Патент USA US2127107код для вставки
2,127,107 Patented Aug. 16, 1938 UNlTED STATES PATENT OFFICE . 72,127,107 PROCESS OF ‘PRODUCING’. coERoxENoL ESTERS ‘ Thomas A. Cassidy, Brooklyn, N. Y., a's'signor to Wilmot and Cassidy, Inc., Brooklyn, vN. Y., a corporation of New York No Drawing. Original application July 24,1934, Serial No. 736,631. Divided and ‘this applica tion October 3, 1936, Serial No. 103,911 8 Claims. (01. 260-335) This application for patent is a division of an in and impart ?uorescence thereto, as above application ?led by me July 24, 1934, Serial No. stated, but that vthey possess the other qualities, 736,631, which is a continuation in part of an above enumerated, necessary to render their use for this'purpose commercially practicable. application for patent ?led by me August‘ 23, vi I, have, ‘for example, found that dimethyl 6,12-‘ v~5 1932, Serial No. 630,087. ‘ ' The present invention relates to a process for coeroxenolaceta'te, when produced by the process producing ?uorescent dyes soluble in high boiling‘ herein-afterdescribed, ‘meets all the most exacting aliphatic and aromatic hydrocarbons, particularly However, known processes for producing or-_ lubricating oil, and more particularly to certain dyes of the heterocyclic group containing oxygen ganic Compounds of the coeroxene class do noti‘lio produce these compounds, including the speci?c in the ring. requirements. ' Y > compound just above mentioned,’ in a form en In marketing petroleum products such as motor fuels, lubricating oils, etc, it is customary to add certain dyes to these products in order that the purchasers may distinguish between the different tirelyacceptable for addition to lubricating oils. The present invention comprises an improved.‘ ‘method of producing these compounds, par- “r5 ti‘cularly applicable to the production of 6,12 brands. In some cases several manufacturers use the same color or different shades of the same dimethyl coeroxenol acetate and other substituted coeroxenol esters, whereby a ‘high yield of the compound may be produced in its purest state color, thereby making it difficult for the pur chaser to know whether or not he is getting the products he orders. The producers, who are and in a form which renders its use as an addi-ii‘g’o marketing arti?cially colored products, are loath tion to lubricating oils highly efficient to produce to change the colors of their products, and in some cases‘it is impracticable to do, as certain the desired green ?uorescence and ineffective to impart to the oil any undesirable characteristics. 1 In manufacturing the improved product I pro colors are now Widely used to designate certain 25 qualities. Again,‘it is not desirable to color cer tain petroleum products, as such coloring would destroy their sales value, the products being graded by their natural colors. ' 7 One vway to distinguish from one anotherdif ferent brands having the same color is to im part fluorescence of different hues to these prod ceed as follows, it being understood that those“2 skilled in the art may deviate, without the exer cise‘ of invention, from the precise details of the prescribed steps, vwhich are preferable rather than mandatory. It will also‘ be understood that > ‘the described speci?c. process is intended for the 30 production of 6,12-dimethyl coeroxenol» acetate vand that obvious modifications of the process are ucts, thereby giving them distinguishing char necessary for the production of other organic color compounds of the coeroxene class. acteristics without substantially altering ' their colors as viewed by transmitted light. case of lubricating In the oils, imparting a green fluorescence actually enhances the value. ' "To a molten mass comprising 220 pounds of; 35 1 paracresol (or a meta or para'substituted phenol) There are many known dyestuffs which'will impart fluorescence to valcohol ‘and water and and 150 pounds of phth-alic anhydride are added 90 pounds of concentrated sulfuric acid or other condensing agent such as phosphorous pentoxidek v 740 fluorescence to, lighter petroleum hydrocarbons; zinc chloride or stannic chloride. 