5098-14-6

Usage

Uses

Used in Pharmaceutical Synthesis:
AMINOMALONONITRILE P-TOLUENESULFONATE is used as a reagent for the synthesis of 1-substituted 5-amino-4-cyano-2-hydroxyimidazoles, which are important intermediates in the development of pharmaceutical compounds. Its role in this synthesis process is crucial for creating new and potentially effective drugs.
Used in Organic Chemistry Research:
In the field of organic chemistry, AMINOMALONONITRILE P-TOLUENESULFONATE is used as a reagent for diazonamide synthesis via heck endocyclization. This application highlights its versatility and utility in creating complex organic molecules, which can be further explored for their potential applications in various industries.
Used in Drug Development:
AMINOMALONONITRILE P-TOLUENESULFONATE may have implications for developing IκB Kinase-β inhibitors. This suggests that the compound could play a role in the creation of new drugs targeting specific biological pathways, potentially leading to treatments for various diseases and conditions.
Overall, AMINOMALONONITRILE P-TOLUENESULFONATE is a versatile reagent with applications in pharmaceutical synthesis, organic chemistry research, and drug development. Its unique properties and ability to participate in various chemical reactions make it an important tool in the creation of new and innovative compounds.

Purification Methods

It forms colourless crystals on recrystallisation from MeCN (1.8g in 100mL) using activated charcoal. Wash the crystals with dry Et2O and dry them at 25o/1mm. Recovery is ~80%. [Ferris et al. Org Synth Coll Vol V 32 1973.]

InChI:InChI=1/C7H8O3S.C3H3N3/c1-6-2-4-7(5-3-6)11(8,9)10;4-1-3(6)2-5/h2-5H,1H3,(H,8,9,10);3H,6H2

Synthetic route

malononitrile sodium salt + toluene-4-sulfonic acid (104-15-4) → 2-aminomalononitrile p-toluenesulfonate (5098-14-6)

Conditions	Yield
With mesitylenesulfonylhydroxylamine 1.) THF, 0 deg C, 2.5 h; 2.) 0 deg C, 1 h; Yield given. Multistep reaction;

malononitrile (109-77-3) → 2-aminomalononitrile p-toluenesulfonate (5098-14-6)

Conditions	Yield
With O-(diphenylphosphinyl)hydroxylamine; sodium hydride 1.) THF, room temp., 1 h, 2.) THF, -78 deg C, 2 h, room temp.; Yield given. Multistep reaction;

2-(hydroxyimino)malononitrile (36568-05-5) + malononitrile (109-77-3) → 2-aminomalononitrile p-toluenesulfonate (5098-14-6)

Conditions	Yield
With sulfuric acid; toluene-4-sulfonic acid; acetic acid; sodium nitrite; Pt/C In water; toluene

methanol (67-56-1) + 2-chloro-benzaldehyde (89-98-5) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → (E)-3-Amino-2-{[1-(2-chloro-phenyl)-meth-(E)-ylidene]-amino}-3-methoxy-acrylonitrile (126210-91-1)

Conditions	Yield
With sodium acetate at 22 - 24℃; for 6h;	99%

methanol (67-56-1) + 4-nitrobenzaldehdye (555-16-8) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → (E,E)-4-amino-3-cyano-4-methoxy-1-(4-nitrophenyl)-2-aza-1,3-butadiene (126210-93-3)

Conditions	Yield
With sodium acetate at 22 - 24℃; for 13h;	99%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 4-Chlorophenyl isothiocyanate (2131-55-7) → 5-amino-2-<(4-chlorophenyl)amino>-4-cyanothiazole (134312-08-6)

Conditions	Yield
With 1-methyl-pyrrolidin-2-one at 22 - 24℃; for 20h;	96%
With 1-methyl-pyrrolidin-2-one at 22 - 24℃;	58%

4-fluorobenzoyl chloride (403-43-0) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-2-(4-fluorophenyl)oxazole-4-carbonitrile (958633-52-8)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; Microwave irradiation;	96%
In 1-methyl-pyrrolidin-2-one at 20℃; for 144h;	53%

oxo-phenyl-acetaldehyde oxime (532-54-7) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 2-amino-3-cyano-5-phenylpyrazine-1-N-oxide (50627-20-8)

