L’-acetonaphthone

Immobilized catalysts on solid supports inherently have benefits because of their easy separation from the products and the possibility of recycling. They are also expected to be useful for combinatorial chemistry and high-throughput experimentation. The polystyrene-bound BINAP/DPEN-Ru complex (beads) in the presence of (CH3)3COK catalyzes the hydrogenation of l -acetonaphthone with an SCR of 12 300 in a 2-propanol-DMF mixture (1 1, v/v) to afford the chiral alcohol in 97% ee (Fig. 32.35) [113]. This supported complex is separable... 

The benzyl adducts are also obtained in the photochemical reactions with other carbonyl compounds [1-NA, l -acetonaphthone (1-AN), 2 -aceto-naphthone (2-AN)] in the presence of Mg2+ in MeCN [188], When benzyltrimethylsilane is replaced by allyltrimethylsilane (CH2=CHCH2 x SiMe3), the corresponding allyl adducts are also obtained [188],... 

Figure 1.4. Vapor/liquid equilibrium for l -acetonaphthone and C02 at 40°C and 50 °C. The symbols indicate experimental measurements and the lines indicate the results of modeling with the Peng-Robinson equation of state.

This work has been extended [96] to l-butenoxy-2-acetonaphthones and 2-butenoxy-l-acetonaphthones. Both types of compounds undergo high-yield internal ortho cycloadditions from their triplet states (Scheme 19). 

Dixon, A. M., Mai, M. A., and Larive, C. K. (1999). NMR investigation of the interactions between 4-fluoro-l-acetonaphthone and the Suwannee river fulvic acid. Environ. Sci. Technol. 33, 958-964. 

Hydroxy-l -acetonaphthone (1 - Aceto-2-naphthed, 2-hydroxyA-a/e naphthcile7ie, meth 2-hydroxy-l-TMphthyl ketone)... 

Figure 6.10. Rate constants for quenching of sensitizers by cis- and trans-stilbenes (open and filled circles, respectively). Sensitizers are as follows (1) tri-phenylene, (2) thioxanthone, (3) phenanthrene, (4) 2-acetonaphthone, (3) 1-naphthyl phenyl ketone, (6) crysene, (7) fluorenone, (8) 1,2,5,6-dibenzanthracene, (9) benzil, (10) 1,2,3,4-dibenzanthracene, (11) pyrene, (12) 1,2-benzanthracene, (13) benzanthrone, (14) 3-acetyl pyrene, (15) acridine, (16) 9,10-dimethyl-l,2-benzanthracene, (17) anthracene, (18) 3,4-benzpyrene.<57> Reprinted by permission of the American Chemical Society.

Lead tetraacetate oxidative cyclization of the A-(l-naphthylvinyl)urethane 30, derived from I -acetonaphthone 28, yields 4-naphthyl-2(3//)-oxazolone 32 as the... 

Since acetonaphthones have 7r,7r configurations in their lowest triplet states, it seems probable that l-benzoyl-2-methylnaphthalene, 30, would also. As suspected, 30 does not undergo photoenolization.362 However, 6-benzoylbenzanthrone, 31, which would also be expected to possess a low-lying triplet, does form a photoenol, as determined by formation of yellow coloration at low temperatures and deuterium exchange at the benzylic position. It is entirely possible that the greater reactivity of the benzyhydryl C—H bond in 31 allows reaction even in a relatively unreactive state, or in an n,tt singlet. 

Figure 7 Tautomers of Schiff bases derived from /J-diketone (a-c), from l-hydroxy-2-acetonaphthone (d, e) and from...

Dimethyl-l-vinylbicyclo[2,l,l]hexan (Formel 68) stellt das Resultat der Bestrahlung einer 5-proz. Losung von Myrcen (Formel 67) in Hexan. oder Benzol in Gegenwart von Benzophenon, (3-Acetonaphthon oder Fluorenon dar (182). 3,3-Dimethyl-l-vinyl-bicyclo[2,2,0]hexan (Formel 69) bildet sich nicht (vgl. Photoisomerisierung des Citrals, S. 497). 

In a related approach, Fan et al. synthesized a series of dendritic BINAP-Ru/chiral diamine ((R,R)-l,2-diphenylethylenediamine DPEN) catalysts for the asymmetric hydrogenation of various simple aryl ketones (Fig. 15) [42]. The resulting systems displayed high catalytic activity and enantioselectivity and allowed facile catalyst recycling. In the case of 1-acetonaphthone and... 

SYNS l-ACETONAPHTHALENE a-ACETO-NAPHTHONE 1-ACETONAPHTHONE 1-ACETYLNAPHTHALENE ETHANONE, 1-(1-NAPHTHALENYL)-(9CI) METHYL a-NAPHTHYL KETONE METHYL 1-NAPHTHYL KETONE a-METHYL NAPHTHYL KETONE 1-(1-NAPHTH-ALENWL)ETHANONE a-NAPHTHYL METHYL KETONE 1-NAPHTHYL METHYL KETONE... 

