[go: up one dir, main page]

US2679459A - Stabilization of organic compounds - Google Patents

Stabilization of organic compounds Download PDF

Info

Publication number
US2679459A
US2679459A US111347A US11134749A US2679459A US 2679459 A US2679459 A US 2679459A US 111347 A US111347 A US 111347A US 11134749 A US11134749 A US 11134749A US 2679459 A US2679459 A US 2679459A
Authority
US
United States
Prior art keywords
methoxyphenol
carbon atoms
tertiary
butyl
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US111347A
Inventor
Robert H Rosenwald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universal Oil Products Co
Original Assignee
Universal Oil Products Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universal Oil Products Co filed Critical Universal Oil Products Co
Priority to US111347A priority Critical patent/US2679459A/en
Application granted granted Critical
Publication of US2679459A publication Critical patent/US2679459A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • C09K15/08—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen containing a phenol or quinone moiety
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0035—Phenols; Their halogenated and aminated derivates, their salts, their esters with carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers

Definitions

  • This invention is particularly applicable to the stabilization of unsaturated gasoline and still more particularly cracked and polymer gasoline. In storage or during treatment these unsaturated gasolines tend to form undesirable gums.
  • the invention is also applicable to the treatment of aviation gasclines which tend to undergo deterioration due to the addition of tetraethyl lead fluid or due to other components in the gasoline.
  • the invention is also particularly applicable to the stabilization of edible fats and oils which generally are of animal or vegetable origin and which tend. to become rancid, especially during long periods of storage priorto use.
  • Typical representatives of these edible fats and oils include linseed oil, menhaden oil, cod liver oil, castor Oil, soya bean oil, rapeseed oil, coconut oil, olive oil, palm oil, corn oil, sesame oil, peanut oil, babassu oil, butter, fat,,la-rd, beef tallow, etc. It is understood that other oils and fats may be treated within the scope of the present invention, including oils and fats which previously have been subjected to various treatments, such as blowing with air, heat treatment, hydrogenation, etc.
  • the present invention is particularly applicable to the treatment of crops by dusting or spraying in order to preserve food accessory factors such as carotene, vitamins, various fatty acids, alcohols, etc.
  • the present invention relates to a method of stabilizing an organic material subject to oxidative deterioration which comprises adding thereto an inhibitor comprising a 2,6-dialkyl-alkoxyphenol.
  • the present invention relates to the stabilization of motor fuel normally tending to deteriorate in storage which comprises 2 adding thereto from about 0.001% to about 0.5% by weight of 2,6-dimethyl-4-methoxyphenol.
  • the present invention relates to a method of stabilizing edible fats and oils normally subject to oxidative deterioration which comprises adding thereto from about 0.001% to about 0.5% by weight of 2-methyl-6tertiary-butyl-4-methoxyphenol.
  • the present invention relates to an organic material subject to .oxidative deterioration containing, as an inhibitor for such deterioration, a 2,6-dialkyl-4- alkoxyphenol.
  • the present invention relates to a novel composition of matter comprising a 2,6 dialkyl alkoxyphenol and particularly 2,6 dimethyl- 4 methoxyphenol, .Z-methyl-6-tertiary-butyl-4-methoxypheno1 and 2-methyl-6-secondary -butyl-4-methoxyphenol.
