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176969-34-9

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  • High Quality 99% 176969-34-9 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid Manufacturer

    Cas No: 176969-34-9

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  • 3-(Difluoromethyl)-1-Methyl-1H-Pyrazole-4-Carboxylic Acid

    Cas No: 176969-34-9

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176969-34-9 Usage

Chemical Properties

Light brown powder

Uses

3-(Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic Acid can be used to prepare pesticides.

Check Digit Verification of cas no

The CAS Registry Mumber 176969-34-9 includes 9 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 6 digits, 1,7,6,9,6 and 9 respectively; the second part has 2 digits, 3 and 4 respectively.
Calculate Digit Verification of CAS Registry Number 176969-34:
(8*1)+(7*7)+(6*6)+(5*9)+(4*6)+(3*9)+(2*3)+(1*4)=199
199 % 10 = 9
So 176969-34-9 is a valid CAS Registry Number.
InChI:InChI=1/C6H6F2N2O2/c1-10-2-3(6(11)12)4(9-10)5(7)8/h2,5H,1H3,(H,11,12)

176969-34-9SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 11, 2017

Revision Date: Aug 11, 2017

1.Identification

1.1 GHS Product identifier

Product name 3-(difluoromethyl)-1-methylpyrazole-4-carboxylic acid

1.2 Other means of identification

Product number -
Other names DFPA

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only.
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:176969-34-9 SDS

176969-34-9Synthetic route

1-(3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)ethan-1-one

1-(3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)ethan-1-one

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With manganese(II) acetate dihydrate; acetic acid at 100℃; for 18h; Reagent/catalyst;100%
With sodium hypochlorite; sodium hydroxide In water at 70℃; for 2h; Temperature; Reagent/catalyst;98%
With sodium hypochlorite In water at 0℃; for 0.166667h; Temperature; Time;98%
ethyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate
141573-95-7

ethyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium hydroxide In toluene at 65℃; for 0.75h;98%
With sodium hydroxide In ethanol; water at 50 - 80℃; for 3h;95%
With water; sodium hydroxide95%
hexylene glycol bis((3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carboxylate)

hexylene glycol bis((3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carboxylate)

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With water; sodium hydroxide In methanol at 60℃; for 4h;96.3%
3‐difluoromethyl‐1‐methylpyrazole-4-carbonyl chloride
141573-96-8

3‐difluoromethyl‐1‐methylpyrazole-4-carbonyl chloride

C12H13Cl2NO
1263184-89-9

C12H13Cl2NO

A

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

B

benzovindiflupyr

benzovindiflupyr

Conditions
ConditionsYield
Stage #1: 3‐difluoromethyl‐1‐methylpyrazole-4-carbonyl chloride; C12H13Cl2NO With triethylamine In 1,4-dioxane at 25 - 82℃; for 3h;
Stage #2: With sodium hydroxide In tert-butyl methyl ether; water for 0.5h;
Stage #3: With hydrogenchloride In tert-butyl methyl ether; water
A 96%
B 92%
3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonitrile
1049772-84-0

3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonitrile

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium hydroxide In water at 90 - 100℃;95%
Stage #1: 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonitrile With water; sodium hydroxide at 95℃; for 4h;
Stage #2: With hydrogenchloride; water at 20℃; Cooling with ice;
92%
With water; sodium hydroxide In methanol for 2h; Solvent; Reflux; Further stages;92.1%
With tetra(n-butyl)ammonium hydrogensulfate; sodium hydroxide In water; toluene at 70℃; for 8h;
hexyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

hexyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With water; sodium hydroxide at 60℃; for 2h;95%
methyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

methyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With manganese(II) nitrate; oxygen; acetic acid; ferric nitrate at 80℃; for 20h;95%
3-(difluoromethyl)-1-methyl-4-(1,3-dioxolan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-4-(1,3-dioxolan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-4-(1,3-dioxolan-2-yl)-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With dihydrogen peroxide In water at 10 - 100℃; for 5h; Reagent/catalyst;
93.2%
3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxan-2-yl)-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With dihydrogen peroxide In water at 10 - 100℃; for 5h;
92.3%
ethylene glycol bis((3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carboxylate)

ethylene glycol bis((3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carboxylate)

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With water; sodium hydroxide In methanol at 60℃; for 4h; Reagent/catalyst;92%
3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxepan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxepan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxepan-2-yl)-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With dihydrogen peroxide In water at 10 - 100℃; for 5h;
92%
3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxolan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxolan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxolan-2-yl)-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With sodium hypochlorite In water at 10 - 100℃; for 5h;
91.8%
3-(difluoromethyl)-4-(1,3-dioxan-2-yl)-1-methyl-1H-pyrazole

