31108-57-3

Usage

Uses

4-Cyanopyrazole is used to catalyze epoxidation of ethene by hydrogen peroixde.

InChI:InChI=1/C4H3N3/c5-1-4-2-6-7-3-4/h2-3H,(H,6,7)

Synthetic route

4-bromo-1H-pyrazole (2075-45-8) + potassiumhexacyanoferrate(II) trihydrate → 1H-pyrazole-4-carbonitrile (31108-57-3)

Conditions	Yield
With C42H58NO3PPdS(2-); potassium acetate; tert-butyl XPhos In 1,4-dioxane; water at 100℃; for 1h; Inert atmosphere; Sealed tube;	90%

α-cyano-β-dimethylaminoacrolein (149139-41-3) → 1H-pyrazole-4-carbonitrile (31108-57-3)

Conditions	Yield
With hydrogenchloride; hydrazine In ethanol for 1h; Heating;	55%

4-bromo-1H-pyrazole (2075-45-8) + [11C]hydrogen cyanide (14904-70-2) → 1H-pyrazole-4-carbonitrile (31108-57-3)

Conditions	Yield
Stage #1: 4-bromo-1H-pyrazole With XPhos In toluene at 20℃; for 0.5h; Stage #2: [11C]hydrogen cyanide In tetrahydrofuran at 100℃; for 0.0166667h;

C24H41BrO + 1H-pyrazole-4-carbonitrile (31108-57-3) → C28H43N3O

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 80℃; for 3h; Inert atmosphere;	97.5%

(2R,5S)-tert-butyl 5-(4-chlorobenzyl)-2-(((methylsulfonyl)oxy)methyl)morpholine-4-carboxylate + 1H-pyrazole-4-carbonitrile (31108-57-3) → (2R,5S)-tert-butyl 5-(4-chlorobenzyl)-2-((4-cyano-1H-pyrazol-1-yl)methyl)morpholine-4-carboxylate

Conditions	Yield
With potassium carbonate In acetonitrile at 100℃; Sealed tube;	97%

3,4-dihydro-2H-pyran (110-87-2) + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole-4-carbonitrile (1448317-12-1)

Conditions	Yield
With toluene-4-sulfonic acid In dichloromethane at 3 - 20℃;	96%

trimethylamine-borane (75-22-9) + 1H-pyrazole-4-carbonitrile (31108-57-3) → {1-(4-cyano)pyrazolyl}borane (18601-58-6)

Conditions	Yield
	95%
	95%

triethyl borane (97-94-9) + 1H-pyrazole-4-carbonitrile (31108-57-3) → bis-[μ-(4-cyano-pyrazolato-N1:N2)]-tetraethyl-bis-boron (14695-72-8)

Conditions	Yield
	93%
	93%

C23H38O2 + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-((R)-2-hydroxy-2-((3R,5R,8R,9R,10S,13S,14S,15R,17S)-3-hydroxy-3,13,15-trimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)propyl)-1H-pyrazole-4-carbonitrile + 1-((S)-2-hydroxy-2-((3R,5R,8R,9R,10S,13S,14S,15R,17S)-3-hydroxy-3,13,15-trimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)propyl)-1H-pyrazole-4-carbonitrile

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 25 - 120℃; for 16h;	A 43% B 93%

methyl 3-(((methylsulfonyl)oxy)methyl)bicyclo[1.1.1]pentane-1-carboxylate + 1H-pyrazole-4-carbonitrile (31108-57-3) → methyl 3-((4-cyano-1H-pyrazol-1-yl)methyl)bicyclo[1.1.1]pentane-1-carboxylate

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃;	93%

ethyl iodide (75-03-6) + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-ethyl-1H-pyrazole-4-carbonitrile

Conditions	Yield
With potassium carbonate In acetonitrile at 80℃; for 16h;	92%

C25H42O3 + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-((R)-2-((3R,5R,8S,9S,10S,13S,14S,17S)-10-ethyl-3-hydroxy-3-(methoxymethyl)-13-methylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)-2-hydroxypropyl)-1H-pyrazole-4-carbonitrile + 1-((S)-2-((3R,5R,8S,9S,10S,13S,14S,17S)-10-ethyl-3-hydroxy-3-(methoxymethyl)-13-methylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)-2-hydroxypropyl)-1H-pyrazole-4-carbonitrile

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 120℃; for 48h;	A 53.4% B 92%

C23H39BrO + 1H-pyrazole-4-carbonitrile (31108-57-3) → C27H41N3O

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 15 - 80℃; for 2h; Inert atmosphere;	91.5%

3-chloromethyl-6-(trifluoromethyl)pyridine (386715-33-9) + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-((6-(trifluoromethyl)pyridin-3-yl)methyl)-1H-pyrazole-4-carbonitrile

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 2h;	90.7%

p-Methoxybenzyl bromide (2746-25-0) + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-(4-methoxybenzyl)-1H-pyrazole-4-carbonitrile (1448317-15-4)

