JPH0530827B2 - - Google Patents
Info
- Publication number
- JPH0530827B2 JPH0530827B2 JP33595390A JP33595390A JPH0530827B2 JP H0530827 B2 JPH0530827 B2 JP H0530827B2 JP 33595390 A JP33595390 A JP 33595390A JP 33595390 A JP33595390 A JP 33595390A JP H0530827 B2 JPH0530827 B2 JP H0530827B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- lower alkyl
- alkyl group
- general formula
- 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- OQEQFNOQDBQLGX-UHFFFAOYSA-N 4-(2,2,2-trifluoroethylsulfanyl)aniline Chemical compound NC1=CC=C(SCC(F)(F)F)C=C1 OQEQFNOQDBQLGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 101100073357 Streptomyces halstedii sch2 gene Proteins 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IGKCQDUYZULGBM-UHFFFAOYSA-N 2,2,2-trifluoroethyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC(F)(F)F)C=C1 IGKCQDUYZULGBM-UHFFFAOYSA-N 0.000 description 2
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- GDJYIXGPYCKDOV-UHFFFAOYSA-N n-phenylthiohydroxylamine Chemical compound SNC1=CC=CC=C1 GDJYIXGPYCKDOV-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- ABRHGSTXPVUNBK-UHFFFAOYSA-N 2,2,2-trifluoroethyl benzenesulfonate Chemical compound FC(F)(F)COS(=O)(=O)C1=CC=CC=C1 ABRHGSTXPVUNBK-UHFFFAOYSA-N 0.000 description 1
- JBHQQXONFHOEQU-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC(F)(F)C(F)(F)F)C=C1 JBHQQXONFHOEQU-UHFFFAOYSA-N 0.000 description 1
- IMDNPHAMGJIKNV-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC(F)(F)C(F)F)C=C1 IMDNPHAMGJIKNV-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical class NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- -1 fluoroalkanol Chemical compound 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
［産業上の利用分野］
本発明は、フルオロアルキルチオアニリン誘導
体及びその製法に関する。
更に詳しくは、本発明は、下記式（）で表わ
されるフルオロアルキルチオアニリン誘導体に関
する。即ち
一般式：
式中、Ａはハロゲン原子、低級アルキル基及び
低級アルコキシ基よりなる群からえらばれた基を
示し、複数ケのＡが存在する場合には、それらは
同一でも異なつていてもよい、
Ｒはフルオル置換−低級アルキル基を示し、
そして、ｍは０、１、２、３又は４を示す、
ただし、ｍが１を示し、上記式中のベンゼン環
に於いてＡが３または５の位置にあつて、且つ−
SCH2−Ｒが４の位置にあるときに、Ａは低級ア
ルキル基を示し、またｍが２を示し、上記式中の
ベンゼン環に於いて、Ａが３及び５の位置にあつ
て且つ−SCH2−Ｒが４の位置にあるときに、少
なくとも１ケのＡは低級アルコキシ基を示す、
上記一般式（）のフルオロアルキルチオアニ
リン誘導体は、例えば下記の方法により製造する
ことができ、本発明は該製法にも関する。
製 法
一般式
式中、Ａ及びｍは前記と同じ、そして
Ｍは水素原子もしくはアルカリ金属原子を示
す、
で表される化合物と、
一般式：
式中、Ｒは前記と同じ、そして
Ｚはアリール基又は低級アルキル基を示す、
で表わされる化合物とを反応させることを特徴と
する前記一般式（）のフルオロアルキルチオア
ニリン誘導体の製造方法。
本発明の前記一般式（）のフルオロアルキル
チオアニリン誘導体は、公知刊行物に一切記載さ
れていない新規な化合物である。そして、一般式
（）の該化合物は、殺虫性ベンゾイルウレア誘
導体の製造中間体として、有用であるばかりでな
く、その中間体であるフルオロアルキルチオアリ
ールイソシアネート誘導体の製造中間体として、
産業上有用なものである。
従つて、本発明の目的は、中間体として有用な
新規なフルオロアルキルチオアニリン誘導体及び
その製法を提供するにある。
［課題を解決するための手段］
本発明の一般式（）の化合物は、例えば、下
記の製法により、製造することができる。
（式中、Ａ、Ｒ、ｍ、Ｍ及びＺは前記と同じ。）
上記反応式において、Ａは、ｍが２、３又は４
を示して複数ケ存在する場合には、それらは同一
でも異なつていてもよい。Ａはハロゲン原子、例
えばフルオル；クロル；ブロム；ヨード、低級ア
ルキル基、例えばメチル；エチル；プロピル；イ
ソプロピル；ｎ−（iso−、sec−又はtert−）ブチ
ル等、及び上記例示と同様な低級アルキル基を有
する低級アルコキシ基よりなる群から選択でき
る。
Ｒは例としては、上記例示と同様な低級アルキ
