JPH01290662A - Production of pyrazolecarboxylic acid chlorides - Google Patents
Production of pyrazolecarboxylic acid chloridesInfo
- Publication number
- JPH01290662A JPH01290662A JP11709588A JP11709588A JPH01290662A JP H01290662 A JPH01290662 A JP H01290662A JP 11709588 A JP11709588 A JP 11709588A JP 11709588 A JP11709588 A JP 11709588A JP H01290662 A JPH01290662 A JP H01290662A
- Authority
- JP
- Japan
- Prior art keywords
- group
- phosgene
- reaction
- formula
- hours
- 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.)
- Granted
Links
- ZLIZZDCWMOGEGA-UHFFFAOYSA-N 1h-pyrazole-5-carbonyl chloride Chemical class ClC(=O)C=1C=CNN=1 ZLIZZDCWMOGEGA-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 16
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000005115 alkyl carbamoyl group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 3
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 9
- -1 1-methylpentyl Chemical group 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000010438 heat treatment Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- YALJPBXSARRWTA-UHFFFAOYSA-N 1,3-dimethylpyrazole-4-carboxylic acid Chemical compound CC1=NN(C)C=C1C(O)=O YALJPBXSARRWTA-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- KFKVECZQALNWSR-UHFFFAOYSA-N 1-methyl-3-(trifluoromethyl)pyrazole-4-carbonyl chloride Chemical compound CN1C=C(C(Cl)=O)C(C(F)(F)F)=N1 KFKVECZQALNWSR-UHFFFAOYSA-N 0.000 description 1
- KWLGFSHSTADSKH-UHFFFAOYSA-N 1h-pyrazole-4-carbonyl chloride Chemical compound ClC(=O)C=1C=NNC=1 KWLGFSHSTADSKH-UHFFFAOYSA-N 0.000 description 1
- RYNFWKBAUMOGOO-UHFFFAOYSA-N 2,5-diethylpyrazole-3-carboxylic acid Chemical compound CCC=1C=C(C(O)=O)N(CC)N=1 RYNFWKBAUMOGOO-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NSLWGDABVLNWBH-UHFFFAOYSA-N 3-methoxy-1-methylpyrazole Chemical compound COC=1C=CN(C)N=1 NSLWGDABVLNWBH-UHFFFAOYSA-N 0.000 description 1
- ZNFXKNGUYQVJOI-UHFFFAOYSA-N 3-methyl-1-(methylcarbamoyl)pyrazole-4-carbonyl chloride Chemical compound CNC(=O)N1C=C(C(Cl)=O)C(C)=N1 ZNFXKNGUYQVJOI-UHFFFAOYSA-N 0.000 description 1
- HLYYXPDTFLUERX-UHFFFAOYSA-N 3-methyl-pyrazole-4-carboxylic acid Chemical compound CC=1NN=CC=1C(O)=O HLYYXPDTFLUERX-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- SFSQKEJNNYYLKZ-UHFFFAOYSA-N 5-methoxy-2-methylpyrazole-3-carboxylic acid Chemical compound COC=1C=C(C(O)=O)N(C)N=1 SFSQKEJNNYYLKZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医薬・農薬等の原料として有用なピラゾール
カルボン酸クロライド類の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing pyrazolecarboxylic acid chlorides useful as raw materials for medicines, agricultural chemicals, etc.
従来のピラゾールカルボン酸クロライド類の製造方法と
しては、チオニルクロライドを用いる方法(特開昭60
−34949号、Agric、l1io1.Che−、
、AL(1)。Conventional methods for producing pyrazole carboxylic acid chlorides include a method using thionyl chloride (Japanese Unexamined Patent Publication No. 1989-1999)
-34949, Agric, l1io1. Che-,
, AL (1).
45 〜50.1984 、 Au5t、J、Che
m、、1983.n、135〜147、)が知られてい
る。45 ~50.1984, Au5t, J, Che
m,, 1983. n, 135-147,) are known.