3-(difluoromethyl)-4-(1,3-dioxan-2-yl)-1-methyl-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-4-(1,3-dioxan-2-yl)-1-methyl-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With dihydrogen peroxide In water at 10 - 100℃; for 5h; Reagent/catalyst;
91.6%
3-(difluoromethyl)-1-methyl-4-(1,3-dioxepan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-4-(1,3-dioxepan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-4-(1,3-dioxepan-2-yl)-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With dihydrogen peroxide In water at 10 - 100℃; for 5h; Reagent/catalyst;
91.5%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde
1094484-55-5

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium hypochlorite at 10 - 100℃; for 5h;91.3%
Stage #1: 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde With sodium hydroxide; dihydrogen peroxide In water at 40 - 45℃; for 1.5h;
Stage #2: With hydrogenchloride In water pH=2.5; Product distribution / selectivity;
69 %Chromat.
With copper(II) oxide; sodium hydroxide In water at 25 - 30℃; for 24h;32 g
3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxetan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxetan-2-yl)-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-4-(2-methyl-1,3-dioxetan-2-yl)-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With sodium hypochlorite In water at 10 - 100℃; for 5h; Reagent/catalyst;
91.3%
2,2-dichloro-1-(3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)ethanone

2,2-dichloro-1-(3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)ethanone

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium hypochlorite; water In chloroform at 24℃; for 4h; Reagent/catalyst; Inert atmosphere;91%
With sodium hypochlorite; sodium hydroxide In water at 22 - 70℃; for 2h;
3-(difluoromethyl)-4-(1,3-dioxetan-2-yl)-1-methyl-1H-pyrazole

3-(difluoromethyl)-4-(1,3-dioxetan-2-yl)-1-methyl-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-4-(1,3-dioxetan-2-yl)-1-methyl-1H-pyrazole With hydrogenchloride In water at 50 - 60℃; for 5h;
Stage #2: With sodium hypochlorite In water at 10 - 100℃; for 5h; Reagent/catalyst;
91%
methyl-3-(dichloromethyl)-1-methyl-1H-pyrazole-4-carboxylate

methyl-3-(dichloromethyl)-1-methyl-1H-pyrazole-4-carboxylate

A

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

B

5-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
1204298-65-6

5-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With 1,3-dimethyl-2-imidazolidinone; hydrogen fluoride; triethylamine at 125 - 155℃; Reagent/catalyst; Temperature; Concentration; Autoclave;A 90.1%
B n/a
3-(difluoromethyl)-4-(furan-2-yl)-1-methyl-1H-pyrazole

3-(difluoromethyl)-4-(furan-2-yl)-1-methyl-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium periodate; rhodium(III) chloride hydrate In tetrachloromethane; water; acetonitrile at 20℃; for 0.75h;90%
3-bromo-1-methyl-1H-pyrazole-4-carboxylic acid

3-bromo-1-methyl-1H-pyrazole-4-carboxylic acid

difluoromethylboronic acid

difluoromethylboronic acid

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 65 - 75℃; for 1.5h; Solvent; Reagent/catalyst; Inert atmosphere;89.2%
(E/Z)-ethyl 2-(ethoxymethylene)-4,4-difluoro-3-oxobutanoate

(E/Z)-ethyl 2-(ethoxymethylene)-4,4-difluoro-3-oxobutanoate

methylhydrazine
60-34-4

methylhydrazine

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: methylhydrazine With benzaldehyde In water; toluene at 25 - 60℃; for 6.16667h; Inert atmosphere;
Stage #2: (E/Z)-ethyl 2-(ethoxymethylene)-4,4-difluoro-3-oxobutanoate In water; toluene at 20 - 30℃; for 19h; Product distribution / selectivity;
86.1%
4-bromo-3-(difluoromethyl)-1-methyl-1H-pyrazole
1089212-38-3

4-bromo-3-(difluoromethyl)-1-methyl-1H-pyrazole

carbon dioxide
124-38-9

carbon dioxide

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 4-bromo-3-(difluoromethyl)-1-methyl-1H-pyrazole With TurboGrignard In 2-methyltetrahydrofuran at -5℃; for 2h; Inert atmosphere; Heating;
Stage #2: carbon dioxide In 2-methyltetrahydrofuran at -25 - 0℃; for 5h; Reagent/catalyst; Solvent; Inert atmosphere;
84.6%
ethyl 4,4-difluoro-3-oxobutyrate
352-24-9

ethyl 4,4-difluoro-3-oxobutyrate

methylhydrazine
60-34-4

methylhydrazine

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: ethyl 4,4-difluoro-3-oxobutyrate With calcium acetate; orthoformic acid triethyl ester at 100 - 110℃; for 2h;
Stage #2: methylhydrazine With sodium hydroxide In 5,5-dimethyl-1,3-cyclohexadiene; water at 10 - 20℃; for 0.5h;
83.3%
carbon dioxide
124-38-9

