Benzyl chloride, alkylation with

Thiourea, unlike urea, readily reacts in the tautomeric form (I) in the presence of suitable reagents, particularly alkyl halides thus benzyl chloride reacts with... 

An imidazoquinazoline constitutes still another compound that does not fall in the classification of a nonsteroid antiinflammatory agent yet shows good platelet anti aggregating activity. Condensation of benzyl chloride 128 with the ethyl ester of glycine gives alkylated product... 

Alkylation of the metallated bis(triphenylphosphinyl)methane (6) with benzyl or methyl chlorides occurred on phosphorus to give the ylides (7). That from benzyl chloride reacted with chlorodiphenylphosphine to give the stable ylide (8). 

The amino group of 5-benzimidazolyl- and 5-benzotriazolylaminomethy-lenemalonates (1471, X = CH and N) was alkylated with methyl iodide in DMF in the presence of potassium carbonate in 43-91% yields (89CCC713). 5-Benzimidazolylaminomethylenemalonate (1471, X = CH) was also alkylated on the amino group with ethyl iodide and benzyl chloride, or with methyl iodide in dimethoxyethane, or dimethyl sulfate in THF in the presence of sodium hydride. 

Lund and coworkers [131] pioneered the use of aromatic anion radicals as mediators in a study of the catalytic reduction of bromobenzene by the electrogenerated anion radical of chrysene. Other early investigations involved the catalytic reduction of 1-bromo- and 1-chlorobutane by the anion radicals of trans-stilhene and anthracene [132], of 1-chlorohexane and 6-chloro-l-hexene by the naphthalene anion radical [133], and of 1-chlorooctane by the phenanthrene anion radical [134]. Simonet and coworkers [135] pointed out that a catalytically formed alkyl radical can react with an aromatic anion radical to form an alkylated aromatic hydrocarbon. Additional, comparatively recent work has centered on electron transfer between aromatic anion radicals and l,2-dichloro-l,2-diphenylethane [136], on reductive coupling of tert-butyl bromide with azobenzene, quinoxaline, and anthracene [137], and on the reactions of aromatic anion radicals with substituted benzyl chlorides [138], with... 

Alkylation, of 2-acetamidothiazoles, 35, 37 with alkali amides, 34, 35 of alkylaminothiazole, 34 with alcohols, 47, 80, 90 of aminothiazoles, with alcohols, 38 with benzyl chloride. 33 with chloracetic acid, 33 with chloracetic esters, 33 with 3-chloropropionic acid, 33 with dimethylaminoethylchloride, 35 with ethylene oxide, 34, 38 with ethyl iodide, 33 with phenethyl chloride, 35 with 2-propynyl bromide. 32 in aprotic solvents, 35 of azothiazoles, 105... 

Codepositions of benzyl chloride with V, Cr, Mn and Fe yield varying quantities of catalytic self-alkylation products plus HCl thus the reaction products serve as catalysts for benzyl chloride alkylation of itself. 

Shape selectivity has also been demonstrated within FAU zeolites. For example, meta selectivity was observed for the NaY-mediated Friedel Crafts alkylation of benzyl chloride (BnCl) with itself. In addition to polymer inhibition, the FAU zeolite favored the formation of the banana-shaped l-(chloromethyl)-3-(phenyl-methyljbenzene (m-3) regioisomer (Equation (4)) 53... 

Alkylation of 3,5-diamino-4/f-l,2,6-thiadiazine 1,1-dioxide (94) with dimethyl sulfate furnishes a 2 1 mixture of the C-methylated (95) and C,A-dimethylated (96) derivatives <81JHC27> and not, as had been reported previously <70UKZ77>, the 2,6-dimethyl-3,5-diimino compound (97). Alkylations with benzyl chloride and with allyl chloride yield only the 4,4-dialkyl derivatives (98 R = PhCH2 44%) and (98 CH2==CHCH2 40%), respectively (Scheme 2) <8UHC27>. 

Since exposure to air reconverts the sulfhydryl groups to disulfides, it is necessary to stabilize the reduced forms by alkylation with benzyl chloride or with iodoacetic acid... 

These arguments are based on the assumption that the transition state is truly intermediate in structure between the reactants and products. If this is not true, the arguments fail and so does the BEP principle. The main case when this happens is when electromeric substituents are attached to a carbon atom which is tetrahedral and saturated in both reactants and products but has sp hybridization and forms part of a delocalized system in the transition state. Compare, for example, the 5 2 reactions of iodide ion with benzyl chloride and with a saturated alkyl chloride RCH2CI, where R is an alkyl group,... 

