|Publication number||US2417118 A|
|Publication date||Mar 11, 1947|
|Filing date||Aug 16, 1941|
|Priority date||Aug 16, 1941|
|Publication number||US 2417118 A, US 2417118A, US-A-2417118, US2417118 A, US2417118A|
|Inventors||Rush F Mccleary, Stiles M Roberts|
|Original Assignee||Texas Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (19), Classifications (13)|
|External Links: USPTO, USPTO Assignment, Espacenet|
fatentecl Mar. 11, 1947 I UNITED STATES PATENT OFFICE COMPOSITION OF MATTER Rush F. McCleary and Stiles M. Roberts, Beacon, N. Y., assignors, by mesne assignments, to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application August 16, 1941,
Serial N0. 407,234
This invention relates to oil-soluble hydroxy aromatic or mercapto aromatic methylene thio ethers and/or the metal derivatives thereof, and to a process for preparing the same.
This invention is a continuation-in-part of the ticularly with respect to inhibition of corrosion and oxidation and the prevention of undesirable deposition upon the engine parts. The resulting lubricating oil compositions containing small proportions of these compounds are described and claimed in the copending applicationof Rush F. McCleary and Stiles M. Roberts, S. N. 393,244, filed May 13, 1941.
The compounds of the present invention may be described as that class ofaromatic compounds which contain at least one radical of the type CH2--S-R1 attached to a nuclear carbon atom and at least one hydroxyl (OH) or sulfhydryl (SH) radical or their metal salts, Specifically these compounds may be represented by the following structural formula in which R may be a hydrogen, alkyl, aryl, cycloalkyl, aralkyl or naphthenyl radical, and R1 may be an alkyl, aryl, cycloalkyl, aralkyl or naphthenyl radical. These radicals may contain further substituents which do not affect the oilsolubility of the compound, as, for example, halogen, sulfur, oxygen, or nitrogen derivatives. X may be either an hydroxyl (OH) or sulfhydryl (SH) radical or metal salts thereof, and n, y and a are integers of 1 or more. y and z are usually either 1, 2, 3 or 4, whereas n may be either 1, 2 or 3, depending upon the valences of the aromatic nucleus not satisfied by other substituents or residual hydrogen, The aromatic nucleus diagrammatically shown may be substituted by a naphthyl, anthracyl or any other condensed aromatic nucleus. The positions of the substituents are purely'diagrammatic and may be connected to any position in the aromatic nucleus. The metal derivatives of this class of compounds which are formed by the substitution of the replaceable hydrogen in the hydroxyl radical (OI-I) or the sulfhydryl radical (SH) include any of the following metals: sodium, potassium, lithium, calcium, barium, strontium, magnesium, zinc, iron, cobalt, nickel, aluminum, manganese, and chromium.
As illustrating the type of compounds within the scope of the above classification, the following compounds are presented, together with their relationship to the general classification. It is to be understood that the above-mentioned metals may be substituted for the replaceable hydrogen in. the following compounds and that the scope of the present invention is not limited to the following specific compounds or their metal salts:
R=alkyl, Ri=alkyl n,y,z=1, X==OH Amylthiomethyl tridecyl phenol X=SH Amylthiomethyl tridecyl thiophenol n,y=1, 2:2, X=OH Di (butylthiomethyl) octyl phenol 'X= SH Di (butylthiomethyl) octylthiophenol 11:1, 1:2, a=1,'X=OH Amylthiomethyl dioctadecyl naphthol X= SH Amylthiomethyl dioctadecyl thionaphthol n=1," ,z=2, X=OH Di (octylthlomethyl) diamyl phenol X= SI-I Di (octylthiomethyll diamyl thiophenol 11:3, y,z=1, X=OH Amylthiomethyl undecyl pyrogallol 11:2, :1, z;2 x=on Di (amylthiomethyl) undecyl resorcinol 11:3, 14:2, 2:1, X=OH Amylthiomethyl dioctyl pyrogallol In the following compounds X is an hydroxyl radical, although the corresponding thio compounds, e. g., where X is a sulfhydryl radical, may also be used: I