ル基のフルオル置換体を例示することができる。
ｍは０、１、２、３又は４を示し、そしてＭは
水素原子及びナトリウム、カリウム等のアルカリ
金属原子よりえらばれた員を示し、Ｚはフエニル
基、ｐ−トリル基等のアリール基、又は前記Ａで
例示したと同様の低級アルキル基を示す。
上記反応式で示される本発明の一般式（）の
化合物の製法において、原料である一般式（）
の化合物の具体例としては、例えば、
２−メルカプトアニリン、
４−メルカプトアニリン、
等を例示することができる。
同様に原料である一般式（）の化合物の具体
例としては、例えば、
２，２，２−トリフルオロエチル−ｐ−トルエ
ンスルホネート、
２，２，３，３−テトラフルオロプロピル−ｐ
−トルエンスルホネート、
２，２，３，３，３−ペンタフルオロプロピル
−ｐ−トルエンスルホネート、
等を例示することができ、また上記例示のｐ−ト
ルエンスルホネート類の代わりに、それらに相当
するメタンスルホネート類、ベンゼンスルホネー
ト類を例示することもできる。
次に代表例を示し、上記製法を具体的に説明す
る。
上記方法を実施する際には、たとえば炭酸ナト
リウム、炭酸カリウム、水酸化ナトリウム、水酸
化カリウム、水素化ナトリウム等の塩基を共存さ
せ非プロトン性極性溶媒を使用し、高純度、高収
量で目的物を得ることができ、斯る溶媒として
は、例えば１，２−ジメトキシエタン、ジメチル
ホルムアミド、ジメチルアセトアミド、ジメチル
スルホキシド、スルホラン、Ｎ−メチル−２−ピ
ロリドン、ヘキサメチルホスホロアミド等をあげ
ることができる。またプロトン性極性溶媒のうち
第３級アルコール、例えばtert−ブタノールも使
用することができる。
上記方法は広い温度範囲内において実施するこ
とができる。例えば、約０℃〜約120℃の間で実
施でき、望ましくは約20℃〜約80℃の間で実施で
きる。また反応は常圧の下で行なうのが望ましい
が、加圧または減圧下で操作することも可能であ
る。
尚、上記製法における原料の一般式（）の化
合物はハロニトロベンゼン、例えば、４−クロル
ニトロベンゼン
[Industrial Application Field] The present invention relates to a fluoroalkylthioaniline derivative and a method for producing the same. More specifically, the present invention relates to a fluoroalkylthioaniline derivative represented by the following formula (). That is, general formula: In the formula, A represents a group selected from the group consisting of a halogen atom, a lower alkyl group, and a lower alkoxy group, and when multiple A's are present, they may be the same or different; R is represents a fluoro-substituted lower alkyl group, and m represents 0, 1, 2, 3 or 4, provided that m represents 1 and A is at the 3 or 5 position in the benzene ring in the above formula; At, and-
When SCH 2 -R is at the 4 position, A represents a lower alkyl group, m is 2, A is at the 3 and 5 positions of the benzene ring in the above formula, and - The fluoroalkylthioaniline derivative of the above general formula (), in which when SCH 2 -R is at the 4-position, at least one A represents a lower alkoxy group, can be produced, for example, by the following method, and the present invention also relates to the manufacturing method. Manufacturing method General formula In the formula, A and m are the same as above, and M represents a hydrogen atom or an alkali metal atom, and a compound represented by the general formula: A method for producing a fluoroalkylthioaniline derivative of the general formula (), characterized in that R is the same as above, and Z represents an aryl group or a lower alkyl group. The fluoroalkylthioaniline derivative of the general formula () of the present invention is a novel compound that has not been described in any known publications. The compound of general formula () is not only useful as an intermediate for producing insecticidal benzoyl urea derivatives, but also as an intermediate for producing fluoroalkylthioarylisocyanate derivatives, which are intermediates thereof.
