Патент USA US3073873код для вставки
United grates Fatent 151cc 3,073,863 Patented data. 15, 15.053 3. f3. EXAMPLE 1 3,073,363 ’ PARATEEN GXY-JMIETYLAM Preparation of p-Nonyl Phenoxyacezyl~p~Amin0phenol HEY it} DERlVATlVE§ ‘ m't, End, and Cl grams to tallies i rporation oi’ in One hundred and sixty-four (164) g. of 1PAP, 12 g. of boric acid, and 608 g. of a toluene solution which contained 423 g. of [3-(p-nonyl)phenoxyacetic acid, were mixed and heated to re?ux temperature under a nitrogen Burton, -..torres, inc, ~ ' 3 May 5, 1.950, .3 a. .1 Claim. ($2. 4 - atmosphere. After re?uxing had continued for about 3 hours, 36 ml. of Water formed in the reaction had been w‘ This invention relates generally to derivatives of p-ami 10 removed as an azetrope with toluene. The resulting reaction mixture was stripped of 112 g. of toluene, and pounds having the formula: the remaining mixture treated with 15 g. of char in 88% nophenols, and more particularly, to a new series of com isopropanol. Attempts to crystallize the product by di luting the solvent to 40% with water were unsuccessful, 15 resulting in a black oil. The oil was stripped of solvent to form a very stilt tar containing the ?nal product. wherein R is selected from the group consisting of alkyl EXAMPLE 2 substituted phenoxy radicals. Compounds coming within this formula have excellent oil solubility, and are useful Preparation of 2,4-Di-Sec0ndary Bm‘yl Phenoxyacetyl as antioxidants for rubber and various resinous polymers. p-Aminophenol The present compositions are prepared by reacting 20 One hundred and sixty-four (164) g. PAP, 12 g. boric acid, and 623 g. of toluene solution containing “PAP”) with an acid which will provide the desired acyl 395 g. of 2,4-di-secondary butyl phenoxyacetic acid were radical RCH2CO—, in the presence of boric acid, as rep mixed and heated to re?ux under nitrogen atmosphere.‘ resented by the following equation: 25 During the ?rst three hours of re?uxing, 32 ml. of water were separated from the reaction mixture. The reaction mixture, which solidi?ed when cooled, was stripped of p - aminophenol (hereinafter sometimes abbreviated toluene at reduced pressure (about 10 mm. Hg), decolor ized with 15 g. of activated carbon, and recrystallized 30 from 40% isopropanol. On cooling during recrystalliza tion, the product tended to oil out, but agitating the re crystallizing mixture at 5 to 10° C. solidi?ed the oil par ticles. The crystallized product was ?ltered off, and washed ?rst with 200 ml. of cold 40% isopropanol, then wherein R has the meaning ascribed to it above. Prefer ably the acid reactant is dissolved in a suitable solvent which will not enter into the reaction but which will 35 with sodium hydrosul?te water, and, ?nally, with tap water. The product was then recrystallized from 40% provide a good reaction medium, such as toluene, and the isopropanol, yielding 287 1g. of a slightly yellow solid; reaction is carried out under reflux conditions. Prefer melting point, 1405-1415” C. ably, also, an inert atmosphere, e.g., carbon dioxide or nitrogen, is provided in the reaction vessel while the re EXAMPLE 3 action is taking place. During the re?ux reaction water 40 Preparation of p-Secondary Butyl Phenoxyacetyl formed in the reaction is removed as an azeotrope with p-Aminophenol toluene. After the reaction has been completed, the toluene is stripped from the reaction mixture, the re Thirty-nine (39) g. PAP, 3 g. boric acid, and 306 g. maining material being then preferably decolorized with of a toluene solution containing 69.5 g. of ?-p-secondary activated carbon in a suitable solvent such as isopropanol, butyl phenoxyacetic acid were mixed and maintained and the decolorized product crystallized from the solvent. 45 at re?ux temperature under nitrogen atmosphere for 61/2 The p-aminophenol and many species of the reactant hours, during which time 10.4 ml. of water was removed acid, which are used as starting materials in preparing therefrom as an azeotrope with toluene. The reaction the present compositions, are commercially available. mixture was stripped of 263 g. of toluene, and the re Those species of the acid which may not be easily pro 50 maining mixture was recrystallized from 40% isopro cured in the market may be prepared by methods well panol. Oil which separated initially during the recrystal known in the art. Representative acids which may be lization was solidi?ed when the recrystallization medium reacted satisfactorily with PAP to produce the instant was cooled to 2° C. The recrystallized product was novel compounds are those derivatives of acetic acid in recovered by ?ltration, washed with isopropanol, and which the R-group, in the above formula, is 2,4-di-second 55 dried to give 67 g. of a product of slight yellow color; ary butyl phenoxy; p-secondary butyl phenoxy; and melting point 119-l20.5° C. What is claimed is: p-nonylphenoxy. Further operative acids are those de rivatives of acetic acid in which the R-group is 2,4-di-secondary butyl phenoxyacetyl-p-aminophenol. References @ited in the ?le of this patent UNITED STATES PATENTS 60 wherein R’ and R" may be hydrogen or an alkyl group provided that R’ and R" are not both hydrogen, and CH3 0 2,423,730 2,653,158 2,711,415 65 2,730,500 2,852,540 2,945,870 wherein x is an integer less than 5. The following speci?c examples illustrate representa tive compounds encompassed by our invention, and a method for their production. Salminen ____________ __ July 8, Young et al. _________ __ Sept. 22, Cottle ______________ __ June 21, Young et al. _________ __ Jan. 10, Young et al. _________ .... Sept 16, Young ______________ __ July 19, 1947 1953 1955 1956 1958 1960 OTHER REFERENCES Lucas: Organic Chemistry (2nd ed.), pages 508-509, published by American Book Company, New York (1953).