Conditions	Yield
In isopropyl alcohol at 20℃; for 48h; Inert atmosphere;	95%
With toluene-4-sulfonic acid In isopropyl alcohol for 5h; Ambient temperature; Yield given;

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + benzoyl chloride (98-88-4) → 5-amino-2-phenyl[1,3]oxazole-4-carbonitrile (5098-18-0)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; Microwave irradiation;	95%
In various solvent(s) at 23 - 25℃;	93%
In 1-methyl-pyrrolidin-2-one at 20℃; for 12h;	79%
In 1-methyl-pyrrolidin-2-one at 20℃; for 192h;	57%
In 1-methyl-pyrrolidin-2-one at 20℃;

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 4-nitro-benzoyl chloride (122-04-3) → 2-(4-nitrophenyl)-5-amino-4-cyano-1,3-oxazole (53657-73-1)

Conditions	Yield
In various solvent(s) at 23 - 25℃;	95%
In 1-methyl-pyrrolidin-2-one at 20℃; for 168h;	90%

4-cyanobenzoyl chlorIde (6068-72-0) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-2-(4-cyanophenyl)oxazole-4-carbonitrile (906512-02-5)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; Microwave irradiation;	95%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 4-methoxy-benzoyl chloride (100-07-2) → 5-amino-2-(4-methoxyphenyl)[1,3]oxazole-4-carbonitrile (53657-71-9)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; Microwave irradiation;	94%
In various solvent(s) at 23 - 25℃;	51%
In 1-methyl-pyrrolidin-2-one at 20℃; for 12h;	51%
In 1-methyl-pyrrolidin-2-one at 20℃;

2-Thiophenecarbonyl chloride (5271-67-0) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-2-(thiophen-2-yl)oxazole-4-carbonitrile (909077-40-3)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; Microwave irradiation;	94%
In 1-methyl-pyrrolidin-2-one at 20℃; for 144h;	6%

(E)-2-(furan-2-yl)-2-oxoacetaldehyde oxime (67867-33-8) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 2-amino-3-cyano-5-(furan-2-yl)pyrazine 1-oxide (120930-04-3)

Conditions	Yield
In isopropyl alcohol at 20℃; for 70h;	92%
In isopropyl alcohol at 20℃; for 70h;	92%
In isopropyl alcohol for 88h; Ambient temperature;	68%

methanol (67-56-1) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) + ortho-bromobenzaldehyde (6630-33-7) → (E)-3-Amino-2-{[1-(2-bromo-phenyl)-meth-(E)-ylidene]-amino}-3-methoxy-acrylonitrile (126249-12-5)

Conditions	Yield
With sodium acetate at 22 - 24℃; for 3h;	92%

bis(trichloromethyl) carbonate (32315-10-9) + 2,5-difluorobenzylamine (85118-06-5) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-4-cyano-1-(2,5-difluorobenzyl)-2-hydroxyimidazole (417942-76-8)

Conditions	Yield
Stage #1: bis(trichloromethyl) carbonate; 2,5-difluorobenzylamine With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at -78℃; Stage #2: 2-aminomalononitrile p-toluenesulfonate With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 24h;	92%

diphenylacetic acid chloride (1871-76-7) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-2-benzhydryl-4-cyano-1,3-oxazole (1465971-36-1)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 20℃;	92%

(S)-N-carbobenzoxy-tert-butylleucine (62965-10-0) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → benzyl (S)-(1-(4-amino-5-cyanooxazol-2-yl)-2,2-dimethylpropyl)carbamate

Conditions	Yield
With pyridine; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride at 20℃; for 18h;	92%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 4-fluorobenzylisocyanate (132740-43-3) → 5-amino-4-cyano-1-(4-fluorobenzyl)-2-hydroxyimidazole (226908-37-8)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran; ethyl acetate	89%
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 24h;

diethylphosphonoacetic acid (3095-95-2) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → O,O-diethyl {2-[5-amino-4-cyano-2-(1,3-oxazolyl)methyl]}phosphonate