  • the 2,6-dialkyl-alkoxyphenols require special methods of preparation and cannot be prepared, for example, by the alkylation of an alkoxyphenol or of a 2-alkyl-4-alkoxyphenol by an olefin or alcohol as this results in the formation of a 2,5-dialkyl-4-alkoxyphenol.
  • the 2,6-dialkyll-alkoxyphenols of the present .invention may be represented by the following general formula:
  • ary butyl-ethoxyphenol 21methyl-6-tertiaryaniyll-ethoxyphenol, Z-methyl-fi-tertiary-amy1- "ethoxyphenol, "2-methyl-6-tertiary-butyl-4-pr0 3 poxyphenol, 2-methyl6-tertiary-amyl 4 propoxyphenol, 2-methyl-6-tertiary-butyl-4-butoxyphenol, 2-methy1-6-tertiary-amyl-4-butoxyphen01, 2-ethyl-6-tertiary butyl-4-methoxyp-henol, 2 ethyl 6 tertiary amyl 4 methoxyphenol, Z-ethyl 6 tertiary-heptyl 4 methoxyphenol,
  • Other satisfactory but not necessarily equivalent compounds include 2,6-dimethyl-4-methoxyphenol, 2,6-dimethyl-4-ethoxyphenol, 2,6-dimethyl 4-propoxypheno1, 2,6-diethyl-4-methoxyphenol, 2,6-diethyl-4-ethoxyphenol, 2,6 diethyl-4-propoxyphenol, 2,6-dipropyl-4-methoxyphenol, 2,6- dipropyl 4 ethoxyphenol, 2,6-dipropyl-4-propoxyphenol, 2,6-dibutyll-methoxyphenol, 2,6- dibutyl-4-ethoxyphenol, 2,6-dibuty1-4-propoxyphenol, Z-methyl 6 ethyl 4 methoxyphenol, 2-methyl-6-ethyl-4-ethoxyphenol, Z-methyl-fiethyl 4 propoxy
  • 2,6-dialkyl-4-alkoxyphenols may be prepared in any suitable manner, special methods of preparation are required because they cannot be manufactured by usual methods of preparation as hereinbefore set forth.
  • a preferred method of manufacturing these compounds is by the use of the Mannich reaction.
  • 2,6-dimethyl-4-methoxyphenol When 2,6-dimethyl-4-methoxyphenol is desired, it may be prepared by the reaction of 4-methoxypheno1 with formaldehyde and a suitable dialkyl amine such as dimeth'yl amine, diethyl amine, dipropyl amine, etc. In some cases, ammonia may be employed instead of the dialkyl amine but usually improved results are obtained with the dialkyl amine.
  • 2-methyl-6-tertiary-butyl-4-methoxyphenol is desired, this is readily prepared by starting with Z-tertiary-butyl-4-methoxyphenol and reacting the same with formaldehyde in the presence of a suitable dialkyl amine. In this instance, at least one mol of formaldehyde per mol of alkoxyphenol is required.
  • the 2-tertiarybutyl4-methoxyphenol is readily prepared by the alkylation of 4-methoxyphenol with tertiary butyl alcohol in the presence of a phosphoric acid catalyst.
  • 4-methoxyphenol may be reacted with tertiary butyl alcohol at a temperature of 75-80 C. in the presence of a catalyst comprising 85% phosphoric acid.
  • the dialkyl amine derivative of 4-alkoxyphenol is hydrogenated to form the desired 2,6-dialkyl- 4-alkoxyphenol.
  • the hydrogenation may be effected in any suitable manner, a preferred method being in the presence of hydrogen and a nickel catalyst at a temperature of from about to about 200 C. or more, preferably at a substantial superatmospheric pressure which generally will range from 100 pounds to 1000 pounds or more per square inch.
  • the inhibitor of the present invention is generally added to Organic materials in an amount of less than 1% by weight and preferably within the range of from about 0.001% to about 0.5%.
  • the inhibitor may be used in conjunction with various dyes, inhibitor activators, metal deactivators, antiknock agents such as tetraethyl lead, etc.
  • a synergist such as phosphoric acid, ascorbic acid, etc.
  • Example I 2,6-dimethyl-4-methoxyphenol was prepared by reacting 4-methoxyphenol with formaldehyde and diethyl amine at room temperature. Over 2 mols of formaldehyde and over 2 mols of diethyl amine were used per mol of 4-methoxyphenol. The reaction occurred readily at room temperature and the product was extracted with caustic to remove unreacted methoxyphenol. The resultant product was then distilled to remove excess diethylamine and finally was recovered by extraction in acid to separate the desired product from by-products of the reaction. The product was washed and then hydrogenated in a pentane solvent with 10-20 weight percent of nickel catalyst, 1000 pounds per square inch of hydrogen at a temperature of C. for a period of 6 hours.
