JPH01258649A - Production of 2,4-dichloro-3-alkyl-6-nitrophenol - Google Patents
Production of 2,4-dichloro-3-alkyl-6-nitrophenolInfo
- Publication number
- JPH01258649A JPH01258649A JP8434888A JP8434888A JPH01258649A JP H01258649 A JPH01258649 A JP H01258649A JP 8434888 A JP8434888 A JP 8434888A JP 8434888 A JP8434888 A JP 8434888A JP H01258649 A JPH01258649 A JP H01258649A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- salt
- general formula
- dichloro
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 239000012320 chlorinating reagent Substances 0.000 claims description 4
- 238000006396 nitration reaction Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 6
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000000802 nitrating effect Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 i-amyl Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- OUCHEIMFQFFHDG-UHFFFAOYSA-N 2,3,5-trichloro-4-ethylbenzenesulfonic acid Chemical compound CCC1=C(Cl)C=C(S(O)(=O)=O)C(Cl)=C1Cl OUCHEIMFQFFHDG-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、特にカラー写真感光材料の分野におけるシア
ン発色剤の中間体として有用な２゜４−ジクロロ−８−
アルキル−６−ア【ノフェノールの前駆体である２、４
−ジクロロ−８−アルキル−６−ニトロフェノールの製
造方法に関する。Detailed Description of the Invention <Industrial Application Field> The present invention provides 2゜4-dichloro-8-
2,4, which is a precursor of alkyl-6-a[nophenol]
-Relating to a method for producing dichloro-8-alkyl-6-nitrophenol.
〈従来の技術〉
特開昭４７−８４８２６号公報および特開昭６１−５７
５８６号公報には、４−クロロ−８−アルキルフェノー
ルをスルホン化し、次いで、塩素化およびニトロ化を行
うことによって目的物である２、４−ジクロロ−８−ア
ルキル−６−ニトロフェノールを製造する方法が記載さ
れている。<Prior art> JP-A-47-84826 and JP-A-61-57
Publication No. 586 describes a method for producing the target product 2,4-dichloro-8-alkyl-6-nitrophenol by sulfonating 4-chloro-8-alkylphenol and then chlorinating and nitrating it. is listed.
また、特開昭６１−６０６８４号公報には、目的物を高
純度、高収率に製造することを目的に、１−アルキル−
４−二トロベンゼンを塩素化し、次いで加水分解する方
法が記載されている。In addition, Japanese Patent Application Laid-Open No. 61-60684 discloses 1-alkyl-
A method for chlorinating and then hydrolyzing 4-nitrobenzene is described.
〈発明が解決しようとする課題〉
前記した４−クロロ−８−アルキルフェノールを出発物
質とする方法は、その出発物質の入手が困難であるとい
う問題がある。すなわち、ｍ−エチルフェノールのよう
なｍ−アルキルフェノールおよびそれから誘導される４
−クロロ−８−アルキルフェノールを高純度に製造する
ことが極めて困難である。<Problems to be Solved by the Invention> The method using the above-mentioned 4-chloro-8-alkylphenol as a starting material has a problem in that the starting material is difficult to obtain. i.e. m-alkylphenols such as m-ethylphenol and 4 derived therefrom.
It is extremely difficult to produce -chloro-8-alkylphenol with high purity.
また、１−アルキル−４−ニトロベンゼンを出発物質と
する方法も、その出発物質は、公知の方法によれはアル
キルベンゼンを混酸を用いてニトロ化するために生成物
がオルトおよびパラ混合物であり精製を必要とし、低収
率でしか製造することができない。Furthermore, in the method using 1-alkyl-4-nitrobenzene as a starting material, since the starting material is nitrated using a mixed acid, the product is an ortho- and para-mixture and requires purification. required and can only be produced with low yields.
本発明者らは、２，４−ジクロロ−８−アルキル−６−
ニトロフェノールを容易かつ経済的に工業的有利に製造
する方法を見出すため沓こ鋭意検討した結果、本発明を
完成するに至った。The inventors have discovered that 2,4-dichloro-8-alkyl-6-
As a result of extensive research to find a method for easily, economically and industrially advantageous production of nitrophenol, the present invention has been completed.