Conditions	Yield
With dicyclohexyl-carbodiimide In pyridine	86%

Benzyl isothiocyanate (622-78-6) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-2-(benzylamino)-1,3-thiazole-4-carbonitrile (624737-93-5)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 40℃; for 72h;	86%
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20 - 40℃; for 72h; Inert atmosphere;	68%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + benzyl isothiocyanate (3173-56-6) → 5-amino-1-benzyl-4-cyano-2-hydroxyimidazole (226908-19-6)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 24h;	85%
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 24h;
With sodium hydroxide; N-ethyl-N,N-diisopropylamine In tetrahydrofuran; ethyl acetate	106%

4,5-dicyano-2-pentylimidazole (177348-43-5) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 1-Amino-2-methyl-propan-2-ol (2854-16-2) → 5-amino-1-(2-hydroxy-2-methylpropyl)-2-pentyl-1H-imidazole-4-carbonitrile (1535168-75-2)

Conditions	Yield
Stage #1: 2-aminomalononitrile p-toluenesulfonate With triethylamine In tetrahydrofuran at 25℃; for 0.5h; Stage #2: 4,5-dicyano-2-pentylimidazole In tetrahydrofuran for 3h; Reflux; Stage #3: 1-Amino-2-methyl-propan-2-ol In tetrahydrofuran at 25℃; for 15h;	85%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 4-Methoxyphenyl isothiocyanate (2284-20-0) → 5-amino-4-cyano-2-<(4-methoxyphenyl)amino>thiazole (134312-06-4)

Conditions	Yield
With 1-methyl-pyrrolidin-2-one at 22 - 24℃; for 20h;	83%
With 1-methyl-pyrrolidin-2-one at 22 - 24℃;	55%

triethyl orthovalerate (919-29-9) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 1-Amino-2-methyl-propan-2-ol (2854-16-2) → 5-amino-2-butyl-1-(2-hydroxy-2-methylpropyl)-1H-imidazole-4-carbonitrile (1375262-90-0)

Conditions	Yield
Stage #1: triethyl orthovalerate; 2-aminomalononitrile p-toluenesulfonate With triethylamine In tetrahydrofuran at 25℃; for 5h; Inert atmosphere; Reflux; Stage #2: 1-Amino-2-methyl-propan-2-ol With triethylamine In tetrahydrofuran at 25℃; for 15h; Inert atmosphere;	83%
Stage #1: triethyl orthovalerate; 2-aminomalononitrile p-toluenesulfonate With triethylamine In tetrahydrofuran for 5h; Reflux; Stage #2: 1-Amino-2-methyl-propan-2-ol With triethylamine In tetrahydrofuran at 25℃; for 15h;	83%

pivaloyl chloride (3282-30-2) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 2-(t-butyl)-4-cyano-5-(2,2-dimethylpropanoyl)amino-1,3-oxazole (958633-58-4)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 20℃; for 72h;	82%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + p-nitrophenyl isothiocyanate (2131-61-5) → 5-amino-4-cyano-1-<(4-nitrophenyl)amino>thiazole (134312-09-7)

Conditions	Yield
With 1-methyl-pyrrolidin-2-one at 22 - 24℃;	81%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + methyl vinyl ketone (78-94-4) → 5,5-dicyano-2-methyl-3H-pyrroline

Conditions	Yield
With triethylamine In dichloromethane at 25℃; for 4h;	81%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + cyclopropanecarboxylic acid chloride (4023-34-1) → 5-amino-2-cyclopropyl-1,3-oxazole-4-carbonitrile

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; Microwave irradiation;	81%

2-aminomalononitrile p-toluenesulfonate (5098-14-6) + isobutyryl chloride (79-30-1) → 2-isopropyl-5-amino-4-cyano-1,3-oxazole (124927-63-5)

Conditions	Yield
In various solvent(s) at 23 - 25℃;	80%

methanol (67-56-1) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) + 2-nitro-benzaldehyde (552-89-6) → (E)-3-Amino-3-methoxy-2-{[1-(2-nitro-phenyl)-meth-(E)-ylidene]-amino}-acrylonitrile (126210-92-2)

