Sodium phenyl derivatives

The use of azide reagents is also important for the synthesis of cyclic sulfur(VI)-nitrogen systems. The reaction of SOCI2 with sodium azide in acetonitrile at -35°C provides a convenient preparation of the trimeric sulfanuric chloride [NS(0)C1]3 (Eq. 2.16). " Thionyl azide, SO(N3)2 is generated by the heterogeneous reaction of thionyl chloride vapour with silver azide (Eq. 2.17). This thermally unstable gas was characterized in situ by photoelectron spectroscopy. The phenyl derivative of the six-membered ring [NS(0)Ph]3 can be prepared from lithium azide and PhS(0)Cl. ... 

The first synthesis of a 3,5-diarylisoxazole from aryl hydroxamic acid chlorides and sodium phenyl acetylides was that effected by Weygand and Bauer in 1927. Beginning in 1946, when Quilico and Speroni showed that acid chlorides of hydroxamic acids on treatment with alkalies readily yielded nitrile oxides,numerous isoxazole and especially A -isoxazoline derivatives have been prepared. 

Diene (VI) was reacted with aniline in methanol in the presence of sodium carbonate to yield N-pheny1-3,4-dimethylenepyrrolidine. However, the purified yield was poor (-20%). The alternate route was a more direct method to prepare the monomer (III) without the side reactions on elimination that could take place in the first synthetic approach. Nevertheless, due to the poor yield, all the monomer (III) used for this work was prepared via the first route. The alternative method does have applicability in the preparation of substituted N-phenyl derivatives as these could be less volatile and more difficult to recover by sublimation. 

Numerous preparative methods have been reported for these acids and their salts and ester derivatives.1 4 Dithiophosphoric acids are accessible from the reaction of phosphorus pentasulfide with alcohols or phenols (Equation 18). Dithiophosphinic acids can be prepared from thiophosphinic chlorides and sodium hydrosulfide (Equation 19), although the phenyl derivative is better prepared using a modified Friedel-Crafts reaction in which phosphorus pentasulfide is reacted with benzene in the presence of anhydrous aluminium trichloride (Equation 20). 

The dissociation pressure of trimethylborane over the adduct is 23 Torr at room temperature and trimethylborane is readily pumped off in vacuo. Tri-ethylborane and triphenylborane did not afford adducts with diphenylketimine also, the B-phenyl derivatives could not be prepared. However, the reaction between di(p-tolyl)methyleneimine hydrochloride and sodium tetraphenylboiate... 

The Dieckmann cyclization of aminomethylenemalonates (1308) in boiling ethanol for 45 min, by the action of alkoxide, gave pyrrole-2,4-dicar-boxylates (1309) in 24-86% yields (77HI821 78CPB2224). Pyrrole-2,4-dicarboxylate (1309, R = H,R = Et) was also prepared in 71% yield from 1308 (R = H, R1 = Et) by reaction with sodium hydride in boiling benzene for 4 hr (78CPB2224). The 1-phenyl derivative (1309, R = Ph, R1 = Et) was prepared in 52% yield in an exothermic reaction of 1308 (R = Ph,... 

Nitrobenzoylamino)-2,2-dimethylpropanamide (143 R = Me) reacts in methanol-DMSO solution with sodium methoxide to yield 5,5-dimethyl-2-(4-nitrophenyl)imidazol-4(5//)-one (144 R = Me). The 4-methoxyphenyl derivative and the parent phenyl derivative react similarly, as do compounds in which variation of the 2-substitutent (R = Pr , Ph, 4-O2NC6H4) was made. The mechanism of the cyclization probably involves initial formation of the anion of the alkanamide (145), which adds to the carbonyl group of the benzamido moiety to yield the tetrahedral oxyanion (146) proton transfer and dehydration then yield the heterocycle (144). The kinetics of hydrolysis in water at 70 °C and pH 2-11 of A-glycidylmorpholine (147) have been reported. ... 