It is industrially useful. Therefore, an object of the present invention is to provide a novel fluoroalkylthioaniline derivative useful as an intermediate and a method for producing the same. [Means for Solving the Problems] The compound of general formula () of the present invention can be produced, for example, by the following production method. (In the formula, A, R, m, M and Z are the same as above.) In the above reaction formula, A means that m is 2, 3 or 4.
If there are multiple numbers, they may be the same or different. A is a halogen atom, such as fluoro; chloro; bromo; iodo; a lower alkyl group, such as methyl; ethyl; propyl; isopropyl; n-(iso-, sec- or tert-)butyl, etc., and lower alkyl as exemplified above. can be selected from the group consisting of lower alkoxy groups having groups. Examples of R include the same fluoro-substituted lower alkyl groups as exemplified above. m represents 0, 1, 2, 3 or 4; M represents a hydrogen atom and a member selected from alkali metal atoms such as sodium and potassium; Z represents an aryl group such as a phenyl group or a p-tolyl group; Or it represents the same lower alkyl group as exemplified in A above. In the method for producing a compound of the general formula () of the present invention shown in the above reaction formula, the general formula () which is a raw material is
Specific examples of the compound include 2-mercaptoaniline, 4-mercaptoaniline, and the like. Similarly, specific examples of compounds of general formula () which are raw materials include 2,2,2-trifluoroethyl-p-toluenesulfonate, 2,2,3,3-tetrafluoropropyl-p
-toluenesulfonate, 2,2,3,3,3-pentafluoropropyl-p-toluenesulfonate, and the like, and in place of the above-mentioned p-toluenesulfonates, corresponding methanesulfonates may be used. and benzenesulfonates. Next, a representative example will be shown and the above manufacturing method will be specifically explained. When carrying out the above method, for example, an aprotic polar solvent is used in the presence of a base such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, etc., and the desired product can be obtained with high purity and high yield. Examples of such solvents include 1,2-dimethoxyethane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, N-methyl-2-pyrrolidone, and hexamethylphosphoramide. . Among protic polar solvents, tertiary alcohols such as tert-butanol can also be used. The above method can be carried out within a wide temperature range. For example, it can be carried out at a temperature between about 0°C and about 120°C, preferably between about 20°C and about 80°C. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. In addition, the compound of general formula () as a raw material in the above production method is halonitrobenzene, for example, 4-chloronitrobenzene.
【式】から、公
知の方法［Journal of the American Chemical
Society、Vol71、1747、（1949）。］に従つて、得
ることができる。
また、上記製法において、原料の一般式（）
の化合物中には、酸化反応に鋭敏なものがある。
そのような場合には、反応に際しては、例えば、
窒素ガスの様な不活性ガス中で、前記の如き、反
応溶媒に溶かし、炭酸カリウム、又はカリウム
tert−ブトキサイドを作用させるか、若しくは、
該メルカプトアニリンの合成操作中に、酸化反応
によつて生じる生成物（該メルカプトアニリンに
相当するジサルフアイド、即ち
From [Formula], a known method [Journal of the American Chemical
Society, Vol71, 1747, (1949). ] can be obtained. In addition, in the above manufacturing method, the general formula of the raw material ()
Some compounds are sensitive to oxidation reactions.
