109-77-3

Basic information

• Product Name: Malononitrile
• Synonyms: AKOS BBS-00004370;METHYLENE DICYANIDE;METHYLENE CYANIDE;MALONODINITRILE;MALONITRILE;MALONONITRILE;MALONIC ACID DINITRILE;MDN
• CAS NO: 109-77-3
• Molecular Formula: C₃H₂N₂
• Molecular Weight: 66.06
• EINECS: 203-703-2
• Product Categories: Dinitriles;Dinitriles & Trinitriles;Agrochemicals;Pharmaceutical intermediates
• Mol File: 109-77-3.mol
• Article Data: 74

Chemical Properties

• Melting Point: 30-32 °C(lit.)
• Boiling Point: 220 °C(lit.)
• Flash Point: 234 °F
• Appearance: White to yellow-brown/Crystalline Low Melting Mass
• Density: 1.049 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.125mmHg at 25°C
• Refractive Index: 1.4150
• Storage Temp.: 2-8°C
• Solubility: 133g/l
• PKA: 11(at 25℃)
• Water Solubility: 13.3 g/100 mL (20 ºC)
• Merck: 14,5711
• BRN: 773697
• CAS DataBase Reference: Malononitrile(CAS DataBase Reference)
• NIST Chemistry Reference: Malononitrile(109-77-3)
• EPA Substance Registry System: Malononitrile(109-77-3)

Safety Data

• Hazard Codes: T,N
• Statements: 23/24/25-50/53
• Safety Statements: 23-27-45-60-61
• RIDADR: UN 2647 6.1/PG 2
• WGK Germany: 3
• RTECS: OO3150000
• F: 8
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 109-77-3(Hazardous Substances Data)

Usage

Chemical Description

Different sources of media describe the Chemical Description of 109-77-3 differently. You can refer to the following data:
1. Malononitrile is a compound with the formula CH2(CN)2.
2. Malononitrile is a versatile reagent used in organic synthesis, while the other three chemicals are derivatives synthesized and studied in the article.
3. Malononitrile is a versatile reagent used in organic synthesis.

Description

Malonitrile is an aliphatic nitrile. It can release cyanide through either chemical or biological transformation. Malonitrile was used decades ago for treating certain forms of mental illness.

Chemical Properties

Different sources of media describe the Chemical Properties of 109-77-3 differently. You can refer to the following data:
1. Malononitrile may polymerize violently on prolonged heating at 130°C or at lower temperatures on contact with strong bases.
2. Solidified melt
3. Malononitrile is a white powder or colorless, odorless crystalline substance.

Uses

Different sources of media describe the Uses of 109-77-3 differently. You can refer to the following data:
1. In organic synthesis.
2. Malononitrile is an important building block for the syntheses of pharmaceuticals (e.g. triamterene, adenine and methotrexate), thiamin (vitamin B1), pesticides dyestuffs for color photography and synthetic fibers (e.g. vinylidene cyanide). Product Data Sheet
3. The chemical properties of malononitrile are determined by the nucleophilicity of the malononitrile anion, formed by deprotonation with relatively weak bases and by the two electrophilic cyano groups.
4. Malononitrile is used in organic synthesis.

Definition

ChEBI: A dinitrile that is methane subtituted by two cyano groups.

Production Methods

Malononitrile is prepared by continuous introduction of preheated acetonitrile and cyanogen chloride into a tube reactor until the reaction mixture reaches a temperature of approximately 780°C.

General Description

A white-colored crystalline solid. Denser than water and soluble in water. Toxic by ingestion and may severely irritate skin and eyes. May polymerize violently if exposed to temperatures above 266°F. Used to make other chemicals.

Air & Water Reactions

Soluble in water.

Reactivity Profile

Malononitrile is a white, low-melting powder (m. p. 30.5° C), toxic, combustible. Violent polymerization on contact with strong bases (sodium hydroxide, potassium hydroxide) or when heated above 130° C. When stored at 70-80° C for 2 months, spontaneous explosion (decomposition) occurred [Bretherick, 5th ed., 1995, p. 394].

Hazard

Toxic by ingestion and inhalation.

Health Hazard

Different sources of media describe the Health Hazard of 109-77-3 differently. You can refer to the following data:
1. Metabolized by body to cyanide and thiocyanate; effects of inhalation of toxic fumes will be related to cyanide. Causes brain and heart damage related to lack of cellular oxygen. It is classified as extremely toxic. Probable oral lethal dose for humans is 5-50 mg/kg, or between 7 drops and 1 teaspoonful, for a 70 kg (150 lb.) person.
2. In the late 1940's, malononitrile was used experimentally in the treatment of schizophrenia and depression. Patients were given an iv infusion of 5% malononi-trile for 10-69 min. The total dose during such treatments was 1-6 mg/kg and treatments were given 2-3 times/wk. Ten to twenty min after beginning infusion, all patients experienced tachycardia. In addition, redness, nausea, vomiting, headache, shivering, muscle spasms, and numbness were reported with varying frequency.
3. Malononitrile is a highly toxic compound by all toxic routes. Its acute toxicity is somewhat greater than that of the aliphatic mononitriles, propionitrile, and butyronitrile. The increased toxicity may be attributed to the greater degree of reactivity in the molecule arising from two- CN functional groups. The acute toxic symptoms in test animals have not been well documented. An intraperitoneal dose of 10 mg/kg was lethal to rats. LD50 value, intravenous (rabbits): 28 mg/kg LD50 value, oral (mice): 19 mg/kg Malononitrile is an eye irritant. The irritation from 5 mg in 24 hours was severe in rabbits’ eyes. There is no report of teratogenic and carcinogenic action in animals or humans.

