Scientific Journal Articles

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This list was compiled by the kind efforts of Guy C. Berry, University Professor Emeritus of Chemistry and Polymer Science, Department of Chemistry, Carnegie Mellon University, Pittsburgh.

 

Tucker, S. A. and A. Lowy (1915). "Preparation, properties and composition of silundum." J. Ind. .Eng. Chem. 7: 565-71.

            Two varieties of silundum are formed, a slate-green, which has the formula Si4C4O and a gray, corresponding to the formula SiC. The temp. of formation lies above 1300 Deg, the first variety (slate-green) being formed up to about 1800 Deg while above this point SiC is formed. Continued heating above 2200 Deg results in the decompn. of silundum with the formation of graphite. The extent of penetration of silundum in the charge depends upon the duration of heating, the process being more complete when the object is embedded in the charge. Silundum is a good conductor of electricity with a negative temp. coeff. for its resistance, possesses a hardness of about 9 (Mohr scale), a sp. gr. of 2.9-3, is not attacked by H, O or N (even at 1100 Deg) or acids. It is attacked by some fused salts such as Na2CO3, NaOH, KOH. T. and L. have developed a new method for detg. C in such materials based on combustion (in electric furnace) in presence of PbO in a current of O. The method is accurate to 0.3% of theoretical. [on SciFinder (R)]

 

Lowy, A. (1916). "An automatic pipet." J. Ind. Eng. Chem. (Washington, D. C.) 8: 734-5.

            L. describes with cuts a pipet provided with a special stopcock that enables the operator automatically to control an exactly measured vol. of liquid drawn into the pipet, obviates adjusting, discharges an exactly measured vol., and is easy to manipulate. [on SciFinder (R)]

 

Lowy, A. (1919). "Modified graphic formulas for organic cyclic compounds." J. Am. Chem. Soc. 41: 1029-30.

            In order that single lines still may be used and at the same time convey the visual meaning and idea of both single and double bonds L. suggests that instead of representing cyclic compds. by simple pentagons, hexagons, etc., as is now frequently done, double bonds be indicated by heavy lines, single bonds by light lines. [on SciFinder (R)]

 

Lowy, A. (1919). "A chart of organic chemistry, aromatic series." Science (Washington, DC, U. S.) 50: 93-5.

            cf. C. A. 13, 1074 The chart reproduced is used in connection with the elementary org. chem. course at the Univ. of Pittsburgh. [on SciFinder (R)]

 

Lowy, A. (1919). "A chart of organic chemistry, aliphatic series." Science (Washington, DC, U. S.) 49: 314.

            The chart is for teaching purposes. [on SciFinder (R)]

 

Lowy, A. and B. B. Westcott (1920). "Some derivatives of 2,4-dinitrobenzaldehyde." J. Am. Chem. Soc. 42: 849-56.

            The 2,4-(O2N)2C6H3CHO (A) was prepd. essentially by the method of Sachs and Kempf (Ber. 35, 2704(1902)). From it the 2,4-dinitrobenzal derivatives of the following amines were made: m-Toluidine (5.4 g. from 2.8 g. MeC6H4NH2 and 5 g. A in 25 cc. AcOH heated 2 hrs. on the H2O bath,) fine, yellow needles from C6H6, m. 130 Deg. 1,3,4-Xylidine (7 g. from 3 g. base and 5 g. A), long, deep yellow, silky needles from Me2CO, m. 210.5 Deg. 3-Nitro-4-toluidine (3.2 g. from 4 g. base and 5 g. A), radiating clusters of fine, light brownish yellow needles from AcOH, m. 195 Deg. Pseudocumidine (4.4 g. from 2.3 g. base and 3.4 g. A), fine, bright yellow, silky needles from C6H6, m. 186.5 Deg. Sodium sulfanilate, (O2N)2C6H3CH:NC6H4SO3Na.H2O (8.2 g. from 5 g. A in 50 cc. alc. and 5 g. H2NC6H4SO3Na in 150 cc. alc.), very fine pale yellow crystals from 1:1 alc., decomp. 249 Deg. Sodium metanilate (5.4 g. from 5 g. A and 5 g. of the salt), very fine, deep yellow needles with 3 H2O from 1:1 alc., decomp. 185 Deg. Sodium naphthionate (7.9 g. from 5 g. A and 6.3 g. of the salt), very fine, bright orange needles with 0.5 H2O from 1:1 alc., decomp. 248 Deg. Condensed with PhNMe2 as in the prepn. of malachite green, A yields a green powder dyeing silk a bluish green. [on SciFinder (R)]

 

Lowy, A. (1920). "Fire caused by yellow phosphorus." J. Ind. Eng. Chem. (Washington, D. C.) 12: 507.

 

Lowy, A (1920). “A Medicated Tooth Paste with its Composition.” J. Dental Research 2: 568

           

Lowy, A. and W. Baldwin (1921). "Derivatives of 2,4,6-trinitrobenzaldehyde. II." J. Am. Chem. Soc. 43: 1961-3.

            cf. C. A. 15, 1526. The following 2,4,6.trinitrobenzal compounds were prepd. by condensing the aldehyde with 1 mol. of the amine in AcOH or hot alc.; they are sol. in Me2CO, CHCl3 and C6H6, insol. in H2O and hydrolyzed to the components by 1:1 HCl; o-phenetidine, yellow, crystd. from alc., m. 178.5 Deg; o-phenetidine, light orange, from alc., m. 177 Deg; o-anisidine, yellow, from CHCl3, m. 171.5 Deg; p-anisidine, yellow, from CHCl3, m. 182 Deg; o-chloroaniline, yellow, from Me2CO, m. 187 Deg; p-chloroaniline, yellow, from Me2CO, m. 180 Deg; 2,4-dichloroaniline, yellow, from Me2CO, m. 198 Deg. When the aldehyde was condensed with o- and p-ClC6H4NH2 and 2,4-Cl2C6H3NH2 in hot AcOH the resulting orange products m. about 100 Deg higher than those prepd. in cold AcOH and were insol. in many solvents except AcOH; preliminary work seems to indicate that they are dimol. condensation products. [on SciFinder (R)]

 

Lowy, A. and C. G. King (1921). "Derivatives of p-nitrobenzaldehyde." J. Am. Chem. Soc. 43: 625-7.

            The following p-nitrobenzal compounds were obtained by heating 1 mol. each of p-O2NC6H4CHO and the amine on the H2O bath. Below are given the m. p., the solvent in which the condensation was effected, the length of heating in hrs. and the % yield, resp. o-Phenelidine, yellow plates, 81 Deg, alc., 3 hrs., 90%; p-bromoaniline, yellow needles, 160.5 Deg, alc., 2 hrs., 92%: o-toluidine, yellow plates, 89 Deg, alc., 2 hrs., 94%; p-toluidine, yellow needles, 122.5 Deg, alc., 1 hr., 95%; I,3,4-xylidine, yellow needles, 88.5 Deg, AcOH, 1 hr., 85%; 3-nitro-4-toluidine, yellow needles, 161.5 Deg, AcOH, 20 min., 70%; p-nitroaniline, yellow needles, 198.5 Deg, AcOH, 0.5 hr., 95%; m-nitroaniline, yellow needles, 152 Deg, alc., 2 hrs., 90%. These compds. seem to be stable towards sunlight. [on SciFinder (R)]

 

Lowy, A. and T. B. Downey (1921). "Derivatives of 2,4-dinitrobenzaldehyde. II." J. Am. Chem. Soc. 43: 346-8.

            cf. C. A. 14, 1828. The following 24-dinitrobenzal compounds were prepd. from 2,4-(O2N)2C6H3CHO and 1 mol. of the amine in alc. (except the 2nd and 3rd, which were prep. in AcOH); all sep. in yellow or orange needles (the % yields are given in parentheses); p-bromoaniline, m. 162.5 Deg (90); 2,4,6,-tribromoaniline, m. 185 Deg (80); o-nitroaniline, m. 174.5 Deg (89); m-isomer, m. 1380 (92); p-compound, m. 169.5 (95); o-phenetidine, m. 141.5 Deg (94); o-anisidine, m. 140 Deg (89); p-isomer, m. 129 (a (90). All are considerably affected by light, especially those' containing halogen; 2,4,6-Br3C6H2NH2 does not condense with the aldehyde in 95% alc. after 6 hrs. heating but in glacial AcOH condensation takes place in 3 hrs. [on SciFinder (R)]

 

Lowy, A. and E. H. Balz (1921). "Derivatives of 2,4,6-trinitrobenzaldehyde." J. Am. Chem. Soc. 43: 341-6.

