1 - -2-nitro-1 -proPENE

Nitropropene Polymers. There are two nitro-propenes which can be considered energetic materials, 1- and 2-nitropropene polymers... 

Nitropropylenes. See under Propene and Derivatives as 1-, 2-Nitro and Di-Nitro Propenes in this Vol... 

Mix 0.25M substituted benzaldehyde, 0.3M nitroethane, 50 ml dry toluene and 5 ml n-butylamine (or other amine), and reflux 3 hours with a Dean-Stark trap (or prepare the nitro-propene as described elsewhere here). Add 50 g iron powder and 1 g FeCl3 optional) and reflux while adding 90 ml concentrated HCI over 3 hours. Reflux 1 hour more, add 2 liters of water and extract 3 times with ether, then dry and evaporate in vacuum (or steam distill until about 3.5 liters of distillate is obtained extract the distillate 3 times with toluene wash the toluene layers with 7 g NaHS03 in 225 ml of water, then 3 times with water and dry, evaporate in vacuum) to get the ketone. Mix 0.13M ketone, 28 g formamide (or dimethyl-formamide if the N.N-dimethylamine is desired) and 3 ml formic acid and heat at 160°. Add 3 more ml formic acid and heat 16 hours at 170-180° adding formic acid from time to time to keep the pH acid. Distill off the water formed (about 16 ml), cool and extract with 3X70 ml benzene. Distill off the benzene and reflux the residue 7 hours with 30 ml concentrated HCI. Chill, basify with 10% NaOH and extract with 3X70 ml ether. Dry and evaporate the ether in... 

Never use excessive heat for drying. I have heard of nitro propene burning faster than gunpowder due to excessive heat. Personally, 1 feel this could have been caused by a nearby pilot light that was left burning. 

Bromo-2,5-Dimethoxyamphetamine, This should be prepared by reducing the above nitro-propene with LAH as described below. Other reductions may or may not be compatible with the electronic character of the bromine atom. This particular reduction can also be used to reduce most any nitrostyrene, nitrobenzene, etc. Note These will work too, CPB, 16, 217 or JACS, 72, 2781, also found in this book. 

Setzt man Allyl-silane mit Nitronium-tetrafluoroborat in Dichlormethan um, so entsteht 3-Nitro-propen in 80%iger Ausbeute3 ... 

The dipolarophile was prepared in a short (three-step) sequence from methyl phenyl sulfone (38% overall yield) and ethyl trifluoroacetate. Desulfonation, followed by reductive N-0 cleavage afforded the syn aminoalcohols [246]. Conjugate additions to the sulfone were described some years earlier [247] more recently, trifluoromethyl pyrroles have been synthesised from the nitro-propene [248]. 

A mixture of 50 g l-(3-methoxy-4,5-methylenedioxyphenyl)-2-nitro-propene and 26 g racemic a-methylbenzylamine was heated on the steam bath. The mixture gradually formed a clear solution with the steady evolution of nitroethane. When the reaction became quiet, there was added a mixture of 20 mL concentrated HC1 in 100 mL H20. The reaction mixture dissolved completely, and as the temperature continued to rise there was the abrupt solidification as the formed myristicinaldehyde crystallized out. This product was removed by filtration and, when combined with a second crop obtained by the hexane extraction of the filtrate, gave 36.9 g of myristicinaldehyde. The mp of 128-129 °C was raised to 133-134 °C by recrystallization from hexane. 

A solution of 6.64 g 3,4-ethylenedioxybenzaldehyde in 40 mL nitroethane was treated with 0.26 g anhydrous ammonium acetate and held at reflux for 3 days. TLC analysis showed that there was much aldehyde remaining unreacted, so an additional 0.7 g ammonium acetate was added, and the mixture held at reflux for an additional 6 h. The excess nitroethane was removed under vacuum. The residue was dissolved in 30 mL hot MeOH which, with patience and slow cooling, finally deposited a heavy yellow-gold powder. This product l-(3,4-ethylenedioxyphenyl)-2-nitro-propene melted at 95-96 °C and weighed 6.03 g when air dried to constant weight. Recrystallization from either MeOH or EtOAc gave the product as a yellow solid, but without any improvement in mp. 

Nitro-propen reagiert mit Phosphorigsaure-trimethylester in Diethylether bei 25° in, 80% Ausbeute zu 1-Methyl-ethenphosphonsaure-dimethylester397 ... 

Die Verwendung von Phosphorigsaure-dialkylester-trimethylsilylester fur Additionsreaktionen bietet praparative Vorteile, da milde Reaktionsbedingungen moglich sind. Bei-spielsweise verlauft die Reaktion mit 1-Nitro-propen zu 100%435 (/ - Me thy l-2-1rime thy Is i -lyloxynitrono-ethanphosphonsaure-dimethylester -diethytester) ... 

A wide array of compounds undergo the Nef reaction. These include simple nitro compounds, as well as complex multifunctional species. For example, the carbohydrate in equation (2) was isolated as its hy-drazone derivative in 72% yield. Nitronate anions generated in situ can be acidified to give good yields of aldehydes and ketones. As an illustration, Michael addition of the dianion of hexanoic acid to 2-nitro-propene gives the expected keto acid after acidification (equation 3). ... 

Nitro-propen addiert lH-Pyrazol (ohne Losnngsmittel 12 h Wasserbad) zu l-(2-Nitro-pro-pyl)-lH-pyrazol [77% Sdp. 123711 Torr (1,47 kPa)]1683. 

Mit 44%Ausbeute wird aus 3-[2-Nitro-propen-(I )-yl]-indol (Quccksilbcr-Mitteldruck-Bogenlampe) 2-Oxo-3-(2-oximino-propylideti)-2,3-dikydro-i idol erhalten1 ... 

Nitro-propene or 2-butene and 1 gave ketofuran adduct 130 and 131 (R = Me), respectively (75CC726, 80JOC2945). A stereoisomeric mixture of hydroxyimino dihydrofuran 132 was obtained in the presence of KE Reaction of 1 with l-nitro-l-(phenylthio)-propene in the presence of KF afforded a diastereomeric mixture of dihydrofuran 133 along with... 

Propane, 1-nitrol Propane-2-nitro Propene (propylene)... 

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