626-35-7

Basic information

• Product Name: Ethyl nitroacetate
• Synonyms: nitro-aceticaciethylester;NITROACETIC ACID ETHYL ESTER;NITRO ETHYL ACETATE;ETHYL NITROACETATE;Ethlnitroacetate;wEthyl nitroacetate, 97%;Ethylnitroacetate,97%;Ethyl nitroacetate 97%
• CAS NO: 626-35-7
• Molecular Formula: C₄H₇NO₄
• Molecular Weight: 133.1
• EINECS: 210-944-7
• Product Categories: C2 to C5;Carbonyl Compounds;Esters;Halogenated Heterocycles ,Quinolines
• Mol File: 626-35-7.mol
• Article Data: 23

Chemical Properties

• Boiling Point: 105-107 °C25 mm Hg(lit.)
• Flash Point: 198 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 1.199 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.212mmHg at 25°C
• Refractive Index: n20/D 1.424(lit.)
• Storage Temp.: Keep Cold
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
• PKA: pK1:5.85 (25°C)
• Water Solubility: Slightly soluble in water. Soluble in chloroform and ethyl acetate.
• BRN: 1210027
• CAS DataBase Reference: Ethyl nitroacetate(CAS DataBase Reference)
• NIST Chemistry Reference: Ethyl nitroacetate(626-35-7)
• EPA Substance Registry System: Ethyl nitroacetate(626-35-7)

Safety Data

• Hazard Codes: Xi
• Statements: 38
• Safety Statements: 23-24/25-37
• WGK Germany: 2
• RTECS: AJ1074000
• TSCA: T
• HazardClass: IRRITANT, KEEP COLD
• Hazardous Substances Data: 626-35-7(Hazardous Substances Data)

Usage

Chemical Properties

clear colourless to slightly yellow liquid

Uses

Different sources of media describe the Uses of 626-35-7 differently. You can refer to the following data:
1. Ethyl Nitroacetate is an ester of nitrocarboxylic acid used as an intermediate in the preparation of unsubstituted amino acids.
2. Ethyl nitroacetate has been used in the synthesis of γ-oxoacids via Michael addition reaction with α,β-unsaturated ketones, fuctionalization of C4-position on pyrimidine and C6-position on 2?-deoxyguanosine to produce novel nucleosides, facile synthesis of α,α-diisobutylglycine, synthesis of DL-4,4-difluoroglutamic acid. It is also used as an intermediate in the preparation of unsubstituted amino acids.

Synthesis Reference(s)

The Journal of Organic Chemistry, 59, p. 1208, 1994 DOI: 10.1021/jo00084a047

Purification Methods

Purify the ester by repeated distillation. IR:max 1748 (CO2), 1570 and 1337 (NO2), and 800cm-1 [Haszeldine J Chem Soc 2525 1953]. The hydrazine salt crystallises from 95% EtOH or MeOH as yellow crystals m 104-105o [Ungnade & Kissinger J Org Chem 22 1661 1957, Emmons & Freeman J Am Chem Soc 77 4391 1955]. [Beilstein 2 IV 537.]

InChI:InChI=1/C4H7NO4/c1-2-9-4(6)3-5(7)8/h2-3H2,1H3

Synthetic route

propylamine (107-10-8) + diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-propylamino-3-oxopropanoate (71510-96-8)

Conditions	Yield
In dichloromethane at 20℃; for 24h;	A n/a B 100%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + 4-methoxy-aniline (104-94-9) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-((4-methoxyphenyl)amino)-3-oxopropanoate (5382-15-0)

Conditions	Yield
In dichloromethane at 20℃; for 24h;	A n/a B 100%

methanol (67-56-1) + diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) → nitroacetic acid ethyl ester (626-35-7) + ethyl methyl malonate (6186-89-6)

Conditions	Yield
In chloroform at 60℃; for 24h;	A n/a B 99%

ethyl 2-nitro-3-oxobutyrate (51026-98-3) → nitroacetic acid ethyl ester (626-35-7)

