PATENT OFFICE 2,094,224 , PYRENE 3,5§8,10-TET‘RA-SULPHONIC ACID and DERIVATIVES THEREOF Ernst Tietze, Cologne-On-The-Rhine, and Otto *' Bayer, Leverkusen-I

Patented Sept. 28, 1937 2,094,224

UNITED STATES PATENT OFFICE 2,094,224 , PYRENE 3,5§8,10-TET‘RA-SULPHONIC ACID AND DERIVATIVES THEREOF Ernst Tietze, Cologne-on-the-Rhine, and Otto *' Bayer, Leverkusen-I. G.-Werk, Germany, as signors to General Aniline Works, Inc., New ‘York, N. Y., a. corporation of Delaware ‘ No Drawing. Application May 1'7, 1935, Serial No. 22,108. In Germany May 25, 1934 4 Claims. (01. 260-155) The present invention relates to new pyrene powdered pyrene are introduced‘within 1/2 hour compounds, more particularly it relates to com into 440 parts by weight of sulphuric acid mono pounds which may be represented by the prob hydrate at a temperature of 10-20° C. While able general formula: cooling, at 20° C., 400 parts by weight of sulphuric acid of an anhydride-content of 65% strength 5 are added, and the reaction mass still contains excess sulphuric acid anhydride. For working up, the whole is poured onto ice at 20° C'., and the aqueous-solution is salted out with 22% of sodium chloride. The crude pyrene-tetrasulphonic acid 10‘ 10 (sodium compound) is a greyish-green powder Which can be easily puri?ed by redissolving. The pure, yellow sodium, salt is easily soluble in water; the, colorless solution possesses a characteristic \/ Weak violet ?uorescence which is increased to a 15' 15 wherein the X’s and the Y’s stand for the high degree in ultraviolet light. sulphonic acid or the hydroxy group in such a By adding 100 parts by weight of kieselguhr to manner that the TS can only stand for different the monohydrate before introducing the pyrene substituents in case the .X’s stand for the same into the same the yield of pyrene-tetrasodium sulphonate is increased. 20 substituents. 7 Those compounds of the above-identi?ed Example '2.—71 parts by weight of calcined formula in which all the four substituents stand sodium sulphate are dissolved in 440 parts by for the sulphonic acid group are obtainable by Weight of sulphuric acid monohydrate, and into exhaustively sulphonating pyrene. Instead of this solution there are introduced at a tempera starting with pyrene there can be used, of course, ture between about 10° and about 20° C. 100 parts 25 the pyrene-3-monosulphonic acid or the pyrene by weight of ?nely powdered pyrene in the course 3,8- or -3,10- disulphonic acids respectively, or a of 1/2 hour, while well stirring. After a short salt thereof, which compounds on further time the reaction mass becomes pasty, but on sulphonating likewise yield the tetrasulphonic stirring for a prolonged time again becomes acid of the above-identi?ed formula. liquid. After, 4-5 hours 400 parts by weight of 30 Those compounds of the above-identi?ed sulphuric acid of an SOs-content of 65% strength formula in which the substituents wholly or par are introduced in such a manner that the tem tially stand for hydroxy groups are obtainable by perature does not exceed 30° C. Thereby the successively substituting in the 3,5,8,l0~tetra sulphonation mixture again becomes completely 3.5 sulphonic acid the sulphonic acid groups by mobile. After standing for 12 hours the mass is 35 V hydroxy groups. This can be achieved by treat poured onto ice, limed with chalk, the calcium ing the tetrasulphonic acid with strongly alkaline salt of the pyrene-tetrasulphonic acid is trans~ reacting agents, such as caustic alkalies. It is formed into' the sodium salt by adding sodium to be mentioned that under moderate conditions carbonate, the calcium carbonate formed is 40 only one sulphonic acid group is‘substituted by ?ltered‘, the ?ltrate is concentrated by evapora a hydroxy group, while, when strengthening the tion, and the sodium~salt of the pyrene~tetra conditions of reaction, i. e. raising the tempera sulphonic acid is separated by salting out. It is tureand/orthe concentration of the alkali, the obtained in a fairly pure form and can be com pletely puri?ed by once re-dissolving and sepa other sulphonic acid groups successively can be 45 45 replaced by hydroxy groups, the exact conditions rating. of working being disclosed in the examples. Example 3.—924 parts by weight of the sodium The new pyrene compounds partially exert re salt of pyrene-3-sulphonic acid are introduced markable and surprising properties. Thus, some into 2650 parts by Weight of sulphuric acid mono of them are dyestuffs dyeing W001 from an acid hydrate at 10-20° C. in the course of 1/2 hour. bath, or they are valuable intermediates for the While cooling, there are introduced in the course manufacture of dyestuffs, of photographic sensi of one hour at 20° C, 2400 parts by weight of tizers and of synthetic drugs. , > sulphuric acid of an SOs-content of 65% strength, The invention is illustrated by the following and thereupon stirring is continued for further examples, without being limited thereto: 15 hours at 25° C. The thin paste is poured onto 55 55 Example 1.