JPH08143538A - Acid azide derivative and its production - Google Patents
Acid azide derivative and its productionInfo
- Publication number
- JPH08143538A JPH08143538A JP28094194A JP28094194A JPH08143538A JP H08143538 A JPH08143538 A JP H08143538A JP 28094194 A JP28094194 A JP 28094194A JP 28094194 A JP28094194 A JP 28094194A JP H08143538 A JPH08143538 A JP H08143538A
- Authority
- JP
- Japan
- Prior art keywords
- fluoro
- benzoic acid
- azide
- chloro
- acid azide
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 150000001540 azides Chemical class 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 11
- YYBSTBMKBAPBCC-UHFFFAOYSA-N ClC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OC)F Chemical compound ClC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OC)F YYBSTBMKBAPBCC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 230000002363 herbicidal effect Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- SLLIPUQKEXRXMS-UHFFFAOYSA-N 4-chloro-2-fluoro-5-(2-methoxy-2-oxoethyl)benzenecarbothioic s-acid Chemical compound COC(=O)CC1=CC(C(S)=O)=C(F)C=C1Cl SLLIPUQKEXRXMS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- TZLVRPLSVNESQC-UHFFFAOYSA-N potassium azide Chemical compound [K+].[N-]=[N+]=[N-] TZLVRPLSVNESQC-UHFFFAOYSA-N 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- -1 Methoxycarbonylmethylthiobenzoic acid azide Chemical compound 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OHUARHUVXFMYHW-UHFFFAOYSA-N 5-acetylsulfanyl-4-chloro-2-fluorobenzoic acid Chemical compound CC(=O)SC1=CC(C(O)=O)=C(F)C=C1Cl OHUARHUVXFMYHW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003302 alkenyloxy group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 3
- 125000005085 alkoxycarbonylalkoxy group Chemical group 0.000 description 3
- 125000005133 alkynyloxy group Chemical group 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- XQXLEDSOQZQJRR-UHFFFAOYSA-N methyl 2-(5-carbonochloridothioyl-2-chloro-4-fluorophenyl)acetate Chemical compound COC(=O)CC1=CC(C(Cl)=S)=C(F)C=C1Cl XQXLEDSOQZQJRR-UHFFFAOYSA-N 0.000 description 3
- FTEFFVSRKVXCJA-UHFFFAOYSA-N methyl 2-[3-chloro-4-(1-chloroethylideneamino)-5-fluorothiophen-2-yl]acetate Chemical compound COC(=O)CC=1SC(F)=C(N=C(C)Cl)C=1Cl FTEFFVSRKVXCJA-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZLPXBWMVZANJJQ-UHFFFAOYSA-N 4-chloro-2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1F ZLPXBWMVZANJJQ-UHFFFAOYSA-N 0.000 description 1
- FSQCACZDIAAIAY-UHFFFAOYSA-N 6-carbamoyl-1-phenylcyclohex-2-ene-1-carboxylic acid Chemical class NC(=O)C1CCC=CC1(C(O)=O)C1=CC=CC=C1 FSQCACZDIAAIAY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GHGPOPSVMKNBKW-UHFFFAOYSA-N BrC1=CC(=C(C(=O)N=[N+]=[N-])C=C1SC(C)C(=O)OCC)F Chemical compound BrC1=CC(=C(C(=O)N=[N+]=[N-])C=C1SC(C)C(=O)OCC)F GHGPOPSVMKNBKW-UHFFFAOYSA-N 0.000 description 1
- HCYYYIPJNVARRC-UHFFFAOYSA-N BrC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OC(C)C)F Chemical compound BrC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OC(C)C)F HCYYYIPJNVARRC-UHFFFAOYSA-N 0.000 description 1
- FALBEHVMBJJBSY-UHFFFAOYSA-N BrC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OC)F Chemical compound BrC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OC)F FALBEHVMBJJBSY-UHFFFAOYSA-N 0.000 description 1
- WLMYJYZKSNDHAL-UHFFFAOYSA-N BrC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OCC)F Chemical compound BrC1=CC(=C(C(=S)N=[N+]=[N-])C=C1CC(=O)OCC)F WLMYJYZKSNDHAL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZUNMRZKUAWSMPY-UHFFFAOYSA-N CC(C(=O)OC)SC1=C(C=C(C(=C1)C(=O)Cl)F)Br Chemical compound CC(C(=O)OC)SC1=C(C=C(C(=C1)C(=O)Cl)F)Br ZUNMRZKUAWSMPY-UHFFFAOYSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- FNBZNOMSPZZERT-UHFFFAOYSA-N methyl 2-[acetyl-[4-chloro-2-fluoro-5-(2-methoxy-2-oxoethyl)thiophen-3-yl]carbamoyl]cyclohexene-1-carboxylate Chemical compound ClC1=C(CC(=O)OC)SC(F)=C1N(C(C)=O)C(=O)C1=C(C(=O)OC)CCCC1 FNBZNOMSPZZERT-UHFFFAOYSA-N 0.000 description 1
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical compound COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RTQUUSNKDIFZJG-UHFFFAOYSA-N o-methyl 2-(5-acetamido-2-chloro-4-fluorophenyl)ethanethioate Chemical compound COC(=S)CC1=CC(NC(C)=O)=C(F)C=C1Cl RTQUUSNKDIFZJG-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、一般式［Ｉ］The present invention relates to the general formula [I]
【０００２】[0002]
【化４】 [Chemical 4]
【０００３】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］で示される酸アジド誘導体およびそ
の製造法に関するものである。[Wherein Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] It is related with the acid azide derivative shown by these, and its manufacturing method.
【０００４】本発明の一般式［Ｉ］で示される酸アジド
誘導体は、医薬、農薬などの製造中間体、例えば、優れ
た除草活性を有する一般式［ＸＩＩＩ］The acid azide derivative represented by the general formula [I] of the present invention is an intermediate for producing pharmaceuticals, agricultural chemicals, etc., for example, the general formula [XIII] having excellent herbicidal activity.
【０００５】[0005]
【化５】 Embedded image
【０００６】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わし、Ｒ2は低級アルキル基または置換もし
くは非置換のフェニル基を表わし、Ｒ3は低級アルコキ
シ基、低級アルケニルオキシ基、低級アルキニルオキシ
基、低級アルコキシアルコキシ基または低級アルコキシ
カルボニルアルコキシ基を表わす。］で示されるＮ−ア
シル−Ｎ−フェニルテトラヒドロフタラミン酸誘導体な
どの製造中間体として有用な化合物である。[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, R 6 represents a lower alkyl group), and R 2 represents a lower alkyl group or a substituted or unsubstituted phenyl group. R 3 represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkoxyalkoxy group or a lower alkoxycarbonylalkoxy group. ] It is a compound useful as a production intermediate such as an N-acyl-N-phenyltetrahydrophthalamic acid derivative represented by
【０００７】[0007]
【従来技術】従来より、酸アジド誘導体は、数多く知ら
れている。しかしながら、一般式［Ｉ］で示される酸ア
ジド誘導体は、これまでに知られておらず、新規な化合
物である。2. Description of the Related Art Many acid azide derivatives have been known so far. However, the acid azide derivative represented by the general formula [I] has not been known so far and is a novel compound.
【０００８】[0008]
【発明の開示】本発明者らは、鋭意、研究を重ねた結
果、一般式［Ｉ］で示される酸アジド誘導体が優れた除
草活性を有する一般式［ＸＩＩＩ］で示されるＮ−アシ
ル−Ｎ−フェニルテトラヒドロフタラミン酸誘導体の製
造中間体として有用な化合物であることを見出し、さら
には、本発明者らは、工業的にも有意性のある一般式
［Ｉ］で示される酸アジド誘導体の新規な製造法につい
て、鋭意、研究を重ねた結果、一般式［ＩＩ］で示され
る置換ベンゼンカルボニルクロリド誘導体と無機アジ化
物との反応により、容易に一般式［Ｉ］で示される酸ア
ジド誘導体を製造することができることを見出し、本発
明を完成した。DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that an acid azide derivative represented by the general formula [I] has an excellent herbicidal activity and an N-acyl-N represented by the general formula [XIII]. -It was found that the compound is useful as an intermediate for the production of a phenyltetrahydrophthalamic acid derivative, and further, the present inventors have found that the acid azide derivative represented by the general formula [I] having industrial significance is As a result of earnestly researching the novel production method, the acid azide derivative represented by the general formula [I] can be easily obtained by the reaction between the substituted benzenecarbonyl chloride derivative represented by the general formula [II] and the inorganic azide. They have found that they can be manufactured and have completed the present invention.
【０００９】すなわち、本発明は、一般式［Ｉ］That is, the present invention has the general formula [I]
【００１０】[0010]
【化６】 [Chemical 6]
【００１１】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］で示される酸アジド誘導体、およ
び、一般式［ＩＩ］[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] The acid azide derivative shown by and general formula [II]
【００１２】[0012]
【化７】 [Chemical 7]
【００１３】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］で示される置換ベンゼンカルボニル
クロリド誘導体と無機アジ化物を反応させることを特徴
とする一般式［Ｉ］[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] The general formula [I] characterized by reacting a substituted benzenecarbonyl chloride derivative represented by
【００１４】[0014]
【化８】 Embedded image
【００１５】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］で示される酸アジド誘導体の製造法
である。[Wherein Y represents a halogen atom and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] It is a manufacturing method of the acid azide derivative shown by these.
