Chloride, alkyl

On acetylation it gives acetanilide. Nitrated with some decomposition to a mixture of 2-and 4-nitroanilines. It is basic and gives water-soluble salts with mineral acids. Heating aniline sulphate at 190 C gives sulphanilic add. When heated with alkyl chlorides or aliphatic alcohols mono- and di-alkyl derivatives are obtained, e.g. dimethylaniline. Treatment with trichloroethylene gives phenylglycine. With glycerol and sulphuric acid (Skraup s reaction) quinoline is obtained, while quinaldine can be prepared by the reaction between aniline, paraldehyde and hydrochloric acid. 

Alkyl and aryl iodides usually react with magnesium more rapidly than the corresponding bromides, and the bromides very much more rapidly than the chlorides. Aryl (as distinct from alkyl) chlorides have usually only a slow reaction with magnesium and are therefore very rarely used. With alkyl and aryl iodides in particular, however, a side reaction often occurs with the formation of a hydrocarbon and magnesium iodide ... 

In the absence of a tertiary amine, the initial reaction is again the formatfon of a trialkyl phosphite and hydrogen chloride. The latter now reacts rapidly with the trialkyl phosphite to give the alkyl chloride and the dialkyl hydrogen... 

Alkyl chlorides react slowly and the yield of the derivative is poor. Tertiary halides give anomalous results. 

Place a mixture of 0-5 g. of finely powdered thiourea, 0-5 g. of the alkyl halide and 5 ml. of alcohol in a test-tube or small flask equipped with a reflux condenser. Reflux the mixture for a j)eriod depending upon the nature of the halide primary alkyl bromides and iodides, 10-20 minutes (according to the molecular weight) secondary alkyl bromides or iodides, 2-3 hours alkyl chlorides, 3-5 hours polymethy lene dibromides or di-iodides, 20-50 minutes. Then add 0 5 g. of picric acid, boil until a clear solution is obtained, and cool. If no precipitate is obtained, add a few drops of water. RecrystaUise the resulting S-alkyl-iso-thiuronium picrate from alcohol. 

Mix together 1 0 g. of pure p-naphthol and the theoretical quantity of 50 per cent, potassium hydroxide solution, add 0-5 g. of the halide, followed by sufficient rectified spirit to produce a clear solution. For alkyl chlorides, the addition of a little potassium iodide is recommended. Heat the mixture under reflux for 15 minutes, and dissolve any potassium halide by the addition of a few drops of water. The p-naphthyl ether usually crystallises out on cooling if it does not, dilute the solution with 10 per cent, sodium hydroxide solution untU precipitation occurs. Dissolve the p-naphthyl ether in the minimum volume of hot alcohol and add the calculated quantity of picric acid dissolved in hot alcohol. The picrate separates out on cooling. Recrystallise it from rectified spirit. 

Many organolithium compounds may be prepared by the interaction of lithium with an alkyl chloride or bromide or with an aryl bromide in dry ethereal solution In a nitrogen atmosphere ... 

The resulting esters differ sufficiently in odour and water solubility to be readily distinguished from the original alcohol. With tertiary alcohols the product is largely the alkyl chloride ... 

By using a lOOX excess of the metal (less than lOO for experiments on a large scale) one can save much time. Some Grignard reactions, especially those with tertiary alkyl chlorides and cyclohexyl chloride, are not easily started and it seemed desirable, therefore, to inform the user of this book about our experiences. 

Tertiary alcohols are converted to alkyl chlorides m high yield within minutes on reaction with hydrogen chloride at room temperature and below... 

Secondary and pnmary alcohols do not react with HCl at rates fast enough to make the preparation of the conespondmg alkyl chlorides a method of practical value There fore the more reactive hydrogen halide HBr is used even then elevated temperatures are required to increase the rate of reaction... 

Thionyl chloride reacts with alcohols to give alkyl chlorides The inorganic byprod nets m the reaction sulfur dioxide and hydrogen chloride are both gases at room tern perature and are easily removed making it an easy matter to isolate the alkyl chloride... 

The resulting free radicals react with chlorine to give the corresponding alkyl chlorides Butyl radical gives only 1 chlorobutane sec butyl radical gives only 2 chlorobutane... 

Thionyl chloride is a synthetic reagent used to convert alcohols to alkyl chlorides... 

The similar yields of the two alkyl chloride products indicate that the rate of attack by chloride on the secondary carbocation and the rate of rearrangement must be very similar... 