            By a modification of the Sachs and Kempf method (cf. also Everding, Ber. 36, 960(1903)) the yield of 2,4,6-(O2N)3C6H2CHO (A) was increased to 60%. The following addition products were prepd. by treating A in boiling alc. containing some H2O with 1 mol, of the amine; aniline, A. PhNH2, red plates, m. 86 Deg; o-toluidine, reddish, m. 106 Deg; beta -naphthylamine, reddish brown; alpha -isomer, reddish brown; diphenylamine, reddish, m. 102 Deg. When treated with glacial AcOH or heated they lose H2O and form the anils; o-toluidine, yellow, m. 177 Deg; beta -naphthylamine, yellow, m. 192 Deg; alpha -isomer, orange, m. 242 Deg; p-toluidine, yellow, m. 179.5 Deg; 1,3,4-xylidine, yellow, m. 203 Deg; p-aminoazobenzene, brick-red, m. 189 Deg; p-aminophenol, yellow, m. 179 Deg; o-aminobenzoic acid, brick-red, m. 146 Deg; m-toluidine, yellow, m. 173.5 Deg. In dil. aq. alc. the tendency is for the addition products to form while in abs. alc. or glacial AcOH the condensation products are usually Obtained directly. Steric hindrance seems to exert a considerable influence on the condensation (cf. Spaeth, C. A. 5, 864); sulfanilic acid does not condense while its Na salt does. In alc. A gives with PhNH2 Sachs and Everding's anal, m. 162 Deg (Ber. 36, 960(1903)) but in glacial AcOH is obtained a light yellow isomer, m. 220 Deg (decompn.). In certain cases the addition products, when dried, undergo change in either direction, i. e., into the components or into H2O and the anal. Further exptl. work is being done on the identification of the theoretically possible optical isomers of the addition products and the syn and antiisomers of the anils. [on SciFinder (R)]

 

Lowy, A. and E. H. Haux (1921). "Electrolytic oxidation of the leuco base of malachite green." Trans. Am. Electrochem. Soc. 40(preprint).

            A tabulation is given of 44 expts. on the electrolytic oxidation of the leuco base. The conclusions are that in order to bring about efficient oxidation the following are necessary: a catalyst, and elevated temp., a low concn. of the leuco base in the anolyte, and H2SO4 as solvent and electrolyte. The highest dye yield was obtained with UO2SO4 as catalyst, Pt cathode, and a nichrome gauze anode in dil. H2SO4 soln., at a temp. of 85 Deg. [on SciFinder (R)]

 

Lowy, A. and R. F. Dunbrook (1922). "Compounds of tellurium tetrabromide with organic bases." J. Am. Chem. Soc. 44: 614-7.

            Pure TeBr4 in abs. Et2O or glacial AcOH treated with amines yields addition products as yellow or orange ppts. containing 2 mols. amine to 1 of TeBr4 if the amine has only one NH2 group and 1 mol. amine to 1 of TeBr4 if the amine has two NH2 groups. The following 2:1 compds. were prepd.: Bisaniline, bis-p-bromoaniline, bisdiphenylamine, bisdimethylaniline, bis-beta -naphthylamine; and the following 1:1 compds.: p-phenylenediamine, m-tolylenediamine, benzidine, tetramethyldiaminodiphenylmethane. The yields were practically quant. The compds. are all yellow amorphous powders (orange when they can be crystd.), stable in the air but decompd. by H2O or alc. with formation of H2TeO3, do not melt, decomp. above 100 Deg, dissolve easily in dil. acids. The PhNH2 compd. on recrystn. from dil. HBr forms a new complex, (PhNH2.HBr)4.TeBr4. Alkaloids (brucine, quinine) also give yellow amorphous products with TeBr4. Attempts to prep. Se and Te dyes analogous to the S dyes obtained by processes involving the use of the element S were unsuccessful. [on SciFinder (R)]

 

Lowy, A. and C. M. Moore (1922). "Electrolytic oxidation of isoeugenol." Trans. Am. Electrochem. Soc. 42.

            German patent 92,007 describes a method of prepg. vanillin by the electrolytic oxidation of isoeugenol. Expts. by the authors in which the electrolytes were NaOH and H2SO4, resp., yielded negative results. Vanillin was found to oxidize readily electrolytically and if formed by electrolytic oxidation would be unstable. Under conditions specified in the patent an appreciable amt. of vanillin is not obtained. Statements in text books that vanillin may be prepd. by this method ought to be modified or corrected. Acetyl, benzoyl or similar derivs. of isoeugenol might yield the desired results. [on SciFinder (R)]

 

Downey, T. B. and A. Lowy (1923). "Derivatives of 2,4-dinitrobenzaldehyde. III." J. Am. Chem. Soc. 45: 1060-5.

            cf. C. A. 15, 1527. The 2,4-dinitrobenzal derivs. of the following amines were obtained in about 90% yield from 1 mol. each of the aldehyde and the amine in alc. on the H2O bath: 2,4-dichloroaniline, bright orange, m. 185 Deg; o-chloroaniline, yellow, m. 167.5 Deg; p-isomer, yellow, m. 161.5 Deg; p-aminoazobenzene, red, m. 229 Deg; o-tolidine (I) (prepd. in AcOH), yellowish red, m. 282 Deg (decompn.). In the last case, when the condensation was effected in alc. there was obtained the intermediate deep purple addn. product, (O2N)2C6H3CHO.H2NC6H3MeC6H3MeNH2, m. 232 Deg, which with a little AcOH in Me2CO gives I and with hot Ac2O yields the orange- yellow Ac deriv. of I, m. 231.5 Deg. Refluxed in AcOH-HCl with 2 mols. of a phenol or condensed with 2 mols. of a tert. arom. amine with ZnCl2 or concd. HCl the aldehyde gave the following 4,4'-[2,2'-dinitrophenylmethylene] derivs.: bisphenol (II), (O2N)2- C6H3CH(C6H4OH)2, yellow, m. 204 Deg, oxidizes in the air to an orange product, forms a brick-red Na salt, acts as an indicator towards acids (pale yellow) and the normal carbonates and the hydroxides of the alkali metals (red) (yield, 10 g. from 6 g. PhOH); bis-o-chlorophenol, yellow, m. 190.5 Deg (yield, 80%); bis-o-cresol, yellow, m. 200.5 Deg (yield 75%); bisguaiacol, yellow, m. 221 Deg (yield, 65%); bissalicylic acid, yellow, m. 268.5, Deg (yield, 40%; bisresorcinol (III), yellow, becomes red 210-5 Deg, gradually chars above 280 Deg (yield, 4 g. from 7 g. m-C6H4(OH)2), forms a dark red Ca salt, (O2N)2C6H3CH- (C6H3O2Ca)2; bisdimethylaniline (2,4-dinitro-malachite green), yellow, m. 151.5 Deg (yield, 80%), oxidized to the color base and dye by the usual methods, both the ZnCl2 salt and the oxalate dyeing silk and wool a blue-green without mordanting; bisdiethylaniline (2,4-dinitro-brilliant green), dirty green; bisbenzylethylaniline, brownish yellow (yield, 32%). Tetrabromo deriv. of II, from II and Br in AcOH, yellow, m. 234 Deg; yield, 70%. The mother liquors from III yield the yellowish red amorphous 9-[2,4-dinitrophenyl]- 3,6-dihydroxyxanthene, also obtained from the aldehyde and m-C6H4(OH)2 with ZnCl2 at 95-130 Deg or with concd. H2SO4 at 60 Deg, forms deep red Na, K and NH4 salts; Ca salt; tetrabromo deriv., red, chars above 290 Deg, forms Na and K salts sol. in H2O with deep red color. [on SciFinder (R)]

 

Lowy, A. and A. R. Ebberts (1923). "A ball-mill electrolytic cell." J. Ind. Eng. Chem. (Washington, D. C.) 15: 1021.

            The app. consists of a stirrer with paddles, glass ball, a thermometer and one electrode above the balls, an electrode on the bottom of the beaker with a connection sealed in the glass. Hg is an advantageous electrode as no sealing is required and no trouble arises due to solids adhering to the electrode surface. Heat is supplied by bath only. [on SciFinder (R)]

 

Howald, A. M. and A. Lowy (1923). "The catalytic ammonolysis of beta -naphthol and chlorobenzene in the vapor state." J. Ind. Eng. Chem. (Washington, D. C.) 15: 397-401.

            A study of the direct action of NH3 on beta -naphthol (A) and on PhCl (B) in the presence of catalysts. A was passed in the vapor state mixed with NH3 over various catalysts at definite temps. The yield of beta -C10H7NH2 (C) was a function of the catalyst, temp., relative amts. of reacting compds. and the rate of flow over the catalyst. Alumina was the best catalyst, 90-5% yields of C being obtained under varying conditions. By passing B and NH3 over various catalysts, a max. yield of 7% of PhNH2 was obtained. Reduced metals of the Fe group were the only catalysts which formed appreciable yields of PhNH2, and these catalysts rapidly became inactive, probably because of poisoning by the chlorides formed. Analogous expts. with PhBr, PhI and p-C6H4Cl2 in the presence of Fe did not give promising results. [on SciFinder (R)]

 

Lowy, A. (1923). "Electrochemistry of organic compounds." J. Ind. Eng. Chem. (Washington, D. C.) 15: 15-6.

            Org. compds. may be decomposed electrolytically as nonelectrolytes by action of products of decompn. of electrolytes. The reactions include oxidation, reduction, halogenation, synthesis, etc. [on SciFinder (R)]

 

Lowy, A. and H. S. Frank (1923). "Electrolytic and chemical chlorination of benzene." Trans. Am. Electrochem. Soc. 43(preprint).

