JPH0233708B2 - - Google Patents
Info
- Publication number
- JPH0233708B2 JPH0233708B2 JP55159046A JP15904680A JPH0233708B2 JP H0233708 B2 JPH0233708 B2 JP H0233708B2 JP 55159046 A JP55159046 A JP 55159046A JP 15904680 A JP15904680 A JP 15904680A JP H0233708 B2 JPH0233708 B2 JP H0233708B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- compound
- solvent
- general formula
- 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkali metal alkoxide Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000003217 pyrazoles Chemical class 0.000 claims description 3
- NPRXQXFTKCBAAY-UHFFFAOYSA-N 4-benzoylpyrazole Chemical class C=1C=CC=CC=1C(=O)C=1C=NNC=1 NPRXQXFTKCBAAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000002904 solvent Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000007796 conventional method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012442 inert solvent Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- HGPHCKKIORAGFH-UHFFFAOYSA-N 4-(2,4-dichlorobenzoyl)-5-methyl-1,2-dihydropyrazol-3-one Chemical compound CC1=NNC(O)=C1C(=O)C1=CC=C(Cl)C=C1Cl HGPHCKKIORAGFH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 238000006462 rearrangement reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QOJQHOGSXXSMKX-UHFFFAOYSA-N 2,4-dichlorobenzohydrazide Chemical compound NNC(=O)C1=CC=C(Cl)C=C1Cl QOJQHOGSXXSMKX-UHFFFAOYSA-N 0.000 description 2
- PTCJJVUWVYVXEH-UHFFFAOYSA-N 4-benzoyl-5-methyl-1,2-dihydropyrazol-3-one Chemical compound N1NC(=O)C(C(=O)C=2C=CC=CC=2)=C1C PTCJJVUWVYVXEH-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KQBHSBBSIQMQJQ-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)N1N=C(C=C1O)C Chemical compound C(C1=CC=CC=C1)(=O)N1N=C(C=C1O)C KQBHSBBSIQMQJQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- 239000002841 Lewis acid Substances 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/28—Two oxygen or sulfur atoms
- C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、一般式
（式中、R1は低級アルキル基を示し、Ｘはハロ
ゲン原子を示す。ｎは０，１または２を示す。）
を有する４―ベンゾイルピラゾール誘導体の製法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula (In the formula, R 1 represents a lower alkyl group, X represents a halogen atom, and n represents 0, 1 or 2.)
The present invention relates to a method for producing a 4-benzoylpyrazole derivative having the following.
前記一般式（）において、低級アルキル基と
してはメチル、エチル、ｎ―プロピルまたはイソ
プロピルのような炭素数１乃至３個を有する直鎖
状または分枝状の低級アルキル基があげられる。
またハロゲン原子とは塩素、臭素、弗素または沃
素を示す。 In the general formula (), examples of the lower alkyl group include linear or branched lower alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, or isopropyl.
Further, the halogen atom refers to chlorine, bromine, fluorine or iodine.
本発明の方法によれば前記一般式（）を有す
る化合物は次のようにして製造することができ
る。即ち一般式
（式中、R1，Ｘおよびｎは前述したものと同意
義を示す。）を有するピラゾール誘導体を触媒と
接触させることによつて得ることができる。 According to the method of the present invention, the compound having the general formula () can be produced as follows. That is, the general formula It can be obtained by contacting a pyrazole derivative having the formula (wherein R 1 , X and n have the same meanings as defined above) with a catalyst.
