0,0-Diethyl 0- 4- phenyl

Biological activities also may correlate with electronic substituent factors alone, eg, the inhibition of acetylcholinesterase by six diethyl phenyl phosphates (36) gave r = 0.95 for... 

Al,A/-diethyl-/)-phenyl-enediami 10 16 2 [93-05-0] pale yeUow 260-262 reduction of ... 

Diethyl phenyl orthoformate (diethoxy phenoxy ethane) [14444-77-0] M 196.3, b... 

A-Fluoro-2,4,6-tnmethylpyndmium inflate (1 mmol) is added m several portions at room temperature to a tetrahydrofuran solution of sodium diethyl phenyl-malonate, obtained from 1 mmol of diethyl phenyl malonate and sodium hydnde at 0 C in tetrahydrofuran The reaction imxture is poured mto dilute hydrochlonc acid and extracted with ether The ether extract is washed with sodium bicarbonate and water and dned over magnesium sulfate The oily residue obtamed after removal of tihe ether is chromatographed on sihca gel (dichloromethane-hexane, 1 1) to give diethyl fluorophenylmalonate in 83% yield... 

Schrader prepared the ester (38) in 60% yield by reaction of sodium p-nitrophenate with diethyl chlorophosphate, using xylene as solvent for the reaction. He made it, but in lower yields, from p-nitrophenol and diethyl chlorophosphate, using, respectively, pyridine and sodium cyanide as acceptors for hydrogen chloride. Schrader also prepared it in 96% yield by nitrating diethyl phenyl phosphate at 0° C. or below. Under the conditions he used, Schrader claims that the nitro group is directed to the para position. No yield is given for the diethyl phenyl phosphate, which he presumably made from sodium phenate and diethyl chlorophosphate. Diethyl chlorophosphate may be prepared in high yield (30) from diethyl phosphite and chlorine. 

It can also be made by nitrating diethyl phenyl phosphate below 0°. It is a red oil, almost insoluble in water, and Schrader found it effective against aphids, while Ball and Allen1 proved it active against the housefly, milkweed bug and cockroach. Later work showed it active against the two-spotted spider mite. 

When diethyl phenyl(phenylamino)methylenemalonate (4) was heated in the presence of p-toluidine at 150°C, the N-(4-methylphenyl)amide of 2-phenylquinoline-3-carboxylate (7, R = H) was obtained (36JCS428). 

When diethyl phenyl(phenylamino)methylenemalonate (4) was dissolved in concentrated sulfuric acid and the solution was kept at ambient temperature for a few days, 2-phenyl-4-hydroxyquinoline-3-carboxylic acid was obtained on the dilution of the reaction mixture with water (36JCS428). 

Heeramaneck and Shah obtained 3-phenylbenzo[/]quinoline-2-carbox-ylate (908) in good yield on the ring closure of diethyl phenyl(2-naphthyla-mino)methylenemalonate by heating in the melt at 185-195°C (37JCS867). 

Nitration of diethyl AT-phenylphosphoramidate and diethyl phenyl phosphate in acetic anhydride or sulphuric acid yields considerable amounts of the m-nitro-... 

Diethyl phenyl ethyl malonate. 1 mole of benzyl cyanide is added dropwise to a solution of 1 mole of ethyl carbonate in 2 liters of anhydrous ethanol containing 5 g of clean sodium metal. This mixture is refluxed (preferably on a steam bath) for 5 hours. It is then cooled and to it is added a cooled mixture of 40 g of sulfuric acid in 100 ml of anhydrous ethanol. This alcoholic solution is refluxed for 5 hours, cooled, neutralized with sodium ethylate (use external indicator). The mixture is evaporated to half bulk, filtered from the sodium sulphate and to it is added 1 mole of clean metallic sodium. Reflux while adding 1 mole of ethyl bromide dropwise. Heat for another 2 hours after the addition is completed. Remove the alcohol by distillation and dissolve the remaining residue in water. Extract the substance from the water with benzene and after drying, the benzene is recovered and the ester should be purified by distilling in vacuo. 

Reaction of both methyl phenyl sulphone and diphenyl sulphone with potasium in liquid ammonia [24] leads to the formation of a dianion, which cleaves to give CfiHs, isolated as benzene. The initial electron transfer cannot be dissociative, as was the case for diethyl phenyl phosphate (p. 163), since the phenyl c-radical is not detected. The radical-anions from these sulphones have sufficiently long lifetime in liquid annmonia to allow reaction with a further electron. 

