5098-14-6

Basic information

• Product Name: AMINOMALONONITRILE P-TOLUENESULFONATE
• Synonyms: DICYANOMETHYLAMMONIUM P-TOLUENESULFONATE;2-AMINOMALONONITRILE-4-METHYLBENZENESULFONATE;AMINOMALONONITRILE 4-TOLUENESULFONATE;AMINOMALONONITRILE P-TOLUENESULFONATE;AMINOMALONONITRILE P-TOLUENESULFONIC ACID;AMINOMALONONITRILE P-TOLUENESULFUNIC ACID;AMINOMALONONITRILE P-TOLUENESULPHONATE;AMINOMALONONITRILE TOSYLATE
• CAS NO: 5098-14-6
• Molecular Formula: C₃H₃N₃*C₇H₈O₃S
• Molecular Weight: 253.28
• EINECS: 225-817-1
• Product Categories: Aromatic Esters;C1 to C5;Cyanides/Nitriles;Nitrogen Compounds;Building Blocks;C1 to C5;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks
• Mol File: 5098-14-6.mol
• Article Data: 3

Chemical Properties

• Melting Point: 174 °C (dec.)(lit.)
• Boiling Point: 484°Cat760mmHg
• Flash Point: 246.5°C
• Appearance: /
• Density: g/cm³
• Vapor Pressure: 3.51E-10mmHg at 25°C
• Storage Temp.: 0-10°C
• Water Solubility: almost transparency
• Stability: Hygroscopic
• BRN: 4050747
• CAS DataBase Reference: AMINOMALONONITRILE P-TOLUENESULFONATE(CAS DataBase Reference)
• NIST Chemistry Reference: AMINOMALONONITRILE P-TOLUENESULFONATE(5098-14-6)
• EPA Substance Registry System: AMINOMALONONITRILE P-TOLUENESULFONATE(5098-14-6)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22
• Safety Statements: 36
• RIDADR: 3439
• WGK Germany: 3
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 5098-14-6(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 5098-14-6 differently. You can refer to the following data:
1. Aminomalononitrile p-toluenesulfonate was used in the syntheiss of 1-substituted 5-amino-4-cyano-2-hydroxyimidazoles.
2. Aminomalononitrile p-toluenesulfonate is a reagent for diazonamide synthesis via heck endocyclization. It may also have implications for developing IκB Kinase-β inhibitors.

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

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

Downstream Products

• 76054-98-3 5-amino-4-cyano-1-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)imidazole 
• 126210-92-2 (E)-3-Amino-3-methoxy-2-{[1-(2-nitro-phenyl)-meth-(E)-ylidene]-amino}-acrylonitrile 
• 417942-76-8 5-amino-4-cyano-1-(2,5-difluorobenzyl)-2-hydroxyimidazole 
• 226908-37-8 5-amino-4-cyano-1-(4-fluorobenzyl)-2-hydroxyimidazole 
• 226908-19-6 5-amino-1-benzyl-4-cyano-2-hydroxyimidazole 
• 655253-56-8 5-amino-2-(1-methyl-4-phenyl-1H-imidazol-5-yl)-1,3-oxazole-4-carbonitrile 
• 836684-66-3 3-(5-amino-4-cyano-imidazol-1-yl)-N-cyclopropyl-4-methyl-benzamide 
• 19994-56-0 2-Amino-3-cyano-5-methylpyrazine 1-oxide 
• 906512-02-5 5-amino-2-(4-cyanophenyl)oxazole-4-carbonitrile 
• 1365531-54-9 2-(4-cyanophenyl)-5-(1H-pyrrol-1-yl)oxazole-4-carbonitrile 
• 196411-04-8 5-amino-2-cyclopropyl-1,3-oxazole-4-carbonitrile 
• 890403-15-3 5-amino-2-cyclohexyloxazole-4-carbonitrile 
• 1465971-36-1 5-amino-2-benzhydryl-4-cyano-1,3-oxazole 
• 5098-18-0 5-amino-2-phenyl[1,3]oxazole-4-carbonitrile 

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