4-methoxyphenyl triethylamine

DCM (anhydrous), DMSO (anhydrous), triethylamine (99 + %), sulfur trioxide-pyridine complex, DMA (anhydrous), potassium tert-butoxide (95%), DCE (anhydrous), 2-(4-methoxyphenyl)ethylamine (98 + %), sodium triacetoxy-borohydride (95%), A/A-diisopropylethylamine (99%), p-toluenesulfonyl chloride (99 + %), and trifluoroacetic acid (99 + %) were obtained from Aldrich Chemical Company, Inc. 4-Hydroxy-2-methoxybenzaldehyde (>98%) was obtained from Fluka Chemie, AG. 

N-Acylation of 2-methyl-5,6-dihydro-4/f-l,3-thiazine with cinnamoyl chloride in the presence of triethylamine furnishes ( )-l-(2-methylenetetrahydro-l,3-thiazin-3-yl)-3-arylprop-2-en-l-ones 122. These products undergo hydrolysis readily due to the j jA -ketene acetal-type bonds present in the molecules and are therefore not stable. Thus ( )-3-(3-(4-methoxyphenyl)acrylamido)propyl ethanethioate 123 is isolated in 92% yield from the corresponding thiazine after column chromatography on Si02 or AI2O3 <2001S135>. 

Dihydro-4//-l,3-thiazines 231 are conveniently prepared by the iodocyclization of A -homoallyl thioamides 230 in the presence of triethylamine (Scheme 28) <2004CL508>. The selectivity of the reaction was dependent on the groups attached to the thioamide, and high diastereoselectivities are achieved with the 1-naphthyl or the 2-methoxyphenyl groups giving the major product 233 with the aryl group in the equatorial position rather than 234. Treatment of thiazines 231 with pyrrolidine resulted in the formation of 6-alkylidene-5,6-dihydro-4//-l,3-thiazines 232. 

Y/ .v-(3-Lactains have been reported to be regioselectively synthesized by [2+2] Staudinger cycloaddition reactions of imine such as (3,4-dimethoxybenzylidene)-(4-methoxyphenyl)-amine and ketenes derived from different acyl chlorides and triethylamine [110]. 

To 20% solution of phosgene in toluene, agitated and cooled to 0°C, are added over 30 min a solution of l-p-fluoro-benzoyl-l-hydroxy-3-N-[N -(2-methoxyphenyl)]piperazinopropane and triethylamine in anhydrous chloroform. It is agitated at ambient temperature for 5 h, cooled to 0°C and the solution saturated with gaseous ammonia. The solution is agitated at ambient temperature for 3 h, filtered and the filtrate dried under reduced pressure, 4-p-fluorophenyl-5-p-(4-o-methoxyphenylpiperazino)ethyl-4-oxazolin-2-one, melting point 154°C (by alcohol) was obtained. 

Methoxyphenyl benzenesulfonylimino tellurium chloride and 5,5-dimethyl-l,3-dioxo-cyclohexane in benzene solution reacted on addition of triethylamine to give 5,5-dimethyl-1,3-dioxo-2-cyclohexyl 5,5-dimethyl-1,3-dioxo-2,2-cyclohexylidene 4-methoxyphenyl tellurium5. 

Dimethyl-l,3-dioxo-2-cyclohexyl 5,5-Dimethyl-l,3-dioxo-2,2-cyclohcxyhdene 4-Methoxyphenyl Tellurium1 1.9 g (4.5 mmol) of 4-methoxyphenyl benzenesulfonylimino tellurium chloride and 1.26 g (9 mmol) of 5,5-dimcthyl-1.3-dioxocyclohexane are suspended in 50 ml of benzene. A solution of 0.46 g (0.6 ml 4.5 mmol) of triethylamine in 10m/of benzene is added dropwise to the stirred suspension and the mixture is allowed to stand for 1 day. The precipitate is filtered off, washed with cold acetonitrile, then with water, and dried in the air yield 1.8 g (79%) m.p. 132° (from acetonitrile). 

A mixture consisting of 3-bromo-6-methoxy-2-(4-methoxyphenyl)-lH-inden-l-one (0.4345 mmol), sodium ethanethiolate (1.09 mmol) and 0.5 ml triethylamine dissolved in 3 ml DMF was heated 24 hours at 80°C and then cooled. The mixture was then poured into water and extracted with EtOAc. Extracts were washed with brine, dried, purified by flash chromatography using 10% EtOAc/petroleum ether, and the product isolated in 89% yield as a dark red solid, mp = 88-90°C. 