(発明が解決しようとする!m1ll)上記のチオニル
クロライドを用いる方法では、ピラゾールカルボン酸類
と極めて激しい反応を起こすため、反応を制御するのが
困難であり、また、その隙に2、激な発熱を伴い、腐食
性の亜硫酸ガスを大量に発生する。そのために副生じた
大量の亜硫酸ガスを処理する装置、煩雑な手間がかかる
等の工業的な製法上の課題がある。(This is what the invention seeks to solve!) In the method using thionyl chloride described above, an extremely violent reaction occurs with the pyrazole carboxylic acids, so it is difficult to control the reaction. , and generates large amounts of corrosive sulfur dioxide gas. Therefore, there are problems in the industrial production process, such as the need for equipment to process large amounts of sulfur dioxide gas produced as a by-product, and the need for complicated labor.
(!!!題を解決するための手段及び作用〕本発明者ら
は、上記課題について鋭意検討の結果、ピラゾールカル
ボン酸類をホスゲン又はトリクロロメチルクロロホーメ
ートと反応させる製造方法を見出し、本発明に到った。(!!! Means and action for solving the problem) As a result of intensive study on the above problem, the present inventors discovered a production method in which pyrazole carboxylic acids are reacted with phosgene or trichloromethyl chloroformate, and the present invention has been realized. It has arrived.
すなわち、−紋穴(+)
(式中、R1は水素原子、ハロゲン原子、低級アルキル
基、低級アルコキシ基又はハロゲン原子若しくは低級ア
ルコキシ基で置換された低級アルキル基、hは低級アル
キル基、低級アルケニル基、アルキルカルバモイル基又
はハロゲン原子で置換された低級アルキル基、ハロゲン
原子で置換された低級アルケニル基を示す、)で表され
るピラゾールカルボン酸類をホスゲン又はトリクロロメ
チルクロロホーメ−1−と反応させることを特徴とすべ
2
(式中、Rh 、、Ihは一般式(1)と同じ。)で表
されるピラゾールカルボン酸クロライド類の製造方法で
ある。That is, -More (+) (wherein R1 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkyl group substituted with a halogen atom or a lower alkoxy group, h is a lower alkyl group, a lower alkenyl , an alkylcarbamoyl group, a lower alkyl group substituted with a halogen atom, or a lower alkenyl group substituted with a halogen atom) is reacted with phosgene or trichloromethylchloroform-1-. This is a method for producing pyrazolecarboxylic acid chlorides represented by the following formula (where Rh, , Ih are the same as in general formula (1)).
一般式(1)のピラゾールカルボン酸類としては、例え
ば、式中R1を非限定的に例示すれば、水素、弗素、塩
素、臭素、沃素、メチル基、エチル基、トプロピル基、
l5o−プロピル基、n−ブチル基、5ec−ブチル基
、1so−ブチル基、ter L−ブチル基、n−ペン
チル基、1〜メチルブチル基、2−メチルブチル基、3
−メチルブチル基、1.1−ジメチルプロピル基、2.
2−ジメチルプロピル基、n−へキシル1&、1−メチ
ルペンチルL 、2−メチルペンチル基、3−メチルペ
ンチル基、1.1−ジメルブチル基、2.2−ジメチル
ブチル基、3.3−ジメチルブチルL 1.2−ジメチ
ルブチル基、1.3−ジメチルブチル基、1−エチル−
2−メチルプロピル基、1−エチルブチル基、2−エチ
ルブチル基、トリフルオロメチル基、クロロメチル基、
トリクロロメチル基、メトキシメチル基、エトキシメチ
ル基、プロポキシメチル基、メトキシ基、エトキシ基及
びプロポキシ基等、またR□としては、メチル基、エチ
ル基、n−プロピル基、1sO−プロピル基、i−ブチ
ル基、5ee−ブチル基、1so−ブチル基、tert
−ブチル基、n−ペンチル基、1−メチルブチル基、2
−メチルブチル基、3−メチルブチル基、1.1−ジメ
チルプロピル基、2.2−ジメチルプロピルLn:ヘキ
シル基、l−メチルペンチル基5.2−メチルペンチル
基、3−メチルペンチル基4−メチルペンチル基、1.