carbon dioxide

3-(difluoromethyl)-4-iodo-1-methyl-1H-pyrazole

3-(difluoromethyl)-4-iodo-1-methyl-1H-pyrazole

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-4-iodo-1-methyl-1H-pyrazole With isopropylmagnesium chloride In tetrahydrofuran at -5℃; for 2h; Inert atmosphere; Heating;
Stage #2: carbon dioxide With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at -25 - 0℃; for 5h; Inert atmosphere;
83.2%
potassium 2-difluoroacetyl-3-(diethylamino)acrylate

potassium 2-difluoroacetyl-3-(diethylamino)acrylate

methylhydrazine
60-34-4

methylhydrazine

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With potassium iodide In water at -30 - -20℃; for 2h; Inert atmosphere;79.6%
sodium 2-difluoroacetyl-3-(dimethylamino)acrylate

sodium 2-difluoroacetyl-3-(dimethylamino)acrylate

methylhydrazine
60-34-4

methylhydrazine

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium iodide In water at -30 - 20℃; for 2h; Inert atmosphere;78.3%
sodium 2-difluoroacetyl-3-(diethylamino)acrylate

sodium 2-difluoroacetyl-3-(diethylamino)acrylate

methylhydrazine
60-34-4

methylhydrazine

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium iodide at -30 - -25℃; for 2h; Inert atmosphere;77.1%
potassium 2-difluoroacetyl-3-(dimethylamino)acrylate

potassium 2-difluoroacetyl-3-(dimethylamino)acrylate

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With methylhydrazine; potassium iodide In water at -30 - -20℃; for 2h; Inert atmosphere;75.9%
sodium 2-difluoroacetyl-3-(2,2,6,6-tetramethylpiperidin-1yl)acrylate

sodium 2-difluoroacetyl-3-(2,2,6,6-tetramethylpiperidin-1yl)acrylate

methylhydrazine
60-34-4

methylhydrazine

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Conditions
ConditionsYield
With sodium iodide at -30 - -20℃; for 2h; Inert atmosphere;75.8%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

3‐difluoromethyl‐1‐methylpyrazole-4-carbonyl chloride
141573-96-8

3‐difluoromethyl‐1‐methylpyrazole-4-carbonyl chloride

Conditions
ConditionsYield
With thionyl chloride In chlorobenzene at 110℃; for 3h;98%
With thionyl chloride In toluene at 90℃;92.1%
With thionyl chloride; N,N-dimethyl-formamide In 1,2-dichloro-ethane for 5h; Reflux;90%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

1-methyl-3-(difluoromethyl)-1H-pyrazole-4-amide
925689-10-7

1-methyl-3-(difluoromethyl)-1H-pyrazole-4-amide

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 0.5h;
Stage #2: With ammonium hydroxide In dichloromethane Cooling with ice;
98%
Multi-step reaction with 2 steps
1: thionyl chloride / 4 h / Reflux
2: ammonium hydroxide / dichloromethane / 4 h / 20 °C
View Scheme
Multi-step reaction with 2 steps
1: thionyl chloride / 4 h / Reflux
2: ammonium hydroxide / tetrahydrofuran
View Scheme
Multi-step reaction with 2 steps
1: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 0.5 h / 20 °C
2: ammonium hydroxide / dichloromethane / 0 °C
View Scheme
Stage #1: 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 20℃; for 0.5h;
Stage #2: With ammonium hydroxide at 0 - 20℃;
methanol
67-56-1

methanol

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

methyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

methyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate

Conditions
ConditionsYield
With sulfuric acid at 75℃; for 8h;97.2%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

tert-butyl alcohol
75-65-0

tert-butyl alcohol

tert-butyl (3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carbamate

tert-butyl (3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carbamate

Conditions
ConditionsYield
With diphenylphosphoranyl azide; N-ethyl-N,N-diisopropylamine at 20 - 90℃; for 4.16667h; Inert atmosphere;94%
With diphenyl phosphoryl azide; N-ethyl-N,N-diisopropylamine at 20 - 90℃; for 4.16667h; Curtius Rearrangement; Inert atmosphere;94%
With diphenyl phosphoryl azide; N-ethyl-N,N-diisopropylamine at 20 - 90℃; for 4.5h; Inert atmosphere;91%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

5-amino-9-syn-isopropyl-benzonorbornene

5-amino-9-syn-isopropyl-benzonorbornene

C20H23F2N3O

C20H23F2N3O

Conditions
ConditionsYield
With bis-(2-oxo-3-oxazolidinyl)phosphoryl chloride; triethylamine In dichloromethane at 20℃; for 21h;92.6%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

