Cyclohexane chloride

Enzymatic hydrolysis is also used for the preparation of L-amino acids. Racemic D- and L-amino acids and their acyl-derivatives obtained chemically can be resolved enzymatically to yield their natural L-forms. Aminoacylases such as that from Pispergillus OTj e specifically hydrolyze L-enantiomers of acyl-DL-amino acids. The resulting L-amino acid can be separated readily from the unchanged acyl-D form which is racemized and subjected to further hydrolysis. Several L-amino acids, eg, methionine [63-68-3], phenylalanine [63-91-2], tryptophan [73-22-3], and valine [72-18-4] have been manufactured by this process in Japan and production costs have been reduced by 40% through the appHcation of immobilized cell technology (75). Cyclohexane chloride, which is a by-product in nylon manufacture, is chemically converted to DL-amino-S-caprolactam [105-60-2] (23) which is resolved and/or racemized to (24)... 

Im Falle von orrfio-Nitro-Gruppen am Benzol-Ring erfolgt zunachst Eliminicrung von Chlorwasserstoff aus dem 2-[(2-Nitro- (bzw. 2,4-Dinitro)-phenylhydrazono]-l-pyridiniono-cyclohexan-chlorid. Die relativ instabilen Betaine gehen leicht in 3-[2-Nitro- (bzw. 2,4-Dinitro)-phenylhydrazono]-cyclohexene fiber ... 

Beckmann rearrangement of cvc7ohexanone oxime. M.p. 68-70 C, b.p. I39 C/12 mm. On healing it gives polyamides. Used in the manufacture of Nylon[6]. Cyclohexanone oxime is formed from cyclohexane and niirosyl chloride. U.S. production 1978 410 000 tonnes, capryl alcohol See 2-octanol. caiH Uc acid See oclanoic acid. 

The oxime is freely soluble in water and in most organic liquids. Recrystallise the crude dry product from a minimum of 60-80 petrol or (less suitably) cyclohexane for this purpose first determine approximately, by means of a small-scale test-tube experiment, the minimum proportion of the hot solvent required to dissolve the oxime from about 0-5 g. of the crude material. Then place the bulk of the crude product in a small (100 ml.) round-bottomed or conical flask fitted with a reflux water-condenser, add the required amount of the solvent and boil the mixture on a water-bath. Then turn out the gas, and quickly filter the hot mixture through a fluted filter-paper into a conical flask the sodium chloride remains on the filter, whilst the filtrate on cooling in ice-water deposits the acetoxime as colourless crystals. These, when filtered anddried (either by pressing between drying-paper or by placing in an atmospheric desiccator) have m.p. 60 . Acetoxime sublimes rather readily when exposed to the air, and rapidly when warmed or when placed in a vacuum. Hence the necessity for an atmospheric desiccator for drying purposes. 

Even saturated hydrocarbons give ketones with acyl chlorides (20). For example, cyclohexane and acetyl chloride react in the presence of aluminum chloride to give l-acetyl-2-methylcyclopentane. 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

Organoperoxysulfonic acids and their salts have been prepared by the reaction of arenesulfonyl chlorides with calcium, silver, or sodium peroxide treatment of metal salts of organosulfonic acids with hydrogen peroxide hydrolysis of di(organosulfonyl) peroxides, RS(0)2—OO—S(02)R, with hydrogen peroxide and sulfoxidation of saturated, non aromatic hydrocarbons, eg, cyclohexane (44,181). 

Stability. Avermectins are highly lipophilic substances and dissolve in most organic solvents such as chloroform, methylene chloride, acetone, alcohols, toluene, cyclohexane, dimethylformamide, dimethyl sulfoxide, and tetrahydrofiiran. Thek solubiUty in water is correspondingly low, only 0.006-0.009 ppm (= mg/L). 

Toray. The photonitrosation of cyclohexane or PNC process results in the direct conversion of cyclohexane to cyclohexanone oxime hydrochloride by reaction with nitrosyl chloride in the presence of uv light (15) (see Photochemical technology). Beckmann rearrangement of the cyclohexanone oxime hydrochloride in oleum results in the evolution of HCl, which is recycled to form NOCl by reaction with nitrosylsulfuric acid. The latter is produced by conventional absorption of NO from ammonia oxidation in oleum. Neutralization of the rearrangement mass with ammonia yields 1.7 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. The novel chemistry is as follows ... 

Dimethoxytrityl chloride (DMT) [40615-36-9] M 338.8, m 114 . Crysts from cyclohexane-acetyl chloride as the hydrochloride and dry over KOH pellets in a desiccator. When dissolved in CgH6 and air is blown through, HCl is removed. It crystallises from Et20. [Justus Liebigs Ann Chem 370 142 1909 Chem Ber 36 2774 7905 Smith et al. J Am Chem Soc 84 430 I962 Smith et al. J Am Chem Soc 85 3821 7965.] If it had hydrolysed considerably (see OH in IR) then repeat the crystallisation from cyclohexane-acetyl chloride — excess of AcCl is removed in vac over KOH. 

The cooled contents of the 2S0-ml. flask containing ferrous chloride (Note 6) are added to the cold sodium cyclopentadienide solution while passing a stream of nitrogen through both flasks. The combined mixture is stirred for 1.25 hours at a temperature just below reflux. Solvent is removed by distillation, and the ferrocene is extracted from the residue with several portions of refluxing petroleum ether (b.p. 40-60°). The product is obtained by evaporation of the petroleum ether solution. Ferrocene may be purified by recrystallization from pentane or cyclohexane (hexane, benzene, and methanol have also been used) or by sublimation. The 3ueld is 31-34 g. (67-73%) (Note 7), m.p. 173-174°. 

