Naphthalene, aryl

The enone 807 is converted into the dienol triflatc 808 and then the conjugated diene 809 by the hydrogenolysis with tributylammonium for-mate[689,690]. Naphthol can be converted into naphthalene by the hydrogenolysis of its triflate 810[691-693] or sulfonates using dppp or dppf as a ligand[694]. Aryl tetrazoyl ether 811 is cleaved with formic acid using Pd on carbon as a catalyst[695]. 

In a similar manner, phthalazine or its alkyl- or aryl-substituted derivatives are obtainable from 1,2-diacylarenes (Scheme 76). Phthalaldehydic acid and its analogs are transformed by hydrazines into the corresponding phthalazin-l(2//)-ones. Phthalazin-l(2iT)-one itself is prepared from naphthalene by oxidation, subsequent treatment with hydrazine and decarboxylation as shown in Scheme 77 (55YZ1423,64FRP1335759). 4-Substituted phthalazin-l(2iT)-ones are prepared in a similar way from 2-acylbenzoic acids. 3-Hydroxyphthalides,... 

Aryl-6-carboethoxy(and 6-carboxy)-4-oxo-2-thioxo-l,3,8-triaza-naphthalenes are converted (100°, 3 hr) 7 7 7b to 2-oxo compounds with chloroacetic acid (cf. 136 and 237). The 4-oxo group is replaced (96°, 1 hr) by hydrazine along with ring-closure involving the 6-carboethoxy group in the 2-thioxo compounds, this substituent is simultaneously converted to an oxo group. 

Although the sulfone activated biphenyl and the ketone activated naphthalene moiety for the displacement polymerization have been reported by Attwood et al. [11], these were rediscovered by Cummings et al. [12] and Hergenrother et al. [13], respectively, for the synthesis of poly(aryl ethers). Recently, Singh and Hay [14] reported polymers containing 0-dibenzoyl benzene (1,2,3) moiety by reaction between bis(O-fluorobenzoyl) benzene or substituted benzene with bisphenates of alkali metal salt in DMAC as follows ... 

In a related study, the reaction of the enamine, l,2-dihydro-3-(2-methoxymethyl-l-pyrrolidin-yl)naphthalene [from 3,4-dihydro-2(l//)-naphthalenonc and (S)-2-(methoxymethyl)pyrrolidine] with 2-aryl-l-nitroethenes gave, after hydrolysis, an 83 17 to 95 5 mixture of the (3S,YR)- and (1/ ,1 T )-nitro ketones31. 

Sulfoxidations are not restricted to MOs but can also be carried out by dioxygenases. For example. Pseudomonas mutant strain UV4 producing a toluene dioxygenase (TOO) and Pseudomonas NCIMB 8859 expressing a naphthalene dioxygenase (NDO) were used to oxidize aryl sulfides to antipodal chiral sulfoxides [203]. 

In contrast to 2,3-dioxygenases, the related ipso/ortho oxygenation of aryl carbox-ylates has received considerable less attention and has hardly been utilized by the synthetic community, so far. Biooxidation of benzoic acid and P-naphthalene carboxylate provide access to corresponding 1,2-dihydroxylated dihydroaryl compounds in excellent stereoselectivity (Scheme 9.35), analogous to TDO- and NDO-mediated ortho/meta oxygenations. Whole-cell-mediated biotransformations were performed with mutant strains of Rahtonia and Pseudomonas and enable access to preparative quantities in >5 gl titers [261,262]. 

Tietze and coworkers [60] observed a combination of a Heck reaction and a C-H-activation by treatment of the alkyne 6/1-111 with Pd°. These authors aimed at compound 6/1-112, but 6/1-110 was obtained as a single product in high yield (Scheme 6/1.29). It can again be assumed that after oxidative addition a cis-carbopalladation of the triple bond takes place to give an alkenyl Pd intermediate which undergoes the C-H-insertion into the neighboring naphthalene and not into the aryl ether moiety. 

The activated nickel powder is easily prepared by stirring a 1 2.3 mixture of NiL and lithium metal under argon with a catalytic amount of naphthalene (1(7 mole % based on nickel halide) at room temperature for 12 h in DME. The resulting black slurry slowly settles after stirring is stopped and the solvent can be removed via cannula if desired. Washing with fresh DME will remove the naphthalene as well as most of the lithium salts. For most of the nickel chemistry described below, these substances did not affect the reactions and hence they were not removed. The activated nickel slurries were found to undergo oxidative addition with a wide variety of aryl, vinyl, and many alkyl carbon halogen bonds. 

Reported structures for homobifunctional aryl azides include a biphenyl derivative and a naphthalene derivative (Mikkelsen and Wallach, 1976), a biphenyl derivative containing a central, cleavable disulfide group (Guire, 1976), and a compound containing a central l,3-diamino-2-propanol bridge between phenyl azide rings that are nitrated (Guire, 1976). The only commercially available homobifunctional photoreactive crosslinker is BASED. 

Because anti/syn ratios in the product can be correlated to the E(0)/Z(0) ratio of the involved boron enolate mixture,10b initial experiments were aimed at the preparation of highly E(0)-enriched boron enolate. The E(0)/Z(0) ratio increases with the bulk of the alkanethiol moiety, whereas the formation of Z(O) enolates prevails with (S )-aryl thioates. (E/Z = 7 93 for benzenethiol and 5 95 for 2-naphthalene thiol esters). E(O) reagent can be formed almost exclusively by reaction of (5)-3,3-diethyl-3-pentyl propanethioate 64 with the chiral boron triflate. High reactivity toward aldehydes can be retained in spite of the apparent steric demand (Scheme 3-22).43... 

Isomerization of 1,3-dienes (12, 36).3 The 1,5-hydrogen shift in isomerization of 1,3-dienes catalyzed by (naphthalene)Cr(CO)3 (1) can be used for synthesis of aryl-substituted exocyclic alkenes, which are not readily available by coupling of aryl halides with exocyclic vinyl halides. 

Synthesis of Fluorinated Poly(Aryl Ether)s Containing 1,4-Naphthalene Moieties... 

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