミド300部に添加し、窒素雰囲気下、メル
カプトエタノール171部（1.15モル倍）を加え30
℃に昇温した。Example 5 300 parts of para-nitrochlorobenzene was added to 300 parts of dimethylformamide, and 171 parts of mercaptoethanol (1.15 times the mole) was added under a nitrogen atmosphere.
The temperature was raised to ℃.
48％水酸化ナトリウム水溶液164部（1.03モル
倍）を４時間で滴下した。滴下終了後更に１時間
同温度にて保温した。反応終了後、反応マスを10
％塩酸で中和し、70℃、60mmHgの減圧下水を留
去し、更に減圧度を高めながらジメチルホルムア
ミドを留去した。最後に140℃、10mmHgで１時間
保つた。系内を常圧にもどした後、水800部を加
え、室温まで冷却した。 164 parts (1.03 mol) of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. After the dropwise addition was completed, the mixture was kept at the same temperature for an additional hour. After the reaction is completed, the reaction mass is reduced to 10
% hydrochloric acid, water was distilled off under reduced pressure of 60 mmHg at 70°C, and dimethylformamide was further distilled off while increasing the degree of vacuum. Finally, it was kept at 140°C and 10mmHg for 1 hour. After returning the inside of the system to normal pressure, 800 parts of water was added and the system was cooled to room temperature.
過により湿ケーキ450部を得た。パラニトロ
フエニル−β−ヒドロキシエチルスルフイドの含
量80％であつた。収率は95％である。 450 parts of wet cake was obtained by filtration. The content of paranitrophenyl-β-hydroxyethyl sulfide was 80%. Yield is 95%.
実施例 ６
実施例４で回収されたジメチルホルムアミドを
更に精留により水を留去した。得られたジメチル
ホルムアミド（水分含有率２重量％）160部にパ
ラニトロクロロベンゼン158部を添加し、メルカ
プトエタノール94部を加え、45℃に昇温した。続
いて水酸化ナトリウムの粉体41部を４時間で添加
た。添加終了後、更に２時間同温度で保温した。
反応終了後、反応マスを中和し析出している塩化
ナトリウムを別した後液をフラツシユ蒸留し
たジメチルホルムアミドを留去した。Example 6 Water was further removed from the dimethylformamide recovered in Example 4 by rectification. 158 parts of para-nitrochlorobenzene was added to 160 parts of the obtained dimethylformamide (water content: 2% by weight), 94 parts of mercaptoethanol were added, and the temperature was raised to 45°C. Subsequently, 41 parts of sodium hydroxide powder was added over a period of 4 hours. After the addition was completed, the mixture was kept at the same temperature for an additional 2 hours.
After the reaction was completed, the reaction mass was neutralized and the precipitated sodium chloride was separated, and the liquid was flash distilled to remove dimethylformamide.
パラニトロフエニル−β−ヒドロキシエチルス
ルフイド193部得た。収率は97％である。 193 parts of para-nitrophenyl-β-hydroxyethyl sulfide was obtained. Yield is 97%.
実施例 ７
パラニトロクロルベンゼン158部を水分含有率
５％のＮ−メチル−２−ピロリドン160部に添加
し、メルカプトエタノール94部（1.2モル倍）を
加え、45℃に昇温した。Example 7 158 parts of para-nitrochlorobenzene was added to 160 parts of N-methyl-2-pyrrolidone with a water content of 5%, 94 parts of mercaptoethanol (1.2 times the mole) was added, and the temperature was raised to 45°C.
続いて水酸化ナトリウムの粉体41部（1.01モル
倍）を５時間にわたつて添加した。添加終了後更
に１時間同温度で保温した。 Subsequently, 41 parts (1.01 mol) of sodium hydroxide powder was added over 5 hours. After the addition was completed, the mixture was kept at the same temperature for an additional hour.
