Hydrides naphthalene derivative

There have been no reports of dibenzo-l,2-azaphosphorines since Edmundson s review (79MI1). However, the naphthalene derivative (1) has been described but its further reactions were not detailed (80IJC(B)404). The tricycle (2) was prepared in low yield by sodium hydride induced cycliza-tion of (3) (79JHC897). 

The chemistry of titanium and zirconium, bis(ij-pentamethylcyclopen-tadienyl) systems is essentially that of monomeric fo-CsfCH iM units. With the cyclopentadienyl systems, nearly all of the chemistry observed is that of dimers. Although the dimeric hydride fi-(tj5 tj5-C,0H8 )-/x(H2 C5H5)2Ti2 (3) is coordinatively saturated and relatively unreactive, the partially unsaturated, dimeric metallocene /t-( 1 i -C H )(,i>-CjH )3Ti1 (10) shows considerable chemical reactivity toward N2 (Section III,D) as well as interesting catalytic properties (Section VI). The behavior of dimer units in the cyclopentadienyl systems is exemplified by the unusual naphthalene ring binding in the naphthyl hydride zirconocene derivative... 

The naphthalene derivative, methyl 4-(T-t-butyldimethylsilyk)xy-4 -hydroxy-5 --methoxy-3 -(5"-oxoheptanoyl)naphth-2 -yl)-2-butenoate, in tetrahydrofuran added to a suspension of potassium hydride. Kryptofix 222 and hexamethylphosphorictriamide in tetrahydrofuran at -78 C and worked up after 3 hours at -78 to -50°C underwent a double condensation to give a 53% yield of methyl (6a-RS,9-RS,10-RS,10a-RS)-9-ethyl-12-t-butyldimethyl silyloxy-5,9-dihydroxy-4-methoxy-6-oxo-6,6a,7,8,9,10,10a,11-octahydronaphth-... 

An interesting reaction of dimsyl anion 88 is the methylation of polyaromatic compounds. Thus naphthalene, anthracene, phenanthrene, acridine, quinoline, isoquinoline and phenanthridine were regiospecifically methylated upon treatment with potassium t-butoxide and DMSO in digyme or with sodium hydride in DMSO123-125. Since ca. 50% of D was found to remain in the monomethyl derivative 93 derived from 9-deuteriophenanthrene 92, the mechanistic route shown in Scheme 2 was suggested125. 

A different behavior is exhibited by naphthalene-1,8-dicarbocal-dehyde (73). No m-naphthane derivatives are obtained on reaction with nitromethane, nitroethane or other methylene components. The basic medium, required for aldol type additions, causes the dialdehyde to undergo Cannizzaro reaction to the naphthopyranon (74) via an intramolecular 1,5-hydride shift, which is sterically favoured by the peri-position of the two aldehyde functions 28). 

The difference in the reactivity of benzylic versus aromatic halogens makes it possible to reduce the former ones preferentially. Lithium aluminum hydride replaced only the benzylic bromine by hydrogen in 2-bromomethyl-3-chloro-naphthalene (yield 75%) [540]. Sodium borohydride in diglyme reduces, as a rule, benzylic halides but not aromatic halides (except for some iodo derivatives) [505, 541]. Lithium aluminum hydride hydrogenolyzes benzyl halides and aryl bromides and iodides. Aryl chlorides and especially fluorides are quite resistant [540,542], However, in polyfluorinated aromatics, because of the very low electron density of the ring, even fluorine was replaced by hydrogen using lithium aluminum hydride [543]. 

Reduction of the B2CI4 addition products of temperatures ranging up to 200° C for the di-naphthalene compound described above, these compounds show infrared bands characteristic of B—H—B bridges 117). On the basis of infrared and NMR evidence, structure (XIV) was suggested for the compound derived from di-tert-... 

With nickel(II) 2-ethylhexanoate and triethylaluminum, tetralin (59) is obtained by hydrogenation of naphthalene (55). Polycyclic aromatics, such as anthracene (57 equation 8), 9-methylanthracene and 9-trifluoroacetylanthracene, are partially hydrogenated to 1,2,3,4-tetrahydroanthracene derivatives by use of [Rh(DPPE)(arene)]+ in methanol and by ruthenium hydride complexes having triphenylphosphine ligands... 

Substituents such as alkene units, alkyne units, and carbonyls can be reduced by catalytic hydrogenation. Lithium aluminum hydride reduces many heteroatom substituents, including nitrile and acid derivatives 56, 57, 104, 105, 106, 107, 108, 109. Polycyclic aromatic compounds such as naphthalene, anthracene, and phenanthrene give electrophilic aromatic substitution reactions. The major product is determined by the number of resonance-stabilized intermediates for attack at a given carbon and the number of fully aromatic rings (intact rings) in the resonance structures 59, 60, 61, 62, 63, 64, 65, 85, 104, 106, 107, 108,109,110,113,114,118. 

The dihydro naphthalene 12 was aromatized by first in situ reduction of the carbonyl functionality with lithium aluminum hydride in THF at 60°C for 4 h. Treatment of the carbinol solution with HCl gas provided rapid dehydration of the carbinol to the naphthalene ring 13. The benzo[a]fluorene derivative, cyclization of the 2-aryl ring onto the carbinol group, was not observed.5 Naphthalene 13 was obtained in 68% yield. Demethylation of the methoxy groups with excess gaseous BCI3 in methylene chloride provided 1 as the HCl salt. 

Fused Systems.—Naphthalene and Derivatives. A new method of aromatization of partially hydrogenated aromatic hydrocarbons overcomes the difficulty of the competing Diels-Alder reaction of reactive arenes. The method is based on deprotonation-hydride elimination in which potassium fencholate (277) serves as the base and fenchone (278) as the hydride acceptor, catalytic amounts only of fencholate being required since it is regenerated in the aromatisation step. In this way, the conversion of 1,2-dihydronaphthalene into naphthalene and of 9,10-dihydroanthracene into anthracene proceeds almost quantitatively. 

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