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran at 0 - 20℃;	87%

ethyl 1-(6-(2-(4-(3-bromopropoxy)-2-methylphenethyl)-5-fluorophenyl)pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate + 1H-pyrazole-4-carbonitrile (31108-57-3) → ethyl 1-(6-(2-(4-(3-(4-cyano-1H-pyrazol-1-yl)propoxy)-2-methylphenethyl)-5-fluorophenyl)pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate

Conditions	Yield
With caesium carbonate In acetonitrile at 80℃; for 16h;	87%

1H-pyrazole-4-carbonitrile (31108-57-3) + benzene (71-43-2) → 1-phenyl-1H-pyrazole-4-carbonitrile (709-04-6)

Conditions	Yield
With 10-phenyl-10H-phenothiazine; 1,1,1,3',3',3'-hexafluoro-propanol; oxygen; lithium perchlorate In 2,2,2-trifluoroethanol under 760.051 Torr; Irradiation; Cooling;	87%

C21H34O2 + 1H-pyrazole-4-carbonitrile (31108-57-3) → C25H37N3O2

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 120℃; for 16h; Inert atmosphere;	84%

C24H41BrO2Si + 1H-pyrazole-4-carbonitrile (31108-57-3) → C28H43N3O2Si

Conditions	Yield
With triethylamine In dichloromethane at 20℃; Inert atmosphere;	82%

1H-pyrazole-4-carbonitrile (31108-57-3) → 4-cyano-N-nitropyrazole

Conditions	Yield
With Iron(III) nitrate nonahydrate; tetrabutylammonium tetrafluoroborate In acetonitrile at 70℃; Inert atmosphere; Electrolysis; Green chemistry;	80%

C30H44O5S + 1H-pyrazole-4-carbonitrile (31108-57-3) → 1-((3-((3R,5R,8R,9R,10S,13S,14S,17S)-3-hydroxy-3,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)oxetan-3-yl)methyl)-1H-pyrazole-4-carbonitrile

Conditions	Yield
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 80℃; for 16h;	79%

Upstream product

• 149139-41-3 α-cyano-β-dimethylaminoacrolein 
• 2075-45-8 4-bromo-1H-pyrazole 
• 14904-70-2 [11C]hydrogen cyanide 

Downstream Products

• 18601-58-6 {1-(4-cyano)pyrazolyl}borane 
• 1333-74-0 hydrogen 
• 75-50-3 trimethylamine 
• 1144022-92-3 1-[2-cyano-4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]phenyl]-1H-pyrazole-4-carbonitrile 
• 1219601-60-1 C₁₁H₉N₃O₂S 
• 709-04-6 1-phenyl-1H-pyrazole-4-carbonitrile 
• 712-72-1 1-(4-methylphenyl)-1H-pyrazole-4-carbonitrile 
• 712-39-0 1-(2-methylphenyl)-1H-pyrazole-4-carbonitrile 

Relevant academic research and scientific papers

Virtually instantaneous, room-temperature [11C]-cyanation using biaryl phosphine Pd(0) complexes

A new radiosynthetic protocol for the preparation of [11C]aryl nitriles has been developed. This process is based on the direct reaction of in situ prepared L·Pd(Ar)X complexes (L = biaryl phosphine) with [11C]HCN. The strategy is operationally simple, exhibits a remarkably wide substrate scope with short reaction times, and demonstrates superior reactivity compared to previously reported systems. With this procedure, a variety of [11C]nitrile-containing pharmaceuticals were prepared with high radiochemical efficiency.

A general, practical palladium-catalyzed cyanation of (hetero)aryl chlorides and bromides

Playing it safe: The nontoxic cyanide source K4[Fe(CN) 6]×3 H2O can be used for the cyanation of (hetero)aryl halides. The application of palladacycle catalysts prevents poisoning during catalyst formation, thereby allowing for low catalyst loadings, fast reaction times, and wide heterocyclic substrate scope.

Cyanoacetaldehyde - New Synthetic Applications of an Old Compound Syntheses with Nitriles, XCI

Various reactions of cyanoacetaldehyde (1), freshly prepared by ozonization of (E)-1,4-dicyano-2-butene or allylcyanide, are described.Thus, conversion of 1 with anilines gave β-phenylaminoacrylonitriles 2a-e.Reaction of 1 with hydrazines led to the corresponding hydrazones 3a-e, which could be cyclized under alkaline conditions to 5-aminopyrazoles 4a-d.An aldol-type condensation product 5a could be obtained by reaction of 1 with sodiumphenoxide.Treatment of 1 with dimethylformamide-dimethylacetal led to the formation of (E)-3-dimethylamino-2-formylpropenenitrile (6), a very useful synthon in synthetic chemistry.For the determination of the structure of 6 the method of steady state diffferential NOEs was used.Reaction of 6 with hydrazines gave 1-substituted-4-cyanopyrazoles 7a-k. Keywords.Cyanoacetaldehyde; Hydrazones; Cyanopyrazoles; Aminopyrazoles.