623-49-4

Basic information

• Product Name: Ethyl cyanoformate
• Synonyms: carbonocyanidicacid,ethylester;Formic acid, cyano-, ethyl ester;Nitriloaceticacidethylester;Ethylcyanoformate,99%;Ethoxycarbonyl Cyanide;NSC 65347;Ethyl carbonocyanidoate;Ethyl cyanoforMate, 99% 10GR
• CAS NO: 623-49-4
• Molecular Formula: C₄H₅NO₂
• Molecular Weight: 99.09
• EINECS: 210-797-9
• Product Categories: Aliphatics;Esters;C2 to C5;Carbonyl Compounds;Building Blocks;C2 to C5;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
• Mol File: 623-49-4.mol
• Article Data: 16

Chemical Properties

• Boiling Point: 115-116 °C(lit.)
• Flash Point: 76 °F
• Appearance: Clear colorless/Liquid
• Density: 1.003 g/mL at 25 °C(lit.)
• Vapor Pressure: 19mmHg at 25°C
• Refractive Index: n20/D 1.381(lit.)
• Storage Temp.: Flammables area
• Solubility: Miscible with chloroform and methanol.
• Sensitive: Moisture Sensitive
• BRN: 635955
• CAS DataBase Reference: Ethyl cyanoformate(CAS DataBase Reference)
• NIST Chemistry Reference: Ethyl cyanoformate(623-49-4)
• EPA Substance Registry System: Ethyl cyanoformate(623-49-4)

Safety Data

• Hazard Codes: T,F
• Statements: 10-23/24/25-34-36/37/38
• Safety Statements: 26-36/37/39-45-24/25-16-7/9
• RIDADR: UN 3275 6.1/PG 2
• WGK Germany: 3
• F: 10-19-21
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 623-49-4(Hazardous Substances Data)

Usage

Chemical Properties

Clear Colourless Liquid

Uses

Different sources of media describe the Uses of 623-49-4 differently. You can refer to the following data:
1. Ethyl cyanoformate is used as reagent in the preparation of N-substituted amindinoformic acid and ethyl-4-quinazoline -2-carboxylate.
2. Ethyl Cyanoformate (cas# 623-49-4) is a compound useful in organic synthesis.
3. Ethyl cyanoformate can be used as a cyanide source for the cyanation of:Activated olefins in the presence of a titanium catalyst.Carbonyl compounds catalyzed by 4-dimethylaminopyridine (DMAP) to yield corresponding cyanohydrin carbonates under metal-free and solvent-free conditions.Aldehydes and 2,2,2-trifluoroacetophenone catalyzed by N-heterocyclic carbene (NHC) to yield corresponding cyanohydrins ethyl carbonates.

Application

Ethyl cyanoformate can be used as a cyanide source for the cyanation of:Activated olefins in the presence of a titanium catalyst.Carbonyl compounds catalyzed by 4-dimethylaminopyridine (DMAP) to yield corresponding cyanohydrin carbonates under metal-free and solvent-free conditions.Aldehydes and 2,2,2-trifluoroacetophenone catalyzed by N-heterocyclic carbene (NHC) to yield corresponding cyanohydrins ethyl carbonates.Ethyl cyanoformate is a general cyanating agent. It can be used in the nucleophilic addition of cyanide to carbonyl compounds, oxidative cyanation of tertiary amines and in the synthesis of β-cyano-substituted acrylates from alkynes.

Purification Methods

Dissolve the cyanoformate in Et2O, dry it over Na2SO4, filter, evaporate and distil it [Malachowsky et al. Chem Ber 70 1016 1937, Adickes et al. J Prakt Chem [2] 133 313 1932, Grundmann et al. Justus Liebigs Ann Chem 577 77 1952]. [Beilstein 2 IV 1862.]

Precautions

Moisture sensitive. Keep the container tightly closed in a dry and well-ventilated place. Incompatible with strong acids, strong bases, strong oxidizing agents and strong reducing agents.

