A-Naphthoyl chloride

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. 

Equimolar amounts of benzonitrile and SnGl4 added to 100% excess a-naphthoyl chloride, and heated slowly to 150° 2,4-diphenyl-6-a-naphthyl-3,5-diazapyry-... 

BenZimidaZolones. This class of pigments derives its name from 5-aminobenzimidazolone/Pj5 -2J-< 7 which upon reaction with diketene or 2-hydtoxy-3-naphthoyl chloride leads to compounds which can be coupled with a variety of diazotized amines. 

AEOs have been analysed by HPLC and UV or fluorescence detection after suitable derivatisation. The derivatising agents proposed so far are phenyl isocyanate [80,81], 1-anthroylnitrile [82], 3,5-dinitro-benzoyl chloride [83], naphthyl isocyanate [84] and naphthoyl chloride [84], However, the lack of fluorescence activity and the need for synthesis through a multistep reaction for some derivatising agents limits their application in a real-world analysis. In fact, only a few of them were applied in the determination of AEOs in environmental samples. Zanette et al. [84] developed derivatisation and separation... 

Aranda and Burk [81] have established an SPME-HPLC-FL method and on-line derivatisation to determine AEs (Brij 56) in water. The surfactant was extracted with a PDMS-DVB fibre and pre-column derivatisation with 1-naphthoyl chloride in the presence of 4-(dimethyl-amino)pyridine as catalyst. The method has a limit of detection of 0.1 mg L-1. 

The most direct route towards functionalized aliphatic polyesters is based on the functionalization of polyester chains. This approach is a very appealing because a wide range of functionalized aliphatic polyesters could then be made available from a single precursor. This approach was implemented by Vert and coworkers using a two-step process. Eirst, PCL was metallated by lithium diisopropylamide with formation of a poly(enolate). Second, the poly(enolate) was reacted with an electrophile such as naphthoyl chloride [101], benzylchloroformate [101] acetophenone [101], benzaldehyde [101], carbon dioxide [102] tritiated water [103], ot-bromoacetoxy-co-methoxy-poly(ethylene oxide) [104], or iodine [105] (Fig. 26). The implementation of this strategy is, however, difficult because of a severe competition between chain metallation and chain degradation. Moreover, the content of functionalization is quite low (<30%), even under optimized conditions. 

Naphthoyl chloride is conveniently prepared from /3-naphthoic acid (Org. Syn. 17, 65) and phosphorus pentachlo-ride. A mixture of 57.4 g. (0.33 mole) of acid and 69 g. (0.33 mole) of phosphorus pentachloride in a 250-cc. modified Claisen distilling flask is warmed on a steam bath in a hood. As soon as the vigorous reaction sets in, the flask is removed from the steam bath until the rapid evolution of hydrogen chloride has moderated, then warmed on the steam bath for one-half hour. After removal of the phosphorus oxychloride at diminished pressure, using a water pump, the acid chloride is distilled. The fraction boiling at i6o-i62°/i 1 mm. (bath temperature 170-180°) weighs 57 60 g. (90-95 per cent of the theoretical amount) and melts at 51-52°. The distillation should be carefully conducted, and a quite colorless product should result. 

The procedure herein described is a modification of that of Haworth and Sheldrick,3 the efficiency of which has been confirmed by many authors.4-7 2-Acetyl-6-methoxynaphthalene has also been prepared by the reaction of methylzinc iodide on 6-methoxy-2-naphthoyl chloride.8... 

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%). 

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