1- nitro-2-phenylethane

Authentic Samples. Authentic samples of identified compounds were obtained from reliable commercial sources or synthesized by established methods. All samples were purified by GLC separation and their identities verified by mass or infrared spectrometry. 1-Nitro-3-niethylbutane and 1-nitro-2-phenylethane were synthesized according to the method of Kornblum et al.(j ) by the reactions of 1-bromo-3-methylbutane and 2-phenylethylbromide with sodium nitrite in dimethylformamlde and urea. 

The nitro compounds, 1-nitro-3-methylbutane and 1-nitro-2-phenylethane, were particularly difficult to identify because they give very weak parent ions with electron ionization (E.I.). However, C.I. mass spectra gave adequate M+1 ions. 

Nitro-2-phenylethane bears a similar relationship to phenylalanine and phenylacetonitrile. The nitro compounds are possibly formed by oxidation of these amino acids. Stone et al., ( ) had previously presented evidence (using radioactive isotopes) that leucine was one of the precursors of 2-isobutylthiazole. 1-Nitro-2-phenylethane is a moderately potent odorant with an odor threshold of 2 ppb and as later discussed probably contributes to the tomato aroma. 

Odor descriptions of dilute water solutions of P-damascenone and 1-nitro-2-phenylethane were also obtained using a panel of 18-20 judges. p-Damascenone as a 10 ppb solution in water was described as having an odor most similar to (1) prunes (2) apple (3) sweet character and (4) tomato in that order (i.e. being most like prunes). The odor of 1 ppm solutions of 1-nitro-2-phenylethane were described as (1) green (2) geranium (3) tomato and (4) oily in that order. 

Methoxy-2-phenylethan-2-one 1 -Phenoxy-2-phenylethan-2-one 1 -Amino-2-phenylethan-2-one l-Pyrrolidinyl-2-phenylethan-2-one l-Dimethylamino-2-phenylethan-2-one l-Diphenylamino-2-phenylethan-2-one l-Phenylmethylsulfanyl-2-phenylethan-2-one l-Phenylsulfanyl-2-phenylethan-2-one l-Phenylselenyl-2-phenylethan-2-one 1 -Cyano-2-phenylethan-2-one 1 -Nitro-2-phenylethan-2-one l-Phenylsulfonyl-2-phenylethan-2-one... 

This method is very useful for the construction of 1-substituted 3,4-dihydroisoquinolines, which if necessary can be oxidized to isoquinolines. A P-phenylethylamine (l-amino-2-phenylethane) is the starting material, and this is usually preformed by reacting an aromatic aldehyde with nitromethane in the presence of sodium methoxide, and allowing the adduct to eliminate methanol and give a P-nitrostyrene (l-nitro-2-phenylethene) (Scheme 3.17). This product is then reduced to the p-phenylethylamine, commonly by the action of lithium aluminium hydride. Once prepared, the p-phenylethylamine is reacted with an acyl chloride and a base to give the corresponding amide (R = H) and then this is cyclized to a 3,4-dihydro-isoquinoline by treatment with either phosphorus pentoxide or phosphorus oxychloride (Scheme 3.18). Finally, aromatization is accomplished by heating the 3,4-dihydroisoquinoline over palladium on charcoal. 

Trifluoroacetaldehyde hydrate (5.4 g, 47 mmol) and anhyd K2C03 (0.1 g, 0.7 mmol) were added at rt to 2-nitro-l-phenylethane (5.9 g, 39 mmol), and the mixture was heated at 50 °C for 12 h. The mixture was cooled and dissolved in Et20 (100 mL), washed with H20, the organic layer separated, dried, and concentrated, giving a viscous oil yield 9.5 g (98%). 

Application of Accelerating Rate Calorimetry (ARC) in Evaluating a Reaction with a Potentially Explosive Nitro Compound. One of our process development projects required the preparation of 2-hydroxy-l-nitro-2-phenylethane via the addition of sodium methoxide to a mixture of one mole of benzaldehyde and one mole of nitromethane in methanol (Scheme 1). 

According to Goddard, styrene reacted with nitryl chloride to yield 1,2-di-chloro-l-phenylethane in 70-80% yield. Another product l-chloro-2-nitro-l-phenyl-ethane was thought to be present, but could not be isolated. On distillation it decomposed, evolving HC1, and o- nitrostyrene was obtained. 

Reduction of T [l-(2-nitrophenyl)-l//-pyrrol-2-yl]sulfonyl -acetone or -1-phenylethan-l-one with sodium borohy-dride and 5% palladium on carbon, a reagent known to convert aromatic nitro compounds to hydroxylamines, triggers intramolecular interaction and gives pyrrolo[l,2- ][3,l,6]benzothiadiazocine derivatives 90 (Equation 11 <2001MI1405, 2004T8807>). This method was further successfully applied to the reductive cyclization of 2- [l-(2-nitrophenyl)-17/-pyrrol-2-yl]sulfanyl acetonitrile. 

