F-Butyl nitrite

The reaction gives better yield with dienes, styrenes, or alkenes substituted with EWGs than with simple alkenes. These groups increase the rate of capture of the aryl radical. The standard conditions for the Meerwein arylation employ aqueous solutions of diazonium ions. Conditions for in situ diazotization by f-butyl nitrite in the presence of CuCl2 and acrylonitrile or styrene are also effective.115... 

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... 

Sugamoto and colleagnes have attempted the rednction-nitrosation of the conjn-gated olefins 33 by the nse of f-bntyl nitrite instead of oxygen (Scheme 24). Various olefins such as styrenes, a,-unsaturated carbonyl compounds and a, S,y,5-unsaturated carbonyl compounds were directly converted to the corresponding acetophenone oximes, a-hydroxyimino carbonyl compounds and y-hydroxyimino-a,/S-unsaturated carbonyl compounds in good or moderate yields by rednction-nitrosation with f-butyl nitrite and triethylsilane in the presence of cobalt(II) porphyrin as a catalyst (Scheme 24). 

The combined use of 3.0 equivalents of f-butyl nitrite and 3.0 equivalents of triethylsilane with 34 was found to be required for the complete consumption of 34. Under these conditions, oxime 35 was obtained in 91% yield along with 2% yield of ketone 36 (Scheme 25). 

Primary alkyl amines RNH2 can be converted1045 to alkyl halides by (1) conversion to RNTs2 (p. 354) and treatment of this with I" or Br in DMF,347 (2) diazotization with f-butyl nitrite and a metal halide such as TiCl4 in DMF,1046 or (3) the Katritzky pyrylium-pyridinium method (p. 354).1,147 Alkyl groups can be cleaved from secondary and tertiary aromatic amines by concentrated HBr in a reaction similar to 0-68, e.g.,104,1... 

Butyl 4-methylbenzenesulfonate, see Butyl toluenesulfonate, 3403 f Butyl methyl ether, 2004 f turf-Butyl methyl ether, 2005 Butyl nitrate, 1656 f Butyl nitrite, 1653 f ferf-Butyl nitrite, 1654... 

Problem 13.51 Inorganic acids such as H2S04, H3P04, and HOC1 (hypochlorous acid) from esters. Write structural formulas for (a) dimethyl sulfate, (b) tribenzyl phosphate, (c) diphenyl hydrogen phosphate, (d) f-butyl nitrite, (e) lauryl hydrogen sulfate (lauryl alcohol is n-C ]H23CH2OH), (/) sodium lauryl sulfate. ... 

Diazotization in organic solvents allows solid diazonium salts to be isolated. Diazotization can be carried out using an ester of nitrous acid, such as pentyl nitrite, in a solvent such as acetic acid or methanol. A procedure has also been described for isolating diazonium tetrafluoroborates, in excellent yield, by carrying out the diazotization with boron trifluoride etherate and f-butyl nitrite in ether or dichlorometh-ane at low temperature. Another method for the preparation of a variety of diazonium salts in a nonaqueous medium makes use of the chemistry of bis(trimethylsilyl)amines (8). These compounds react in dichloromethane with nitrosyl chloride and other nitrosating agents which are generated in situ. Thus, benzenediazonium chloride was isolated (96%) from bis(trimethylsilyl)aniline. 

Treatment of 2-amino-6-substituted purine nucleosides with f-butyl nitrite and catalytic amounts of SbCla in a chlorinated hydrocarbon solvent gave 2-chloro-6-substi-tuted derivatives smoothly (Eq. 1). The corresponding 2-bromo analogs were obtained when SbBrs was used in a brominated hydrocarbon solvent (Eq. 1) [6]. 

Methyl nitrite on an Ag(lll) surface undergoes decomposition on irradiation at X > 365 nm or by 50 eV electrons. The decomposition involves the extrusion of NO from both irradiation methods but X-ray irradiation (50 eV) also supplies evidence for the formation of methyl radicals, formaldehyde and methanol48. The orientation of the methyl nitrite monolayer on the silver is consistent with the NO extrusion process49. f-Butyl nitrite also undergoes loss of NO when a thin film assembled on silver(l 11) is irradiated at 355 nm50. 

Aryl halides are frequently prepared from the corresponding aryldiazonium salts by diazotation procedures. However, diazonium salts can be subjected directly to very mild Heck arylation conditions, which deliver coupled products (entry 19). Preferably, the reaction is executed in nonaqueous solvents such as acetonitrile, acetone, or methylene chloride with sodium acetate as base and with palladiumbis(dibenzylideneacetone) as catalyst. Alternatively, a combination of the amine and f-butyl nitrite, in a mixture of acetic acid and monochloroacetic acid, can provide the desired product directly, which makes the isolation of a diazonium salt unnecessary (entry 20). " It is also possible to use aromatic acid anhydrides as oxidative addition precursors (entry 21). Clearly, anhydrides are very interesting starting materials for a number of Heck reactions due to price and absence of halide salt formation. 

Castle, K.J., J. Abbott, X. Peng, and W. Kong (2000), Photodissociation of f-butyl nitrite between 220 and 250 nm Internal energy distribution of NO, Chem. Phys. Lett., 318, 565-570. 

McMillan, GR., l.G Calvert, and S.S. Thomas (1964b), Nitrosomethane formation in photolysis of f-butyl nitrite, J. Phys. Chem., 68, 116-120. 

Rdsslein, M., E. Kades, K. Bergmann, and J.R. Huber (1995), Alignment detected photofragment yield spectroscopy demonstratred by photodissociation of f-butyl nitrite in a supersonic jet, Chem. Phys. Lett., 235, 242-246. 

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