JPS6412273B2 - - Google Patents
Info
- Publication number
- JPS6412273B2 JPS6412273B2 JP5361081A JP5361081A JPS6412273B2 JP S6412273 B2 JPS6412273 B2 JP S6412273B2 JP 5361081 A JP5361081 A JP 5361081A JP 5361081 A JP5361081 A JP 5361081A JP S6412273 B2 JPS6412273 B2 JP S6412273B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- dichlorobenzoyl
- dimethyl
- reaction
- solvent
- 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
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- -1 carbonylmethyl halide compound Chemical class 0.000 claims description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- OXZUYNHPYJTNEM-UHFFFAOYSA-N C(=O)=COC1=NNC=C1 Chemical class C(=O)=COC1=NNC=C1 OXZUYNHPYJTNEM-UHFFFAOYSA-N 0.000 claims description 4
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 claims description 3
- IUSOXUFUXZORBF-UHFFFAOYSA-N n,n-dioctyloctan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCC[NH+](CCCCCCCC)CCCCCCCC IUSOXUFUXZORBF-UHFFFAOYSA-N 0.000 claims description 3
- XMSHRLOQLUNKSN-UHFFFAOYSA-N destosyl pyrazolate Chemical compound CC1=NN(C)C(O)=C1C(=O)C1=CC=C(Cl)C=C1Cl XMSHRLOQLUNKSN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- FKERUJTUOYLBKB-UHFFFAOYSA-N pyrazoxyfen Chemical group C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OCC(=O)C1=CC=CC=C1 FKERUJTUOYLBKB-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、１，３−ジメチル−４−（２，４−
ジクロロベンゾイル）−５−置換カルボニルメト
キピラゾール（以下DDSPと略す）の製造方法に
関し、詳しくは、相間移動触媒、助触媒及び溶媒
の存在下に、１，３−ジメチル−４−（２，４−
ジクロロベンゾイル）−５−ヒドロキシピラゾー
ル（以下DDHPと略す）とカルボニルメチルハ
ライド系化合物（以下CMHと略す）とを反応さ
せて、DDSPを製造する方法である。
本出願人はDDSPが除草剤の有効成分として優
れた作用効果を示すことを見いだし、特開昭54−
41872、特願昭54−26564、同54−116358などで特
許出願を行なつた。これらには、DDHPとCMH
とを反応させてDDSPを製造する方法が、一般的
な製造方法として提案されているが、具体的には
その反応性を高めるために、CMHとして当該ブ
ロマイド系化合物を使用した反応例が記載されて
いる。
しかしながら、この製造方法では、原料のカル
ボニルメチルブロマイド系化合物が高価であるこ
と、及びそれから分離して副生する臭素化物の分
離、回収には煩雑な処理が必要であることから、
改良が求められている。
更に本出願人は、特願昭55−105947で、前記欠
点を改良したDDSPの製造方法を出願している
が、この方法では溶媒として高価なアセトニトリ
ルなどのニトリル系化合物を用いる為に、工業的
実施にはなお改良が求められている。
本発明者達は、各種反応条件について検討を重
ねたところ、相間移動触媒、助触媒及び溶媒の存
在下に前述の反応を行なつた場合、目的物の生成
が高まることの知見を得、本発明を完成した。
すなわち、本発明は脱酸剤の存在下に、１，３
−ジメチル−４−（２，４−ジクロロベンゾイル）
−５−ヒドロキシピラゾールと、一般式Cl−
CH2CO−Ｒ（式中、Ｒはフエニル基である）で表
わされるカルボニルメチルハライド系化合物とを
反応させて、一般式（）
（式中Ｒは前述の通り）で表わされる１，３−ジ
メチル−４−（２，４−ジクロロベンゾイル）−５
−置換カルボニルメトキシピラゾールを製造する
方法において、溶媒として水に離溶性の不活性な
炭化水素及び水を用い、かつトリオクチルアンモ
ニウムクロライド又はベンジルトリブチルアンモ
ニウムクロライドからなる相間移動触媒及び沃化
カリウムからなる助触媒を用いて前記反応を行な
うことを特徴とする１，３−ジメチル−４−（２，
４−ジクロロベンゾイル）−５−置換カルボニル
メトキシピラゾールの製造方法である。
本発明方法によつて製造される目的物１，３−
ジメチル−４−（２，４−ジクロロベンゾイル）−
５−置換カルボニルメトキシピラゾールは、１，
３−ジメチル−４−（２，４−ジクロロベンゾイ
ル）−５−フエナシルオキシピラゾールである。
そこで、さらにこの目的物の具体的な製法に関
して詳記する。
本発明方法では、溶媒中に、原料のDDHP、
CMH、脱酸剤、相間移動触媒及び助触媒を添加
したり、或は各原料、脱酸剤、相間移動触媒及び
助触媒に、前記溶媒を添加したりして、普通30℃
〜還流温度で反応が行なわれる。
この反応では通常、脱酸剤として塩基性無機物
質が使用され、例えば炭酸ナトリウム、炭酸カリ
ウム、水酸化ナトリウム、水酸化カリウムなどが
使用され、なかでも炭酸ナトリウム、炭酸カリウ
ムの使用が工業的には好ましい。この脱酸剤の使
用量は、DDHP1モル当り一般に0.5〜３モル、望
ましくは0.55〜1.5モルである。
本発明の相間移動触媒とは、本発明で使用する
溶媒として水に離溶性の不活性な炭化水素及び水
の混合物を使用するとき、その水相にDDHP、
脱酸剤、助触媒などを含み、また油相を形成する
炭化水素にCMHを含むものであつて、この２相
間にて油相、水相にも溶け、水相でDDHPの塩
類と接触して過剰にある水溶液中のアニオンと自
分のアニオンとを交換し、油相に移動して
DDHPとCMHとが反応するような脱酸反応を促
進するものである。
その具体例は次の第１表に示されるが、本発明
ではトリオクチルアンモニウムクロライド又はベ
