Triethylbenzylammonium chloride

To 75 ml of a 50 aqueous solution of KOH were added 0.25 mol of chloroform, 0.2 g of triethylbenzylammonium chloride and 0.10 mol of freshly distilled 1,2-cyclononadiene (see this chapter, Exp. 20) and the mixture was stirred vigorously for 10-12 h. Water (200 ml) was added and the products were extracted with diethyl ether. The extracts were dried over magnesium sulfate, concentrated in a water-pump vacuum and the residue was distilled through a short Vigreux column. The adduct, b.p. 80 C/0.15 mmHg, n j 1.5300, was obtained in 75% yield. 

Triethylbenzylammonium chloride and potassium fluoride containing 1% water can provide chlorine-fluorine exchange of activated halides in the absence of a solvent. This mixture also can displace the chlorine of a chlorodifluoromethyl group to form a trifluoromethyl group [62] (equation 36). 

Triethylamine, 61,83,87,88,94,99,100,112 Triethylamine N-oxide, 84 Triethylbenzylammonium chloride, 49 Triethylsilane, 104,127.128 Trifluoroacetic acid, 59 Trimethyi-m-dimethylaminophenylsilane, 40 Trimethyl orthoformate, 109... 

In the mid-1960s a series of papers by Makosza and Serafinowa (1965, 1966) appeared under the common title Reactions of Organic Anions , in which the catalytic alkylation of phenylacetonitrile and its derivatives carried out in the presence of concentrated NaOH and the catalyst triethylbenzylammonium chloride (TEBA) was described. This was the beginning of phase-transfer catalysis (PTC), and since then thousands of papers haven been published on the subject. 

The Sn2 reaction of triphenylphosphine with triethylbenzylammonium chloride (the tertiary amine is thus the leaving group) was studied under solvent-free microwave conditions. The reaction occurred only under the action of MW [83] irradiation (Eq. 53). 

Interestingly enough, a closely related protocol was successfully proposed for the synthesis of spirooxindoles-containing tetrahydrochromene skeletons when aromatic aldehydes were switched for isatin derivatives. This high-yielded reaction was performed with dimedone, 4-hydroxycoumarin, or barbituric acids in water using triethylbenzylammonium chloride (TEBA) as catalyst (Scheme 36) [125]. A Knoevenagel condensation occurred first between isatin and malonitrile derivative, followed by Michael addition of 1,3-dicarbonyl substrates and cyclization to the cyano moiety. 

Another modern modification involves coupling of UNs 30 and /1-ketoesters 36 in aqueous emulsion in the presence of an interphase catalyst triethylbenzylammonium chloride (TEBAC) (06JCM228). 

A two-phase solid-liquid transfer catalytic system has been developed for aromatic aldehydes and for aliphatic aldehydes which are branched at the a-carbon.116 The aldehyde and the a-chloroester are stirred in dimethylformamide in the presence of solid potassium carbonate and triethylbenzylammonium chloride. The isolated yield of glycidic ester compares favourably with that of the procedure above. 

Confirmation of this effect was obtained by carrying out experiments in the presence of added nucleophiles (in the form of triethylbenzylammonium chloride, or tetrabutylammonium bromide)which modified both the product ratio and the overall reaction rate. 

A solution of the iodonium salt (912 mg, 2 mmol) in chloroform (10 ml) was added to a solution of sodium p-chlorobenzene sulphinate (496 mg, 2.5 mmol) and triethylbenzylammonium chloride (22.8 mg, 0.1 mmol) in water (10 ml). The mixture was stirred at room temperature for 5 h then the organic layer was separated, the water layer extracted with chloroform (3 x 10 ml) and the combined organic layers washed with water (3 x 20 ml) and dried. After concentration, the residue was chromatographed on silica gel (hexane-chloroform) to give the pure sulphone (472 mg, 92%) m.p. 80-82°C. 

A notable improvement in halogenation procedures by polyhalomethanes has been introduced by the group of Makosza616 who utilize 50% sodium hydroxide solution in the presence of triethylbenzylammonium chloride (TEBA) as a PTC. With this system phenyl-acetonitrile, fluorene and trichloroethylene are chlorinated by tetrachloromethane. Another useful PTC is Bu4NOH617. Similar procedures are practiced for the chlorination of sulfones618 and ketones619,620. The latter would normally react in secondary reactions under the above conditions. This is utilized for the direct a-hydroxylation of alkyl aryl ketones which are useful photoinitiators (equation 73)621 ... 

The submitters used Merck styrene 99%, stabilized with 4-tert-butylpyrocatechol. Triethylbenzylammonium chloride was prepared by refluxing equimolar amounts of triethylamine and benzyl chloride in ethanol for 2 hr and removing the solvent in vacuo. The salt is commercially available. The other reagents were technical grade. 

This compound is commercially available from Aldrich Chemical Company, Inc. Alternatively, it can be made very cheaply and simply by mixing benzyl chloride (1 eq) with triethyl-amine (2.5 eq). The mixture is allowed to stand for 4-7 days at room temperature. Filtration of the solid and drying in vacuum give triethylbenzylammonium chloride suitable for use in nearly quantitative yield. 

TRICYCLO[8.2.2.24>71HEXADECA-4,6,10,12,13,1 S-HEXAENE-5,6,-11, 12-TETRACARBOXYLIC ACID, TETRAMETHYL ESTER [37437-90-4], 41 Tridecanoic acid, 13 Triethylbenzylammonium chloride, 7, 68... 

Cyclopropanedicarboxylic acid (8,9) (598-10-7) Triethylbenzylammonium chloride Ammonium, benzyltriethyl-, chloride (8) Benzenemethanaminium, N,N,N-triethyl-, chloride (9) (56-37-1)... 

A detailed study of the N-methylation of 2,3,3-trimethylindolenine with methyl sulfate using triethylbenzylammonium chloride as a phase-transfer catalyst has appeared. The reported yields of high-purity (96-99%) Fischer s base were 90-92%.19 N-alkylation is the most practical method for preparing a Fischer s base with alkyl groups having, for example, thienyl,20 hydroxy, carboxy, or sulfonate substituents. 

A related reaction involves a-substituted aryl nitriles having a sufficiently acidic a hydrogen, which can be converted to ketones by oxidation with air under phase transfer conditions. The nitrile is added to NaOH in benzene or DMSO containing a catalytic amount of triethylbenzylammonium chloride (TEBA). " This reaction could not be applied to aliphatic nitriles, but an indirect method for achieving this conversion is given in 19-60. a-Dialkylamino nitriles can be converted to ketones, R2C(NMe2)CN —> R2C=0, by hydrolysis with Q1SO4 in aqueous methanol or by autoxidation in the presence of r-BuOK. ... 

The cyclopentadiene dimer, when treated with potassium permanganate and triethylbenzylammonium chloride as a phase-transfer agent, furnishes an 83% yield of exo,cis-diol resulting from the hydroxylation of the double bond in the cyclohexene ring [900] (equation 82). 

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