—101 parts by weight of ?nely ice, limed with chalk and the calcium salt of the 2 2,094,224 pyrene-tetrasulphonic acid is transformed into by acidifying with acetic acid, the crude 3,5,23,10 the sodium salt by adding sodium carbonate. tetrahydroxypyrene is precipitated. For purify The reaction mixture is ?ltered, and from the ing the ?ltered crude product is extracted with ?ltrate the sodium salt of the pyrene-tetra methyl or ethyl alcohol or glacial acetic acid, the sulphonic acid is salted out with common salt at extracts are ?ltered with the addition of char 90° C. After one day’s stirring at room tempera coal and diluted with water, whereby the tetra ture, the sodium salt is ?ltered with suction, hydroxypyrene crystallizes in the form of large pressed and dried at 100° C. Thus is obtained V ‘lustrous lea?ets. The compound melts at 234 the pure tetrasodium salt of pyrene-3,5,8,10— ' 236° C. with decomposition. By treating with tetrasulphonic acid. Yield 80% of theory. oxidizing agents it can easily be transformed into 10 If, after pouring onto ice, the sodium salt is the naphthalene-1,4,5,8-tetracarboxylic acid. salted out with sodium sulphate or sodium chlo The tetrahydroxypyrene possesses an excellent ride from the aqueous sulphuric acid solution, affinity for animal and cellulosic ?bres and yields there is also obtained a pure product, but the out on after-treating the dyeings- with chromate dark put is decreased by about 5-8%. ' ‘ ' brown shades of very good fastness properties. 15 Example 4.-120 parts by Weight of pyrene Example 7 .—By substituting in Example 6 the 3,5,8,10-tetrasodium sulphonate arerdissolved in aqueous caustic soda of 25% strength by milk of 400 parts by weight of water and after the ad lime which has been prepared by slaking 450 dition of '75 parts by weight of caustic soda re parts by weight of quicklime with 1800 parts by 20 ?uxed for 24 hours. The reaction mass is weight of water, and heating the reaction mass in 20 Worked up by acidifying with formic acid and a rotary iron autoclave for 12 hours at 240-250° salting out with common salt. By once recrys 0., there is likewise obtained the 3,5,8,10-tetra tallizing from dilute aqueous sodium chloride so hydroxypyrene of the melting point 234-236“ C. lution the 3-hydroxypyrene-5,8,10-tri-sodium By exhaustively methylating with dimethyl sul sulphonate is obtained in the form of ?ne yellow. phate in alkaline solution, there is obtained the needles. The neutral or alkaline solutions of the 3,5,8,IO-tetramethoxypyrene of melting point sodium salt ?uoresce with a strong green colora I'll-173° C. tion; the acid solution, especially the'aqueous Example 8.—61 parts by weight of pyrene alcoholic acid solution, ?uoresces with an intense 3,5,8,10-tetrasodium sulphonate are heated in a 30 blue coloration. The hydroxy-trisulphonic acid rotary iron autoclave with 800 parts by weight of 30 dyes wool from an acid bath, and the dyeing aqueous ammonia of 20% strength for 18 hours yields on after-treating with basic substances, at 200-210“ C. The reaction mass is worked up such as triethanolamine, hexahydroaniline, ba by distilling oif in vacuum the bulk of the am rium hydroxide and the like, powerful greenish 35 monia and salting out with sodium chloride the yellow shades of an extraordinary clarity. sodium salt of the hydroxypyrene-trisulphonic 3.5 Example 5.-—60 parts by weight of pyrene acid. The compound obtained is identical with 3,5,8,10-sodium tetrasulphonate are stirred in that obtained in accordance with Examples. a copper crucible into 120 parts by weight of 50% The mother liquor contains as by-product 3-am caustic soda lye at 130° C. and fused for 30 min inopyrene-5,8,IO-trisulphonic acid. utes at 130-140°'C. The melt is dissolved in We claim: 40 water, acidi?ed with formic acid and salted out 1. Pyrene compounds of the general formula: ‘with sodium chloride. The crude product ob— tained is puri?ed by recrystallizing from water. Thus are obtained yellowish-brown compact crys 45 tals of a dihydroxypyrenedisulphonic acid having 45 a good solubility in water. The solutions of the dihydroxypyrene-disodium sulphonate fluoresce in the case of a neutral or alkaline reaction with an intense green, with an acid reaction with a 50 Vivid blue coloration. The dihydroxypyrene-di 50 sulphonic acid possesses an excellent a?inity for animal ?bres. The unsightly direct coloration yields on after-treating with chromate clear full wherein the X’s and Y’s stand for the sulphonic dark brown shades of excellent fastness proper acid or the hydroxy group in such a manner that 55 ties. ' . the Y’s can only stand for different substituents Example 6.--366 parts by weight of pyrene in case the X’s stand for the same substituents. 3,5,8,10—tetrasodium sulphonate are fused in a 2. Pyrene-3,5,8,l0-tetrasulphonic acid yielding rotary iron autoclave with 1440 parts by weight colorless water soluble alkali metal sats.. of aqueous caustic soda lye of 25% strength for 3. 3,5-dihydroxypyrene-8,lo-disulphonic acid. 12 hours at 240-2500 C., until the green ?uores 4, 3,5,8,IO-tetrahydroxypyrene. 602 cence of a test portion diluted with water has disappeared. To the dark melt there is added ERNST TIETZE. a small quantity of sodium hydrosulphite, and OTTO BAYER.