The ditetrazolium salts (309) have been patented for use in electrochromic electrodes which are used in display devices <89JAP01230026) and tetrazolium salts have also been developed for cell bioassays for neurotoxins active on voltage-sensitive sodium channels <93MI 417-03). Tests for inhibition of corrosion of zinc and brass carried out on 5-aminotetrazole showed it to be ineffective relative to other azoles <86MI 417-01). A number of tetrazoles including the 5-amino, 5-methyl, and 5-phenyl derivatives have been separately incorporated into surfactants used for corrosion inhibition with copper in water <9lMl4l7-07). Photopolymerizable resin compositions which are highly resistant... 

As discussed, electron-donating groups at Cl in bicyclo[2.2.1]heptane systems promote the rearrangement to bicyclo[3.1.1]heptane derivatives. Photolysis of 1-methyl bicyclo[2.2.1]heptan-2-one tosylhydrazone in 1,2-dimethoxyethane in the presence of sodium hydroxide gave 2-methyl-bicyclo[3.1. l]heptan-2-ol (26a) in 7.5% yield in addition to bicyclo[2.2.1]heptane derivatives, while the 1-phenyl derivative gave the ring-contracted product 26b in only 2% yield.91... 

Thiopyran 5,5-dioxide (9) accepted several amines RR NH by addition in the presence of triethylamine to give cyclic sulfones 589a in variable yields.26 Similarly, 3-phenyl derivative 289 gave 589b with piperidine, whereas no addition took place with sodium methoxide.300... 

Nucleophilic displacement of 2-chloro-3-phenylquinoxaline with methylamine at 100°-150° and with sodium phenoxide in excess of phenol of 100° gives the expected 2-methylamino- and 2-phenoxy-3-phenylquinoxalines.155 2-Chloroquinoxaline and its 3-phenyl derivative undergo ring closure with aminoacetaldehyde dimethylacetal to an imidazo[l,2-a]quinoxaline.136 Nucleophilic substitution of 2-chloro-quinoxaline with hydroxide ion in water is accelerated by cationic micelles and retarded by anionic micelles. These results were correlated with reactions of l-chloro-2,4-dinitrobenzene, and the characteristics of their transition states were discussed.137... 

Monocyclic l,2-dihydro-l,2-azaborines (3) easily form polymers with the exception of the 2-phenyl derivative (109 R = Ph), probably because of interaction between the two rings. In contrast, the alkyl substituted monocyclic system (155) is stable towards polymerization although it is easily oxidized by air and hydrolyzed by water. This stability order between (3) and (155) was predicted by semi-empirical methods. However, the ring system (7), isosteric with pyridine, seems to be the most stable of the monocyclic systems. Some of its alkyl derivatives remain unchanged after 50 h in concentrated sulfuric acid at 80 °C. After reflux in 1M sodium hydroxide almost all of the compound was recovered. 

Polyfluorophenylacetaldehydes show a novel nucleophilic ring closure reaction pentafluorophenylacetaldehyde, treated with sodium hydride in DMF, gives 4,5,6,7-tetrafluorobenzofuran (123, R = H) (13% yield). Under the same conditions, 2-pentafluorophenylaceto-phenone gives the 2-phenyl derivative (123, R = Ph) (76% yield).323... 

The l,X-naphthyridines react with phenyllithium to afford the corresponding 2-phenyl derivatives.32 When 1,8-naphthyridine is treated with butyl-lithium, the 2-butyl derivative is obtained, whereas reaction of dithiane with butyl lithium followed by addition of 1,8-naphthyridine generates bisnaph-thyridine 49. An interesting application of the dimethyl sulfoxide-sodium... 

The tricarbonylchromium entity promotes ipso-Smiles rearrangement of the O-phenyl derivatives of ephedrine and pseudoephedrine to the N-phenyl derivatives [32]. Indeed, treatment of the sodium alkoxide derived from (1 R,2S)-ephedrine with fluorobenzene complex... 

Treating the isoxazolopyridazine (197 R = H) with 2-4 N sodium hydroxide gives the cyano-pyrazoles (198) (Scheme 13). In contrast, the 7V-phenyl derivative (197 R = Ph) gives pyrazole (199 R = Ph) as a major product together with a small amount of compound (198 R = Ph) <85H(23)365>. Treatment of compound (200) with alkali results in the formation of the 1,2-diazepine derivative... 