〓〓〓〓〓
反応終了後、反応マスを中和し、析出している
塩化ナトリウムを別後、液をフラツシユ蒸留
し、Ｎ−メチル−２−ピロリドンを留出した。〓〓〓〓〓
After the reaction was completed, the reaction mass was neutralized and the precipitated sodium chloride was separated, and the liquid was flash distilled to distill off N-methyl-2-pyrrolidone.
パラニトロフエニル−β−ヒドロキシエチルス
ルフイド192部を得た。収率は96％であつた。 192 parts of para-nitrophenyl-β-hydroxyethyl sulfide were obtained. The yield was 96%.
実施例 ８
パラニトロクロロベンゼン158部を水分含有率
３％のジメチルアセトアミド160部に添加しメル
カプトエタノール115部を加え50℃に昇温した。Example 8 158 parts of para-nitrochlorobenzene was added to 160 parts of dimethylacetamide with a water content of 3%, 115 parts of mercaptoethanol was added, and the temperature was raised to 50°C.
水酸化ナトリウムの粉体41部を５時間にわたつ
て添加した。添加終了後、更に１時間同温度で保
温した。反応終了後、反応マスを中和し、析出し
ている塩化ナトリウムを別した後、ジメチルア
セトアミドに溶解しているパラニトロフエニル−
β−ヒドロキシエチルスルフイドの含量を分析し
たところ収率95％でパラニトロフエニル−β−ヒ
ドロキシエチルスルフイドが得られている事がわ
かつた。 41 parts of sodium hydroxide powder was added over 5 hours. After the addition was completed, the mixture was kept at the same temperature for an additional hour. After the reaction is completed, the reaction mass is neutralized and the precipitated sodium chloride is separated, and then the p-nitrophenyl dissolved in dimethylacetamide is removed.
Analysis of the content of β-hydroxyethyl sulfide revealed that para-nitrophenyl-β-hydroxyethyl sulfide was obtained with a yield of 95%.
実施例 ９
実施例４で回収されたジメチルホルムアミドを
更に精留により水を留去した。得られたジメチル
ホルムアミド（水分含有率２重量％）80部にパラ
ニトロクロロベンゼン79部を添加し、メルカプト
エタノール47部（1.2モル倍）を加え、40℃に昇
温した。水酸化カリウムの粉体29部（1.03モル
倍）を４時間で添加した。添加終了後、更に１時
間同温度で保温した。反応終了後、反応マスを中
和し、実施例４と同様の処理を行なつてパラニト
ロフエニル−β−ヒドロキシエチルスルフイド含
量85％のオイルを81部得た。収率は95％である。Example 9 Water was further removed from the dimethylformamide recovered in Example 4 by rectification. 79 parts of para-nitrochlorobenzene was added to 80 parts of the obtained dimethylformamide (water content: 2% by weight), 47 parts of mercaptoethanol (1.2 times the mole) was added, and the temperature was raised to 40°C. 29 parts (1.03 mole times) of potassium hydroxide powder was added over 4 hours. After the addition was completed, the mixture was kept at the same temperature for an additional hour. After the reaction was completed, the reaction mass was neutralized and treated in the same manner as in Example 4 to obtain 81 parts of oil having a para-nitrophenyl-β-hydroxyethyl sulfide content of 85%. Yield is 95%.
比較例 １
パラニトロクロロベンゼン79部をエタノール80
部に添加し、メルカプトエタノール59部（1.5モ
ル倍）を加え、50℃に昇温した。Comparative Example 1 79 parts of para-nitrochlorobenzene was mixed with 80 parts of ethanol.
59 parts (1.5 mol) of mercaptoethanol were added, and the temperature was raised to 50°C.
水酸化ナトリウム21部（1.05モル倍）を４時間
にわたつて添加した。 21 parts (1.05 mole times) of sodium hydroxide was added over 4 hours.
添加終了後、同温度で保温を続けたところ保温
１時間ぐらいより系内の粘度が上昇し、ついに
は、高粘度スラリー状となつた。 After the addition was completed, the system was kept at the same temperature for about 1 hour, and the viscosity in the system increased, eventually turning into a highly viscous slurry.
