3473-63-0

Basic information

• Product Name: Formamidine acetate
• Synonyms: IMINOFORMAMIDE ACETATE;FORMAMIDINE ACETATE SALT;FORMAMIDINE,ACETIC ACID;FORMAMIDINE ACETIC ACID SALT;FORMAMIDINE ACETATE;FAA;Methanimidamideacetate;Formamidinium acetate
• CAS NO: 3473-63-0
• Molecular Formula: CH₄N₂*C₂H₄O₂
• Molecular Weight: 104.11
• EINECS: 222-442-5
• Product Categories: Pharmaceutical Intermediates;API
• Mol File: 3473-63-0.mol
• Article Data: 3

Chemical Properties

• Melting Point: 158-161 °C (dec.)(lit.)
• Boiling Point: 117.1 °C at 760 mmHg
• Flash Point: 40 °C
• Appearance: Clear colorless to light yellow/Liquid
• Density: 1.124
• Vapor Pressure: 0.00686mmHg at 25°C
• Storage Temp.: -20°C
• Solubility: 832g/l
• Water Solubility: 832 g/L (21 ºC)
• Sensitive: Hygroscopic
• BRN: 3563488
• CAS DataBase Reference: Formamidine acetate(CAS DataBase Reference)
• NIST Chemistry Reference: Formamidine acetate(3473-63-0)
• EPA Substance Registry System: Formamidine acetate(3473-63-0)

Safety Data

• Hazard Codes: Xi
• Statements: 43-36/37/38
• Safety Statements: 36/37-37/39-26-36/37/39-27
• WGK Germany: 2
• F: 3-9-21
• TSCA: Yes
• Hazardous Substances Data: 3473-63-0(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystalline powder

Uses

Different sources of media describe the Uses of 3473-63-0 differently. You can refer to the following data:
1. Formamidine acetate is used as an intermediate in the synthesis of active pharmaceutical ingredients. It is also used as a condensing agent for the preparation of pyrimidine and imidazole heterocycles.
2. Formamidine acetate salt is widely used in the preparation of formamidinium lead triiodide (FAPbI3) perovskites for perovskite solar cells. It is also used in the synthesis of formamidinium lead bromide nanocrystals for use as emitters in display applications.

Purification Methods

Unlike the hydrochloride, the acetate salt is not hygroscopic. It is recrystallised from a small volume of acetic acid, by addition of EtOH and the crystals are washed with EtOH then Et2O and dried in a vacuum. [Taylor et al. Org Synth 46 39 1966, Beilstein 2 IV 82.]

InChI:InChI=1/C2H4O2.CH4N2/c1-2(3)4;2-1-3/h1H3,(H,3,4);1H,(H3,2,3)/p-1

Synthetic route

orthoformic acid triethyl ester (122-51-0) → formamidine acetic acid (3473-63-0)

Conditions	Yield
With ammonia; acetic acid	80%

CYANAMID (420-04-2) + acetic acid (64-19-7) → formamidine acetic acid (3473-63-0)

Conditions	Yield
With 5%-palladium/activated carbon; hydrogen In water for 3.5h;	63%

acetic acid (64-19-7) + orthoformic acid triethyl ester (122-51-0) → formamidine acetic acid (3473-63-0)

Conditions	Yield
With ammonia Reflux;

C14H13BrN2O2 (951655-39-3) + formamidine acetic acid (3473-63-0) → C15H11BrN2O2 (951655-40-6)

Conditions	Yield
In 2-methoxy-ethanol at 100℃; for 4h;	100%

benzyl N-[4-(3-amino-2-cyano-5,6-dihydro-4H-cyclopenta[b]pyrrol-1-yl)phenyl]carbamate (1402559-18-5) + formamidine acetic acid (3473-63-0) → benzyl N-[4-(4-amino-7,8-dihydro-6H-cyclopenta[2,3]pyrrolo[2,4-d]pyrimidin-5-yl)phenyl]carbamate (1402558-20-6)

Conditions	Yield
In ethanol at 80℃; for 3h;	100%
In ethanol at 80℃; for 1.5h;

formamidine acetic acid (3473-63-0) + ethyl 1-benzyl-3-oxopiperidine-4-carboxylate hydrochloride (52763-21-0) → 7-benzyl-5,6,7,8-tetrahydro-3H-pyrido[3,4-d]pyrimidin-4-one (69981-00-6)

Conditions	Yield
With sodium ethanolate In ethanol for 2.5h; Inert atmosphere; Reflux; Large scale;	100%

2-amino-4-bromo-5-chlorobenzoic acid (150812-32-1) + formamidine acetic acid (3473-63-0) → 4-hydroxy-6-chloro-7-bromo-quinazoline (17518-98-8)