く課題を解決するための手段〉
本発明は、下記一般式（２）
〔式中、Ｒは炭素数１〜８の直鎖または分枝のアルキル
基を表わす。〕
で示される化合物またはその塩を加水分解して下記一般
式面、
Ｓｏ、Ｈ
〔式中、Ｒは前記の意味を有する。〕
で示される化合物またはその塩を得、得られた一般式■
で示される化合物をニトロ化することを特徴とする下記
一般式（Ｉ）、
〔式中、Ｒ１，を前記の意味を有する。〕で示される２
、４−ジクロロ−８−アルキル−６−ニトロフェノール
の製造方法を提供する。Means for Solving the Problems> The present invention is directed to the following general formula (2) [wherein R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms]. ] The compound represented by these or a salt thereof is hydrolyzed to form the following general formula: So, H [wherein R has the above-mentioned meaning. ] Obtain the compound or its salt represented by the general formula ■
The following general formula (I) is characterized in that the compound represented by the formula (I) is nitrated, wherein R1 has the above-mentioned meaning. 2 indicated by ]
, provides a method for producing 4-dichloro-8-alkyl-6-nitrophenol.
本発明において前記一般式■で示される化合物は、下記
一般式（２）
〔式中、Ｒは前記の意味を有する。〕
で示される化合物を塩素化すること普こよって得ること
ができる。In the present invention, the compound represented by the above general formula (2) is represented by the following general formula (2) [wherein R has the above-mentioned meaning]. ] It can generally be obtained by chlorinating the compound shown below.
前記一般式（Ｉ）〜■において、Ｒで表わされるアルキ
ル基としては、メチル、エチル、ｎ−プロピル、ｉ−プ
ロピル、ｎ−ブチル、ｔ−ブチル、ｉ−アミル、ｎ−オ
クチルなどが例示され、本発明の方法は、Ｒがエチルま
たはｉ−プロピルである化合物に持に有利に適用するこ
とができる。In the general formulas (I) to (2) above, examples of the alkyl group represented by R include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-amyl, n-octyl, etc. , the method of the invention can be applied with particular advantage to compounds in which R is ethyl or i-propyl.
また、前記一般式面、（２）及び（２）で示される各化
合物の塩としては、アルカリ金属塩、アルカリ土類金属
塩、アミン塩などが例示され、通常用いられる塩は、例
えば、ナトリウム塩、カリウム塩、マグネシウム塩など
である。In addition, examples of the salts of the compounds represented by the above general formulas (2) and (2) include alkali metal salts, alkaline earth metal salts, amine salts, etc. Salts commonly used include, for example, sodium salt, potassium salt, magnesium salt, etc.
一般式（至）で示される化合物またはその塩の塩素化は
、触媒の存在下または非存在下に塩素化剤を用い溶媒中
で行うことができる。Chlorination of the compound represented by the general formula (-) or a salt thereof can be carried out in a solvent using a chlorinating agent in the presence or absence of a catalyst.
塩素化に用いる溶媒としては無機酸、有機酸、極性有機
溶媒、ハロゲン化炭化水素などが例示される。Examples of the solvent used for chlorination include inorganic acids, organic acids, polar organic solvents, and halogenated hydrocarbons.
無機酸としては硫酸、塩酸などの鉱酸が用いられ、必要
により無水Ｈｑ、クロルスルホン酸を混合して用いても
よい。As the inorganic acid, mineral acids such as sulfuric acid and hydrochloric acid are used, and if necessary, anhydrous Hq and chlorosulfonic acid may be used in combination.
有機酸としては、酢酸、トリフロロ酢酸、モノクロロ酢
酸、ジクロロ酢酸などがあげられる。Examples of organic acids include acetic acid, trifluoroacetic acid, monochloroacetic acid, and dichloroacetic acid.
