Naphthalene 1-naphthyl

In another paper from the Jackson Laboratories of the du Pont Company (Calcott et al., 34) there is reported a repetition of some of the reactions of Simons and Archer, as well as additional ones. Mono-, di-, and 1,2,4,5 tetraisopropylbenzene were obtained from propylene and benzene both l -chloro-i-butylbenzene and di-(l/-chloro)-d-butylben-zene were obtained from 3-chloro-2-methyl-propene-l and benzene p-f-butyltoluene and di-i-butyltoluene were obtained from diisobutylene and toluene tetraisopropylnaphthalene was obtained from propylene and naphthalene naphthyl-stearic acid was obtained from oleic acid and naphthalene mixed isopropyltetrahydronaphthalene was obtained from propylene and tetrahydronaphthalene 2,4,6-triisopropylphenol was obtained from propylene and phenol a mixture of monoisopropylated m-cresols was obtained from propylene and wi-cresol and di-(s-hexyl)-diphenyl oxide was obtained from hexene-3 and diphenyl oxide. 

Use Intermediate (phthalic anhydride, naphthol, Tertralin, Decalin, chlorinated naphthalenes, naphthyl and naphthol derivatives, dyes), moth repellent, fungicide, smokeless powder, cutting fluid, lubricant, synthetic resins, synthetic tanning, preservative, textile chemicals, emulsion breakers, scintillation counters, antiseptic. 

F irst and second figures are for, respectively, adult and larval spot shrimp 10 h exposure mean values calculated from T able 2 of reference for exposure of adults to pH]- or p C] naphthalene naphthyl glucuronide and a part of the dihydrodiol component may be impurities, j May not include quinones. 

The commercial product, m.p. 53-55°, may be used. Alternatively the methyl -naphthyl ketone may be prepared from naphthalene as described in Section IV,136. The Friedel - Crafts reaction in nitrobenzene solution yields about 90 per cent, of the p-ketone and 10 per cent, of the a-ketone in carbon disulphide solution at — 15°, the proportions ore 65 per cent, of the a- and 35 per cent, of the p-isomer. With chlorobenzene ns the reaction medium, a high proportion of the a-ketone is also formed. Separation of the liquid a-isomer from the solid p-isomer in Such mixtures (which remain liquid at the ordinary temp>erature) is readily effected through the picrates the picrate of the liquid a-aceto compound is less soluble and the higher melting. 

Isopropylnaphthalenes produced by alkylation of naphthalene with propjdene have gained commercial importance as chemical intermediates, eg, 2-isopropylnaphthalene [2027-17-OJ, and as multipurpose solvents, eg, mixed isopropylnaphthalenes. Alkylation of naphthalene with alkyl haUdes (except methyl hahdes), acid chlorides, and acid anhydrides proceeds in the presence of anhydrous aluminum chloride by Friedel-Crafts reactions (qv). The products are alkylnaphthalenes or alkyl naphthyl ketones, respectively (see Alkylation). 

Another large use of naphthalene is as a raw material for the manufacture of 1-naphthyl-A/-methylcarbamate [63-25-2] (carbaryl, Sevin). Cmde or semirefined coal-tar or petroleum naphthalene can be used for carbaryl manufacture. Carbaryl is used extensively as a replacement for DDT and other products that have become environmentally unacceptable (see InsectcontrolTECHNOLOGY). 

Naphthalene diozonide Naphthyl amineperchlorate Nickel picrate... 

Naphthalene, 216 Naphthalene picrate, 217 Naphthalene sulphonaie ofsodiiim, 218-/ J-Naphthol, 219 Naphthol yellow, 224 /i Naphthyl acetate, 222 /j-Naphthyl methyl ether, 220 /-Nitracetanilide, 153 w-Nitraniline, 154 /-Nitraniline, 153 Nitric acid (fuming), 22 NitroVienzene, 142 w-Nitrobenzoic acid, 200 Nitrogen, qualitative e rimation, 2 quantitative estimation, 13 Nitrophenol, 183 Nitrosohenzene, 146 /-Nitrosodimethylaniline, 157 Niirosoplienol, 159... 