In A,A-dimethylformamide, antz-debromination of erjt/ ro-l,2-dibromo-l-(4-nitrophenyl)-2-phenylethane with (zz-C4H9)4N CN gives 99 emol/mol 4-nitro-trazr>s-stilbene. As the solvent composition approaches pure ethanol, the proportion of a-bromo-4-nitro-czs -stilbene, the product of azztz-dehydrobromination, increases to 90 emol/mol. The E2C reaetion involves a looser activated eomplex, better solvated by protie solvents than its tighter E2Br-like eounterpart [396]. 

Two aroma reconstitution experiments have been performed for tomato paste. In the first experiment [81 ] a synthetic mixture containing the odorants nos. 2, 8, 9, 15, 17 (3-isomer), 21 and l-nitro-2-phenylethane was used. The concentration of the first six odorants was in the range shown in Table 6.46. In the second experiment [82] the aroma model contained the 15 odorants in the concentration equal to those reported in Table 6.46. A comparison indicated that the aroma of this mixture was very close to the aroma of the original. Obviously, l-nitro-2-phenylethane does not contribute to the aroma of tomato paste. 

Methylene compounds with two neighboring sulfone groups can also be used for diazo transfer reactions as shown in 1964 by Klages and Bott. They obtained diazobis(ethylsulfonyl)methane (2.127) and diazobis[(diethylamino)sulfonyl)]me-thane (2.128) in aqueous ethanol and NaOH at - 5 °C and in ether with methyl-lithium at room temperature, respectively. In a similar way, methylene compounds activated by a sulfone and a carbonyl group, yield diazo derivatives, e.g., 1-diazo-l-(4 -toluene)sulfonyl propan-2-one (2.129, van Leusen et al., 1965), 2-diazo-2-(me-thylsulfonyl)-2-phenylethan-l-one (2.130, Illger et al., 1972), l-diazo-l-[(4 -nitro-phenyl)sulfonyl)]propan-2-one (2.131, Hodson et al., 1968), and other a-diazo-)ff-oxo-)ff -sulfonyl compounds (Monteiro, 1987 b) and similar diazoalkanes (van Leusen and Strating, 1988). 

Potatoes 2-Isopropyl-3-methoxypyrazine together with 2,5-dimethylpyrazine (see pyrazines) dominate in raw potatoes. Key compounds in boiled potatoes are meAional and 2-ethyl-3,6-dimethylpyrazine. Tomatoes The highest flavor values in fresh tomatoes are exhibited by (Z)-3- and ( )-2-hexenals (see alkenals), j3- ionone, hexanal (see alkanals), 8-damascenone, I-penten-3-one (CsHgO, Mr 84.12, CAS [1629-58-9], 3-methylbutanal (see alkanals), and 2-isobutylthiazole. The most important flavor components in tomato pulp are dimethyl sulfide, )8-damascenone, )5-ionone, 3-methylbutanal, I-nitro-2-phenylethane (CgH,N02, Mr 151.16, CAS [24330-46-91), eugenol, methional, and 3-methylbutanoic acid. ... 

Interaminense, L. D., dos Ramos-Alves, R E., de Siqueira, R. J., Xavier, R E., Duarte, G. R, Magalhaes, P. J. et al. (2013). Vasorelaxant effects of l-nitro-2-phenylethane, the main constituent of the essential oil of Aniba canelilla, in superior mesenteric arteries from spontaneously hypertensive rats. 

Ethylphenol has been isolated from the oleoresin of Picea abies (94). Notably, nitro compounds have also been found, namely l-nitro-2-phenylethane in wood and bark of Ocotea pretiosa and Aniba canelilla (65), and thalictoside (19) and its glucose 6-caffeoate in the bark of Parabenzoin praecox (157). A glucoside, salidroside, of 4-hydroxy-hydroxyethylbenzene has been isolated from the bark of Salix triandra (169). 

Gottlieb O R, Magalhaes M T 1959 Occurrence of l-nitro-2-phenylethane in Ocotea pretiosa and Aniba canelilla. J Org Chem 24 2070-2071... 

Phenylalanine l-nitro-2-phenylethane, phenyla-cetaldehyde, phenylethanol Tomato [97]... 

In this context the recently documented, specific incorporation of l-nitro-2-phenylethane (85) into benzylglucosinolate in T. majus, comparable with that of DL-phenylalanine, deserves attention. Definite proof that the nitro-com-pound, or maybe rather its aci-tautomer (86), plays the role as a true intermediate, foreshadowed several years ago, is still outstanding and will supposedly require studies at the enzymic level. If confirmed, the subsequent steps, (86) -> (87) -> (88), appear unexceptional and not without in vitro analogies. What remains a fact is that phenylacetaldoxime in the intact plant gives rise to the production of l-nitro-2-phenylethane, present in shoots of T. majus, albeit in concentrations as low as SO pg per 100 g of fresh weight. ... 

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