InChI:InChI=1/C4H5NO2/c1-2-7-4(6)3-5/h2H2,1H3

Synthetic route

ethyl (triphenylphosphoranylidene)acetate (1099-45-2) → ethyl cyanoformate (623-49-4) + <(Ethoxycarbonyl)methyl>triphenylphosphoniumnitrat

Conditions	Yield
With dinitrogen tetraoxide In tetrahydrofuran for 12h;	A 73% B 92%

trimethylsilyl cyanide (7677-24-9) + chloroformic acid ethyl ester (541-41-3) → ethyl cyanoformate (623-49-4)

Conditions	Yield
With dmap for 24h; Ambient temperature;	83%

5-acetoxy-3-methoxycarbonyl-5H-1,2-benzodiazepine → 3-indoxyl acetate (608-08-2) + ethyl cyanoformate (623-49-4)

Conditions	Yield
In dichloromethane for 0.133333h; Irradiation;	A 74% B n/a

tri-n-butyltin cyanide (2179-92-2) + chloroformic acid ethyl ester (541-41-3) → ethyl cyanoformate (623-49-4) + tributyltin chloride

Conditions	Yield
In neat (no solvent) at 70℃; for 2.5h;	A 57% B n/a

sodium cyanide (773837-37-9) + chloroformic acid ethyl ester (541-41-3) → ethyl cyanoformate (623-49-4)

Conditions	Yield
With tetrabutylammomium bromide In dichloromethane; water at 0℃; for 1h;	52%

diethyl 1,2,4,5-tetrazine-3,6-dicarboxylate (122747-88-0) + 2,2-dimethylpropylidynephosphine (78129-68-7) → 4-tert-Butyl-1-(2,4,5-tri-tert-butyl-[1,3]diphosphol-1-yl)-1H-[1,2,3]azadiphosphole-5-carboxylic acid ethyl ester (122747-90-4) + ethyl cyanoformate (623-49-4) + N2

Conditions	Yield
In toluene at 110℃; for 24h; sealed tube;	A 48% B n/a C n/a

ethyl 4,4,4-trifluoro-3,3-dihydroxy-2-(hydroxyimino)butanoate → ethyl cyanoformate (623-49-4)

Conditions	Yield
With acetic anhydride In chloroform for 1h; Reagent/catalyst; Reflux;	48%

oct-1-ene (111-66-0) + 3,4-bis(ethoxycarbonyl)-1,2,5-oxadiazole 2-oxide (18417-40-8) → 2,5-Dihexyl-tetrahydro-isoxazolo[2,3-b]isoxazole-3a-carboxylic acid ethyl ester (86497-63-4) + ethyl cyanoformate (623-49-4)

Conditions	Yield
In xylene for 24h; Heating;	A 38% B n/a

3,4-bis(ethoxycarbonyl)-1,2,5-oxadiazole 2-oxide (18417-40-8) + anethole (104-46-1) → 3-(ethoxycarbonyl)-4-methyl-5-(p-methoxyphenyl)isoxazole (51291-35-1) + ethyl cyanoformate (623-49-4)

Conditions	Yield
at 150℃; for 24h;	A 2% B 32%

ethanol (64-17-5) + carbon monoxide (201230-82-2) + phenylsulfonyloxyacetonitrile (10531-13-2) → ethyl cyanoformate (623-49-4)

Conditions	Yield
With dicobalt octacarbonyl at 80℃; under 30002.4 Torr; for 6h;	30%
With dicobalt octacarbonyl at 80℃; under 30002.4 Torr; for 6h; Product distribution; var. temp. pressure and reaction time;

2-vinyloxynaphthalene (7309-03-7) + 3,4-bis(ethoxycarbonyl)-1,2,5-oxadiazole 2-oxide (18417-40-8) → 2,5-Bis-(naphthalen-2-yloxy)-tetrahydro-isoxazolo[2,3-b]isoxazole-3a-carboxylic acid ethyl ester (86497-62-3) + ethyl cyanoformate (623-49-4)

Conditions	Yield
In xylene for 24h; Heating;	A 21% B n/a

diethyl 2-oxo-3-triphenylphosphoranylidenebutanedioate (29393-95-1) → diethyl 2,3-dioxosuccinate (59743-08-7) + triphenylphosphine oxide-nitric acid complex (18365-29-2) + ethyl cyanoformate (623-49-4)