本発明を実施するにあたり、反応は前記一般式
（）を有する化合物を等モル以上の触媒の存在
下、加熱することによつて容易に遂行される。使
用される触媒としては、塩化アルミニウム、イミ
ダゾール、アルカリ金属炭酸塩およびアルカリ金
属アルコキシドから選ばれる。アルカリ金属炭酸
塩としては、例えば炭酸ナトリウムまたは炭酸カ
リウムがあげられる。アルカリ金属アルコキシド
としては、例えばナトリウムメトキシド、カリウ
ムエトキシド、ナトリウムイソプロポキシドまた
はカリウムtert―ブトキシドがあげられる。ま
た、反応溶剤中でこれらのアルカリ金属アルコキ
シドが形成されるような系を用いてもよい。例え
ば、イソプロパノール中に金属ナトリウムを溶か
せば、ナトリウムイソプロポキシドを含む溶液が
得られるが、このようなアルコール溶液をそのま
ま反応溶剤として使用することもできる。 In carrying out the present invention, the reaction is easily carried out by heating the compound having the general formula () in the presence of equimolar or more of a catalyst. The catalyst used is selected from aluminum chloride, imidazole, alkali metal carbonates and alkali metal alkoxides. Examples of alkali metal carbonates include sodium carbonate and potassium carbonate. Examples of alkali metal alkoxides include sodium methoxide, potassium ethoxide, sodium isopropoxide or potassium tert-butoxide. Furthermore, a system in which these alkali metal alkoxides are formed in the reaction solvent may be used. For example, if metallic sodium is dissolved in isopropanol, a solution containing sodium isopropoxide can be obtained, but such an alcohol solution can also be used as it is as a reaction solvent.
反応は一旦、前記一般式（）を有する化合物
が転位触媒の塩を形成して進むが、この中間の塩
を単離後転位反応を行つてもよいし、単離するこ
となく転位反応を行つてもよい。 The reaction proceeds once the compound having the general formula () forms a rearrangement catalyst salt, but the rearrangement reaction may be performed after isolating this intermediate salt, or the rearrangement reaction may be performed without isolation. It's good to wear.
反応は溶剤の存在下または不存在下で行なわれ
るが、反応を円滑に行なうには溶剤を使用する方
が好ましく、使用される溶剤としては本反応に関
与しなければ特に限定はなく、例えばジエチルエ
ーテル、テトラヒドロフランまたはジオキサンの
ようなエーテル類；塩化メチレンまたは四塩化炭
素のようなハロゲン化炭化水素類；イソプロパノ
ールまたはtert―ブタノールのような２級または
３級アルコール類；メチルエチルケトンまたはメ
チルイソブチルケトンのようなケトン類；ベンゼ
ンまたはクロルベンゼンのような芳香族炭化水素
類およびこれらの溶剤の混合溶剤があげられる。 The reaction is carried out in the presence or absence of a solvent, but in order to carry out the reaction smoothly, it is preferable to use a solvent, and the solvent used is not particularly limited as long as it does not take part in this reaction. For example, diethyl Ethers such as ether, tetrahydrofuran or dioxane; halogenated hydrocarbons such as methylene chloride or carbon tetrachloride; secondary or tertiary alcohols such as isopropanol or tert-butanol; such as methyl ethyl ketone or methyl isobutyl ketone. Ketones; aromatic hydrocarbons such as benzene or chlorobenzene, and mixed solvents of these solvents.
転位触媒は前記式（）の化合物に対して等モ
ル以上、好ましくは約1.0〜6.0倍モル、特に約1.5
〜3.0倍モルを出来るだけ微細な粒子に粉砕し、
前記式（）の化合物と混和加熱して溶融撹拌す
るか、若しくは前述した不活性溶剤との共存下、
80〜200℃好ましくは100〜160℃で加熱撹拌する。
反応時間は通常30分から５時間を要する。 The rearrangement catalyst is used in an amount equal to or more than the mole of the compound of formula (), preferably about 1.0 to 6.0 times, particularly about 1.5 times the mole.
Grind ~3.0 times the mole into as fine particles as possible,
Mixed with the compound of the formula () and heated to melt and stir, or in the coexistence with the above-mentioned inert solvent,
Heat and stir at 80-200°C, preferably 100-160°C.
The reaction time usually takes 30 minutes to 5 hours.
無溶剤下では一般に転位反応の進行とともに固
化し、撹拌が困難となることが多い。このような
場合には、前述した不活性溶剤の適当量を添加す
る。重要なことは前記式（）の化合物と転位触
媒との接触を十分に保つことにあり、溶剤の使用
はできる限り少量に止めることが望ましい。ま
た、微量の水分の存在は反応を促進させるため好
ましいが、同時に遊離の安息香酸の副生は避けら
れないので溶剤中の水分含量は１％以内にとどめ
ることが望ましい。 In the absence of a solvent, it generally solidifies as the rearrangement reaction progresses, making stirring often difficult. In such cases, an appropriate amount of the inert solvent described above is added. What is important is to maintain sufficient contact between the compound of formula () and the rearrangement catalyst, and it is desirable to use as little solvent as possible. Further, the presence of a small amount of water is preferable because it accelerates the reaction, but at the same time, the by-product of free benzoic acid is unavoidable, so it is desirable to keep the water content in the solvent within 1%.