In such a case, the reaction may include, for example,
In an inert gas such as nitrogen gas, dissolve potassium carbonate or potassium in a reaction solvent as described above.
act with tert-butoxide, or
During the synthesis of the mercaptoaniline, a product generated by the oxidation reaction (a disulfide corresponding to the mercaptoaniline, i.e.
【式】を分離す
ることなく、水素化ナトリウムを作用させるとに
より、上記製法の反応を行なうのがよい。
上記製法における同じく原料である一般式
（）の化合物は、スルホニルクロリド類とフル
オルアルカノール類とから、公知の方法
［Journal of the American Chemical Society、
Vol.86、4645、（1964）、同じくVol.75、5978、
（1953）、The Journal of Organic Chemistry、
Vol.35、3195、（1970）。］を用いて、得ることが
できるが、これらの方法は収量、目的化合物の単
離の繁雑さ、及び経費の面等から、満足すべきも
のではない。本発明においては、これらの問題点
を解消するために、相間移動触媒、例えば、トリ
エチルベンジルアンモニウムクロリド、テトラメ
チルアンモニウムブロミド等を用いることによつ
て、スルホニルクロリド、フルオルアルカノー
ル、及び水酸化ナトリウムとから、容易に、且つ
高純度、高収量で得ることができる。
次に実施例により本発明の内容を具体的に説明
するが、本発明はこれのみに限定されるべきもの
ではない。
［実施例］
実施例 １
４−メルカプトアニリン（12.5ｇ）をＮ，N′−
ジメチルホルムアミド（80ml）に溶かし、窒素雰
囲気下に、カリウムtert−ブトキシド（12ｇ）を
添加する。20〜30℃で２，２，２−トリフルオロ
エチルベンゼンスルホネート（23ｇ）を滴下し、
滴下終了後30〜40℃に１時間、80〜90℃に５時間
撹拌を続け、反応を完結する。減圧下に低沸点物
及び溶媒を留去した後、水（200ml）を加えて撹
拌する。生じた油状物質をトルエン（200ml）で
抽出し、５％水酸化ナトリウム水溶液、水の順で
洗浄し、無水硫酸ナトリウムで乾燥する。トルエ
ンを留去して得られる残渣を減圧下に蒸留する
と、下記式で表わされる目的の４−（２，２，２
−トリフルオロエチルチオ）アニリン（16.9ｇ）
が得られる。
bp.100〜105℃／0.8mmHg
実施例１と同様の方法により合成された化合物
を第１表に示す。It is preferable to carry out the reaction in the above production method by reacting with sodium hydride without separating [Formula]. The compound of general formula (), which is also a raw material in the above production method, is prepared from sulfonyl chlorides and fluoroalkanols by a known method [Journal of the American Chemical Society,
Vol.86, 4645, (1964), also Vol.75, 5978,
(1953), The Journal of Organic Chemistry,
Vol.35, 3195, (1970). ], but these methods are not satisfactory in terms of yield, complexity of isolation of the target compound, cost, etc. In the present invention, in order to solve these problems, a phase transfer catalyst such as triethylbenzylammonium chloride, tetramethylammonium bromide, etc. is used to transfer sulfonyl chloride, fluoroalkanol, and sodium hydroxide. can be easily obtained with high purity and high yield. EXAMPLES Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto. [Example] Example 1 4-mercaptoaniline (12.5 g) was converted into N,N'-
Dissolve in dimethylformamide (80 ml) and add potassium tert-butoxide (12 g) under nitrogen atmosphere. 2,2,2-trifluoroethylbenzenesulfonate (23 g) was added dropwise at 20-30°C.