【００１６】本発明の化合物である一般式［Ｉ］で示さ
れる酸アジド誘導体としては、例えば、２，４−ジフル
オロ−５−メトキシカルボニルメチルチオ安息香酸アジ
ド、４−クロロ−２−フルオロ−５−メトキシカルボニ
ルメチルチオ安息香酸アジド、４−ブロモ−２−フルオ
ロ−５−メトキシカルボニルメチルチオ安息香酸アジ
ド、２，４−ジフルオロ−５−エトキシカルボニルメチ
ルチオ安息香酸アジド、４−クロロ−２−フルオロ−５
−エトキシカルボニルメチルチオ安息香酸アジド、４−
ブロモ−２−フルオロ−５−エトキシカルボニルメチル
チオ安息香酸アジド、２，４−ジフルオロ−５−（１−
プロポキシカルボニルメチルチオ）安息香酸アジド、４
−クロロ−２−フルオロ−５−（１−プロポキシカルボ
ニルメチルチオ）安息香酸アジド、４−ブロモ−２−フ
ルオロ−５−（１−プロポキシカルボニルメチルチオ）
安息香酸アジド、２，４−ジフルオロ−５−イソプロポ
キシカルボニルメチルチオ安息香酸アジド、４−クロロ
−２−フルオロ−５−イソプロポキシカルボニルメチル
チオ安息香酸アジド、４−ブロモ−２−フルオロ−５−
イソプロポキシカルボニルメチルチオ安息香酸アジド、
２，４−ジフルオロ−５−（１−メトキシカルボニルエ
チルチオ）安息香酸アジド、４−クロロ−２−フルオロ
−５−（１−メトキシカルボニルエチルチオ）安息香酸
アジド、４−ブロモ−２−フルオロ−５−（１−メトキ
シカルボニルエチルチオ）安息香酸アジド、２，４−ジ
フルオロ−５−（１−エトキシカルボニルエチルチオ）
安息香酸アジド、４−クロロ−２−フルオロ−５−（１
−エトキシカルボニルエチルチオ）安息香酸アジド、４
−ブロモ−２−フルオロ−５−（１−エトキシカルボニ
ルエチルチオ）安息香酸アジド、２，４−ジフルオロ−
５−［１−（１−プロポキシカルボニル）エチルチオ］
安息香酸アジド、４−クロロ−２−フルオロ−５−［１
−（１−プロポキシカルボニル）エチルチオ］安息香酸
アジド、４−ブロモ−２−フルオロ−５−［１−（１−
プロポキシカルボニル）エチルチオ］安息香酸アジド、
２，４−ジフルオロ−５−（１−イソプロポキシカルボ
ニルエチルチオ）安息香酸アジド、４−クロロ−２−フ
ルオロ−５−（１−イソプロポキシカルボニルエチルチ
オ）安息香酸アジド、４−ブロモ−２−フルオロ−５−
（１−イソプロポキシカルボニルエチルチオ）安息香酸
アジド、２，４−ジフルオロ−５−（１−メトキシカル
ボニルプロピルチオ）安息香酸アジド、４−クロロ−２
−フルオロ−５−（１−メトキシカルボニルプロピルチ
オ）安息香酸アジド、４−ブロモ−２−フルオロ−５−
（１−メトキシカルボニルプロピルチオ）安息香酸アジ
ド、２，４−ジフルオロ−５−（１−エトキシカルボニ
ルプロピルチオ）安息香酸アジド、４−クロロ−２−フ
ルオロ−５−（１−エトキシカルボニルプロピルチオ）
安息香酸アジド、４−ブロモ−２−フルオロ−５−（１
−エトキシカルボニルプロピルチオ）安息香酸アジド、
２，４−ジフルオロ−５−［１−（１−プロポキシカル
ボニル）プロピルチオ］安息香酸アジド、４−クロロ−
２−フルオロ−５−［１−（１−プロポキシカルボニ
ル）プロピルチオ］安息香酸アジド、４−ブロモ−２−
フルオロ−５−［１−（１−プロポキシカルボニル）プ
ロピルチオ］安息香酸アジド、２，４−ジフルオロ−５
−（１−イソプロポキシカルボニルプロピルチオ）安息
香酸アジド、４−クロロ−２−フルオロ−５−（１−イ
ソプロポキシカルボニルプロピルチオ）安息香酸アジ
ド、４−ブロモ−２−フルオロ−５−（１−イソプロポ
キシカルボニルプロピルチオ）安息香酸アジド、２，４
−ジフルオロ−５−（１−メトキシカルボニルブチルチ
オ）安息香酸アジド、４−クロロ−２−フルオロ−５−
（１−メトキシカルボニルブチルチオ）安息香酸アジ
ド、４−ブロモ−２−フルオロ−５−（１−メトキシカ
ルボニルブチルチオ）安息香酸アジド、２，４−ジフル
オロ−５−（１−エトキシカルボニルブチルチオ）安息
香酸アジド、４−クロロ−２−フルオロ−５−（１−エ
トキシカルボニルブチルチオ）安息香酸アジド、４−ブ
ロモ−２−フルオロ−５−（１−エトキシカルボニルブ
チルチオ）安息香酸アジド、２，４−ジフルオロ−５−
［１−（１−プロポキシカルボニル）ブチルチオ］安息
香酸アジド、４−クロロ−２−フルオロ−５−［１−
（１−プロポキシカルボニル）ブチルチオ］安息香酸ア
ジド、４−ブロモ−２−フルオロ−５−［１−（１−プ
ロポキシカルボニル）ブチルチオ］安息香酸アジド、
２，４−ジフルオロ−５−（１−イソプロポキシカルボ
ニルブチルチオ）安息香酸アジド、４−クロロ−２−フ
ルオロ−５−（１−イソプロポキシカルボニルブチルチ
オ）安息香酸アジド、４−ブロモ−２−フルオロ−５−
（１−イソプロポキシカルボニルブチルチオ）安息香酸
アジド、２，４−ジフルオロ−５−（１−メトキシカル
ボニル−２−メチルプロピルチオ）安息香酸アジド、４
−クロロ−２−フルオロ−５−（１−メトキシカルボニ
ル−２−メチルプロピルチオ）安息香酸アジド、４−ブ
ロモ−２−フルオロ−５−（１−メトキシカルボニル−
２−メチルプロピルチオ）安息香酸アジド、２，４−ジ
フルオロ−５−（１−エトキシカルボニル−２−メチル
プロピルチオ）安息香酸アジド、４−クロロ−２−フル
オロ−５−（１−エトキシカルボニル−２−メチルプロ
ピルチオ）安息香酸アジド、４−ブロモ−２−フルオロ
−５−（１−エトキシカルボニル−２−メチルプロピル
チオ）安息香酸アジド、２，４−ジフルオロ−５−［１
−（１−プロポキシカルボニル）−２−メチルプロピル
チオ］安息香酸アジド、４−クロロ−２−フルオロ−５
−［１−（１−プロポキシカルボニル）−２−メチルプ
ロピルチオ］安息香酸アジド、４−ブロモ−２−フルオ
ロ−５−［１−（１−プロポキシカルボニル）−２−メ
チルプロピルチオ］安息香酸アジド、２，４−ジフルオ
ロ−５−（１−イソプロポキシカルボニル−２−メチル
プロピルチオ）安息香酸アジド、４−クロロ−２−フル
オロ−５−（１−イソプロポキシカルボニル−２−メチ
ルプロピルチオ）安息香酸アジド、４−ブロモ−２−フ
ルオロ−５−（１−イソプロポキシカルボニル−２−メ
チルプロピルチオ）安息香酸アジドなどを挙げることが
できる。Examples of the acid azide derivative represented by the general formula [I] which is the compound of the present invention include 2,4-difluoro-5-methoxycarbonylmethylthiobenzoic acid azide and 4-chloro-2-fluoro-5-. Methoxycarbonylmethylthiobenzoic acid azide, 4-bromo-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid azide, 2,4-difluoro-5-ethoxycarbonylmethylthiobenzoic acid azide, 4-chloro-2-fluoro-5.