            The previous work is briefly reviewed and some inconsistencies are pointed out. The authors show that C6H6 can be chlorinated electrically and that I2 aids appreciably as a carrier. H2O acts as a carrier in the chem. chlorination. [on SciFinder (R)]

 

Tesh, K.S. and Lowy, A. (1924). “The Electrolytic Preparation of Salicylic Aldehyde from Salicylic Acid.” Trans. Electrochem. Soc. 45:37-45

 

Hjort, E.V. and Lowy, A. (1924). “The Selenium Optical Densimeter for Colorimetric Work.” J. Optical Soc. Am and Rev. Sci. Instruments. 9:43-51

 

King, C. G. and A. Lowy (1924). "Derivatives of p-nitrobenzaldehyde. II." J. Am. Chem. Soc. 46: 757-62.

            cf. C. A. 15, 1714. The following p-nitrobenzal derivs. were prepd.: o-bromoaniline, m. 106 Deg; m-deriv., m. 102 Deg; 2,6-dibromoaniline, m. 137 Deg; 2,4,6-tribromoaniline, m. 142.5 Deg; 3-bromo-4-toluidine, m. 112 Deg; p-xylidine, m. 100 Deg; o-nitroaniline, m. 169 Deg. All are golden yellow and are hydrolyzed by 1:1 HCl to the aldehyde and amine. 4,4'-[p-Nitrophenylmethylene]bisphenoltetrabromide, O2NC6H4CH(C6H2Br2OH)2, yellow, m. 215 Deg; the alk. soln. is orange-red. Ca and Ba salts, amorphous, orange powders. Di-Ac deriv., pale yellow, m. 168 Deg. [p-Nitrophenylmethylene]bisresorcinol dibromide, yellow, amorphous powder, turns red 170 Deg chars above 200 Deg. 4,4'-[p-Nitrophenylmethylene]bis-o-nitrophenol, orange, amorphous powder, m. 177 Deg. The corresponding o-methylanisole and thymol derivs. were also prepd. The di-Br deriv. of the latter, m. 155 Deg, of which the di-Bz deriv., light yellow, m. 82 Deg. Reduction of p-O2NC6H4CH:NC6H4Me-p gave unstable compds. [on SciFinder (R)]

 

Wood, A. E., A. Lowy, et al. (1924). "Action of petroleum-refining agents on pure organic sulfur compounds dissolved in naphtha." J. Ind. Eng. Chem. (Washington, D. C.) 16: 1116-20.

            A systematic investigation of the chem. effect of H2SO4, Na2PbO2, Na2PbO2 + S, CuO, NaOCl and AlCl3 on mercaptans, alkyl sulfides, alkyl disulfides, thiophene, H2S, CS2, sulfoxides, sulfones and free S. The effects, whether, chem. reaction, soln. or none, are tabulated. [on SciFinder (R)]

 

Lowy, A. (1924). "Coal products chart." J. Ind. Eng. Chem. (Washington, D. C.) 16: 26.

           

Ebberts, A. R. and A. Lowy (1924). "The electrolytic reduction of beta -anthraquinonesulfonic acid." Trans. Am. Electrochem. Soc. 45(preprint).

            A preliminary study was made on the electrolytic reduction of beta -anthraquinonesulfonic acid. In H2SO4 soln. the golden yellow color of beta -anthraquinonesulfonic acid is converted to an olive-green "vat" (beta -anthraquinolsulfonic acid), which on aeration reverts to the original substance. On further reduction, the olive-green "vat" is converted to a yellow soln. (probably beta -anthronesulfonic acid), which on aeration does not revert to the original substance. Reduction of Na beta -anthraquinonesulfonate produces the typical red "vat," which on aeration reverts to the original salt. [on SciFinder (R)]

 

Dunbrook, R. F. and A. Lowy (1924). "The electrolytic oxidation of p-nitrotoluene and p-chlorotoluene to their respective acids." Trans. Am. Electrochem. Soc. 45(preprint).

            The electrolytic oxidation of p-nitrotoluene and p-chlorotoluene to the corresponding acids has been carried out in HNO3 soln. of 20 to 30% concn., with use of Pt electrodes. For the electrolytic oxidation of p-nitrotoluene to p-nitrobenzoic acid the optimum conditions were, a temp. of 100 Deg, with a c. d. of 4 amp. per dm.2, with 20% HNO3 soln. as anolyte. The yield was 34.1% of the acid. For the oxidation of p-chlorotoluene to p-chlorobenzoic acid the best results were obtained with Pt anode. a temp. of 100 Deg and a c. d. of 0.5 amp. per dm.2 and 20% HNO3 soln., with glacial acetic acid as a solvent. Acetic acid has a very beneficial effect on the yield of p-chlorobenzoic acid, and increased the current efficiency to 96.0%. [on SciFinder (R)]

 

Lewers, W. W. and A. Lowy (1925). "Comparative study of azo dyes made with H acid and acetyl-H acid." J. Ind. Eng. Chem. (Washington, D. C.) 17: 1289-90.

            A series of dyes was prepd. from 33 diazo compds.; as the coupling component were used H acid and acetyl-H acid. The latter series was hypsochromic, and in general faster to the action of acids and alkalies. [on SciFinder (R)]

 

Parrett, A. N. and A. Lowy (1926). "Catalytic reduction of alpha -nitronaphthalene to alpha -naphthylamine." J. Am. Chem. Soc. 48: 778-82.

            alpha -C10H7NO2 (I) (5 g.) in 100 cc. glycol contg. 0.2 g. Pd black is reduced in 7.5 hrs. under 3 1/3 atm. pressure, giving 89.4% alpha -C10H7NH2 (II); 84.6% in 3 hrs., and 98.4% at 6 2/3 atm. in 3 hrs. The % of reduction increases with an increase in temp. from 50 Deg to 100 Deg. The efficiency of solvents increases in the order: C3H6(OH)3, C3H4(OH)2, H2O and iso-PrOH. Pd and Pt oxides produce high % of II in 1.5 hrs. Molten I was reduced by Pd oxide with a yield of 93.9% and with Ni with a yield of 14.3%. [on SciFinder (R)]

 

Croco, C. W. and A. Lowy (1926). "Electrochemical chlorination and bromination of benzene." Trans. Am. Electrochem. Soc. 50: 12 pp.

            It is possible to chlorinate benzene by stirring it with concd. HCl and electrolyzing. The main product is chlorobenzene. This investigation showed that the amt. of chlorobenzene was the same in both the electrolytic and the non-electrolytic expts. The electrolytic method, however, gave a small amt. of more highly chlorinated products which were not found with the non-electrolytic method. Therefore, it is concluded that the principal action of the Cl generated electrolytically was electrochemical in nature, along with a slight amt. of electrolytic action. In bromination, the electrolytic and non-electrolytic expts. produced bromobenzene in about equal amts., and this was the only product observed. This reaction is an electrochemical one. [on SciFinder (R)]

 

Conn, J. E. and A. Lowy (1926). "The electrolytic oxidation of p-bromotoluene and of o-nitrotoluene." Trans. Am. Electrochem. Soc. 50: 12 pp.

            p-Bromotoluene and o-nitrotoluene were subjected to electrolytic oxidation in dil. HNO3 soln., of such a concn. as would bring about only slight chem. oxidation. p-Bromotoluene was converted to p-bromobenzoic acid with excellent yields. The favorable conditions are: (a) an electrolyte of 20% HNO3; (b) Pt electrode; (c) vigorous stirring; (d) a c. d. of 0.50 amp. per sq. dm.; and (e) temp. of 100 Deg. o-Nitrotoluene was converted to o-nitrobenzoic acid in low yields. A resinous material, oxalic acid and CO2 were the other products formed on oxidation. No solvents were used. [on SciFinder (R)]

 

Nevyas, J. and A. Lowy (1926). "The electrochemical reduction of indigo." Trans. Am. Electrochem. Soc. 50: 12 pp.

            A quant. study has been made of the influence of variations in c. d., temp. and concn. of electrolyte upon the current efficiency of the electrochem. reduction of indigo, in finely divided suspension in solns. of NaOH with a Hg cathode. It is shown that the current efficiency (a) decreases with increasing current density, (b) increases with increasing temp., and (c) increases with increasing concn. of alkali. An app. has been developed for studying electrochem. reductions, which permits of the electrolysis of a compd. and the withdrawal of a sample of catholyte in an O-free atm. [on SciFinder (R)]

 

Kesler, C. C., A. Lowy, et al. (1927). "Preparation of abietic acid from rosin and preparation of some of its derivatives." J. Am. Chem. Soc. 49: 2898-903.

