JPH0417188B2 - - Google Patents
Info
- Publication number
- JPH0417188B2 JPH0417188B2 JP18902483A JP18902483A JPH0417188B2 JP H0417188 B2 JPH0417188 B2 JP H0417188B2 JP 18902483 A JP18902483 A JP 18902483A JP 18902483 A JP18902483 A JP 18902483A JP H0417188 B2 JPH0417188 B2 JP H0417188B2
- Authority
- JP
- Japan
- Prior art keywords
- acetylamino
- general formula
- fluoro
- formula
- acid
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- -1 ligroin Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WJTZZPVVTSDNJJ-UHFFFAOYSA-N 2-fluorobenzenethiol Chemical compound FC1=CC=CC=C1S WJTZZPVVTSDNJJ-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
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- HIULNHONUJTOTQ-UHFFFAOYSA-N 2-chloro-4-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(F)C=C1Cl HIULNHONUJTOTQ-UHFFFAOYSA-N 0.000 description 1
- FCFPJKHVCHKCMP-UHFFFAOYSA-N 2-chloro-4-fluorobenzenesulfonyl chloride Chemical compound FC1=CC=C(S(Cl)(=O)=O)C(Cl)=C1 FCFPJKHVCHKCMP-UHFFFAOYSA-N 0.000 description 1
- JIFAWAXKXDTUHW-UHFFFAOYSA-N 2-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1F JIFAWAXKXDTUHW-UHFFFAOYSA-N 0.000 description 1
- ZSZKAQCISWFDCQ-UHFFFAOYSA-N 2-fluorobenzenesulfonyl chloride Chemical compound FC1=CC=CC=C1S(Cl)(=O)=O ZSZKAQCISWFDCQ-UHFFFAOYSA-N 0.000 description 1
- QBGQIMOGHUXVKB-UHFFFAOYSA-N 2-phenyl-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical class O=C1C(CCCC2)=C2C(=O)N1C1=CC=CC=C1 QBGQIMOGHUXVKB-UHFFFAOYSA-N 0.000 description 1
- XRBWNHAYOYZIPT-UHFFFAOYSA-N 5-acetamido-2-bromo-4-fluorobenzenesulfonic acid Chemical compound CC(=O)NC1=CC(S(O)(=O)=O)=C(Br)C=C1F XRBWNHAYOYZIPT-UHFFFAOYSA-N 0.000 description 1
- NKKSARYWJOJMIS-UHFFFAOYSA-N 5-acetamido-2-bromo-4-fluorobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC(S(Cl)(=O)=O)=C(Br)C=C1F NKKSARYWJOJMIS-UHFFFAOYSA-N 0.000 description 1
- DLHFJDDBXHTWJP-UHFFFAOYSA-N 5-acetamido-2-chloro-4-fluorobenzenesulfonic acid Chemical compound CC(=O)NC1=CC(S(O)(=O)=O)=C(Cl)C=C1F DLHFJDDBXHTWJP-UHFFFAOYSA-N 0.000 description 1
- MCYNMHHOXKSIAC-UHFFFAOYSA-N 5-acetamido-2-chloro-4-fluorobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC(S(Cl)(=O)=O)=C(Cl)C=C1F MCYNMHHOXKSIAC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 235000010716 Vigna mungo Nutrition 0.000 description 1
- 240000001417 Vigna umbellata Species 0.000 description 1
- 235000011453 Vigna umbellata Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical class ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- BCYGKMDWQBWUSC-UHFFFAOYSA-N n-(4-bromo-2-fluorophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Br)C=C1F BCYGKMDWQBWUSC-UHFFFAOYSA-N 0.000 description 1
- GVRKNSAEOVXHOS-UHFFFAOYSA-N n-(4-chloro-2-fluorophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1F GVRKNSAEOVXHOS-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、一般式
〔式中、Ｒは低級アルキル基、低級アルケニル
基または低級アルキニル基を表わし、Ｘは塩素原
子または臭素原子を表わす。〕