-Ethoxycarbonylmethylthiobenzoic acid azide, 4-
Bromo-2-fluoro-5-ethoxycarbonylmethylthiobenzoic acid azide, 2,4-difluoro-5- (1-
Propoxycarbonylmethylthio) benzoic acid azide, 4
-Chloro-2-fluoro-5- (1-propoxycarbonylmethylthio) benzoic acid azide, 4-bromo-2-fluoro-5- (1-propoxycarbonylmethylthio)
Benzoic acid azide, 2,4-difluoro-5-isopropoxycarbonylmethylthiobenzoic acid azide, 4-chloro-2-fluoro-5-isopropoxycarbonylmethylthiobenzoic acid azide, 4-bromo-2-fluoro-5-
Isopropoxycarbonylmethylthiobenzoic acid azide,
2,4-Difluoro-5- (1-methoxycarbonylethylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-methoxycarbonylethylthio) benzoic acid azide, 4-bromo-2-fluoro- 5- (1-methoxycarbonylethylthio) benzoic acid azide, 2,4-difluoro-5- (1-ethoxycarbonylethylthio)
Benzoic acid azide, 4-chloro-2-fluoro-5- (1
-Ethoxycarbonylethylthio) benzoic acid azide, 4
-Bromo-2-fluoro-5- (1-ethoxycarbonylethylthio) benzoic acid azide, 2,4-difluoro-
5- [1- (1-propoxycarbonyl) ethylthio]
Benzoic acid azide, 4-chloro-2-fluoro-5- [1
-(1-Propoxycarbonyl) ethylthio] benzoic acid azide, 4-bromo-2-fluoro-5- [1- (1-
Propoxycarbonyl) ethylthio] benzoic acid azide,
2,4-Difluoro-5- (1-isopropoxycarbonylethylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-isopropoxycarbonylethylthio) benzoic acid azide, 4-bromo-2- Fluoro-5
(1-Isopropoxycarbonylethylthio) benzoic acid azide, 2,4-difluoro-5- (1-methoxycarbonylpropylthio) benzoic acid azide, 4-chloro-2
-Fluoro-5- (1-methoxycarbonylpropylthio) benzoic acid azide, 4-bromo-2-fluoro-5-
(1-Methoxycarbonylpropylthio) benzoic acid azide, 2,4-difluoro-5- (1-ethoxycarbonylpropylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-ethoxycarbonylpropylthio)
Benzoic acid azide, 4-bromo-2-fluoro-5- (1
-Ethoxycarbonylpropylthio) benzoic acid azide,
2,4-Difluoro-5- [1- (1-propoxycarbonyl) propylthio] benzoic acid azide, 4-chloro-
2-Fluoro-5- [1- (1-propoxycarbonyl) propylthio] benzoic acid azide, 4-bromo-2-
Fluoro-5- [1- (1-propoxycarbonyl) propylthio] benzoic acid azide, 2,4-difluoro-5
-(1-isopropoxycarbonylpropylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-isopropoxycarbonylpropylthio) benzoic acid azide, 4-bromo-2-fluoro-5- (1- Isopropoxycarbonylpropylthio) benzoic acid azide, 2,4
-Difluoro-5- (1-methoxycarbonylbutylthio) benzoic acid azide, 4-chloro-2-fluoro-5-
(1-Methoxycarbonylbutylthio) benzoic acid azide, 4-bromo-2-fluoro-5- (1-methoxycarbonylbutylthio) benzoic acid azide, 2,4-difluoro-5- (1-ethoxycarbonylbutylthio) Benzoic acid azide, 4-chloro-2-fluoro-5- (1-ethoxycarbonylbutylthio) benzoic acid azide, 4-bromo-2-fluoro-5- (1-ethoxycarbonylbutylthio) benzoic acid azide, 2, 4-difluoro-5
[1- (1-propoxycarbonyl) butylthio] benzoic acid azide, 4-chloro-2-fluoro-5- [1-
(1-propoxycarbonyl) butylthio] benzoic acid azide, 4-bromo-2-fluoro-5- [1- (1-propoxycarbonyl) butylthio] benzoic acid azide,
2,4-Difluoro-5- (1-isopropoxycarbonylbutylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-isopropoxycarbonylbutylthio) benzoic acid azide, 4-bromo-2- Fluoro-5
(1-Isopropoxycarbonylbutylthio) benzoic acid azide, 2,4-difluoro-5- (1-methoxycarbonyl-2-methylpropylthio) benzoic acid azide, 4
-Chloro-2-fluoro-5- (1-methoxycarbonyl-2-methylpropylthio) benzoic acid azide, 4-bromo-2-fluoro-5- (1-methoxycarbonyl-
2-Methylpropylthio) benzoic acid azide, 2,4-difluoro-5- (1-ethoxycarbonyl-2-methylpropylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-ethoxycarbonyl-) 2-Methylpropylthio) benzoic acid azide, 4-bromo-2-fluoro-5- (1-ethoxycarbonyl-2-methylpropylthio) benzoic acid azide, 2,4-difluoro-5- [1
-(1-Propoxycarbonyl) -2-methylpropylthio] benzoic acid azide, 4-chloro-2-fluoro-5
-[1- (1-Propoxycarbonyl) -2-methylpropylthio] benzoic acid azide, 4-bromo-2-fluoro-5- [1- (1-propoxycarbonyl) -2-methylpropylthio] benzoic acid azide 2,4-difluoro-5- (1-isopropoxycarbonyl-2-methylpropylthio) benzoic acid azide, 4-chloro-2-fluoro-5- (1-isopropoxycarbonyl-2-methylpropylthio) benzoic acid Examples thereof include acid azide and 4-bromo-2-fluoro-5- (1-isopropoxycarbonyl-2-methylpropylthio) benzoic acid azide.
【００１７】次に、本発明における一般式［Ｉ］で示さ
れる酸アジド誘導体の製造法を詳細に説明する。Next, the method for producing the acid azide derivative represented by the general formula [I] in the present invention will be described in detail.
【００１８】[0018]
【化９】 [Chemical 9]
【００１９】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］ 本発明の製造法においては、一般式［ＩＩ］で示される
置換ベンゼンカルボニルクロリド誘導体と無機アジ化物
とを適当な溶媒中、１０分間〜１２時間反応させること
により、容易に本発明の化合物である一般式［Ｉ］で示
される酸アジド誘導体を製造することができる。[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). In the production method of the present invention, the substituted benzenecarbonyl chloride derivative represented by the general formula [II] is reacted with the inorganic azide in a suitable solvent for 10 minutes to 12 hours, whereby the compound of the present invention can be easily obtained. An acid azide derivative represented by the general formula [I] can be produced.
【００２０】一般式［ＩＩ］で示される置換ベンゼンカ
ルボニルクロリド誘導体としては、例えば、２，４−ジ
フルオロ−５−メトキシカルボニルメチルチオ安息香酸
クロリド、４−クロロ−２−フルオロ−５−メトキシカ
ルボニルメチルチオ安息香酸クロリド、４−ブロモ−２
−フルオロ−５−メトキシカルボニルメチルチオ安息香
酸クロリド、２，４−ジフルオロ−５−エトキシカルボ
ニルメチルチオ安息香酸クロリド、４−クロロ−２−フ
ルオロ−５−エトキシカルボニルメチルチオ安息香酸ク
ロリド、４−ブロモ−２−フルオロ−５−エトキシカル
ボニルメチルチオ安息香酸クロリド、２，４−ジフルオ
ロ−５−（１−プロポキシカルボニルメチルチオ）安息
香酸クロリド、４−クロロ−２−フルオロ−５−（１−
プロポキシカルボニルメチルチオ）安息香酸クロリド、
４−ブロモ−２−フルオロ−５−（１−プロポキシカル
ボニルメチルチオ）安息香酸クロリド、２，４−ジフル
オロ−５−イソプロポキシカルボニルメチルチオ安息香
酸クロリド、４−クロロ−２−フルオロ−５−イソプロ
ポキシカルボニルメチルチオ安息香酸クロリド、４−ブ
ロモ−２−フルオロ−５−イソプロポキシカルボニルメ
チルチオ安息香酸クロリド、２，４−ジフルオロ−５−
（１−メトキシカルボニルエチルチオ）安息香酸クロリ
ド、４−クロロ−２−フルオロ−５−（１−メトキシカ
ルボニルエチルチオ）安息香酸クロリド、４−ブロモ−
２−フルオロ−５−（１−メトキシカルボニルエチルチ
オ）安息香酸クロリド、２，４−ジフルオロ−５−（１
−エトキシカルボニルエチルチオ）安息香酸クロリド、
４−クロロ−２−フルオロ−５−（１−エトキシカルボ
ニルエチルチオ）安息香酸クロリド、４−ブロモ−２−
フルオロ−５−（１−エトキシカルボニルエチルチオ）
安息香酸クロリド、２，４−ジフルオロ−５−［１−
（１−プロポキシカルボニル）エチルチオ］安息香酸ク
ロリド、４−クロロ−２−フルオロ−５−［１−（１−
プロポキシカルボニル）エチルチオ］安息香酸クロリ
ド、４−ブロモ−２−フルオロ−５−［１−（１−プロ
ポキシカルボニル）エチルチオ］安息香酸クロリド、
２，４−ジフルオロ−５−（１−イソプロポキシカルボ
ニルエチルチオ）安息香酸クロリド、４−クロロ−２−
フルオロ−５−（１−イソプロポキシカルボニルエチル
チオ）安息香酸クロリド、４−ブロモ−２−フルオロ−
５−（１−イソプロポキシカルボニルエチルチオ）安息
香酸クロリド、２，４−ジフルオロ−５−（１−メトキ
シカルボニルプロピルチオ）安息香酸クロリド、４−ク
ロロ−２−フルオロ−５−（１−メトキシカルボニルプ
ロピルチオ）安息香酸クロリド、４−ブロモ−２−フル
オロ−５−（１−メトキシカルボニルプロピルチオ）安
息香酸クロリド、２，４−ジフルオロ−５−（１−エト
キシカルボニルプロピルチオ）安息香酸クロリド、４−
