65193-87-5

Basic information

• Product Name: 3-Bromopropionaldehydedimethylacetal
• Synonyms: 2-Cyanoethylacetoacetate;Butanoic acid, 3-oxo-,2-cyanoethyl ester;2-Cyanoethyl 3-Oxobutyrate
• CAS NO: 65193-87-5
• Molecular Formula: C₇H₉NO₃
• Molecular Weight: 155.15
• Mol File: 65193-87-5.mol
• Article Data: 16

Chemical Properties

• Boiling Point: 288.196°C at 760 mmHg
• Flash Point: 124.214°C
• Appearance: /
• Density: 1.124g/cm³
• Vapor Pressure: 0.002mmHg at 25°C
• Refractive Index: 1.437
• Storage Temp.: Sealed in dry,Store in freezer, under -20°C
• PKA: 10.04±0.46(Predicted)
• CAS DataBase Reference: 3-Bromopropionaldehydedimethylacetal(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Bromopropionaldehydedimethylacetal(65193-87-5)
• EPA Substance Registry System: 3-Bromopropionaldehydedimethylacetal(65193-87-5)

Safety Data

• Hazardous Substances Data: 65193-87-5(Hazardous Substances Data)

Usage

Uses

2-Cyanoethyl Acetoacetate is an intermediate in the synthesis of Felodipine-d3 (F232377), a labelled dihydropyridine calcium channel blocker.

InChI:InChI=1/C7H9NO3/c1-6(9)5-7(10)11-4-2-3-8/h2,4-5H2,1H3

Synthetic route

2,2,6-trimethyl-4H-1,3-dioxin-4-one (5394-63-8) + 3-Hydroxypropionitrile (109-78-4) → 2-cyanoethylacetoacetate (65193-87-5)

Conditions	Yield
In o-xylene at 141℃; for 2h;	98.3%
In 5,5-dimethyl-1,3-cyclohexadiene at 140 - 145℃; for 1h;	90%
In xylene at 140 - 145℃; for 1h;	81.6%

acetoacetic acid methyl ester (105-45-3) + 3-Hydroxypropionitrile (109-78-4) → 2-cyanoethylacetoacetate (65193-87-5)

Conditions	Yield
With N-Bromosuccinimide In toluene at 90℃; for 3h;	95.2%
With Candida antarctica lipase B at 40℃; under 10 Torr;	88%

4-methyleneoxetan-2-one (674-82-8) + 3-Hydroxypropionitrile (109-78-4) → 2-cyanoethylacetoacetate (65193-87-5)

Conditions	Yield
With triethylamine In ethyl acetate at 20 - 60℃;	86%
With triethylamine In ethyl acetate at 80℃; Reagent/catalyst; Large scale;	85.8%
With sodium acetate for 16h; Ambient temperature;

5-acetyl-2,2-dimethyl-1,3-dioxane-4,6-dione (72324-39-1) + 3-Hydroxypropionitrile (109-78-4) → 2-cyanoethylacetoacetate (65193-87-5)

Conditions	Yield
In toluene Heating; Yield given;

3-Chlorostyrene (2039-85-2) + 2-cyanoethylacetoacetate (65193-87-5) → 2-acetyl-3-(3-chlorophenyl)-acrylic acid (2-cyanoethyl) ester (314775-78-5)

Conditions	Yield
piperidine; acetic acid In propanol, 2 at 20℃;	100%

N-(3-trifluoromethylphenyl)urea (13114-87-9) + 2-cyanoethylacetoacetate (65193-87-5) + 4-cyanobenzaldehyde (105-07-7) → 4-(4-cyanophenyl)-6-methyl-2-oxo-1-[3-(trifluoromethyl)phenyl]-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid 2-cyanoethyl ester (671776-88-8)

Conditions	Yield
With ethyl phosphate In tetrahydrofuran for 18h; Heating / reflux;	100%

2-cyanoethylacetoacetate (65193-87-5) + methyl 3-aminocrotonate (21731-17-9) + benzo[c][1,2,5]oxadiazole-4-carbaldehyde (32863-32-4) → C19H18N4O5

Conditions	Yield
In isopropyl alcohol Inert atmosphere; Reflux;	97%

4-formyl-3-methoxy-benzonitrile (21962-45-8) + 2-cyanoethylacetoacetate (65193-87-5) → 2-(4-cyano-2-methoxybenzylidene)-3-oxobutyric acid 2-cyanoethyl ester