Conditions	Yield
With Nitrogen dioxide In dichloromethane Ambient temperature; Yields of byproduct given;	A 20% B n/a C n/a
With Nitrogen dioxide In dichloromethane Ambient temperature; Yield given;	A 20% B n/a C 15%
With Nitrogen dioxide In dichloromethane Ambient temperature; Yields of byproduct given;	A n/a B n/a C 15%

phenylmagnesium bromide + Ethyl oxamate (617-36-7) → triphenylmethyl alcohol (76-84-6) + biphenyl (92-52-4) + ethyl cyanoformate (623-49-4)

Ethyl oxamate (617-36-7) → ethyl cyanoformate (623-49-4)

Conditions	Yield
With phosphorus pentaoxide
With phosphorus pentachloride der nach der Zugabe von Ligroin gefaellte Niederschlag wird gepresst, getrocknet und destilliert;
With phosphorus pentoxide at 135 - 140℃;
With phosphorus pentoxide
With phosphorus pentoxide Heating;

sodium cyanide (143-33-9) + chloroformic acid ethyl ester (541-41-3) → ethyl cyanoformate (623-49-4)

Conditions	Yield
With tetrabutylammomium bromide In dichloromethane; water

cyanoformic acid iminoethyl ether → ethyl cyanoformate (623-49-4)

Conditions	Yield
With hydrogenchloride

isonitrosoacetic acid ester → ethyl cyanoformate (623-49-4)

Conditions	Yield
With acetic anhydride

hydrogenchloride (7647-01-0) + Cyan-imidoameisensaeureethylester (13369-04-5) → ammonium chloride + ethyl cyanoformate (623-49-4)

E-ethyl cyano(phenylhydrazono)acetate (27097-85-4) → N-carboethoxyaniline (101-99-5) + ethyl cyanoformate (623-49-4) + 1-phenylcyanamide (622-34-4)

Conditions	Yield
at 500℃; under 0.02 Torr; Product distribution;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + trimethylsilyl cyanide (7677-24-9) + chloroformic acid ethyl ester (541-41-3) → ethyl cyanoformate (623-49-4)

water (7732-18-5) → CN(1-)*H2O = CN(H2O)(1-) (68579-77-1) + ethyl cyanoformate (623-49-4)

Conditions	Yield
With (CN)2CO2C2H5(1-) In neat (no solvent, gas phase) High Pressure; react. in a pulsed ionization high-pressure mass spectrometer; not isolated, detected by high-pressure mass spectrometry;

sulfur dioxide (7446-09-5) → isocyanosulfite(1-) + ethyl cyanoformate (623-49-4)

Conditions	Yield
With (CN)2CO2C2H5(1-) In neat (no solvent, gas phase) High Pressure; react. in a pulsed ionization high-pressure mass spectrometer; not isolated, detected by high-pressure mass spectrometry;

carbon dioxide (124-38-9) → CN(1-)*CO2 + ethyl cyanoformate (623-49-4)

Conditions	Yield
With (CN)2CO2C2H5(1-) In neat (no solvent, gas phase) byproducts: NCCO2(1-); High Pressure; react. following a 50μs, 2000-eV electron beam pulse in a mixt. of (CN)CO2C2H5:CO2:CH4 at a total ion source pressure of 5.0 torr at 55°C in a pulsed ionization high-pressure mass spectrometer; not isolated, detected by high-pressure mass spectrometry;

potassium cyanide + chloroformic acid ethyl ester (541-41-3) → ethyl cyanoformate (623-49-4)

Conditions	Yield
With sodium iodide In water at 60 - 70℃; for 24h;

ethyl cyanoformate (623-49-4) → triethyl 1,3,5-triazine-2,4,6-tricarboxylate (898-22-6)

Conditions	Yield
acid	100%
With hydrogenchloride for 336h; Inert atmosphere;	98%
With hydrogenchloride at 20℃; for 144h;	88%

5-phenyl-1,3,4-oxathiazol-2-one (5852-49-3) + ethyl cyanoformate (623-49-4) → ethyl 3-phenyl-1,2,4-thiadiazole-5-carboxylate (50483-79-9)