Iodide ion (I ) Alkyl chlorides and bromides are converted to alkyl iodides by treatment with sodium iodide in acetone Nal is soluble in acetone but NaCI and NaBr are insoluble and crystallize from the reaction mixture making the reac tion irreversible... 

Iodide ion Alkyl chloride Alkyl iodide Chloride or... 

The order of alkyl halide reactivity in nucleophilic substitutions is the same as their order m eliminations Iodine has the weakest bond to carbon and iodide is the best leaving group Alkyl iodides are several times more reactive than alkyl bromides and from 50 to 100 times more reactive than alkyl chlorides Fluorine has the strongest bond to car bon and fluonde is the poorest leaving group Alkyl fluorides are rarely used as sub states m nucleophilic substitution because they are several thousand times less reactive than alkyl chlorides... 

A substantial body of evidence indicates that allylic carbocations are more stable than simple alkyl cations For example the rate of solvolysis of a chlonde that is both tertiary and allylic is much faster than that of a typical tertiary alkyl chloride... 

Nucleophilic substitution in acyl chlorides is much faster than in alkyl chlorides... 

The sp hybridized carbon of an acyl chloride is less sterically hindered than the sp hybridized carbon of an alkyl chloride making an acyl chloride more open toward nude ophilic attack Also unlike the 8 2 transition state or a carbocation intermediate m an Stvfl reaction the tetrahedral intermediate m nucleophilic acyl substitution has a stable arrangement of bonds and can be formed via a lower energy transition state... 

Tertiary alkyl chlorides have been converted to the tertiary nittiles with trimethylsilyl nittile ia dichioromethane ia the presence of SnCl (131). The reaction was appHed to the synthesis of several bridgehead nittiles, such as 1-adamantyl and 1-diamantyl nittiles from the corresponding chloro or bromo derivatives usiag SnCl or AIBr. catalysts (132). 

The direct reaction of other alkyl chlorides, such as butyl chloride, results in unacceptably low overall product yields along with the by-product butene resulting from dehydrochlorination. AH alkyl haHdes having a hydrogen atom in a P- position to the chlorine atom are subject to this complication. 

Replacement ofiMliphaticHydrocgilwith Chloride. Lower alcohols such as methanol (qv) can be converted to the corresponding alkyl chlorides by carrying out the reaction... 

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. 

Cl NO2 chlorides nitro compounds chloro nitro alkyl chloride... 

Uses. The largest usage of PCl is to produce phosphonic acid, H PO, which in reaction with iminodiacetic acid and formaldehyde forms a glyphosate intermediate that is decarboxymethylated to glyphosate, an effective nonselective herbicide (see Herbicides). Phosphoms trichloride is also a convenient chlorinating reagent for producing various acyl and alkyl chlorides. 

OleFns and Fatty Alcohols. Alkylbenzyldimethylammonium (ABDM) quatematies are usually prepared from a-olefin or fatty alcohol precursors. Manufacturers that start from the fatty alcohol usually prefer to prepare the intermediate alkyldimethylamine direcdy by using dimethylamine and a catalyst rather than from fatty alkyl chloride. Small volumes of dialkyldimethyl and alkyltrimethyl quatematies in the Cg—range are also manufactured from these precursors (Fig. 4). 

The reactions of thionyl chloride with organic compounds having hydroxyl groups are important. Alkyl chlorides, alkyl sulfites, or alkyl chlorosulfites form from its reaction with aUphatic alcohols, depending on reaction conditions, stoichiometry, and the alcohol stmcture ... 

All lation. In alkylation, the dialkyl sulfates react much faster than do the alkyl haHdes, because the monoalkyl sulfate anion (ROSO ) is more effective as a leaving group than a haHde ion. The high rate is most apparent with small primary alkyl groups, eg, methyl and ethyl. Some leaving groups, such as the fluorinated sulfonate anion, eg, the triflate anion, CF SO, react even faster in ester form (4). Against phenoxide anion, the reaction rate is methyl triflate [333-27-7] dimethyl sulfate methyl toluenesulfonate [23373-38-8] (5). Dialkyl sulfates, as compared to alkyl chlorides, lack chloride ions in their products chloride corrodes and requires the use of a gas instead of a Hquid. The lower sulfates are much less expensive than lower bromides or iodides, and they also alkylate quickly. 

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