Conditions	Yield
With piperidine; acetic acid In isopropyl alcohol at 0 - 30℃; for 3.5h; Solvent; Temperature; Large scale;	97%
With piperidine; acetic acid In isopropyl alcohol at 0 - 30℃; for 4.5h; Solvent; Temperature; Knoevenagel Condensation; Large scale;	97%
With piperidine; acetic acid In dichloromethane for 23h; Reflux;	80.5%
With piperidine; acetic acid In dichloromethane Reflux;	48%

4-nitrobenzaldehdye (555-16-8) + 2-cyanoethylacetoacetate (65193-87-5) → 4-(4-nitrophenyl)-3-(2-cyanoethoxy)carbonyl-3-buten-2-one (166809-85-4)

Conditions	Yield
With piperidine; acetic acid In isopropyl alcohol for 48h; Ambient temperature;	96%

3-nitro-benzaldehyde (99-61-6) + 2-cyanoethylacetoacetate (65193-87-5) + ethyl aminocrotonate (626-34-6, 7318-00-5, 41867-20-3) → 3-(2-cyanoethyl) 5-ethyl 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate (75130-25-5)

Conditions	Yield
In isopropyl alcohol Inert atmosphere; Reflux;	95%

isopropyl 3-aminocrotonate (14205-46-0) + 3-nitro-benzaldehyde (99-61-6) + 2-cyanoethylacetoacetate (65193-87-5) → 3-(2-cyanoethyl) 5-isopropyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylate (74936-70-2)

Conditions	Yield
In isopropyl alcohol Inert atmosphere; Reflux;	95%

ammonium thiocyanate (1147550-11-5) + 2-cyanoethylacetoacetate (65193-87-5) → 2-cyanoethyl (E)-3-amino-2-thiocyanatobut-2-enoate

Conditions	Yield
With fluorescein free acid In acetonitrile at 20℃; UV-irradiation;	94%
With fluorescein In acetonitrile at 20℃; for 6h; Irradiation;	76%

2-cyanoethylacetoacetate (65193-87-5) + 2,3-dichlorobenzylaldehyde (6334-18-5) + methyl 3-aminocrotonate (14205-39-1) → 4-(2,3-dichlorophenyl)-1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate methyl ester-(2-cyanoethyl)ester (110962-94-2)

Conditions	Yield
In isopropyl alcohol for 6h; Reflux;	88.5%

4-nitrobenzaldehdye (555-16-8) + 2-cyanoethylacetoacetate (65193-87-5) + urea (57-13-6) → 6-methyl-4-(4-nitro-phenyl)-2-oxo-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid 2-cyano-ethyl ester (898798-67-9)

Conditions	Yield
With copper(l) iodide; boron trifluoride diethyl etherate; acetic acid In tetrahydrofuran for 18h; Biginelli condensation; Heating;	88%

2-cyanoethylacetoacetate (65193-87-5) + methyl 3-aminocrotonate (21731-17-9) + 2-nitro-benzaldehyde (552-89-6) → 1,4-Dihydro-2,6-dimethyl-3-methoxycarbonyl-4-(2-nitrophenyl)-5-(2-cyanoethoxy)-carbonyl-pyridine

Conditions	Yield
In ethanol Inert atmosphere; Reflux;	87%

3-nitro-benzaldehyde (99-61-6) + 2-cyanoethylacetoacetate (65193-87-5) + methoxyethyl 3-amino-2-butenoate (50899-10-0) → J-6-163 (75130-29-9, 118934-79-5, 118934-80-8)

Conditions	Yield
In isopropyl alcohol for 8h; Concentration; Reflux;	85.7%

3-nitro-benzaldehyde (99-61-6) + 2-cyanoethylacetoacetate (65193-87-5) → 2-cyanoethyl 2-(3-nitrobenzylidene)-3-oxobutanoate (102993-38-4)

Conditions	Yield
With ammonium acetate In isopropyl alcohol at 20℃; for 15h;	80.8%
at 5 - 70℃;

2-cyanoethylacetoacetate (65193-87-5) → 3-amino-2-butenoic acid 2-cyanoethyl ester

Conditions	Yield
With ammonium acetate; ammonia In water at 0℃; for 18h; Darkness;	77.2%
With ammonium hydroxide; acetic acid In water at 20℃; for 2h;	19%

