Naphthyl sulfonates

The reaction of butyllithium and /erf-butyl-1-naphthyl sulfone in diethyl ether at reflux for 5 hours followed by quenching the reaction mixture with water gives trans-X,2-dihydro-1-/m-butylsulfonyl-2-butylnaphthalene 2 3. 

Naphthyl-benzyl-sulfone spalten vorwiegend in Naphthalinsulfinsduren und Toluol. Lediglich Methyl-naphthyl-sulfone bilden hauptsachlich Naphthalin und Methansulfin-sdure1. 

Naphthyl sulfones 253 are susceptible to nucleophilic attack at the 2-position of the naphthalene ring by the alkyllithium 134 secondary sulfonamides 254, on the other hand, surprisingly undergo perilithiation with alkyllithiums.133... 

Cathodic reduction at zinc of chloroethyl /1-naphthyl sulfide 1, chloropropyl /1-naphthyl sulfide 2 and chloroethyl /1-naphthyl sulfone 3 in methanol (equation 3) gave a complex mixture of products including alkyl / -naphthyl sulfides 4 and alkyl /1-naphthyl sulfones 523. 

The reaction of naphthosulfone (36, Scheme 11) with the lithium aluminum hydride takes two directions. The first route consists in reduction to naphthothiete (34) with subsequent transformations represented in Scheme 10 (34—>56—>57—>58 59) on quenching dilithium intermediate 57 with water (R = H). The second path involves opening the hetero ring with the nucleophile without reduction (36—>65 67) also analogous to (34 -> -> -> 59) for naphtho[l,8-Z c]thiete proper (cf. Schemes 10 and 11). Methyl naphthyl sulfone (67) thus obtained was also prepared by an independent synthesis by treating naphtho[l,8-Z c]sulfone (36) with methyllithium followed by quenching with water (36 66—>67). 

Apart from aryl halides, other very easily available substrates for nickel-catalysed biaryl (II) synthesis are aryl sulfonates (XII). Method D is very efficient in the homocoupling reactions of substituted aryl sulfonates in good to excellent yields [15], Table 6. Substituted aryl sulfonates are readily obtained from phenols and trifluoromethanesulfonic anhydride, benzenesulfonyl-, tosyl- or methanesulfonyl chloride in pyridine, or in a suitable inert solvent such as dichloromethane in the presence of triethylamine or Hiinig s base. Among other nickel complexes, Ni(dppe)Cl2 and Ni(dppf)Cl2 have been used (10 mo1%) as slightly less versatile catalysts for the homo-couplings of naphthyl sulfonates in refluxing THF, DMF or their mixtures [42]. 

Several limitations of this model show that it is not the main mechanism for dissolution inhibition in DNQ/novolac systems. First, the reaction does not occur with all inhibitors. Diazodiones such as Meldrum s Diazo do not undergo base-catalyzed azo-coupling, but they are effective inhibitors (77). Also, Murata et al (72) showed that efficient dissolution inhibition can be observed with inhibitors that do not have diazo functionality. For example, phenyl naphthyl sulfonate is a better dissolution inhibitor than the corresponding phenyl DNQ sulfonate indicating that the dissolution inhibition ability can be attributed to the sulfonate ester of the DNQ, not the DNQ chromophore itself (Figure 2). Despite the shortcomings of the Stonewall Model, it was an important contribution to the understanding of dissolution inhibition, because it was the first microscopic, molecular-interaction model for inhibition. 

Conformationally constrained bispropargyl sulfones with an ort/io-alkenyl moiety under basic condition undergo isomerization to monoallene followed by a 6n-electrocyclization. Further isomerization and 6a -electrocyclization has been reported to result in bis-naphthyl sulfones (Scheme 40). ... 

Naphthalene (Table IX, p. 182). The course of the sulfonation of naphthalene is strikingly dependent upon both the reaction temperature and time at low temperatures the product is almost exclusively the -isomer (96%), at 165° the product consists of approximately 85% /5-naphthalenesulfonic acid, 15% a-naphthalenesulfonic acid, and traces of the 1,6-disulfonic acid and of /S-naphthyl sulfone (1%). The pure a-acid is isolated from the former sulfonation as follows the reaction mixture is diluted with water, filtered from unchanged naphthalene, and evaporated somewhat under vacuum at a low temperature the -acid dihydrate separates slowly, and is recrystallized from dilute hydrochloric acid (m.p. 90 ). The pure /3-acid is obtained from the high-temperature sulfonation as follows the reaction mixture is diluted with water and filtered from the sulfone, then shaken with benzene to remove the last traces of the sulfone the water layer is evaporated, and the /3-acid separates as the trihydrate on cooling to 10°. The pure trihydrate (m.p. 83 ) is obtained after several recrystallizations from 10% hydrochloric acid, in which it is practically insoluble at 10 . The trihydrate is converted into the monohydrate (m.p. 124 ) on drying in a desiccator... 

