Патент USA US2408233код для вставки
Patented Sept. 24, 1946 UNITED STATES PATENT OFFICE 2,408,232 CHEMICAL CODIPOUNDS AND. PROCESSES Herschel G. Smith, Wallingford, and Troy L. Can trell, Lansdowne, Pa., assignors to Gulf Oil Cor poration, Pittsburgh, Pa.,' .a corporation of Pennsylvania ' No Drawing. Application January 7; 1946, Serial N0. 639,701 5 Claims. (Cl. 260-461) . 1 2 This invention relates to new chemical compounds and processes and more particularly to new aromatic amine salts of 3-methyl-butyl, 2- . It is insoluble in water and soluble in mineral oils to the extent of 11.70 parts in 100 parts of oil at 20° C. It has the structural formula: ethyl-hexyl orthophosphate which are useful for . ~ H3? 1'1 1? fl) H (‘3,139 various technical purposes especially in the petro- leum industry. This application _ is a continuation-in-part of ‘ 5 : our copending application, Serial NO- 453,458, ?led ' HTO_(|JT$_OTI_O_(IJ_OH Hi0 H H H E 02115 The following examples illustrate but do not August 3, 1942, which application is in turn a limitiourinvehtion _ , continuation-in-part of our application, Serial No. 10 . 421,842, ?led December 5, 1941. Application Serial 7 . Example I No. 453,458 became U. S. Patent No. 2,397,377 on > One hundred and twenty-one pounds of di March 26,1946. methylam'line were added to an iron vessel This invention has as an object the production equipped with an air lance and 281 pounds of 3 of new chemical compounds that are technically 15 methyl-butyl, 2-ethyl-hexyl orthophosphate were useful.‘ A further object is to prepare these new introduced over a period of one hour; the slow compounds by novel and easily conducted procrate of addition being desirable to maintain the esses. A still further object is to utilize these temperature of the reaction mixture below 185° F. new compounds for‘ various technical purposes. At the conclusion of this reaction, the tempera Other objects will appearhereinafter. 20 ture was 180° F., and the pH of the mixture ‘was These objects are accomplished in accordance 2.0. A pH of 3.0 was desired; 12.0 pounds of di with the present invention by making aromatic aminesalts of 3-methyl-butyl, 2-ethyl-hexyl orthophosphate. Salts having the following forniula: ' H3? ?r 1,1 ‘If ' ‘ 25 the following properties: 1,1 134m Gravity: °A.P.I ______________________ __ 11-c-o-o-o-r-o-C-o-H H35 7‘if 1 h methylaniline were added, which brought the pH to, 3.0. The reaction product was an oily sub stance, readily soluble in mineral oils and having , ‘5H III (132m R 'IlI/R _ I 7, ' ~ ‘ ' - V1scos1ty,S.U.V.100 F_______________ __ 468 Pour: °F __________ _1__________________ __ ~50 30 The reactionv product described above has the structural formula: ' V 35 the class consisting of methyl and ethyl groups and hydrogen, are the preferred products of the = I " H ‘ H H H a 7 ' V ' H i‘ i ‘i is H*"_i_i“i_j_°_i*i? i , wherein R represents a substituentselected from present invention. 7.4 Speci?c gravity, 60°/60° F _______ __' _____ __ 1.019 [/H H CH a 5 ON I ' g \ ~ 0 3 CH3 In preparing these new salts, the selected aro- 40 As the dimethylaniline isoamyl octyl phosphate matic amine is reacted ‘ with B-methyl-butyl,‘ 2is substantially insoluble in water, the pH equiva ethyl-hexyl orthophosphate to obtain :the desired vlent is measured by the following expedient. Nor aromatic amine salt thereof; the pH of the reac- ‘ mal butanol (which contains a'small amount of tion mixture being adjusted to within the range water) is adjusted to exact neutrality, pH=7.0,. 2.0 to 5.5 in so preparing and recovering the 45 and the sample is dissolved therein. The pH?of amine salt. For example, dimethyl-aniline is the solution is then measured in the ordinary way brought into reaction. with S-methyl-butyl, 2as ‘for aqueous solutions, by electrometric or ethyl-hexyl orthophosphate, and the pH of the colorimetricmethod-s. The butanol appears to reaction mixture is adjusted to within the range serve as a blending agent, for dissolving the sam 2 to 4. With the theoretical molecular ratio of 50 ple in the water. the two reactants, namely 1:1, the product is apt to be slightly too acid, with a pH below 2, and this is taken care of by using a slight excess of the dimethylaniline so that the molecular ratio is between 1:1 and 1:1.1. v It will be noted that the measured pH of the aminophosphate is ‘low despite the fact that a slight excess of amine is present. This is because the reaction involves neutralizing a rather strong ‘35 acid with a very Weak base; lsoamyl octyl orthophosphate, which is also called 3-methyl-butyl, 2-ethyl-hexyl orthophos» ' Example H ‘ '_ phate, is a brown, oily liquid; its speci?c gravity One hundred and forty-nine Pounds of 01161711 is 1.009 at 24°/4° C., and its viscosity is 210, 75 and ylaniline were added to an iron vessel equipped 29 centipoises at 25,, 50 and 75° C. respectively. 