4-hydroxyphenyl triethylamine

Chemical off—on switching of the chemiluminescence of a 1,2-dioxetane (9-benzyhdene-10-methylacridan-l,2-dioxetane [66762-83-2] (9)) was first described in 1980 (33). No chemiluminescence was observed when excess acetic acid was added to (9) but chemiluminescence was recovered when triethylamine was added. The off—on switching was attributed to reversible protonation of the nitrogen lone pair and modulation of chemically induced electron-exchange luminescence (CIEEL). Base-induced decomposition of a 1,2-dioxetane of 2-phen5l-3-(4 -hydroxyphenyl)-l,4-dioxetane (10) by deprotonation of the phenoHc hydroxy group has also been described (34). 

After the reaction, 1 ml of water was added to the reaction mixture, and the mixture was adjusted to a pH of 1,0 with concentrated hydrochloric acid while being cooled, and then stirred for 30 minutes. The insoluble matters were filtered off, and the filtrate was adjusted to a pH of 5.5 with triethylamine. This solution was concentrated under reduced pressure, and the residue was diluted with 20 ml of acetone to precipitate white crystals. The crystals were collected by filtration and washed with ethanol to obtain 1.46 g of white crystals of7-[D(-)-0 -emino-(4-hydroxyphenyl)acetamido]-3-methyl-3-cephem-4-carboxylicacid having a decomposition point of 197°C. 

In this compound, 1,2-bis (3-thienyl)cyclopentene was designed as molecular backbone and two brandishing porphyrin macrocycles were chosen as substituents. It was prepared by the esterification of 5,10,15-tris(tolyl)-20-(4-hydroxyphenyl)-porphyrin and l,2-bis(5-carboxy-2-methyl-3-thienyl) cyclopentene in the presence of pyridine and triethylamine. 

S )-DimethyM-(3-hydroxyphenyl)piperidine was treated with Boc-L-valine and benzotriazol-l-yl-oxy-tris-(dimethylamino)phosphonium hexafluorophosphate in THF containing triethylamine. The intermediate was deprotected by dissolving in CH2C12 and treating with trifluoroacetic acid. Thereafter, the imine was reduced using borane dissolved in dimethyl sulfide and the product isolated. 

Quinocydopropenes were first synthesized via addition of chlorophenylcarbene to (4-benzyl-oxyphenyl)phenylacetylene (22), ionization to the cyclopropenylium ion, thermal debenzyl-ation, and treatment with triethylamine. The 4-hydroxyphenyl moiety of the cation was smoothly brominated at the 3- and 5-positions by A-bromosuccinimide, leading to the dibromo-quinocyclopropene. While quinocyclopropene 23, with no substituents in the six-membered ring, was unstable, dibromo compound 24 was stable to light and heat but reactive to alkali. 

The effects of amine substitution on the photophysics and photochemistry of 2-(2 -hydroxyphenyl)benzothiazoles must also involve electron transfer processes. Salt-base equilibria and the effects this has on the fluorescence of dipyrrylmethenes in the presence of triethylamine have also been measured s... 

In a reaction related to that of phenol with dimethylsulphoxide, the same group of workers have treated dimethyl 3,3 -sulphinylpropionate in dichloromethane with a dichloromethane solution of thionyl chloride at -60X. After 15 mins., phenol was introduced at -55°C, followed after 1 hour by triethylamine at -50 C, to afford upon work-up, dimethyl 3-(2-hydroxyphenyl)-3,3 -thiodi-propionate in 84% yield(ref 46). 

The reaction of phenyl(2,4,6-triniethylphenyl)phosphine with a substituted ben-zoquinone in the presence of a chiral phosphapaUadacycle complex 252a as a catalyst and triethylamine in chloroform at —45°C proceeded in a new type of addition manner to give a high yield of a 4-hydroxyphenyl phenyl(2,4,6-trimethylphenyl)phosphinite (5p)-253 with 98% enantioselectivity, which is a versatile intermediate readily convertible into various phosphines and their derivatives with high enantiomeric purity [168]. The asymmetric stepwise double hydropho-sphination reaction of bis(enones) 254 with phenylphosphine and 252b allowed intermolecular construction of chiral tertiary bulky / -heterocycles 255 in one pot in high yields (Scheme 80) [169]. 

Materials. Poly(ethylene glycol) diisocyanate with PEG molecular weight 3,400 and M /M = 1.03 was obtained from Shearwater Polymers and was stored at -10°C under nitrogen atmosphere prior to use. Triethylamine, 3,5-dihydroxybenzylalcohol, 18-crown-6 and l,l,l-tris(4-hydroxyphenyl) ethane -all from Aldrich a- bromo-p-tolunitrile, LiAlH4 and K2CO3 from ACROS (Fisher Scientific), were used without further purification. Dichloromethane and tetrahydrofuran (THF) were dried over P2O5 and benzophenone-sodium, respectively, and distilled immediately before use. 

Thionyl chloride added dropwise at 25-35° with vigorous stirring to a suspension of salicylhydroxamic acid (prepn. s. 403) in abs. tetrahydrofuran, stirring continued 15-30 min. until a soln. results, coned, in vacuo at 35°, the crude intermediate 5-(2-hydroxyphenyl)-l,3,2,4-zj3-dioxa-thiazoline S-oxide dissolved in abs. dioxane, stirred vigorously, cooled, and treated dropwise below 30° with triethylamine — 3-hydroxy-l,2-benzisoxazole. Y 70-90%. F. e. s. H. Bos-hagen, B. 100, 954 (1967). 

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