3,3-diphenylpropyl 3-amino-4-(2-(1-morpholine)ethoxy)crotonate + 3-Chlorostyrene (2039-85-2) + 2-cyanoethylacetoacetate (65193-87-5) → 3-cyanoethyl 5-(3,3-diphenyl-1-propyl) 4-(3-chlorophenyl)-2-methyl-6-(2-(1-morpholine)ethoxy)methyl-1,4-dihydropyridine-3,5-dicarboxylate

Conditions	Yield
	77%

3-nitro-benzaldehyde (99-61-6) + 2-cyanoethylacetoacetate (65193-87-5) + 2-(nicotinoylamino)ethyl-3-aminocrotonate (154049-22-6) → 2-cyanoethyl 2-(nicotinoylamino)ethyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylate (167409-41-8)

Conditions	Yield
In isopropyl alcohol for 5h; Heating;	76%

3-nitro-benzaldehyde (99-61-6) + 2-cyanoethylacetoacetate (65193-87-5) + methyl 3-aminocrotonate (14205-39-1) → 2,6-dimethyl-4-(3-nitrophenyl)-5-methoxycarbonyl-1,4-dihydropyridine-3-carboxylic acid 2-cyanoethyl ester (75130-24-4)

Conditions	Yield
In isopropyl alcohol at 70 - 80℃; Large scale;	75.5%

2-chloro-benzaldehyde (89-98-5) + 2-cyanoethylacetoacetate (65193-87-5) + methyl 3-aminocrotonate (21731-17-9) → C19H19ClN2O4 (1376614-02-6)

Conditions	Yield
In ethanol Inert atmosphere; Reflux;	75%

3,3-diphenylpropyl 3-amino-4-(2-(N-benzyloxycarbonyl-4-piperedine)ethoxy)crotonate + 3-Chlorostyrene (2039-85-2) + 2-cyanoethylacetoacetate (65193-87-5) → 3-(2-cyanoethyl) 5-(3,3-diphenyl-1-propyl) 4-(3-chlorophenyl)-2-methyl-6-(2-(N-benzyloxycarbonyl-4-piperidine)ethoxy)methyl-1,4-dihydropyridine-3,5-dicarboxylate

Conditions	Yield
	74%

2-trifluoromethylphenyl thiourea (1736-71-6) + 2-cyanoethylacetoacetate (65193-87-5) + 4-cyanobenzaldehyde (105-07-7) → 2-cyanoethyl 4-(4-cyanophenyl)-6-methyl-2-thioxo-1-[3-(trifluoromethyl)phenyl]-1,2,3,4-tetrahydro-5-pyrimidinecarboxylate

Conditions	Yield
With trimethylsilylphosphate In 1,4-dioxane at 80℃; for 3h;	72.3%

4-nitrobenzaldehdye (555-16-8) + 2-cyanoethylacetoacetate (65193-87-5) + methyl 3-aminocrotonate (14205-39-1) → 3-(2cyanoethyl) 5-methyl 2,6-dimethyl-4-(4'-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate

Conditions	Yield
In ethanol for 3h; Heating;	72%

(E)-3-phenyl-2-propene-1-yl 3-aminocrotonate + 3-Cyanobenzaldehyde (24964-64-5) + 2-cyanoethylacetoacetate (65193-87-5) → 5-(3-phenyl-2-propene-1-yl) 3-(2-cyanoethyl) 4-(3-cyanophenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate

Conditions	Yield
	72%

2-cyanoethylacetoacetate (65193-87-5) → 2-cyanoethyl 3-amino-2-butenoate (88977-32-6)

Conditions	Yield
With ammonium hydroxide; acetic acid at 20℃; for 2h;	71%

Upstream product

• 674-82-8 4-methyleneoxetan-2-one 
• 109-78-4 3-Hydroxypropionitrile 
• 105-45-3 acetoacetic acid methyl ester 
• 5394-63-8 2,2,6-trimethyl-4H-1,3-dioxin-4-one 
• 72324-39-1 5-acetyl-2,2-dimethyl-1,3-dioxane-4,6-dione 

Downstream Products

• 210829-68-8 5-Carbamoyl-2,6-dimethyl-4-(4-nitro-phenyl)-1,4-dihydro-pyridine-3-carboxylic acid 2-cyano-ethyl ester 
• 898798-67-9 6-methyl-4-(4-nitro-phenyl)-2-oxo-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid 2-cyano-ethyl ester 
• 314775-78-5 2-acetyl-3-(3-chlorophenyl)-acrylic acid (2-cyanoethyl) ester 

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