For substituted cyclohexanes, the slow-exchange condition is met at temperatures below about —50 C. Table 3.5 presents data for the half-life for conformational equilibration of cyclohexyl chloride as a function of temperature. From these data, it can be seen that conformationally pure solutions of equatorial cyclohexyl chloride could be maintained at low temperature. This has been accomplished experimentally. Crystallization of cyclohexyl chloride at low temperature affords crystals containing only the... 

In the chlorination by trichloromethanesulfonyl chloride, cyclohexane is about three times as reactive as toluene. 

Organolithium compounds can readily be prepared from metallic Li and this is one of the major uses of the metal. Because of the great reactivity both of the reactants and the products, air and moisture must be rigorously excluded by use of an inert atmosphere. Lithium can be reacted directly with alkyl halides in light petroleum, cyclohexane, benzene or ether, the chlorides generally being preferred ... 

The chiral bicyclic imidazolidine 74 is deprotonated at the 2 position by s-BuLi and the resulting anion adds to alkyl halides, acid chlorides, chlorofor-mates, phenyl isocyanate, and aldehydes. The use of this compound as a chiral formyl anion equivalent seems to be limited, however, since the diastereoselectiv-ity in the addition to aldehydes is poor and hydrolysis of the products 75 to give aldehydes also produces cyclohexane-1,2-diamine, necessitating isolation of the aldehyde as its 2,4-dinitrophenylhydrazone (96SL1109 98T14255). 

Nitrosyl chloride reacts with aliphatic hydrocarbons at room temperature under the influence of light to give a complex mixture of substitution products. When the reaction is run on cyclohexane at —25°, however, the pure oxime hydrochloride crystallizes from the reaction mixture with virtually no side products. 

To 10 g of cyclohexane-1,4-oxide is added 48% aqueous hydrobromic acid (60 g). The phases are mixed thoroughly and allowed to stand at room temperature until the solution separates into two layers (usually 5 days). The mixture is saturated with sodium chloride and extracted twice with 25-ml portions of ether. The ether layer is washed with an equal volume of saturated sodium bicarbonate solution, then with the same amount of water. Finally, the ether solution is dried over anhydrous sodium sulfate, the ether is evaporated, and the residue is allowed to cool, whereupon crystallization should follow. The crude product may be recrystallized from petroleum ether giving material of mp 81-82° (yield, 11 g). 

The mixture was refluxed for 45 minutes, cooled under nitrogen, and 19.8 g (0.10 mol) of 1-amino-1-cyclohexane<arboxylic acid chloride HCI was added portionwise at -10°C over 20 minutes. The mixture was stirred for an additional hour while the temperature rose to 20°C. The reaction mixture was poured into 200 ml of cold water with stirring and the two-phase mixture clarified by filtration. Dilute sodium hydroxide solution was added to the filtrate at 5° to 10°C to pH 5.4. 

Sodium methoxide (1.2 g) in dimethylformamide (150 ml) was stirred with 3,5-dim ethoxy-4 reaction mixture was then treated with /3-morpholinoethyl chloride (3.4 g) and heated for 1 hour at 140°C, then evaporated to dryness, and treated with water to give a solid material. The mixture was filtered, washed and crystallized from cyclohexane to give 3,5-di-methoxv-4 -chloro-4-( morpholinoethoxy)-benzophenone (6.5 g), MP 91°C to 92°C. The product was then reacted at about 0°C with gaseous hydrogen chloride in ether to give, after crystallization from isopropanol, the corresponding hydrochloride which hada MPof 187.9°C. 

A suspension of 30 g of sodium hydride in benzene (30 ml) was added dropwise to 52 g of 8-chlorodibenzo[b,f] thiepin-10(11 H)-one dissolved in dimethylformamide (800 ml), and the mixture was heated at 100°C for 2 hours. To this, there were added 68 g of 2-dimethylamino-ethyl chloride, and the mixture was heated at 60°C for 39 hours. The reaction mixture, after cooled, was poured into ice-water, and the solution was extracted with ethyl acetate. The ethyl acetate layer, after washed with water, was extracted with 10% hydrochloric acid, when oil was precipitated. The aqueous layer, in which oil was precipitated, was washed with ether, made neutral with concentrated sodium hydroxide solution and then extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over magnesium sulfate, and concentrated to give oil, which was allowed to stand to provide solid. The solid was washed with petroleum ether and recrystallized from cyclohexane to yield 42.5 g of 8melting point 90°C to 91°C. Male-ate as colorless needle, melting point 204°C to 204.5°C. 

Tndecanedione, 47, 95 Tnethylamine, 46, 18 dehydrobromination of o-bromo-y-butyrolactone with, 46, 23 dehydrobromination of or.a -dibromo-dibenzyl ketone, 47, 62 dehydrochlormation of cyclohexane-carbonyl chloride, 47, 34 in synthesis of nicotinic anhydride with phosgene, 47, 90 Tnethyl orthoformate, condensation with N,N diphenylethylene-diaminc, 47,14... 

Total Ionic Strength Adjustment Buffer (TISAB). Dissolve 57 mL acetic acid, 58 g sodium chloride and 4g cyclohexane diaminotetra-acetic acid (CDTA) in 500 mL of de-ionised water contained in a large beaker. Stand the beaker inside a water bath fitted with a constant-level device, and place a rubber tube connected to the cold water tap inside the bath. Allow water to flow slowly into the bath and discharge through the constant level this will ensure that in the... 

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