反応終了後、本発明の方法の目的化合物は常法
によつて反応混合物から採取される。例えば反応
終了後、反応混合物より溶剤を留去することによ
つて目的化合物が転位触媒の塩として得られる。
得られたこれらの塩類は、通常酸を加えてPH３以
下に調整することにより目的化合物を遊離の状態
で単離することができる。このものは更に再結晶
法等の常法により精製してその純品を得ることが
できる。 After completion of the reaction, the target compound of the method of the present invention is collected from the reaction mixture by a conventional method. For example, after the reaction is completed, the target compound is obtained as a salt of the rearrangement catalyst by distilling off the solvent from the reaction mixture.
The desired compound of the obtained salts can be isolated in a free state by adjusting the pH to 3 or less by usually adding an acid. This product can be further purified by conventional methods such as recrystallization to obtain a pure product.
本発明の方法を実施するに当つて、原料化合物
として用いた前記式（）を有する化合物は１―
ベンゾイル―５―ヒドロキシ―３―メチルピラゾ
ール（特公昭48−33132号公報）を除き新規な化
合物である。 In carrying out the method of the present invention, the compound having the above formula () used as a raw material compound is 1-
These compounds are new except for benzoyl-5-hydroxy-3-methylpyrazole (Japanese Patent Publication No. 48-33132).
前記一般式（）を有する化合物は次のような
一連の反応によつて製造される。 The compound having the general formula () is produced by the following series of reactions.
（式中、R1，Ｘおよびｎは前述したものと同意
義を示し、R2は低級アルキル基を示す。）
以下各工程について説明する。 (In the formula, R 1 , X and n have the same meanings as described above, and R 2 represents a lower alkyl group.) Each step will be explained below.
Ａ―１工程は前記一般式（）を有する化合物
を製造する工程であり、ケトエステル（）に対
し等モルのヒドラジン（）を接触させることに
よつて達成される。反応は溶剤の存在下で好適に
行なわれる。使用される溶剤としては本反応に関
与しなければ特に限定はなく、例えばメタノー
ル、エタノールまたはイソプロパノールのような
アルコール類；ジオキサンまたはテトラヒドロフ
ランのようなエーテル類；クロロホルムまたは塩
化メチレンのようなハロゲン化炭化水素類および
これらの溶剤の混合剤があげられる。反応温度は
特に限定はなく通常反応は室温で行なわれる。反
応に要する時間は５乃至20時間である。 Step A-1 is a step for producing a compound having the above general formula (), and is achieved by bringing an equimolar amount of hydrazine () into contact with the ketoester (). The reaction is preferably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not participate in this reaction, and includes, for example, alcohols such as methanol, ethanol, or isopropanol; ethers such as dioxane or tetrahydrofuran; halogenated hydrocarbons such as chloroform or methylene chloride. and mixtures of these solvents. The reaction temperature is not particularly limited, and the reaction is usually carried out at room temperature. The time required for the reaction is 5 to 20 hours.
反応終了後、目的化合物は常法によつて反応混
合物から採取される。例えば反応混合物より溶剤
を留去することによつて得られる。粗製の目的化
合物は常法例えば再結晶法等によつて精製するこ
ともできる。 After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. For example, it can be obtained by distilling off the solvent from the reaction mixture. The crude target compound can also be purified by conventional methods such as recrystallization.