1 The mix is then heated with agitation to about but few, if any, are known to be soluble in, and adapted to impart ?uorescence to, lubricating oils ' 160° C. and maintained at that temperature for and which at the same time are known to be “about ?ve hours. At the conclusion of this heat stable to light, heat and storage-to be unaffected . ing step the mass is dumped into (say) 300’ some are known to be soluble in, and impart by metals, to be'completely neutral in reaction and not to impart to such oils any qualities which would make them commercially impracticable. Certain dyestuffs'of the heterocyclic group con - gallons of water to which is added 100 pounds of 5'45 taining oxygen in the ring which are free from soluble material which it then contains is sepa rated by iiltration and dried. This insoluble ma-'- ‘50 nitrogen and sulphur, namely, organic com pounds of the coeroxene class (by which term I mean to include coeroxene, its derivatives and caustic soda or any other strong base such as caustic vpotash or'lithium hydroxide. This mix is then boiled for about one hour and the in terial is an intermediate product dimethyl 2,7. fluoran and amounts to 200lbs. . 100 pounds of the dimethyl 2,7-?uoran (or any substitution products) I have found to be soluble in and effective to impart ?uorescence of‘ different ‘ di-substituted 2,7- or 3,6-?uoran produced by the procedure above described by or any obvious vari- 5'5 shades of green and of varying degrees of intens ity to both aliphatic and aromatic hydrocarbons. ation thereof) is added to 700 pounds of fuming So‘ far as I know, none of the dyestuifs of the sulfuric acid (oleum) at 20°-25° TC. and the mix class mentioned have ever been added to com- _ .is- continuously agitated for about eight hours, mercial lubricating oil.“ ‘When ‘added thereto I after which it is diluted by pouring into 1200 60 have found that'they are not only soluble there pounds of water to'which ‘has been added‘about $60 2 2,127,107 an equal weight of ice. The product is a sub? stituted coeroxonol ‘sulfate-speci?cally, follow eroxenol ester of high purity and yield and suit able for addition to lubricating oil to impart fluorescence thereto which comprises reducing a solution of dimethyl 6,12-coeroxonol sulphate.'_ 1 , substituted coeroxonol in an alkaline medium To this product is added 900 poundsof 28% containing an organic solvent soluble in water ammonia, 1800 pounds of ice and 1200 pounds of and that does not react with the subsequently ing the precise procedure above described, a red water, whereby the dimethyl 6,12-coeroxonol base is precipitated. It is of alight grey color. When dried the yield of the base is 95. pounds. - 10 added esterifying agent and then esterifying. 2, The process of producing dimethyl 6,12 coeroxenol acetate of high purity and yield which After the dimethyl 6,12-coeroxonol base is ob tained the‘ heterocyclic compound dimethyl c0 eroxene may be obtained‘ by reducing the base. This heterocyclic compound, its substitution prod ucts and derivatives, as well as its isomers and ' homologues, produce a green ?uorescence when dissolved in aliphatic or aromatichydrocarbons. For instance, dimethyl 6,12-coeroxenol, its isomers and homoiogues may be used as well as the acetates, benzoates, phthalates or any organic 20 acid ester, of dimethyl 6,12-coer0xenol and its isomers or homologues. Dimethyl 76,12_-c0 comprises reducing dimethyl 6,12-coeroxonol in 10 an alkaline medium containing an organic sol vent soluble in water and that does not react with acetic anhydride and then esterifying by addition of acetic anhydride. 3. The process of producing dimethyl 6,12 15 coeroxenol acetate of high purity and yield which comprises treating dimethyl 6,12-coeroxonol with pyridine, caustic alkali and zinc dust and ester— ifying by the addition of acetic anhyride. 4. The process of producing a substituted 20 coeroxenol ester of high purity and yield which ,eroxenol is not as stable to heat and light as are - comprises treating a di-substituted fluoran with dimethyl 6,12-coerox'ene and the derivatives and sulphuric acid and thereby producing a sub substitution products ofdimethyl 6,12-coeroxeno1 25 so that its use,v is not recommended when any of the other products herein mentioned are avail able. r in the knowledge of those skilled in the art to ob 30 tain the above-mentioned derivatives and sub stitution productsand also others not mentioned ‘which will impart a fluorescence to aliphatic and aromatic hydrocarbons. However, I believe it to be impossible, by the employment of any 35 known process, to secure a commercially econom~ ical yield or to secure a product of satisfactory purity, strength, color, or stability to heat or in not react with the subsequently added esterifying agent, and then esterifying to producethe sub~ stituted coeroxenol ester. 