で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロフエニルスルフイド（以下、本発
明化合物と記す。）およびその製造法に関する。
本発明化合物を加水分解した後、無水３，４，
５，６−テトラヒドロフタル酸と反応させること
によつて製造することができる一般式
〔式中、ＲおよびＸは前記と同じ意味を表わ
す。〕
で示される２−フエニル−４，５，６，７−テト
ラヒドロ−2H−イソインドール−１，３−ジオ
ン誘導体は、トウモロコシ、コムギ、イネ、ダイ
ズ等の主要作物に対して問題となるような薬害は
示さず、かつ多くの雑草に対して充分な除草効力
を有する。
本発明化合物は、標準的には、一般式
〔式中、Ｘは前記と同じ意味を表わす。〕
で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロベンゼンチオールと、一般式
RY 〔〕
〔式中、Ｒは前記と同じ意味を表わし、Ｙはハ
ロゲン原子を表わす。〕
で示されるハライド類とを溶媒中、脱ハロゲン化
水素剤の存在下、０℃〜80℃で、0.5時間〜５時
間反応させることによつて製造することができ
る。
反応に供される試剤の量は、５−（Ｎ−アセチ
ルアミノ）−４−フルオロ−２−ハロベンゼンチ
オール〔〕１当量に対して、ハライド類〔〕
は１〜1.5当量、脱ハロゲン化水素剤は１〜1.5当
量である。
上記製造方法において使用できる溶媒として
は、ヘキサン、ヘプタン、リグロイン、石油エー
テル等の脂肪族炭化水素、ベンゼン、トルエン、
キシレン等の芳香族炭化水素、クロロホルム、四
塩化炭素、ジクロロエタン、クロロベンゼン、ジ
クロロベンゼン等のハロゲン化炭化水素、ジエチ
ルエーテル、ジイソプロピルエーテル、ジオキサ
ン、テトラヒドロフラン、エチレングリコールジ
メチルエーテル等のエーテル、蟻酸エチル、酢酸
エチル、酢酸ブチル、炭酸ジエチル等のエステ
ル、ニトロエタン、ニトロベンゼン等のニトロ化
物、アセトニトリル、イソブチロニトリル等のニ
トリル、ピリジン、トリエチルアミン、Ｎ，Ｎ−
ジエチルアニリン、トリブチルアミン、Ｎ−メチ
ルモルホリン等の第三級アミン、ホルムアミド、
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチ
ルアセトアミド等の酸アミド、ジメチルスルホキ
シド、スルホラン等の硫黄化合物、水等あるい
は、それらの混合物がある。
また、脱ハロゲン化水素剤としては、ピリジ
ン、トリエチルアミン、Ｎ，Ｎ−ジエチルアニリ
ン等の有機塩基、水酸化ナトリウム、水酸化カリ
ウム、炭酸ナトリウム、炭酸カリウム等の無機塩
基、ナトリウムメトキシド、ナトリウムエトキシ
ド等のアルカリ金属アルコキシド等がある。
溶媒が水またはその混合物であるときは、テト
ラブチルアンモニウムブロミド、ベンジルトリブ
チルアンモニウムクロリド等の相間移動触媒を用
いるのが好ましい。
反応終了後の反応液は、有機溶媒による抽出お
よび濃縮等通常の後処理を行うか、さらに必要に
応じ、クロマトグラフイー、再結晶等の操作によ
つて精製することにより、目的の本発明化合物が
得られる。
なお、上記方法の原料化合物である一般式
〔〕の５−（Ｎ−アセチルアミノ）−４−フルオ
ロ−２−ハロベンゼンチオールは、以下の方法に
より効率よく、製造することができる。
すなわち、一般式
〔式中、Ｘは前記と同じ意味を表わす。〕
で示される２−フルオロ−４−ハロアセトアニリ
ドとこれに対して当量ないし過剰量の発煙硫酸を
無溶媒下または濃硫酸を溶媒として、０℃〜100
℃で0.5時間〜５時間反応させ、スルホン化する
ことによつて、一般式
〔式中、Ｘは前記と同じ意味を表わす。〕
で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロベンゼンスルホン酸を製造し、次
いでこのナトリウム、カリウム等のアルカリ金属
塩またはピリジン等の有機塩基塩と、これに対し
て1.0〜５当量の五塩化燐、オキシ塩化燐等の塩
素化剤とを溶媒中または無溶媒下、０℃〜200℃
で0.5時間〜５時間反応させ、塩素化することに
よつて、一般式
〔式中、Ｘは前記と同じ意味を表わす。〕
で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロベンゼンスルホニルクロリドを製
造し、さらにこれを通常のベンゼンスルホニルク
ロリド類のベンゼンチオール類への還元法、例え
ば、硫酸−亜鉛、塩酸−塩化第一錫、酢酸−亜鉛
等の還元剤を用いて、室温〜120℃、15分〜12時
間反応させ、還元することによつて製造すること
ができる。
なお、原料化合物である一般式〔〕の２−フ
ルオロ−４−ハロアセトアニリドは、特開昭51−
51521号公報に記載の製造法によつて製造するこ
とができる。
以下に、本発明を製造例および参考例でさらに
詳しく説明する。
製造例 （本発明化合物３の製造法）
５−（Ｎ−アセチルアミノ）−２−ブロモ−４−
フルオロベンゼンチオール10.46ｇを３％水酸化
ナトリウム80mlに懸濁し、テトラブチルアンモニ
ウムブロミド0.13ｇを加えた後、１−ブロモ−２
−プロピン8.48ｇを滴下した。室温で12時間撹拌
した後、酢酸エチルで抽出し、抽出液を乾燥、濃
縮してＮ−〔４−ブロモ−２−フルオロ−５−（２
プロピニルチオ）フエニル〕アセトアミド11.74
ｇを得た。m.p.106℃〜107℃
このような製造法によつて製造できる本発明化
合物のいくつかを、第１表に示す。
The present invention is based on the general formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, and X represents a chlorine atom or a bromine atom. ] The present invention relates to 5-(N-acetylamino)-4-fluoro-2-halophenyl sulfide (hereinafter referred to as the compound of the present invention) represented by the following and a method for producing the same. After hydrolyzing the compound of the present invention, anhydrous 3,4,