Conditions	Yield
With sulfuric acid In methanol for 1h;	97%
In ethanol at 15 - 25℃; for 10h;

ethyl chloronitroacetate (14011-27-9) + triphenylphosphine (603-35-0) → nitroacetic acid ethyl ester (626-35-7) + Triphenylphosphine oxide (791-28-6)

Conditions	Yield
In methanol; benzene at 20℃; for 12h;	A 71.5% B 96%

ethanol (64-17-5) + nitroacetic acid (625-75-2) → nitroacetic acid ethyl ester (626-35-7)

Conditions	Yield
With dicyclohexyl-carbodiimide In tetrahydrofuran at 0℃;	90%
With dicyclohexyl-carbodiimide In tetrahydrofuran at 0 - 20℃; for 24h; Inert atmosphere; Sonication;	17%
With sulfuric acid
With sulfuric acid at -15 - 3℃;
With hydrogenchloride

ethyl cyanoformate (623-49-4) → nitroacetic acid ethyl ester (626-35-7)

Conditions	Yield
With acetic acid In nitromethane; dimethyl sulfoxide	83%
With potassium hydroxide; nitrogen In nitromethane; dimethyl sulfoxide	68%
With N2 In tetrahydrofuran; nitromethane

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + 1-amino-2-propene (107-11-9) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-(allylamino)-3-oxopropanoate (118081-79-1)

Conditions	Yield
In chloroform at 20℃; for 24h;	A n/a B 80%

ethyl-2-azidoacetate (637-81-0) → nitroacetic acid ethyl ester (626-35-7)

Conditions	Yield
With HOF* CH3CN In chloroform at 0℃;	75%

ethyl chloronitroacetate (14011-27-9) + propionaldehyde (123-38-6) → nitroacetic acid ethyl ester (626-35-7) + ethyl α-chloro-α-nitro-β-hydroxyvalerate (84115-12-8)

Conditions	Yield
With zinc; iodine In diethyl ether for 25h; Heating; reaction with other aliphatic carbonyl compounds;	A n/a B 72%
With zinc; iodine In diethyl ether 1) 5 h, reflux, 2) 20 h, r.t.;	A n/a B 72%

N-ethylethane-1,2-diamine (110-72-5) + diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-[2-(ethylamino)ethylamino]-3-oxopropanoate

Conditions	Yield
In dichloromethane at 20℃; for 24h; chemoselective reaction;	A n/a B 72%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + 1,2-diaminopropan (78-90-0, 10424-38-1) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-[(2-amino-2-methyl)ethylamino]-3-oxopropanoate

Conditions	Yield
In chloroform at 20℃; for 24h; chemoselective reaction;	A n/a B 70%

ethyl acetoacetate (141-97-9) → nitroacetic acid ethyl ester (626-35-7) + diethyl 1,2,5-oxadiazole-3,4-dicarboxylate 2-oxide (18417-40-8)

Conditions	Yield
Stage #1: ethyl acetoacetate With sulfuric acid; nitric acid In dichloromethane at -5 - -3℃; Flow reactor; Stage #2: With ethanol at 30℃; Flow reactor;	A 70% B 22 %Spectr.

morpholine (110-91-8) + diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) → nitroacetic acid ethyl ester (626-35-7) + 3-(4-Morpholinyl)-3-oxopropansaeure-ethylester (37714-64-0)

Conditions	Yield
In chloroform at 20℃; for 24h;	A n/a B 68%

ethyl bromoacetate (105-36-2) → nitroacetic acid ethyl ester (626-35-7) + ethyl 2-hydroxyacetate (623-50-7)

Conditions	Yield
With Amberlite IRA 900 NO2- form In acetonitrile at -15℃;	A 65% B 28%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + isopropylamine (75-31-0) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-isopropylamino-3-oxopropanoate (71510-97-9)