クロロ−２−フルオロ−５−（１−エトキシカルボニル
プロピルチオ）安息香酸クロリド、４−ブロモ−２−フ
ルオロ−５−（１−エトキシカルボニルプロピルチオ）
安息香酸クロリド、２，４−ジフルオロ−５−［１−
（１−プロポキシカルボニル）プロピルチオ］安息香酸
クロリド、４−クロロ−２−フルオロ−５−［１−（１
−プロポキシカルボニル）プロピルチオ］安息香酸クロ
リド、４−ブロモ−２−フルオロ−５−［１−（１−プ
ロポキシカルボニル）プロピルチオ］安息香酸クロリ
ド、２，４−ジフルオロ−５−（１−イソプロポキシカ
ルボニルプロピルチオ）安息香酸クロリド、４−クロロ
−２−フルオロ−５−（１−イソプロポキシカルボニル
プロピルチオ）安息香酸クロリド、４−ブロモ−２−フ
ルオロ−５−（１−イソプロポキシカルボニルプロピル
チオ）安息香酸クロリド、２，４−ジフルオロ−５−
（１−メトキシカルボニルブチルチオ）安息香酸クロリ
ド、４−クロロ−２−フルオロ−５−（１−メトキシカ
ルボニルブチルチオ）安息香酸クロリド、４−ブロモ−
２−フルオロ−５−（１−メトキシカルボニルブチルチ
オ）安息香酸クロリド、２，４−ジフルオロ−５−（１
−エトキシカルボニルブチルチオ）安息香酸クロリド、
４−クロロ−２−フルオロ−５−（１−エトキシカルボ
ニルブチルチオ）安息香酸クロリド、４−ブロモ−２−
フルオロ−５−（１−エトキシカルボニルブチルチオ）
安息香酸クロリド、２，４−ジフルオロ−５−［１−
（１−プロポキシカルボニル）ブチルチオ］安息香酸ク
ロリド、４−クロロ−２−フルオロ−５−［１−（１−
プロポキシカルボニル）ブチルチオ］安息香酸クロリ
ド、４−ブロモ−２−フルオロ−５−［１−（１−プロ
ポキシカルボニル）ブチルチオ］安息香酸クロリド、
２，４−ジフルオロ−５−（１−イソプロポキシカルボ
ニルブチルチオ）安息香酸クロリド、４−クロロ−２−
フルオロ−５−（１−イソプロポキシカルボニルブチル
チオ）安息香酸クロリド、４−ブロモ−２−フルオロ−
５−（１−イソプロポキシカルボニルブチルチオ）安息
香酸クロリド、２，４−ジフルオロ−５−（１−メトキ
シカルボニル−２−メチルプロピルチオ）安息香酸クロ
リド、４−クロロ−２−フルオロ−５−（１−メトキシ
カルボニル−２−メチルプロピルチオ）安息香酸クロリ
ド、４−ブロモ−２−フルオロ−５−（１−メトキシカ
ルボニル−２−メチルプロピルチオ）安息香酸クロリ
ド、２，４−ジフルオロ−５−（１−エトキシカルボニ
ル−２−メチルプロピルチオ）安息香酸クロリド、４−
クロロ−２−フルオロ−５−（１−エトキシカルボニル
−２−メチルプロピルチオ）安息香酸クロリド、４−ブ
ロモ−２−フルオロ−５−（１−エトキシカルボニル−
２−メチルプロピルチオ）安息香酸クロリド、２，４−
ジフルオロ−５−［１−（１−プロポキシカルボニル）
−２−メチルプロピルチオ］安息香酸クロリド、４−ク
ロロ−２−フルオロ−５−［１−（１−プロポキシカル
ボニル）−２−メチルプロピルチオ］安息香酸クロリ
ド、４−ブロモ−２−フルオロ−５−［１−（１−プロ
ポキシカルボニル）−２−メチルプロピルチオ］安息香
酸クロリド、２，４−ジフルオロ−５−（１−イソプロ
ポキシカルボニル−２−メチルプロピルチオ）安息香酸
クロリド、４−クロロ−２−フルオロ−５−（１−イソ
プロポキシカルボニル−２−メチルプロピルチオ）安息
香酸クロリド、４−ブロモ−２−フルオロ−５−（１−
イソプロポキシカルボニル−２−メチルプロピルチオ）
安息香酸クロリドなどを挙げることができる。Examples of the substituted benzenecarbonyl chloride derivative represented by the general formula [II] include 2,4-difluoro-5-methoxycarbonylmethylthiobenzoic acid chloride and 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid chloride. Acid chloride, 4-bromo-2
-Fluoro-5-methoxycarbonylmethylthiobenzoic acid chloride, 2,4-difluoro-5-ethoxycarbonylmethylthiobenzoic acid chloride, 4-chloro-2-fluoro-5-ethoxycarbonylmethylthiobenzoic acid chloride, 4-bromo-2- Fluoro-5-ethoxycarbonylmethylthiobenzoic acid chloride, 2,4-difluoro-5- (1-propoxycarbonylmethylthio) benzoic acid chloride, 4-chloro-2-fluoro-5- (1-
Propoxycarbonylmethylthio) benzoic acid chloride,
4-Bromo-2-fluoro-5- (1-propoxycarbonylmethylthio) benzoic acid chloride, 2,4-difluoro-5-isopropoxycarbonylmethylthiobenzoic acid chloride, 4-chloro-2-fluoro-5-isopropoxycarbonyl Methylthiobenzoic acid chloride, 4-bromo-2-fluoro-5-isopropoxycarbonylmethylthiobenzoic acid chloride, 2,4-difluoro-5-
(1-Methoxycarbonylethylthio) benzoic acid chloride, 4-chloro-2-fluoro-5- (1-methoxycarbonylethylthio) benzoic acid chloride, 4-bromo-
2-Fluoro-5- (1-methoxycarbonylethylthio) benzoic acid chloride, 2,4-difluoro-5- (1
-Ethoxycarbonylethylthio) benzoic acid chloride,
4-chloro-2-fluoro-5- (1-ethoxycarbonylethylthio) benzoic acid chloride, 4-bromo-2-
Fluoro-5- (1-ethoxycarbonylethylthio)
Benzoic acid chloride, 2,4-difluoro-5- [1-
(1-Propoxycarbonyl) ethylthio] benzoic acid chloride, 4-chloro-2-fluoro-5- [1- (1-
Propoxycarbonyl) ethylthio] benzoic acid chloride, 4-bromo-2-fluoro-5- [1- (1-propoxycarbonyl) ethylthio] benzoic acid chloride,
2,4-Difluoro-5- (1-isopropoxycarbonylethylthio) benzoic acid chloride, 4-chloro-2-
Fluoro-5- (1-isopropoxycarbonylethylthio) benzoic acid chloride, 4-bromo-2-fluoro-
5- (1-isopropoxycarbonylethylthio) benzoic acid chloride, 2,4-difluoro-5- (1-methoxycarbonylpropylthio) benzoic acid chloride, 4-chloro-2-fluoro-5- (1-methoxycarbonyl) Propylthio) benzoic acid chloride, 4-bromo-2-fluoro-5- (1-methoxycarbonylpropylthio) benzoic acid chloride, 2,4-difluoro-5- (1-ethoxycarbonylpropylthio) benzoic acid chloride, 4 −
Chloro-2-fluoro-5- (1-ethoxycarbonylpropylthio) benzoic acid chloride, 4-bromo-2-fluoro-5- (1-ethoxycarbonylpropylthio)
Benzoic acid chloride, 2,4-difluoro-5- [1-
(1-Propoxycarbonyl) propylthio] benzoic acid chloride, 4-chloro-2-fluoro-5- [1- (1
-Propoxycarbonyl) propylthio] benzoic acid chloride, 4-bromo-2-fluoro-5- [1- (1-propoxycarbonyl) propylthio] benzoic acid chloride, 2,4-difluoro-5- (1-isopropoxycarbonylpropyl) Thio) benzoic acid chloride, 4-chloro-2-fluoro-5- (1-isopropoxycarbonylpropylthio) benzoic acid chloride, 4-bromo-2-fluoro-5- (1-isopropoxycarbonylpropylthio) benzoic acid Chloride, 2,4-difluoro-5
(1-Methoxycarbonylbutylthio) benzoic acid chloride, 4-chloro-2-fluoro-5- (1-methoxycarbonylbutylthio) benzoic acid chloride, 4-bromo-
2-Fluoro-5- (1-methoxycarbonylbutylthio) benzoic acid chloride, 2,4-difluoro-5- (1
-Ethoxycarbonylbutylthio) benzoyl chloride,
4-chloro-2-fluoro-5- (1-ethoxycarbonylbutylthio) benzoic acid chloride, 4-bromo-2-
Fluoro-5- (1-ethoxycarbonylbutylthio)
Benzoic acid chloride, 2,4-difluoro-5- [1-
(1-Propoxycarbonyl) butylthio] benzoic acid chloride, 4-chloro-2-fluoro-5- [1- (1-
Propoxycarbonyl) butylthio] benzoic acid chloride, 4-bromo-2-fluoro-5- [1- (1-propoxycarbonyl) butylthio] benzoic acid chloride,
2,4-Difluoro-5- (1-isopropoxycarbonylbutylthio) benzoic acid chloride, 4-chloro-2-
Fluoro-5- (1-isopropoxycarbonylbutylthio) benzoic acid chloride, 4-bromo-2-fluoro-
5- (1-isopropoxycarbonylbutylthio) benzoic acid chloride, 2,4-difluoro-5- (1-methoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 4-chloro-2-fluoro-5- ( 1-Methoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 4-bromo-2-fluoro-5- (1-methoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 2,4-difluoro-5- ( 1-ethoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 4-
Chloro-2-fluoro-5- (1-ethoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 4-bromo-2-fluoro-5- (1-ethoxycarbonyl-
2-Methylpropylthio) benzoic acid chloride, 2,4-
Difluoro-5- [1- (1-propoxycarbonyl)
2-Methylpropylthio] benzoic acid chloride, 4-chloro-2-fluoro-5- [1- (1-propoxycarbonyl) -2-methylpropylthio] benzoic acid chloride, 4-bromo-2-fluoro-5 -[1- (1-propoxycarbonyl) -2-methylpropylthio] benzoic acid chloride, 2,4-difluoro-5- (1-isopropoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 4-chloro- 2-Fluoro-5- (1-isopropoxycarbonyl-2-methylpropylthio) benzoic acid chloride, 4-bromo-2-fluoro-5- (1-
Isopropoxycarbonyl-2-methylpropylthio)
Examples thereof include benzoic acid chloride.