極性有機溶媒としては、ニトロベンゼン、ｐ−クロルニ
トロベンゼン、Ｎ、Ｎ−ジメチルホルムアミドなどがあ
げられる。Examples of the polar organic solvent include nitrobenzene, p-chloronitrobenzene, N,N-dimethylformamide, and the like.
ハロゲン化炭化水素としては、塩化メチレン、クロロホ
ルム、四塩化炭素、モノまたはジクロロベンゼンなどが
あげられる。Examples of halogenated hydrocarbons include methylene chloride, chloroform, carbon tetrachloride, mono- or dichlorobenzene, and the like.
これらの溶媒中、無機酸、ハロゲン化炭化水素が好まし
く、とりわけ、硫酸などの無機酸が好ましい。Among these solvents, inorganic acids and halogenated hydrocarbons are preferred, and inorganic acids such as sulfuric acid are particularly preferred.
塩素化に用いてもよい触媒としては、たとえば、塩化鉄
、塩化アンチモン、塩化アルミニウム、ヨウ素などがあ
げられる。その使用量は特に限定されないが、好ましく
は、一般式（２）で示される化合物またはその塩に対し
て１〜１０重１％である。Examples of catalysts that may be used for chlorination include iron chloride, antimony chloride, aluminum chloride, and iodine. The amount used is not particularly limited, but is preferably 1 to 10% by weight based on the compound represented by general formula (2) or a salt thereof.
塩素化剤としては特に制限されないが好ましくは塩素ガ
ス、塩化スルフリルなどが用いられる。The chlorinating agent is not particularly limited, but chlorine gas, sulfuryl chloride, and the like are preferably used.
塩素化は、前記一般式［相］で示される化合物またはそ
の塩の含量が最高値またはその付近に到達するまで行う
。より詳しくは、一般式（２）で示される化合物または
その塩の含量が、塩素化反応混合物〔一般式ＧＶ）で示
される化合物またはその塩と塩素化によって生成した化
合物の和〕に対し、好ましくは６０重量％以上、更に好
ましくは７０〜９０重量％に到達するまで塩素化を行う
。そのためには、塩素化剤は一般式（至）で示される化
合物またはその塩に対して２〜６モル比、好ましくは、
２．５〜４．６モル比、更に好ましくは２．７〜４モル
比用いる。また、反応ｍ度は通常０８〜１５０℃である
が、好ましくは２０゜〜８０℃である。Chlorination is carried out until the content of the compound represented by the general formula [phase] or its salt reaches the maximum value or its vicinity. More specifically, the content of the compound represented by the general formula (2) or its salt is preferably based on the chlorination reaction mixture [the sum of the compound represented by the general formula GV or its salt and the compound produced by chlorination]. Chlorination is carried out until it reaches 60% by weight or more, more preferably 70 to 90% by weight. For this purpose, the chlorinating agent should be used in a molar ratio of 2 to 6, preferably
A molar ratio of 2.5 to 4.6, more preferably 2.7 to 4 is used. Further, the reaction temperature is usually 08° to 150°C, preferably 20° to 80°C.
前記一般式（ｌＩＩ）で示される化合物またはその塩の
加水分解は溶媒中でアルカリ化合物を用いて行うことが
できる。Hydrolysis of the compound represented by the general formula (lII) or a salt thereof can be carried out in a solvent using an alkali compound.
加水分解に用いる溶媒としては、水、有機溶媒およびそ
れらの混合溶媒などがあげられる。Examples of the solvent used for hydrolysis include water, organic solvents, and mixed solvents thereof.
有機溶媒としては、たとえば脂肪族アルコール、ケトン
、エーテルなどがあげられる。それらの中、好ましくは
、ブタノール、アミルアルコール、ヘキシルアルコール
、ヘプチルアルコール、オクチルアルコール、グリコー
ル、カルビトート、ジメチルスルホキシド、スルホラン
、ジオキサンなどがあげられる。Examples of organic solvents include aliphatic alcohols, ketones, and ethers. Among them, preferred are butanol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, glycol, carbitote, dimethyl sulfoxide, sulfolane, dioxane and the like.
