Sistemas binários de monoderivados isómeros da naftalena

Abstract

S U M M A R Y

Binary Systems of Isomeric Naphtalene Monoderivalives

The reciprocal behavior of isomeric naphtalene monoderivatives has not yet been sufficiently studied. J. IMMERMANS (1936) established the opinion that due to the enlargement of the principal

(67) Tese de Doutoramento (Sfio Paulo, 3942), pg. 45-48. (68) Tese de Doutoramento (São Paulo, 1940), pg. 45. (69) G. V. JADHAV e M. ASLAM. J. Univ. B»mbay, Scet. A. 15. N.o 21. 16 (1947) ; Chem. Abatr. 12, 1250 (1948). 27 part of the molecules in the naphtalene group in comparison with that of the benzene group the differences of the position of the substituents were "relativily negligible". Thus, the formation of mixed cryslals of the isomers may be favoured in this series. The study of the solid-liquid phase diagrains of 22 binary systems of 1- and 2-naphlalene isomers, execuled by the thaw-melting method (C.A. 20. 093, 1938, 312Ü; 21, 14, 35, 6503), showed however in all cases the formation of simple eutectics of the components. On the basis of this result the thesis may be established that 1- and 2-naphtalene isomers, are not generally able to form mixed cryslals together. The invesligated binary systems are the following: 1- and 2-Naphtol (I), eutectic at 72.3° and 36 wl.% l (cf. C.A. 38, 2556). 1- and 2- Naphtylamine (II), eutectic at 36.5° and 17.5% II (cf. C.A, 38, 2556). 1- and 2-Nitronaphtalene (III), eutectic at 30.4"and 43% III (not at 18%, 44%; cf. C.A. 37, 5961). 1- and 2-Naphtonitrite (IV), eutectic at ab. 15° and 35% IV. 1- and 2-Naphtoic acid (V), eutectic at 127.7° and 42% V. 1- and 2-Naphtoxiacetic acid (VI), eutectic at 142.2° and 68% VI. Benzyloxy-l-naphtalene and -2-naphlalene (VIII), eutectic at 61° and 26% VII. Benzythio-1-naphlalene and -2-naphlalene (VIII), eutectic at 60.8° and 45% VIII. 1- and 2-Naphlylacetale (IX), eutectic at 28° and 33% IX. 1- and 2-Naphtyl benzoate (X), eutectic at 45.5° and 17.5% X. 1- and 2-Naphtyl thiobenzoate (XI), eutectic at 84° and 58% XI. N-Phenyl-1- and 2-naphtylamine (XII), euteclic at 45.7° and 23% XII. 1- and 2-Formonaphtalide (XIII), eutectic at 98.5° and 55% XIII. 1- and 2-Acetonaphtalide (XIV), eutectic at 99.8° and 65.5% XIV. 1- and 2-Benzonaphtalide (XV), eutectic at 123° and 53% XV. 1- and 2-Naphtoanilide (XVI), eutectic at 133° and 45% XVI. 1,1'- and 2,2'-Dinaphtyl oxide (XVII), euteclic at 76.3° and 51% XVII. 1,1- and 2,2'-Dinaphtyl sulfide (XVIII), eutectic at 95° and 22% XVIII. 2-Nitrobenzeneselenenyl 1- and 2-naphtalene-thiolate (XIX), eutectic at 70.5° and 65% XX. 1,1'- and 2,2'-Dinaphtyl disulfide (XX), eutectic at 76° and 16% XX. 1,1'- and 2,2,-Dinaphtyl diselenide (XXI), eutectic at 70° and 31% XXI. Í-Naphyl 1-naphtoate and 2-naphtyl 2-naphtoate (XXII), eutectic at 108.8° and 31% XXII. New Compounds are: Benzylthio-2-naphtalene, C17H14S, m.p. 90.7, colorless cryslals; prepared by heating equivalent parts of 2-thionaphtol, sodium hydroxide and benzyl chloride in ethanol. Recrystalised from hot alcohol. 1-Naphtyl 1-naphtoate, C21H14O2, m.p. 124.5°, colorless cryslals; prepared by heating in the water bath a mixture of 1-naphtoy1 chloride and 1-naphtol. Recrystalised from ethanol and isopropanol. 28 2,2'-Dinaphtyl diselenide, prepared by saponificalion of 2-naphtyl selenocyanate in methanoi by introduction of ammonia at 20º, was found to melt at 139.2° and not at 126-7° (cf. LOEVENICH et al., Ber. 62, 2862 (1929). 1,1'-Dinaphtyl disulfide, m.p. 88.5°, had a metastable form melting at about 72° which after melting or after remaining for a long time in the mother liquor transforms into the stable form.