Meyers has demonstrated that chiral oxazolines derived from valine or rert-leucine are also effective auxiliaries for asymmetric additions to naphthalene. These chiral oxazolines (39 and 40) are more readily available than the methoxymethyl substituted compounds (3) described above but provide comparable yields and stereoselectivities in the tandem alkylation reactions. For example, addition of -butyllithium to naphthyl oxazoline 39 followed by treatment of the resulting anion with iodomethane afforded 41 in 99% yield as a 99 1 mixture of diastereomers. The identical transformation of valine derived substrate 40 led to a 97% yield of 42 with 94% de. As described above, sequential treatment of the oxazoline products 41 and 42 with MeOTf, NaBKi and aqueous oxalic acid afforded aldehydes 43 in > 98% ee and 90% ee, respectively. These experiments demonstrate that a chelating (methoxymethyl) group is not necessary for reactions to proceed with high asymmetric induction. 

Methoxy-Naphthalene (Me thy 1-0-naphthyl-ether). Cryst, mp 13—14°, bp 274°. Sol in eth, chlf benz. Prepn from K-0-napthalate by heating with methyl chloride at 300°... 

Methyl-[ 5,7-dinitro-8-hydroxy-naphthyl-(l)] -ether, 2,4-Dinitro-8-methoxy-naphthol-(l) ). (02N)2CioH4(OH).O.CH3, mw 264.21, N 10.61%, OB to C02 -121.12%, gold plates from ale, mp 179—80° (decompn). Sol in dil alkali ale. Prepn from 2,4-dinitro-1,8-dime thoxy-naphthalene by reaction with 2N NaOH Ref Beil 6, 5284 ... 

Di n itr o-8- Hyd roxy 1 -Acetoxy-Naphtha bob (2,4-Dinitro-8-acetoxy-naphthol-(l), acetic acid-r >.7-dinit.ro-8-hvdrnxv-nanhthv14r1 V tf rl f5 7. dinitro-8-hydroxy-naphthyl-(l)-acetate]. H0.(O2N)2C10H4.OCOCH3, mw 292.22, N 9.59%, OB to C02 —149.81%, gold prisms from AcOH, mp 200° (decompn). Sol in ale boiling AcOH. Prepn from 1,8-diacetoxy-naphthalene by reaction with dil nitric acid (d 1.4g/cc) at 25-30°... 

Trinitro-5-hydroxy-l-acetoxy-naphthalene, acetic acid-[2,6,8-trinitro-5-hydroxy-1 -naphthyl-ester], [2,6,8-trinitro-5-hyd roxy-1 -naphthyl] -acetate). (O2N)3C10H3(OCOCH3).OH, mw 337.22, N 12.46%, OB to C02 -87.78%, yellow needles... 

Gore et al.426 have used chloroform as a solvent for acetylation catalysed by aluminium chloride and at 45-55 °C find that a 2-methoxy substituent in naphthalene increases the reactivity of the 1 position 1.72 times, of the 6 position 3.8 times, and of the 8 position, 0.9 times the former and latter of these results indicate a considerable steric effect. Likewise, a 2-bromo substituent caused the reactivity of the 6 and 8 positions to be 0.63 and 0.58 times that of the corresponding positions in the unsubstituted compound. At 20-25 °C the relative reactivities of some polycyclics were as follows427 1-naphthyl, 1.0 3-phenanthryl 0.64 9-phenanthryl, 0.02 1-phenanthryl, 0.29 2-naphthyl, 0.28 2-phenanthryl, 0.12 4-phenanthryl, 0.0085. Some of these results seem to be due to steric hindrance, and the large difference in reactivity of naphthalene and biphenyl seems erroneous. 

Tri-(l-naphthyl)phosphine is cleaved by alkali metals in THF solution. " Reaction with sodium gives the naphthalene radical-ion, with lithium the perylene radical-ion, and with potassium the radical-ion (22). Hydrocarbon radical-ion formation was thought to occur via naphthalene derived from the metal naphthalenide. E.s.r. spectra of further examples of phosphorus-substituted picrylhydrazyl radicals have been reported. ... 

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. 

Compound 1 is completely hydrogenated to the saturated ketone, 4-(6-methoxy-2-naphthyl)-3-butan-2-one. Compound 2 is hydrogenated in high ytield (90%) to the saturated ketone, 2-acetyl-5,8-dimethoxy-tetrahydro-naphthalene, which can be obtained in the pure form by fractional crystallization from chloroform. 

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