30 5. The process of producing a substituted co eroxenol ester of high purity and yield which comprises treating a di-substituted ?uoran with sulphuric acid and thereby producing a sub stituted coeroxonol sulphate, precipitating the 35 substituted coeroxonol base, reducing the coer oxonol base in an alkaline medium containing storage. The following procedure for obtaining the dimethyl 6,12-coeroxenol acetate mentioned pyridine and esterifying by the addition of acetic has been found to overcome all the objections in ample the dimethyl 6,12-coeroxonol base-is ob 6.'The process of producing dimethyl 6,12 coeroxenol acetate of high purity and yield which comprises treating dimethyl 2,7-?uoran with sul furic acid and thereby producing dimethyl 6,12 tained, 100 pounds ofthe same are mixed with coeroxonol sulphate, precipitating the dimethyl herent in known processes. . After the coeroxonol base—in the speci?c ex 45 400 pounds of water, 40 pounds of caustic soda or other strong base and 280 pounds of pyridine, or equivalents thereof, e. g., methyl pyridines (picolines), dimethyl vpyridenes (lutidines) or other organic solvents soluble in water that do not react with acetic anhydride, such as acetone and dioxan. The mixture is heated to 90° C. and agitated. “ _ Thereafter is added 30 pounds of ‘zinc dust or iron powder. The entire mixture is then agitated for about two hours at 90° C. and cooled to 30° C. after which there is added slowly a suitable acid esterifying agent, such as acetic anhyride, pro pionic anhydride, butyric anhyride or benzoyl chloride. The mixture is maintained for about 60 two hours at 30° C. and is added to 400 gallons ‘of water, ?ltered and the product washed and dried. Assuming the addition of the preferred acid esterifying agent-acetic anhydride—the yield is 70-100 pounds of dimethyl‘6,l2 coeroxenol. 65 substituted coeroxonol base, reducing the co 25 eroxonol base in an alkaline medium containing an organic solvent soluble in water and that does . After thecoeroxonol base is obtained it is with .40 stituted coeroxonol sulphate, precipitating the acetate. \ The pyridine orequivalent bases play a dual. role, one that of acting as a solvent for the co anhydride. - 6,12-coeroxonol base, reducing said base in ad 45 mixture with water, caustic alkali and pyridine,‘ and esterifying by the addition of acetic anhy dride. 7. The process of producing dimethyl 6,12 coeroxenol acetate of high purity and yield which 50 comprises melting together paracresol and phthalic anhydride, adding sulphuric acid, treat dual role of pyridine plays an extremely impor What I claim and desire to protect by Lettersv Patent is? , 7.5 1. The process of producing a substituted co ' ing the mix with caustic alkali to thereby produce as an intermediate product dimethyl 2,7-fluoran, treating said intermediate product with sulfuric 55 acid and thereby producing dimethyl 6,12 coeroxonol sulphate, precipitating the dimethyl 6,12-coeroxonol base, reducing said base in ad mixture with water, caustic alkali and pyridine, and esterifying by the addition of acetic anhy dride. V 8. The process of producing dimethyl 6,12 coeroxenol acetate of high purity and yield which comprises treating approximately 220 parts of paracresol and 150 parts of phthalic anhydride 65 with a condensing agent, and treating the re .sulting mixture with caustic alkali to thereby produce dimethyl 2,7-?uoran, treating said in termediate product with sulphuric acid to pro eroxonol base to facilitate reduction and the other‘ that of a carrier or catalyst for the esterifying' 70 agent (acetic anhydride or equivalent). This 1 duce dimethyl 6,12-coeroxonol sulphate, pre tant part in the process. ‘ cipitating the dimethyl 6,12-coeroxonol base, re ducing said base in admixture with water, caustic alkali and pyridine, and esterifying by the addi tion of acetic anhydride. THOMAS A. CASSIDY.