            Rosin was isomerized by pasing HCl through the melted rosin with stirring for 20 min., or by adding 1% HCl to a hot 33% EtOH soln. and boiling 15 min.; NaOH was then added to neutralize the HCl and 25% of the acid content of the rosin; crystn. gives the complex salt, C19H29CO2Na.3C20H30O2, m. 177 Deg; mineral acid gives the free abietic acid, m. 166 Deg. Esters were prepd. by the use of the proper p-MeC6H4SO3H deriv. or, with the phenols, by the action of COCl2 upon the Na salts. Me, b14 225-6 Deg, d415 1.050, n 1.5344; Et, b4 204-7 Deg, d416 1.032, n 1.5265; Pr, b4 237-40 Deg, d415 1.015, n 1.5229; iso-Pr, b4 214-7 Deg, d415 1.010, n 1.5200; Bu, b3 247-50 Deg, d416 1.014, n 1.5192, iso-Bu, b4 222-5 Deg, d415 1.008, n 1.5171; iso-Am, b4 254-7 Deg, d415 1.001, n 1.5165; allyl, b5 282.-5 Deg, d415 1.024, n 1.5242; Ph, b4 330-3 Deg, d415 1.056, n 1.5354; hexalin, b4 299-302 Deg d415 1.061, n 1.535; m-tolyl, b4 310-3 Deg, d415 1.039; alpha -naphthyl, b2 290 Deg (decompn.) d415 1.116; terpineol, b2 310 Deg (decompn.), d415 1.082; benzyl, b4 294-7 Deg, d415 1.036, n 1.551; cholesteryl, m. 122-5 Deg; menthyl, m. 77-83 Deg; bornyl, m. 75-80 Deg; cetyl, m. 42 Deg. The soly. of cellulose nitrate in the different esters, the flexibility and adhesion of the film and its strength and elasticity indicate that these esters possess properties allowing their use wherever a neutral or softening effect is desired. [on SciFinder (R)]

 

Powers, P. O., A. Lowy, et al. (1927). "Oxidation and hydrolysis of light wood oil." J. Ind. Eng. Chem. (Washington, D. C.) 19: 306-8.

            HNO3 was found the most satisfactory oxidizing agent, 6% concn. being sufficient, and higher concns. being of no apparent advantage. Refluxing for 6 hrs. converted about 50% of the oil into H2O-sol. products (org. acids), and only half of the H2O-insol. part distd. within the range of the original oil. V2O5 catalyzes the reaction and apparently accelerates oxidation to acids rather than to side reactions. CaO is a satisfactory hydrolytic agent, improving the color and odor of the residual oil and giving MeOH (contg. Me ketones, some Me2CO, and chiefly MeCOEt) and org. acids, the resp. yields and the compn. of the org. acids varying with the source and compn. of the oil used. Treatment of light wood oil with strong NaHSO3 soln. removes about 40% by vol. (aldehydes and Me ketones); and hydrolysis of the residue with CaO gave somewhat lower yields of org. acids. [on SciFinder (R)]

 

Davidson, J. M. and A. Lowy (1929). "Reactions of vinyl chloride and benzene in the presence of aluminium chloride." J. Am. Chem. Soc. 51: 2978-82.

            CH2:CHCl, C6H6 and AlCl3 give Ph2CHMe (I), 9,10-dimethyldihyroanthracene (II) and an anthracene-type resin. No styrene or metastyrene was formed. PhCHClMe is considered as the most probable intermediate. Increased amts. of AlCl3 at low temps. decreased the amts. of I. The amts. of II were increased by using a higher temp. or by the presence of I. Hg caused the formation of PhEt and considerably decreased the amt. of resin formed. Certain phys. and chem. properties of the resin have been studied. [on SciFinder (R)]

 

Rasch, C. H. and A. Lowy (1929). "The electrochemical oxidation of anthracene to anthraquinone with a new type of electrode." Trans. Am. Electrochem. Soc. 56: 6 pp.

            A new type of electrode consists of a base or framework of metal, which Supports the oxide of the metal intimately mixed with an organic depolarizer. Exptl. work was conducted to oxidize anthracene. to anthraquinone by using a lead grid filled with a mixt. of PbO2 and anthracene as the anode. The new type electrode gave a much greater yield and current efficiency than where the depolarizer was suspended in the electrolyte. This principle is recommended with other electrode combinations for org. electrolytic reductions and oxidations. [on SciFinder (R)]

 

McClure, R. E. and A. Lowy (1929). "The electrochemical preparation of phenylhydrazine." Trans. Am. Electrochem. Soc. 56(preprint): 11 pp.

            The purpose of this investigation was to prep. phenylhydrazine by the electrochem. reduction of certain benzenediazonium compds., and to study the influence of the usual variable factors common to electrochem. reactions. A current efficiency of 36.5% was obtained by the reduction of benzenediazonium chloride, with a c. d. of 5.12 amp. per sq. dm., a temp. of 0-8 Deg, and a Hg cathode. A current efficiency of 47.6% was obtained by the reduction of K isodiazobenzene sulfonate, with a c. d. of 1.9 amp. per sq. dm., a temp. of 90 Deg to 95 Deg and a Hg cathode. [on SciFinder (R)]

 

Hubbuch, L. P. and A. Lowy (1929). "The electrochemical reduction of azo dyes to their respective amino compounds." Trans. Am. Electrochem. Soc. 55: 13 pp.

            Six azo dyes, methyl orange, Metanil Yellow, Acid Scarlet, Crimson, Congo red and Fast Brown O, representing 6 different types, were reduced electrochemically to their resp. amino compds. in a Na2CO3 soln., at a Hg cathode. In general, the conditions found favorable for this reduction were a temp. of 95 Deg, a c. d. of 0.885 amp./sq. dm., and a concn. of 7.5 g. of dye per 200 cc. of soln. It is shown that azo dyes, without an amino or a hydroxyl group in the ortho or para position to the azo group, can be reduced electrochemically in an alk. soln. to their corresponding amines. [on SciFinder (R)]

 

Landolt, G. L., E. G. Hill, et al. (1930). "Flotation research on the relative activity of the various constituents of crude cresylic acid." Eng. Min. J. 129: 351-2.

            A study of the relative activities of the various constituents of crude cresvlic acid. when used as frothing and collecting agents in floating a Pb-Zn ore, showed that cresols were better than xylenols, with the degree of activity depending greatly upon the position of the groups on the benzene ring for each group of isomers. The decreasing order of the activity was: m-, p-, o-cresol; 1,3,4-xylenol, 1,4,5-xylenol, 1,2,4-xylenol, phenol and 1,3,2-xylenol. Expts. with 3 grades of crude cresylic acids contg. different ratios of cresols and xylenols showed the cresols superior to the xylenols when equal vols. were used. Propylphenol is a better agent than either o- or p-cresol. The value of crude cresylic acid as a frothing agent apparently depends largely upon the proportion of m-cresol it contains. Four tables and 2 curves give the data. [on SciFinder (R)]

 

Goldblatt, L. A., A. Lowy, et al. (1930). "Nitration of abietic acid and the study of some of its nitrogen derivatives." J. Am. Chem. Soc. 52: 2132-6.

            Abietic acid (100 g.), m. 166 Deg, [alpha ]D20 -67 Deg, in 200 cc. 95% EtOH, heated to boiling until soln. results and then treated with 15 5-cc. portions of HNO3 (d. 1.42) at 0.5-min. intervals, gives 30 g. of a di-NO2 compd., C19H26N2O6 (I), m. 170-1 Deg, [alpha ]D20 -118 Deg (0.6% in 95% EtOH), and 75 g. of a yellow N-contg. product (II), decamps. above 100 Deg, alpha D20 -36 Deg (0.5% in EtOH). I in 30% NaOH yields a Na salt. The Et ester, m. 157.5-7.8 Deg, also results upon nitration of Et abictat. I is reduced by Zn and AcOH or HCl and by alk. Na2S2O4; on catalytic reduction, 1.74 mols. H are absorbed, giving a compd. (II), m. 171.5-2 Deg, which evolves NH3 in hot EtOH or when treated with cold aq. NaOH. II is a hydroxylated NO2 deriv. of abietic acid, which gives a dark red soln. in aq. alkali; these solns. completely absorb O from air. No cryst. reduction products could be obtained from II. The Na salt is light yellow and yields only uncrystallizable tars with Me2SO4 or Et2SO4. [on SciFinder (R)]

 

McClure, R. E. and A. Lowy (1931). "Preparation of aromatic mercuric chlorides from aromatic diazoniurn chlorides." J. Am. Chem. Soc. 53: 319-21.

            Arom. mercuric chlorides are obtained by stirring a mixt. of RN2Cl and Hg at about 5 Deg. In this way the following compds. were prepd.: PhHgCl, 45%; p-MeC6H4HgCl, 52%; o-MeC6H4HgCl, 72%; 2,5-Me2C6H3HgCl, 64%; alpha -C10H7HgCl, 20%. PhN2Cl and black pptd. Hg give 20% PhHgCl. [on SciFinder (R)]

 

Lowy, A. (1931). "Comparison of American and European final examinations." J. Chem. Educ. 8: 1345-7.

 

Lowy, A. (1931) “Recent Developments in Organic Electrochemistry.” Trans. Electrochem. Soc. 59:15-16

           

Lowy, A. (1932). "Chart of recent aliphatic chemicals. I." Ind. Eng. Chem., News Ed. 10: 6.