【００２１】また、無機アジ化物としては、例えば、ア
ジ化ナトリウム、アジ化カリウムなどを挙げることがで
きる。無機アジ化物は、通常、一般式［ＩＩ］で示され
る置換ベンゼンカルボニルクロリド誘導体１当量に対し
て、０．８当量〜１．５当量、好ましくは０．９当量〜
１．２当量、さらに好ましくは０．９５当量〜１．０５
当量使用するのがよい。この範囲より少ない場合には、
未反応の一般式［ＩＩ］で示される置換ベンゼンカルボ
ニルクロリド誘導体が多量に残るため、収率低下の原因
となり、経済的に不利となり、また、未反応の一般式
［ＩＩ］で示される置換ベンゼンカルボニルクロリド誘
導体の除去のために後処理工程に負荷がかかるため、好
ましくない。また、この範囲より多く使用しても、目的
とする一般式［Ｉ］で示される酸アジド誘導体の収量に
ほとんど変化はなく、過剰に添加した無機アジ化物が、
未反応のまま、多量に残るだけであり、経済的に不利と
なり、また、未反応の無機アジ化物の除去のために後処
理工程に負荷がかかるため、好ましくない。Examples of the inorganic azide include sodium azide and potassium azide. The inorganic azide is usually 0.8 equivalent to 1.5 equivalents, preferably 0.9 equivalent to 1 equivalent of the substituted benzenecarbonyl chloride derivative represented by the general formula [II].
1.2 equivalents, more preferably 0.95 equivalents to 1.05
It is recommended to use equivalent amount. If less than this range,
A large amount of unreacted substituted benzenecarbonyl chloride derivative represented by the general formula [II] remains, which causes a decrease in yield and is economically disadvantageous. Further, unreacted substituted benzene represented by the general formula [II] is represented. It is not preferable because the post-treatment step is burdened to remove the carbonyl chloride derivative. Moreover, even if it is used in excess of this range, the yield of the desired acid azide derivative represented by the general formula [I] is hardly changed, and the excessively added inorganic azide is
It remains unreacted and remains in a large amount, which is economically disadvantageous, and a post-treatment step is burdened to remove unreacted inorganic azide, which is not preferable.
【００２２】また、溶媒としては、例えば、アセトン、
メチルエチルケトン、メチルイソブチルケトンなどのケ
トン類、メタノール、エタノール、プロパノール、ブタ
ノールなどのアルコール類、ジエチルエーテル、ジオキ
サン、テトラヒドロフラン（ＴＨＦ）、エチレングリコ
ールジメチルエーテルなどのエーテル類、酢酸、プロピ
オン酸、酪酸などの有機酸類などを挙げることができ
る。As the solvent, for example, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, ethers such as diethyl ether, dioxane, tetrahydrofuran (THF) and ethylene glycol dimethyl ether, organic acids such as acetic acid, propionic acid and butyric acid. And so on.
【００２３】反応温度は、通常、−７０℃〜１００℃、
好ましくは−５０℃〜７０℃、さらに好ましくは−３０
℃〜５０℃とするのがよい。この範囲より低い温度の場
合には、反応が充分に進行せず、収率低下の原因とな
り、経済的に不利となる、あるいは、反応速度が低下し
て反応終了までに長時間を要するなどの問題を生ずる場
合があり、好ましくない。また、この範囲より高い温度
の場合には、反応中に分解などが起こる場合があり、収
率低下の原因となり、経済的に不利となり、また、分解
生成物などの除去のために後処理工程に負荷がかかるた
め、好ましくない。The reaction temperature is usually -70 ° C to 100 ° C,
Preferably -50 ° C to 70 ° C, more preferably -30 ° C.
It is preferable to set the temperature to 50 ° C. When the temperature is lower than this range, the reaction does not proceed sufficiently, which causes a decrease in yield, which is economically disadvantageous, or the reaction rate is low and it takes a long time to complete the reaction. This may cause problems and is not preferable. Further, if the temperature is higher than this range, decomposition or the like may occur during the reaction, which causes a decrease in yield, which is economically disadvantageous, and a post-treatment step for removing decomposition products and the like. It is not preferable because it puts a load on.
【００２４】本発明の製造法においては、反応終了後、
反応液をある程度、濃縮するかまたは濃縮せず、そのま
ま、水に投入することにより析出した生成物を乾燥し、
目的の一般式［Ｉ］で示される酸アジド誘導体を得るこ
とができる。In the production method of the present invention, after completion of the reaction,
To some extent, the reaction solution is concentrated or not concentrated, and as it is, it is added to water to dry the precipitated product,
The desired acid azide derivative represented by the general formula [I] can be obtained.
【００２５】なお、上記反応の出発物質である一般式
［ＩＩ］で示される置換ベンゼンカルボニルクロリド誘
導体は、例えば、ＵＳＰ−３７８００２７に記載の製造
法によって製造される一般式［ＩＩＩ］The substituted benzenecarbonyl chloride derivative represented by the general formula [II], which is the starting material for the above reaction, can be prepared, for example, by the production method described in USP-3780027.
【００２６】[0026]
【化１０】 [Chemical 10]
【００２７】［式中、Ｙはハロゲン原子を表わす。］で
示される５−塩化スルホニル−２−フルオロ−４−ハロ
安息香酸を一般式［ＩＶ］[In the formula, Y represents a halogen atom. ] 5-sulfonyl chloride-2-fluoro-4-halobenzoic acid represented by the formula [IV]
【００２８】[0028]
【化１１】 [Chemical 11]
【００２９】［式中、Ｒ4は低級アルキル基を表わ
す。］で示される低級アルキルカルボン酸、赤リンおよ
びヨウ素系触媒の存在下、還元することにより一般式
［Ｖ］[In the formula, R 4 represents a lower alkyl group. ] In the presence of a lower alkyl carboxylic acid represented by
【００３０】[0030]
【化１２】 [Chemical 12]
【００３１】［式中、Ｙはハロゲン原子を表わし、Ｒ4
は低級アルキル基を表わす。］で示される置換安息香酸
誘導体を得、これと一般式［ＶＩ］[In the formula, Y represents a halogen atom, and R 4
Represents a lower alkyl group. ] The substituted benzoic acid derivative shown by this, and this and general formula [VI]
【００３２】[0032]
【化１３】 [Chemical 13]
【００３３】［式中、Ｈａｌ−は塩素原子または臭素原
子を表わし、Ｒ1は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は
水素原子または低級アルキル基を表わし、Ｒ6は低級ア
ルキル基を表わす。）を表わす。］で示されるハロカル
ボン酸エステル誘導体とを塩基の存在下、反応させるこ
とにより一般式［ＶＩＩ］[In the formula, Hal- represents a chlorine atom or a bromine atom, R 1 represents -CHR 5 CO 2 R 6 (provided that R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group. Represents.) Represents. ] By reacting with a halocarboxylic acid ester derivative represented by the formula [VII]
【００３４】[0034]
【化１４】 Embedded image
【００３５】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］で示される置換ベンゼンカルボン酸
誘導体を得、これを塩素化することにより製造すること
ができる。[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] It can manufacture by obtaining the substituted benzene carboxylic acid derivative shown by these, and chlorinating this.