  • Example III 2 methyl -6- secondary butyl -4- methoxyphenol was prepared in substantially the same manner as described in the preceding examples. In this instance, 2-secondary-butyl-4-methoxyphenol was utilized as one of the primary reactants.
  • a method of stabilizing an organic material subject to oxidative deterioration which comprises adding thereto an inhibitor comprising a 2,6-dialkyl-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
  • a method of stabilizing motor fuel subject to oxidative deterioration which comprises adding thereto a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
  • a method of stabilizing edible fats and oils subject to oxidative deterioration which comprises adding thereto an inhibitor comprising a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
  • a method of stabilizing lard subject to oxidative deterioration which comprises adding thereto from about 0.001% to about 0.5% by Weight of 2-methyl-6-tertiary-butyl-4-methoxyphenol.
  • Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2,6-dia1kyl-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
  • deterioration containing not more than 1% by 6.
  • Edible fats and oils subject to oxidative weight of a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
  • Lard subject to oxidative deterioration containing from about 0.001% to about 0.5% by weight of 2-methyl-6-tertiary-butyl-4-methoxyphenol.
  • Motor fuel subject to oxidative deterioration containing not more than about 1% by weight of a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms,
  • the other alkyl group contains not more than about 4 carbon atoms
  • the alkoxy group contains not more than about 4 carbon atoms.
  • a method of stabilizing motor fuel subject to oXidative deterioration which comprises adding thereto from about 0.001% to about 0.5% by Weight of 2-methyl-6-tertiary-buty1-4-methoxyphenol.
  • Gasoline subject to oxidative deterioration containing from about 0.001% to about 0.5% by weight of 2-methyl6-tertiary-butyl-4-methoxyphenol.
  • Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2 alkyl -6- tertiary butyl 4- ethoxyphenol, said alkyl group containing not more than about 4 carbon atoms.
  • Edible fats and oils subject to oxidative deterioration containing no more than 1% by weight of 2-methy1 -6- tertiary-butyl -4- ethoxyphenol.
  • Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2 alkyl 6 tertiary amyl 4- ethoxyphenol, said alkyl group containing not more than about 4 carbon atoms.
  • Edible fats and oils subject to oxidative deterioration containing no more than 1% by weight of 2-inethyl-6tertiary-amyl-4-methoxyphenol.
  • Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2 alkyl 6 tertiary octyl 4- alkoxyphenol, said alkyl group containing not more than about 4 carbon atoms.
  • Edible fats and oils subject to oxidative deterioration containing no more than 1% by weight of 2-methyl-B-tertiary-octyl-4-methoxyphenol.
  • Organic material subject. to oxidative deterioration containing, as an inhibitor for said deterioration, a 2,6-di-tertiary-alkyl-4-alkoxyphenol, one of said alkyl groups containing from about 3 to about 10 carbon atoms, the other alkyl group containing not more than about 4 carbon atoms, and the alkoxy group containing not more than about 4 carbon atoms.
  • Edible fats and oils subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2,6-di-tertiary-butyl-4-methoxyphenol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Description