Ａ―２工程は前記一般式（）を有する化合物
を製造する工程であり、前記一般式（）を有す
る化合物を等モル乃至やや過剰の塩基触媒の存在
下、不活性溶剤中で接触させることによつて達成
される。反応に使用される塩基触媒としては、例
えばナトリウムメトキシド、ナトリウムエトキシ
ドまたはカリウムtert―ブトキシドのようなアル
コキシド類；水素化ナトリウムまたは水素化カリ
ウムのような水素化金属類；炭酸ナトリウムまた
は炭酸カリウムのような炭酸塩類；ｎ―ブチルリ
チウムのような有機リチウム類等があげられる。
使用される不活性溶剤としては、例えばメタノー
ルまたはエタノールのようなアルコール類；エチ
ルエーテルまたはテトラヒドロフランのようなエ
ーテル類；アセトンまたはメチルイソブチルケト
ンのようなケトン類；ヘキサメチルホルムアミド
のようなアミド類およびこれらの溶剤の混合溶剤
があげられる。反応温度は特に限定はなく通常−
40℃乃至５℃程度で行なわれる。反応に要する時
間は２乃至24時間である。 Step A-2 is a step for producing a compound having the above general formula (), in which the compound having the above general formula () is brought into contact with each other in an inert solvent in the presence of an equimolar to slightly excess base catalyst. It is achieved by doing so. Base catalysts used in the reaction include, for example, alkoxides such as sodium methoxide, sodium ethoxide or potassium tert-butoxide; metal hydrides such as sodium hydride or potassium hydride; sodium carbonate or potassium carbonate. and organic lithiums such as n-butyllithium.
Inert solvents used include, for example, alcohols such as methanol or ethanol; ethers such as ethyl ether or tetrahydrofuran; ketones such as acetone or methyl isobutyl ketone; amides such as hexamethylformamide; Examples include mixed solvents of solvents. The reaction temperature is not particularly limited and is usually -
It is carried out at a temperature of about 40°C to 5°C. The time required for the reaction is 2 to 24 hours.
反応終了後、目的化合物は常法により反応混合
物から採取される。例えば反応混合物より溶剤を
留去することによつて得られる。粗製の目的化合
物は常法例えば再結晶法等によつて精製すること
もできる。 After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. For example, it can be obtained by distilling off the solvent from the reaction mixture. The crude target compound can also be purified by conventional methods such as recrystallization.
前記一般式（）を有する化合物のうち、R1
がメチル基であるものは、ジケテン（）とヒド
ラジン（）を反応させて得られたヒドラジド
（）を酸触媒の存在下脱水閉環することによつ
ても得ることができる（Ｂ法）。 Among the compounds having the general formula (), R 1
is a methyl group can also be obtained by dehydrating and ring-closing hydrazide () obtained by reacting diketene () and hydrazine () in the presence of an acid catalyst (method B).
Ｂ―１工程は前記一般式（）を有する化合物
を製造する工程であり、ジケテン（）とヒドラ
ジン（）を不活性溶剤中で接触させることによ
つて達成される。 Step B-1 is a step for producing a compound having the general formula (), and is achieved by bringing diketene () and hydrazine () into contact in an inert solvent.
使用される溶剤としては本反応に関与しないも
のであれば特に限定はなく、例えばベンゼンまた
はトルエンのような芳香族炭化水素類；クロロホ
ルムまたはテトラクロルエタンのようなハロゲン
化炭化水素類；エチルエーテルまたはテトラヒド
ロフランのようなエーテル類；アセトニトリルま
たはプロピオニトリルのようなニトリル類等があ
げられる。反応温度は特に限定はなく通常反応は
室温付近で行なわれる。反応に要する時間は２乃
至６時間である。 The solvent used is not particularly limited as long as it does not participate in this reaction; for example, aromatic hydrocarbons such as benzene or toluene; halogenated hydrocarbons such as chloroform or tetrachloroethane; ethyl ether or Examples include ethers such as tetrahydrofuran; nitrites such as acetonitrile or propionitrile. The reaction temperature is not particularly limited, and the reaction is usually carried out around room temperature. The time required for the reaction is 2 to 6 hours.
反応終了後、目的化合物は常法によつて反応混
合物から採取される。 After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method.
Ｂ―２工程は前記一般式（）を有する化合物
を製造する工程であり、前記一般式（）を有す
る化合物を酸触媒の存在下、不活性溶剤中で接触
させることによつて達成される。 Step B-2 is a step for producing a compound having the general formula (), and is achieved by contacting the compound having the general formula () in the presence of an acid catalyst in an inert solvent.