The general formula can be prepared by reacting with 5,6-tetrahydrophthalic acid [In the formula, R and X have the same meanings as above. ] 2-phenyl-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione derivatives are harmful to major crops such as corn, wheat, rice, and soybean. It does not cause any phytotoxicity and has sufficient herbicidal efficacy against many weeds. Compounds of the invention typically have the general formula [In the formula, X represents the same meaning as above. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenethiol represented by the general formula RY [] [wherein R represents the same meaning as above and Y represents a halogen atom. ] It can be produced by reacting the halides shown in the following in a solvent in the presence of a dehydrohalogenating agent at 0°C to 80°C for 0.5 to 5 hours. The amount of reagents used in the reaction is 1 equivalent of 5-(N-acetylamino)-4-fluoro-2-halobenzenethiol [] and halides []
is 1 to 1.5 equivalents, and the dehydrohalogenation agent is 1 to 1.5 equivalents. Solvents that can be used in the above production method include aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl formate, ethyl acetate, Esters such as butyl acetate and diethyl carbonate, nitrates such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-
Tertiary amines such as diethylaniline, tributylamine, N-methylmorpholine, formamide,
Examples include acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, water, and mixtures thereof. In addition, dehydrohalogenating agents include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, sodium methoxide, and sodium ethoxide. There are alkali metal alkoxides such as When the solvent is water or a mixture thereof, it is preferred to use a phase transfer catalyst such as tetrabutylammonium bromide, benzyltributylammonium chloride. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as extraction and concentration with an organic solvent, or, if necessary, is further purified by operations such as chromatography and recrystallization to obtain the desired compound of the present invention. is obtained. Note that 5-(N-acetylamino)-4-fluoro-2-halobenzenethiol of general formula [], which is a raw material compound in the above method, can be efficiently produced by the following method. That is, the general formula [In the formula, X represents the same meaning as above. ] 2-fluoro-4-haloacetanilide and an equivalent to an excess amount of oleum in the absence of a solvent or in concentrated sulfuric acid at 0°C to 100°C.
By reacting at ℃ for 0.5 to 5 hours and sulfonation, the general formula [In the formula, X represents the same meaning as above. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid shown by is produced, and then an alkali metal salt such as sodium or potassium or an organic base salt such as pyridine is added to this. 1.0 to 5 equivalents of chlorinating agent such as phosphorus pentachloride or phosphorus oxychloride in a solvent or without a solvent at 0°C to 200°C.