Patented May 25, 1954 STABILIZATION OF ORGANIC COMPOUNDS Robert H. Rosenwald, Western Springs, 111., as-
Signor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware UNITED STATES PATENT OFFICE No Drawing. Application August 19, 1949,
- Serial No. 111,347
- oil, mineral oil, transformer oil, lubricating oil,
fuel oil, drying oil, greases, edible fats and oils, acetylenes and particularly vinyl acetylene, butadiene, isoprene, styrene and other vinyl aromatics, various unsaturated alcohols, acids, esters, ethers, ketones, etc.
This invention is particularly applicable to the stabilization of unsaturated gasoline and still more particularly cracked and polymer gasoline. In storage or during treatment these unsaturated gasolines tend to form undesirable gums. The invention is also applicable to the treatment of aviation gasclines which tend to undergo deterioration due to the addition of tetraethyl lead fluid or due to other components in the gasoline.
The invention is also particularly applicable to the stabilization of edible fats and oils which generally are of animal or vegetable origin and which tend. to become rancid, especially during long periods of storage priorto use. Typical representatives of these edible fats and oils include linseed oil, menhaden oil, cod liver oil, castor Oil, soya bean oil, rapeseed oil, coconut oil, olive oil, palm oil, corn oil, sesame oil, peanut oil, babassu oil, butter, fat,,la-rd, beef tallow, etc. It is understood that other oils and fats may be treated within the scope of the present invention, including oils and fats which previously have been subjected to various treatments, such as blowing with air, heat treatment, hydrogenation, etc.
In another embodiment the present invention is particularly applicable to the treatment of crops by dusting or spraying in order to preserve food accessory factors such as carotene, vitamins, various fatty acids, alcohols, etc.
In one embodiment the present invention relates to a method of stabilizing an organic material subject to oxidative deterioration which comprises adding thereto an inhibitor comprising a 2,6-dialkyl-alkoxyphenol.
In a specific embodiment the present invention relates to the stabilization of motor fuel normally tending to deteriorate in storage which comprises 2 adding thereto from about 0.001% to about 0.5% by weight of 2,6-dimethyl-4-methoxyphenol.
In another specific embodiment the present invention relates to a method of stabilizing edible fats and oils normally subject to oxidative deterioration which comprises adding thereto from about 0.001% to about 0.5% by weight of 2-methyl-6tertiary-butyl-4-methoxyphenol.
In another specific embodiment the present invention relates to an organic material subject to .oxidative deterioration containing, as an inhibitor for such deterioration, a 2,6-dialkyl-4- alkoxyphenol.
In still another embodiment the present invention relates to a novel composition of matter comprising a 2,6 dialkyl alkoxyphenol and particularly 2,6 dimethyl- 4 methoxyphenol, .Z-methyl-6-tertiary-butyl-4-methoxypheno1 and 2-methyl-6-secondary -butyl-4-methoxyphenol.
The 2,6-dialkyl-alkoxyphenols require special methods of preparation and cannot be prepared, for example, by the alkylation of an alkoxyphenol or of a 2-alkyl-4-alkoxyphenol by an olefin or alcohol as this results in the formation of a 2,5-dialkyl-4-alkoxyphenol.
The 2,6-dialkyll-alkoxyphenols of the present .invention may be represented by the following general formula:
ary butyl-ethoxyphenol, 21methyl-6-tertiaryaniyll-ethoxyphenol, Z-methyl-fi-tertiary-amy1- "ethoxyphenol, "2-methyl-6-tertiary-butyl-4-pr0 3 poxyphenol, 2-methyl6-tertiary-amyl 4 propoxyphenol, 2-methyl-6-tertiary-butyl-4-butoxyphenol, 2-methy1-6-tertiary-amyl-4-butoxyphen01, 2-ethyl-6-tertiary butyl-4-methoxyp-henol, 2 ethyl 6 tertiary amyl 4 methoxyphenol, Z-ethyl 6 tertiary-heptyl 4 methoxyphenol,
' 2-propyl 6 tertiary-butyl 4 methoxyphenol,
2-propyl 6 tertiary-amyl 4 methoxyphenol, 2-butyl-6-tertiary butyl-4-methoxyphenol, etc. Other satisfactory but not necessarily equivalent compounds include 2,6-dimethyl-4-methoxyphenol, 2,6-dimethyl-4-ethoxyphenol, 2,6-dimethyl 4-propoxypheno1, 2,6-diethyl-4-methoxyphenol, 2,6-diethyl-4-ethoxyphenol, 2,6 diethyl-4-propoxyphenol, 2,6-dipropyl-4-methoxyphenol, 2,6- dipropyl 4 ethoxyphenol, 2,6-dipropyl-4-propoxyphenol, 2,6-dibutyll-methoxyphenol, 2,6- dibutyl-4-ethoxyphenol, 2,6-dibuty1-4-propoxyphenol, Z-methyl 6 ethyl 4 methoxyphenol, 2-methyl-6-ethyl-4-ethoxyphenol, Z-methyl-fiethyl 4 propoxyphenol, Z-methyl 6 ethyl-4- butoxyphenol, 2-methyl-6propyl4methoxyphenol, 2 methyl 6 propyl 4 ethoxyphenol, Z-methyl-6propyl-4-propoxyphenol, 2-propyl-6- butyl 4 methoxyphenol, 2 propyl-S-buty1-4- ethoxyphenol, 2-propyl-6-butyl-4-propoxyphen01, etc.