Conditions	Yield
In ethanol for 16h; Reflux;	100%
In ethanol for 16h; Reflux;

benzyl N-[4-(3-amino-2-cyano-5,6-dihydro-4H-cyclopenta[b]pyrrol-1-yl)-2-methoxyphenyl]carbamate + formamidine acetic acid (3473-63-0) → benzyl N-[4-(4-amino-7,8-dihydro-6H-cyclopenta[2,3]pyrrolo[2,4-d]pyrimidin-5-yl)-2-methoxyphenyl]carbamate

Conditions	Yield
In ethanol at 80℃; for 3h; Inert atmosphere;	100%

benzyl N-[4-(3-amino-2-cyano-5,6-dihydro-4H-cyclopenta[b]pyrrol-1-yl)-2-(trifluoromethyl)phenyl]carbamate + formamidine acetic acid (3473-63-0) → benzyl N-[4-(4-amino-7,8-dihydro-6H-cyclopenta[2,3]pyrrolo[2,4-d]pyrimidin-5-yl)-2-(trifluoromethyl)phenyl]carbamate

Conditions	Yield
In ethanol for 4h; Reflux;	100%

benzyl N-[4-(3-amino-2-cyano-5,6-dihydro-4H-cyclopenta[b]pyrrol-1-yl)-2-fluorophenyl]carbamate (1402559-15-2) + formamidine acetic acid (3473-63-0) → benzyl N-[4-(4-amino-7,8-dihydro-6H-cyclopenta[2,3]pyrrolo[2,4-d]pyrimidin-5-yl)-2-fluorophenyl]carbamate (1402558-98-8)

Conditions	Yield
In ethanol at 90℃; for 2.5h; Inert atmosphere;	100%

1-(tert-butyl) 3-methyl (6R)-6-methyl-4-oxopiperidine-1,3-dicarboxylate + formamidine acetic acid (3473-63-0) → tert-butyl (R)-4-hydroxy-7-methyl-7,8-dihydropyrido[4,3-d]pyrimidine-6(5H)-carboxylate

Conditions	Yield
With sodium methylate In methanol at 70℃; for 16h;	100%

4-fluoroanthranilic acid (446-32-2) + formamidine acetic acid (3473-63-0) → 7-fluoro-3,4-dihydroquinazolin-4-one (16499-57-3)

Conditions	Yield
In ethanol for 11h; Time; Reflux;	99.6%
With 2-methoxy-ethanol for 18h; Heating / reflux;	65%
Stage #1: 4-fluoroanthranilic acid; formamidine acetic acid In 2-methoxy-ethanol for 18h; Heating / reflux; Stage #2: With ammonia; water for 1h;	65%

4-fluoroanthranilic acid (446-32-2) + formamidine acetic acid (3473-63-0) → 7-fluoro-3H-quinazolin-4-one (16499-57-3)

Conditions	Yield
In ethanol for 24h;	99%
In ethanol for 24h; Reflux;	96.4%
In ethanol at 80℃; for 24h;	96.4%

formamidine acetic acid (3473-63-0) + 2,5-diamino-4-chloro-6-[1'α,2'β-bis(hydroxymethyl)cyclobutane-1'-yl]methylaminopyrimidine → 2-amino-6-chloro-9-[1'α,2'β-bis(hydroxymethyl)cyclobutane-1'-yl]methylpurine

Conditions	Yield
In butan-1-ol at 135℃; for 10h;	99%

formamidine acetic acid (3473-63-0) + 17-cyclopropylmethyl-7-[(dimethylamino)methylene]-14-hydroxy-4,5α-epoxy-3-methoxymorphinan-6-one (259827-12-8) → 17-cyclopropylmethyl-6,7-dehydro-3-methoxy-14-hydroxy-4,5α-epoxy-6,7:4',5'-pyrimidinomorphinan

Conditions	Yield
With sodium methylate In methanol for 3h; Heating;	99%

formamidine acetic acid (3473-63-0) + 4-(4-amino-5-cyano-1H-pyrrol-3-yl)-2,2-dimethyl-6-methylsulfanylmethyltetrahydro-[1,3]dioxolo[4,5-c]pyrrole-5-carboxylic acid tert-butyl ester (607389-15-1) → 4-(4-amino-5H-pyrrolo[3,2-d]pyrimidin-7-yl)-2,2-dimethyl-6-methylsulfanylmethyltetrahydro-[1,3]dioxolo[4,5-c]pyrrole-5-carboxylic acid tert-butyl ester (741684-59-3)

Conditions	Yield
In ethanol for 20h; Heating;	99%
In ethanol for 20h; Heating / reflux;	99%
In ethanol for 4h; Heating;