ンジルトリブチルアンモニウムクロライドが使用
される。
The present invention provides 1,3-dimethyl-4-(2,4-
Regarding the method for producing 5-substituted carbonylmethoxypyrazole (dichlorobenzoyl)-5-substituted carbonylmethoxypyrazole (hereinafter abbreviated as DDSP), in detail, 1,3-dimethyl-4-(2,4-
This is a method for producing DDSP by reacting dichlorobenzoyl)-5-hydroxypyrazole (hereinafter abbreviated as DDHP) with a carbonylmethyl halide compound (hereinafter abbreviated as CMH). The present applicant discovered that DDSP exhibits excellent effects as an active ingredient of herbicides, and
41872, Patent Application No. 54-26564, No. 54-116358, etc. These include DDHP and CMH
A method of producing DDSP by reacting with CMH has been proposed as a general production method, but specifically, a reaction example using the bromide compound as CMH has been described in order to increase its reactivity. ing. However, in this production method, the raw material carbonylmethyl bromide compound is expensive, and the separation and recovery of the by-product bromide separated from it requires complicated processing.
Improvements are required. Furthermore, the present applicant has applied for a method for manufacturing DDSP that improves the above-mentioned drawbacks in Japanese Patent Application No. 55-105947, but this method uses expensive nitrile compounds such as acetonitrile as a solvent, making it difficult to manufacture industrially. Improvements are still needed in implementation. After repeated studies on various reaction conditions, the present inventors discovered that the production of the target product increases when the above-mentioned reaction is carried out in the presence of a phase transfer catalyst, co-catalyst and solvent. Completed the invention. That is, in the present invention, in the presence of a deoxidizing agent, 1,3
-dimethyl-4-(2,4-dichlorobenzoyl)
-5-hydroxypyrazole and general formula Cl-
By reacting with a carbonylmethyl halide compound represented by CH 2 CO-R (in the formula, R is a phenyl group), the general formula () 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5 represented by (wherein R is as described above)
- A method for producing a substituted carbonylmethoxypyrazole, using a water-dissolvable inert hydrocarbon and water as the solvent, and a phase transfer catalyst consisting of trioctylammonium chloride or benzyltributylammonium chloride and an assistant consisting of potassium iodide. 1,3-dimethyl-4-(2,
This is a method for producing 4-dichlorobenzoyl)-5-substituted carbonylmethoxypyrazole. Target product 1,3- produced by the method of the present invention
Dimethyl-4-(2,4-dichlorobenzoyl)-
5-substituted carbonylmethoxypyrazole is 1,
3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenacyloxypyrazole. Therefore, the specific method for producing this target product will be described in detail. In the method of the present invention, the raw material DDHP,
By adding CMH, a deoxidizer, a phase transfer catalyst and a cocatalyst, or by adding the above solvent to each raw material, a deoxidizer, a phase transfer catalyst and a cocatalyst, the temperature is usually 30°C.