            The chart shows the sources and interrelationships of a no. of the chemicals that have been produced for research and industrial purpose during the past few years. [on SciFinder (R)]

 

Wardner, C. A. and A. Lowy (1932). "Nitration of m-diphenylbenzene and derivatives of nitro-m-diphenylbenzene." J. Am. Chem. Soc. 54: 2510-5.

            m-C6H4Ph2 (I) (50 g.) and 200 cc. Ac2O, thoroughly mixed, cooled to 0 Deg and treated dropwise with 17.5 cc. HNO3 (d. 1.5) during 20 min., gradually warmed after 15 min. to 25 Deg (20 min.) and then heated at 50 Deg for 30 min., gave 36 g. of the NO2 deriv. (II), b1 197-8 Deg, which did not crystallize. I (20 g.) was added to a mixt. of 30 cc. H2SO4, 15 cc. HNO3 (d. 1.42) and 7.5 cc. H2O at 40 Deg during 20 min., 10 cc. HNO3 added and after the product became pasty, the nitrating acid decanted; 7 g. of a di-NO2 deriv. (III), m. 214 Deg, was obtained. The tri-NO2 deriv. can be prepd. from either I or II. Oxidation of I with CrO3 in AcOH yielded a nitradiphenylcarboxylic acid, m. 227 Deg. II gave p-O2NC6H4CO2H; III could not be oxidized. Two possible formulas for I are 2-nitro-5'-phenylbiphenyl and 1,3-diphenyl-4-nitrobenzene. Catalytic reduction of I gives the NH2 deriv., m. 64 Deg (6 g. from 10 g. I); HCl salt; Ac deriv., m. 117 Deg; Bz deriv., m. 152 Deg. The diazo soln. yields m-diphenylbenzeneazo-beta -naphthol, red; the following compds. were also coupled with the diazo compd.: 1,8-dihydroxynaphthalene-3,6-disulfonic acid, red-purple; 1-naphthol-4-sulfonic acid, bright red; 1,8-aminonaphthol-3,6-disulfonic acid, blue-purple; 2-napbthol-7-sulfonic acid, bright red; 1,8-aminonaphthol-2,4-disulfonic acid, purple; 2-naphthol-3,6-disulfonic acid, light purple. [on SciFinder (R)]

 

Payne, C. R. and A. Lowy (1932). "Highly cracked gasoline." J. Ind. Eng. Chem. (Washington, D. C.) 24: 432-6.

            A study was made of the compn. of the fractions of a highly cracked gasoline before and after heating for 6 hrs. under 68 atm. pressure at 300 Deg. The treatment decreased the percentage of unsatd. hydrocarbons in the fractions isolated but increased the naphthenes in the distillate up to 201.5 Deg. Polymerization is believed responsible for an increase in the quantity of the fraction b. above 201.5 Deg, disappearance of the probable presence of cycloalkenes, and formation of hydrocarbons contg. H easily replaceable by halogens. C6H6 and PhMe were identified in the cracked gasoline; the presence of methylcyclobutane was inferred in the fraction b. 29.4-35.0 Deg; the proportion of unsatd. hydrocarbons tended to decrease with increase in the b. p.; and the phys. properties indicate that the percentage of paraffins decreases, and that of naphthenes and aromatics increases with increase in the b. p. [on SciFinder (R)]

 

Rasch, C. H. and A. Lowy (1932). "The electrochemical oxidation of anthraquinone." Trans. Electrachem. Soc. 62: 8 pp.

            By the electrolytic oxidation of anthraquinone in strong H2SO4 soln. hydroxylated anthraquinones were produced. Low temp. increased the yield. Boric acid does not aid in the electrochem. oxidation. Hydroxyanthraquinonesulfonic acids are also produced during the electrolysis. Spectroscopic detns. revealed that mixts. of hydroxylated anthraquinones were produced. Quinizarin has been isolated from the mixtures and its presence definitely proved by its m. p. and Ac deriv. and verified spectroscopically. Electrodes used as anodes contg. anthraquinone as a solid depolarizer were not suitable in acid or alk. solns. for the formation of hydroxylated anthraquinones. [on SciFinder (R)]

 

White, G. H., Jr. and A. Lowy (1932). "The electrolytic oxidation of leuco bases of the triphenylmethane series of dyestuffs." Trans. Electrochem. Soc. 61: 12 pp.

            The leuco bases of 4 triphenylmethane dyes have been oxidized electrolytically by 2 different procedures, which may be considered as general methods for the series. By the 1st method, leuco bases which are insol. in water and alkalies have been oxidized as solid depolarizers in C and leuco base mixts. By this method, it is shown that the depolarizer must be in direct contact with the electrode where electrochem. action takes place. It is shown further that a high concn. of solid org. depolarizer can be incorporated with C to form a conducting anode mixt. The 2nd method deals with leuco bases which are sol. in alkalies. It is shown that these leuco bases can be oxidized in a soln. of Na2CO3 when used as sol. depolarizers in the usual way. Comparative dyeing tests have been made with the dyes produced electrolytically and those produced by chem. methods. [on SciFinder (R)]

 

White, E.G. and Lowy, A (1932) “The Electrochemical Oxidation of Naphthalene Using a New Type Electrode” Trans. Electrochem. Soc. 62: 223-231

 

Lowy, A. (1933). "Chart of products derived from acetylene." Ind. Eng. Chem., News Ed. 11: 156.

            cf. C. A. 26, 1232. [on SciFinder (R)]

 

Levin, D. E. and A. Lowy (1933). "Derivatives of dihydroeugenol and certain pharmacological properties of some of the compounds." J. Am. Chem. Soc. 55: 1995-2000.

            Dihydroeugenol (I), b1 94-5 Deg, b5 112-3 Deg, b10 119-21 Deg, b15 126-7 Deg, b25 138-9 Deg; Na salt. Fuming HNO3 in Et2O at 26 Deg gives the 5-NO2 deriv. (II), yellow-orange, m. 33.8-4.2 Deg; K salt, red. 5-Nitroeugenol (III) and its K salt were also prepd. I and AcCl in C5H5N and Ac2O give the Ac deriv., b2 115 Deg; Bz deriv., m. 73 Deg, ClCH2CO2K and I in 40% KOH give dihydroeugenolglycolic acid, m. 104 Deg. Catalytic reduction of II or III gives 5-aminodihydroeugenol (IV), m. 83-4 Deg, HCl salt, decomps. 191-2 Deg. Dihydroeugenolazo-beta -naphthol, red; -1,8-aminonaphthol-3,6-disulfonic acid, deep purple; -2-hydroxy-3-naphthanilide, deep blue; -1-naphthol-4-sulfonic acid, purple. IV and BzCl in CHCl3-C5H5N give the Bz deriv. (5-benzoylamino-1-propyl-3-methoxy-4-benzoxybenzene), m. 162 Deg; Ac deriv., m. 155 Deg; p-nitrobenzal deriv., yellow, m. 133-4 Deg. The effects on respiration, blood action and other pharmacol. actions are described. [on SciFinder (R)]

 

Martin, S. M., Jr., W. A. Gruse, et al. (1933). "Distribution of gum-forming constituents in cracked gasoline." J. Ind. Eng. Chem. (Washington, D. C.) 25: 381-6.

            A gasoline made by cracking a solar oil at 600 Deg and fractionated in 5.6 Deg fractions yielded appreciable amts. of gum in fractions whose b. p. corresponded with the b. p. of some diolefin. Treating with H2SO4 or maleic anhydride or hydrogenating produced gum stability at 38 Deg but not at 50 Deg. [on SciFinder (R)]

 

Arnold, C. L., A. Lowy, et al. (1934). "Isolation and study of the humic acids from peat." Bur. Mines Rep. Invest. No. 3258: 9 pp.

            The humic acids isolated in this study show all the characteristics of negatively charged colloids. They have some properties of both suspensoids and emulsoids, predominantly the latter. The humic acids and their salts can be prepd. as reversible colloids. Their dispersibility depends on their phys. condition, which is detd. by the conditions under which they are purified and dried. They are peptized by dil. solns. of salts of the alkali metals and by many aq. org. solvents. The org. sols are much less stable toward electrolytes than the aq. sols. Osmoticpressure measurements indicate a much lower mol. wt. for Na humate than for the other humic sols, pointing to ionic dissocn. of the Na salt. The ash content of humic acids after purification by dialysis is due chiefly to colloidal clay. Removal of SiO2 in the clay with HF decomposes the humic acids. Equiv.-wt. detns. indicate that either there is not a stoichiometric reaction between the metal ions and the humic acids, or that the compds. originally formed are altered during dialysis. The pH of the humic acids solns. is approx. 3.8. Na humates increase in acidity during dialysis. The humic acids are not readily nitrated, sulfonated or reduced. They contain no substances capable of yielding furfural when distd. with HCl. They should not be extd. with hot alk. solns. as they absorb O with evolution of CO2. The humic acids oxidize easily; 3% H2O2 will convert them largely to CO2, H2O and simple org. acids; this indicates that the mols. are not made up predominantly of benzenoid-type structures. The humic acids do not act similarly to lignin when distd. with Zn in H2. Heated in H2, humic acids evolve CO2 at 140-50 Deg. The N and S compds. present are very stable; most are present after heating to 400 Deg. The methoxy content is too low to be a part of any hypothetical humic acid mol. The humic acids can be sepd. into 2 fractions by alc. HCl. A Zeisel detn. on the sol. fraction indicates an equiv. wt. of approx. 580. [on SciFinder (R)]

 

Silver, S. L. and A. Lowy (1934). "Friedel-Crafts type reactions on biphenyl." J. Am. Chem. Soc. 56: 2429-31.