In the absence of a sufficiently good leaving group, stable adducts are formed. Thus 5-acetyl-2-(p-methoxyphenyl)thiopyrylium cation (58) reacts with ethanethiol in benzene to yield the 2H adduct 289 (75T3059). 2-Methylthio-4,6-diphenylthiopyrylium (159) ion reacts with sodium thio-phenoxide to give the 2H adduct 293 (86S916). Heating of the adduct 293 yields the Z-2,2 -bithiopyranylidene 294 with a minor amount of the E isomer. Compound 294 can also be directly obtained by reaction of cation 159 with thiophenol and triethylamine. 

Reaction of 2, 3 -ene-3 -phenyIseIenone 13 with. V-mcthylhydroxylamine in tetrahydrofuran in the presence of triethylamine at about 20 °C gives l-[2,3-dideoxy-5-0-[(4-methoxyphenyl) diphenylmethyl]-2-(yV-methyI-JV-hydroxyamino)-3-phenylseIenonyl-/J-D-ribofuranosyl]uracil (25) in a poor yield, which is unstable upon storage. Addition of 1,2-ethanediol and 1,8-diazabicy-clo[5.4.0]undec-7-ene to the reaction mixture at 40 CC converted 25 to the stable 3 -phenylse-lcnyl derivative 26, which is isolated in 45% yield106. 

Bis[4-methoxyphenyl] ditellurium was converted 4,4 -dimethoxybiphenyl in 82% yield by heating the ditellurium with an equimolar amount of Pd(0) [from palladium(II) acetate and triethylamine] in hexamethylphosphoric triamide at 65° for seven hours under an atmosphere of argon . 

The terminal alkyne, 3-(4-methoxyphenyl)-1-propyne (1.2 moles) and 4-iodotoluene in benzene containing 2 moles triethylamine, catalytic amounts of palladium(ll) acetate and triphenylphosphine when heated in an autoclave at 119 C for 4 hours under pressure with carbon monoxide (300psi.) afforded an 85% yield of the alkylidenebutenolide, 3-(4-methoxybenzylidene)-5-(4-methylphenyl)furan-2(3H)-one (ref. 134). 

Diethylamino-4-(4-methoxyphenyl)isothiazole-1,1-dioxide (17 Ar = 4-MeOPh) on treatment with one equivalent of bromine gave the dibromo derivative (18) which upon heating or by reaction with triethylamine furnished the mono bromo compound (19) on elimination of HBr. Palladium catalysed coupling of (19) with a variety of organostannanes provided good yields of 5-substituted isothiazoles (20) <97T15859>. 

A mixture of 0.67 g 3-hydroxy-4-methoxybenzaldehyde (4.4 mmol), 2.0 g 3,4,5-trimethoxyphenylacetic acid (8.84 mmol), 4 mL acetic anhydride, and 2 mL triethylamine was refluxed for 3 h. After acidification with 6 mL cone. HCl, the resulting solid was filtered off and recrystalUzed from ethanol to give 950 mg -2-(3, 4, 5 -trimethoxyphenyl)-3-(3 -hydroxy-4 -methoxyphenyl)prop-2-enoic acid as fine yellow needles, in a yield of 60%, m.p., 237-239°C. 

Phenyl cyanate followed by triethylamine added to p-acetylphenyl dicyano-acetimidate (prepared from malononitrile and p-methoxyphenyl cyanate) in... 

A stirred refluxing ethanolic soln. of 3-(4-methoxyphenacyI)phthalide treated consecutively with an aq. soln. of 2 moles hydrazine dihydrochloride and 4 moles triethylamine, and heating continued 2-3 hrs. -> 2-(4-methoxyphenyl)-3,3a-di-hydro-8H-pyrazolo[5,l-a]isoindol-8-one (Y 88.5%) stirred and refluxed 5 hrs. with 2,3-dichloro-5,6-dicyanobenzoquinone, added in 2 portions, in benzene 2-(4-methoxyphenyl)-8H-pyrazolo[5,l-a]isoindol-8-one (Y 83%). F. e. s. E. W. Bous-quet et al., J. Org. Chem. 40, 2208 (1975). 

Triethylamine added at 60° to Na previously dispersed at 110° under dry Ng in xylene containing a little oleic acid, then phenylacetylene in xylene added drop-wise at a rate to keep the temp, at ca. 60°, after the exothermic reaction has ceased warmed 0.5 hr. at the same temp., bis-(p-methoxyphenyl)carbodiimide in xylene added dropwise at room temp, during 10 min., finally dimethyl sulfoxide in xylene added with water-cooling, and the product isolated after 0.5 hr. -> N,N -bis-(p-methoxyphenyl)phenylpropiolamidine. Y 65%. - No significant reaction occurs in the absence of dimethyl sulfoxide. F. e., also with ethylmagnesium bromide instead of Na, s. H. Fujita et al.. Bull. Chem. Soc. Japan 45, 1846 (1972). 

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