Conditions	Yield
In dichloromethane at 40℃; for 24h;	A n/a B 62%

ethanol (64-17-5) + methyl 2-nitroacetate (2483-57-0) → nitroacetic acid ethyl ester (626-35-7) + nitromethane (75-52-5) + carbon dioxide (124-38-9)

Conditions	Yield
With di(n-butyl)tin oxide at 100℃; for 1.5h; Catalytic behavior; Reagent/catalyst; Temperature; Sealed tube; Inert atmosphere;	A 61% B n/a C n/a

2-(N,N-dimethylamino)ethanol (108-01-0) + diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-(2-dimethylaminoethoxy)-3-oxo-propanoate (1010190-08-5)

Conditions	Yield
In chloroform at 20℃;	A n/a B 60%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + isopropyl alcohol (67-63-0) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-isopropoxy-3-oxopropanoate (50780-97-7)

Conditions	Yield
at 65℃; for 24h;	A n/a B 59%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + 4-nitro-aniline (100-01-6) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-((4-nitrophenyl)amino)-3-oxopropanoate (10390-08-6)

Conditions	Yield
In chloroform at 60℃; for 24h;	A n/a B 55%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + diethylamine (109-89-7) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-(diethylamino)-3-oxopropanoate (33567-70-3)

Conditions	Yield
In chloroform at 60℃; for 48h;	A n/a B 50%

ethyl chloronitroacetate (14011-27-9) + acetaldehyde (75-07-0) → nitroacetic acid ethyl ester (626-35-7) + ethyl α-chloro-α-nitro-β-hydroxybutyrate (84115-11-7)

Conditions	Yield
With zinc; iodine In diethyl ether 1) 5 h, reflux, 2) 1 h, r.t.;	A n/a B 47%

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + aniline (62-53-3) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-oxo-3-(phenylamino)propionate (53341-66-5)

Conditions	Yield
In dichloromethane at 40℃; for 24h;	A n/a B 45%

4-nitro-5-methylisoxazole (1122-06-1) + ethanol (64-17-5) → nitroacetic acid ethyl ester (626-35-7) + ethyl acetate (141-78-6)

Conditions	Yield
for 4h; Heating;	A 44% B n/a

diethyl 2-nitro-3-oxopentanedioate (1010117-23-3) + tert-butylamine (75-64-9) → nitroacetic acid ethyl ester (626-35-7) + ethyl 3-(tert-butylamino)-3-oxopropanoate (17797-87-4)

Conditions	Yield
In dichloromethane at 40℃; for 24h;	A n/a B 41%

ethyl chloronitroacetate (14011-27-9) → nitroacetic acid ethyl ester (626-35-7) + nitrosulfoacetic acid ethyl ester sodium salt (113689-77-3)

Conditions	Yield
With sodium metabisulfite In ethanol for 0.25h; Heating;	A 33% B 29%

chloroacetic acid ethyl ester (105-39-5) → nitroacetic acid ethyl ester (626-35-7)

Conditions	Yield
With poly(vinylbenzyltriphenylphosphonium nitrite) In benzene for 24h; Ambient temperature;	33%
With poly(vinylbenzyltriphenylphosphonium)*NO2(-) In benzene for 24h; Ambient temperature;	33%

diethyl nitromalonate (603-67-8) → nitroacetic acid ethyl ester (626-35-7)

Conditions	Yield
With potassium hydroxide Neutralisieren mit Salzsaeure;

nitroacetic acid ethyl ester (626-35-7) + 1,3-diphenyl-propen-3-one (614-47-1) → 2-nitro-5-oxo-3,5-diphenylpentanoic acid ethyl ester (24424-11-1)

Conditions	Yield
With (S)-1-(3,5-bis(trifluoromethyl)phenyl)-3-(1-(dimethylamino)-3-methylbutan-2-yl)thiourea at 50℃; for 6h; Michael addition; neat (no solvent); optical yield given as %de;	100%
With diethylamine In ethanol for 18h; Heating;	87%
With sodium hydroxide; poly-L-alanine In water; toluene for 744h; Ambient temperature; the addition of ethyl nitroacetate to the chalcone in presence stereoselective catalyst;	60 % Chromat.