60 with an air lance, and 281 pounds of 3-methyl 2,408,232 3 4 formed ‘under the conditions of vthe jpI-I determi nation. While aniline 3-methyl-butyl, Z-ethyl-hexyl butyl, Z-ethyl-hexyl orthophosphate were intro duced over a ‘period of one hour; the slow rate of addition being desirable to maintain the tem perature of the reaction mixture below 185° F. At the conclusion of this reaction, the tempera phosphate is an effective foam suppressor for use in lubricating oils, it is more advantageous to employ the foam suppressors prepared from 3 ture was 180° F. and the pH of the mixture was 2.0. A pH of 3.5 was desired; a further 15 pounds methyl—butyl, Z-ethyl-hexyl phosphate and di methyl or diethyl aniline. This advantageous of diethylaniline were added, which brought the class of foam suppressors may be represented by pH to 3.5. The reaction product was an oily liq 10 the following formula: uid which was readily soluble in mineral oils. The reaction product of diethylaniline with 3 methyl-butyl, Z-ethyl-hexyl orthophosphate has the following structural formula: 15 20 wherein R’ represents a methyl or ethyl group. While the preparation of the aniline, .dimethyl aniline, and diethylaniline salts of S-methyl As the diethylaniline isoamyl voctyl phosphate is substantially insoluble in water, the pH equiv alent is measured by the expedient described above in Example I. butyl, Z-ethyl-hexyl orthophosphate has been 25 so limited but pertains broadly to the prepara tion of any aromatic amine salt of S-methyl Here again, the measured pH of the amino-phosphate is low despite the fact that a slight excess of amine is present. speci?cally described above, this invention is not butyl, 2-ethyl-hexyl orthophosphate. Among the aromatic amines which may be used to pre 30 pare such salts there may be mentioned aniline, ortho-toluidine, meta-toluidine, para-toluidine, Example III the various isomeric xylidines, the anisidines, the phenetidines, the nitroanilines, the chloroani lines, the aminophenols, the aminocresols, the phenylene diamines, the aminobiphenyls, alpha Ninety-three pounds of aniline were added to an iron vessel equipped with an air lance and 281 pounds of 3-methyl-butyl, Z-ethyl-hexyl 0r naphthylamine,v beta-naphthylamine, ‘N-methyl thophosphate were introduced over a period of one hour; the slow rate of addition being desir able to maintain the temperature of the reaction mixture below 212° F. At the conclusion of this reaction, the temperature was 180° F. and the pH of the mixture was 2.0. A pH of 3.5 was de sired; a further 9 pounds of aniline were added, aniline, N-ethyl aniline, N-methyl beta-naph thylamine, diphenylamine, phenyl beta-naph thylamine, N-dimethyl aniline, N-diethyl aniline, N-dibutyl aniline, N-diamyl aniline, N-methyl di phenylamine, N-methyl phenyl beta-naphthyl amine, N-dimethyl alpha-naphthylamine, etc. While our invention has been described above which brought the pH to 3.5. The reaction prod with reference to various speci?c examples and embodiments, it will be understood that the in vention is not limited to such illustrative examples and embodiments, but may be variously practiced within the scope of the claims herein made. uct was an oily liquid which was readily soluble in mineral oils. The reaction product of aniline with 3-methyl butyl, Z-ethyl-hexyl orthophosphate has the fol lowing structural formula: What we claim is: 50 1. An aromatic amine salt of 3-rnethyl-butyl, Z-ethyl-hexyl orthophosphate. 2. An aromatic amine salt of 3-methy1-buty1, 2-ethyl-hexyl orthophosphate having the for mula: As the aniline isoamyl octyl phosphate is sub stantially insoluble in water, the pH equivalent 60 is measured by the following expedient. Normal Harrow-Ores‘ Hi? i r i’O H H.H CgH5 E30 H H l/ R—1TI—R butanol (which contains .a small amount of water) is adjusted to exact neutrality, pI-I='7.0, and the sample is dissolved therein. The pH_ of the solution is then measured in the ordi nary way as for aqueous solutions, by electro metric or colorimetric methods. The butanol appears to serve ‘as a blending agent for dissolv ing the sample in water. It will be noted that the measured pH of this aminophosphate is low despite the fact that a slight excess of amine is present. This is be cause the reaction involves neutralizing a rather strong acid with a very weak base. Moreover, traces of mono-, di- and tribasic acids may be 75 wherein R represents a substituent selected from the class consisting of methyl and ethyl groups and hydrogen. 3. The aniline salt of B-methyl-butyl, 2-ethy'l hexyl orthophosphate. 4. The dimethylaniline salt of '3-methyl-ibutyl, Z-ethyl-hexyl orthophosphate. 5. The diethylaniline salt of B-methyl-butyl, 2 ethyl-hexyl ortho-phosphate. HERSCHEL G. SMITH. TROY L. CANTRELL.