Patented Nov. 21, 1933 1935,712

UNITED STATES PATENT office 1935,712. KETONEHYDRAzoNES, AND PROCEss oF MAKING THE SAME Ernst Herdieckerhoff, opladen, and Fritz Ballauf, Elberfeld, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a cor poration of Delaware No Drawing. Application August 20, 1930, Serial No. 476,714, and in Germany March 2, 1928 8 Claims. (CI. 260-129) The present invention relates to a process of the free phenylhydrazine-Sulfonic acid and neu preparing ketone hydrazones of phenylhydra tralizing the aqueous suspension thereof by the Zine-Sulfonic acids and to the new products ob addition of alkali, there may of course be started tainable thereby, more particularly it relates to with an alkali metal salt of phenylhydrazine-sul 5 Compounds of the probable general formula: fonic acid, all methods referred to above falling 55 within the scope of the invention. Instead of using the alkali metal compounds of the phenyl R hydrazine Sulfonic acids, there may be worked NH-N=c? with other water Soluble salts, such as the mag O nesium SaltS. 60 Yo.. Our new ketone hydrazones are in the form of their alkali metal Salts generally colorleSS Wherein one ac stands for a sulfonic acid group, crystalline substances, easily soluble in water the other ac's stand for hydrogen, R1 stands for and are valuable intermediate products in the 15 methyl or a radical of the benzene series, or Ri manufacture of dyestuffs. 65 and -CH3 jointly stand for the n-pentamethyl The invention is illustrated by the following ene radical. examples, without being limited thereto: When the o-, m- or p-phenylhydrazine-Sul Eacd.imple i.-45 grams of phenyihydrazine-mi fonic acids are heated in aqueous solution or in sulfonic acid (pure) are made into a suspension 20 a water miscible inert organic solvent, such as with 100 ccs. of water and heated with just suffi- to alcohol, with the about molecular quantity of cient caustic Soda to produce alkaline reaction. acetone, acetophenone or a Bz-substitution prod The Sulfonic acid is then dissolved as the Sodium uct thereof and cyclohexanone, no reaction worth salt. 35-40 grams of acetophenone are added to mentioning occurs. When the solution is ren this solution, which is then neutralized with dered alkaline (to phenol-phthaleine), for exam thorough shaking by means of hydrochloric acid 5 ple, with alkali hydroxide or sodium carbonate, until the alkaline reaction to litmus just disap then also formation of hydrazone does not occur. pears. On heating the reaction of the phenyl Now we have found that the reaction with for hydrazine-sulfonic acid with the acetophenone mation of hydrazone proceeds Smoothly by neu then takes place almost instantaneously. The 30 tralizing the alkaline solution of the phenyl solution is heated for several hours longer to SO hydrazine-o-, -m- or -p-sulfonic acid by means 95° C. On cooling the hydrazone of the formula: of any desired acid, for example, dilute hydro chloric acid or Sulfuric acid, until red litmus pa . . . . . CH, ! per no longer ShoWS any alkaline reaction, and this Solution in admixture With the ketone is heated to temperatures between about 50 and - " " ( ) 85 100° C.; then the reaction commences innedi Crystallizes out in Satisfactory yield in the form ately, and the ketone present as an oil in the of the sodium salt. aqueous Solution disappears. On cooling, the Eacample 2-45 grams of phenylhydrazine-m- 40 hydrazone Separates in beautiful crystals in form Sulfonic acid are treated with 40-45 grams of 90 of the alkali metal Salt of the Sulfonic acid. The p-methylacetophenone as described in Example same result is obtained by preparing an aqueous Suspension of the phenylhydrazine-Sulfonic acid, 1. The ketone hydrazone of the formula: neutralizing slowly and carefully with an alkali CHs 45 until the point is reached at Which the acid reac tion has disappeared and red litmus is not yet { X-NH-N=c( 95 colored blue, adding an about equimolecular SO3 amount of the ketone and heating to about 50 crystallizes out in the form of its sodium salt in 100° C. The reaction immediately commences beautiful needles in almost quantitative yield. 50 and is soon complete. Instead of starting with Eacample 3-45 grams of phenylhydrazine-m-, 100 1,935,712 sulfonic acid are treated with 45 grams of p crystallizes out in the form of its sodium salt. chloroacetophenone as described in Example 1. Eacample 9-40 grams of phenylhydrazine-o- The ketone hydrazone of the formula: Sulfonic acid are treated with 25 grams of cyclo CH hexanone as described in Example 7.). The ke /... tone hydraZOne of the following formula: 80 CH-CH soil \{ D-O) - CE crystallizes out in the form of its sodium salt; CH-CH, SO 0 the yield is likewise satisfactory. 85 Eacample 4-40 grams of phenylhydrazine-m- crystallizes out in the form of its sodium salt. sulfonic acid are treated with 15-20 grams of We claim: acetone as described in Example 1. As acetone 1. The process which comprises heating about has a lower boiling point than water the reaction . equimolecular proportions of a compound of the 5 can in this case be carried out at a lower tem group consisting of alkali metal and magnesium perature. On account of the solubility of the So Salts of a phenylhydrazine -sulfonic acid and a dium salt of the desired hydrazone it is desirable ketOne of the group consisting of acetone, ace to evaporate the solution somewhat when the re tophenone, B2-chlorine- and -methyl-substitu action is complete. The hydraZOne of the for tion products of acetophenone, and cyclohexa mula: none, in aqueous Solution neutrally reacting to 20 litmus with the addition of a water-miscible, inert CH3 Organic Solvent, at a temperature between about N 50° and about 100° C. { X-NH-N=0C CH3 2. The process which comprises heating about 25 $o H equimolecular proportions of the sodium salt of 300 then crystallizes out in the form of its sodium phenylhydrazine-m-sulfonic acid and a ketone salt with a satisfactory yield. of the group consisting of acetone, acetophenone, Eacample 5-40 grams of phenylhydrazine-p- BZ-chlorine- and -methyl-substitution products sulfonic acid are treated with 40 grams of p of acetophenone, and cyclohexanone, in aqueous 30 chloroacetophenone as described in Example 1. Solution neutrally reacting to litmus, at a ten- 105 On account of the comparatively greater solu perature between about 50 and about 100° C. bility of the p-sulfonic acid derivatives it is de 3. The process which comprises heating about sirable to add a little sodium chloride to the hot equimolecular proportions of the sodium salt of sodium hydrazone solution, when the reaction is phenylhydrazine-m-Sulfonic acid and aceto 35 complete. The ketone hydrazone of the formula: phenone in aqueous solution neutrally reacting 11. to litmus, at a temperature of 95° C. CH3 4. Ketone hydrazones of the general formula: Hosk)-NH-N=C v 40 11. crystallizes in the form of its sodium salt. The yield is considerably improved; it amounts to about 80-90% of the theoretical. : Eacample 6-40 grams of phenylhydrazine-p- wherein one a stands for a sulfonic acid group, 12 45 sulfonic acid are treated with 20 grams of acetone the other ac's stand for hydrogen, R1 stands for as described in Example 4. The ketone hydra methyl or a radical of the benzene series, or -R1 Zone of the formula: - - and -CH3 jointly stand for the n-pentamethylene radical, being in the form of their alkali metal salts generally colorless crystalline substances, 125 Hos-O-NH-N=c( : easily Soluble in water and being valuable inter - W CE . . . mediate products in the manufacture of dye crystallizes out in the form of its sodium salt in Stuffs. . beautiful needles. 5. Ketone hydrazones of the general formula: Eacample 7-45 grams of phenylhydrazine-o- 13 55 Sulfonic acid are treated with 35-40 grams of - R1 acetophenone as described in Example 1. The ketone hydrazone of the following formula: CH