nitroacetic acid ethyl ester (626-35-7) + benzaldehyde (100-52-7) → ethyl α-nitrocinnamate (18315-80-5, 18315-86-1, 16508-09-1)

Conditions	Yield
With [(S)-6-((hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl)methyl)picolinaldehyde]functionalized Rh-[Zr6(μ3-O)4(μ3-OH)4(1,4-benzenedicarboxylate)6]-NH2 In toluene at 100℃; for 24h; Catalytic behavior; Reagent/catalyst; Temperature; Knoevenagel Condensation;	100%
With zirconium(IV) chloride; triethylamine In tetrahydrofuran at 0℃; Reflux; Inert atmosphere; Molecular sieve;	83%
With pyridine; titanium tetrachloride

nitroacetic acid ethyl ester (626-35-7) + Carbonic acid 2-ethoxy-allyl ester ethyl ester → 4-Ethoxy-2-nitro-pent-4-enoic acid ethyl ester

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 45℃; for 24h;	100%

nitroacetic acid ethyl ester (626-35-7) + (2R,3S,4S,5R)-1,6-dicyclohexyl-2,5-di-O-(methanesulfonyl)-2,3,4,5-hexanetetraol (216855-05-9) → (4RS,5S)-5-cyclohexylmethyl-3-ethoxycarbonyl-4-hydroxy-2-isoxazoline 2-oxide (216855-31-1)

Conditions	Yield
With 1H-imidazole; sodium periodate In ethanol; water at 20℃; Oxidation; Henry reaction;	100%

nitroacetic acid ethyl ester (626-35-7) + 3-diethylamino-1-phenyl-propan-1-one (94-38-2) → ethyl 2-nitro-5-oxo-5-phenylpentanoate (91958-55-3)

Conditions	Yield
In toluene Condensation; Heating;	100%
In toluene Heating;	98%

nitroacetic acid ethyl ester (626-35-7) + phenylacetylene (536-74-3) → ethyl 5-phenylisoxazole-3-carboxylate (7063-99-2)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In chloroform at 60℃; for 40h;	100%
With dmap; 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride In acetonitrile at 80℃; for 0.05h; microwave irradiation;	99%
With 2,2,6,6-tetramethyl-piperidine-N-oxyl; oxygen In water at 60℃; for 4h; Reagent/catalyst; Temperature; Green chemistry;	96%

norborn-2-ene (498-66-8) + nitroacetic acid ethyl ester (626-35-7) → ethyl 3-oxa-4-azatricyclo[5.2.1.02,6]dec-4-ene-5-carboxylate

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In chloroform at 60℃;	100%
With 1,4-diaza-bicyclo[2.2.2]octane In chloroform at 60℃; for 40h;	100%
With triethylamine; copper diacetate In chloroform at 60℃; for 20h;
With 1,4-diaza-bicyclo[2.2.2]octane In water at 60℃; for 66h;	95 %Spectr.

nitroacetic acid ethyl ester (626-35-7) + norbornene (498-66-8) → 3-oxa-4-aza-tricyclo[5.2.1.02,6]dec-4-ene-5-carboxylic acid ethyl ester

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In chloroform at 60℃; for 40h;	100%

nitroacetic acid ethyl ester (626-35-7) + propargyl alcohol (107-19-7) → ethyl 5-(hydroxymethyl)isoxazole-3-carboxylate (123770-62-7)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In ethanol at 80℃; for 20h;	100%
With 1,4-diaza-bicyclo[2.2.2]octane In ethanol; chloroform at 80℃; for 72h;	98%
With 1,4-diaza-bicyclo[2.2.2]octane In ethanol at 80℃; for 72h;	97%

nitroacetic acid ethyl ester (626-35-7) + N,N-dimethyl-formamide dimethyl acetal (4637-24-5) → (Z)-3-dimethylamino-2-nitroacrylic acid ethyl ester (64273-40-1)

