Cyclohexyl nitrate

Chemical/Physical. The gas-phase reaction of cyclohexane with OH radicals in the presence of nitric oxide yielded cyclohexanone and cyclohexyl nitrate as the major products (Aschmann et al., 1997). 

Amyl nitrite is first synthesized. During the last decades of the twentieth century, amyl nitrite and similar compounds (e.g., butyl, isobutyl, isoamyl, isopropyl, and cyclohexyl nitrates and nitrites) become the chemical basis of poppers. ... 

Adipic acid yields for the combined air-nitric acid process are as high as 80 per cent. Cyclohexyl nitrate is recovered from the off-gas from the oxidizers and may be oxidized to recover adipic acid. ... 

Deamination of primary and secondary amines. Reaction of cyclohexylamine, nitrogen tetroxide, and DBU (or DBN) in ether at -78° furnishes cyclohexyl nitrate in 757 yield. In the absence of the base, a mixture of the nitrate, cyclo-hexanol, and another product is obtained in about 507 yield. The new conditions are also applicable to primary alkyl amines n-octylamine / -octyl nitrate (817o yield). The reaction proceeds with retention of configuration in the case of 3a- and 3 -aminocholesterol. 

Alkyl derivatives other than halides have been used to form pyridinium salts. Potassium ethyl sulphate gives the ethyl-pyridinium salt i and dimethyl sulphate is nd alkyl toluenesulphonates i quaternize pyridine. Primary and secondary alkyl nitrates and polymethylene dinitrates have also been used, but with t-butyl and cyclohexyl nitrate only elimination occurs320. 2,4,6-Trinitro-anisole and -phenetole convert pyridine into the alkylpyridinium picrates32i. 

The absorption of the C=0 and —ONO2 groups in 2-oxo-cyclohexyl-l-nitrate appears to occur with little interaction between the two chromophores. See figure IX-I-10. The sum of the cross sections of cyclopentyl nitrate (a surrogate for cyclohexyl nitrate) and cyclohexanone (filled circles), is seen to follow the cross section data for the nitrocarbonyl over the 275-315 nm region of the absorption. 

One principal use of cyclohexanol has been in the manufacture of esters for use as plasticizers (qv), ie, cyclohexyl and dicyclohexyl phthalates. In the finishes industry, cyclohexanol is used as a solvent for lacquers, shellacs, and varnishes. Its low volatiUty helps to improve secondary flow and to prevent blushing. It also improves the miscibility of cellulose nitrate and resin solutions and helps maintain homogeneity during drying of lacquers. Reaction of cyclohexanol with ammonia produces cyclohexylamine [108-91-8], a corrosion inhibitor. Cyclohexanol is used as a stabilizer and homogenizer for soaps and synthetic detergent emulsions. It is used also by the textile industry as a dye solvent and kier-boiling assistant (see Dye carriers). 

Nitration of 2-cyclohexyl-8-hydroxy-2,3,4,6,11,11 u-hexahydro-1 //-pyra-zino[l,2-6]isoquinoline-l,4-dione with 70% HNO3 at room temperature for 30 min afforded an 1 1 mixture of 7- and 9-nitro derivatives (98MIP7). 

Trans-l and ds-3-bromoflavanone Ih were synthesized by the use of the v procedure of Bognar et al. (ref. 9). Cyclohexyl amine and N,N-dimethylformamide (DMF) was purified by distillation, potassium nitrate (Reanal) was used as received. 

Kinetic measurements were performed on a Hitachi 150-20 UV/VIS spectrophotometer. Dehydrobrominations were studied in DMF solution using cyclohexyl amine (CHA) as the base. Applied CHA concentrations were 2, 2.5, 3, 3.5, 4 and 5 10 3 mole.dm-3, initial concentration of 1 was 5 10 5 mole.dm-3 in every case (pseudo-first-order conditions). Ionic strength was adjusted to lO l mole.dm 3 with potassium nitrate. Kinetic curves / D(t) / were recorded at fix wavelength, X = 290 ran and the temperature was maintained at 30, 35.5, 40°C. Stock solutions were made daily for la and freshly for every measurement of Ih. The reaction was started by injection of solution of 1 to the thermostated solution of CHA. 