1L=1, 111:3, 2:2 Di (butylthiomethyl) phenol 11:1, y:2, 2:3 Tri (octylthiomethyl) phenol n,y,2:2 Di (amylthiomethyl) resorcinol :2, 111:1, 2:3 Tri (amylthiomethyl) resorcinol :cycloallcyl, R1:allcyZ 11,1l],2=1 Butylthiomethyl cyclohexyl phenol 11,11: 1, 2:2 Di (butylthiomethyl) cyclohexyl phenol 11:1, 11:2, 2:1 Butylthiomethyl oli-cyclohexyl phenol 11:2, y,2:1 Octylthiomethyl cyclohexyl resorcinol 11:2, 11:1, 2:2 Di (octylthiomelghyl) cyclohexyl resorcinol mi /=2, 2:1 Octylthiomethyl di-cyclohexyl resorcinol R:aralkyl, R1:aZkyl 11,'J,2:1 Hexylthiomethyl benzyl naphthol n,y:1, 2:2 Di (hexylthiomethyl) benzyl na-phthol 11:1, 11:2, 2:1 Hexylthiomethyl dibenzyl naphthol 11:2, 11,2:1 Hexylthiomethyl benzyl resorcinol 11:2, 1:1, 2:2 Di (hexylthiomethyl) benzyl resorcinol 11,2]:2, 2:1 Hexylthiomethyl dibenzyl resorcinol R:aryl, R1:alkyZ 11,y,2:1 Amylthiomethyl phenyl phenol 11,11: 1, 2:2 Di (amylthiomethyl) phenyl phenol 71 1, 11:2, 23:1 Amylthiomethyl diphenyl phenol 1 :2, 12:1 Amylthiomethyl phenyl resorcinol 11:2, y: 1, 2:2 Di (amylthiomethyl) phenyl resorcinol 11,7 :2, 2:1 Amylthiomethyl diphenyl resorcinol R:naphthenyl, R1:aZkyZ 11,y,2:1 Octylthiomethyl naphthenyl naphthol 11,y:1, 2:2 Di (octylthiomethyl) naphthenyl naphthol 11:3, 112:1 Ootylthiomethyl naphthenyl pyrogallol 771:2, 11 1, 2:2 Di (octylthiomethyl) naphthenyl resorcinol Di (phenylthiomethyl) unclecyl resorcinol 11,y:2, 2:1 Phenylythiomethyl dioctyl resorcinol R:hydroge11, R1:a1'yZ 11:1, 1:3, 2:2 Di (phenylthiomethyl) phenol 11:1, 14:2, 2:3 Tri (phenylthiomethyl) phenol 11,y,2:2 Di (phenylthiomethyl) resorcinol R:allcyl, R1=cyclohexyl 11,y,2=1
Cyclohexylthiomethyl octadecyl naphthol Di (cyclohexylthiomethyl) octadecyl naphthol Di (cyclohexylthiomethyl) dioctadecyl naphthol 71:2, 1 ,2:1 Cyclohexylthiomethyl octyl resorcinol Di (cyolohexylthiomethyl) octyl resorcinol 11,y:2, 2:1 Cyclohexylthiornethyl dioctyl resorcinol R:hyd1'oge11, R1:cycloalkyl 71:1, 21:3, 2:2 Di (cyclohexylthiomethyl) phenol 11:1, 11:2, 2:3 Trl (cyclohexylthiomethyl) phenol 11:3, 11:1, 2:2 Di (cyclohexylthiomethyl) pyrogallol MJ= D1 (cyclohexylthiomethyl) hydroquinone R:alkyl, R1:arallcyl /J, =1 Benzylthiomethyl octyl phenol 11,11: 1, 2:2 Di (benzylthiomethyl) octyl phenol 11:1, 1:2, 2:1 Benzylthiomethyl dioctyl phenol 11:1, 11,2:2 Di (benzylthiomethyl) clioctyl phenol 11:2, 11,2:1 Benzylthiomethyl undeoyl hydroquinone n 2, 11:1, 21:2 Di (benzylthiomethyl) undecyl hydroquinone n,y=2, z='1 Benzylthiomethyl diundecyl hydroquinone R=hydrogen, R1=araZlcyZ 12:1, 11:3, z=2 Di (benzylthiomethyl) phenol 71:1, 1:2, 2:3 Tri (benzylthiomethyl) phenol n,y,e=2 Di (benzylthiomethyl) resorclnol R=alicyl, R1=naphthenyl n,y,z=1 Naphthenylthiomethyl octyl naphthol 11,11: 1, 2:2 Di (naphthenylthiomethyl) octyl naphthol n= 1, 11:2, z=1 Naphthenylthiomethyl dioctyl naphthol 11:2, y,z=l Naphthenylthiomethyl undecyl resorcinol 11:2, 1:1, 2:2 Di (naphthenylthiomethyl) undecyl resorcinol R=hydrogen, Ri=naphthenyl n=l, y=3, z=2 Di- (naphthenylthiomethyl) phenol 11:1, 11:2, 2:3 Tri (naphthenylthiomethyl) phenol n,y,z=2 Di (naphthenylthiomethyl) resorcinol R=tertiary aminomethyl, R1=alkyZ n=1, y=2, 2:1 Amylthiomethyl di (dimethylaminomethyl) phenol n==1, y=1, z=2 Di (amylthiomethyl) dimethylaminomethyl phenol 11:2, 31:1, 2:1 Amylthiomethyl morpholinomethyl resorcino Any of the known classical methods of syn thesis may be used in the preparation of these compounds and the following reactions are given as illustrating two of the methods preferable to the present invention, The first is the reaction of a mercaptan and a dimethyl amino methyl derivative of a hydroxy aromatic compound:
The second is the reaction of an alkylated phenol, formaldehyde, and a mercaptan, as follows:
CHr-S-R -l CHQO HSRi Example I In preparing amylthiomethyl octyl phenol according to reaction N o, 1, 106 grams of dimethylaminomethyl octyl phenol and 210 grams of amyl mercaptan were intimately mixed with agitation and refluxed for 35 hours. Dimethylamine was given off and after the evolution was complete. the reaction mixture was transferred to a distilling flask and distilled under vacuum. The product was collected at to 190 C. at three millimeters pressure. The resulting amylthiomethyl octyl phenol was obtained as a clear, light yellow liquid (B. P. -170" C. at three millimeters mercury) and analyzed 9.3% sulfur.
Example II Example III 13 grams of magnesium ribbon was stirred with 200 cc. absolute ethyl alcohol and 200 cc. absolute methyl alcohol until the metal was substantially dissolved. 160 grams of amylthiomethyl octylphenol was added and the alcohol solvent substantially distilled off. Toluene was added and then distilled 011 to eliminate the remaining portions of alcohol solvent. Additional toluene was added and the solution was filtered through clay. The solvent was removed by distillation under vacuum and the residue dissolved in an equal weight of hydrocarbon oil. The resulting concentrate of magnesium amylthiomethyl octyl phenol in an equal weight of hydrocarbon oil analyzed 5.2% ash.
Example IV mercury. The residual amylthiomethyl di (dimethylaminomethyl) phenol appeared as a light brown oil and analyzed 7.42% sulfur and 9.02% nitrogen.
- Example V In preparing tri (benzylthiomethyl) phenol according to reaction No. 1, 133 grams of tri (dimethylaminomethyl) phenol and 186 grams benzyl mercaptan were intimately mixed with agitation and heated to 140-145" C. for three hours. Upon completion of the evolution of dimethyl amine, the product was filtered through clay and the resulting tri (benzylthiomethyl) phenol was obtained as a clear greenish-yellow oily liquid which analyzed 16.2% sulfur.
. Example VI in preparing the barium salt of tri (benzylthiomethyl) phenol of Example V, 50 grams of the product of Example V, 17 grams barium hydroxide, and 300 cc. toluene were stirred together and refluxed under an automatic water separator. The product was filtered through clay and the solvent removed by heating in vacuum. A resulting barium tri (benzylthiomethyl) phenolate was obtained as a clear light brown viscous residue which analyzed 17.! ash.
Obviously many modifications and variations of the invention as herein set forth may be made without departing from the spirit and the scope thereof, and, therefore, only such limitations should be imposed as are indicated in the appended claims.
1. As a new compound, di (dimethylaminomethyl) amylthiomethyl phenol.
2. Barium (amylthiomethyl) octyl phenolate.
3. As a composition of matter a compound possessing the structure.
in which Y and Z are alkyl groups and X is a member of the class consisting of hydrogen and metal equivalents thereof.
4. As a composition of matter a compound possessing the structure in which X is a member of the class consisting of hydrogen and metal equivalents thereof, Y and Z are alkyl groups; and m and n are small integers.
5. An aromatic methylene thioether the following general formula having 6. An aromatic methylene thloether having the following general formula wherein R is a radical selected from the group consisting of hydrogen and a hydrocarbon radical, R1 is a hydrocarbon radical and y and z are integers of at least one.
7. An aromatic methylene thioether having the following general formula wherein R is a radical selected from the group consisting of hydrogen and a hydrocarbon radi cal, R1 is a hydrocarbon radical, M is a metal equivalent and y and z are integers of at least one.
8. A method of preparing an aromatic methylene thioether which comprises reacting an aromatic compound containing at least one hydroxyl radical with formaldehyde and an alkyl mercaptan.