4,5-diamino-3-chloro-2-phenylamino-benzoic acid methyl ester (606144-35-8) + formamidine acetic acid (3473-63-0) → 7-chloro-6-phenylamino-3H-benzoimidazole-5-carboxylic acid methyl ester

Conditions	Yield
In ethanol at 80℃; for 44h;	99%
In ethanol at 80℃; for 44h;	99%

2-amino-3-bromo-5-methylbenzoic acid (13091-43-5) + formamidine acetic acid (3473-63-0) → 8-bromo-6-methylquinazolin-4-ol (215115-09-6)

Conditions	Yield
In ethanol at 80℃; for 48h;	99%

4-bromo-N-1-(4-ethoxyphenyl)benzene-1,2-diamine (1038383-44-6) + formamidine acetic acid (3473-63-0) → 5-bromo-1-(4-ethoxyphenyl)-1H-benzo[d]imidazole (1420044-32-1)

Conditions	Yield
In 2-methoxy-ethanol for 2h; Reflux;	99%
Stage #1: 4-bromo-N-1-(4-ethoxyphenyl)benzene-1,2-diamine; formamidine acetic acid In ethanol at 20℃; for 9h; Reflux; Stage #2: In water for 0.5h;	94%

1-amino-1H-imidazole-5-carboxylic acid methyl ester (865444-80-0) + formamidine acetic acid (3473-63-0) → imidazo[5,1-f][1,2,4]triazin-4(3H)-one

Conditions	Yield
In ethanol at 80 - 90℃; for 16h;	99%

ethyl 3-amino-5-chloro-4,6-dimethylfuro[2,3-b]pyridine-2-carboxylate + formamidine acetic acid (3473-63-0) + formamide (77287-34-4, 77287-35-5, 60100-09-6) → 8-chloro-7,9-dimethylpyrido[3',2': 4,5]furo[3,2-d]pyrimidin-4-ol

Conditions	Yield
at 150℃; for 1.5h; Sealed tube;	99%

ethyl α-fluoropropionylacetate (227184-02-3) + formamidine acetic acid (3473-63-0) → C6H7FN2O

Conditions	Yield
With sodium methylate In methanol for 24h; Pinner Triazine Synthesis;	99%

formamidine acetic acid (3473-63-0) + formamide (77287-34-4, 77287-35-5, 60100-09-6) + ethyl 3-amino-4,6-dimethyl-furo[2,3-b]pyridine-2-carboxylate (59615-73-5) → 7,9-dimethylpyrido[3',2':4,5]furo[3,2-d]pyrimidin-4-ol (59615-79-1)

Conditions	Yield
at 150℃; for 1.5h; Sealed tube;	98.8%

isopropyl 5-amino-3,4-dimethylfuro[2,3-c]pyridazine-6-carboxylate + formamidine acetic acid (3473-63-0) + formamide (77287-34-4, 77287-35-5, 60100-09-6) → 3,4-dimethylpyrimido[4',5':4,5]furo[2,3-c]pyridazin-8-ol

Conditions	Yield
at 150℃; for 1.5h; Sealed tube;	98.8%

formamidine acetic acid (3473-63-0) + ethyl 2-amino-4,5-bis(2-methoxyethoxy)-benzoate (179688-27-8) → 6,7-bis(2-methoxyethoxy)-3,4-dihydroquinazolin-4-one (179688-29-0)

Conditions	Yield
Stage #1: formamidine acetic acid; ethyl 2-amino-4,5-bis(2-methoxyethoxy)-benzoate In butan-1-ol at 80℃; for 5h; Inert atmosphere; Stage #2: In Isopropyl acetate for 1h; Reflux;	98%
In ethanol at 55℃; for 3h; Concentration; Temperature; Solvent; Green chemistry;	98.5%
In 2-methoxy-ethanol at 125℃; for 8h;	63.5%

formamidine acetic acid (3473-63-0) + 4-piperidino-3-cyano-2H-pyran-2-one (94835-37-7) → 6'-phenyl-3,4,5,6-tetrahydro-2H-[1,4']bipyridinyl-3'-carbonitrile

Conditions	Yield
potassium hydroxide In N,N-dimethyl-formamide for 0.833333h;	98%
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.833333h;	95%

formamidine acetic acid (3473-63-0) + 2-oxo-4-piperidin-1-yl-6-p-tolyl-2H-pyran-3-carbonitrile (757235-51-1) → 6'-p-tolyl-3,4,5,6-tetrahydro-2H-[1,4']bipyridinyl-3'-carbonitrile