加水分解に用いるアルカリ化合物は、たとえば、アルカ
リ金属またはアルカリ土類金属の水酸化物、酸化物、炭
酸塩などであり、水酸化ナトリウムや水酸化カリウムな
どが好ましく用いられる。アルカリ化合物の使用風は一
般式ωで示される化合物１モルに対し、２〜２０モル、
好ましくは８〜１０モルである。The alkali compound used for hydrolysis is, for example, a hydroxide, oxide, carbonate, etc. of an alkali metal or alkaline earth metal, and sodium hydroxide, potassium hydroxide, etc. are preferably used. The alkali compound used is 2 to 20 mol per mol of the compound represented by the general formula ω,
Preferably it is 8 to 10 mol.
加水分解反応は通常は常圧下に行うが加圧下に行っても
よい。反応温度は１１０℃〜２８０℃、好ましくは１２
０〜１８０℃である。The hydrolysis reaction is usually carried out under normal pressure, but may also be carried out under increased pressure. The reaction temperature is 110°C to 280°C, preferably 12
The temperature is 0 to 180°C.
加水分解後、生成物を単離し、次いでニトロ化を行い目
的とする前記一般式（Ｉ）で示される２゜４−ジクロロ
−８−アルキル−６−ニトロフェノールを得ることがで
きる。After hydrolysis, the product is isolated and then nitrated to obtain the desired 2.4-dichloro-8-alkyl-6-nitrophenol represented by the general formula (I).
ニトロ化は公知のいずれの方法によっても行うことがで
きる、例えば、一般式（［１）で示される化合物を稀硫
酸中で、ニトロ化剤として硝酸又は混酸などを用いて行
うことができる。この場合、通常は、硝酸を化学量論量
のや＼過剰〜大過剰用い、０〜１００℃、好ましくは２
０〜５０℃の温度でニトロ化を行って前記一般式（Ｉ）
で示される化合物を得ることができる。Nitration can be carried out by any known method. For example, the compound represented by the general formula ([1)] can be heated in dilute sulfuric acid using nitric acid or a mixed acid as a nitration agent. In this case, nitric acid is usually used in a stoichiometric amount to a large excess at a temperature of 0 to 100°C, preferably 2°C.
Nitration is carried out at a temperature of 0 to 50°C to obtain the general formula (I)
A compound represented by can be obtained.
本発明の方法によれば、入手が容易な４−アルキルベン
ゼンスルホン酸を用い、目的とする一般式（Ｉ）で示さ
れる化合物を高純度に、工業的有利に製造することがで
きる。According to the method of the present invention, the target compound represented by the general formula (I) can be produced with high purity and with industrial advantage using easily available 4-alkylbenzenesulfonic acid.
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。例
中、部２％は各々重量部、重量％を表わす、
参考例１
９６％硫酸１０００部齋こヨウ素５部を溶解した後、こ
れに４−エチルベンゼンスルホン酸１８６部を入れ攪拌
下４０〜６０℃で塩素約２８６部を導入した。このとき
塩素化混合物中における２、（，５−トリクロロ−５−
エチルベンゼンスルホン酸の割合は７８．８％となった
。次にこれを水２７００部に投入し希釈後、２８％水酸
化ナトリウム水溶液４００部を加え結晶を析出させた。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples. In the examples, parts 2% represent parts by weight and weight %, respectively. Reference Example 1 After dissolving 1000 parts of 96% sulfuric acid and 5 parts of saline iodine, 186 parts of 4-ethylbenzenesulfonic acid was added thereto and the mixture was stirred for 40 to 60 minutes. Approximately 286 parts of chlorine were introduced at . At this time, 2,(,5-trichloro-5-
The proportion of ethylbenzenesulfonic acid was 78.8%. Next, this was poured into 2,700 parts of water to dilute it, and then 400 parts of a 28% aqueous sodium hydroxide solution was added to precipitate crystals.