反応に使用される酸触媒としてはｐ―トルエン
スルホン酸のようなスルホン酸類；塩化アルミニ
ウムまたはトリフルオロボロンのようなルイス
酸；酢酸またはプロピオン酸のようなカルボン酸
類；塩酸または硫酸のような鉱酸類等があげら
れ、前記一般式（）を有する化合物に対して
0.5乃至10重量％添加する。使用される不活性溶
剤としては例えばベンゼンまたはトルエンのよう
な芳香族炭化水素類；クロロホルムまたはテトラ
クロルエタンのようなハロゲン化炭化水素類；エ
チルエーテルまたはテトラヒドロフランのような
エーテル類；およびこれらの溶剤の混合溶剤があ
げられる。反応温度は特に限定はなく通常反応は
0゜乃至150℃程度で行なわれる。反応に要する時
間は２乃至12時間である。 Acid catalysts used in the reaction include sulfonic acids such as p-toluenesulfonic acid; Lewis acids such as aluminum chloride or trifluoroboron; carboxylic acids such as acetic acid or propionic acid; mineral acids such as hydrochloric acid or sulfuric acid. etc., and for compounds having the above general formula ()
Add 0.5 to 10% by weight. Inert solvents used include, for example, aromatic hydrocarbons such as benzene or toluene; halogenated hydrocarbons such as chloroform or tetrachloroethane; ethers such as ethyl ether or tetrahydrofuran; Examples include mixed solvents. There is no particular restriction on the reaction temperature, and the reaction is usually
It is carried out at a temperature of about 0° to 150°C. The time required for the reaction is 2 to 12 hours.
反応終了後、目的化合物は常法によつて反応混
合物から採取される。例えば反応混合物を水洗し
溶剤を留去することによつて得られる。粗製の目
的化合物は常法例えば再結晶法等によつて精製す
ることもできる。 After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. For example, it can be obtained by washing the reaction mixture with water and distilling off the solvent. The crude target compound can also be purified by conventional methods such as recrystallization.
本発明の方法によつて得られるピラゾール誘導
体（）は、除草剤（特公昭54−36648号参照）
の合成中間体として有用な化合物である。例え
ば、前記一般式（）を有する化合物を一般式
R3−Ｙ （）
（式中、R3は低級アルキル基を示し、Ｙは酸残
基を示す。）を有する化合物と反応させることに
よつて一般式
（式中、R1，R3，Ｘおよびｎは前述したものと
同意義を示す。）を有する除草剤を得ることがで
きる。 The pyrazole derivative () obtained by the method of the present invention is a herbicide (see Japanese Patent Publication No. 54-36648).
It is a compound useful as a synthetic intermediate. For example, by reacting a compound having the general formula () with a compound having the general formula R 3 -Y () (wherein R 3 represents a lower alkyl group and Y represents an acid residue). general formula (wherein R 1 , R 3 , X and n have the same meanings as defined above) can be obtained.
次に実施例および参考例をあげて本発明の方法
を更に具体的に説明するが、本発明はこれによつ
て限定されるものではない。 Next, the method of the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention is not limited thereto.
実施例 １
４―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール1.0ｇをジクロ
ルエタン50mlに溶解後、塩化アルミニウム0.74ｇ
を加え90〜95℃で４時間加熱した。冷後、反応液
を氷50ｇと濃塩酸２mlの混合液中に注加し、析出
した結晶を取した後、メタノールより再結晶し
て融点250〜253℃を有する目的化合物0.69ｇを得
た（収率69％）。Example 1 4-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole Dissolve 1.0 g of 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole in 50 ml of dichloroethane. After that, aluminum chloride 0.74g
was added and heated at 90-95°C for 4 hours. After cooling, the reaction solution was poured into a mixture of 50 g of ice and 2 ml of concentrated hydrochloric acid, the precipitated crystals were collected, and recrystallized from methanol to obtain 0.69 g of the target compound with a melting point of 250-253°C ( yield 69%).
尚、原料化合物において、δ5.02に見られた４
位のプロトンのシグナルが消失した。 In addition, in the raw material compound, 4 observed at δ5.02
The proton signal at position disappeared.