After completion of the dropwise addition, stirring was continued at 30-40°C for 1 hour and at 80-90°C for 5 hours to complete the reaction. After distilling off the low boilers and solvent under reduced pressure, water (200 ml) was added and stirred. The resulting oily substance is extracted with toluene (200 ml), washed successively with 5% aqueous sodium hydroxide solution and water, and dried over anhydrous sodium sulfate. When the residue obtained by distilling off toluene is distilled under reduced pressure, the desired 4-(2,2,2
-trifluoroethylthio)aniline (16.9g)
is obtained. bp.100~105℃/0.8mmHg Compounds synthesized by the same method as in Example 1 are shown in Table 1.
【表】【table】
【表】
上記実施例１で原料として用いる２，２，２−
トリフルオロエチル−ｐ−トルエンスルホネート
は、下記参考例１により合成することができる。
参考例 １
２，２，２−トリフルオルエタノール（105
ｇ）、トルエン（200ml）、ｐ−トルエンスルホニ
ルクロリド（190.5ｇ）及びトリエチルベンジル
アンモニウムクロリド（2.5ｇ）とから成る溶液
に、20〜35℃で水酸化ナトリウム（42ｇ）と水
（100ｇ）とから成る水溶液を滴下する。50〜60℃
に４時間撹拌を続けた後、トルエン（800ml）を
加え、静置する。分取した有機層を、水洗後、無
水硫酸ナトリウム上で乾燥し、低沸点物を減圧下
に留去する。残渣にｎ−ヘキサン（600ml）を加
え、激しく撹拌しながら、氷冷すると、結晶とし
て、目的の２，２，２−トリフルオロエチル−ｐ
−トルエンスルホネート（250ｇ）が得られる。
mp.40〜41℃上記参考例１とほぼ同様な方法によ
り、合成された前記一般式（）の化合物を下記
に例示する。
[Table] 2,2,2- used as raw material in Example 1 above
Trifluoroethyl-p-toluenesulfonate can be synthesized according to Reference Example 1 below. Reference example 1 2,2,2-trifluoroethanol (105
g), toluene (200 ml), p-toluenesulfonyl chloride (190.5 g) and triethylbenzylammonium chloride (2.5 g) at 20-35°C from sodium hydroxide (42 g) and water (100 g). Drop an aqueous solution of 50~60℃
After stirring for 4 hours, toluene (800 ml) was added and left to stand. The separated organic layer is washed with water, dried over anhydrous sodium sulfate, and low-boiling substances are distilled off under reduced pressure. Add n-hexane (600 ml) to the residue, cool with ice while stirring vigorously, and the desired 2,2,2-trifluoroethyl-p crystals form.
-Toluenesulfonate (250 g) is obtained.
mp.40-41°C Compounds of the general formula () synthesized by substantially the same method as in Reference Example 1 above are illustrated below.