The reaction is carried out at ~reflux temperature. In this reaction, a basic inorganic substance is usually used as a deoxidizing agent, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. Among them, the use of sodium carbonate and potassium carbonate is industrially preferred. preferable. The amount of the deoxidizing agent used is generally 0.5 to 3 mol, preferably 0.55 to 1.5 mol per 1 mol of DDHP. The phase transfer catalyst of the present invention means that when a mixture of a water-dissociable inert hydrocarbon and water is used as a solvent in the present invention, the aqueous phase includes DDHP,
It contains a deoxidizing agent, a promoter, etc., and also contains CMH in the hydrocarbon that forms the oil phase.It dissolves in the oil phase and the water phase between these two phases, and comes into contact with the salts of DDHP in the water phase. exchanges the excess anion in the aqueous solution with its own anion and transfers it to the oil phase.
It promotes deoxidation reactions such as the reaction between DDHP and CMH. Specific examples thereof are shown in Table 1 below, and trioctylammonium chloride or benzyltributylammonium chloride is used in the present invention.
【表】
この相間移動触媒の使用量は、原料DDHPに
対して0.05〜10重量％であり、望ましくは0.1〜
2.0重量％である。
更に、本発明方法において塩素原子である
CMHを用いる場合、前記相間移動触媒の他に加
える助触媒は沃化カリウムであり、この助触媒を
原料DDHP1モルに対して0.1〜10モル％添加す
る。この添加により、高い生成率を助長して目的
物を得ることができる。
具体的には、第２表の参考実施例No.６及び８で
目的物の収率76％であるものが、助触媒の添加に
より、実施例No.５及び７の収率93.0％及び94％に
それぞれ増加することによつて示される。
また溶媒については前記のとおり、水に難溶性
の不活性な炭化水素及び水をそれぞれ単独で添加
し反応系内で混合使用したり、或はこれらを混合
物として反応系内に添加し使用したりするもの
で、その炭化水素としてはベンゼン、トルエン、
キシレン、クロロベンゼン、ｏ−ジクロロベンゼ
ン、ｏ−クロロトルエン、クロロホルム、ジクロ
ロメタン、ジクロロエタン、四塩化炭素などが挙
げられる。工業的には水とトルエン、水とキシレ
ン、水とジクロロエタンなどの混合溶媒を使用す
ることが好ましい。溶媒の使用量は、反応原料を
溶解し、撹拌を可能にする程度であればよく、一
般に原料DDHPに対して等量〜30倍量であり、
望ましくは２〜10倍量である。
本発明方法の反応時間は、原料物質、脱酸剤又
は触媒の種類、それらの使用量、反応温度などに
よつて一概に規定できないが、通常0.5〜５時間
である。普通、工業的には反応生成物を分液、水
洗、溶媒留去、冷却などの通常の分離精製手段が
施されて例えば90％以上の高収率で目的物DDSP
が得られる。
次に、本発明方法の具体的実施例を記載する。
実施例 １（参考）
DDHP8.6ｇ、水25ml及び水酸化カリウム1.9ｇ
の溶液に、第１表の相間移動触媒としてBTBAC
の50％水溶液0.5ｇを加え、更にフエナシルブロ
マイド6.3ｇ及びトルエン45mlを加えて加温し、
55〜60℃で２時間反応させた。反応終了後、水層
を分液除去し、有機層を水洗、芒硝で乾燥させた
後、溶媒を減圧留去して１，３−ジメチル−４−
（２，４−ジクロロベンゾイル）−５−フエナシル
オキシピラゾール（以下DDSPPと略称）の粗結
晶12.1ｇを得た。（収率96.5％）
実施例 ２〜８
前記実施例１の場合と同様にして、反応及び精
製処理を行ない、第２表の結果を得た。[Table] The amount of this phase transfer catalyst used is 0.05 to 10% by weight based on the raw material DDHP, preferably 0.1 to 10% by weight.
It is 2.0% by weight. Furthermore, in the method of the present invention, a chlorine atom
When CMH is used, the co-catalyst added in addition to the phase transfer catalyst is potassium iodide, and this co-catalyst is added in an amount of 0.1 to 10 mol % based on 1 mol of raw material DDHP. This addition can promote a high production rate to obtain the desired product. Specifically, in Reference Examples No. 6 and 8 in Table 2, the yield of the target product was 76%, but by adding a cocatalyst, the yield of Example No. 5 and 7 was 93.0% and 94%. % respectively. Regarding the solvent, as mentioned above, an inert hydrocarbon that is poorly soluble in water and water may be added individually and used as a mixture in the reaction system, or they may be added as a mixture and used in the reaction system. The hydrocarbons include benzene, toluene,
Examples include xylene, chlorobenzene, o-dichlorobenzene, o-chlorotoluene, chloroform, dichloromethane, dichloroethane, and carbon tetrachloride. Industrially, it is preferable to use a mixed solvent such as water and toluene, water and xylene, or water and dichloroethane. The amount of solvent used is sufficient as long as it dissolves the reaction raw materials and enables stirring, and is generally an equivalent amount to 30 times the amount of the raw material DDHP.