元素分析値（％）C11H8Cl2N2O2として
計算値 Ｃ，48.73；Ｈ，2.97；Ｎ，10.33；
Cl，26.15
実測値 Ｃ，48.63；Ｈ，3.01；Ｎ，10.24；
Cl，26.52
上記実施例１の方法に準じて塩化アルミニウム
を触媒として用い、
１―ベンゾイル―３―メチル―５―ヒドロキシ
ピラゾールから、４―ベンゾイル―３―メチル―
５―ヒドロキシピラゾール［融点279〜280℃（収
率60％）］を、
１―（２―クロロベンゾイル）―３―メチル―
５―ヒドロキシピラゾールから、４―（２―クロ
ロベンゾイル）―３―メチル―５―ヒドロキシピ
ラゾール［融点232〜236℃（収率62％）］を製造
した。Elemental analysis value (%) Calculated value as C 11 H 8 Cl 2 N 2 O 2 C, 48.73; H, 2.97; N, 10.33; Cl, 26.15 Actual value C, 48.63; H, 3.01; N, 10.24; Cl, 26.52 According to the method of Example 1 above, using aluminum chloride as a catalyst, 1-benzoyl-3-methyl-5-hydroxypyrazole was converted to 4-benzoyl-3-methyl-
5-Hydroxypyrazole [melting point 279-280°C (yield 60%)] was converted into 1-(2-chlorobenzoyl)-3-methyl-
4-(2-chlorobenzoyl)-3-methyl-5-hydroxypyrazole [melting point 232-236°C (yield 62%)] was produced from 5-hydroxypyrazole.
実施例 ２
４―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール1.0ｇをtert―ブ
タノール50mlに溶解後、カリウムtert―ブトキシ
ド1.53ｇおよびイミダゾール0.35ｇを加え80℃で
12時間加熱した。冷後、減圧下に溶剤を留去し残
留物を氷水中に注加し、塩酸酸性とした後析出し
た結晶を取し乾燥した。メタノールより再結晶
して目的化合物0.69ｇを得た（収率69％）。Example 2 4-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole 1.0 g of 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole was added to 50 ml of tert-butanol. After dissolving in the solution, add 1.53 g of potassium tert-butoxide and 0.35 g of imidazole and heat at 80℃.
Heated for 12 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was poured into ice water, acidified with hydrochloric acid, and the precipitated crystals were collected and dried. Recrystallization from methanol gave 0.69 g of the target compound (yield 69%).
尚、生成物は実施例１で製造した化合物と一致
した。 The product was identical to the compound produced in Example 1.
実施例 ３
４―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール1.0ｇをイソプ
ロパノール50mlに溶解後、炭酸カリウム1.71ｇを
加え還流下15時間加熱した。冷後、減圧下に溶剤
を留去し残留物を氷水中に注加し、塩酸酸性とし
た後析出した結晶を取し乾燥した。メタノール
より再結晶して目的化合物0.52ｇを得た（収率52
％）。Example 3 4-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole Dissolve 1.0 g of 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole in 50 ml of isopropanol. Thereafter, 1.71 g of potassium carbonate was added and heated under reflux for 15 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was poured into ice water, acidified with hydrochloric acid, and the precipitated crystals were collected and dried. Recrystallization from methanol gave 0.52 g of the target compound (yield: 52
%).
尚、生成物は実施例１で製造した化合物と一致
した。 The product was identical to the compound produced in Example 1.
実施例 ４
４―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
イソプロパノール50mlに金属ナトリウム0.28ｇ
を溶解させた後、１―（２，４―ジクロルベンゾ
イル）―５―ヒドロキシ―３―メチルピラゾール
1.0ｇを加え還流下12時間加熱した。冷後、減圧
下に溶剤を留去し残留物を氷水中に注加し、塩酸
酸性とした後析出した結晶を取し乾燥した。メ
タノールより再結晶して目的化合物0.31ｇを得た
（収率31％）。Example 4 4-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole 0.28 g of sodium metal in 50 ml of isopropanol
After dissolving 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole
1.0 g was added and heated under reflux for 12 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was poured into ice water, acidified with hydrochloric acid, and the precipitated crystals were collected and dried. Recrystallization from methanol gave 0.31 g of the target compound (yield 31%).
尚、生成物は実施例１で製造した化合物と一致
した。 The product was identical to the compound produced in Example 1.
実施例 ５
４―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ３―メチルピラゾール1.0ｇをtert―ブタ
ノール50mlに溶解後、イミダゾール0.42ｇを加え
還流下15時間加熱した。冷後、減圧下に溶剤を留
去し残留物を氷水中に注加し、塩酸酸性とした後
析出した結晶を取し乾燥した。メタノールより
再結晶して目的化合物0.38ｇを得た（収率38％）。Example 5 4-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole 1.0 g of 1-(2,4-dichlorobenzoyl)-5-hydroxy 3-methylpyrazole is added to 50 ml of tert-butanol. After dissolving, 0.42 g of imidazole was added and heated under reflux for 15 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was poured into ice water, acidified with hydrochloric acid, and the precipitated crystals were collected and dried. Recrystallization from methanol gave 0.38 g of the target compound (yield 38%).