Diethyl malonate yield after 24 h at 373 K. Selectivity for diethyl phenyl malonate. Yield after 20 h. 

Another work of Duhamel and Ancel [59] related this synthesis of retinal via (3-ionylideneacetaldehyde. Condensation of methallyl-magnesium chloride with diethyl phenyl orthoformate (EtC CHOPh) led after bromination of the ene-acetal, deshydrohalogenation (NaOH 50%), ethanol elimination with hexamethyldisilazane (HMDS) and ISiMes, to the bromo-dienol ether. This latter was submitted to bromine lithium exchange and the lithio enol ether was then condensed with p ionylideneacetaldehyde to give retinal, Fig. (28). 

At rt l-fluoro-2,4,6-trimethylpyridinium triflate (Id 0.14g, 1 mmol) was added in several portions to a THF solution of the sodium salt of diethyl phenylmalonate [prepared in situ by treating diethyl phenyl-malonate (0.236 g, 1 mmol) with 60% NaH in oil (0.024 g, 1 mmol) in THF (2 mL) at 0°C]. After 30 min the reaction mixture was poured into dil HC1 and extracted with Et20. The extract was washed with aq NaHCO, and then with H20, dried (anhyd MgS04), filtered, and evaporated. The resulting residue was column chromatographed (silica gel, CH2Cl2/hexane 1 1) to give an oil yield 83%. 

Diethyl phenyl orthoformate (diethoxy phenoxy ethane) [14444-77-0] M 196.3, b lll Vllmm, 122°/13mm, d20 1.0099, n2D° 1.4799. Fractionated through an efficient column under vacuum [Smith Acta Chem Scand 10 1006 7956]. 

It is commonly assumed that the base-catalyzed hydrolysis of substituted dialkyl (i.e., dimethyl or diethyl) phenyl phosphates occurs by nucleophilic attack of OH" at the phosphorus with the phenolate being the leaving group (see also Section 13.4) ... 

Second-Order Rates Constants, kB, and pKia Values of the Phenol Moieties for a Series of Monosubstituted Diethyl Phenyl Phosphates at 25°C... 

Tetrakis(2,6-diethylphenyl)digermene 3 is reportedly converted into hexakis(2,6-diethyl-phenyl)cyclotrigermane 12b on heating in solution1-). The proposed mechanism involves the dissociation of digermene 3 into two germylenes Dep2Ge 40, followed by their... 

Diethyl-(4-methoxy-methyl-anilino)- E2, 296 Diethyl-(N-methyl-anilino)- E2, 295, 296 Diethyl-phenoxy- El, 2SI Diethyl-phenyl- -phenylimid XU/1, 177 Difluor-difluormethyl- E2, 836, 854 Difluor-(fluorsulfonyl-methyl)- E2, 857 Difluor-methyl- E2, 836, 854 Difluor-phenyl- E2, 854 Difhior-trifluormethyl- E2, 905 Difluor-triphenyl- E2, 881 Diisopropyloxy-hexyl- El, 135 Diisopropyloxy-methyl- E2, 200, 480 Diisopropyloxy-phenyl- E2. 134, 135, 207 Diisopropyloxy-propyl- E2, 200 Dimcthoxy-methyl- E2, 480 Dimethoxy-phenyl- E2, 204ff, 207, 393, 856, 864 Dimethylamino-diphenyl- E2, 18, 227 Dimethylamino-ethinyl- E2, 230 Dimethylamino-fluor-trifluormethyl- E2, 435 (4-Dimethylamino-phenyl)-diphcnyl- E2, 108 (4-Dimcthylamino-phenyl)-diphcnyl- -(2-nitro-phenylthioimid) E2, 108 Dimethylamino-l-propinyl- E2, 230 (l,l-Dimethyl-butyloxy)-ethyl-methyl- E2, 20, Dimethyl-(diphenylmethylen-amino)- E2, 106 Dimethyl-fluor- E2, 161 Dimethyl-phenyl- E2, 99, 103 Dimethyl-phenyl- -(2-aminocarbonyl-hydrazinocar-bonylimid) E2, 113... 

The reference cited [5] also gives procedures for related magnesiations of other carboxylic acids, phenylacetronitrile, t-butyl acetate, acetophenone, methyl phenyl sulfone, and diethyl phenyl-methanephosphonate. 

---