反応マスを分析したところ、アゾキシ体が約20
％も生成していた。 Analysis of the reaction mass revealed that the azoxy compound was about 20
% was also generated.
目的のパラニトロフエニル−β−ヒドロキシエ
チルスルフイドの生成は約70％であり、他に多数
の不明成分が生成していた。 The production of the desired para-nitrophenyl-β-hydroxyethyl sulfide was approximately 70%, and many other unknown components were also produced.
比較例 ２
パラニトロクロロベンゼン300部を、ジメチル
ホルムアミド300部と水15部に添加し、メルカプ
トエタノール170.9部（1.15モル倍）を加え40〜
45℃に昇温した。（窒素雰囲気下）
そこへ、無水炭酸ナトリウム106.4部（0.527モ
ル倍）を加えた。Comparative Example 2 300 parts of para-nitrochlorobenzene was added to 300 parts of dimethylformamide and 15 parts of water, and 170.9 parts of mercaptoethanol (1.15 times the mole) was added.
The temperature was raised to 45°C. (Under nitrogen atmosphere) 106.4 parts (0.527 mole times) of anhydrous sodium carbonate was added thereto.
昇温して100℃で６時間保温したところでサン
プリングしたところ、原料のパラニトロクロロベ
ンゼンが26％も残つていた。 When the temperature was raised and kept at 100°C for 6 hours, a sample was taken and 26% of the raw material para-nitrochlorobenzene remained.
比較例 ３
パラニトロクロロベンゼン300部を、ジメチル
ホルムアミド300部と水15部に添加し窒素雰囲気
下メルカプトエタノール170.9部（1.15モル倍）
を加えた。そこへ、室温下無水炭酸カリウム
138.7部（0.527モル倍）を一度に加えた。Comparative Example 3 300 parts of para-nitrochlorobenzene was added to 300 parts of dimethylformamide and 15 parts of water, and 170.9 parts of mercaptoethanol (1.15 times the mole) was added under a nitrogen atmosphere.
added. There, at room temperature, anhydrous potassium carbonate
138.7 parts (0.527 mole times) were added at once.
反応系内が66℃まで上昇した。更に65〜70℃の
温度で保温した。６時間保温したところでサンプ
リングしたところ原料のパラニトロクロロベンゼ
ンが10％も残つていた。 The temperature inside the reaction system rose to 66°C. It was further kept warm at a temperature of 65-70°C. When we took a sample after keeping it warm for 6 hours, we found that 10% of the raw material para-nitrochlorobenzene remained.
〓〓〓〓〓
〓〓〓〓〓
Claims (1)
イド類から選ばれる少なくとも１種の有機溶媒と
水との混合溶媒を反応媒体とし、パラニトロハロ
ベンゼンとメルカプトエタノールとを30゜乃至50
℃の温度範囲でアルカリ金属水酸化物を添加しな
がら反応させることを特徴とするパラニトロフエ
ニル−β−ヒドロキシエチルスルフイドの製造方
法。 ２ 反応媒体として有機溶媒に対する水の割合が
２乃至30重量％である混合溶媒を用いる特許請求
の範囲第１項に記載の製造方法。 ３ アルカリ金属水酸化物の使用量が、パラニト
ロハロベンゼンに対して1.0乃至1.03モルである
特許請求の範囲第１項または第２項に記載の製造
方法。[Scope of Claims] 1 A mixed solvent of water and at least one organic solvent selected from N-alkyl-substituted amides and sulfoxides is used as a reaction medium, and para-nitrohalobenzene and mercaptoethanol are mixed at 30° to 50° C.
