Methyl triethylammonium

Alkylation of alcohols with 2-(methoxyethoxy)methyl chloride (MEMC1, bp 50-52 C/1.7 kPa) (HAZARD carcinogenic) under an assortment of conditions pioneered by Corey still retain favour. These include reaction of the lithium or sodium alkoxide (generated from sodium or potassium hydride) with ME MCI in THF or DME at 0 °C (10-60 min) and reaction of the alcohol with MEMCI in dichloromethane in the presence of /-Pr NEt at room temperature for 3 h. For hindered alcohols, sodium iodide can be added to generate the more reactive 2-methoxyethoxymethyl iodide in situ. Alternatively, reaction of the alcohol with [(2-methoxyethoxy)methyl]triethylammonium chloride (prepared from MEMO and trie thy lamine) in refluxing acetonitrile is recommended for acid-sensitive substrates such as tertiary alcohols [Scheme 4,271],500... 

CioHi,N20sPS-CeHieN+ Uridine 3 -(methyl triethylammonium thiophosphate) URDTPE 32 377... 

MTEA methyl- triethylammonium Na 10 Na2O 20 MTEA BrrAlzOjrlOO Si02 2000 H2O (v) ZSM-12 (MTW) N ao.sCMTE A) 1 3 Alo.8Si27.2O56... 

In the reaction of Q,/3-unsaturated ketones and esters, sometimes simple Michael-type addition (insertion and hydrogenolysis, or hydroarylation, and hydroalkenylation) of alkenes is observed[53,54]. For example, a simple addition product 56 to methyl vinyl ketone was obtained by the reaction of the heteroaromatic iodide 55[S5]. The corresponding bromide affords the usual insertion-elimination product. Saturated ketones are obtained cleanly by hydroarylation of o,/3l-unsaturated ketones with aryl halides in the presence of sodium formate, which hydrogenolyses the R—Pd—I intermediate to R— Pd—H[56]. Intramolecular hydroarylation is a useful reaction. The diiodide 57 reacts smoothly with sodium formate to give a model compound for the afla-toxin 58. (see Section 1.1.6)[57]. Use of triethylammonium formate and BU4NCI gives better results. 

Fig. 2-15. Reversed-phase retention of the first eluted and the seeond eluted enantiomers of 5-methyl-5-phenylhydantoin as a funetion of mobile phase eomposition. The eolumn was a 250 x 4.6 mm vaneomyein CSR The buffer was triethylammonium aeetate at pH 7.0. The flow rate was 1.0 mL min at ambient temperature (23 °C).

CONVERSION OF PRIMARY ALCOHOLS TO URETHANES via THE INNER SALT OF METHYL (CARBOXYSULFAMOYL)TRIETHYLAMMONIUM HYDROXIDE METHYL n-HEXYLCARBAMATE... 

The above procedure describes the only known preparation of the inner salt of methyl (carboxysulfamoyl)triethylammonium hydroxide and illustrates the use of this reagent to convert a primary alcohol to the corresponding urethane.2 Hydrolysis of the urethane would then provide the primary amine. The method is limited to primary alcohols secondary and tertiary alcohols are dehydrated to olefins under these conditions, often in synthetically useful yields.2... 

To mention a few synthetic appHcations of trialkylsilanols, trimethylsilanol 4 adds readily to 2-chloroacrylonitrile in diethyl ether in the presence of triethylamine as triethylammonium trimethylsilanolate followed by ehmination of triethylamine hydrochloride to give 99 [32] (cf. discussion of the strongly nucleophihc properties of ammonium trimethylsilanolate 155 in Section 4.2.1). The stable potassium trimethylsilanolate 97 has also been used for the saponification of esters (Section 4.7). Dimethylphenylsilanol 100 adds readily to a,y9-unsaturated carbonyl compounds such as methyl vinyl ketone 764 in the presence of Pd(OAc)2 in a Heck-Suzuki-type reaction to give the sihcon-free /9-phenylmethylvinylketone 101 [33]. 

Copper(ll) acetylacetonate Copper, bis(2,4-pentanedionato-0,0 )- (9) (46369-53-3) Methyl diazoacetate Acetic acid, diazo-, methyl ester (8,9) (6832-16-2) Triethylammonium fluoride Triethylamine hydrofluoride (8) Elhanamine, N,N-diethyl-, hydrofluoride (9) (29585-72-6)... 

