Bromo-triethyl

Reacting 6 with triethyl phosphite (TEP) as the solvent gave compound 60 (01T(57)5453). The bromo derivative 46, with an equimolecular amount of TEP, afforded 29, which could be trasformed into 61 by reacting with an excess of TEP, showing a reversal of the usual regiochemistry observed in the nucleophilic addition of other 3-aminosubsdtuted isothiazole 5,5-dioxides. Reactivity of this new class of isothiazole dioxides was studied (Section II.B.l.a). 

Johnson s classic synthesis of progesterone (1) commences with the reaction of 2-methacrolein (22) with the Grignard reagent derived from l-bromo-3-pentyne to give ally lie alcohol 20 (see Scheme 3a). It is inconsequential that 20 is produced in racemic form because treatment of 20 with triethyl orthoacetate and a catalytic amount of propionic acid at 138 °C furnishes 18 in an overall yield of 55 % through a process that sacrifices the stereogenic center created in the carbonyl addition reaction. In the presence of propionic acid, allylic alcohol 20 and triethyl orthoacetate combine to give... 

Dipolar cycloaddition reactions, of nitrones to olefins, 46, 97 of 3-phenylsydnone, 46, 98 Dispiro[5.1.5.1]tetradecane-7,14-dione, photolysis to cyclohexylidene-cyclohexane, 47, 34 preparation from cyclohexanecarbonyl chloride and triethylamine, 47, 34 Displacement of bromine from 1-bromo-2-fluoroheptane to give 2-fluoro-heptyl acetate, 46, 37 N,N -Disubstituted formamidines from triethyl orthoformate and primary amines, 46, 41 N,N-Disubstituted thioureas from secondary amines and silicon tetra-isothiocyanate, 45, 69 N,N-Disubstituted ureas from secondary amines and silicon tetraiso-cyanate, 45, 69... 

Fuostifoline (47), a furo[3,2-a]carbazole, was isolated from Murraya euchrestifolia. Timdri s total synthesis of 47 commenced with alkylation of bromocresol 43 with bromoacetaldehyde diethyl acetal and P4Oio-promoted cyclization to furnish 5-bromo-7-methylbenzofuran (44) [47]. The Suzuki coupling of boronic acid 45, derived from 44, with o-bromonitrobenzene yielded biaryl 46. Nitrene generation, achieved via deoxygenation of nitro compound 46 using triethyl phosphite, was followed by cyclization to fuostifoline (47). 

In Chapter vi the introduction of the 2-fluoroethyl group by the action of l-bromo-2-fluoroethane on triethyl phosphite,3 giving diethyl 2-fluoroethylphosphonate (XI), is considered ... 

Triethylamine, 46, 18 dehydrobromination of oi-bromo-y-butyrolactone with, 45, 23 Triethyl phosphonoacetate, reaction of sodium derivative with cyclohexanone to yield ethyl cyclo-hexylideneacetate, 46, 45 Trifluoroacetic anhydride, 45, 98 Teiphenylalctminum, 46,107... 

Our experimental results were obtained when investigating the following compounds 3s 5l-cyclo-3 -methyl-2,7,8,12,13,17,-18-heptaethyl-22H,24H-porphine (1) 3l,5l-cyclo-3l-exomethyl-en-2,7,18,12,13,17,18-heptaethyl-22H,24H-porphine (2) 3l,5l-cyclo-3 -methyl-5 -oxy-2,7,8,12,13,17,18-heptaethyl-22H,24H-porphine (3) phylloerythrin methyl ester (4) deoxophylloerythin methyl ester (5) 10-ethoxy-phylloerythrin methyl ester (6) pheopor-phyrin-ac dimethyl ester (7) 2-vinylpheoporphyrin-as dimethyl ester (8) 4-vinylprotopheophytin a (9) 3, 5 -cyclo-5 -ethyl-10,15,20-tri-propyl-22H,24H-porphine (10) 3j5 -cyclodimer (11) which consists of two molecules 1 and 2 2,3,12,13-tetraethyl-21H,23H-porphine (12) 3 5 -cyclo-3 -methyl-2,12,13-triethyl-22H,24H-porphine (13) 2,3,12,13-tetraethyl -7-bromo-21H,23H-porphine (14) and 2,3,12,13-tetramethyl-21H, 23H-porphine (15). Structural formulas are shown in Figure 1. 

The electrophilic substitution of the 3-aryl compounds (265, R = Ar, R = H) exemplified by the formation of 5-bromo- (265, R = Ar, R = Br) and 5-nitro derivatives (265, R = Ar, R = NOj) has been put forward as evidence against the meso-ionic formulation 265. lliis approach is unacceptable since ground state charge distribution cannot be deduced from reaction products. The aluminum-amalgam reduction of meso-ionic l,2,3-thiadiazol-4-ones (265) yields either N-mercaptoacetyl-A-arylhydrazines or Ar-acyl-A-arylbydrazines. Triethyl-oxonium tetrafluoroborate and meso-ionic l,2,3-thiadiazol-4-ones (265) yield 1,2,3-thiadiazolium tetrafluoroborates (267). The effect of solvent on the ultraviolet spectra of meso-ionic l,2,3-thiadiazol-4-ones (265) has been reported. ... 

Sugars containing a carbon-phosphorus bond have been prepared by application of the Michaelis-Arbuzov reaction to bromodeoxy sugars. Thus, the reaction of 5-bromo-5-deoxy-l,2-0-isopropylidene-3-O-methyl-a-D-xylofuranose (131) with triethyl phosphite yields the corresponding diethyl phosphonate (132) compound 132 was employed for the synthesis of a sugar derivative having phosphorus as... 

A mixture consisting of the step 1 product (30 g), 200 ml THF, and 48 ml triethyl-amine was cooled to 0°C and then treated with the dropwise addition of 6-bromo-hexanoyl chloride (36.5 g) dissolved in 150 ml THF over 25 minutes. After stirring for 2 hours the reaction was partitioned between water and diethyl ether and the organic component washed with dilute hydrochloric acid, water, dried, filtered, and concentrated. The residue was crystallized from isopropyl alcohol and the product isolated. 

Recent field evidence indicates that the occurrence of these reaction products may be relatively common in hypoxic groundwaters which have been contaminated by bromoaliphatic compounds. Schwarzenbach et al. (1) reported the presence of a complex mixture of alkyl and chloroalkyl sulfides in a hypoxic groundwater polluted by a variety of bromo- and chloroaliphatic compounds. Ethanethiol (at a concentration of approximately 2 pM) was detected by Jackson et al. (5Q) in groundwater contaminated by a variety of chlorinated and brominated solvents beneath a municipal/industrial landfill. In addition, Watts and Brown (51 cited in 2) have reported the presence of ethanethiol, diethyl disulfide and triethyl disulfide in Florida groundwaters contaminated by 1,2-dibromoethane. 

The introduction of phosphoryl fragment at position 5 of indole and indoline molecules was described in [35], 5-Bromo-2-methylindoline reacts with an excess of phosphite, which acts as solvent and reagent, in the presence of nickel chloride, giving 5-diethoxyphosphoryl-2-methylindoline (58). 5-Bromo-2-methylindole reacts with triethyl phosphite in mesitylene (catalyst nickel chloride) with the formation of 5-diethoxyphosphoryl-2-methylindole (59) ... 

---