Conditions	Yield
at 20 - 100℃; for 3.5h;	100%
at 20 - 90℃; for 2.25h; Inert atmosphere;

nitroacetic acid ethyl ester (626-35-7) + N,N-Dimethylacrylamide (2680-03-7) → ethyl 5-[(dimethylamino)carbonyl]-4,5-dihydro-isoxazole-3-carboxylate (1184832-29-8)

Conditions	Yield
With N-methylcyclohexylamine; copper diacetate In chloroform at 60℃; for 20h;	100%
With sodium hydroxide In water at 60℃; for 20h;	72%

nitroacetic acid ethyl ester (626-35-7) + 4-fluorobenzaldehyde (459-57-4) → ethyl 3-(4-fluorophenyl)-2-nitroprop-2-enoate (61924-52-5)

Conditions	Yield
With [Zr6(μ3-O)4(μ3-OH)4(4,4'-biphenyldicarboxylate)6]-NH2 In toluene at 100℃; for 24h; Knoevenagel Condensation;	100%

nitroacetic acid ethyl ester (626-35-7) + heptanal (111-71-7) → C11H19NO4

Conditions	Yield
With [Zr6(μ3-O)4(μ3-OH)4(1,4-benzenedicarboxylate)6][(S)-6-((hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl)methyl)picolinaldehyde]-NH2 In toluene at 100℃; for 24h; Reagent/catalyst; Knoevenagel Condensation;	100%

nitroacetic acid ethyl ester (626-35-7) + 4-bromo-2-(ethylamino)-3-methyl-benzoic acid → 7-bromo-1-ethyl-4-hydroxy-8-methyl-3-nitro-quinolin-2-one

Conditions	Yield
Stage #1: 4-bromo-2-(ethylamino)-3-methyl-benzoic acid With bis(trichloromethyl) carbonate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; Stage #2: nitroacetic acid ethyl ester With triethylamine In tetrahydrofuran at 60℃; Inert atmosphere;	100%
Stage #1: 4-bromo-2-(ethylamino)-3-methyl-benzoic acid With bis(trichloromethyl) carbonate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; Stage #2: nitroacetic acid ethyl ester With triethylamine In tetrahydrofuran at 60℃; Inert atmosphere;	100%

nitroacetic acid ethyl ester (626-35-7) + 3-methyl-4-nitro-5-(4-chlorostyryl)isoxazole (51978-97-3, 53557-97-4) → C16H16ClN3O7

Conditions	Yield
With triethylamine In neat (no solvent) at 20℃; Reagent/catalyst; Michael Addition;	100%

nitroacetic acid ethyl ester (626-35-7) + 3-<(dimethylamino)methyl>-4-(trimethylsilyl)indole (92012-94-7) → ethyl 2-nitro-3-<4-(trimethylsilyl)indol-3-yl>propanoate (92012-96-9)

Conditions	Yield
In acetonitrile Heating;	99%

nitroacetic acid ethyl ester (626-35-7) + 4-bromo-hex-4-en-3-one (811470-76-5) → (4,5-trans)-3-(ethoxycarbonyl)-4-methyl-5-propanoyl-2-isoxazoline 2-oxide

Conditions	Yield
With triethylamine In diethyl ether for 36h;	99%

nitroacetic acid ethyl ester (626-35-7) + (E)-1,1,1-trifluoro-4-phenyl-3-buten-2-one (3108-32-5, 86571-25-7) → 1,1,1-trifluoro-5-nitro-4-phenyl-pentan-2-one

Conditions	Yield
With potassium fluoride In ethanol; water	99%

nitroacetic acid ethyl ester (626-35-7) + (E)-1,1,1-trifluoro-4-phenyl-3-buten-2-one (3108-32-5, 86571-25-7) → ethyl 6,6,6-trifluoro-2-nitro-5-oxo-3-phenylhexanoate