【００３６】本発明の化合物である一般式［Ｉ］The compound of the present invention represented by the general formula [I]
【００３７】[0037]
【化１５】 [Chemical 15]
【００３８】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わす。］で示される酸アジド誘導体は、例え
ば、下記ルートにより、優れた除草活性を有するＮ−ア
シル−Ｎ−フェニルテトラヒドロフタラミン酸誘導体へ
と誘導することができる。[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] The acid azide derivative represented by the above can be derived to an N-acyl-N-phenyltetrahydrophthalamic acid derivative having excellent herbicidal activity by the following route, for example.
【００３９】すなわち、一般式［Ｉ］That is, the general formula [I]
【００４０】[0040]
【化１６】 Embedded image
【００４１】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素または低級ア
ルキル基を表わし、Ｒ6は低級アルキル基を表わす。）
を表わす。］で示される酸アジド誘導体を一般式［ＶＩ
ＩＩ］[In the formula, Y represents a halogen atom, and R 1
Is -CHR 5 CO 2 R 6 (provided that, R 5 represents hydrogen or a lower alkyl group, R 6 represents a lower alkyl group.)
Represents ] The acid azide derivative represented by the general formula [VI
II]
【００４２】[0042]
【化１７】 [Chemical 17]
【００４３】［式中、Ｒ2は低級アルキル基または置換
もしくは非置換のフェニル基を表わす。］で示されるカ
ルボン酸誘導体、または、一般式［ＩＸ］[In the formula, R 2 represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] The carboxylic acid derivative shown by or general formula [IX]
【００４４】[0044]
【化１８】 Embedded image
【００４５】［式中、Ｒ2は低級アルキル基または置換
もしくは非置換のフェニル基を表わす。］で示されるカ
ルボン酸無水物誘導体の存在下、分解することにより一
般式［Ｘ］[In the formula, R 2 represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] By decomposing in the presence of a carboxylic acid anhydride derivative represented by the general formula [X]
【００４６】[0046]
【化１９】 [Chemical 19]
【００４７】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わし、Ｒ2は低級アルキル基または置換もし
くは非置換のフェニル基を表わす。］で示されるアニリ
ド誘導体を得、これを本発明者らが既に提案した平成６
年特許願第４２０５号に記載の方法にしたがい、脱水塩
素化剤の存在下で反応させることにより一般式［ＸＩ］[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, R 6 represents a lower alkyl group), and R 2 represents a lower alkyl group or a substituted or unsubstituted phenyl group. Represents ] The anilide derivative represented by
According to the method described in Japanese Patent Application No. 4205, by reacting in the presence of a dehydrating chlorinating agent, a compound of the general formula [XI]
【００４８】[0048]
【化２０】 Embedded image
【００４９】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わし、Ｒ2は低級アルキル基または置換もし
くは非置換のフェニル基を表わす。］で示されるイミド
イルクロリド誘導体とし、これと一般式［ＸＩＩ］[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, R 6 represents a lower alkyl group), and R 2 represents a lower alkyl group or a substituted or unsubstituted phenyl group. Represents ] The imidoyl chloride derivative shown by this and this and general formula [XII]
【００５０】[0050]
【化２１】 [Chemical 21]
【００５１】［式中、Ｒ3は低級アルコキシ基、低級ア
ルケニルオキシ基、低級アルキニルオキシ基、低級アル
コキシアルコキシ基または低級アルコキシカルボニルア
ルコキシ基を表わす。］で示されるカルボン酸誘導体と
を脱酸剤の存在下、反応させることにより、一般式［Ｘ
ＩＩＩ］[In the formula, R 3 represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkoxyalkoxy group or a lower alkoxycarbonylalkoxy group. ] By reacting with a carboxylic acid derivative represented by the formula [X]
III]
【００５２】[0052]
【化２２】 [Chemical formula 22]
【００５３】［式中、Ｙはハロゲン原子を表わし、Ｒ1
は−ＣＨＲ5ＣＯ2Ｒ6（ただし、Ｒ5は水素原子または低
級アルキル基を表わし、Ｒ6は低級アルキル基を表わ
す。）を表わし、Ｒ2は低級アルキル基または置換もし
くは非置換のフェニル基を表わし、Ｒ3は低級アルコキ
シ基、低級アルケニルオキシ基、低級アルキニルオキシ
基、低級アルコキシアルコキシ基または低級アルコキシ
カルボニルアルコキシ基を表わす。］で示されるＮ−ア
シル−Ｎ−フェニルテトラヒドロフタラミン酸誘導体へ
と誘導できる。[In the formula, Y represents a halogen atom, and R 1
Represents —CHR 5 CO 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, R 6 represents a lower alkyl group), and R 2 represents a lower alkyl group or a substituted or unsubstituted phenyl group. R 3 represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkoxyalkoxy group or a lower alkoxycarbonylalkoxy group. ] N-acyl-N-phenyl tetrahydrophthalamic acid derivative shown by these can be derived.
【００５４】上記の一般式［ＸＩＩＩ］で示されるＮ−
アシル−Ｎ−フェニルテトラヒドロフタラミン酸誘導体
は、優れた除草活性を有し、畑地、水田、果樹、牧草
地、芝生地、森林あるいは非農耕地などに広く適用でき
るものであり、かつ、作物に対して高い安全性を示す化
合物である。したがって、本発明の一般式［Ｉ］で示さ
れる新規化合物である酸アジド誘導体は、除草剤として
有用な化合物である一般式［ＸＩＩＩ］で示されるＮ−
アシル−Ｎ−フェニルテトラヒドロフタラミン酸誘導体
の製造中間体として有用な化合物であり、また、本発明
の製造法は、その一般式［Ｉ］で示される酸アジド誘導
体を容易に製造することができる製造法として有用であ
る。N-represented by the above general formula [XIII]
The acyl-N-phenyltetrahydrophthalamic acid derivative has excellent herbicidal activity and is widely applicable to fields, paddy fields, fruit trees, meadows, lawns, forests, non-agricultural lands, etc. On the other hand, it is a compound showing high safety. Therefore, the acid azide derivative which is a novel compound represented by the general formula [I] of the present invention is an N-type compound represented by the general formula [XIII] which is a compound useful as a herbicide.
The compound is useful as an intermediate for the production of an acyl-N-phenyltetrahydrophthalamic acid derivative, and the production method of the present invention can easily produce the acid azide derivative represented by the general formula [I]. It is useful as a manufacturing method.
【００５５】[0055]
【実施例】以下、実施例および参考例により本発明を具
体的に説明する。参考例１ ５−塩化スルホニル−４−クロロ−２−フルオロ安息香
酸の製造（一般式［ＩＩＩ］で示される化合物） 氷冷下、４−クロロ−２−フルオロ安息香酸７．２ｇ
（４１．４ｍｍｏｌ）をクロル硫酸２５．０ｇに加え
た。室温まで昇温し、３０分間反応させ、次いで１２０
℃まで昇温し、４時間反応させた。反応液を室温まで冷
却し、氷水に注ぎ込み、これを酢酸エチル１００ｍｌで
２回抽出した。抽出液を水、飽和食塩水で洗浄し、無水
硫酸マグネシウムで乾燥後、減圧下、溶媒を留去し、粗
生成物を得た。The present invention will be specifically described below with reference to examples and reference examples. Reference Example 1 5-Sulfonyl chloride-4-chloro-2-fluorobenzoate
Production of acid (compound represented by general formula [III]) 7.2 g of 4-chloro-2-fluorobenzoic acid under ice cooling
(41.4 mmol) was added to 25.0 g of chlorosulfuric acid. Warm to room temperature, react for 30 minutes, then 120
The temperature was raised to ° C and the reaction was carried out for 4 hours. The reaction solution was cooled to room temperature, poured into ice water, and this was extracted twice with 100 ml of ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product.
