Naphthaldehydic acid

Chemical/Physical. Ozonation in water at 60 °C produced 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, 1-naphthoic acid, and 1,8-naphthaldehydic acid (Calvert and Pitts, 1966). 

Naphthaldehydic acid, see Acenaphthylene Naphthalene, see Acenaphthene, Bis(2-ethylhexyl)... 

See Naphthaldehydic Acid. Formylphanylglydne Phen ormyhmino-acetic odd)... 

Aq. 45%-KOH added in one portion to a vigorously stirred suspension of ace-naphthenenequinone in dimethyl sulfoxide as cosolvent, stirring continued 8 hrs. at room temp., transferred to a separatory funnel, the bottom layer of KOH-soln. removed, the top layer dil. with water, Celite added, filtered, neutralized with coned. HCl to pH 7, and stirred 1 hr. 1,8-naphthaldehydic acid. Y 86%. H. Bader and Y. H. Chiang, Synthesis 1976, 249. 

In a 500 ml. flask, fitted with a reflux condenser, place 53 g. of 1-chloro-methylnaphthalene (Section IV.23), 84 g, of hexamethylenetetramine and 250 ml. of 1 1 acetic acid [CAUTION 1-Chloromethylnaphtha-lene and, to a lesser degree, a-naphthaldehyde have lachrymatory and vesicant properties adequate precautions should therefore be taken to avoid contact with these substances.] Heat the mixture under reflux for 2 hours it becomes homogeneous after about 15 minutes and then an oil commences to separate. Add 100 ml. of concentrated hydrochloric acid and reflux for a further 15 minutes this will hydrolyse any SchifiF s bases which may be formed from amine and aldehyde present and will also convert any amines into the ether-insoluble hydrochlorides. Cool, and extract the mixture with 150 ml. of ether. Wash the ether layer with three 50 ml. portions of water, then cautiously with 50 ml. of 10 per cent, sodium carbonate solution, followed by 50 ml. of water. Dry the ethereal solution with anhydrous magnesium sulphate, remove the ether by distillation on a steam bath, and distil the residue under reduced pressure. Collect the a-naphthaldehyde at 160-162718 mm. the yield is 38 g. 

P-Hydroxy-a-naphthaldehyde, Equip a 1 litre three-necked flask with a separatory funnel, a mercury-sealed mechanical stirrer, and a long (double surface) reflux condenser. Place 50 g. of p-naphthol and 150 ml. of rectified spirit in the flask, start the stirrer, and rapidly add a solution of 100 g. of sodium hydroxide in 210 ml. of water. Heat the resulting solution to 70-80° on a water bath, and place 62 g. (42 ml.) of pure chloroform in the separatory funnel. Introduce the chloroform dropwise until reaction commences (indicated by the formation of a deep blue colour), remove the water bath, and continue the addition of the chloroform at such a rate that the mixture refluxes gently (about 1 5 hours). The sodium salt of the phenolic aldehyde separates near the end of the addition. Continue the stirring for a further 1 hour. Distil off the excess of chloroform and alcohol on a water bath use the apparatus shown in Fig. II, 41, 1, but retain the stirrer in the central aperture. Treat the residue, with stirring, dropwise with concentrated hydrochloric acid until... 

Chapter IV. a-Chloromethylnaphthalene (IV,23) benzylamine (Gabriel synthesis) (IV,39) i r.N -dialkylanilines (from amines and trialkyl orthophosphates) (IV,42) a-naphthaldehyde (Sommelet reaction) (IV,120) a-phenyl-cinnamic acid (Perkin reaction using triethylamine) (IV,124) p-nitrostyrene (IV,129) p-bromonaphthalene and p naphthoic acid (from 2 naphthylamine-1 -sulphonic acid) (IV,62 and IV,164) diphenic acid (from phenanthrene) (IV,165). 

Naphtoe-aldehyd, n. naphthaldehyde, naphthoic aldehyde, -skure, /. naphthoic acid. 

In Refomiatsky reactions of + )-trans-(2-phenyleyclohex-l-yl)bromoacetaie with benz-aldehydc, acetophenone. 1-naphthaldehyde and butanal, the corresponding /1-hydroxycarboxylic acids arc obtained, after saponification, in 11-89% ee ... 