尚、生成物は実施例１で製造した化合物と一致
した。 The product was identical to the compound produced in Example 1.
実施例 ６
４―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール1.0ｇをイソプ
ロパノール50mlに溶解後、炭酸カリウム1.71ｇお
よびイミダゾール0.39ｇを加え80℃で15時間加熱
した。冷後、減圧下に溶剤を留去し残留物を氷水
中に注加し、塩酸酸性とした後析出した結晶を
取した。メタノールより再結晶して目的化合物
0.69ｇを得た（収率69％）。Example 6 4-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole Dissolve 1.0 g of 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole in 50 ml of isopropanol. Thereafter, 1.71 g of potassium carbonate and 0.39 g of imidazole were added and heated at 80° C. for 15 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was poured into ice water, acidified with hydrochloric acid, and the precipitated crystals were collected. Recrystallize from methanol to obtain the target compound.
0.69g was obtained (yield 69%).
尚、生成物は実施例１で製造した化合物と一致
した。 The product was identical to the compound produced in Example 1.
参考例 １
メチル２，４―ジクロルベンゾイルヒドラゾア
セトアセテート
メタノール100ml中にアセト酢酸メチルエステ
ル2.26ｇおよび２，４―ジクロルベンゾイルヒド
ラジン4.0ｇを加え、室温で17時間撹拌した。撹
拌終了後、メタノールを留去した。残留物に塩化
メチレンを加え、希釈後水洗し無水硫酸ナトリウ
ムで乾燥後濃縮乾固した。得られた粗結晶をイソ
プロピルエーテルより再結晶して融点149〜150℃
を有する目的化合物5.91ｇを得た（収率100％）。Reference Example 1 Methyl 2,4-dichlorobenzoylhydrazoacetoacetate 2.26 g of methyl acetoacetate and 4.0 g of 2,4-dichlorobenzoylhydrazine were added to 100 ml of methanol, and the mixture was stirred at room temperature for 17 hours. After the stirring was completed, methanol was distilled off. Methylene chloride was added to the residue, which was diluted, washed with water, dried over anhydrous sodium sulfate, and concentrated to dryness. The obtained crude crystals were recrystallized from isopropyl ether to a melting point of 149-150℃.
5.91 g of the target compound having the following were obtained (yield: 100%).
参考例 ２
Ｎ―アセトアセチル―N′―２，４―ジクロル
ベンゾイルヒドラジン
テトラヒドロフラン130ml中に２，４―ジクロ
ルベンゾイルヒドラジン３ｇおよびジケテン3.6
ｇを加え、室温で4.5時間撹拌した。反応液を濃
縮乾固し、得られた粗結晶をイソプロピルエーテ
ルで洗滌乾燥して融点172〜173℃を有する目的化
合物3.75ｇを得た（収率88.9％）。Reference example 2 N-acetoacetyl-N'-2,4-dichlorobenzoylhydrazine 3 g of 2,4-dichlorobenzoylhydrazine and 3.6 diketene in 130 ml of tetrahydrofuran
g and stirred at room temperature for 4.5 hours. The reaction solution was concentrated to dryness, and the obtained crude crystals were washed with isopropyl ether and dried to obtain 3.75 g of the target compound having a melting point of 172-173°C (yield: 88.9%).