9. A method of preparing an aromatic methylene thioether which comprises reacting an aromatic compound containing a hydroxyl radical with formaldehyde and an alkyl mercaptan and thereafter converting the free hydroxyl radica1 to its corresponding metal salt.
10. A method of preparing an aromatic methylene thioether which comprises reacting an alkyl phenol with formaldehyde and an alkyl mercaptan.
RUSH F. MCCLEARY. STILES M. ROBERTS.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,111,260 Brunner 'Mar. 15, 1938 2,223,693 Martin et al Dec. 3, 1940 2,249,626 Cook et al. July 15, 1941 FOREIGN PATENTS Number Country Date 450,760 British to Johnson July 20, 1936 OTHER REFERENCES Manchot, Annalen, vol. 345, pages 322-323. Baumann, Berichte, vol. 24, page 1446.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2111260 *||Sep 19, 1936||Mar 15, 1938||Gen Aniline Works Inc||Water-soluble addition compounds, containing sulphur, of alkyl or aralkyl halides and processes of preparing them|
|US2223693 *||Nov 15, 1937||Dec 3, 1940||Firm J R Geigy S A||Thioacetalsulphonic acids and a process of making same|
|US2249626 *||Mar 13, 1941||Jul 15, 1941||American Cyanamid Co||Lubricating composition|
|GB450760A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2466963 *||Jun 16, 1945||Apr 12, 1949||Thiokol Corp||Polysulfide polymer|
|US2668768 *||Oct 17, 1949||Feb 9, 1954||Universal Oil Prod Co||Stabilization of edible fats and oils|
|US2734867 *||Jul 25, 1952||Feb 14, 1956||Additive for lubricants|
|US2795613 *||Apr 28, 1954||Jun 11, 1957||Hoffmann La Roche||Basic derivative of 2-methyl-4-cyclohexyl-phenol and process for the manufacture thereof|
|US2831030 *||Oct 13, 1953||Apr 15, 1958||Universal Oil Prod Co||Composition of matter|
|US2976324 *||Nov 17, 1958||Mar 21, 1961||Dow Chemical Co||Bisphenol sulfide|
|US2976325 *||Nov 17, 1958||Mar 21, 1961||Dow Chemical Co||Substituted phenolic sulfides|
|US3457315 *||Apr 1, 1966||Jul 22, 1969||Syntex Corp||Methylthio methyl phenolic compounds and method of producing same|
|US3903173 *||Apr 21, 1970||Sep 2, 1975||Ciba Geigy Ag||Lower alkylthiomethylene containing phenols|
|US4091037 *||Mar 31, 1977||May 23, 1978||Bayer Aktiengesellschaft||Preparation of alkylthiomethylphenols|
|US4108831 *||Jun 2, 1975||Aug 22, 1978||The Goodyear Tire & Rubber Company||Hydroxyalkylthio phenolic antioxidants|
|US4707300 *||Mar 9, 1987||Nov 17, 1987||The Goodyear Tire & Rubber Company||Autosynergistic phenolic antioxidant reaction product|
|US4820756 *||Jun 22, 1987||Apr 11, 1989||Ciba-Geigy Corporation||Thioether substituted phenols and their use as stabilizers|
|US4874885 *||Dec 15, 1987||Oct 17, 1989||Ciba-Geigy Corporation||Process for the preparation of mercaptomethylphenols|
|US5008459 *||Dec 22, 1987||Apr 16, 1991||Ciba-Geigy Corporation||Substituted phenols as stabilizers|
|US5376290 *||Oct 18, 1991||Dec 27, 1994||Ciba-Geigy Corporation||Substituted phenols as stabilizers|
|US5427701 *||Jul 14, 1994||Jun 27, 1995||Ciba-Geigy Corporation||Substituted phenols as stabilizers|
|DE1593821B1 *||Mar 17, 1967||Aug 5, 1971||Advance Prod Gmbh||Verfahren zur Herstellung von Dialkylhydroxybenzylsulfiden|
|EP1146038A1 *||Apr 12, 2000||Oct 17, 2001||Kumho Monsanto, Inc.||Novel antioxidant and method of producing the same|
|U.S. Classification||564/388, 568/51, 568/40, 564/390|
|Cooperative Classification||C10M2219/089, C07C323/00, C10M2219/087, C10M2219/084, C10N2230/12, C10M2219/086, C10M1/08|
|European Classification||C07C323/00, C10M1/08|