Conditions	Yield
With potassium fluoride In ethanol at 20℃; for 2h;	99%

nitroacetic acid ethyl ester (626-35-7) + (E)-1,1,1,-trifluoro-4-(thophen-2-yl)but-3-en-2-one (209967-65-7) → 1,1,1-trifluoro-5-nitro-4-(2-thienyl)pentan-2-one

Conditions	Yield
With potassium fluoride In ethanol; water	99%

nitroacetic acid ethyl ester (626-35-7) + (E)-1,1,1-trifluoro-4-(3-methoxyphenyl)but-3-en-2-one (204708-11-2) → 1,1,1-trifluoro-4-(3-methoxyphenyl)-5-nitropentan-2-one

Conditions	Yield
With potassium fluoride In ethanol; water	99%

nitroacetic acid ethyl ester (626-35-7) + 6-methoxy 7-methyl benzo[d][1,3]dioxole-5-carbaldehyde (187040-23-9) → C14H15NO7 (1003600-22-3)

Conditions	Yield
With titanium tetrachloride; N-ethyl-N,N-diisopropylamine In tetrahydrofuran Knoevenagel condensation;	99%
Stage #1: 6-methoxy 7-methyl benzo[d][1,3]dioxole-5-carbaldehyde With titanium tetrachloride In tetrahydrofuran at -5 - 20℃; Knoevenagel condensation; Stage #2: nitroacetic acid ethyl ester With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at -5 - 20℃; Knoevenagel condensation;	99%

nitroacetic acid ethyl ester (626-35-7) + (Z)-2-benzoyl-3-phenylacrylic acid ethyl ester (17451-18-2, 39626-31-8, 125105-17-1) → trans-3,5-diphenyl-2,3-dihydrofuran-2,4-dicarboxylic acid diethyl ester

Conditions	Yield
With triethylamine In acetonitrile at 60℃; for 4h;	99%

nitroacetic acid ethyl ester (626-35-7) + norbornene (498-66-8) → 3-oxa-4-aza-tricyclo[5.2.1.0(2,6)]dec-4-ene-5-carboxylic acid ethyl ester

Conditions	Yield
With N-methylcyclohexylamine; copper diacetate In chloroform at 60℃; for 20h; sealed tube;	99%

nitroacetic acid ethyl ester (626-35-7) + (E)-diphenyl-β-(trifluoromethyl)vinylsulfonium trifluoromethanesulfonate (1226574-99-7) → C7H8F3NO4 (1330063-02-9)

Conditions	Yield
Stage #1: nitroacetic acid ethyl ester With 1,8-diazabicyclo[5.4.0]undec-7-ene In dimethyl sulfoxide at 27℃; for 0.166667h; Inert atmosphere; Stage #2: (E)-diphenyl-β-(trifluoromethyl)vinylsulfonium trifluoromethanesulfonate In dimethyl sulfoxide at 27℃; Inert atmosphere;	99%

nitroacetic acid ethyl ester (626-35-7) + hex-5-enenitrile (5048-19-1) → C10H14N2O3 (1374526-16-5)

Conditions	Yield
With sodium hydroxide In water at 60℃; for 16h;	99%

nitroacetic acid ethyl ester (626-35-7) + i-propyl 2-oxo-4-phenylbut-3-enoate (111160-44-2) → (3R)-1-ethyl 6-isopropyl 2-nitro-5-oxo-3-phenylhexanedioate

Conditions

Yield

Stage #1: nitroacetic acid ethyl ester With BF4*C8H12CuN4(1+); (S)-2-((2-(hydroxydi-p-tolylmethyl)pyrrolidin-1-yl)methyl)-6-(trifluoromethyl)phenol; lithium carbonate In toluene at 0℃; for 1h; Michael Addition; Inert atmosphere; Stage #2: i-propyl 2-oxo-4-phenylbut-3-enoate In toluene at 0℃; Catalytic behavior; Reagent/catalyst; Temperature; Time; Michael Addition; Inert atmosphere; enantioselective reaction;