Claims (1)
低級アルコキシ基よりなる群からえらばれた基を
示し、複数ケのＡが存在する場合には、それらは
同一でも異なつていてもよい、 Ｒはフルオル置換−低級アルキル基を示し、 そして、ｍは０、１、２、３又は４を示す、 ただし、ｍが１を示し、上記式中のベンゼン環
に於いてＡが３または５の位置にあつて、且つ−
SCH2−Ｒが４の位置にあるときに、Ａは低級ア
ルキル基を示し、またｍが２を示し、上記式中の
ベンゼン環に於いて、Ａが３及び５の位置にあつ
て且つ−SCH2−Ｒが４の位置にあるときに、少
なくとも１ケのＡは低級アルコキシ基を示す、 で表わされるフルオロアルキルチオアニリン誘導
体。 ２ 式： で表わされる４−（２，２，２−トリフルオロエ
チルチオ）アニリンである特許請求の範囲第１項
記載の化合物。 ３ 一般式： 式中、Ａはハロゲン原子、低級アルキル基及び
低級アルコキシ基よりなる群からえらばれた基を
示し、複数ケのＡが存在する場合には、それらは
同一でも異なつていてもよい、 ｍは０、１、２、３又は４を示す、 ただし、ｍが１を示し、上記式中のベンゼン環
に於いてＡが３または５の位置にあつて、且つ−
SCH2−Ｒが４の位置にあるときに、Ａは低級ア
ルキル基を示し、またｍが２を示し、上記式中の
ベンゼン環に於いて、Ａが３及び５の位置にあつ
て且つ−SCH2−Ｒが４の位置にあるときに、少
なくとも１ケのＡは低級アルコキシ基を示す、そ
して、Ｍは水素原子もしくはアルカリ金属原子を
示す、 で表さわれる化合物と、 一般式： 式中、Ｒはフルオル置換−低級アルキル基を示
し、そして、Ｚはアリール基又は低級アルキル基
を示す、 で表わされる化合物とを反応させることを特徴と
する、 一般式（）： 式中、Ａ、Ｒ及びｍは前記と同じ、 で表わされるフルオロアルキルチオアニリン誘導
体の製法。[Claims] 1 General formula () In the formula, A represents a group selected from the group consisting of a halogen atom, a lower alkyl group, and a lower alkoxy group, and when multiple A's are present, they may be the same or different; R is represents a fluoro-substituted lower alkyl group, and m represents 0, 1, 2, 3 or 4, provided that m represents 1 and A is at the 3 or 5 position in the benzene ring in the above formula; At, and-
When SCH 2 -R is at the 4 position, A represents a lower alkyl group, m is 2, A is at the 3 and 5 positions of the benzene ring in the above formula, and - A fluoroalkylthioaniline derivative represented by: when SCH2 -R is at position 4, at least one A represents a lower alkoxy group. 2 formula: The compound according to claim 1, which is 4-(2,2,2-trifluoroethylthio)aniline represented by: 3 General formula: In the formula, A represents a group selected from the group consisting of a halogen atom, a lower alkyl group, and a lower alkoxy group, and when multiple A's are present, they may be the same or different; m is 0, 1, 2, 3 or 4, provided that m represents 1, A is at the 3 or 5 position in the benzene ring in the above formula, and -
When SCH 2 -R is at the 4 position, A represents a lower alkyl group, m is 2, A is at the 3 and 5 positions of the benzene ring in the above formula, and - When SCH 2 -R is at position 4, at least one A represents a lower alkoxy group, and M represents a hydrogen atom or an alkali metal atom; and a compound represented by the general formula: In the formula, R represents a fluoro-substituted lower alkyl group, and Z represents an aryl group or a lower alkyl group, characterized by reacting with a compound represented by the following general formula (): A method for producing a fluoroalkylthioaniline derivative represented by the following formula, where A, R and m are the same as above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33595390A JPH03178960A (en) | 1983-12-14 | 1990-11-30 | Fluoroalkylthioaniline derivative and production thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23417683A JPS60126262A (en) | 1983-12-14 | 1983-12-14 | Fluoroalkylthioaryl isocyanate derivative, its intermediate and their preparation |
| JP33595390A JPH03178960A (en) | 1983-12-14 | 1990-11-30 | Fluoroalkylthioaniline derivative and production thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23417683A Division JPS60126262A (en) | 1983-12-14 | 1983-12-14 | Fluoroalkylthioaryl isocyanate derivative, its intermediate and their preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03178960A JPH03178960A (en) | 1991-08-02 |
| JPH0530827B2 true JPH0530827B2 (en) | 1993-05-11 |
Family
ID=26531408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33595390A Granted JPH03178960A (en) | 1983-12-14 | 1990-11-30 | Fluoroalkylthioaniline derivative and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03178960A (en) |
-
1990
- 1990-11-30 JP JP33595390A patent/JPH03178960A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03178960A (en) | 1991-08-02 |
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