60 wherein R1 stands for methyl or a radical of the 85. benzene series, or -R1 and -CH3 jointly stand for the n-pentamethylene radical, being in the form st (OCE of their alkali metal Salts generally colorless SO3 Crystalline Substances, easily soluble in Water 65 crystallizes out in the form of its sodium salt. and being valuable intermediate products in the 4f Eacample 8-40 grams of phenylhydrazine-o- manufacture of dyestuffs. sulfonic acid are treated with 15 grams of acetone 6. The ketone hydrazone of the following as described in Example 7. The ketone hydra formula: zone of the following formula: . . . . "A 70 (DuskSOH C 45 being in form of its sodium salt a colorless crystalline substance, easily soluble in water and 150 1,985,712 3 being a valuable intermediate product in the 8. The ketone hydrazone of the following manufacture of dyestuffs. formula: 7. The ketone hydrazone of the following C formula: . . OH Hos-K C-NH-N=c(N being in form of its sodium salt a colorless CE Crystalline Substance, easily soluble in water and being in form of its sodium salt a colorless being a valuable intermediate product in the O crystalline Substance, easily soluble in water and manufacture of dyestuffs. 85 being a valuable intermediate product in the - ERNIST HEROECKERHOFF, manufacture of dyestuffs. ERITZ BALLAUF,

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