これを戸別し、乾燥して白色結晶の粗２，８．５−トリ
クロロー４−エチルベンゼンスルホン酸ナトリウム８０
８部を得た。（収率８１．６％） ＨＰＬＣ分析値、２
，８．５−トリクロロ−４−エチルベンゼンスルホン酸
ナトリウム、： ８２．５％、２．８，５．６−テトラ
クロロ−４−エチルベンゼンスルホン酸ナトリウム：１
Ｂ、０％、３．６−ジクロロ−４−エチルベンゼンスル
ホン酸ナトリウム：８８％。This is taken from house to house and dried to form white crystals of crude sodium 2,8.5-trichloro-4-ethylbenzenesulfonate.
I got 8 copies. (Yield 81.6%) HPLC analysis value, 2
, 8.5-Sodium trichloro-4-ethylbenzenesulfonate: 82.5%, Sodium 2.8,5.6-tetrachloro-4-ethylbenzenesulfonate: 1
B, 0%, sodium 3.6-dichloro-4-ethylbenzenesulfonate: 88%.
参考例２
原料に４−イソプロピルベンゼンスルホン酸２００部を
用いるほかは実施例１と同様に行った。粗２，８．５−
トリクロロー４−イソプロピルベンゼンスルホン酸ナト
リウムの収！８１４部。（収率７５．５％）、ＨＰＬＣ
分析値、２，８．５−トリクロロ−４−イソプロピルベ
ンゼンスルホン酸ナトリウムニア８．８％、２，８，５
．６−テトラクロロ−４−イソプロピルベンゼンスルホ
ン酸ナトリウム：１６．５％、８．５−ジクロロ−４−
イソプロピルベンゼンスルホン酸ナトリウム＝４．８％
。Reference Example 2 The same procedure as Example 1 was carried out except that 200 parts of 4-isopropylbenzenesulfonic acid was used as the raw material. Crude 2,8.5-
Yield of sodium trichloro-4-isopropylbenzenesulfonate! 814 copies. (yield 75.5%), HPLC
Analysis value, sodium 2,8.5-trichloro-4-isopropylbenzenesulfonate 8.8%, 2,8,5
．． Sodium 6-tetrachloro-4-isopropylbenzenesulfonate: 16.5%, 8.5-dichloro-4-
Sodium isopropylbenzenesulfonate = 4.8%
.
実施例１
エチレングリコール２００部にＫＯ）ｆ８２部を加え溶
解した。次いで参考例１で得た粗２．８．５−トリクロ
ロ−４−エチルベンゼンスルホン酸ナトリウム８２部を
加え攪拌しながら１４０〜１６０℃で１２時間反応させ
た。反応終了後、水２００部を加え希釈し、次Ｇこ希硫
酸でｐＨを８〜６に調整し析出した結晶を戸別した。水
を含んだこの結晶を２６％硫酸８５０部に投入し、２ｂ
〜５０℃で攪拌しながら６２％硝酸７４部を滴下し、同
温度で１時間攪拌した後、５℃まで冷却した。Example 1 82 parts of KO)f was added to 200 parts of ethylene glycol and dissolved. Next, 82 parts of crude sodium 2.8.5-trichloro-4-ethylbenzenesulfonate obtained in Reference Example 1 was added and reacted at 140 to 160°C for 12 hours with stirring. After the reaction was completed, 200 parts of water was added to dilute the mixture, the pH was adjusted to 8 to 6 with dilute sulfuric acid, and the precipitated crystals were collected from house to house. This crystal containing water was added to 850 parts of 26% sulfuric acid, and 2b
74 parts of 62% nitric acid was added dropwise while stirring at ~50°C, and after stirring at the same temperature for 1 hour, the mixture was cooled to 5°C.