Conditions	Yield
With sodium acetate at 22 - 24℃; for 72h;	80%

(S)-1-amino-2-propanol (2799-17-9) + trimethyl orthovalerate (13820-09-2) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → (S)-5-amino-2-butyl-1-(2-hydroxypropyl)-1H-imidazole-4-carbonitrile (1535168-78-5)

Conditions	Yield
Stage #1: 2-aminomalononitrile p-toluenesulfonate With triethylamine In tetrahydrofuran at 25℃; for 0.5h; Stage #2: trimethyl orthovalerate In tetrahydrofuran for 3h; Reflux; Stage #3: (S)-1-amino-2-propanol In tetrahydrofuran at 25℃; for 15h;	80%

(2-aminoethyl)methylsulfide (18542-42-2) + trimethyl orthovalerate (13820-09-2) + 2-aminomalononitrile p-toluenesulfonate (5098-14-6) → 5-amino-2-butyl-1-(2-(methylthio)ethyl)-1H-imidazole-4-carbonitrile

Conditions	Yield
Stage #1: 2-aminomalononitrile p-toluenesulfonate With triethylamine In tetrahydrofuran at 25℃; Stage #2: trimethyl orthovalerate In tetrahydrofuran for 3.5h; Reflux; Inert atmosphere; Stage #3: (2-aminoethyl)methylsulfide With triethylamine In tetrahydrofuran at 25℃; for 18h;	78.5%

Upstream product

• 104-15-4 toluene-4-sulfonic acid 
• 109-77-3 malononitrile 
• 36568-05-5 2-(hydroxyimino)malononitrile 

Downstream Products

• 59599-15-4 5'-O-Benzoyl-2-α-D-arabinofuranosyl-4-amino-5-cyano-imidazol 
• 38716-35-7 5-amino-2-(tri-O-benzoyl-β-D-ribofuranosyl)-1(3)H-imidazole-4-carbonitrile 
• 131195-28-3 (E,E)-1-(4-acetoxyphenyl)-4-amino-3-cyano-4-methoxy-2-aza-1,3-butadiene 
• 131195-35-2 2,2,5,5-tetracyano-trans-3,6-bis(4-acetoxyphenyl)piperazine 
• 131195-30-7 (E,E)-4-amino-1-(4-carbomethoxyphenyl)-3-cyano-4-methoxy-2-aza-1,3-butadiene 
• 131195-38-5 2,2,5,5-tetracyano-trans-3,6-bis(4-carbomethoxyphenyl)piperazine 
• 50627-20-8 2-amino-3-cyano-5-phenylpyrazine-1-N-oxide 
• 5098-17-9 2-ethyl-5-amino-4-cyano-1,3-oxazole 
• 126210-91-1 (E)-3-Amino-2-{[1-(2-chloro-phenyl)-meth-(E)-ylidene]-amino}-3-methoxy-acrylonitrile 
• 126210-93-3 (E,E)-4-amino-3-cyano-4-methoxy-1-(4-nitrophenyl)-2-aza-1,3-butadiene 
• 131195-27-2 (E,E)-4-amino-3-cyano-1-(4-ethoxyphenyl)-4-methoxy-2-aza-1,3-butadiene 
• 131195-34-1 2,2,5,5-tetracyano-trans-3,6-bis(4-ethoxyphenyl)piperazine 
• 131557-53-4 5-amino-1-(4-chlorophenyl)-1H-imidazole-4-carbonitrile 
• 131557-54-5 5-Amino-1-(2-chloro-phenyl)-1H-imidazole-4-carbonitrile 

Relevant academic research and scientific papers

Process for the production of aminomalonic acid dinitrile salts

Process for the production of aminomalonic acid dinitrile salts from malonic acid dinitrile by the hydrogenation of its oximation product.

O-(DIPHENYLPHOSPHINYL)HYDROXYLAMINE: A NEW REAGENT FOR ELECTROPHILIC C-AMINATION

O-(Diphenylphosphinyl)hydroxylamine efficiently aminates a variety of stabilised carbanions and certain Grignard reagents.