            Ph2 or Me p-xenyl ketone and AcCl with AlCl3 give 43 or 51% of (p-AcC6H4)2. Ph2 and (ClCH2-CO)2O give chloromethyl p-xenyl ketone (I). ClCH2COCl with Ph2 or I give 35 or 52% of (p-ClCH2COC6H4)2. Ph2 and (COCl)2 give a mixt. of di-p-xenyl ketone and p-xenil. Ph2 and PhSO2Cl give 43% of p-xenylsulfonylbenzene. Ph2 and SOCl2 give p-xenyl-p-sulfinylbiphenyl. These products were identified by the prepn. of various derivs. Vinyl chloride, under variable temp. conditions, forms complex products which cannot be sepd. by fractional distn. [on SciFinder (R)]

 

Andrews, L. H. and A. Lowy (1934). "Catalytic reduction of azo types of compounds." J. Am. Chem. Soc. 56: 1411-12.

            Azobenzene (I) can be easily hydrogenated at room temp. (45 lb. pressure) without the presence of H2SO4, with a Pt catalyst, to give mainly PhNH2 (II); if I is hydrogenated in the absence of H2SO4 until the H absorption corresponds to that required for reduction to (PhNH)2 (III), a mixt. of III, II and some unchanged I results; if the above type of reaction is carried out at low temp. (5-8 Deg), the yield of III is increased; if H2SO4 is added to the reaction mixt. with the idea of stopping the reduction at the III stage by converting it to the insol. sulfate, the reduction takes place at a much slower rate at room or higher temp. and, in fact, the catalyst may become completely inactive; however, further addns. of catalyst cause the reaction to proceed; the addn. of H2SO4 under these conditions results in very little, if any, increase in the yield of III. When H2SO4 is contained in the reduction mixt. and the hydrogenation carried out at low temp., the reduction goes rapidly and smoothly and results in a larger yield of III. I can be reduced to II in EtOH when shaken with H2 at 99 Deg in the presence of Ni to give a good yield of II; when 1 mol. of H2 per mol. of I is allowed to be absorbed, III, II and unchanged I are present; if the temp. is 55 Deg the H2 absorption takes place much more slowly with an increase in the amt. of II and decrease in the amt. of III formed; Ni is not as satisfactory as Pt for this type of reduction. p-Aminoazobenzene is reduced by Pt in 20 min. (45 lb. pressure) to p-C6H4-(NH2)2 and II. [on SciFinder (R)]

 

Arnold, C. L., A. Lowy, et al. (1935). "The isolation and study of the humic acids from peat." Fuel 14: 107-11.

            See C. A. 29, 1922.3. [on SciFinder (R)]

 

Kane, H. L. and A. Lowy (1936). "Reactions of alkyl sulfates, tetraethyl orthosilicate and diethyl carbonate in Friedel-Crafts syntheses." J. Am. Chem. Soc. 58: 2605-8.

            The best yields of monoalkylated benzene obtained with the following esters were: Me2SO4 59.8, Et2SO4 71.4, (iso-Pr)2SO4 44.2, Bu2SO4 43.6, (EtO)4Si 53.3 and Et2CO3 56.4%. The general conditions affecting the yield, such as reaction time, temp. and proportion of reagents, are reported; the best ratio of AlCl3 to ester was 1.44 moles to 1, except in the case of the silicate, where it was 2.88 to 1. Attempts to alkylate C10H8 with Et2SO4 led to hydrocarbon oils which could not be fractionated into sep. ethylated derivs. Attempts to use a flow method with Et2SO4 gave much reduced yields. No EtCl could be obtained by the action of Et2SO4 or Et2CO3 on AlCl3 in ligroin. [on SciFinder (R)]

 

Brandes, O. L., W. A. Gruse, et al. (1936). "Propylene polymerization." J. Ind. Eng. Chem. (Washington, D. C.) 28: 554-9.

            With 0.1 mol. ZnCl2, the polymerization of C3H6 at 150-300 Deg for 1-3 hrs. yields up to 74% liquid product, of which up to 92% b. <200 Deg. Naphthenes, olefins and paraffins in the C8-C12 range, and no aromatics, are formed. [on SciFinder (R)]

 

Phillips, J. and A. Lowy (1937). "Titration of aromatic amines with nitrous acid." Ind. Eng. Chem., Anal. Ed. 9: 381-2.

            Most aromatic amines cannot be titrated directly with HNO2 but by adding an excess of NaNO2 and titrating the excess with standard aniline-HCl soln. the results are fairly satisfactory. Eleven aromatic amines were tested. [on SciFinder (R)]

 

Phillips, J. and A. Lowy (1937). "The electrolytic reduction of trinitro aromatic compounds to their respective triamines." Trans. Electrochem. Soc. 71: 10 pp.

            The following compds. were reduced electrolytically: 2,4,6-trinitrobenzoic acid to 2,4,6-triaminobenzoic acid; picric acid to 2,4,6-triaminophenol; 2,4,6-trinitrotoluene to 2,4,6-triaminotoluene. The effect of changing various conditions was studied. The yields were detd. in many expts. by titration of the triamine with standard NaNO2 soln. Methods for the isolation and purification of the triamino compds. are given. The conversion of triaminobenzoic acid to phloroglucinol is also studied. The following conditions have been found to give the best yields of the triamine: a closed cell, a perforated Pb cathode, a Pt strip anode contained in a porous alundum thimble, HCl (1:1) as the catholyte, and a cathodic c. d. of 3 to 4 amp./sq. dm. [on SciFinder (R)]

 

Lowy, A. (1938). "Electrolytic chemicals, 1918-1938." Chem. Industries 43: 22-3,25-6.

           

Berman, N. and A. Lowy (1938). "Reactions of trialkyl phosphates, alkyl acetates and tert-butyl hypochlorite in the Friedel-Crafts synthesis." J. Am. Chem. Soc. 60: 2596-7.

            (RO)3PO, AcOR or tert-BuOCl condenses with C6H6(A1Cl3) to give the corresponding alkylated benzene. Thus, 435 g. C6H6 and 68.5 g. A1Cl3 at 0 Deg, treated with 25 g. (EtO)3PO and stirred for 8 hrs. at 20-5 Deg, give 27 g. PhEt (61.5%) and 8 g. higher-boiling fraction. (Iso-PrO)3PO (prepn. in 45% yield given) gives 52.1% of iso-PrPh; (BuO)3PO, 71.5% of sec-BuPh; iso-PrOAc gives up to 57.8% of iso-PrPh; sec-BuOAc, 53.7% of sec-BuPh; using more than 2 mols. AlCl3 to 1 mol. ester gives only 15.6% sec-BuPh, with 19 g. of higher-boiling fraction; on the other hand, with 0.0428 mol. AlCl3 to 0.431 mol. ester, no reaction took place. AcOCHMeCH2CHMe2 gives 60.4% of beta -methyl-delta -phenylhexane, Hg being a necessary catalyst. tert-BuOCl gives 43.1% of tert-BuPh; without AlCl3 no reaction took place. Iso-PrOAc and AlCl3 at 15 Deg for 5.5 hrs. and at 50 Deg for 2 hrs. do not give iso-PrCl, although some reaction was apparent. [on SciFinder (R)]

 

Goodman, H. G., Jr. and A. Lowy (1938). "Friedel-Crafts reactions on m-diphenylbenzene." J. Am. Chem. Soc. 60: 2155-7.

            m-C6H4Ph2 (I) (30 g.) and 10.2 g. AcCl with 20.7 g. AlCl3 in PhNO2, mixed at 28 Deg and then heated at 45 Deg for 5 h., give 10 g. of the p-Ac deriv. (II) of I, m. 104 Deg; this also results in 5 g. yield from 20 g. I and 9.1 g. Ac2O. Reaction of II with AcCl and AlCl3 gives the p,p'-di-Ac deriv. of I, m. 152 Deg; this could not be obtained directly from I. I (20 g.) and 15.3 g. BzCl give 13 g. of the p-Bz deriv., m. 117 Deg. ClCH2COCl (11.3 g.) in CS2 gives 3 g. of the p,p'-bis (w-chloroacetyl) deriv. of I, m. 150 Deg. PhSO2Cl (19.4 g.) yields 4 g. of the p-benzenesulfonyl deriv. of I, m. 119 Deg (no solvent used). I (23 g.) and 14.8 g. of C6H4(CO)2O in o-C6H4Cl2 yield 35.5 g. of a mixt. of m-diphenylbenzenephthaloylic acid (III), which could not be crystd. and fuses at 90-100 Deg. The structure of the above compds. (with the exception of III) was detd. by oxidn. with CrO3 in AcOH to the corresponding acids. With NaOCl in MeOH II yields m-diphenylbenzene-p-carboxylic acid, m. 221 Deg. Attempts to form a substituted anthraquinone type by ring closure of III failed with Ac2O, AlCl3, FeCl3 and P2O5; H2SO4 gave a pos. result but sulfonation occurred simultaneously. [on SciFinder (R)]