Methyl (carboxysulfamoyl)triethylammonium hydroxide, inner salt (Burgess reagent). 

E-2-bromomethyleneglutaric esters (>70%) have been obtained from the corresponding 2-bromo-2-bromomethylglutarates using a 25% excess tetra-n-butyl-ammonium fluoride in HMPA [24], A similar procedure converts dimethyl 2-bromo-2-bromomethylsuccinate into dimethyl Z-2-bromomethylenefumarate [25], whereas methyl 2,2-bis(bromomethyl)ethanoate yields the 2-bromomethyl-propenoate when reacted with aqueous sodium hydroxide in the presence of benzyl-triethylammonium chloride [26]. No hydrolysis of the ester is evident at 0°C, but becomes apparent at 25 °C. 

Finally, manganese carbonyl complexes also show potential for effecting interesting phase transfer catalyzed carbonylation reactions. Alkynes react with carbon monoxide and methyl iodide in methylene chloride, using 5N NaOH as the aqueous phase, benzyl-triethylammonium chloride as the phase transfer catalyst, and either bromopentacarbonylmanganese or dimanganese decacarbonyl to afford... 

On treatment with (carboxysulfamoyl)triethylammonium hydroxide inner salt methyl ester (Burgess reagent), the adducts of ketones yielded 1-vinylcyclopropyl selenides, but the adducts of aldehydes, e.g. 4, rearranged to cyclobut-1-enyl selenides.176... 

Triethylammonium uridine 3, 5 -cyclic phosphate153 5-Bromo-2 -deoxyuridine154 D-Arabinofuranosyl-5-bromouracil155 5-Bromouridine154 5-Bromouridine-methyl sulfoxide complex156... 

The electrochemical behavior of malonyl-a-aminopyridines 661 was investigated by Gullu et al. in acetonitrile or a mixture of trifluoroacetic acid and dichloromethane containing tetrabutylammonium tetrafluoro-borate or triethylammonium trifluoroacetate in a water-jacketed, two-compartment glass cell equipped with a platinum disk anode at 1.50 V (Ag/ Ag+) and a carbon-rod secondary electrode (91T675). Controlled potential anodic oxidation of 661 afforded labile coupled carboxylic acids 662 (R2 = COOH), which easily decarboxylated to compounds 662 (R2 = H) under the work-up conditions. Sometimes, the carboxylic acid 662 (R2 = COOH) could be isolated or when the reaction mixture was treated with methanol, methyl ester 662 (R = H, R1 = Bu, R2 = COOMe) was obtained in 40% yield. 

FIGURE 7 Effect of mobile phase composition on the resolution of enantiomers of different racemates in reversed-phase HPLC on antibiotic CSPs. (a) First ( , O) and second ( , ) enantiomers of 5-methyl-5-phenylhydantoin on a Chirobiotic T column using an acetonitrile-triethylammonium acetate buffer (—) and a methanol-triethylammo-... 

FIGURE 10 Effect of temperature on enantiomeric resolution on antibiotic CSPs. (a) k, a, and Rs for proglumide (O), 5-methyl-5-phenylhydantoin ( ) and iV-corbyl-DL-pheny-lalanine (x) on Chirobiotic V column using acetonitrile-1 % triethylammonium acetate buffer (10 90, v/v) as the mobile phase and (b) separation of enantiomers of /1-methyl phenylalanine on the Chirobiotic T column using water-methanol (10 90, v/v) as the mobile phase at (A) 1°C, (B) 20°C, (C) 50°C. 1 = erythro-L 2 = erythro-D 3 = threo-L 4 = threo-D. (From Refs. 1 and 22.)... 

The two materials MEM(TCNQ)2 and TEA(TCNQ)2 (MEM+ = N-methyl-N-ethylmorpholinium, TEA+ = triethylammonium) are among the best... 

Pyridin-2-olat Triethylammonium-[4-amino-3,5-dicyan-6-(trichlor-methyl)- ] E7b/2, 419 [NC-CH2- C(NHj) = C(CN)-COOR + CI3C-CN]... 

Methyl-2-phenyl-hydrazid)-Triethylammonium-Salz El6a, 816 (Hydrazin + COS)... 

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