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.833333h;	98%
potassium hydroxide In N,N-dimethyl-formamide for 0.833333h;	97%

formamidine acetic acid (3473-63-0) + 6-(4-methoxyphenyl)-2-oxo-4-(piperidin-1-yl)-2H-pyran-3-carbonitrile (757235-52-2) → 6'-(4-methoxyphenyl)-3,4,5,6-tetrahydro-2H-[1,4']bipyridinyl-3'-carbonitrile

Conditions	Yield
potassium hydroxide In N,N-dimethyl-formamide for 1h;	98%

2-amino-4-bromobenzoic acid (20776-50-5) + formamidine acetic acid (3473-63-0) → 7-bromo-3H-quinazolin-4-one (194851-16-6)

Conditions	Yield
In 2-ethoxy-ethanol for 13h; Heating / reflux;	98%

formamidine acetic acid (3473-63-0) + 2-amino-4-benzyloxy-5-methoxybenzoic acid benzyl ester (205259-41-2) → 7-(benzyloxy)-6-methoxyquinazolin-4(3H)-one (179688-01-8)

Conditions	Yield
In 2-methyl-propan-1-ol at 97℃; for 6h; Product distribution / selectivity;	98%
In 2-methyl-propan-1-ol at 97℃; for 6h;	98%
In iso-butanol at 95℃; for 6h;	86%

formamidine acetic acid (3473-63-0) + anthranilic acid nitrile (1885-29-6) → 4-Aminoquinazoline (15018-66-3)

Conditions	Yield
In 2-ethoxy-ethanol for 1h; Heating;	97%

6-(benzo[d][1,3]dioxol-5-yl)-2-oxo-4-(piperidin-1-yl)-2H-pyran-3-carbonitrile (876150-29-7) + formamidine acetic acid (3473-63-0) → 6'-(benzo[1,3]dioxol-5-yl)-3,4,5,6-tetrahydro-2H-[1,4']bipyridinyl-3'-carbonitrile

Conditions	Yield
potassium hydroxide In N,N-dimethyl-formamide for 1.16667h;	97%

methyl 4-amino-1-ethyl-1H-pyrazole-5-carboxylate (923283-57-2) + formamidine acetic acid (3473-63-0) → 1-ethyl-1H-pyrazolo[4,3-d]pyrimidin-7-ol (674788-53-5)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In butan-1-ol at 110℃; for 1h;	97%

Upstream product

• 122-51-0 orthoformic acid triethyl ester 
• 420-04-2 CYANAMID 
• 64-19-7 acetic acid 

Downstream Products

• 55628-59-6 (1S)-1-(6-amino-7⁽⁹⁾H-purin-8-yl)-O⁵-benzoyl-D-1,4-anhydro-ribitol 
• 10325-61-8 7-Amino-oxazolo<5,4-d>pyrimidin 
• 65246-80-2 3-phenylisoxazolo<5,4-d>pyrimidine 
• 32673-41-9 4-hydroxymethyl-1H-imidazole hydrochloride 
• 59995-64-1 thienamycin 
• 130641-22-4 (R)-5-((1R,2R)-1-Carbamoyl-2-hydroxy-propyl)-3-(2-formimidoylamino-ethylsulfanyl)-1-formyl-4,5-dihydro-1H-pyrrole-2-carboxylic acid 
• 288-32-4 1H-imidazole 
• 822-55-9 (1H-imidazol-4-yl)methanol 
• 52997-82-7 4-(pyridin-2-yl)pyrimidine 
• 137234-87-8 6-Ethyl-5-fluoropyrimidin-4(3H)-one 

Relevant articles and documents

Sustainable and cost-efficient electro-synthesis of formamidine acetate from cyanamide in aqueous acidic electrolyte

Formamidine represents a versatile building block in synthetic organic chemistry. We developed a new electrochemical synthesis of formamidine acetate by cathodic reduction of cyanamide in an aqueous electrolyte and in high yield. The crude product could be used for further conversions, such as to pyrimidines without purification. Compared to established synthetic routes neither prior processing of cyanamide was necessary, nor precious transition-metal catalyst were required, nor any reagent waste was produced, and only biocompatible and sustainable solvents were employed for this process, following the requirements ofgreen chemistry.

SIMPLE AMIDINIUM CARBOXYLATES - AN MO TREATMENT OF MOLECULAR GEOMETRY AND ELECTRONIC STRUCTURE

Carboxylates of amidines (I,II), substituted guanidine (III) and iso(thio)ureas (IV,V) were prepared.Nonempirical quantum chemical treatment of the electronic structure of simple compounds I-V, based on total molecular geometry optimization, their preparation and physicochemical data are reported.Interaction between the two amidinium nitrogens and carboxylate oxygens is mediated by hydrogen bonds and alternation of charge distribution.