Conditions	Yield
In para-xylene at 160℃; for 0.166667h; Microwave irradiation;	100%
In ethyl acetate at 160℃; for 0.166667h; microwave irradiation;	94%
In dodecane

ethyl cyanoformate (623-49-4) + 4-methyl-4-(1-methyl-2,3-dihydro-1H-indol-3-yl)-pentan-2-one (385842-52-4) → 5-methyl-5-(1-methyl-2,3-dihydro-1H-indol-3-yl)-3-oxo-hexanoic acid ethyl ester (385842-53-5)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium diisopropyl amide In tetrahydrofuran	100%

ethyl cyanoformate (623-49-4) + 4-N,N-dimethylphenyl triethylsilyl ketone (461051-92-3) → ethyl-2-cyano-2-(4-N,N-dimethylphenyl)-2-triethylsiloxy acetate

Conditions	Yield
With potassium cyanide; 18-crown-6 ether In toluene at 110℃; for 12h; cyanation/Brook rearrangement/C-acylation;	100%

3-methoxy-benzaldehyde (591-31-1) + ethyl cyanoformate (623-49-4) → (2S)-O-ethoxycarbonyl-2-hydroxy-2-(3-methoxyphenyl)-acetonitrile

Conditions	Yield
With potassium cyanide; 18-crown-6 ether; chiral salen-based titanium In dichloromethane at -40℃; for 24h;	100%
With 3,3'-di-naphthalen-2-yl-biphenyl-2,2'-diol; titanium(IV) isopropylate; quinindine; isopropyl alcohol In toluene at -20℃; for 7h; Strecker reaction; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	99%
With chiral [(salen)TiO]2 In dichloromethane at -40℃; for 17h;	94%
With chiral bimetallic titanium(salen) In dichloromethane at -40℃; for 17h;	94%
With potassium cyanide; 18-crown-6 ether; titanium(salen) complex In dichloromethane at -40℃; for 24h;

ortho-anisaldehyde (135-02-4) + ethyl cyanoformate (623-49-4) → (2S)-O-ethoxycarbonyl-2-hydroxy-2-(2-methoxyphenyl)-acetonitrile

Conditions	Yield
With potassium cyanide; 18-crown-6 ether; chiral salen-based titanium In dichloromethane at -40℃; for 24h;	100%
With chiral [(salen)TiO]2 In dichloromethane at -40℃; for 48h;	95%
With chiral bimetallic titanium(salen) In dichloromethane at -40℃; for 48h;	95%

2-methylphenyl aldehyde (529-20-4) + ethyl cyanoformate (623-49-4) → (2S)-O-ethoxycarbonyl-2-hydroxy-2-(2-methylphenyl)-acetonitrile

Conditions	Yield
With potassium cyanide; 18-crown-6 ether; chiral salen-based titanium In dichloromethane at -40℃; for 24h;	100%
With 2,6-dimethylpyridine; 2C2H5O4S(1-)*C72H104N4O16V2(2+) In dichloromethane at -20℃; for 12h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	97%
With 1H-imidazole; C2H5O4S(1-)*C36H54N2O4V(1+) In dichloromethane at -20℃; for 18h; Inert atmosphere; optical yield given as %ee;	96%
With potassium cyanide; 18-crown-6 ether; titanium(salen) complex In dichloromethane at -40℃; for 24h;

4-methyl-benzaldehyde (104-87-0) + ethyl cyanoformate (623-49-4) → (2S)-O-ethoxycarbonyl-2-hydroxy-2-(4-methylphenyl)-acetonitrile

Conditions	Yield
With potassium cyanide; 18-crown-6 ether; chiral salen-based titanium In dichloromethane at -40℃; for 24h;	100%
With 3,3'-di-naphthalen-2-yl-biphenyl-2,2'-diol; titanium(IV) isopropylate; quinindine; isopropyl alcohol In toluene at -20℃; for 5h; Strecker reaction; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	97%
With 2,6-dimethylpyridine; 2C2H5O4S(1-)*C72H104N4O16V2(2+) In dichloromethane at -20℃; for 12h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	97%
With 1H-imidazole; C2H5O4S(1-)*C36H54N2O4V(1+) In dichloromethane at -20℃; for 24h; Inert atmosphere; optical yield given as %ee;	91%
With potassium cyanide; 18-crown-6 ether; titanium(salen) complex In dichloromethane at -40℃; for 24h;

4-chlorobenzaldehyde (104-88-1) + ethyl cyanoformate (623-49-4) → (2S)-O-ethoxycarbonyl-2-hydroxy-2-(4-chlorophenyl)-acetonitrile

