Alkyl nitrite butyl

Solvents and ses Amyl, butyl, alkyl nitrites Nitrous oxide... 

The submitters used amyl nitrite U.S.P. from Mallinckrodt Chemical Works isoamyl nitrite supplied by Matheson, Coleman and Bell is apparently the same material. They found that other alkyl nitrites (ethyl, w-butyl, 1-butvl, amyl) may be used with equal success. Subsequent to the checking of this procedure, they reported that the amount of nitrite can be reduced to a 20% molar excess. 

One of the two enthalpies of formation for the tertiary alkyl nitrites is most probably incorrect. As seen in Table 1, not only is the slope for the liquid-phase data less negative than that for the gas-phase data, but it is much less steep than all other liquid-phase data of which we know. Part of the discrepancy is due to the inverted order of the archival enthalpies of vaporization t-butyl nitrite = 34.4 kJmol-1 and t-pentyl nitrite = 33.5 kJ mol 1. 

Many alkyl nitrites are thermally unstable and may readily decompose or explode on heating [1], Methyl nitrite explodes more violently than ethyl nitrite [2], Lower alkyl nitrites have been known to decompose and burst the container, even in refrigerated storage [3], Individually indexed compounds are f Butyl nitrite, 1658 f fert-Butyl nitrite, 1659... 

Alkyl nitrites can also be used in anhydrous media and, for example, 4-hydroxyben-zenediazonium tetrafluoroborate is isolated in 89% yield after diazotization with isopcntyl nitrite, hydrogen fluoride and boron trifluoride in ethanol/diethyl ether.96 Diazotization can also be performed in dichloromethane or ethers (diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane) with terl-butyl nitrite and boron trifluoride-diethyl ether complex which generates nitrosyl fluoride in situ.229 Excess boron trifluoride is used to trap water and tert-butyl alcohol, so that the reaction can be considered as being performed under complete anhydrous conditions. Yields are higher in dichloromethane, but 1,2-dimethoxyethane is preferred for less soluble amines. This procedure has been successfully applied to the synthesis of mono-and difluorobenzo[c]phcnanthrenes.230... 

Photolysis studies of alkyl nitrites in the vapor phase has been limited to the verification of the presence of a nitroso dimer moiety among the products by ultraviolet spectrophotometry. The principal product of photolysis of butyl nitrite in the vapor phase is the trans-isomer of the dimer of nitrosomethane43 86 87 281 286 the reaction has been explained by a mechanism involving fragmentation of alkoxy-radicals. 

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. 

Amyl nitrite is generally sold in small glass bottles or, in rare cases, small vials or ampoules. It is chemically related to nitroglycerine. It is part of a group of closely related chemicals known as alkyl nitrites. In street terminology, amyl, butyl, isobutyl, isoamyl, isopropyl, and cyclohexyl nitrates and nitrites are collectively... 

The laws and punishment regarding possession of poppers in the United States vary from state to state. In some states, it is illegal to inhale any type of fumes for the purpose of intoxication. For example, in New York, possession or use of any alkyl nitrite, including amyl, butyl, and isobutyl, is a Class A misdemeanor, which carries a jail term of up to one year. The judge also has other punishment options, including imposing a fine and driver s license suspension or revocation. In Connecticut, conviction for possession of amyl nitrite without a prescription carries a penalty for a first offense of up to seven years in prison and a fine of up to 50,000. The maximum penalty for a second conviction is 15 years in prison and a fine of 100,000. 

Pressure-dependent gas phase NMR studies of syn-anti exchange in alkyl nitrite/C02 mixtures reported PiP values of 312,166,26, and <3 torr for MeONO, ethyl nitrite, n-propyl nitrite, and n-butyl nitrite, respectively [75], For all the nitrites studied, experimental rate constants were modeled using RRKM theory. This study concluded that the agreement between the rate constants calculated using RRKM... 