Liittringhaus et al. 68) have isolated many interesting substances from the byproducts ( 8%) of the Bayer process. The mechanism has been fully clarified and shown to be an aryne route. When chlorobenzene or diphenylether are treated with sodium phenyl, the products are ortho metalated derivatives and benzyne. These give the same products which are formed in the industrial phenol synthesis. The most interesting compounds are 2- and 4-hydroxy biphenyl, 2,6-diphenyl- and 2,4-diphenyl-phenol l). For similar syntheses see 69). 

The solvent-free phenyl derivatives of the heavier alkali metals have not been structurally characterized. Phenyl sodium dimers crystallize in the presence of donors such as, PMDTA and TMEDA. Using the bulky mesityl-substituted derivatives, a solvent-free arylsodium compound has been characterized [Na(C6H3Mes2-2,6)]2. ... 

Interaction of ferrocene and diazonium compounds, which is followed by loss of nitrogen, leads to a large number of derivatives 17, HI, 1, 14s, 30S) most of them, naturally, are aryl-substituted compounds. Ferrocene cannot only be mercuriated, but can also be metalled by lithium butyl or similar compounds such as sodium phenyl. A great variety of pt ibilities for substitution is afforded by the interaction of ferrocenyl lithium and halogen-containing compounds 5, 128, 143, 162). Carboxylic acids, in particular, may easily be obtained by formation of the lithium derivative of ferrocene and treatment with carbon dioxide. 

Mercury dicyclohexyl.—This compound proved more difficult to isolate than the phenyl derivative, but has been obtained by the action of mercuric bromide on a large excess of magnesium cyclohexyl bromide. It is much less stable than mercury diphenyl, decomposing even in a few hours to a black oil when kept over phosphorus pentoxide in the dark in a vacuum desiccator. Mercury dicyciohexyl forms white, hard granules, M.pt. 78° to 79° C., which are more soluble than mercury diphenyl, and combines directly with mercuric halides or cyanide in any solvent to form cyclohexylmercuric salts. It has also been prepared by the sodium amalgam method, when it is said to form white needles, M.pt. 189° C., -which can be sublimed in small quantities in vacuo ... 

The molar rtfraction [R] and magnetic rotation [M] were measured with the sodium D line the value of [R] for the azido group was derived from alkyl azides. In phenyl derivatives it increases to about 10-2 . This results from conjugation of N3 with the aromatic ring optical exaltation effect) [M] is related to the Faraday effect (sec reference 16 for a simple discussion, and reference 18a for a recent review. 

Alkyl and aryltin(IV) diphenyldithioarsenates R Sn(S2AsPh2)4 ( = 2, R = Me, Bu , Ph = 3, R = Me, cy, Ph) are available from the organotin halides and the sodium salt of diphenyldithioarsenates. The dialkyl and trialkyltin species are four-coordinate by spectroscopy whereas the phenyl derivatives are six-coordinate. A structural study of Me2Sn(S2AsMc2)2 reveals a four-coordinate tin center with monodentate coordination of the dithioarsenate." ... 

Aryl groups are widely employed as the protector. Some kinds of phenyl derivatives can be removed by basic hydrolysis. The removal, particularly from phosphodiesters, frequently requires high tempera-ture.<34.i35 Pqj example, the 4-chloro-2-nittophenyl ester (106 equation 63) is hydrolyzed by sodium... 

Under the classical conditions (pyridine, CHCI3, room temperature or 40-60 C), diethyl malonate did not react with aryllead triacetates and the a-methyl and a-phenyl derivatives reacted slowly to give poor yields (-25%) of the corresponding a-aryl a-substituted malonic acid diesters. Moderate to good yields were obtained by reacting the sodium salt of substituted malonic esters with aryllead triacetates in THF in the presence of pyridine, but the sodium salt of diethyl malonate again failed to react. 

In the now classical synthesis, protonation of sodium phenyl ethynyltellurolate (170) yields mixtures of the isomeric ditellurofulvene (171) <81CC828> however, the four-membered 1,3-di-telluraethane derivative (172) becomes the main product when the reaction is carried out in HCl/... 

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