1−ジメルブチル基、2.2−ジメチルブチル基、3.
3−ジメチルブチルL 1.2−ジメチルブチル基、1
.3−ジメチルブチル基、l−エチル−2−メチルプロ
ピルLl−エチルブチル基、2−エチルブチル基、β、
β、β、−トリフルオロエチル基、2−プロペニル基、
1−メチル−2−プロペニル5.2−メチル−2−プロ
ペニル基、3−クロロプロペニル基、2−ブテニル基、
メチルカルバモイル基、エチルカルバモイル!及びプロ
ピルカルバモイル基等である。Examples of the pyrazole carboxylic acids of general formula (1) include, but are not limited to, R1 in the formula: hydrogen, fluorine, chlorine, bromine, iodine, methyl group, ethyl group, topropyl group,
15o-propyl group, n-butyl group, 5ec-butyl group, 1so-butyl group, ter L-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3
-methylbutyl group, 1.1-dimethylpropyl group, 2.
2-dimethylpropyl group, n-hexyl 1&, 1-methylpentyl L, 2-methylpentyl group, 3-methylpentyl group, 1.1-dimelbutyl group, 2.2-dimethylbutyl group, 3.3-dimethyl Butyl L 1.2-dimethylbutyl group, 1.3-dimethylbutyl group, 1-ethyl-
2-methylpropyl group, 1-ethylbutyl group, 2-ethylbutyl group, trifluoromethyl group, chloromethyl group,
Trichloromethyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxy group, ethoxy group, propoxy group, etc., and as R□, methyl group, ethyl group, n-propyl group, 1sO-propyl group, i- butyl group, 5ee-butyl group, 1so-butyl group, tert
-butyl group, n-pentyl group, 1-methylbutyl group, 2
-Methylbutyl group, 3-methylbutyl group, 1.1-dimethylpropyl group, 2.2-dimethylpropyl Ln: hexyl group, l-methylpentyl group 5.2-methylpentyl group, 3-methylpentyl group 4-methylpentyl Base, 1.
1-dimerbutyl group, 2.2-dimethylbutyl group, 3.
3-dimethylbutyl L 1.2-dimethylbutyl group, 1
.. 3-dimethylbutyl group, l-ethyl-2-methylpropyl Ll-ethylbutyl group, 2-ethylbutyl group, β,
β, β, -trifluoroethyl group, 2-propenyl group,
1-methyl-2-propenyl 5.2-methyl-2-propenyl group, 3-chloropropenyl group, 2-butenyl group,
Methylcarbamoyl group, ethylcarbamoyl! and propylcarbamoyl group.
本発明の反応は、溶液又は懸濁状態で行うため、溶媒中
で行うのが好ましい。また溶媒としては反応に不活性な
ものであればよい0例えば、ベンゼン、トルエン、キシ
レン等の芳香族炭化水素類、テトラヒドロフラン、エチ
レングリコールジメチルエーテル、ジエチレングリコー
ルジメチルエーテル、ジオキサン等のエーテル類、酢酸
エチル、酢酸ブチル、プロピオン酸エチル等のエステル
類、N、N−ジメチルホルムアミド、1.3−ジメチル
−2−イミダゾリジノン、ジメチルスルホキサイド等の
非プロトン性掻性溶媒、テトラクロロエチレン、クロロ
ベンゼン等の/Sロゲン化炭化水素類、ピリジン、ピコ
リン等の有機塩基類が挙げられるが、これらに限られる
わけではない、また、これらの)容媒を混合して反応溶
媒として用いることも可能である。Since the reaction of the present invention is carried out in a solution or suspension state, it is preferably carried out in a solvent. The solvent may be anything inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dioxane, and ethyl acetate and butyl acetate. , esters such as ethyl propionate, aprotic scratchy solvents such as N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide, /S chloride of tetrachloroethylene, chlorobenzene, etc. Examples include, but are not limited to, hydrocarbons and organic bases such as pyridine and picoline. It is also possible to mix these solvents and use them as a reaction solvent.