Until relatively recently no kinetic studies on the nitrosation of alcohols had been reported, presumably since the reactions are very rapid and require special techniques. Some kinetic measurements on the reverse reaction, the hydrolysis of alkyl nitrites have been reported here conventional kinetic methods were used. Early workers examined the reactions of the series methyl, ethyl, i-propyl and t-butyl nitrites in an acetic acid-acetate buffer and found a small increase in rate constant along the series (Skrabal et a ., 1939). Later Allen measured the rate constants for the hydrolysis of a number of alkyl nitrites in aqueous dioxan solvent for both acid- and base-catalysed reactions (Allen, 1954). The rate constants for the O-nitrosation of alcohols were determined indirectly by measurement of the overall equilibrium constant for the process, by noting the change in the rate constant for the nitrosation of phenol in the presence of added alcohols. These, combined with the known data for the reverse hydrolysis reaction, enabled the rate constants for the forward reaction to be obtained (Schmid and Riedl, 1967). The reactivity sequence MeOH > EtOH > i-PrOH > t-BuOH was deduced, and attributed to a steric effect. 

For the preparation of small amounts of the isonitroso-ketcme it is more convenient to employ a higher-boiling alkyl nitrite, such as butyl nitrite (p. 7), which can be added directly to the reaction mixture by substituting a dropping funnel for the tube Ti. Butyl nitrite must be freshly prepared or redistilled shortly before use. 

More recently another modification for the preparation of peptide azides was introduced by Alfeeva et al-f l using tetrabutylammonium nitrite as auxiliary reagent. In contrast to the alkyl nitrites which are relatively unstable and therefore have to be purified prior to use by distillation, tetrabutylammonium nitrite is a crystalline and stable compound, which is soluble in anhydrous dipolar aprotic solvents. Moreover, in this procedure the acidity of the reaction mixture is adjusted with anhydrous p-toluenesulfonic acid instead of HCl in anhydrous organic solvents. These conditions are experimentally convenient and more easily controlled than those of the Honzl-Rudinger method. Comparative model reactions performed with ferf-butyl nitrite and tetrabutylammonium nitrite produced nearly identical peptide yields. To date, there are no reports of the condensation of larger fragments and peptide cyclization by this azide procedure. 

Before we talk about this group of aromatic Sfjl reactions in more detail, let s consider how to make the diazonium salt. The reagent we need is the reactive nitrogen electrophile NO. You met NO in Chapter 20, but to remind you, it forms when the nitrite anion (usually sodium nitrite) is treated with acid at around 0 °C. Protonation of nitrite gives nitrous acid, HONO protonation again gives a cation, which can lose water to form NO. Butyl nitrite (or other alkyl nitrites) can also be used as a source of NO. ... 

Similar reactions have been carried out by various investigators using ethyl nitrite, amyl nitrite,and other alkyl nitrites in aqueous or alcoholic solution in the presence of potassium hydroxide or potassium ethylate. In the procedure given below butyl nitrite is used. It is more easily prepared and handled than ethyl nitrite. It may also be used for the preparation of sodium azide. 

The use of dry aryldiazonium salts of naphthalene-1-sulfonic [70], naphthalene-1,5-disulfonic [70], ZnCl2 complex [70], hexafluorophosphoric or tetrafluoroboric acid [61] in non-aqueous medium under as mild as possible reaction conditions is substantial to reach higher yields of biaryls. An alternative method for non-aqueous GBH reaction is the aprotic diazotation of aromatic amines with alkyl nitrites such as butyl or pentyl nitrite with subsequent arylation of aromatic compound, as demonstrated by Cadogan [71,72]. This method is realized by simple heating the mixture of aromatic amine, alkyl nitrite and liquid arene at an elevated temperature. When a mixture of 3-aminopyridine (46), benzene and pentyl nitrite is heated at reflux, 3-phenylpyridine (47) is obtained with a 55% yield [71], Scheme 16. 

The alkyl nitrites that can be abused by inhalation (cyclohexyl nitrite, isobutyl nitrite, isopentyl nitrite) are a special case in that (1) they are extremely unstable and break down rapidly in vivo to the corresponding alcohols and (2) usually also contain other isomers (butyl nitrite, pentyl nitrite). Any products submitted for analysis will usually contain the corresponding alcohols as well as the nitrites. 

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