While the 2,6-dialkyl-4-alkoxyphenols may be prepared in any suitable manner, special methods of preparation are required because they cannot be manufactured by usual methods of preparation as hereinbefore set forth. A preferred method of manufacturing these compounds is by the use of the Mannich reaction. For example, When 2,6-dimethyl-4-methoxyphenol is desired, it may be prepared by the reaction of 4-methoxypheno1 with formaldehyde and a suitable dialkyl amine such as dimeth'yl amine, diethyl amine, dipropyl amine, etc. In some cases, ammonia may be employed instead of the dialkyl amine but usually improved results are obtained with the dialkyl amine. In this particular preparation, it is desired to introduce two methyl groups in the aromatic ring and, therefore, at least 2 mols of formaldehyde are employed per mol of 4-alkoxyphenol. In general, it is also desirable to use an excess of dialkyl amine and this generally will be over 2 mols per mol of the alkoxy phenol. When the dialkyl amine comprises diethyl amine, the resultant product will be a diethyl-aminomethyl derivative. When an ethyl group or diethyl groups are desired, acetaldehyde will be used in place of formaldehyde. Similarly, when propyl or dipropyl groups are desired, ropaldehyde is utilized, etc.
When 2-methyl-6-tertiary-butyl-4-methoxyphenol is desired, this is readily prepared by starting with Z-tertiary-butyl-4-methoxyphenol and reacting the same with formaldehyde in the presence of a suitable dialkyl amine. In this instance, at least one mol of formaldehyde per mol of alkoxyphenol is required. The 2-tertiarybutyl4-methoxyphenol is readily prepared by the alkylation of 4-methoxyphenol with tertiary butyl alcohol in the presence of a phosphoric acid catalyst. Thus, 4-methoxyphenol may be reacted with tertiary butyl alcohol at a temperature of 75-80 C. in the presence of a catalyst comprising 85% phosphoric acid.
The dialkyl amine derivative of 4-alkoxyphenol is hydrogenated to form the desired 2,6-dialkyl- 4-alkoxyphenol. The hydrogenation may be effected in any suitable manner, a preferred method being in the presence of hydrogen and a nickel catalyst at a temperature of from about to about 200 C. or more, preferably at a substantial superatmospheric pressure which generally will range from 100 pounds to 1000 pounds or more per square inch.
The inhibitor of the present invention is generally added to Organic materials in an amount of less than 1% by weight and preferably within the range of from about 0.001% to about 0.5%. When used in gasoline, it is understood that the inhibitor may be used in conjunction with various dyes, inhibitor activators, metal deactivators, antiknock agents such as tetraethyl lead, etc. When used in edible fats and oils, it is understood that the inhibitor may be used in conjunction with a synergist, such as phosphoric acid, ascorbic acid, etc.
The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.
Example I 2,6-dimethyl-4-methoxyphenol was prepared by reacting 4-methoxyphenol with formaldehyde and diethyl amine at room temperature. Over 2 mols of formaldehyde and over 2 mols of diethyl amine were used per mol of 4-methoxyphenol. The reaction occurred readily at room temperature and the product was extracted with caustic to remove unreacted methoxyphenol. The resultant product was then distilled to remove excess diethylamine and finally was recovered by extraction in acid to separate the desired product from by-products of the reaction. The product was washed and then hydrogenated in a pentane solvent with 10-20 weight percent of nickel catalyst, 1000 pounds per square inch of hydrogen at a temperature of C. for a period of 6 hours.
0.02% by Weight of the 2,6-dimethyl-4-methoxyphenol, prepared in the above manner, was added to a Pennsylvania cracked gasoline having a blank induction period of 90 minutes and this served to increase the induction period thereof to 395 minutes.
0.02% by weight of the 2,6-dimethyl-4-methoxyphenol was added to a lard having a normal stability period of 3 hours and served to increase the stability period thereof to 18.75 hours.
Example If 2- methyl-6-tertiary-butyl 4 methoxyphenol was prepared in substantially the same manner as described in Example I except that Z-tertiarybutyl-4-methoxyphenol was utilized in place of 4-methoxyphenol as the primary reactant.