SYNS P-ACETONAPHTHALENE ACETONAPHTHONE p-ACETONAPHTHONE 2-ACETONAPHTHONE p-ACETYLNAPHTHALENE 2-ACETYLNAPHTHALENE FEMA No. 2723 METHYL-p-NAPHTHYL KETONE (FCC) METHYL-2-NAPHTHYL KETONE p-METHYL NAPHTHYL KETONE l-(2-NAPHTHALENYL)ETHANONE p-... 

SYNS ACETYLETHYL TETRAMETHYLTETRALIN 6-ACETYL-l,l,4,4-TETRAMETHYL-7-ETHYL-l,2,3,4,-TETRALIN 7-ACETYL-l,1,4,4-TETRAMETHYL-l,2,3,4-TETRAHYDRONAPHTHALENE AETT ETHANONE-l-(3-ETHYL-5,6,7,8-TETRAHYDRO-5,5,8,8-TETRAMETHYL-2-NAPHTHALENYL)(9CI) 3 -ETHYL-5, 6, 7, 8 -TETRAHYDRO-5, 5, 8 -TETRAMETH-YI 2 -ACETONAPHTHONE l-(3-ETHYL-5,6,7,8-TETRAHYDRO-5,5,8,8-TETRAMETHYL-2-NAPHTH-ALENYL)-ETHANONE MUSK 36A POLYCYCLIC MUSK VERSALIDE... 

DPEN/KOH [95] catalyst system is decreased by 10-15% in the hydrogenation of acetophenone or 2 -acetonaphthone. Pivalophenone, a sterically demanding aromatic ketone, is hydrogenated by RuCp Cl(> -cod)/(S)-(l-ethyl-2-pyrrolidinyl)-methylamine/KOH catalyst to afford the R alcohol in 81% e.e. [96], [NH2(C2H5)2j-[ RuCl[(S)-tolbinap] 2(,M-Cl)3] hydrogenates 2 -halo-substituted acetophenones under 85 atm H2 in up to >99% optical yield [97], A stable six-membered intermediate where the Ru metal is chelated by carbonyl oxygen and halogen at the 2 position is supposed [5cj. 

Figure 4.2 Plots of ECD data as In KTy2 versus 1,000/7. Nitrobenzene, pentafluoroni-trobenzene, and 1-acetonaphthone exhibit both an a and a (3 region. They are designated Eql(l/2) for equilibrium compounds with one state and two regions. The electron affinities are determined from the slope in the a region. The intercepts for all but pentafluoroni-trobenzene are the same, indicating that Qan is 1.0. The Qan for the latter is less than 1.0, the parameters are given in Table 4.1. The range of electron affinities is 0.16 eV to 1.50 eV. Data [1, 5, 8],...

In Figure 4.2 a and (3 regions are shown for nitrobenzene, pentafluoronitroben-zene, and acetonaphthone. These are designated Eql(l/2). They are compared to the Eql(l/1) molecules, naphthalene and acetophenone. Independent investigators using a constant current mode of electron collection obtained the data for naphthalene [5]. The data for the nitrocompounds were obtained in our laboratories... 

Among the many examples of asymmetric hydrogenation catalysts that have been developed, chiral complexes prepared from 1,2-dianiines and RuCb/diphosphines provide one example of the most powerful catalysts for this reaction. Polymer-supported fR -BINAP was treated with RuCh and fR,R -l,2-diphenylethylenedi-amrne to give the polymeric chiral complex 180 (Scheme 3.56) this serves as an excellent precatalyst for the asymmetric hydrogenation of aromatic ketones to give the chiral secondary alcohols in quantitative yields with 84—97% ee-values [115]. For example, the asymmetric hydrogenation of I -acetonaphthone with (R,RR)-180 occurred in quantitative conversion within 26 h with 98% ee. The enantioselectivity, turnover number (TON) and turnover frequency (TOF) in this reaction... 

The following sodium sulfonates, RC0CH2S03Na, have been prepared similarly 2, 4, 6 -trimethylacetophenone-2-, propiophenone-2-, isobutyrophenone-2-sulfonate acetonaphthone-2-sulfonate 3,3-dimethyl-2-oxo-l-butanesulfonate and 2-oxo-2-(2/-thienyl)ethanesulfonate. Aldehydes such as phenylacetaldehyde, isobutyraldehyde, and heptanal can also be converted into their oc-sulfonic acids, R—CO—SO3H, in this way. 

A -Methylanilino)acetophenones undergo Type II cyclization on irradiation in diethyl ether to give l,3-diarylazetidin-3-ols. Analogous cyclizations were observed in 2-(A-methylanilino)-2 -acetonaphthone and 2-(A-methylanilino)-l-tetralone. Likewise, the heteroaryl A-methylanilinomethyl ketones (142) are converted on irradiation in diethyl ether, into isomeric 3-heteroaryl-1-phenylazetidin-3-ols (143)," and A -benzyl-a-aminoacetophenones gave cis-2,3-diarylazetidin-3-ols on n n excitation. ... 

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