A few modem nitrovasodilators have been designed and developed to improve pharmacokinetic properties. Two examples discussed below are (6-chloropyridin-2-yl)methyl nitrate and trans-2-amino-2-methyl-./V-[4-(nitro-oxy)cyclohexyl]propanamide. 

Chemical/Physical. In the gas phase, cycloate reacts with hydroxyl and NO3 radicals but not with ozone. With hydroxy radicals, cleavage of the cyclohexyl ring was suggested leading to the formation of a compound tentatively identified as C2H5(Cff0)NC(0)SC2H5. The calculated photolysis lifetimes of cycloate in the troposphere with hydroxyl and NO3 radicals are 5.2 h and 1.4 d, respectively. The relative reaction rate constants for the reaction of cycloate with OH and nitrate radials are 3.54 x lO " and 3.29 x 10 cm /molecule-sec, respectively (Kwok et al., 1992). 

Lomustine Lomustine, l-(2-chloroethyl)-3-cyclohexyl-l-nitrosourea (30.2.4.3), is made by reacting ethanolamine with cyclohexylisocyanate, which forms l-(2-hydroxyethyl)-3-cyclohexylurea (30.2.4.1). Upon reaction with thionyl chloride, the hydroxyl gronp in it is replaced with a chlorine atom, giving l-(2-chloroethyl)-3-cyclohexylurea (30.2.4.2). This is nitrated in non-aqueons conditions with formic acid and sodinm nitrite to give lomustine (30.2.4.3) [67,68]. 

N-(2-HydroxyethyIj-cyclohexylamine. Its nitrated deriv N-(2-Nitroxyethyl)-cyclohexylnitramine (Cyclohexyl-NENA),... 

Di(cyclohexyl) etbylenediamine or N,N -Dicy-clobexy 1-1,2-diaminoetbane, C6Hn.NH.CH2.CH2.NH.C6Hii, is the parent compd of its nitrated derivs ... 

There now exists a large body of supporting evidence for the chain mechanism. Donaruma and Carmody121 found that nitrosocyclohexane dissolved in cyclohexane in an environment of 0.5-6 atm of NO at 25-51°C produced the nitrate, nitrite, and nitro compounds of cyclohexyl. These products imply the presence of N02, and the results can be interpreted by the chain mechanism. Forst and Rice152 pyrolyzed 40 torr of azomethane at 303°C in the presence of 15NO and found that, at high NO pressures, part of the product N2 came entirely from the NO. 

N-Cyclohexyl-2,4-dinitroaniline or 2,4-Dinitro -1-cyclohexyl ami nobenzene, C6H3(N02)2.NH.C6H, mw 265.26, N 15.84% yel crysts, mp 155 readily sol in benz acet si sol in light petroleum ale insol in w was prepd by heating for 3 hrs on a w bath a soln of 1-chloro-2,4-dinitrobenzene 45% aq cyclohexylamine. Nitration yields an expl compd... 

Commission banned the sale of butyl nitrite. However, the most commonly found poppers today contain cyclohexyl nitrite, which has a similar effect as amyl butyl nitrite. With cyclohexyl nitrite legal and readily available in the United States, the illegal use and sale of amyl and butyl nitrite is limited. Researchers point out that regardless of the legal status, the dangers of using any nitrite or nitrate are similar. 

Chloro-2-cyclohexylisoindolin-l-one (102.9 g) was dissolved in concentrated sulfuric acid (665 ml) potassium nitrate (723 g) in concentrated sulfuric acid (166 ml) was added at 0 °C. The reaction mixture was allowed to warm to room temperature and stirred at 25°C for 12 hours. The reaction mixture was poured onto ice to give a cream solid which, after recrystallization from benzene, gave 5-chloro-2-cyclohexyl-6-nitroisoindolin-l-one (46.7 g, 44%) as a white solid, MP 164°C to 168°C. 

---