Fire Hazard

When heated to decomposition, Malononitrile emits highly toxic fumes (cyanide). May polymerize violently on prolonged heating. Avoid heat. Hazardous polymerization may occur, at prolonged heating at 266F or contact with strong bases at lower temperatures.

Industrial uses

Malononitrile is used primarily as an intermediate in the synthesis of drugs and vitamins (thiamine). It has also been employed in the manufacture of photosensitizes, acrylic fibers and dyestuffs and as an oil-soluble polar additive in lubricating oil. Malononitrile was used formerly in treatment of various forms of mental illness such as alteration of psychic functions and schizophrenic disorders.

Safety Profile

Poison by ingestion, skin contact, subcutaneous, intravenous, and intraperitoneal routes. A severe eye irritant. Combustible when exposed to heat or flame. Polymerizes violently when heated to 130°C or on contact with strong base. May spontaneously explode when stored at 70-80°C. To fight fire, use water, fog, spray, foam. When heated to decomposition it emits toxic fumes of NOx and CN-. See also NITRILES.

Potential Exposure

Malononitrile is used in organic synthesis; as a lubricating oil additive; for thiamine synthesis; for pteridine-type anticancer agent synthesis; and in the synthesis of photosensitizers, acrylic fibers, and dyestuffs. It has also been used in the treatment of various forms of mental illness. It has been used as a leaching agent for gold

Environmental Fate

When heated to decomposition, nitriles may release cyanide. Malonitrile appears to decompose rapidly in contact with soil and sediment.

Metabolism

The in vitro metabolsim of malononitrile has been described by Stern et al. In the presence of thiosulphate, brain, liver and kidney slices metabolized malononitrile to thiocyanate. The formation of thiocyanate from malononitrile and thiosulphate was greatest in the presence of liver slices, lowest in brain, and intermediate with kidney slices. The liver enzyme system was saturated at a concentration of 3.3 mM malononitrile and a pH optimum of 7.0. This enzyme system was inhibited by cysteine and glutathione and inactivated by boiling. Stern et al indicated that thiosulphate increased cyanide and thiocyanate formed from malononitrile in tissue slices.

Shipping

UN2647 Malononitrile, Hazard Class: 6.1; Labels: 6.1-Poisonous materials. UN3439 Nitriles, solid, toxic, n.o.s., Hazard Class: 6.1; Labels: 6.1-Poisonous materials, Technical Name Required

Purification Methods

Crystallise the nitrile from water, EtOH, *benzene or chloroform. Distil it in a vacuum from, and store over, P2O5. [Bernasconi et al. J Am Chem Soc 107 7692 1985, Gratenhuis J Am Chem Soc 109 8044 1987, Beilstein 2 IV 1892.]

Toxicity evaluation

The acute toxicity of malonitrile and related alkyl nitriles is thought to be due to release of cyanide through metabolism of the parent compound. Signs of acute malonitrile intoxication including dyspnea, ataxia, and convulsions are similar to those noted with acute cyanide intoxication. The onset and duration indicate that these nitriles require metabolism to elicit toxicity. Cyanide and thiocyanate have both been found in urine and blood after malonitrile exposure.

Incompatibilities

Incompatible with strong bases. May polymerize violently on prolonged heating @ 129C, or in contact with strong bases at lower temperatures. Nitriles may polymerize in the presence of metals and some metal compounds. They are incompatible with acids; mixing nitriles with strong oxidizing acids can lead to extremely violent reactions. Nitriles are generally incompatible with other oxidizing agents such as peroxides and epoxides. The combination of bases and nitriles can produce hydrogen cyanide. Nitriles are hydrolyzed in both aqueous acid and base to give carboxylic acids (or salts of carboxylic acids). These reactions generate heat. Peroxides convert nitriles to amides. Nitriles can react vigorously with reducing agents. Acetonitrile and propionitrile are soluble in water, but nitriles higher than propionitrile have low aqueous solubility. They are also insoluble in aqueous acids.