C14H19N

C14H19N

C20H23F2N3O

C20H23F2N3O

Conditions
ConditionsYield
With bis-(2-oxo-3-oxazolidinyl)phosphoryl chloride; triethylamine In dichloromethane at 20℃; for 3h;91.7%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

tert-butyl (3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carbamate

tert-butyl (3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl)carbamate

Conditions
ConditionsYield
With diphenylphosphoranyl azide; N-ethyl-N,N-diisopropylamine In tert-butyl alcohol at 20 - 90℃; for 4.5h; Inert atmosphere;91%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

N,O-dimethylhydroxylamine*hydrochloride
6638-79-5

N,O-dimethylhydroxylamine*hydrochloride

N-methoxy,N-methyl-1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxylic amide

N-methoxy,N-methyl-1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxylic amide

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃; for 0.5h;
Stage #2: N,O-dimethylhydroxylamine*hydrochloride In dichloromethane at 20℃;
91%
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃;91%
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

3-(difluoromethyl)-4-iodo-1-methyl-1H-pyrazole

3-(difluoromethyl)-4-iodo-1-methyl-1H-pyrazole

Conditions
ConditionsYield
With potassium iodate; sulfuric acid; iodine; acetic acid In sulfolane at 45 - 60℃; for 1.33h;90%
Multi-step reaction with 3 steps
1.1: diphenylphosphoranyl azide; N-ethyl-N,N-diisopropylamine / 4.17 h / 20 - 90 °C / Inert atmosphere
2.1: trifluoroacetic acid / dichloromethane / 2.5 h / 20 °C
3.1: hydrogenchloride; sodium nitrite / water / 1 h / 0 °C
3.2: 0.5 h
View Scheme
Multi-step reaction with 3 steps
1.1: N-ethyl-N,N-diisopropylamine; diphenyl phosphoryl azide / 4.17 h / 20 - 90 °C / Inert atmosphere
2.1: trifluoroacetic acid / dichloromethane / 2.5 h / 20 °C
3.1: hydrogenchloride; sodium nitrite / water / 1 h / 0 °C
3.2: 0.5 h / 20 °C
View Scheme
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid
176969-34-9

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

C12H17BrN2O2S

C12H17BrN2O2S

N-(2-bromophenyl)-2-(1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylamino)-cyclohexylsulfonamide

N-(2-bromophenyl)-2-(1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylamino)-cyclohexylsulfonamide

Conditions
ConditionsYield
Stage #1: 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 0℃; for 2h; Inert atmosphere;
Stage #2: C12H17BrN2O2S In dichloromethane at 0℃; for 3h; Inert atmosphere;
90%

176969-34-9Relevant articles and documents

PRODUCING METHOD FOR 3-DIFLUOROMETHYLPYRAZOLE COMPOUND, PRODUCING METHOD FOR 3-DIFLUOROMETHYLPYRAZOLE-4-CARBOXYLIC ACID COMPOUND, AND PYRAZOLIDINE COMPOUND

-

Paragraph 0185-0189, (2021/03/05)

Provided are producing methods for a 3-difluoromethylpyrazole compound and a 3-difluoromethylpyrazole-4-carboxylic acid compound, which include, in a reaction solvent containing a specific solvent, subjecting a difluoroacetyl group-containing compound, a hydrazine compound, and formaldehyde to a cyclocondensation reaction, and subsequently oxidizing the obtained pyrazole compound precursor, and a pyrazolidine compound represented by a specific formula in these producing methods.

Preparation method and application of pyrazole derivative

-

Paragraph 0037-0038, (2020/05/08)

The invention relates to a preparation method of a pyrazole derivative. The compound shown in the formula I reacts with a silanization reagent shown in a formula II to generate an intermediate productshown in a formula III, the intermediate product shown in the formula III reacts with a halogenated acid derivative shown in a formula IV to generate a halogenated compound shown in a formula V, andthe halogenated compound shown in the formula V reacts under acidic conditions to generate a pyrazole derivative shown in a formula VI. The preparation method of the pyrazole derivative is suitable for industrial production.

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate compounds, and preparation method and application thereof

-

Paragraph 0028; 0031-0032, (2020/01/25)

The invention discloses 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate compounds, and a preparation method and an application thereof. The 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylatecompounds are 2-(benzoyloxy)ethyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate compounds, and have a structural formula represented by formula (I) shown in the description; and in the formula(I), a substituent group R is a phenyl group or a substituted phenyl group, and a substituent group on the benzene ring of the substituted phenyl group is halogen or a C1-C3 alkyl group. The 2-(benzoyloxy)ethyl 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate compounds are new compounds with bactericidal activity, have a good inhibition rate on Fusarium graminerum at the concentration of 50ppm, and provide a basis for research and development of new pesticides.

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