 

Kleibacher, W.M. and Lowy, A. (1938) “Chemical Reactions of Thiophthalic Anhydride.” Pittsburgh. University. Graduate School. Abstracts of Theses. 14:184-190

 

O'Brochta, J. and A. Lowy (1939). "Thio compounds derived from o-aroylbenzoic acids." J. Am. Chem. Soc. 61: 2765-8.

            o-BzC6H4CO2H (I) (20 g.) and 20 g. P2S5 in 700 cc. C6H6, refluxed 25 hrs., give 11 g. of 3,3'-diphenyldiphthalidyl sulfide (II), m. 247 Deg; II also results in 5-g. yield by heating 10 g. I and 10 g. P2S5 at 115 Deg for 1 hr. and in 60-g. yield from the chloride from 100 g. I in 400 cc. C6H6 by passing H2S through the boiling soln. until evolution of HCl ceases. NaOH fission of II gives a pos. test for S++; refluxing with 5% EtOH-KOH gives I, the S being eliminated as H2S. H2SO4 gives anthraquinone. Oxidation with CrO3 or HNO3 gives I and 30% H2O2 gives I and phenylphthalide (III); boiling with Pb(OAc)4 gives PbS and I; reactions with PhNH2, PhOH and PhNHNH2 yield compds. obtained from I and these reagents. Refluxing II and Cu dust in cymene for 3 hrs. gives 3,3'-diphenylbiphthalidyl. With AlCl3 in C6H6 II gives thiodiphenylphthalide, m. 162 Deg, III being recovered from the mother liquors. P2S5 gives dithiodi(phenylphthalide). Addn. of 50 g. P2S5 to 50 g. I in boiling xylene and refluxing 4 hrs. gives, after a complex purification, 7 g. of 2-phenyl-3,4-benzothiophene (IV), reddish brown, m. 236-7 Deg, which is not hydrolyzed by EtOH-NaOH and is unchanged by heating with Cu in Ph2 or by Na or HgO in xylene. o-(p-MeC6H4CO)C6H4CO2H gives 30% of 3,3'-di(p-tolyl)diphthalidyl sulfide, m. 212 Deg; the acid chloride and H2S give 60%; (p-chlorophenyl)analog, m. 232 Deg, 40% with P2S5 or 68% with the acid chloride and H2S. p-Tolyl analog of IV, m. 217 Deg, 28%; p-chlorophenyl analog, m. 241-2 Deg, 12%. p-Chlorophenylphthalide, m. 124 Deg, 50% yield. [on SciFinder (R)]

 

Albert, W. C. and A. Lowy (1939). "The electrochemical reduction of furfural." Trans. Electrochem. Soc. 75: 8 pp.

            Furfural has been reduced electrochemically to give a new compd., hydrofuroin, with its isomer, isohydrofuroin, C4H3O.CHOH.CHOH.C4H3O. Small amts. of furfuryl alc. and some resin are also formed. The effect of various factors such as cathode material, c. d., temp. and pH of the catholyte has been studied, and optimum conditions for obtaining yields of hydrofuroins up to 63% were obtained at a Pb cathode in a 10% KH2PO4 soln., at a c. d. of 0.005 amp./sq. cm. [on SciFinder (R)]

 

Van Meter, C. T., J. A. Bianculli, et al. (1940). "p-(p-Aminophenyl)benzenesulfonamide and derivatives. I." J. Am. Chem. Soc. 62: 3146-8.

            p-PhC6H4NHAc (I) (40 g.), added during 1 hr. to 200 cc. ClSO3H at a temp. below 5 Deg and crystn. from PhMe, gives 25 g. of p-(p-acetaminophenyl)benzenesulfonyl chloride (II), decomps. above 110 Deg; II (16 g.) and 32 g. (NH4)2CO3 in 200 cc. concd. NH4OH, stirred for 1 hr. at room temp. and 2 hrs. at 40 Deg, give 12 g. of the amide (III), m. 289 Deg (decompn.); this also results by passing NH3 into II in PhMe. Refluxing 6 g. III with 100 cc. H2O and 100 cc. concd. HCl for 3 hrs. and addn. of concd. NH4OH give 3 g. of p-(p-aminophenyl)benzenesulfonamide (IV), m. 261 Deg (decompn.); soly. at 20 Deg, 1 g. in 60 cc. Me2CO, 300 cc. MeOH, 500 cc. EtOH, 2000 cc. ether and 5000 cc. CHCl3; 1 g. dissolves in 1100 cc. boiling H2O and 125 cc. boiling EtOH. The MeOH and EtOH solns. exhibit a blue fluorescence. The diazo compd. gives a reddish orange azo compd. with alk. beta -C10H7OH. The HCl salt of IV forms glistening plates from 20% HCl, and regenerates IV with NH4OH. IV in NaOH gives the amorphous Na deriv., p-H2NC6H4C6H4SO2NHNa-p. I (20 g.), treated as above but without isolation and purification of intermediates, yields 14 g. of IV. The configuration of IV was detd. by the following series of reactions: I and ClSO3H gives p-AcNHC6H4C6H4SO2Cl-p, which, refluxed with 20% HCl for 5 hrs., gives p-H2NC6H4C6H4SO3H-p (V). With HNO2 V gives p-HOC6H4C6H4SO3H-p, fusion of which with NaOH yields (p-HOC6H4)2. [on SciFinder (R)]

 

Lowy, A., S. Swann, Jr., et al. (1940). "Review of electro.ovrddot.organic chemistry 1939." Trans. Electrochem. Soc. 77: 45-8.

 

Lowstuter, W. R. and A. Lowy (1940). "The electrochemical oxidation of 1-hexanol." Trans. Electrochem. Soc. 77: 8 pp.

            1-Hexanol was oxidized electrochemically, giving caproic acid and hexyl caproate. Besides these main products, small amts. of CO2, CO and a high-boiling residue were obtained. Hexaldehyde and decane were not found to be present in the products of the electrolysis. A study was made of the various factors influencing the oxidation, such as anode material, temp., c.d., solvent and alc. concn. of the anolyte for the electrolytic oxidation of 1-hexanol. The best results were obtained with: (a) 5% H2SO4 as electrolyte; (b) c. d., 1.1 amp./sq. dm.; (c) temp. 12 Deg; (d) electrolytically prepd. PbO2 anode; (e) anolyte concn., 82 g. 1-hexanol in 800 cc. of electrolyte; current efficiency, 59.9% calcd. only as oxidation to caproic acid. [on SciFinder (R)]

 

Van Meter, C. T. and A. Lowy (1941). "p-(p-Aminophenyl)benzenesulfonamide and derivatives. II." J. Am. Chem. Soc. 63: 1330-1.

            cf. C. A. 35, 87.8. The following general method was used for the following compds.: p-AcNHC6H4C6H4SO2Cl-p (5 g.) in 180 cc. Me2CO and 5 cc. C5H5N and 1.6 g. PhNH2 in 20 cc. Me2CO, heated to 50 Deg and allowed to stand at room temp. for 24 hrs., the reaction product dild. with 3 vols. of cold H2O and the ppt. washed free of C5H5N, give 86% of the Ac deriv. of I, m. 237 Deg; refluxing 1 g. with 30 cc. EtOH and 10 cc. concd. HCl gives 80% of p-(p-aminophenyl)-N-phenylbenzenesulfonamide (I), m. 186 Deg; the N-benzyl-amide, m. 184 Deg, results in 80% yield from the Ac deriv., m. 208 Deg (75% yield); the N-cyclohexylamide, m. 219 Deg results in 89% yield from the Ac deriv., m. 244 Deg (76% yield); the N-p-xenylamide, m. 216 Deg, is formed in 80% yield from the Ac deriv., m. 250 Deg (70% yield); N4-[p-(p-aminophenyl)phenylsulfonyl]sulfanilamide, m. 252 Deg (decompn.), in 72% yield from the Ac deriv., m. 274 Deg (80% yield); 4-[p-(p-aminophenyl)phenylsulfonamido]biphenyl-4'-sulfonamide, m. 277 Deg (decompn.), results in 87% yield from the Ac deriv., m. 299 Deg (90% yield). [on SciFinder (R)]

 

Epelberg, J. and A. Lowy (1941). "Alkylation of biphenyl using alkayl sulfates in Friedel-Crafts syntheses." J. Am. Chem. Soc. 63: 101-3.