Secondary and tertiary alkyl halides are not suitable because they react with alkox ide bases by E2 elimination rather than by 8 2 substitution Whether the alkoxide base IS primary secondary or tertiary is much less important than the nature of the alkyl halide Thus benzyl isopropyl ether is prepared m high yield from benzyl chloride a pri mary chloride that is incapable of undergoing elimination and sodium isopropoxide... 

FiaaHy, a-olefias find their way iato the surfactant and disiafectant market through conversion, first to alkyl dimethyl amine, then to benzyl chloride quats (BAUMAC) and amine oxides. The former are used broadly as disiafectants, often ia combination with cleaning products. The latter is a direct active ia consumer and iadustrial cleaning products. 

QuaterniZation. Quaternary ammonium compounds are formed by alkylation of alkyl, alkyl dimethyl, dialkyl, and dialkylmethyl fatty amines with methyl chloride, dimethyl sulfate, or benzyl chloride (1,3,7,12,29). 

A wide variety of quaternaries can be prepared. Alkylation with benzyl chloride may produce quaternaries that are biologically active, namely, bactericides, germicides, or algaecides. Reaction of a tertiary amine with chloroacetic acid produces an amphoteric compound, a betaine. 

Alkylations of cinnolin-4(lf/)-one (8) with methyl iodide, ethyl iodide, dimethyl and diethyl sulfates, isopropyl bromide, benzyl chloride, etc. take place predominantly at position 2 to give 2-alkyl-4-hydroxycinnolinium anhydro salts (83), together with small amounts of l-methylcinnolin-4-one (84). 

The stereoselective reactions in Scheme 2.10 include one example that is completely stereoselective (entry 3), one that is highly stereoselective (entry 6), and others in which the stereoselectivity is modest to low (entries 1,2,4, 5, and 7). The addition of formic acid to norbomene (entry 3) produces only the exo ester. Reduction of 4-r-butylcyclohexanone (entry 6) is typical of the reduction of unhindered cyclohexanones in that the major diastereomer produced has an equatorial hydroxyl group. Certain other reducing agents, particularly sterically bulky ones, exhibit the opposite stereoselectivity and favor the formation of the diastereomer having an axial hydroxyl groi. The alkylation of 4-t-butylpiperidine with benzyl chloride (entry 7) provides only a slight excess of one diastereomer over the other. 

A study of alkylations with a group of substituted benzyl halides and a range of Friedel-Crafts catalysts has provided insight into the trends in selectivity and orientation that accompany changes in both the alkyl group and the catalysts. There is a marked increase in substrate selectivity on going from / -nitrobenzyl chloride to /i-methoxybenzyl chloride. For example, with titanium tetrachloride as the catalyst, Aitoi Abenz increases from 2.5 to 97. This increase in substrate selectivity is accompanied by an increasing preference for para substitution. With /i-nitrobenzyl chloride, the ortho para ratio is 2 1 (the... 

Alkylation at the ind-N of l,2,3,4-tetrahydro-j8-carbolines has been carried out with alkyl halide after treatment with sodamide in the usual manner. Cyanoethylation of a p /r-V-substituted tetrahydro-jS-carboline in the presence of Triton B yields the corresponding 9-cyanoethyl derivative. Similarly, treatment of p / -V-methyl-l,2,3,4,4a,9b-hexahydro-y-carboline with sodamide, followed by benzyl chloride, leads to the ind-A -benzyl-substituted derivatives. l-Oxo-l,2,3,4-tetrahydro-j8-carboline yields the ind-A -methyl derivative directly with dimethyl sulfate.Prolonged treatment with sodium hydride, followed by methyl iodide, yields the 2,9-dimethyl derivative. Heating with sodium hydride in acetone followed by the addition of dimethyl sulfate gives rise to the ind-V-methyl derivative. ... 

Substitution of a 2-pyridyl residue for the phenyl attached rectly to nitrogen affords a series of potent antihistamines, eparation of these compounds, too, is accomplished by a series alkylation reactions. It is further probable that the order the reaction can be readily interchanged. Thus, alkylation 2-aminopyridine with the chloroethyldimethylamine side chain ads to the diamine, 59. Alkylation with benzyl chloride af-rds tripelenamine (60) reaction with p-methoxybenzyl chloride ads to pyrilamine (61), °... 

Reaction of dibenzylamine with ethylene oxide affords the amino alcohol, 82. Treatment of that product with thionyl chloride gives the a-sympathetic blocking agent, dibenamine (83). (Condensation of phenol with propylene chlorohydrin (84) gives the alcohol, 85. Reaction with thionyl chloride affords the chloride (86). Use of the halide to alkylate ethanolamine affords the secondary amine (87). Alkylation of this last with benzyl chloride... 

Reduction of phenylacetone in the presence of methylamine rather than ammonia gives methamphetamine (53), an agent similar in action to the primary amine. Alkylation of 53 with benzyl chloride affords the analog, benzphetamine (54). ... 

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