Waste Disposal

Generators of waste containing this contaminant (≥100 kg/mo) must conform to EPA regulations governing storage, transportation, treatment, and waste disposal

Synthetic route

6-hydrazino-1,3-dimethyl-1H-pyrimidine-2,4-dione (123506-40-1) + Benzylidenemalononitrile (2700-22-3) → 1,7-Dihydro-5,7-dimethyl-3-phenyl-4H-pyrazolo<3,4-d>pyrimidin-4,6(5H)-dion (35221-08-0) + Benzylmalononitrile (1867-37-4) + malononitrile (109-77-3)

Conditions	Yield
In propan-1-ol for 2h; Heating;	A 90% B 97% C 90%

6-hydrazino-1,3-dimethyl-1H-pyrimidine-2,4-dione (123506-40-1) + 2-cyano-3-phenylacrylamide (709-79-5) → 1,7-Dihydro-5,7-dimethyl-3-phenyl-4H-pyrazolo<3,4-d>pyrimidin-4,6(5H)-dion (35221-08-0) + Benzylmalononitrile (1867-37-4) + malononitrile (109-77-3)

Conditions	Yield
In propan-1-ol for 2h; Heating;	A 90% B 97% C 90%

6-hydrazino-1,3-dimethyl-1H-pyrimidine-2,4-dione (123506-40-1) + ethyl benzylidenecyanoacetate (2025-40-3) → 1,7-Dihydro-5,7-dimethyl-3-phenyl-4H-pyrazolo<3,4-d>pyrimidin-4,6(5H)-dion (35221-08-0) + Benzylmalononitrile (1867-37-4) + malononitrile (109-77-3)

Conditions	Yield
In propan-1-ol for 2h; Heating;	A 90% B 97% C 90%

sodium cyanide (773837-37-9) + 1,2-dibromomethane (74-95-3) → malononitrile (109-77-3)

Conditions	Yield
With sodium iodide In dimethyl sulfoxide at 150℃; for 15h; Temperature; Sealed tube; Inert atmosphere;	95.14%

potassium cyanide + 1,2-dibromomethane (74-95-3) → malononitrile (109-77-3)

Conditions	Yield
With potassium iodide at 160℃; for 8h; Sealed tube; Inert atmosphere;	95.01%

3-(Chloromethyl)-2-benzoxazolinethione (55042-38-1) + potassium cyanide (151-50-8) → 3-<(2-Benzoxazolyl)thiomethyl>-2(3H)-benzoxazolethione (71528-27-3) + malononitrile (109-77-3)

Conditions	Yield
In acetone for 24h; Product distribution; Mechanism; Heating;	A 95% B n/a

cyanoacetic acid amide (107-91-5) → malononitrile (109-77-3)

Conditions	Yield
With pyridine; phosgene In 1,2-dichloro-ethane at 75℃; for 15h; Solvent; Temperature; Reagent/catalyst;	94%
With phosgene; trichlorophosphate at 70 - 73℃; for 5 - 7h; Temperature;	93.59%
With pyridine; trichlorophosphate In water	76%

phosgene (75-44-5) + cyanoacetic acid amide (107-91-5) → malononitrile (109-77-3)

Conditions	Yield
With pyridine In 1,2-dichloro-ethane at 75℃; for 15h; Reagent/catalyst; Solvent; Temperature;	94%

3-chloromethyl-3H-benzothiazole-2-thione (41526-42-5) + potassium cyanide (151-50-8) → 3-<(2-Benzothiazolyl)thiomethyl>-2(3H)-benzothiazolethione (77860-11-8) + malononitrile (109-77-3)

Conditions	Yield
In acetone for 24h; Product distribution; Mechanism; Heating;	A 92% B n/a

potassium cyanide + dichloromethane (75-09-2) → malononitrile (109-77-3)

Conditions	Yield
With potassium iodide at 155℃; for 12h; Sealed tube; Inert atmosphere;	91.04%

2-(N-morpholinyl)methyl-4-nitrophenol (69245-79-0) → 4-amino-2-morpholinomethylphenol (76226-59-0) + malononitrile (109-77-3)

Conditions	Yield
With hydrazine hydrate	A 91% B 52%

hydrogen cyanide (74-90-8) + chloroacetonitrile (107-14-2) → malononitrile (109-77-3)

Conditions	Yield
at 160℃; Temperature; Inert atmosphere;	89.53%

sodium cyanide (773837-37-9) + dichloromethane (75-09-2) → malononitrile (109-77-3)

Conditions	Yield
With aluminum (III) chloride; tetrabutylammomium bromide at 90℃; for 8h; Reagent/catalyst;	89%

malonodiamide (108-13-4) → malononitrile (109-77-3)

Conditions	Yield
With phosphorus pentoxide under 15.0015 - 37.5038 Torr; for 1h; Temperature; Heating;	86%
With phosphorus pentaoxide
With phosphorus pentoxide at 250℃; under 15001.5 - 37503.8 Torr; for 1h; Temperature;
under 15.0015 - 37.5038 Torr; for 1h; Temperature; Heating;

bromomalononitrile (1885-22-9) → malononitrile (109-77-3)

