Trinitromethane → HCID 12489465、化合物

HRID 1578163ノート

反応式

HRID 1578163 の反応式
[CH:1]([N+:8]([O-:10])=[O:9])([N+:5]([O-:7])=[O:6])[N+:2]([O-:4])=[O:3].[CH2:11]=[C:12]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:13]([O:15][CH2:16][CH3:17])=[O:14]>CO>[N+:2]([C:1]([N+:8]([O-:10])=[O:9])([N+:5]([O-:7])=[O:6])[CH2:11][CH:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:18]([O:20][CH2:21][CH3:22])=[O:19])([O-:4])=[O:3]

参加物

4

反応物 2

HCID 10602TrinitromethaneHCID 951181,3-Diethyl 2-methylenepropanedioate

生成物 1

HCID 12489465HCID 12489465、化合物

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

Carefully controlled reaction conditions are required because the addition of a nucleophile (nitro- or halonitroalkyl ion) to a methylenemalonate ester gives the salt of an alkylmalonate which is itself capable of undergoing further nucleophilic reactions. Nitroform, a strong acid, reacts with diethyl methylenemalonate in aqueous methanol at ambient temperature, without a base as catalyst, to produce diethyl 2,2,2-trinitroethylmalonate. The same conditions may also be used to produce dimethyl 2,2,2-trinitroethylmalonate. The reaction of 1,1-dinitroethane with methylenemalonates does not take place under these conditions, presumably because the nitro compound is not sufficiently ionized. However, the addition of triethylamine to an ether solution of 1,1-dinitroethane and dimethyl methlenemalonate at 0° C. resulted in a 72% yield of dimethyl 2,2-dinitropropylmalonate. In the same manner, diethyl 2,2-dinitropropylmalonate may be prepared. Finally, the addition fluorodinitromethane to methylenemalonates in ether solution in the presence of catalytic amounts of pyridine produces good yields of dimethyl and diethyl 2-fluoro-2,2-dinitroethylmalonates.

出典と根拠

ORDレコード
ord-f39463d76a6c424c917a8b4e775dee02
出典データセット
uspto-grants-1981_09
特許番号
US04291171

反応ノート

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