析出した結晶を透過、水洗し乾燥し、２．４−シクロロ
ー８−エチル−６−二トロフエノール１６．６部を得た
。（収率７８．１％）、融点４６．２℃〜４７．２℃、
元素分析、実測値、Ｃ：４０．４９％、Ｈ：８．０４％
、Ｎ：５．８８％、Ｃ１：２９．８％、計算値、Ｃ：４
０．７１％、Ｈ：２．９９％、Ｎ：５．９８％、Ｃ１：
８０．０４％。The precipitated crystals were filtered, washed with water, and dried to obtain 16.6 parts of 2,4-cyclo8-ethyl-6-nitrophenol. (yield 78.1%), melting point 46.2°C to 47.2°C,
Elemental analysis, actual value, C: 40.49%, H: 8.04%
, N: 5.88%, C1: 29.8%, calculated value, C: 4
0.71%, H: 2.99%, N: 5.98%, C1:
80.04%.
実施例２〜５
下表に記載した反応条件以外は実施例１と同ｆｉｔζ行
って下表のとおり結果を得た。Examples 2 to 5 The same fitζ as in Example 1 was carried out except for the reaction conditions listed in the table below, and the results were obtained as shown in the table below.
＼
＼
＼
実施例６
ＫＯＨ８２部のかわりに、ＮａＯＨ２４部を使用する他
は実施例１と同様に行った。２゜４−ジクロロ−８−エ
チル−６−二トロフエノールの収量１２．６部（収率６
８．１％）。＼ ＼ ＼ Example 6 The same procedure as in Example 1 was carried out except that 24 parts of NaOH was used instead of 82 parts of KOH. Yield of 2゜4-dichloro-8-ethyl-6-nitrophenol: 12.6 parts (yield: 6
8.1%).
実施例７
粗２．８．５−トリクロロー４−エチルベンゼンスルホ
ン酸ナトリウム８２部のかわりに参考例２で得られた粗
２，８．５−トリクロロー４−イソプロピルベンゼンス
ルホン酸ナトリウム８５部を使用する他は実施例１と同
様に行った。２．４−ジクロロ−８−イソプロピル−６
−二トロフエノールの収ｆｉ１１．４部（収率５Ｂ、８
％）、融点８５．２〜８６．７℃、元素分析、実測値、
Ｃ：４Ｂ、４０％、Ｈ：８．７１％、Ｎ：５．５７％、
ＣＭ２８．２％、計算値、Ｃ：４８．２８％、Ｈ：８．
６６、Ｎ：５．６０％、Ｃ１：２８．８５％。Example 7 85 parts of crude sodium 2,8.5-trichloro-4-isopropylbenzenesulfonate obtained in Reference Example 2 was used instead of 82 parts of crude sodium 2,8.5-trichloro-4-ethylbenzenesulfonate. was carried out in the same manner as in Example 1. 2.4-dichloro-8-isopropyl-6
- Nitrophenol yield 11.4 parts (yield 5B, 8
%), melting point 85.2-86.7°C, elemental analysis, measured value,
C: 4B, 40%, H: 8.71%, N: 5.57%,
CM28.2%, calculated value, C: 48.28%, H: 8.
66, N: 5.60%, C1: 28.85%.
Claims (4)
基を表わす。〕 で示される化合物またはその塩を加水分解して下記一般
式（II）、 ▲数式、化学式、表等があります▼（II） 〔式中、Ｒは前記の意味を有する。〕 で示される化合物またはその塩を得、得られた一般式（
II）で示される化合物をニトロ化することを特徴とする
下記一般式（ I ）、 ▲数式、化学式、表等があります▼（ I ） 〔式中、Ｒは前記の意味を有する。〕 で示される２，４−ジクロロ−３−アルキル−６−ニト
ロフェノールの製造方法。(1) General formula (III) below, ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms. ] The following general formula (II) is obtained by hydrolyzing the compound or a salt thereof, ▲ Numerical formula, chemical formula, table, etc. ▼ (II) [In the formula, R has the above meaning. ] A compound or a salt thereof is obtained, and the obtained general formula (
There are the following general formulas (I), ▲mathematical formulas, chemical formulas, tables, etc., which are characterized by nitration of the compound represented by II) (I) [wherein R has the above meaning. ] A method for producing 2,4-dichloro-3-alkyl-6-nitrophenol shown below.