Conditions	Yield
With bis(triethylgermyl)mercury In tetrahydrofuran at 20℃; for 0.333333h;	78.3%
With 3-Methyl-2-phenyl-2,3-dihydrobenzothiazoline; tris(2,2'-bipyridyl)ruthenium dichloride In [D3]acetonitrile at 20℃; for 0.7h; Irradiation;

1,3,5-trichloro-2,4,6-triazine (108-77-0) + cyanoacetic acid amide (107-91-5) → isocyanuric acid (108-80-5) + malononitrile (109-77-3)

Conditions	Yield
N,N-dimethyl-formamide In acetonitrile at 50 - 60℃; for 11 - 12h;	A n/a B 67%
N,N-dimethyl-formamide In tetrahydrofuran at 50 - 60℃; for 11 - 12h;	A n/a B 53%
N,N-dimethyl-formamide In 1,4-dioxane at 50 - 60℃; for 11 - 12h;	A n/a B 44%

octyl 2-cyanoacetate (15666-97-4) + ethenetetracarbonitrile (670-54-2) → n-Octyl tricyanoacrylate + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran at 65℃; for 0.75h;	A 63% B n/a

1,3,5-trichloro-2,4,6-triazine (108-77-0) + cyanoacetic acid amide (107-91-5) → malononitrile (109-77-3)

Conditions	Yield
N,N-dimethyl-formamide In ethyl acetate at 50 - 60℃; for 11 - 12h;	52%

benzyl 2-cyanoacetate (14447-18-8) + ethenetetracarbonitrile (670-54-2) → Benzyl tricyanoacrylate + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran at 65℃; for 0.75h;	A 48% B n/a

aniline hydroiodide (45497-73-2) + Hexacyanocyclopropane (139952-06-0) → anilino-ethenetricarbonitrile (41996-49-0) + malononitrile (109-77-3)

Conditions	Yield
In ethyl acetate at 40℃; Mechanism; other amine hydroiodides, reaction time 3-5 min;	A 46% B n/a

cyanoacetic acid tert-butyl ester (1116-98-9) + ethenetetracarbonitrile (670-54-2) → tert-butyl tricyanoethylenecarboxylate (833447-41-9) + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran for 40h; Michael addition; Reflux;	A 41% B n/a

cyanoacetic acid n-propyl ester (14447-15-5) + ethenetetracarbonitrile (670-54-2) → n-Propyl tricyanoacrylate + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran at 65℃; for 0.75h;	A 38% B n/a

allyl cyanoacetate (13361-32-5) + ethenetetracarbonitrile (670-54-2) → allyl tricyanoethylenecarboxylate (1142329-69-8) + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran for 40h; Michael addition; Reflux;	A 26% B n/a

9-Cyano-10-methyl-10-thiaanthracene (59181-71-4) + ethenetetracarbonitrile (670-54-2) → 9-Cyano-9-methylthioxanthene (59181-21-4) + 9-Cyano-9-(dicyanomethyl)thioxanthene (59215-71-3) + thio-xanthene-9-one (492-22-8) + 2,2,3,3-Tetracyanobutane (66223-43-6) + malononitrile (109-77-3)

Conditions	Yield
In tetrahydrofuran Mechanism;	A 8.5% B 11% C 13% D 24% E 120 mg

ethenetetracarbonitrile (670-54-2) + ethyl 2-cyanoacetate (105-56-6) → ethyl tricyanoethylenecarboxylate (153814-39-2) + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran at 65℃; for 0.75h;	A 22% B n/a
With pyridine In tetrahydrofuran for 40h; Michael addition; Reflux;	A 14% B n/a

ethenetetracarbonitrile (670-54-2) + methyl 2-cyanoacetate (105-34-0) → methyl tricyanoethylenecarboxylate (101342-43-2) + malononitrile (109-77-3)

Conditions	Yield
With pyridine In tetrahydrofuran for 40h; Michael addition; Reflux;	A 4% B n/a

acrylonitrile (107-13-1) → malononitrile (109-77-3)

Conditions	Yield
durch Copolymerisation(Herstellung);

acetonitrile (75-05-8) + cyanogen chloride (506-77-4) → malononitrile (109-77-3)

Conditions	Yield
With carbon dioxide at 650℃;

(phenylsulfonyl)phosphorimidic trichloride (5666-55-7) + malonoyl dichloride (1663-67-8) → malononitrile (109-77-3)

Conditions	Yield
at 130℃;

furfural (98-01-1) + malononitrile (109-77-3) → 2-cyano-3-(2-furanyl)acrylonitrile (3237-22-7)

Conditions	Yield
With 1-butyl-1,4-diazabicyclo[2.2.2]octanylium hydrotetrafluoroborate In water at 20℃; for 0.0166667h; Knoevenagel condensation;	100%
With 1,4-diaza-bicyclo[2.2.2]octane In water at 20℃; for 0.0166667h; Knoevenagel Condensation; Green chemistry;	100%
With hydroquinone; p-benzoquinone In water at 20℃; for 3h; Reagent/catalyst; Knoevenagel Condensation; Inert atmosphere; Sealed tube;	100%

piperonal (120-57-0) + malononitrile (109-77-3) → 2-benzo[1,3]dioxol-5-ylmethylene-malononitrile (2972-82-9)