【００５６】得られた粗生成物をｎ−ヘキサン／酢酸エ
チルより再結晶し、目的の５−塩化スルホニル−４−ク
ロロ−２−フルオロ安息香酸７．４ｇを得た。 融点＝１４９．０℃〜１５０．０℃1 Ｈ−ＮＭＲ（ＣＤＣｌ3，δｐｐｍ） ７．５４（ｄ，Ｊ＝９．７Ｈｚ，１Ｈ），８．８５
（ｄ，Ｊ＝１３．０Ｈｚ，１Ｈ），１０．７４（ｂｓ，
１Ｈ）参考例２ ５−アセチルチオ−４−クロロ−２−フルオロ安息香酸
の製造（一般式［Ｖ］で示される化合物） ５−塩化スルホニル−４−クロロ−２−フルオロ安息香
酸７．６７ｇ（２８．１ｍｍｏｌ）、赤リン２．２０ｇ
（７０．２ミリグラム原子）およびヨウ素０．１５ｇ
（０．５６ｍｍｏｌ）を酢酸８０ｍｌ中に混合し、１０
０℃〜１１０℃で３時間反応させた。反応液を室温まで
冷却し、未反応の赤リンをろ別した後、ろ液を濃縮し、
残渣を氷水に注ぎ込み、これを酢酸エチル１００ｍｌで
２回抽出した。抽出液を水、飽和食塩水で洗浄し、無水
硫酸マグネシウムで乾燥後、減圧下、溶媒を留去し、粗
生成物を得た。The obtained crude product was recrystallized from n-hexane / ethyl acetate to obtain 7.4 g of the target 5-sulfonyl chloride-4-chloro-2-fluorobenzoic acid. Melting point = 149.0 ° C. to 150.0 ° C. 1 H-NMR (CDCl 3 , δ ppm) 7.54 (d, J = 9.7 Hz, 1 H), 8.85
(D, J = 13.0 Hz, 1H), 10.74 (bs,
1H) Reference Example 2 5-acetylthio-4-chloro-2-fluorobenzoic acid
(Compound represented by general formula [V]) 5-Sulfonyl chloride-4-chloro-2-fluorobenzoic acid 7.67 g (28.1 mmol), red phosphorus 2.20 g
(70.2 mg atom) and 0.15 g iodine
(0.56 mmol) in 80 ml of acetic acid,
The reaction was performed at 0 ° C to 110 ° C for 3 hours. The reaction solution was cooled to room temperature, unreacted red phosphorus was filtered off, and the filtrate was concentrated,
The residue was poured into ice water, and this was extracted twice with 100 ml of ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product.
【００５７】得られた粗生成物をｎ−ヘキサン／酢酸エ
チルより再結晶し、目的の５−アセチルチオ−４−クロ
ロ−２−フルオロ安息香酸６．８５ｇを得た。 融点＝１４０．０℃〜１４１．５℃1 Ｈ−ＮＭＲ（ＣＤＣｌ3，δｐｐｍ） ２．５０（ｓ，３Ｈ），７．４０（ｄ，Ｊ＝１０．１Ｈ
ｚ，１Ｈ），８．１９（ｄ，Ｊ＝７．９Ｈｚ，１Ｈ），
１１．２９（ｂｓ，１Ｈ）参考例３ ４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸の製造（一般式［ＶＩＩ］で示される
化合物） ５−アセチルチオ−４−クロロ−２−フルオロ安息香酸
７．４０ｇ（３０．０ｍｍｏｌ）、ブロモ酢酸メチル
６．８８ｇ（４５．０ｍｍｏｌ）、メタノ−ル３５ｍｌ
を混合し、水酸化カリウム５．８９ｇ（１０５ｍｍｏ
ｌ）を水７ｍｌに溶解した溶液を５℃〜１０℃で滴下し
た。滴下終了後、１５℃〜２０℃で１時間反応させ、氷
水に注ぎ込んだ。濃塩酸でｐＨ＝１〜２に調整後、酢酸
エチルで抽出し、抽出液を水および飽和食塩水で洗浄
し、無水硫酸マグネシウムで乾燥後、減圧下、溶媒を留
去し、粗生成物を得た。The resulting crude product was recrystallized from n-hexane / ethyl acetate to obtain 6.85 g of the target 5-acetylthio-4-chloro-2-fluorobenzoic acid. Melting point = 140.0 ° C. to 141.5 ° C. 1 H-NMR (CDCl 3 , δppm) 2.50 (s, 3H), 7.40 (d, J = 10.1H)
z, 1H), 8.19 (d, J = 7.9Hz, 1H),
11.29 (bs, 1H) Reference Example 3 4-chloro-2-fluoro-5-methoxycarbonylme
Production of tylthiobenzoic acid (represented by general formula [VII]
Compound) 7.40 g (30.0 mmol ) of 5-acetylthio-4-chloro-2-fluorobenzoic acid, 6.88 g (45.0 mmol) of methyl bromoacetate, 35 ml of methanol
Were mixed, and potassium hydroxide 5.89 g (105 mmo
A solution prepared by dissolving l) in 7 ml of water was added dropwise at 5 ° C to 10 ° C. After completion of dropping, the mixture was reacted at 15 ° C to 20 ° C for 1 hour and poured into ice water. After adjusting the pH to 1-2 with concentrated hydrochloric acid, the mixture was extracted with ethyl acetate, the extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give a crude product. Obtained.
【００５８】得られた粗生成物をｎ−ヘキサン／酢酸エ
チルより再結晶し、目的の４−クロロ−２−フルオロ−
５−メトキシカルボニルメチルチオ安息香酸７．６９ｇ
を得た。The resulting crude product was recrystallized from n-hexane / ethyl acetate to give the desired 4-chloro-2-fluoro-
5-Methoxycarbonylmethylthiobenzoic acid 7.69 g
I got
【００５９】融点＝１４７．０℃〜１４９．０℃1 Ｈ−ＮＭＲ（ＣＤＣｌ3，δｐｐｍ） ３．７２（ｓ，２Ｈ），３．７７（ｓ，３Ｈ），７．３
１（ｄ，Ｊ＝１０．１Ｈｚ，１Ｈ），８．１５（ｄ，Ｊ
＝７．０Ｈｚ，１Ｈ），１０．１（ｂｓ，１Ｈ）参考例４ ４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸クロリドの製造（一般式［ＩＩ］で示
される化合物） ４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸８．１７ｇ（２９．３ｍｍｏｌ）、塩
化チオニル６６．４ｇ（５５８ｍｍｏｌ）を混合し、還
流下に２時間反応させ、過剰の塩化チオニルおよび揮発
成分を留去し、残渣をｎ−ヘキサン／ベンゼンより再結
晶して、目的の４−クロロ−２−フルオロ−５−メトキ
シカルボニルメチルチオ安息香酸クロリド６．２ｇを得
た。Melting point = 147.0 ° C. to 149.0 ° C. 1 H-NMR (CDCl 3 , δppm) 3.72 (s, 2H), 3.77 (s, 3H), 7.3
1 (d, J = 10.1 Hz, 1H), 8.15 (d, J
= 7.0 Hz, 1H), 10.1 (bs, 1H) Reference Example 4 4-chloro-2-fluoro-5-methoxycarbonylme
Manufacture of tilthiobenzoic acid chloride (shown by the general formula [II]
Compound) 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid 8.17 g (29.3 mmol) and thionyl chloride 66.4 g (558 mmol) are mixed and reacted under reflux for 2 hours to obtain an excess amount. Thionyl chloride and volatile components were distilled off, and the residue was recrystallized from n-hexane / benzene to obtain 6.2 g of the target 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid chloride.
【００６０】融点＝７８．０℃〜８０．０℃1 Ｈ−ＮＭＲ（ＣＤＣｌ3，δｐｐｍ） ３．７２（ｓ，２Ｈ），３．７７（ｓ，３Ｈ），７．３
２（ｄ，Ｊ＝１０．１Ｈｚ，１Ｈ），８．２１（ｄ，Ｊ
＝７．０Ｈｚ，１Ｈ）実施例１ ４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸アジドの製造（一般式［Ｉ］で示され
る化合物） ４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸クロリド５．５０ｇ（１８．５ｍｍｏ
ｌ）をアセトン４０ｍｌに溶解し、水７ｍｌに溶解した
アジ化ナトリウム１．２ｇ（１８．５ｍｍｏｌ）を０℃
〜５℃で滴下し、滴下終了後、０℃〜５℃で２０分間反
応させた。反応終了後、反応液を氷水に注ぎ込み、析出
した生成物をろ集し、乾燥して、目的の４−クロロ−２
−フルオロ−５−メトキシカルボニルメチルチオ安息香
酸アジド５．２６ｇを得た。Melting point = 78.0 ° C. to 80.0 ° C. 1 H-NMR (CDCl 3 , δppm) 3.72 (s, 2H), 3.77 (s, 3H), 7.3
2 (d, J = 10.1Hz, 1H), 8.21 (d, J
= 7.0 Hz, 1H) Example 1 4-chloro-2-fluoro-5-methoxycarbonylme
Preparation of tilthiobenzoic acid azide (represented by general formula [I]
Compound) 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid chloride 5.50 g (18.5 mmo
l) was dissolved in 40 ml of acetone and 1.2 g (18.5 mmol) of sodium azide dissolved in 7 ml of water was added at 0 ° C.
After the dropwise addition was completed, the reaction was carried out at 0 ° C to 5 ° C for 20 minutes. After completion of the reaction, the reaction solution was poured into ice water, and the precipitated product was collected by filtration and dried to give the desired 4-chloro-2 product.
5.26 g of -fluoro-5-methoxycarbonylmethylthiobenzoic acid azide was obtained.