Conditions	Yield
With potassium cyanide; 18-crown-6 ether; chiral salen-based titanium In dichloromethane at -40℃; for 24h;	100%
With 3,3'-di-naphthalen-2-yl-biphenyl-2,2'-diol; titanium(IV) isopropylate; quinindine; isopropyl alcohol In toluene at -20℃; for 7h; Strecker reaction; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	90%
With potassium cyanide; 18-crown-6 ether; titanium(salen) complex In dichloromethane at -40℃; for 24h;

potassium cyanide (151-50-8) + benzaldehyde (100-52-7) + ethyl cyanoformate (623-49-4) → (S)-mandelonitrile ethyl carbonate (6443-66-9)

Conditions	Yield
di-μ-oxo-di((R,R)-N,N'-bis((alicylaldehydo)ethylenediamine))dititanium(IV) In dichloromethane at -78 - -40℃; for 24h; Product distribution / selectivity;	100%
di-μ-oxo-di((S,S)-N,N'-bis((salicylaldehydo)ethylenediamine))dititanium(IV) In dichloromethane at -40℃; for 19h; Product distribution / selectivity;	n/a

ethyl cyanoformate (623-49-4) → potassium cyanoformate

Conditions	Yield
With potassium hydroxide In tetrahydrofuran; water at 0 - 20℃; for 12h;	100%

ethyl 2-(2-[ethyl(phenyl)amino]phenyl)acetate + ethyl cyanoformate (623-49-4) → 1,2-diethyl 2-(2-[ethyl(phenyl)amino]phenyl)propanedioate

Conditions	Yield
Stage #1: ethyl 2-(2-[ethyl(phenyl)amino]phenyl)acetate With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1.16667h; Stage #2: ethyl cyanoformate In tetrahydrofuran at -78 - 20℃; for 17.5h;	100%

potassium cyanide + β-naphthaldehyde (66-99-9) + ethyl cyanoformate (623-49-4) → 2-ethoxycarbonyl (R)-2-hydroxy-2-(2-naphthyl)-acetonitrile

Conditions	Yield
With C40H62AlFN3O2(1+)*CF3O3S(1-) In chloroform; 1,2-dichloro-ethane at -50℃; for 72h; Catalytic behavior; Reagent/catalyst; Inert atmosphere; Schlenk technique; enantioselective reaction;	100%
With C40H62AlFN3O2(1+)*CF3O3S(1-) In chloroform; 1,2-dichloro-ethane at -50℃; for 24h; Reagent/catalyst; Schlenk technique; Inert atmosphere;	99%

potassium cyanide + 3-methoxy-benzaldehyde (591-31-1) + ethyl cyanoformate (623-49-4) → 2-ethoxycarbonyl (R)-2-hydroxy-2-(3-methoxyphenyl)-acetonitrile

Conditions	Yield
With C40H62AlFN3O2(1+)*CF3O3S(1-) In chloroform; 1,2-dichloro-ethane at -50℃; for 24h; Inert atmosphere; Schlenk technique; enantioselective reaction;	100%
With C40H62AlFN3O2(1+)*CF3O3S(1-) In chloroform; 1,2-dichloro-ethane at -50℃; for 24h; Schlenk technique; Inert atmosphere;	99%

(E)-3-phenylpropenal (14371-10-9) + potassium cyanide + ethyl cyanoformate (623-49-4) → 2-ethoxycarbonyl (R)-2-hydroxy-2-phenyl-but-3-enonitrile

Conditions	Yield
With C40H62AlFN3O2(1+)*CF3O3S(1-) In chloroform; 1,2-dichloro-ethane at -50℃; for 48h; Inert atmosphere; Schlenk technique; enantioselective reaction;	100%
With C40H62AlFN3O2(1+)*CF3O3S(1-) In chloroform; 1,2-dichloro-ethane at -50℃; for 72h; Schlenk technique; Inert atmosphere;	99%

ethyl cyanoformate (623-49-4) → 1H-tetrazole-5-carboxylic acid ethyl ester (55408-10-1)