Similarly, 5-thiazole alkanoic acids and their salts are obtained from thioamides and /3-halo -y-keto acids (695). Thus thioarylamides condensed with 3-aroyl-3-bromopropionic acid (88) in isopropanolic solution in the presence of Na COs give first 4-hydroxy-2-aryl-A-2-thiazoline-5-acetic acid intermediates (89), which were dehydrated in toluene with catalytic amounts of p-toluene sulfonic acid to 2,4-diaryl-5-thiazole acetic acid (90) (Scheme 39) (657), with R = H or Me Ar = Ph, o-, m- or p-tolyl, o-, m-, or P-CIC6H4, 0-, m-, or p-MeOC(iH4, P-CF3C6H4, a-thienyl, a-naphthyl (657). 

Some 5-substituted 2-aminothiazoles with alkyl (15, 173, 175, 224, 366, 396), ester (173, 184, 220), aryl (115, 265, 396, 414), a-naphthyl (463), sulfur and sulfones derivatives (329, 373), isonitrosomethyl (772), and chloro groups were synthetized from the corresponding a-haloaldehyde and thiourea in lower yield (Table 11-14). 

Abbreviations EPR, electron paramagnetic resonance FITC, fluorescein-5 -isothiocyanate lAEDANS, iV-iodoacetyl-N -(5-sulfo-l-naphthyl)ethylenediamine NCD, fluorescent yV-cyclohexyl-N -(4-dimethyl-amino-a-naphthyl)carbodiimide RITC, rhodamine-5 -isothiocyanate DPPE, dipalmitoylphosphatidyl-ethanolamine PE, egg phosphatidyl-ethanolamine ANS, 8-anilino-l-naphthalene sulfonate DPH, diphenylhexatriene e-ADP, l,iV -ethanoadenosine-5 -diphosphate TNP-ADP, 2 [3 ]-0-(2,4,6-trinitrophe-nyl)adenosine-5 -diphosphate. 

Nucleophilic addition to a, -unsaturated sulfones has long been known. For example, treatment of divinyl sulfone with sodium hydroxide has been known to afford bis( -hydroxyethyl) sulfone "", while the reaction of a- and -naphthyl allyl sulfones and allyl benzyl sulfone " with alkali hydroxide or alkoxide gave -hydroxy or alkoxy derivatives. In the latter reaction, the allyl group underwent prototropy to the 1-propenyl group, which in a subsequent step underwent nucleophilic attack . Amines, alcohols and sulfides are known to add readily to a, -unsaturated sulfones, and these addition reactions have been studied widely. In this section, the addition of carbon nucleophiles to a, ji-unsaturated sulfones and the reactions of the resulting a-sulfonyl carbanions will be examined. 

The /rau.v-2-naphthyl cyclohexyl sulfone 15 can be prepared readily in either enantiomeric form. The corresponding ester enolates can be alkylated in good yield and diastereoselectivity.98 In this case, the steric shielding is provided by the naphthyl... 

The second synthesis of the enantiomer of this sulfone entails two transformations. First, (-)-a-naphthyl p-tolyl [ 0] sulfoxide 141 was converted into the corresponding [ 0] sulfoxide 141 by the method of Johnson (with inversion of configuration). Its oxidation with m-chloroperbenzoic acid afforded the chiral sulfone (+)-142 (Scheme 8). The latter procedure was also used for the preparation of chiral (-)-[ H2lbenzyl p-tolyl [ 0 0]sulfone (143) from (-)-[ H2] benzyl p-tolyl sulfoxide 37. 

Dimethylbiphenyl-2,2 -dicarboxylic acid, l,l -binaphthyl-2,2 -diyl hydrogen phosphate, camphor-10-sulfonic acid, acenocoumarol, proglumide, Af-succinyl-1-phenylethylamine, 3,4-dihydro-4-(2-naphthyl)-1,3,6-trimethyl pyrimidine-2(lH)-one-5-carboxylic acid... 

Other studies on the PFR in the presence of cyclodextrins include substrates with different acyl moieties (phenyl propionate and phenyl valerate) [261] 1-naphthyl acetate [262,263], 1-naphthyl benzoate [263], sulfonate esters, [264,265], benzenesulfonylanilides [266], acetanilide [259,267], and benzanilide [259,268]. 

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