0.02% by weight of the Z-methyl-S-tertiarybutyll-methoxyphenol, prepared in the above manner, was added to another sample of the Pennsylvania cracked gasoline and served to increase the induction period thereof to 380 minutes.
When 0.02% by weight of the 2nnethyl-6- tertiary-butyl-4-methoxyphenol was added to another sample of the lard having a normal stability period of 3% hours, it served to increase the stability period thereof to 35 hours.
Example III 2 methyl -6- secondary butyl -4- methoxyphenol was prepared in substantially the same manner as described in the preceding examples. In this instance, 2-secondary-butyl-4-methoxyphenol was utilized as one of the primary reactants.
0.02% by weight of the 2-methyl-6-secondarybutyl-4-methoxyphenol was added to another sample of the cracked gasoline and served to increase the induction period thereof to 350 minutes.
0.02% by weight of the Z-methyl-fi-secondarybutyl-4-methoxyphenol, when added to another sample of the lard, increased the stability period thereof to 24 hours.
I claim as my invention:
1. A method of stabilizing an organic material subject to oxidative deterioration which comprises adding thereto an inhibitor comprising a 2,6-dialkyl-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
2. A method of stabilizing motor fuel subject to oxidative deterioration which comprises adding thereto a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
3. A method of stabilizing edible fats and oils subject to oxidative deterioration which comprises adding thereto an inhibitor comprising a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
4. A method of stabilizing lard subject to oxidative deterioration which comprises adding thereto from about 0.001% to about 0.5% by Weight of 2-methyl-6-tertiary-butyl-4-methoxyphenol.
5. Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2,6-dia1kyl-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms. deterioration containing not more than 1% by 6. Edible fats and oils subject to oxidative weight of a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms, the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
7. Lard subject to oxidative deterioration containing from about 0.001% to about 0.5% by weight of 2-methyl-6-tertiary-butyl-4-methoxyphenol.
8. Motor fuel subject to oxidative deterioration containing not more than about 1% by weight of a 2,6-dialkyl-4-alkoxyphenol in which one of the alkyl groups is a branched chain alkyl radical of from about 3 to about 10 carbon atoms,
the other alkyl group contains not more than about 4 carbon atoms, and the alkoxy group contains not more than about 4 carbon atoms.
9. A method of stabilizing motor fuel subject to oXidative deterioration which comprises adding thereto from about 0.001% to about 0.5% by Weight of 2-methyl-6-tertiary-buty1-4-methoxyphenol.
10. Gasoline subject to oxidative deterioration containing from about 0.001% to about 0.5% by weight of 2-methyl6-tertiary-butyl-4-methoxyphenol.
11. Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2 alkyl -6- tertiary butyl 4- ethoxyphenol, said alkyl group containing not more than about 4 carbon atoms.
12. Edible fats and oils subject to oxidative deterioration containing no more than 1% by weight of 2-methy1 -6- tertiary-butyl -4- ethoxyphenol.
13. Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2 alkyl 6 tertiary amyl 4- ethoxyphenol, said alkyl group containing not more than about 4 carbon atoms.
14. Edible fats and oils subject to oxidative deterioration containing no more than 1% by weight of 2-inethyl-6tertiary-amyl-4-methoxyphenol.
15. Organic material subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2 alkyl 6 tertiary octyl 4- alkoxyphenol, said alkyl group containing not more than about 4 carbon atoms.
16. Edible fats and oils subject to oxidative deterioration containing no more than 1% by weight of 2-methyl-B-tertiary-octyl-4-methoxyphenol.
17. Organic material subject. to oxidative deterioration containing, as an inhibitor for said deterioration, a 2,6-di-tertiary-alkyl-4-alkoxyphenol, one of said alkyl groups containing from about 3 to about 10 carbon atoms, the other alkyl group containing not more than about 4 carbon atoms, and the alkoxy group containing not more than about 4 carbon atoms.
18. Edible fats and oils subject to oxidative deterioration containing, as an inhibitor for said deterioration, a 2,6-di-tertiary-butyl-4-methoxyphenol.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Kraybill et al.: Studies on Antioxidants, Bull. 2, April 1948, Am. Meat Inst. Found.

