P-Naphthoyl chloride

Rosenmund Reaction. A catalyst poison prepared from quinoline and sulfur is useful for controlling the reaction of p-naphthoyl chloride (19) with hydrogen gas and palladium on barium sulfate catalyst. If control of the reaction is not maintained by catalyst poisoning to reduce activity, further reduction beyond the desired /3-naphthaldehyde product (20) is often observed (eq 13). ... 

A single acyl group has been introduced into P-cyclodextrin, either at a 2- or a 3-position, by exposure to benzoyl- or a- or P-naphthoyl chloride in alkaline aqueous acetonitrile. A Lipid A disaccharide esterified with (5)-3-hydroxytetra-decanoic acid and a Lipid A monosaccharide carrying a fluorinated JV-acyl group are referred to in Chapters 3 and 9, respectively. 

The combination of [IrCl(cod)Cl]2 complex with P(t-Bu)3 efficiently catalyzes aromatic homologation using internal alkyne [70]. For example, the reaction of benzoyl chloride 153 with 4-octyne 154 afforded 1,2,3,4-tetrapropylnaphthalene 155 (Equation 10.41). The reaction with 2-thenoyl and 2-naphthoyl chlorides also affords benzothiophene and anthracene, respectively, in high yields. The reaction would proceed as follows (Scheme 10.9) (i) oxidative addition of aroyl chloride... 

Fit a 250-ml three-necked flask with a reflux condenser, a high-speed sealed stirrer (1) and a gas inlet tube extending to a point just above the bottom of the stirrer. Place 28.5 g (0.15 mol) of 2-naphthoyl chloride (Expt 6.161), 100 ml of sodium-dried xylene, 3 g of palladium-barium sulphate catalyst and 0.3 ml of the stock poison solution (Section 4.2.54, p. 452) in the flask. Connect the top of the condenser by a rubber tube to a 6-mm glass tube extending to the bottom of a 250-ml conical flask containing 200 ml of distilled water and a few drops of phenolphthalein indicator arrange a burette charged with c. 1m sodium hydroxide solution (prepared from the pure solid) for delivery into the flask. The apparatus must be sited in the fume cupboard. 

Naphthoyl chloride. This compound may be prepared from 57.4 g (0.33 mol) of 2-naphthoic acid and 69 g (0.33 mol) of phosphorus pentachloride following the procedure described above for p-nitrobenzoyl chloride. After removing the phosphorus oxychloride by distillation, the product is collected as a fraction of b.p. 160-162 °C/11 mmHg. This solidifies on cooling to a colourless solid, m.p. 51-52°C The yield is 60 g (95%). 

The submitters prepared pure 1-naphthoyl chloride, b.p. 95-96° (0.2 mm.), from pure 1-naphthoic acid in 95% yield by treatment with thionyl chloride or phosphorus pentachloride. The pure 1-naphthoic acid used was prepared by carbonation of... 

The checkers prepared 1-naphthoyl chloride by treatment of 1-naphthoic acid, m.p. 157-161°, obtained from Aldrich Chemical Co., with phosphorus pentachloride. 

The checkers obtained 26.1-26.5 g. (83-84.5%) of 1-(diazoacetyljnaphthalene, m.p. 47-49.5°, when 1-naphthoyl chloride prepared from commercial 1-naphthoic acid was used (ef. Notes 1 and 2). Recrystallization from hexane gave 24.6 g. (78%) of l-(diazoacetyl)naphthalene, m.p. 49.5-52°, that was used in Part B. 

A mixture of 30 g. (0.16 mole) of a-naphthoyl chloride (p. 209) [Org. Syntheses Coll. Vol. 2, 425 (1943)], 30 g. (0.19 mole) of 8-methylnaphthalene, and 100 g. of carbon disulfide is cooled in an ice bath and 30 g. (0.22 mole) of powdered aluminum chloride is added slowly in small portions. The reaction mixture is stirred for 3 hours while protected from atmospheric moisture with a calcium chloride tube. The carbon disulfide is decanted from the red-brown residue, and the residue is decomposed by the gradual addition of ice and hydrochloric acid. The resulting mixture plus the carbon disulfide layer is steam-distilled to remove unreacted -methylnaphthalene. The aqueous layer is decanted from the residue in the steam distillation vessel, and the residue is treated with dilute sodium hydroxide solution. The solid remaining is washed with water and dried. The yield of crude 2-methyl-l,T-dinaphthyl ketone is 90%. Pure ketone, m.p. 140-141°, may be obtained by several recrystallizations from ethanol including activated carbon treatment. 

Dibenzanthracene, m.p. 262°, is prepared in similar manner from 2-methyl-l,2 -dinaphthyl ketone. The ketone, m.p. 170-171°, is prepared from /ff-naphthoyl chloride and yj-methylnaphthalene in similar manner to the procedure given above. 

Scheme20 Synthesis of L-cystine-based hydrogelators 111, 112 and 113 (a) liq. NH3, -33°C (b) HCl/MeOH (c) 111 water, NaOAc, benzoyl chloride 112 EtsN, DMSO/CHCh.p-toluoyl chloride, 113 EtsN, DMSO/CHCI3, 2-naphthoyl chloride...

Zinc foam (100 g) was shaken for 5 min with mercury(n) chloride (10 g), concentrated hydrochloric acid (5 ml), and water (150 ml), then the aqueous layer was poured off, and the amalgamated zinc was treated with water (75 ml), concentrated hydrochloric acid (175 ml), toluene (100 ml), and the carbonyl compound to be reduced (50 g). When necessary, glacial acetic acid (3-5 ml) may be added to increase the solubility in the aqueous layer. The mixture is heated to brisk ebullition under reflux. At each of three 6-hourly intervals hydrochloric acid (50 ml) is added, the total time of boiling being thus about 24 h. As examples, 3-oxo-3-phenyl-, -3-m-tolyl-, -3-p-tolyl-, -3-(l-naphthoyl)-, and -3-(2-naphthoyl)-propionic acid, benzoylnaphthalene, 2-acetylnaphthalene among other materials were reduced more satisfactorily than in absence of toluene. A comparison of the toluene method with the old method is provided, for instance, by Martin who obtained a 72-78 % yield in a preparation by himself by the old method, compared with 90% by the new method. 

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