By reacting for 0.5 to 5 hours and chlorinating, the general formula [In the formula, X represents the same meaning as above. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride is produced, and this is further reduced by a conventional method for reducing benzenesulfonyl chlorides to benzenethiols, for example, sulfuric acid-zinc , hydrochloric acid-stannic chloride, acetic acid-zinc, or the like, by reaction and reduction at room temperature to 120°C for 15 minutes to 12 hours. In addition, 2-fluoro-4-haloacetanilide of the general formula [], which is a raw material compound, is
It can be produced by the production method described in Japanese Patent No. 51521. The present invention will be explained in more detail below using production examples and reference examples. Production example (method for producing compound 3 of the present invention) 5-(N-acetylamino)-2-bromo-4-
After suspending 10.46 g of fluorobenzenethiol in 80 ml of 3% sodium hydroxide and adding 0.13 g of tetrabutylammonium bromide, 1-bromo-2
- 8.48 g of propyne was added dropwise. After stirring at room temperature for 12 hours, extraction was performed with ethyl acetate, and the extract was dried and concentrated to give N-[4-bromo-2-fluoro-5-(2
Propynylthio)phenyl]acetamide 11.74
I got g. mp106°C to 107°C Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1.
【表】
参考例 １
Ｎ−（４−ブロモ−２−フルオロフエニル）ア
セトアミド173.2ｇを濃硫酸80mlに懸濁し、10℃
〜20℃で60％発煙硫酸340mlを滴下後、20℃で２
時間撹拌した。その後、反応液を10℃〜20℃で氷
水500ｇに滴下し、析出した結晶を取して冷水
400mlで洗浄した。
この結晶を減圧加温下乾燥し、５−（Ｎ−アセ
チルアミノ）−２−ブロモ−４−フルオロベンゼ
ンスルホン酸175.8ｇを得た。m.p.300℃以上
同様の方法にて、Ｎ−（４−クロロ−２−フル
オロフエニル）アセトアミドより、５−（Ｎ−ア
セチルアミノ）−２−クロロ−４−フルオロベン
ゼンスルホン酸を得た。m.p.300℃以上
参考例 ２
５−（Ｎ−アセチルアミノ）−２−ブロモ−４−
フルオロベンゼンスルホン酸175.8ｇにピリジン
130ｇを加えて１時間撹拌し、析出した結晶を
取してジエチルエーテルで洗浄した。このように
して得られた該スルホン酸のピリジン塩199.5ｇ
をクロロホルム560mlに懸濁し、五塩化燐140.7ｇ
を加えた後、60℃〜70℃で１時間撹拌した。反応
液を放冷し、水を加え、クロロホルムで抽出し、
抽出液を乾燥、濃縮して、５−（Ｎ−アセチルア
ミノ）−２−ブロモ−４−フルオロベンゼンスル
ホニルクロリド73.25ｇを得た。m.p.155〜156℃
同様の方法にて、５−（Ｎ−アセチルアミノ）−
２−クロロ−４−フルオロベンゼンスルホン酸よ
り、５−（Ｎ−アセチルアミノ）−２−クロロ−４
−フルオロベンゼンスルホニルクロリドを得た。
m.p.138℃〜139℃
参考例 ３
５−（Ｎ−アセチルアミノ）−２−ブロモ−４−
フルオロベンゼンスルホニルクロリド73.25ｇを
酢酸630mlに溶解し、亜鉛289.7ｇを加えた後、６
時間還流した。反応液を放冷し、水を加え、酢酸
エチルで抽出し、抽出液を水洗してから、炭酸水
素ナトリウム水溶液で中和した後、乾燥、濃縮し
て、５−（Ｎ−アセチルアミノ）−２−ブロモ−４
−フルオロベンゼンチオール31.38ｇを得た。m.
p.157〜158℃
同様の方法にて、５−（Ｎ−アセチルアミノ）−
２−クロロ−４−フルオロベンゼンスルホニルク
ロリドより、５−（Ｎ−アセチルアミノ）−２−ク
ロロ−４−フルオロベンゼンチオールを得た。
m.p.156℃〜158℃。[Table] Reference example 1 173.2 g of N-(4-bromo-2-fluorophenyl)acetamide was suspended in 80 ml of concentrated sulfuric acid and heated at 10°C.
After dropping 340ml of 60% oleum at ~20℃,
Stir for hours. After that, the reaction solution was added dropwise to 500 g of ice water at 10°C to 20°C, the precipitated crystals were removed, and the mixture was cooled with cold water.