1. A method for producing para-nitrophenyl-β-hydroxyethyl sulfide, which comprises reacting while adding an alkali metal hydroxide at a temperature range of .degree. 2. The manufacturing method according to claim 1, which uses a mixed solvent in which the ratio of water to organic solvent is 2 to 30% by weight as the reaction medium. 3. The manufacturing method according to claim 1 or 2, wherein the amount of alkali metal hydroxide used is 1.0 to 1.03 mol based on para-nitrohalobenzene.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5748482A JPS58174357A (en) | 1982-04-06 | 1982-04-06 | Preparation of mononitrophenyl-beta-hydroxyethyl sulfide |
| US06/477,443 US4612394A (en) | 1982-04-06 | 1983-03-21 | Process for producing aminophenyl-β-hydroxyethylsulfone |
| DE8383301683T DE3373093D1 (en) | 1982-04-06 | 1983-03-25 | Process for producing aminophenyl-beta-hydroxyethylsulfone |
| EP83301683A EP0092909B1 (en) | 1982-04-06 | 1983-03-25 | Process for producing aminophenyl-beta-hydroxyethylsulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5748482A JPS58174357A (en) | 1982-04-06 | 1982-04-06 | Preparation of mononitrophenyl-beta-hydroxyethyl sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58174357A JPS58174357A (en) | 1983-10-13 |
| JPS6111945B2 true JPS6111945B2 (en) | 1986-04-05 |
Family
ID=13056980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5748482A Granted JPS58174357A (en) | 1982-04-06 | 1982-04-06 | Preparation of mononitrophenyl-beta-hydroxyethyl sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58174357A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5758661A (en) * | 1980-09-25 | 1982-04-08 | Nippon Kayaku Co Ltd | Production of p-nitrophenyl-beta-hydroxyethylsulfide |
-
1982
- 1982-04-06 JP JP5748482A patent/JPS58174357A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5758661A (en) * | 1980-09-25 | 1982-04-08 | Nippon Kayaku Co Ltd | Production of p-nitrophenyl-beta-hydroxyethylsulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58174357A (en) | 1983-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0165135B1 (en) | Process for preparing trifluoromethylated carboxylic acids | |
| JP2005526049A (en) | Preparation of benzisoxazole methanesulfonyl chloride and its method of amidation to form zonisamide | |
| JP3223586B2 (en) | Method for producing 2,5-bis (mercaptomethyl) -1,4-dithiane | |
| JP6922890B2 (en) | A method for producing a solution composition containing a monoetherified product, a method for producing a solution composition, and a method for producing a polymerizable compound. | |
| JPS6111945B2 (en) | ||
| JPS6241655B2 (en) | ||
| JPS61282355A (en) | Manufacture of 4,4'-dinitrostilbene-2,2'-disulfonate | |
| WO2007012183A1 (en) | Process for the production of bicalutamide | |
| US5079381A (en) | Method for the preparation of 4-methylsulfonyl benzoic acid derivatives and intermediates | |
| CA2059821C (en) | 2,5-dichlorophenylthioglycolic acid derivative and method for its production | |
| EP0162404B1 (en) | Process for preparing 2-alkyl-5-haloacetylbenzenesulfonamide | |
| JP3089373B2 (en) | Method for producing 2-mercapto-phenothiazine | |
| SU961559A3 (en) | Process for producing 5-mercapto-1,2,3-triazoles | |
| JP2009221185A (en) | Method for producing toluidine compound | |
| FR2564834A1 (en) | PROCESS FOR THE PREPARATION OF ALKYL 3-CHLOROSULFONYLTHIOPHENE-2-CARBOXYLATE | |
| JPS6140661B2 (en) | ||
| JPH02172969A (en) | Production of dithiol di(meth)acrylate | |
| KR100518933B1 (en) | Method for purifying Oxazoline- azetidinone derivative | |
| JP2789400B2 (en) | 2,5-Dichlorophenylthioglycolic acid derivative and method for producing the same | |
| JPS5993064A (en) | Preparation of acetonyl isocyanurate | |
| JPH0254336B2 (en) | ||
| JPH05331150A (en) | Production of 2-alkoxy-3-sulfanylamidopyrazine | |
| JPH054382B2 (en) | ||
| JPH0310618B2 (en) | ||
| WO2019240140A1 (en) | Method for producing solid triazolinedione compound, solid triazolinedione compound, and method for producing triazolinedione compound |