基を表わす。〕 で示される化合物またはその塩を塩素化して得られる下
記一般式（III）、 ▲数式、化学式、表等があります▼（III） 〔式中、Ｒは前記の意味を有する〕 で示される化合物またはその塩を加水分解して下記一般
式（II）、 ▲数式、化学式、表等があります▼（II） 〔式中、Ｒは前記の意味を有する。〕 で示される化合物またはその塩を得、得られた一般式（
II）で示される化合物をニトロ化することを特徴とする
請求項１に記載の一般式（ I ）で示される２，４−ジ
クロロ−３−アルキル−６−ニトロフェノールの製造方
法。(2) General formula (IV) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (IV) [In the formula, R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms. ] Compounds represented by the following general formula (III) obtained by chlorinating the compound represented by or its salt, ▲Mathematical formula, chemical formula, table, etc.▼(III) [In the formula, R has the above meaning] Or its salt can be hydrolyzed to form the following general formula (II), ▲ Numerical formula, chemical formula, table, etc. ▼ (II) [In the formula, R has the above meaning. ] A compound or a salt thereof is obtained, and the obtained general formula (
The method for producing 2,4-dichloro-3-alkyl-6-nitrophenol represented by general formula (I) according to claim 1, characterized in that the compound represented by II) is nitrated.
請求項１または２に記載の製造方法。(3) The manufacturing method according to claim 1 or 2, wherein the hydrolysis is carried out using an alkali compound in a solvent.
塩素化剤を用いて行う請求項２に記載の製造方法。(4) The manufacturing method according to claim 2, wherein the chlorination is carried out in a solvent using a chlorinating agent in the presence or absence of a catalyst.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8434888A JPH01258649A (en) | 1988-04-05 | 1988-04-05 | Production of 2,4-dichloro-3-alkyl-6-nitrophenol |
| US07/319,718 US5012015A (en) | 1988-03-09 | 1989-03-07 | Process for producing 2,4-dichloro-3-alkyl-6-nitrophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8434888A JPH01258649A (en) | 1988-04-05 | 1988-04-05 | Production of 2,4-dichloro-3-alkyl-6-nitrophenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01258649A true JPH01258649A (en) | 1989-10-16 |
Family
ID=13828008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8434888A Pending JPH01258649A (en) | 1988-03-09 | 1988-04-05 | Production of 2,4-dichloro-3-alkyl-6-nitrophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01258649A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136109A (en) * | 1990-08-28 | 1992-08-04 | Taoka Chemical Company, Ltd. | Process for preparing 2,4-dichloro-3-alkyl-6-nitrophenols |
| JPH04231867A (en) * | 1990-05-15 | 1992-08-20 | Boehringer Mannheim Gmbh | Highly sensitive ion measuring method, use of material suitable for method thereof and corresponding reagent |
| US5292966A (en) * | 1992-03-18 | 1994-03-08 | Hoechst Aktiengesellschaft | Process for the preparation of 2-nitro-3, 6-dichlorophenol |
-
1988
- 1988-04-05 JP JP8434888A patent/JPH01258649A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04231867A (en) * | 1990-05-15 | 1992-08-20 | Boehringer Mannheim Gmbh | Highly sensitive ion measuring method, use of material suitable for method thereof and corresponding reagent |
| JP2665412B2 (en) * | 1990-05-15 | 1997-10-22 | ベーリンガー・マンハイム・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Highly sensitive ion measurement method, use of substances suitable for the method, and corresponding reagents |
| US5136109A (en) * | 1990-08-28 | 1992-08-04 | Taoka Chemical Company, Ltd. | Process for preparing 2,4-dichloro-3-alkyl-6-nitrophenols |
| US5292966A (en) * | 1992-03-18 | 1994-03-08 | Hoechst Aktiengesellschaft | Process for the preparation of 2-nitro-3, 6-dichlorophenol |
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