参考例 ３
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
メチル２，４―ジクロルベンゾイルヒドラゾア
セトアセテート303mgをメタノール10mlおよびジ
メチルホルムアミド５mlとの混液に溶解後、−５
℃以下でナトリウムメトキシド56mgを加え、更に
同温度で24時間撹拌した。撹拌終了後、反応混合
液を2N―塩酸溶液でPH＝３に調製後1/3容まで濃
縮して多量の水中に注加した。次いで塩化メチレ
ンで抽出を行ない、抽出液を濃縮し得られた粗結
晶をイソプロピルエーテルで洗滌し乾燥して融点
161〜163℃を有する目的化合物214mgを得た（収
率79.0％）。Reference Example 3 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole After dissolving 303 mg of methyl 2,4-dichlorobenzoyl hydrazoacetoacetate in a mixture of 10 ml of methanol and 5 ml of dimethylformamide, -5
56 mg of sodium methoxide was added at a temperature below 0.degree. C., and the mixture was further stirred at the same temperature for 24 hours. After stirring, the reaction mixture was adjusted to pH=3 with 2N hydrochloric acid solution, concentrated to 1/3 volume, and poured into a large amount of water. Next, extraction was performed with methylene chloride, the extract was concentrated, and the resulting crude crystals were washed with isopropyl ether and dried to determine the melting point.
214 mg of the target compound having a temperature of 161-163°C was obtained (yield 79.0%).
参考例 ４
１―（２，４―ジクロルベンゾイル）―５―ヒ
ドロキシ―３―メチルピラゾール
Ｎ―アセトアセチル―N′―ジクロルベンゾイ
ルヒドラジン2.5ｇとｐ―トルエンスルホン酸10
mgをジクロルエタン60ml、テトラクロルエタン20
mlおよびベンゼン55mlの混液に溶解後、85〜90℃
で1.5時間加熱した。冷後、溶剤を減圧下に濃縮
し、固形残留物をイソプロピルエーテルで洗滌
後、シリカゲル・カラムクロマトグラフイ（溶出
剤；ベンゼン：酢酸エチル＝５：１）に付し、分
画精製して融点161〜163℃を有する目的化合物
1.28ｇを得た（収率54.7％）。Reference example 4 1-(2,4-dichlorobenzoyl)-5-hydroxy-3-methylpyrazole N-acetoacetyl-N'-dichlorobenzoylhydrazine 2.5 g and p-toluenesulfonic acid 10
mg, dichloroethane 60ml, tetrachloroethane 20ml
85-90℃ after dissolving in a mixture of ml and 55ml of benzene.
The mixture was heated for 1.5 hours. After cooling, the solvent was concentrated under reduced pressure, and the solid residue was washed with isopropyl ether and subjected to silica gel column chromatography (eluent: benzene:ethyl acetate = 5:1) to fractionate and purify the melting point. Target compound with temperature of 161-163℃
1.28g was obtained (yield 54.7%).
Claims (1)
ゲン原子を示す。ｎは０，１または２を示す。）
を有するピラゾール誘導体を、塩化アルミニウ
ム、イミダゾール、アルカリ金属炭酸塩およびア
ルカリ金属アルコキシドから選ばれる触媒の存在
下反応させることを特徴とする式 （式中、R1，Ｘおよびｎは前述したものと同意
義を示す。）を有する４―ベンゾイルピラゾール
誘導体の製法。[Claims] 1 formula (In the formula, R 1 represents a lower alkyl group, X represents a halogen atom, and n represents 0, 1 or 2.)
a pyrazole derivative having the formula in the presence of a catalyst selected from aluminum chloride, imidazole, alkali metal carbonate and alkali metal alkoxide A method for producing a 4-benzoylpyrazole derivative having the formula (wherein R 1 , X and n have the same meanings as defined above).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55159046A JPS5782374A (en) | 1980-11-12 | 1980-11-12 | Preparation of pyrazole derivative |
| KR1019810003944A KR860001878B1 (en) | 1980-11-12 | 1981-10-19 | Preparation process for pyrazide derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55159046A JPS5782374A (en) | 1980-11-12 | 1980-11-12 | Preparation of pyrazole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5782374A JPS5782374A (en) | 1982-05-22 |
| JPH0233708B2 true JPH0233708B2 (en) | 1990-07-30 |
Family
ID=15685039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55159046A Granted JPS5782374A (en) | 1980-11-12 | 1980-11-12 | Preparation of pyrazole derivative |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5782374A (en) |
| KR (1) | KR860001878B1 (en) |
-
1980
- 1980-11-12 JP JP55159046A patent/JPS5782374A/en active Granted
-
1981
- 1981-10-19 KR KR1019810003944A patent/KR860001878B1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| KR860001878B1 (en) | 1986-10-24 |
| JPS5782374A (en) | 1982-05-22 |
| KR830007573A (en) | 1983-11-04 |
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