Conditions	Yield
In ethanol; water at 75℃; for 0.166667h; Knoevenagel Condensation;	100%
With strong base anion-exchange resin In water at 20℃; for 1.4h; Knoevenagel condensation;	98%
With antimony(III) chloride for 0.0666667h; Knoevenagel condensation; microwave irradiation;	96%

cyclohexanone (108-94-1) + malononitrile (109-77-3) → 2-(cyclohexylidene)malononitrile (4354-73-8)

Conditions	Yield
hydrotalcite structure integrating fluoride ions In DMF (N,N-dimethyl-formamide) at 25℃; for 2h; Conversion of starting material; Knoevenagel Condensation;	100%
With 1-butyl-1,4-diazabicyclo[2.2.2]octanylium hydrotetrafluoroborate In water at 20℃; for 0.0333333h; Knoevenagel condensation;	100%
Ru(+)Cp*(NCCHCO2Et)(-)*(PPh3)2 In tetrahydrofuran at 25℃; for 5h; Condensation; Aldol reaction;	99%

4-chlorobenzaldehyde (104-88-1) + malononitrile (109-77-3) → 4-chlorobenzylidenemalonodinitrile (1867-38-5)

Conditions	Yield
at 150℃; for 1h; Knoevenagel condensation;	100%
hydrotalcite structure integrating fluoride ions In DMF (N,N-dimethyl-formamide) at 25℃; for 0.25h; Conversion of starting material; Knoevenagel Condensation;	100%
With 1-butyl-1,4-diazabicyclo[2.2.2]octanylium hydrotetrafluoroborate In water at 20℃; for 0.0333333h; Knoevenagel condensation;	100%

2-chloro-benzaldehyde (89-98-5) + malononitrile (109-77-3) → o-chlorobenzylidene malononitrile (2698-41-1)

Conditions	Yield
With poly(4-vinylpyridine) supported on MCM-48 at 25℃; for 0.133333h; Knoevenagel condensation; neat (no solvent);	100%
Stage #1: malononitrile; piperidine In water at 20 - 30℃; Stage #2: 2-chloro-benzaldehyde In water at 50℃; Product distribution / selectivity; Knoevenagel Condensation;	99.5%
In N,N-dimethyl-formamide for 1h; Knoevenagel Condensation;	99.9%

1-naphthaldehyde (66-77-3) + malononitrile (109-77-3) → (1-naphthylmethylidene)malononitrile (2972-83-0)

Conditions	Yield
With aluminum oxide Inert atmosphere; Neat (no solvent);	100%
With 1,4-diaza-bicyclo[2.2.2]octane In water at 20℃; for 0.05h; Knoevenagel Condensation; Green chemistry;	100%
With polystyrene-supported DABCO In methanol at 25℃; for 0.8h; Knoevenagel Condensation; Green chemistry;	99%

3-nitro-benzaldehyde (99-61-6) + malononitrile (109-77-3) → 3-nitrobenzylidenemalononitrile (2826-32-6)

Conditions	Yield
With C7H15N4(1+)*BF4(1-) In water at 20℃; for 0.0166667h; Knoevenagel Condensation; Green chemistry;	100%
With sodium sulfide; aluminum oxide In dichloromethane at 20℃; for 0.0833333h; Knoevenagel reaction;	99%
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 30℃; for 0.25h; Knoevenagel condensation;	99%

4-nitrobenzaldehdye (555-16-8) + malononitrile (109-77-3) → 4-Nitrobenzylidenemalononitrile (2700-23-4)

Conditions	Yield
at 150℃; for 1h; Knoevenagel condensation;	100%
In various solvent(s) at 20℃; for 3h; Knoevenagel condensation;	100%
hydrotalcite structure integrating fluoride ions In acetonitrile at 25℃; for 1.5h; Conversion of starting material; Knoevenagel Condensation;	100%

benzaldehyde (100-52-7) + malononitrile (109-77-3) → Benzylidenemalononitrile (2700-22-3)

Conditions	Yield
With calcite grains for 0.5h; Product distribution; Further Variations:; Reagents; Knoevenagel condensation; ball-milling conditions;	100%
at 150℃; for 1h; Knoevenagel condensation;	100%
With 3-(1-piperazino)propyl functionalised silica gel In acetonitrile Knoevenagel condensation;	100%

4-hydroxy-benzaldehyde (123-08-0) + malononitrile (109-77-3) → 2-(4-hydroxyphenylmethylene)malononitrile (3785-90-8)

Conditions	Yield
at 150℃; for 1h; Knoevenagel condensation;	100%
hydrotalcite structure integrating fluoride ions In acetonitrile at 25℃; for 1.5h; Conversion of starting material; Knoevenagel Condensation;	100%
With polymer supported poly(propylene imine)dendrimer In ethanol at 20℃; for 0.166667h; Knoevenagel Condensation; Green chemistry;	100%

