Octyl nitrite

The photolysis of 1-octyl nitrite 6 yields 4-nitroso-l-octanol 8 in 45% yield, via cyclic transition state 7—the formation of regioisomeric nitroso alcohols is not observed ... 

The silver salts are removed by filtration, slurried with two 100-ml. portions of dry ether, and the ether washings are added to the ethereal solution of reaction products (Note 6). The combined ethereal solutions are distilled at atmospheric pressure through a 2 x 45 cm. column packed with 4-mm. Pyrex helices (Note 7). The residue remaining after removal of the ether is fractionated under reduced pressure. The yellow liquid distilling at 37°/3 mm. has wf 1.4127-1.4129 and weighs 11.3 g. (14%) this is 1-octyl nitrite. It is followed by an interfraction of b.p. 38-70°/3 mm., n 1.4133-1.4320, yield 6.83 g., which contains some nitrite, some 1-octanol, and a little l-nitrooctane. Finally, pure, colorless l-nitrooctane distils at 66°/2 mm., k 1.4321-1.4323, yield 59.6-63.6 g. (75-80%) (Notes 8 and 9). 

Octyl alcohol, 34, 3 -Octyl fluoride, 36, 42 1-Octyl nitrite, 38, 75 Olefins from amine oxides, 39, 41, 42 Oleic acid, 37, 66, 68, 77 39, 15 Oleoyl chloride, 37, 66 Orthocarbonic acid, tetraethyl ESTER, 32, 68... 

Vitrellae are thin walled glass capsules containing volatile substance (drops) (e.g. amyl or octyl nitrite) and protected by absorbent cotton wool and an outer silk bag. This capsule is crushed and the vapours are inhaled in the treatment of angina. 

The involvement of an intramolecular hydrogen abstraction in the Barton reaction is not necessarily limited to those molecules with rigid stereochemistry. In fact, simple aliphatic nitrites undergo the Barton reaction with equal ease. Thus, the principal product obtained from the photolysis of ra-octyl nitrite20 in benzene solution is the dimer of 4-nitroso-l-octanol however, photolysis of n-octyl nitrite in n-heptane20 produced a mixture of 7/-nitroso heptanes in addition to 4-nitroso-l-octanol in the ratio l 4.5,f respectively. The formation of y-nitroso heptane obviously results from an attack of the intermediate alkoxy radical on the solvent molecule. The intermediate alkyl radical then collapses, according to eq. 2. For the sake of convenience we have indi-... 

The photolysis of n-octyl nitrite in n-heptane provides a favorable situation for comparing the tendency of an alkoxyl radical to undergo the Barton-type intramolecular reaction or, alternatively, the intermolecular reaction as indicated in eqs. 1 and 2. Calculations23 reveal that both intramolecular and intermolecular hydrogen abstraction involving a second-... 

Irradiation of octyl nitrite has already been described Kabasakalian et al. have also studied the behavior of its lower homologs.24 It was observed that primary alkyl nitrites with more than four carbon atoms in a chain produced essentially identical yields (37 to 45%) of nitroso dimer formed by the Barton reaction until the minimum straight-chain length of four carbon atoms was reached. Butyl nitrite underwent internal hydrogen abstraction in poor yield. This is the result of a more difficult abstraction of a primary hydrogen as compared to a secondary hydrogen atom available in compounds with longer chains. Reaction paths 2 and 4 predominated to afford 1-butanol and butanal as the major products. 

Also developed by Hill is a (diotochemical system (equations 41 to 48) based on a polyoxoacid, H3PWi2O40 (P)> The excited state of the acid probably oxidizes the alkane in the first step. The radical can then either attack the solvent to give an iminium radical, wiiich leads to ketone on hydrolysis, or it can be oxidized to the caifaonium ion, in wdiich case attack on the solvent leads instead to the -alkyl-acetamide. If the substrate has two adjacent tertiary C—bonds, then alkenes tend to be formed, llie Barton reaction, normally kmwn as an intramolecular C—activation, can give some intermolecular reaction in some examples. Thus, vdien n-octyl nitrite is rf)otolyzed in heptane, some nitrosoheptane is observed. ... 

Compounds having active methylene groups react with nitrous acid to form oximino derivatives. The attack on the a-methylene group of ketones is illustrated by the action of ethyl nitrite on methyl ethyl ketone, and by the action of methyl nitrite on propiophenone, to form biacetyl monoxime (60%) and isonitrosopropiophenone (68%), respectively. Methyl and ethyl nitrites are passed in gaseous form into the ketones in the presence of hydrochloric acid. In other preparations, n-butyl, amyl, or octyl nitrite in liquid form is employed. ... 

Quantum yield measurements for the photolyses of isopropyl , l-butyl , t-pentyl and -octyl nitrites are given in Table 33. These refer to the radical forming step (a) in some cases, radical recombination occurs, as evidenced by the lower than unity quantum yields. In the case of isopropylnitrite it was shown that molecular elimination of HNO in a primary process does not occur, and that the syn and anti conformers decompose with the same quantum efficiency. 

Nitrate esters can also be made by the oxidation of nitrite esters (Vol. I, p.2). This reaction can also be carried out through a photolysis of nitrite esters. Such is, for example, the photolysis of octyl nitrite in heptane saturated with oxygen of the probable mechanism as below [47, 48] ... 

Alkyl nitrites. An efficient method for the preparation of 2-octyl nitrite described by Kornblum and Oliveto is as follows. A solution of 0.6 mole of 2-octanol in 240 ml. of pyridine is stirred at 0-10°, and 0.95 mole of nitrosyl chloride is allowed to evaporate into the solution in the course of about 3 hrs. Petroleum ether and water are run into the mixture, and the organic layer is washed, dried, and distilled. Reaction of the alcohol with sodium nitrite and sulfuric acid afforded the ester in only 59% yield. 

There appear to have been no further studies on the thermal decomposition of alkyl nitrites until 1949. Then two more complex nitrites were studied. Komblum and Oliveto (1949) examined the thermal decomposition of optically active 2-octyl nitrite in the liquid phase at 100°C. Optically pure r(-2-octanol was obtained in excellent yield, thus showing that 2-octoxyl radicals were produced, and that these did not racemize. 

Some details about the reduction of hydroximinocamphor (325) and its conversion into the pyrazine (326) have been published.In addition to its preparation with 2-octyl nitrite on camphor,this compound (325) is also one of the... 

In a three-necked flask fitted with a stirrer and a dropping funnel were plaeed 43.2 g 2-methyl-2-octanol (0.3 mol) and 41.4 g sodium nitrite (0.6 mol) dissolved in a minimum amount of water. The mixture was cooled to 0°C and then, with continuous stirring, 71 g Al2(S04)3 18H2O (0.12 mol) dissolved in sufficient water to give a40% solution was added over a period of 1 h. After the addition was complete, the reaction mixture was stirred at ice temperatures for 2 h more and poured into a separatory funnel the aqueous layer was removed, and the yellow organic layer was washed three times with water and dried over anhydrous sodium sulfate. Rectification gave 37.8 g 2-methyl-2-octyl nitrite, in a yield of 72%, b.p., 56°C (3 mmHg). 

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