Conditions	Yield
With trimethylsilylazide; dibutyltin diacetate In benzene at 30℃; for 60h;	99%
With diethylaluminium azide In toluene at 20℃; for 1h;	94%
With sodium azide In butanone at 75℃; for 2h;	82%

ethyl cyanoformate (623-49-4) + acetylacetone (123-54-6) → 1-amino-2,2-diacetyl-1-(ethoxycarbonyl)ethylene (72373-95-6)

Conditions	Yield
[Ni{F3CC(O)CHC(O)C6F13}2] In dichloromethane at 20℃; for 24h;	99%
With triethylamine; zinc(II) chloride In dichloromethane

benzaldehyde (100-52-7) + ethyl cyanoformate (623-49-4) → O-ethoxycarbonyl 2-hydroxy-2-phenylacetonitrile (6443-66-9)

Conditions	Yield
With n-butyllithium In dichloromethane at -20℃; for 3h;	99%
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 25℃; for 11h;	99%
With dmap In acetonitrile at 20℃; for 8h; Inert atmosphere;	99%

(E)-3-phenylpropenal (14371-10-9) + ethyl cyanoformate (623-49-4) → <1-Cyan-3-phenyl-2-propenyl>-ethyl-carbonat (100573-40-8)

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 31℃; for 8h;	99%
With potassium cyanide; 18-crown-6 ether for 48h; Ambient temperature;	90%

(4R,5R)-1-Acetoxy-4-isopropenyl-5-methyl-5-vinylcyclohex-1-ene (149404-74-0) + ethyl cyanoformate (623-49-4) → (1R,4R,5R)-5-Isopropenyl-4-methyl-2-oxo-4-vinyl-cyclohexanecarboxylic acid ethyl ester (202194-28-3)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; methyllithium In tetrahydrofuran; diethyl ether 1.) -78 deg C, 1 h, 2.) -78 deg C, 35 min;	99%

dimethyl 2,2-di(but-2-yn-1-yl)malonate (107428-05-7) + ethyl cyanoformate (623-49-4) → 3-ethyl 6,6-dimethyl 1,4-dimethyl-6,7-dihydro-5H-cyclopenta[c]pyridine-3,6,6-tricarboxylate

Conditions	Yield
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In dichloromethane at 20℃; for 3h;	99%

ethyl cyanoformate (623-49-4) + di(2-pentynyl) ether (114764-03-3) → 4,7-diethyl-1,3-dihydro-furo[3,4-c]pyridine-6-carboxylic acid ethyl ester

Conditions	Yield
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In dichloromethane at 20℃; for 1h;	99%

ethyl cyanoformate (623-49-4) + N,N-bis(2-butynyl)-(4-methylphenyl)sulfonamide (170751-34-5) → ethyl 4,7-dimethyl-2-p-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine-6-carboxylate

Conditions	Yield
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In dichloromethane at 20℃; for 1h;	99%

4-methoxy-benzaldehyde (123-11-5) + ethyl cyanoformate (623-49-4) → (2S)-O-ethoxycarbonyl-2-hydroxy-2-(4-methoxyphenyl)-acetonitrile

Conditions	Yield
With 3,3'-di-naphthalen-2-yl-biphenyl-2,2'-diol; titanium(IV) isopropylate; quinindine; isopropyl alcohol In toluene at -20℃; for 7h; Strecker reaction; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	99%
With potassium cyanide; chiral salen-based titanium In dichloromethane at -40℃; for 24h;	98%
With 2,6-dimethylpyridine; 2C2H5O4S(1-)*C72H104N4O16V2(2+) In dichloromethane at -20℃; for 12h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	96%
di-μ-oxo-di((R,R)-N,N'-bis((alicylaldehydo)ethylenediamine))dititanium(IV) In dichloromethane at -84 - -40℃; for 20h; Product distribution / selectivity;	92%
With 1H-imidazole; C2H5O4S(1-)*C36H54N2O4V(1+) In dichloromethane at -20℃; for 60h; Inert atmosphere; optical yield given as %ee;	90%

2,4-dichlorobenzaldeyhde (874-42-0) + ethyl cyanoformate (623-49-4) → cyano(2,4-dichlorophenyl)methyl ethyl carbonate

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 22℃; for 58h;	99%
With 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	91%

ortho-anisaldehyde (135-02-4) + ethyl cyanoformate (623-49-4) → 2-ethoxycarbonyl-2-hydroxy-2-(2-methoxylphenyl)-acetonitrile (408310-12-3)