溶媒の添加量は、ピラゾールカルボン酸itモルに対し
0.5〜iol、好ましくは1〜41で用いるのが効率
的である。The amount of the solvent to be added is effectively 0.5 to 1 mol, preferably 1 to 41 mol per mol of pyrazole carboxylic acid.
ピラゾールカルボン酸類に対するホスゲン又はトリクロ
ロメチルクロロホーメートの添加量は、ピラゾールカル
ボ7611モルに対し1.0〜10.0モル、好ましく
は1.0〜5.0モルがよい。The amount of phosgene or trichloromethyl chloroformate added to the pyrazole carboxylic acids is 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, per 7611 mol of pyrazole carbo.
反応温度は、常温からそれぞれの溶液の沸点の間で反応
させることができる。The reaction temperature can be between room temperature and the boiling point of each solution.
反応時間は、ピラゾールカルボン酸類の溶液中にホスゲ
ンを吹き込む場合、加熱還流下、5〜50時間、好まし
くは8〜20時間である。また、ピラゾールカルボン酸
類の溶液にトリクロロメチルクロロホーメートを滴下す
る場合、加熱還流下、2〜40時間、好ましくは5〜2
0時間である。When blowing phosgene into a solution of pyrazole carboxylic acids, the reaction time is 5 to 50 hours, preferably 8 to 20 hours under heating and reflux. In addition, when trichloromethyl chloroformate is added dropwise to a solution of pyrazole carboxylic acids, the solution is heated under reflux for 2 to 40 hours, preferably 5 to 2 hours.
It is 0 hours.
反応終了後、反応液は濾過し濾液を濃縮することにより
ピラゾールカルボン酸クロライド類を得ることができる
。得られたピラゾールカルボン酸クロライド類の純度分
析は、ガスクロマトグラフィーによる。After the reaction is completed, the reaction solution is filtered and the filtrate is concentrated to obtain pyrazolecarboxylic acid chlorides. The purity of the obtained pyrazole carboxylic acid chloride was analyzed by gas chromatography.
本発明における好ましい実施B様については次のとおり
である。Preferred embodiment B of the present invention is as follows.
温度計、攪拌機、凝縮器を備えた反応器に所定量のピラ
ゾールカルボン酸類と所定の溶媒を仕込んだ溶液又は懸
濁液に、ホスゲンを吹き込み又はトリクロロメチルクロ
ロホーメートを滴下して所定温度で還流下、所定時間反
応を行う。Phosgene is blown into a solution or suspension containing a predetermined amount of pyrazole carboxylic acids and a predetermined solvent in a reactor equipped with a thermometer, stirrer, and condenser, and trichloromethyl chloroformate is added dropwise to the solution or suspension, and the mixture is refluxed at a predetermined temperature. Below, the reaction is carried out for a predetermined period of time.
反応終了後、反応液を濾過し濾液を濃縮することにより
目的のピラゾールカルボン酸クロライド類を得ることが
できる。After the reaction is completed, the desired pyrazolecarboxylic acid chloride can be obtained by filtering the reaction solution and concentrating the filtrate.
なお、濃縮時の留出液は再度反応系へ溶媒として回収す
ることができる。Note that the distillate during concentration can be recovered as a solvent to the reaction system again.
以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例1゛
100sffiの三゛ンロフラスコに1.3−ジメチル
ピラゾール−4−カルボン酸5g(0,036モル)を
トルエン50mJ!に懸濁させ、加熱還流下、ホスゲン
を320−l/時間の流量で10時間吹き込んだ(ホス
ゲン。Example 1 5 g (0,036 mol) of 1,3-dimethylpyrazole-4-carboxylic acid was added to 50 mJ of toluene in a 100 sffi three-lens flask! phosgene was blown into the suspension at a flow rate of 320 l/hr for 10 hours under heating under reflux (phosgene.