4-methoxy-benzaldehyde (123-11-5) + malononitrile (109-77-3) → 2-(4-methoxyphenylmethylene)malononitrile (2826-26-8)

Conditions	Yield
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 30℃; for 0.25h; Knoevenagel condensation;	100%
With [3-(3-silica-supported-propyl)-1-(2,4,6-trimethylphenyl)-1H-imidazol-3-ium iodide]*10SiO2 at 100℃; for 16h; Knoevenagel condensation;	100%
With ethylenediamine-modified poly(vinyl chloride) at 20℃; for 0.05h; Solvent; Knoevenagel Condensation; Green chemistry;	100%

vanillin (121-33-5) + malononitrile (109-77-3) → 2-(4-hydroxy-3-methoxybenzylidene)malononitrile (3696-12-6)

Conditions	Yield
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 30℃; for 0.333333h; Knoevenagel condensation;	100%
With polymer supported poly(propylene imine)dendrimer In ethanol at 20℃; for 0.0833333h; Knoevenagel Condensation; Green chemistry;	99%
With Zn(1+)*C5H8NO2(1-) In water at 80℃; for 0.166667h; Knoevenagel Condensation;	99%

3,4-dimethoxy-benzaldehyde (120-14-9) + malononitrile (109-77-3) → 3,4-dimethoxybenzylidenemalononitrile (2972-80-7)

Conditions	Yield
With polymer supported poly(propylene imine)dendrimer In ethanol at 20℃; for 0.0833333h; Knoevenagel Condensation; Green chemistry;	100%
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 30℃; for 0.333333h; Knoevenagel condensation;	99%
With antimony(III) chloride for 0.0416667h; Knoevenagel condensation; microwave irradiation;	97%

acrylonitrile (107-13-1) + malononitrile (109-77-3) → 4,4-dicyano-heptanedinitrile (63877-68-9)

Conditions	Yield
With 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane hydroxide at 20℃; for 0.0166667h; Michael Addition; Green chemistry;	100%
With 1-butyl-3-methylimidazolium hydroxide at 20℃; for 1h; Michael addition;	96%
With tetra(n-butyl)ammonium hydroxide In N,N-dimethyl-formamide for 3h; electrolysis;	95%

acetophenone (98-86-2) + malononitrile (109-77-3) → 2-(1-phenylethylidene)propanedinitrile (5447-87-0)

Conditions	Yield
With ethylenediamine-modified poly(vinyl chloride) at 20℃; for 0.116667h; Solvent; Knoevenagel Condensation; Green chemistry;	100%
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 50℃; for 0.5h; Knoevenagel condensation;	98%
With MIL-53(Fe) metal organic framework encapsulated on silica-coated nickel ferrite magnetic nanoparticles In ethanol at 20℃; for 2h; Knoevenagel Condensation;	95%

ortho-anisaldehyde (135-02-4) + malononitrile (109-77-3) → 2-(2-methoxybenzylidene)malononitrile (2834-10-8)

Conditions	Yield
hydrotalcite structure integrating fluoride ions In DMF (N,N-dimethyl-formamide) at 25℃; for 0.25h; Conversion of starting material; Knoevenagel Condensation;	100%
With polyacrylonitrile fiber functionalized with N,N-dimethyl-1,3-propanediamine In ethanol at 20℃; for 1h; Knoevenagel condensation;	99%
With polyacrylonitrile fiber modified with triethylenetetramine In water at 20℃; for 1.5h; Knoevenagel condensation;	99%

4-dimethylamino-benzaldehyde (100-10-7) + malononitrile (109-77-3) → p-(N-dimethylamino benzylidene) malononitrile (2826-28-0)

Conditions	Yield
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 30℃; for 0.333333h; Knoevenagel condensation;	100%
With polymer supported poly(propylene imine)dendrimer In ethanol at 20℃; for 0.0833333h; Knoevenagel Condensation; Green chemistry;	100%
With potassium hydrogen phthalate In water at 20℃; for 0.116667h; Knoevenagel Condensation; Green chemistry;	99%

3,4-dihydronaphthalene-1(2H)-one (529-34-0) + malononitrile (109-77-3) → 1,2,3,4-tetrahydro-1-naphthylidene malononitrile (2510-03-4)

Conditions	Yield
With aluminum oxide Inert atmosphere; Neat (no solvent);	100%
With ammonium acetate; acetic acid In toluene for 10h; Reflux; Dean-Stark;	93%
With 1-butyl-3-methylimidazolium hydroxide at 25 - 30℃; for 0.666667h; Knoevenagel condensation;	89%

2-nitro-benzaldehyde (552-89-6) + malononitrile (109-77-3) → 2-(2-nitrobenzylidene)malononitrile (2826-30-4)