The amount is preferably 2 to 10 times as much. The reaction time of the method of the present invention cannot be absolutely defined depending on the raw material, the type of deoxidizing agent or catalyst, the amount used thereof, the reaction temperature, etc., but is usually 0.5 to 5 hours. Normally, in an industrial setting, the reaction product is subjected to normal separation and purification methods such as liquid separation, water washing, solvent distillation, and cooling to obtain the target product DDSP with a high yield of 90% or more.
is obtained. Next, specific examples of the method of the present invention will be described. Example 1 (reference) DDHP 8.6g, water 25ml and potassium hydroxide 1.9g
of BTBAC as a phase transfer catalyst in Table 1.
Add 0.5 g of a 50% aqueous solution of and further add 6.3 g of phenacyl bromide and 45 ml of toluene and heat.
The reaction was carried out at 55-60°C for 2 hours. After the reaction, the aqueous layer was separated and removed, the organic layer was washed with water and dried with sodium sulfate, and the solvent was distilled off under reduced pressure to give 1,3-dimethyl-4-
12.1 g of crude crystals of (2,4-dichlorobenzoyl)-5-phenacyloxypyrazole (hereinafter abbreviated as DDSPP) were obtained. (Yield 96.5%) Examples 2 to 8 Reactions and purification treatments were carried out in the same manner as in Example 1, and the results shown in Table 2 were obtained.
Claims (1)
（２，４−ジクロロベンゾイル）−５−ヒドロキシ
ピラゾールと、一般式Cl−CH2CO−Ｒ（式中Ｒは
フエニル基である）で表わされるカルボニルメチ
ルハライド系化合物とを反応させて、 一般式 （式中Ｒは前述の通り）で表わされる１，３−ジ
メチル−４−（２，４−ジクロロベンゾイル）−５
−置換カルボニルメトキシピラゾールを製造する
方法において、溶媒として水に難溶性の不活性な
炭化水素及び水を用い、かつトリオクチルアンモ
ニウムクロライド又はベンジルトリブチルアンモ
ニウムクロライドからなる相間移動触媒及び沃化
カリウムからなる助触媒を用いて前記反応を行な
うことを特徴とする１，３−ジメチル−４−（２，
４−ジクロロベンゾイル）−５−置換カルボニル
メトキシピラゾールの製造方法。[Claims] 1. In the presence of a deoxidizing agent, 1,3-dimethyl-4-
(2,4-dichlorobenzoyl)-5-hydroxypyrazole and a carbonylmethyl halide compound represented by the general formula Cl-CH 2 CO-R (wherein R is a phenyl group) are reacted, 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5 represented by (wherein R is as described above)
- A method for producing a substituted carbonylmethoxypyrazole, using an inert hydrocarbon poorly soluble in water and water as a solvent, and a phase transfer catalyst consisting of trioctylammonium chloride or benzyltributylammonium chloride and an assistant consisting of potassium iodide. 1,3-dimethyl-4-(2,
A method for producing 4-dichlorobenzoyl)-5-substituted carbonylmethoxypyrazole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5361081A JPS57167971A (en) | 1981-04-09 | 1981-04-09 | Preparation of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5- substituted carbonylmethoxypyrazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5361081A JPS57167971A (en) | 1981-04-09 | 1981-04-09 | Preparation of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5- substituted carbonylmethoxypyrazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57167971A JPS57167971A (en) | 1982-10-16 |
| JPS6412273B2 true JPS6412273B2 (en) | 1989-02-28 |
Family
ID=12947663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5361081A Granted JPS57167971A (en) | 1981-04-09 | 1981-04-09 | Preparation of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5- substituted carbonylmethoxypyrazole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57167971A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5594368A (en) * | 1978-12-18 | 1980-07-17 | Hodogaya Chem Co Ltd | Preparation of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5- pyrazolyl4-toluenesulfonate |
-
1981
- 1981-04-09 JP JP5361081A patent/JPS57167971A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57167971A (en) | 1982-10-16 |
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