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 28℃; for 20h;	99%
With 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	98%
Stage #1: ortho-anisaldehyde With 1-pentyl-3-methylimidazolium bromide at 20℃; for 0.166667h; Stage #2: ethyl cyanoformate at 20℃; for 2.08333h;	96%
With dmap at 27℃; for 0.75h; Neat (no solvent);	94%
With polyacrylonitrile fiber In water at 20℃; for 0.666667h; Catalytic behavior;	82%

3-nitro-benzaldehyde (99-61-6) + ethyl cyanoformate (623-49-4) → ethoxycarbonyloxy-(3-nitro-phenyl)-acetonitrile

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 25℃; for 11h;	99%

4-methoxy-benzaldehyde (123-11-5) + ethyl cyanoformate (623-49-4) → carbonic acid, cyano(4-methoxyphenyl)methyl ethyl ester (66867-32-1)

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 25℃; for 15h;	99%
With 3-(diethylamino)propyltrimethoxysilane supported on silica-alumina In toluene at 20℃; for 3h; Inert atmosphere;	98%
With dmap at 27℃; for 0.75h; Neat (no solvent);	92%

4-chlorobenzaldehyde (104-88-1) + ethyl cyanoformate (623-49-4) → cyano(4-chlorophenyl)methyl ethyl carbonate

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 24℃; for 12h;	99%
With 3-(diethylamino)propyltrimethoxysilane supported on silica-alumina In toluene at 20℃; for 3h; Inert atmosphere;	99%
With 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	94%

furfural (98-01-1) + ethyl cyanoformate (623-49-4) → carbonic acid, cyano(2-furyl)methyl ethyl ester (20893-23-6)

Conditions	Yield
With 1-methoxy-2-methyl-1-(trimethylsiloxy)propene at 25℃; for 9h;	99%
With dmap In acetonitrile at 20℃; for 8h; Inert atmosphere;	97%
With polyacrylonitrile fiber In water at 20℃; for 0.666667h; Catalytic behavior;	85%

Upstream product

• 151-50-8 potassium cyanide 
• 541-41-3 chloroformic acid ethyl ester 
• 2179-92-2 tri-n-butyltin cyanide 
• 7647-01-0 hydrogenchloride 
• 13369-04-5 Cyan-imidoameisensaeureethylester 
• 7732-18-5 water 
• 7446-09-5 sulfur dioxide 
• 124-38-9 carbon dioxide 
• 773837-37-9 sodium cyanide 
• 280-57-9 1,4-diaza-bicyclo[2.2.2]octane 
• 7677-24-9 trimethylsilyl cyanide 
• 27097-85-4 E-ethyl cyano(phenylhydrazono)acetate 
• 122747-88-0 diethyl 1,2,4,5-tetrazine-3,6-dicarboxylate 
• 78129-68-7 2,2-dimethylpropylidynephosphine 

Downstream Products

• 1906-82-7 ethyl acetamidoacetate 
• 7672-01-7 2-phenylquinazoline-4-carboxylic acid 
• 1499-53-2 ethyl hippurate 
• 30863-21-9 2-trichloromethyl-4,6-bis(ethoxycarbonyl)-1,3,5-triazine 
• 30863-22-0 2,4-bis(trichloromethyl)-6-ethoxycarbonyl-1,3,5-triazine 
• 101-99-5 N-carboethoxyaniline 
• 93700-81-3 (4-hydroxy-2-methoxy-phenyl)-glyoxylic acid ethyl ester 
• 69098-01-7 2-oxo-2-(2,4,6-trihydroxyphenyl)acetic acid 
• 597-49-9 3-ethylpentan-3-ol 
• 7029-49-4 4-ethyl-4-hydroxy-hexan-3-one 
• 854677-12-6 (4-ethoxy-2-hydroxy-phenyl)-glyoxylic acid 
• 99548-75-1 (2,3-dihydroxy-4-methoxy-phenyl)-glyoxylic acid 
• 91498-01-0 (2-hydroxy-3,4-dimethoxy-phenyl)-glyoxylic acid ethyl ester 
• 99548-39-7 (2,4-dihydroxy-5-methoxy-phenyl)-glyoxylic acid 

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