Conditions	Yield
With Fe3O4(at)SiO2-N1-(3-trimethoxysilylpropyl)diethylenetriamine nanoparticles catalyst In toluene at 75℃; for 0.75h; Solvent; Knoevenagel Condensation;	100%
With hydroquinone; p-benzoquinone In water at 20℃; for 3h; Knoevenagel Condensation; Inert atmosphere; Sealed tube;	100%
With Zr(IV)-salen-MCM-41 In water at 35℃; for 0.5h; Catalytic behavior; Solvent; Knoevenagel Condensation;	99%

Benzophenone imine (1013-88-3) + malononitrile (109-77-3) → 2-(diphenylmethylene)malononitrile (10394-96-4)

Conditions	Yield
at 20℃; for 0.0833333h; Inert atmosphere; Neat (no solvent);	100%
With ammonium acetate; acetic acid In tetrahydrofuran at 20℃; for 1.08333h; Dean-Stark; Schlenk technique; Inert atmosphere;	85%

m-bromobenzoic aldehyde (3132-99-8) + malononitrile (109-77-3) → 2-(3-bromobenzylidene)malononitrile (2972-74-9)

Conditions	Yield
With glycine In dichloromethane	100%
With ethanolamine-phosphoric acid functionalized polyacrylonitrile fibers, hydrophobized with benzylamine (Bn-PANEAPF) In water at 20℃; for 2h; Knoevenagel Condensation; Green chemistry;	99%
In various solvent(s) at 50℃; for 3h; Knoevenagel condensation;	98%

9-fluorenone (486-25-9) + malononitrile (109-77-3) → 2-fluoren-9-ylidene-malononitrile (1989-32-8)

Conditions	Yield
for 0.0833333h; Inert atmosphere; Neat (no solvent);	100%
With piperidine In ethanol at 20℃; for 0.5h; Knoevenagel condensation;	87%
With ethanol; ammonia

malononitrile (109-77-3) + cyanogen chloride (506-77-4) → sodium tricyanomethanide (36603-80-2)

Conditions	Yield
With phosphoric acid; sodium hydroxide In methanol; water at 25 - 30℃; for 3.5h; pH=7.0 - 7.2; Product distribution / selectivity;	100%
With ethanol; sodium

4-methyl-benzaldehyde (104-87-0) + malononitrile (109-77-3) → 2-(4-methylbenzylidene)malononitrile (2826-25-7)

Conditions	Yield
With L-arginine at 20℃; for 0.0833333h; Knoevenagel condensation; Ionic liquid;	100%
With 1,4-diaza-bicyclo[2.2.2]octane In water at 20℃; for 0.0333333h; Knoevenagel Condensation; Green chemistry;	100%
With 2C9H3O6(3-)*2C27H18N6*3Ni(2+)*15H2O*5C2H6O In dichloromethane at 60℃; for 2h; Knoevenagel Condensation; Inert atmosphere;	100%

benzyl bromide (100-39-0) + malononitrile (109-77-3) → 2,2-dibenzylmalononitrile (3779-31-5)

Conditions	Yield
With potassium carbonate; tetrabutylammomium bromide for 96h; Ambient temperature;	100%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 80℃; for 2h;	91%
With 1-butyl-3-methylimidazolium hydroxide at 100℃; under 51.7148 Torr; for 0.0833333h; microwave irradiation;	82%

4-fluorobenzaldehyde (459-57-4) + malononitrile (109-77-3) → 4-fluorobenzylidenemalononitrile (2826-22-4)

Conditions	Yield
With 1-(3-silica-supported propyl)-3-[(3-{[1-(3-silica-supported propyl)-4,5-dihydro-1H-imidazol-3-ium-3-yl]methyl}-2,4,6-trimethylphenyl)methyl]-4,5-dihydro-1H-imidazol-3-ium chloride at 100℃; for 4h; Knoevenagel condensation;	100%
With 2C9H3O6(3-)*2C27H18N6*3Ni(2+)*15H2O*5C2H6O In dichloromethane at 60℃; for 2h; Knoevenagel Condensation; Inert atmosphere;	100%
With N,N-dimethyl-N-hydroxyethylammonium acetate at 20℃; for 0.0333333h; Knoevenagel Condensation;	99%

benzil (134-81-6) + malononitrile (109-77-3) → 2-(2-oxo-1,2-diphenylethylidene)malononitrile (23195-86-0)

Conditions	Yield
With third generation polystyrene supported poly(amidoamine) dendrimer In ethanol at 50℃; for 2h; Knoevenagel condensation;	100%
With N,N-dimethyl-aniline In ethanol
With potassium carbonate In ethanol for 8h; Reflux;

4-methoxycinnamaldehyde (1963-36-6) + malononitrile (109-77-3) → 4-(4-methoxyphenyl)-1,1-dicyano-1,3-butadiene (122055-54-3)

Conditions	Yield
With L-arginine at 20℃; for 0.0666667h; Knoevenagel condensation; Ionic liquid;	100%
With piperidine
Knoevenagel Condensation; Alkaline conditions;

dipentyl ketone (927-49-1) + malononitrile (109-77-3) → 2-(1-pentyl-hexylidene)-malononitrile (13017-59-9)