0.144モル)0反応終了後、反応液を濾過し濾液を
濃縮して5.5gの1.3−ジメチルピラゾール−4−
カルボン酸クロライドを得た。純度98.0%で収率は
98.0%であった。After completion of the reaction, the reaction solution was filtered and the filtrate was concentrated to give 5.5 g of 1.3-dimethylpyrazole-4-
Carboxylic acid chloride was obtained. The purity was 98.0% and the yield was 98.0%.
実施例2
実施例1と同様の装置に、1.3−ジエチルピラゾール
−5−カルボン酸6.7g(0,04モル)をジオキサ
ン100■lに懸濁させ加熱還流下、トリクロロメチル
クロロホーメート11.9g(0,06モル)を8時間
滴下した0滴下終了後、更に2時間攪拌を続けた。Example 2 In the same apparatus as in Example 1, 6.7 g (0.04 mol) of 1,3-diethylpyrazole-5-carboxylic acid was suspended in 100 μl of dioxane and heated under reflux to dissolve trichloromethyl chloroformate. After 11.9 g (0.06 mol) was added dropwise for 8 hours, stirring was continued for an additional 2 hours.
反応終了後、反応液を濾過し濾液を:a縮して1.3−
ジメチルピラゾール−5−カルボン酸クロライド6゜2
gを得た。純度97.5%、収率95.0%であった。After the reaction is completed, the reaction solution is filtered and the filtrate is condensed to give 1.3-
Dimethylpyrazole-5-carboxylic acid chloride 6゜2
I got g. The purity was 97.5% and the yield was 95.0%.
実施例3
実施例1と同様の装置に、l−メチル−3−トリフルオ
ロメチルピラゾール−4−カルボン酸6.7g(0,0
3モル)を酢酸ブチル80m lに懸濁させ加熱還流下
、ホスゲンを140m j! 7時間の流量で14時間
吹き込んだ(ホスゲン:0.09モル)0反応終了後、
反応液を濾過し濾液を濃縮して1−メチル−3−トリフ
ルオロメチルピラゾール−4−カルボン酸クロライド6
.7gを得た。純度97.0%、収率95.0%であっ
た。Example 3 Into the same apparatus as in Example 1, 6.7 g (0,0
3 mol) was suspended in 80 ml of butyl acetate, heated under reflux, and 140 ml of phosgene was added. After the completion of the reaction, which was blown for 14 hours at a flow rate of 7 hours (phosgene: 0.09 mol),
The reaction solution was filtered and the filtrate was concentrated to obtain 1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid chloride 6.
.. 7g was obtained. The purity was 97.0% and the yield was 95.0%.
実施例4
実施例1と同様の装置に、1−メチル−3−メトキシピ
ラゾール−5−カルボン酸6.2g(0,04モル)を
ジメチルスルホキシド100s lに熔解し、温度14
0℃でホスゲンを500* l 7時間の流量で8時間
吹き込んだ(ホスゲン:Q、 18モル)0反応終了後
、反応液を濾過し濾液を濃縮して1−メチル−3−メト
キシピラゾール、5−カルボン酸クロライド6.6gを
得た。純度98.0%、収率97.0%であった実施例
5
実施例1と同様の装置に、1−アリル−3−メチルピラ
ゾール−4−カルボン酸5.0g(0,03モル)をク
ロロベンゼン100+mj!に懸濁させ加熱還流下、ホ
スゲンを180m 11時間の流量で15時間吹き込ん
だ(ホスゲン:0.12モル)0反応終了後、反応液を
濾過し濾液を濃縮して1−アリル−3−メチルピラゾー
ル−4−カルボン酸クロライド5.3gを得た。純度9
7゜0%、収率98.0%であった。Example 4 In the same apparatus as in Example 1, 6.2 g (0.04 mol) of 1-methyl-3-methoxypyrazole-5-carboxylic acid was dissolved in 100 sl of dimethyl sulfoxide, and the temperature was 14.