Dissolve 71 g. of P-methylnaphthalene in 460 g. (283 ml.) of A.B. carbon tetrachloride and place the solution in a 1 -litre three-necked flask equipped with a mechanical stirrer and reflux condenser. Introduce 89 g. of JV-bromosuccinimide through the third neck, close the latter with a stopper, and reflux the mixture with stirring for 16 hours. Filter ofiT the succinimide and remove the solvent under reduced pressure on a water bath. Dissolve the residual brown oil (largely 2-bromomethyl naphthalene) in 300 ml. of A.R. chloroform, and add it to a rapidly stirred solution of 84 g. of hexamine in 150 ml. of A.R. chloroform contained in a 2-litre three-necked flask, fitted with a reflux condenser, mechanical stirrer and dropping funnel maintain the rate of addition so that the mixture refluxes vigorously. A white solid separates almost immediately. Heat the mixture to reflux for 30 minutes, cool and filter. Wash the crystalline hexaminium bromide with two 100 ml. portions of light petroleum, b.p. 40-60°, and dry the yield of solid, m.p. 175-176°, is 147 g. Reflux the hexaminium salt for 2 hours with 760 ml. of 60 per cent, acetic acid, add 160 ml. of concentrated hydrochloric acid, continue the refluxing for 5 minutes more, and cool. Extract the aldehyde from the solution with ether, evaporate the ether, and recrystallise the residue from hot -hexane. The yield of p-naphthaldehyde, m.p. 69-60°, is 60 g. 

Most of the methods for preparation of /3-naphthaldehyde have been given previously.2 A recent procedure describes the preparation of /3-naphthaldehyde from 2-bromomethylnaphthalene and hexamethylenetetramine in boiling acetic acid.3 The method of reduction of nitriles by stannous chloride was discovered by Stephen.4... 

Chemical/Physical. An aqueous solution containing chlorine dioxide in the dark for 3.5 d at room temperature oxidized 2-methylnaphthalene into the following l-chloro-2-methylnaphtha-lene, 3-chloro-2-methylnaphthalene, l,3-dichloro-2-methylnaphthalene, 3-hydroxymethylnaphtha-lene, 2-naphthaldehyde, 2-naphthoic acid, and 2-methyl-l,4-naphthoquinone (Taymaz et al., 1979). 

Remarkable positive shifts of the °red values of the singlet excited states of the metal ion-carbonyl complexes as compared to those of the triplet excited states of uncomplexed carbonyl compounds (Table 2) result in a significant increase in the redox reactivity of the Lewis acid complexes versus uncomplexed carbonyl compounds in the photoinduced electron-transfer reactions. For example, photoaddition of benzyltrimethylsilane with naphthaldehydes and acetonaphthones proceeds efficiently in the presence of Mg(C104)2 in MeCN, although... 

Naphthaldehyde and furaldehyde (L) react with ZrC to give the ZrCl4,2L adducts, whereas phthalaldehyde forms ZrCl4,L. These coloured compounds are non-electrolytes and appear to involve an octahedral ZrCl402 chromo-phore. Kojic acid (30) and maltol (31) form 1 1 and 1 2 complexes with... 

The checkers found that crude chloromethylnaphthalene obtained from the preparation in Organic Syntheses could be used with good results. Naphthalene, paraformaldehyde, hydrochloric acid, and phosphoric acid are heated under reflux according to the procedure described. After the crude product is washed with water, 10% potassium carbonate, and water, it is dissolved directly in 500 ml. of glacial acetic acid, diluted with 500 ml. of water, and treated with hexamethylenetetramine by the procedure described above. The over-all yield of almost colorless 1-naphthaldehyde is 162 g., b.p. 162-164°/18 mm. Wq 1.6503 (52% yield based on naphthalene). 

Naphthaldehyde has been made from a-naphthonitrile by reduction with stannous chloride, and from naphthalene by the action of aluminum chloride, hydrogen cyanide, and hydrochloric acid. The best preparation is the Sommelet reaction from a-chloro- or a-bromomethylnaphthalene and hexamethylenetetramine in aqueous alcohol is.is. .is.w or glacial acetic acid. This method has been improved in the present procedure by the use of 50% acetic acid as solvent. 

According to the submitters, this reaction is quite satisfactory on a small scale and can be used with other acid chlorides. In a 0.05-mole run carried out in the same manner, an 83 per cent yield of 0-naphthaldehyde was obtained. i-Acetoxy-3-naphthaldehyde, m p. 112-1140, was obtained in 70 per cent yield from c.85 g. of the corresponding acid chloride. Methyl... 

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