Conditions	Yield
	100%
With 5% active carbon-supported ruthenium In ethanol at 78℃; for 18h;	94.7%
With ammonium acetate; acetic acid

carbon disulfide (75-15-0) + malononitrile (109-77-3) + methyl iodide (74-88-4) → [Bis(methylthio)methylene]malononitrile (5147-80-8)

Conditions	Yield
With potassium carbonate; tetrabutylammomium bromide In benzene at 60℃; for 3h;	100%
Stage #1: malononitrile With potassium carbonate In dimethyl sulfoxide at 20℃; for 0.166667h; Large scale reaction; Stage #2: carbon disulfide In dimethyl sulfoxide at 0 - 22℃; for 0.5h; Large scale reaction; Stage #3: methyl iodide In dimethyl sulfoxide at 5 - 20℃; Large scale reaction;	99%
Stage #1: carbon disulfide; malononitrile With potassium carbonate In dimethyl sulfoxide at 0 - 20℃; for 2h; Stage #2: methyl iodide In dimethyl sulfoxide at 0 - 20℃; for 12h;	93.9%

Upstream product

• 1300-21-6 Dichloroethane 
• 107-91-5 2-Cyanoacetamide 
• 7647-14-5 Sodium chloride 
• 10025-87-3 Phosphorus oxychloride 
• 105-56-6 Ethyl cyanoacetate 

Downstream Products

• 117620-77-6 3-CYANO-7-ETHOXYCOUMARIN 
• 37578-06-6 2-AMINO-6-METHYL-4,5,6,7-TETRAHYDROTHIENO[2,3-C]PYRIDINE-3-CARBONITRILE 
• 70291-62-2 2-AMINO-5,6-DIHYDRO-4H-CYCLOPENTA[B]THIOPHENE-3-CARBONITRILE 
• 13229-92-0 3-CYANO-7-METHOXYCOUMARIN 
• 51768-01-5 2-AMINO-6-CHLORO-3,5-DICYANOPYRIDINE 
• 105184-38-1 3,5-Difluorophenylacetic acid 
• 51516-67-7 5-AMINO-1-(4-CHLOROPHENYL)-1H-PYRAZOLE-4-CARBONITRILE 
• 104366-23-6 2-AMINO-3-CYANO-4-CHLORO-5-FORMYLTHIOPHENE 
• 18588-61-9 2,4-DIAMINOPYRIMIDINE-5-CARBOXYLIC ACID 
• 1004-39-3 4,6-DIAMINO-2-MERCAPTOPYRIMIDINE 
• 52372-39-1 Solvent Red 197 
• 1004-38-2 2,4,6-Triaminopyrimidine 
• 78473-10-6 2-AMINO-3,5-DICYANOPYRIDINE 
• 128-97-2 1,4,5,8-Naphthalenetetracarboxylic acid 
• 1005-39-6 4,6-DIAMINO-2-METHYLMERCAPTOPYRIMIDINE 
• 120162-55-2 Azimsulfuron 
• 141505-33-1 Levosimendan 
• 16115-08-5 4,6-Dimethyl-2-hydroxypyridine 
• 16357-69-0 4-AMINOPYRIMIDINE-5-CARBONITRILE 
• 16462-27-4 2,4-DIAMINOPYRIMIDINE-5-CARBONITRILE 
• 24517-64-4 2-Amino-3-cyanopyridine 
• 28448-11-5 2-AMINO-4-METHYL-QUINOLINE-3-CARBONITRILE 
• 3335-44-2 2-OXO-6-PHENYL-4-(TRIFLUOROMETHYL)-1,2-DIHYDRO-3-PYRIDINECARBONITRILE 
• 42225-04-7 2-AMINO-6-METHYL-4,5,6,7-TETRAHYDRO-1-BENZOTHIOPHENE-3-CARBONITRILE 
• 4651-91-6 2-AMINO-4,5,6,7-TETRAHYDRO-1-BENZOTHIOPHENE-3-CARBONITRILE 
• 5334-43-0 5-AMINO-1-PHENYLPYRAZOLE-4-CARBONITRILE 
• 5345-47-1 2-Aminonicotinic acid 
• 61320-65-8 2-AMINO-3-CYANO-4-METHYL-5-CARBMETHOXY THIOPHENE 
• 74239-96-6 [2-[4-(dihexylamino)-2-methylbenzylidene]benzo[b]thien-3(2H)-ylidene]malononitrile S,S-dioxide 
• 770-30-9 4-AMINO-2-(METHYLTHIO)PYRIMIDINE-5-CARBONITRILE 
• 77651-38-8 2-AMINO-5,6-DIHYDRO-4H-CYCLOPENTA[B]THIOPHENE-3-CARBOXAMIDE 

Recommend Products

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• 64-17-5  ethanol 
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• 13166-10-4  isopropylidenemalonodinitrile 
• 67-64-1  acetone 
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