Phosgene was blown in at a flow rate of 500*l for 7 hours at 0°C for 8 hours (phosgene: Q, 18 mol). After the reaction was completed, the reaction solution was filtered and the filtrate was concentrated to obtain 1-methyl-3-methoxypyrazole, -6.6 g of carboxylic acid chloride was obtained. Example 5 with a purity of 98.0% and a yield of 97.0% Into the same apparatus as in Example 1, 5.0 g (0.03 mol) of 1-allyl-3-methylpyrazole-4-carboxylic acid was added. Chlorobenzene 100+mj! After the reaction was completed, the reaction solution was filtered and the filtrate was concentrated to obtain 1-allyl-3-methyl. 5.3 g of pyrazole-4-carboxylic acid chloride was obtained. Purity 9
The yield was 98.0%.
実施例6
実施例1と同様の装置に、1−メチルカルバモイル−3
−メチルピラゾール−4−カルボン酸9.1g(0,0
5モル)をピリジン130膳2に懸濁させ、加熱還流下
、トリクロロメチルクロロホーメー)13.8g(0゜
07モル)を10時間で滴下した9滴下終了後、更に2
.5時間撹拌した。反応終了後、反応液を濾過し濾液を
濃縮して1−メチルカルバモイル−3−メチルピラゾー
ル−4−カルボン酸クロライド9.7gを得た。Example 6 In the same apparatus as in Example 1, 1-methylcarbamoyl-3
-Methylpyrazole-4-carboxylic acid 9.1g (0,0
5 mol) was suspended in 130 m2 of pyridine, and 13.8 g (0.07 mol) of trichloromethylchloroforme was suspended in 130 m2 of pyridine, and 13.8 g (0.07 mol) of trichloromethylchloroforme was added dropwise over 10 hours.
.. Stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and the filtrate was concentrated to obtain 9.7 g of 1-methylcarbamoyl-3-methylpyrazole-4-carboxylic acid chloride.
純度97.0%、収率93.0%であった。The purity was 97.0% and the yield was 93.0%.
実施例7
実施例1と同様の装置に、l−へキシル−3−メチルピ
ラゾール−4−カルボン酸8.4g(0,04モル)を
エチレングリコールジメチルエーテル120+ej!に
懸濁させ、加熱還流下、ホスゲンを250m l 7時
間の流量で18時間吹き込んだ(ホスゲン:0.20モ
ル)、吹き込み終了後、更に2,0時間撹拌した0反応
終了後、反応液を濾過し濾液をa縮してl−へキシル−
3−メチルピラゾール−4−カルボン酸クロライド8.
7gを得た。純度96.0%、収率91.0%であった
。Example 7 In the same apparatus as in Example 1, 8.4 g (0.04 mol) of l-hexyl-3-methylpyrazole-4-carboxylic acid was added to 120+ej! of ethylene glycol dimethyl ether. 250 ml of phosgene was blown in for 18 hours at a flow rate of 7 hours under heating under reflux (phosgene: 0.20 mol). After the blowing was completed, the mixture was further stirred for 2.0 hours. Filter and condense the filtrate to l-hexyl
3-Methylpyrazole-4-carboxylic acid chloride8.
7g was obtained. The purity was 96.0% and the yield was 91.0%.