99%

Upstream product

• 64-17-5 ethanol 
• 625-75-2 nitroacetic acid 
• 603-67-8 diethyl nitromalonate 
• 108-24-7 acetic anhydride 
• 141-97-9 ethyl acetoacetate 
• 830-67-1 ethyl 1H-benzo[d][1,2,3]triazole-1-carboxylate 
• 75-52-5 nitromethane 
• 14011-27-9 ethyl chloronitroacetate 
• 123-38-6 propionaldehyde 
• 51026-98-3 ethyl 2-nitro-3-oxobutyrate 
• 60-29-7 diethyl ether 
• 857828-38-7 cyclohexylidene-nitro-acetic acid ethyl ester 
• 7664-41-7 ammonia 
• 110-91-8 morpholine 

Downstream Products

• 63971-99-3 ethyl 3-(1H-indol-3-yl)-2-nitropropanoate 
• 101794-13-2 3-benzoylamino-2-nitro-3-phenyl-propionic acid ethyl ester 
• 261511-10-8 Ethyl 3-(acetylamino)-2-nitro-3-phenylpropionate 
• 444880-23-3 3-ethylamino-3-(4-chloro-phenyl)-2-nitro-propionic acid ethyl ester 
• 18315-86-1 Z-β-ethoxycarbonyl-β-nitrostyrene 
• 58651-44-8 2-Nitro-3-p-toluidinoacrylsaeureaethylester 
• 52617-55-7 5-nitro-4-(4-nitro-phenyl)-2-oxy-4,5-dihydro-isoxazole-3-carboxylic acid ethyl ester 
• 52617-54-6 5-nitro-4-(3-nitro-phenyl)-2-oxy-4,5-dihydro-isoxazole-3-carboxylic acid ethyl ester 
• 52617-56-8 4-(4-methoxy-phenyl)-5-nitro-2-oxy-4,5-dihydro-isoxazole-3-carboxylic acid ethyl ester 
• 31731-23-4 3-(2-nitroethyl)indole 
• 16782-23-3 ethyl 3-phenyl-2-nitropropionate 
• 156122-25-7 ethyl 2-benzyl-3-phenyl-2-nitropropionate 
• 131934-12-8 [(Z)-Hydroxyimino]-(4-methoxy-phenyl)-acetic acid ethyl ester 
• 131934-11-7 ethyl (o-methoxybenzoyl)formate oxime 

Relevant articles and documents

Transesterification of Methyl 2-Nitroacetate to Superior Esters

Methyl 2-nitroacetate and methyl acetoacetate have in common the presence of an electron-withdrawing substituent geminal to the methyl ester function but the well-known ease of thermal transesterification of methyl acetoacetate has not been found in methyl 2-nitroacetate. The latter gives uncatalysed thermal transesterification only in low yield and at a temperature higher than that of methyl acetoacetate. Comparative experiments provided further insight into the reactions; protic and Lewis acid catalysts promoted the smooth exchange of the alkanoyl groups, observing first the transesterification of methyl 2-nitroacetate with ethanol, already proved difficult to proceed. Dibutyltin(IV)oxide (DBTO) catalyst offered the spur to set up a convenient synthetic methodology from methyl 2-nitroacetate, encompassing higher molecular weight and functionalised alcohols: aliphatic, unsaturated and oxidation sensitive species were suited to react, delivering the corresponding 2-nitroacetate esters in good yields in most cases.

Catalytic Enantioselective Desymmetrization of Norbornenoquinones via C(sp2)-H Alkylation

The enantioselective Diels-Alder (DA) reaction with monosubstituted p-benzoquinones is an unmet challenge. A new approach for the enantioselective synthesis of monosubstituted quinone-DA adducts is presented based on C(sp2)-H alkylative desymmetrization of meso-DA adducts. Catalyzed by a tertiary amino-thiourea derivative, this reaction utilizes nitroalkanes as the alkylating agents and generates densely functionalized products bearing at least four contiguous stereogenic centers remote from the reaction site with excellent enantioselectivities.