            Ph2 (308 g.) and 680 cc. o-C6H4Cl2, treated with 300 g. AlCl3, cooled to 5-8 Deg, then treated dropwise during 4.5 hrs. with 462 g. Et2SO4, the ice bath removed after 10 hrs., the reaction allowed to proceed at 24 Deg for 4 hrs. and the product decompd. with HCl, give 363 g. of an oil, sepd. by distn. into 78 cc. of EtC6H4Ph, b20 160-4 Deg, and 123 cc. di-Et derivs., b20 181-5 Deg. Similarly 308 g. Ph2 with Me2SO4 gives 80 cc. of MeC6H4Ph, b20 149-51 Deg, and 68 cc. of di-Me derivs., b20 163-7 Deg. Oxidation of the monoalkyl derivs. indicates that they are mixts. of the m- and p-isomers, with the m-isomer predominating. The dialkyl derivs. are also mixts. of isomers, oxidation giving a mixt. of the 4,4'-, 3,4'- and 2,3'-biphenyldicarboxylic acids, sepd. as the di-Me esters. [on SciFinder (R)]

 

Lowy, A. and et al. (1941). "Report of Committee on Organic Electrochemistry." Trans. Electrochem. Soc. 79: 28-9.

            cf. C. A. 34, 3994.2. A review emphasizing the high spots in the 1940 developments. [on SciFinder (R)]

 

Fontaine, T. D., H. S. Olcott, et al. (1942). "Amino acid composition of cottonseed globulin preparations." J. Ind. Eng. Chem. (Washington, D. C.) 34: 116-18.

            The globulins were prepd. by alkali extn. followed by acid pptn. and also by salt extn. followed by diln. About 80% of the amino acids were detd. They are arginine 11.5-13.6, histidine 2.8-3.2, lysine 4.9-5.4, cystine 1.1, methionine 1.7-3.2, phenylalanine 8.1-9.1, tyrosine 3.5, tryptophan 1.3-1.5, serine 2.9, threonine 2.9, leucine 8.4-9.0, isoleucine 2.2-2.5, valine 6.1-7.5 and dicarboxylic acids (estd. by amide N detn.) 17.5-19.7%. [on SciFinder (R)]

 

Bianculli, J.A. and Lowy, A (1942) “p-(p-aminophenyl) benzenesulfonamide and Derivatives.” Pittsburgh University. Graduate School. Abstracts of Theses. 17:43-48

 

Miron, Simon and Lowy, A. (1942) “Preparation of bis-(Substituted Arloxy) Methanes.” Pittsburgh. University. Graduate School. Abstracts of Theses. 17:294-300

 

Abrams, Ellis and Lowy, A. (1943) “Derivatives of Metadiphenylbenzene.” Pittsburgh. University. Graduate School. Abstracts of Theses. 18:7-15

 

Morgan, M. S., R. S. Tipson, et al. (1944). "Some derivatives of cis-3,6-endomethylene-Delta 4-tetrahydrophthalic acid." J. Am. Chem. Soc. 66: 404-7.

            cis-3,6-Endomethylene-Delta 4-tetrahydrophthalic anhydride (I) (250 g.) in 500 cc. dry dioxane and 30 g. Raney Ni, shaken in an atm. of H at 45 Deg and an initial pressure of 2050 lb./sq. in. for 90 min. gives 97% of the hexahydro deriv. (II), m. 167.5-8 Deg. The potentiometric titration curves of the corresponding acids detd. by a glass-electrode titration assembly, are given and compared with curves for (CH2CO2H)2 and o-C6H4(CO2H)2. I, refluxed with abs. MeOH for 90 min., give a quant. yield of the mono-Me ester, m. 76-8.5 Deg; that of II m. 77-9 Deg. I and MeOH with p-MeC6H4SO3H, boiled 10 hrs., give 69% of the di-Me ester, b9 129-30 Deg, d214 1.164, n20D 1.4852; this is unchanged on standing in abs. MeOH satd. with dry NH3 at 0 Deg when kept at 0 Deg for 3 days. Di-Et ester of I, b8 138-40 Deg, d214 1.100, n20D 1.4761, 59%; di-Bu ester, b8 174-6.6 Deg, d214 1.044, n20D 1.4721, 85%. I (16.4 g.) and 18 g. (NH4)2CO3, heated slowly to 200 Deg, give 7.3 g. of the imide, m. 186.5-7 Deg; passage of dry NH3 over molten I at 170 Deg gives 84% of the imide; the imide of II m. 174-5.5 Deg and is best crystd. by boiling in dil. NH4OH (2:1) for 30 min. and cooling to 5 Deg. I (8.2 g.) and 5 ml. PhNH2 in 60 ml. C6H6 give the N-phenylimide, m. 144 Deg; II (8.3 g.) in 25 ml. CHCl3, treated slowly with 4.4 ml. of PhNH2, gives 12 g. of a product m. 175-6 Deg (decompn.); this may be the anilic acid but recrystn. from AcOH or EtOH gives the N-phenylimide, m. 152-3 Deg; an attempt to isolate the Na salt (addn. of 10% Na2CO3 to the acid in 50% EtOH at 25 Deg) gives the anil. The N-p-tolylimide of I m. 156.5-7 Deg. The imides and PhCH2Cl in EtONa, refluxed 1 hr., give the N-benzylimides of I, m. 82.5-3.5 Deg, and of II, 101-3 Deg. I and II (0.05 mole), added in small portions to 20 ml. concd. NH4OH and intimately ground, with final addn. of 10 ml. EtOH, give the monoamide NH4 salt of I, m. 172 Deg (decompn.), and of II, m. 177 Deg (decompn.). Addn. of concd. HCl to the salt suspended in H2O at 0-5 Deg gives the amidic acid of I, m. 136 Deg (decompn.) and of II, m. 165-6 Deg (decompn.); the acids were too unstable to purify; soln. of the acids by boiling in CO2-free H2O for 40 min. and evapn. to dryness in a vacuum desiccator give the NH4 acid salts: I, m. 148 Deg (decompn.); II, m. 149-50 Deg (decompn.). The acid from I and NH4OH give the di-NH4 salt of indefinite m. p. The imide of I in concd. NH4OH, refluxed 20 min., gives the unchanged imide and not the diamide. II and C6H6 with AlCl3, heated at 45 Deg for 30 min., give 87% of 3-benzoylnorcamphane-2-carboxylic acid, m. 170-3 Deg; this is not cyclized to an anthraquinone with concd. H2SO4. I did not react in this manner. [on SciFinder (R)]

 

Kapff, S. F., J. R. Bowman, et al. (1945). "Correlation of chemical constitution and oxidation susceptibility of lubricating-oil components." J. Inst. Pet. 31: 453-74.

            Development of nonvolatile acidity and increase of viscosity are taken to be indexes of the susceptibility of a petroleum oil to oxidation. In order to study the subject of oxidation susceptibility, 12 l. of a Pennsylvania lubricating oil stock was sepd. into fractions by distg. under high vacuum in a pot still and the residues in a mol. still. The final distillate fractions were each further subdivided by solvent extn. into about 10 fractions. There proved to be no overlap of properties between successive exts. The final 150 exts. were examd. as to their chem. character by Waterman analyses and readiness to oxidize. A refined lubricating oil was subjected to the same treatment. One-g. samples in small test tubes were held at 160 Deg for 96 hrs. for the acidity tests; for the tests of increase of viscosity the temp. was 155 Deg. It proved to be unnecessary to bubble air through the samples. The nonvolatile acidity was detd. by titrating 0.05 g. of oil dissolved in tert-BuOH with a 0.005 N soln. of N(CH3)4OH in iso-PrOH, with thymolphthalein as the indicator. The fractions rich in naphthenes were most stable, the aromatic hydrocarbons showed somewhat greater tendency to develop nonvolatile acidity, the fractions rich in paraffins, much greater oxidizability. On the basis of increase of viscosity, the components rich in naphthenes, again, showed the highest stability but here paraffinic fractions ranked 2nd and fractions rich in aromatic hydrocarbons were least stable. There is some reason to believe that the most paraffinic components in the oil are poly-n-alkylcycloparaffins. If this is true, it may be in some way related to the fact that there are no isoparaffins in lubricating oils. [on SciFinder (R)]

 

Miron, S. and A. Lowy (1951). "Bis(substituted phenoxy)methanes." J. Am. Chem. Soc. 73: 1872-3.

            Refluxing the Na salt of the phenol, CH2I2, and iso-AmOH yielded the substituted phenoxy methanes, (RC6H4O)2CH2, for which reflux period (hrs.), crystn. solvent, yield (%), and m.p. are: p-Ph, 2, Me2CO, 63, 180.2-80.9 Deg; o-Ph, 3, 70% EtOH, 54, 104.0-48. Deg; p-tert-Am, - , 64, b1 185-6 Deg, m. 41.5-1.9 Deg; o-cyclohexyl, 5, 85% EtOH, 53, 95.9-6.6 Deg; p-benzyl, 6, EtOH, 59, 74.8-5.4 Deg; p-Cl, 6, petr. ether, 62, 69.7-70.2 Deg o-Cl, 6, petr. ether, 57, 87.8-8.6 Deg; 2,4-Cl[(2,4-ClC6H3O)2CH2], 4.5, 80% EtOH, 74, 100.4-0.8 Deg; p-Br, 3, 80% EtOH, 62, 74.0-4.5 Deg; p-formyl, 12, 50% EtOH, 60, 84-5 Deg. [on SciFinder (R)]