本発明の方法によれば、反応の制御もしやすく、また、
副生物の処理もなく、目的のものを高純度・高収率で得
ることができる。また、得られたピラゾールカルボン酸
クロライド類は、医薬、農薬等の中間体として、精製操
作を加えることなく、次工程に用いることができ、工業
的に有用な方法である。According to the method of the present invention, the reaction can be easily controlled, and
The desired product can be obtained with high purity and high yield without the need to treat by-products. Furthermore, the obtained pyrazolecarboxylic acid chlorides can be used in the next step as intermediates for medicines, agricultural chemicals, etc. without any purification operations, and this is an industrially useful method.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
ル基、低級アルコキシ基又はハロゲン原子若しくは低級
アルコキシ基で置換された低級アルキル基、R_2は低
級アルキル基、低級アルケニル基、アルキルカルバモイ
ル基又はハロゲン原子で置換された低級アルキル基、ハ
ロゲン原子で置換された低級アルケニル基を示す。)で
表されるピラゾールカルボン酸類をホスゲン又はトリク
ロロメチルクロロホーメートと反応させることを特徴と
する一般式(II) ▲数式、化学式、表等があります▼(II) (式中、R_1、R_2は一般式( I )と同じ。)で
表されるピラゾールカルボン酸クロライド類の製造方法
。[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a lower A lower alkyl group substituted with an alkoxy group, R_2 represents a lower alkyl group, a lower alkenyl group, an alkylcarbamoyl group, a lower alkyl group substituted with a halogen atom, or a lower alkenyl group substituted with a halogen atom. General formula (II) characterized by reacting pyrazole carboxylic acids with phosgene or trichloromethyl chloroformate ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 and R_2 are the general formula (I ). Method for producing pyrazole carboxylic acid chlorides represented by ).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11709588A JPH0788362B2 (en) | 1988-05-16 | 1988-05-16 | Process for producing pyrazole carboxylic acid chlorides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11709588A JPH0788362B2 (en) | 1988-05-16 | 1988-05-16 | Process for producing pyrazole carboxylic acid chlorides |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01290662A true JPH01290662A (en) | 1989-11-22 |
JPH0788362B2 JPH0788362B2 (en) | 1995-09-27 |
Family
ID=14703273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11709588A Expired - Lifetime JPH0788362B2 (en) | 1988-05-16 | 1988-05-16 | Process for producing pyrazole carboxylic acid chlorides |
Country Status (1)
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JP (1) | JPH0788362B2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0757987A4 (en) * | 1994-04-27 | 1997-04-16 | Nissan Chemical Ind Ltd | Pyrazolecarboxylic acid derivative and plant disease control agent |
WO2007068375A1 (en) | 2005-12-17 | 2007-06-21 | Bayer Cropscience Ag | Carboxamides for controlling undesired micro-organisms in plant protection |
US7329633B2 (en) | 2002-02-19 | 2008-02-12 | Bayer Cropscience Ag | Disubstituted pyrazolylcarboxanilides |
US7799739B2 (en) | 2005-12-17 | 2010-09-21 | Bayer Cropscience Ag | Biphenylcarboxamides for controlling micro-organisms |
US8017558B2 (en) | 2005-12-17 | 2011-09-13 | Bayer Cropscience Ag | Carboxamides for controlling micro-organisms in plant and material protection |
US8580971B2 (en) | 2005-03-02 | 2013-11-12 | Bayer Cropscience Ag | Alkyl-analide producing method |
-
1988
- 1988-05-16 JP JP11709588A patent/JPH0788362B2/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0757987A4 (en) * | 1994-04-27 | 1997-04-16 | Nissan Chemical Ind Ltd | Pyrazolecarboxylic acid derivative and plant disease control agent |
US5817829A (en) * | 1994-04-27 | 1998-10-06 | Nissan Chemical Industries, Ltd. | Pyrazolecarboxylic acid derivatives and plant disease control agent |
US7329633B2 (en) | 2002-02-19 | 2008-02-12 | Bayer Cropscience Ag | Disubstituted pyrazolylcarboxanilides |
US7521397B2 (en) | 2002-02-19 | 2009-04-21 | Bayer Cropscience Ag | Disubstituted pyrazolyl carboxanilides |
US8580971B2 (en) | 2005-03-02 | 2013-11-12 | Bayer Cropscience Ag | Alkyl-analide producing method |
WO2007068375A1 (en) | 2005-12-17 | 2007-06-21 | Bayer Cropscience Ag | Carboxamides for controlling undesired micro-organisms in plant protection |
US7799739B2 (en) | 2005-12-17 | 2010-09-21 | Bayer Cropscience Ag | Biphenylcarboxamides for controlling micro-organisms |
US8017558B2 (en) | 2005-12-17 | 2011-09-13 | Bayer Cropscience Ag | Carboxamides for controlling micro-organisms in plant and material protection |
Also Published As
Publication number | Publication date |
---|---|
JPH0788362B2 (en) | 1995-09-27 |
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