Washed with 400ml. The crystals were dried under reduced pressure and heat to obtain 175.8 g of 5-(N-acetylamino)-2-bromo-4-fluorobenzenesulfonic acid. mp300°C or higher In the same manner, 5-(N-acetylamino)-2-chloro-4-fluorobenzenesulfonic acid was obtained from N-(4-chloro-2-fluorophenyl)acetamide. mp300℃ or higher Reference example 2 5-(N-acetylamino)-2-bromo-4-
175.8g of fluorobenzenesulfonic acid and pyridine
130 g was added and stirred for 1 hour, and the precipitated crystals were collected and washed with diethyl ether. 199.5 g of the pyridine salt of the sulfonic acid thus obtained
was suspended in 560 ml of chloroform, and 140.7 g of phosphorus pentachloride was added.
After adding, the mixture was stirred at 60°C to 70°C for 1 hour. The reaction solution was allowed to cool, water was added, and extracted with chloroform.
The extract was dried and concentrated to obtain 73.25 g of 5-(N-acetylamino)-2-bromo-4-fluorobenzenesulfonyl chloride. mp155-156℃ Using the same method, 5-(N-acetylamino)-
From 2-chloro-4-fluorobenzenesulfonic acid, 5-(N-acetylamino)-2-chloro-4
-Fluorobenzenesulfonyl chloride was obtained.
mp138℃～139℃ Reference example 3 5-(N-acetylamino)-2-bromo-4-
After dissolving 73.25 g of fluorobenzenesulfonyl chloride in 630 ml of acetic acid and adding 289.7 g of zinc,
Refluxed for an hour. The reaction solution was allowed to cool, water was added, and extraction was performed with ethyl acetate. The extract was washed with water, neutralized with an aqueous sodium bicarbonate solution, dried, and concentrated to give 5-(N-acetylamino)- 2-bromo-4
-31.38 g of fluorobenzenethiol was obtained. m.
p.157-158℃ In the same manner, 5-(N-acetylamino)-
5-(N-acetylamino)-2-chloro-4-fluorobenzenethiol was obtained from 2-chloro-4-fluorobenzenesulfonyl chloride.
mp156℃~158℃.
Claims (1)
基または低級アルキニル基を表わし、Ｘは塩素原
子または臭素原子を表わす。〕 で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロフエニルスルフイド。 ２ 一般式 〔式中、Ｘは塩素原子または臭素原子を表わ
す。〕 で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロベンゼンチオールと一般式 RY 〔式中、Ｒは低級アルキル基、低級アルケニル
基または低級アルキニル基を表わし、Ｙはハロゲ
ン原子を表わす。〕 で示されるハライド類とを反応させることを特徴
とする一般式 〔式中、ＲおよびＸは前記と同じ意味を表わ
す。〕 で示される５−（Ｎ−アセチルアミノ）−４−フル
オロ−２−ハロフエニルスルフイドの製造法。[Claims] 1. General formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, and X represents a chlorine atom or a bromine atom. ] 5-(N-acetylamino)-4-fluoro-2-halophenyl sulfide. 2 General formula [In the formula, X represents a chlorine atom or a bromine atom. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenethiol and the general formula RY [wherein R represents a lower alkyl group, lower alkenyl group, or lower alkynyl group, and Y represents a halogen atom represents. ] A general formula characterized by reacting with a halide represented by [In the formula, R and X have the same meanings as above. ] A method for producing 5-(N-acetylamino)-4-fluoro-2-halophenyl sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18902483A JPS6081163A (en) | 1983-10-07 | 1983-10-07 | 5-(n-acetylamino)-4-fluoro-2-halophenyl sulfide and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18902483A JPS6081163A (en) | 1983-10-07 | 1983-10-07 | 5-(n-acetylamino)-4-fluoro-2-halophenyl sulfide and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6081163A JPS6081163A (en) | 1985-05-09 |
| JPH0417188B2 true JPH0417188B2 (en) | 1992-03-25 |
Family
ID=16234021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18902483A Granted JPS6081163A (en) | 1983-10-07 | 1983-10-07 | 5-(n-acetylamino)-4-fluoro-2-halophenyl sulfide and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6081163A (en) |
-
1983
- 1983-10-07 JP JP18902483A patent/JPS6081163A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6081163A (en) | 1985-05-09 |
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