【００６１】 融点＝６９．０〜７０．０℃（ｄｅｃｏｍｐ．）1 Ｈ−ＮＭＲ（ＣＤＣｌ3，δｐｐｍ） ３．６９（ｓ，２Ｈ），３．７４（ｓ，３Ｈ），７．２
８（ｄ，Ｊ＝１０．１Ｈｚ，１Ｈ），８．０４（ｄ，Ｊ
＝７．０Ｈｚ，１Ｈ）参考例５ ５−アセチルアミノ−２−クロロ−４−フルオロフェニ
ルチオ酢酸メチルの製造（一般式［Ｘ］で示される化合
物） ４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸アジド１．０ｇ（３．２９ｍｍｏｌ）
を酢酸７ｍｌに溶解し、室温下で濃硫酸２滴を滴下した
後、７０℃まで加温し、２時間反応させた。反応終了
後、室温まで冷却し、反応液を濃縮し、残渣を氷水に注
ぎ込み、酢酸エチルで抽出した。抽出液を水および飽和
食塩水で洗浄し、無水硫酸マグネシウムで乾燥後、減圧
下、溶媒を留去し、結晶を得た。酢酸エチル／ｎ−ヘキ
サンより再結晶を行い、目的の５−アセチルアミノ−２
−クロロ−４−フルオロフェニルチオ酢酸メチル０．５
１ｇを得た。Melting point = 69.0 to 70.0 ° C. (decomp.) 1 H-NMR (CDCl 3 , δppm) 3.69 (s, 2H), 3.74 (s, 3H), 7.2
8 (d, J = 10.1 Hz, 1H), 8.04 (d, J
= 7.0 Hz, 1H) Reference Example 5 5 -Acetylamino -2-chloro-4-fluorophenyl
Production of methyl ruthioacetate (Compound represented by the general formula [X]
Product) 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid azide 1.0 g (3.29 mmol)
Was dissolved in 7 ml of acetic acid, 2 drops of concentrated sulfuric acid was added at room temperature, and the mixture was heated to 70 ° C. and reacted for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, the reaction mixture was concentrated, the residue was poured into ice water, and the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give crystals. Recrystallization from ethyl acetate / n-hexane gives the desired 5-acetylamino-2.
Methyl chloro-4-fluorophenylthioacetate 0.5
1 g was obtained.
【００６２】参考例６ Ｎ−（４−クロロ−２−フルオロ−５−メトキシカルボ
ニルメチルチオフェニル）−アセトイミドイルクロリド
の製造（一般式［ＸＩ］で示される化合物） ５−アセチルアミノ−２−クロロ−４−フルオロフェニ
ルチオ酢酸メチル１０ｇ（３４．３ｍｍｏｌ）と五塩化
リン７．１４ｇ（３４．３ｍｍｏｌ）を２５０ｍｌのベ
ンゼンに懸濁させ、６０℃に加温し、１時間撹拌した。
反応後、反応液を減圧下、濃縮し、定量的に、油状物と
してＮ−（４−クロロ−２−フルオロ−５−メトキシカ
ルボニルメチルチオフェニル）−アセトイミドイルクロ
リドを得た。 Reference Example 6 N- (4-chloro-2-fluoro-5-methoxycarbo
Nylmethylthiophenyl) -acetimidoyl chloride
(Compound represented by the general formula [XI]) 10 g (34.3 mmol) of methyl 5-acetylamino-2-chloro-4-fluorophenylthioacetate and 7.14 g (34.3 mmol) of phosphorus pentachloride in 250 ml. It was suspended in benzene, heated to 60 ° C., and stirred for 1 hour.
After the reaction, the reaction solution was concentrated under reduced pressure to quantitatively obtain N- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -acetimidoyl chloride as an oil.
【００６３】参考例７ Ｎ−アセチル−Ｎ−（４−クロロ−２−フルオロ−５−
メトキシカルボニルメチルチオフェニル）−３，４，
５，６−テトラヒドロフタラミン酸メチルエステルの製
造（一般式［ＸＩＩＩ］で示される化合物） Ｎ−（４−クロロ−２−フルオロ−５−メトキシカルボ
ニルメチルチオフェニル）−アセトイミドイルクロリド
１０．６ｇ（３４．３ｍｍｏｌ）と３，４，５，６−テ
トラヒドロフタラミン酸モノメチルエステル６．９５ｇ
（３７．７ｍｍｏｌ）をベンゼン５０ｍｌに溶解し、ベ
ンゼン１０ｍｌに溶解したトリエチルアミン４．１６ｇ
（４１．２ｍｍｏｌ）を１０℃以下で滴下した。滴下
後、６０℃で３時間、撹拌した。放冷後、水、飽和食塩
水で洗浄後、無水硫酸マグネシウムで乾燥した。溶媒を
濃縮し、結晶を得た。メタノールより再結晶を行い、
５．０９ｇのＮ−アセチル−Ｎ−（４−クロロ−２−フ
ルオロ−５−メトキシカルボニルメチルチオフェニル）
−３，４，５，６−テトラヒドロフタラミン酸メチルエ
ステルを得た。 Reference Example 7 N-acetyl-N- (4-chloro-2-fluoro-5-
Methoxycarbonylmethylthiophenyl) -3,4
Manufacture of 5,6-tetrahydrophthalamic acid methyl ester
Preparation ( Compound represented by the general formula [XIII]) N- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -acetimidoyl chloride 10.6 g (34.3 mmol), 3,4,5, 6.95 g of 6-tetrahydrophthalamic acid monomethyl ester
(37.7 mmol) was dissolved in 50 ml of benzene, and 4.16 g of triethylamine dissolved in 10 ml of benzene.
(41.2 mmol) was added dropwise at 10 ° C or lower. After dropping, the mixture was stirred at 60 ° C. for 3 hours. After allowing to cool, it was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. The solvent was concentrated to give crystals. Recrystallize from methanol,
5.09 g of N-acetyl-N- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl)
-3,4,5,6-Tetrahydrophthalamic acid methyl ester was obtained.
【００６４】[0064]
【発明の効果】本発明の一般式［Ｉ］で示される酸アジ
ド誘導体は、農薬、医薬など、例えば、除草剤として有
用な化合物であるＮ−アシル−Ｎ−フェニルテトラヒド
ロフタラミン酸誘導体などの中間体として有用な化合物
であり、また、本発明の製造法により、その一般式
［Ｉ］で示される酸アジド誘導体を容易に製造すること
ができる。INDUSTRIAL APPLICABILITY The acid azide derivative represented by the general formula [I] of the present invention is a compound useful as a herbicide such as N-acyl-N-phenyltetrahydrophthalamic acid derivative which is useful as a herbicide. The compound is useful as an intermediate, and the acid azide derivative represented by the general formula [I] can be easily produced by the production method of the present invention.
Claims (5)
Ｏ2Ｒ6（ただし、Ｒ5は水素原子または低級アルキル基
を表わし、Ｒ6は低級アルキル基を表わす。）を表わ
す。］で示される酸アジド誘導体。1. A compound represented by the general formula [I]: [In the formula, Y represents a halogen atom, and R 1 is —CHR 5 C.
O 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] The acid azide derivative shown by these.
４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸アジドである請求項１に記載の酸アジ
ド誘導体。2. The acid azide derivative according to claim 1, wherein the acid azide derivative represented by the general formula [I] is 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid azide.
Ｏ2Ｒ6（ただし、Ｒ5は水素原子または低級アルキル基
を表わし、Ｒ6は低級アルキル基を表わす。）を表わ
す。］で示される置換ベンゼンカルボニルクロリド誘導
体と無機アジ化物を反応させることを特徴とする一般式
［Ｉ］ 【化３】 ［式中、Ｙはハロゲン原子を表わし、Ｒ1は−ＣＨＲ5Ｃ
Ｏ2Ｒ6（ただし、Ｒ5は水素原子または低級アルキル基
を表わし、Ｒ6は低級アルキル基を表わす。）を表わ
す。］で示される酸アジド誘導体の製造法。3. A compound represented by the general formula [II]: [In the formula, Y represents a halogen atom, and R 1 is —CHR 5 C.
O 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] The substituted benzenecarbonyl chloride derivative represented by the formula [I] [In the formula, Y represents a halogen atom, and R 1 is —CHR 5 C.
O 2 R 6 (wherein R 5 represents a hydrogen atom or a lower alkyl group, and R 6 represents a lower alkyl group). ] The manufacturing method of the acid azide derivative shown by these.
４−クロロ−２−フルオロ−５−メトキシカルボニルメ
チルチオ安息香酸アジドである請求項３に記載の酸アジ
ド誘導体の製造法。4. The method for producing an acid azide derivative according to claim 3, wherein the acid azide derivative represented by the general formula [I] is 4-chloro-2-fluoro-5-methoxycarbonylmethylthiobenzoic acid azide.
求項３または請求項４に記載の酸アジド誘導体の製造
法。5. The method for producing an acid azide derivative according to claim 3 or 4, wherein the inorganic azide is sodium azide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28094194A JPH08143538A (en) | 1994-11-15 | 1994-11-15 | Acid azide derivative and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28094194A JPH08143538A (en) | 1994-11-15 | 1994-11-15 | Acid azide derivative and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08143538A true JPH08143538A (en) | 1996-06-04 |
Family
ID=17632056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28094194A Pending JPH08143538A (en) | 1994-11-15 | 1994-11-15 | Acid azide derivative and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08143538A (en) |
-
1994
- 1994-11-15 JP JP28094194A patent/JPH08143538A/en active Pending
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