A-NAPHTHYL ISOTHIOCYANATE

In a 500-ml. round-bottomed flask fitted with a reflux condenser are placed 16.2 g. (0.08 mole) of dry a-naphthylthiourea (Note 1) and 180 ml. of redistilled chlorobenzene. The flask is heated at the reflux temperature by means of an electric heating mantle. Evolution of ammonia begins almost at once, and all of the solid dissolves after 30-45 minutes. The solution is maintained at reflux for 8 hours (Note 2) and then evaporated on a steam bath at water-pump pressure to remove all of the chlorobenzene. The residue crystallizes on cooling and is extracted with four 30-ml. portions of boUing hexane (Note 3). Removal of solvent from the combined hexane extracts affords pale yellow crystals of melting point unchanged (Note 4). 

The checkers found that a 24-hour heating period increased the yield of [Pg.57]

Naphthylacetamide, 32, 94 a-Naphthylcyanamide, 31, 20 /3-Naphthyl ethyl ether, 32, 97 a-NAPHTHYL isothiocyanate, 36, 56 /3-Naphthyl isothiocyanate, 36, 57 -Naphthyl methyl ether, 32, 100 a-Naphthylphenylacetylene, 34, 43 a-Naphthylthiourea, 36, 56 Neophyl chloride, 32, 90 Nickel, dicyclopentadienyl-, 36, 35 Nicotinamide, 30, 3 33, 52 Nicotinic acid, 6-hydroxy-, 36, 44 Nocotinonitrile, 33, 52... 

Abbreviations EPR, electron paramagnetic resonance FITC, fluorescein-5 -isothiocyanate lAEDANS, iV-iodoacetyl-N -(5-sulfo-l-naphthyl)ethylenediamine NCD, fluorescent yV-cyclohexyl-N -(4-dimethyl-amino-a-naphthyl)carbodiimide RITC, rhodamine-5 -isothiocyanate DPPE, dipalmitoylphosphatidyl-ethanolamine PE, egg phosphatidyl-ethanolamine ANS, 8-anilino-l-naphthalene sulfonate DPH, diphenylhexatriene e-ADP, l,iV -ethanoadenosine-5 -diphosphate TNP-ADP, 2 [3 ]-0-(2,4,6-trinitrophe-nyl)adenosine-5 -diphosphate. 

Naphthyl isothiocyanate 635 1-Naphthylthiourea (16.16 g) is heated in chlorobenzene (180 ml) at 150° under reflux for 8 h, then the chlorobenzene is distilled off, first at 20 mm, then at 1 mm. The residue is extracted with hexane (four 30-ml portions), which leaves a mixture of 1-naphthylthiourea and di-l-naphthylthiourea (0.65 g each) undissolved. The hexane solutions are united and evaporated, leaving 1-naphthyl isothiocyanate (12.75 g, 86%), needles, m.p. 58-58.5°. 

Naphthyl 2-hydroxybenzoate 1-Naphthylhydroxylamine 1-Naphthyl Isothiocyanate A/-2-Naphthyl-2-naphthalenamlne... 

For example, heating a-naphthyl isocyanate with phenyl isothiocyanate affords phenyl isocyanate . Tolylene diisocyanate (TDI) can be used as a higher-boiling isocyanate source. Thus, heating TDI with allylisothiocyanate affords allyl isocyanate. ... 

A soln. of ca. 20% excess 1-naphthyl isothiocyanate in pyridine containing collidine added to an aq. soln. of 2-amino-2-deoxy-D-glucose hydrochloride, and the product isolated after a few min. at room temp. -> 5-hydroxy-1-naphthyl-4-(D-araZ>mo-tetrahydroxybutyl)imidazolidine-2-thione. Y 77%. F. e., also bicyclic products, s. J. E. Scott, Carbohydrate Res. 14, 389 (1970). 

Aryl isothiocyanates can be prepared by the action of thio-phosgene on the arylamine (this reaction fails with naphthyl compounds), by fission of a 5ym-diaryIthiourea with acidic reagents (this reaction involves the loss of half the amine used), and by the decomposition of an ammonium aryldithiocar-bamate (low yields are reported for naphthyl and other compounds).The procedure described here is that of Baxter, Cymerman-Craig, Moyle, and White. ... 

In an analogous manner, reactions of 66 with 69 (prepared by direct chlorination of an acyl isothiocyanate, Ar-C(=0)N=C=S, 68) were found to form a series of aryl-substituted derivatives of 70, (Ar=Ph, p-Me.C6H4, m- and p- C1.C6H4, p-Br.C6H4, p-MeO.C6H4, p-02N.C6H4 and 2-naphthyl). The recovered yields of 70 were typically 70-77%. These... 

Sample preparation Mix 300 pL of a 30 pM solution in dichloromethane with 10 pL 20 mM l-(6-methoxy-2-naphthyl)ethyl isothiocyanate in anhydrous dichloromethane and 50 pL 0.1% triethylamine in dichloromethane, vortex thoroughly, heat at 50° for 1.5 h, inject an aliquot. (Synthesize l-(6-metho -2-naphthyl)ethyl isothiocyanate as follows (protect from light). Dissolve 500 mg (S)-(+)-naproxen in 50 mL dry toluene, slowly add 5 mL freshly distilled thionyl chloride, reflux for 1 h, evaporate to dryness under vacuum, dry the acyl chloride (mp 87.5°) under vacuum over KOH for 2 days. Dissolve 0.5 mmoles acyl chloride in 5 mL acetone, stir at 0°, add 0.6 mmoles sodium azide dissolved in ice water, stir at 0° for 30 min, add 10 mL ice-cold water, filter, dry solid in a desiccator under vacuum. Dissolve the solid in 1 mL toluene or dichloromethane (dried over 3 A molecular sieve), reflux for 10 min, evaporate, store resulting isocyanate (mp 51°) under vacuum over a desiccant. Dissolve 0.5 mmole isocyanate in 5 mL acetone, add 20 mL 8.5% phosphoric acid, heat to 80° for 1.5 h, adjust to pH 13, extract with diethyl ether dichloromethane 4 1. Wash the organic layer twice with water, dry over anhydrous sodium sulfate, evaporate to dryness, dissolve in 1 mL toluene, evaporate to give the amine from... 

Reagents (I) l-(l-naphthylethyl) isocyanate (II) l-(4-dimethylamino-l-naphthyl)ethyI-amine (III) l-(4Tdimethylamino-l-naphthyI)acetic acid (IV) a-methoxy-a-methyl-l-naph-thalenecarboxylic acid (V) a-methoxy-a-trifluoromethylphenacetyl chloride (VI) carboxylic acid analog of (V) (VII) a-methoxy-4-nitrobenzylamine (VIII) acid chloride analog of (VII) (IX) camphor-10-sulfonyl chloride and (X) neomenthyl isothiocyanate. 

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