Claims (1)

  1. 6. EDIBLE FATS AND OILS SUBJECT TO OXIDATIVE WEIGHT OF A 2,6-DIALKYL-4-ALKOXYPHENOL IN WHICH ONE OF THE ALKYL GROUPS IS A BRANCHED CHAIN ALKYL RADICAL OF FROM ABOUT 3 TO ABOUT 10 CARBON ATOMS, THE OTHER ALKYL GROUP CONTAINS NOT MORE THAN ABOUT 4 CARBON ATOMS, AND THE ALKOXY GROUP CONTAINS NOT MORE THAN ABOUT 4 CARBON ATOMS.
US111347A 1949-08-19 1949-08-19 Stabilization of organic compounds Expired - Lifetime US2679459A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US111347A US2679459A (en) 1949-08-19 1949-08-19 Stabilization of organic compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US111347A US2679459A (en) 1949-08-19 1949-08-19 Stabilization of organic compounds

Publications (1)

Publication Number Publication Date
US2679459A true US2679459A (en) 1954-05-25

Family

ID=22337995

Family Applications (1)

Application Number Title Priority Date Filing Date
US111347A Expired - Lifetime US2679459A (en) 1949-08-19 1949-08-19 Stabilization of organic compounds

Country Status (1)

Country Link
US (1) US2679459A (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2833634A (en) * 1953-01-26 1958-05-06 Ethyl Corp Synergistic antioxidants and their use
US2836568A (en) * 1955-12-02 1958-05-27 Ethyl Corp Stabilized fuel antiknock
US2888503A (en) * 1955-12-29 1959-05-26 Universal Oil Prod Co 2, 6 dialkoxy, 4 alkyl phenol antiozidants
US2888502A (en) * 1955-12-29 1959-05-26 Universal Oil Prod Co Antiozidation of rubber with 2, 6 dialkoxy-4-allyl phenol
US2942033A (en) * 1960-06-21 Stabilization of polyoxyalkylene
US2957903A (en) * 1959-03-24 1960-10-25 Du Pont Stabilization of organic isocyanates
US3017443A (en) * 1957-12-30 1962-01-16 Universal Oil Prod Co Method of incorporating a mixture of 2, 6-dialkoxy-4-alkylphenol and 2, 2'-alkylene-bis-(4, 6-dialkylphenol) in rubber, and resulting product
US3271456A (en) * 1962-03-26 1966-09-06 Exxon Research Engineering Co Oxygenated organic compounds of improved odor
US3409683A (en) * 1967-06-07 1968-11-05 Union Carbide Corp Stabilization of alkylidenebicycloheptenes
US3415891A (en) * 1964-02-07 1968-12-10 Takeda Chemical Industries Ltd Stabilization of polyoxyalkylene polyols with ascorbic acid type stabilizer
US3423469A (en) * 1962-04-30 1969-01-21 Monsanto Co Polyphenyl ether compositions
US3873466A (en) * 1971-09-17 1975-03-25 Ici Ltd Stabilisation of fats and oils with phenolic antioxidants
US3969383A (en) * 1974-01-07 1976-07-13 Ciba-Geigy Corporation Fat compositions stabilized with esters of fatty acids and tertiary lower alkyl substituted hydroquinones and method therefrom
US4552682A (en) * 1982-09-30 1985-11-12 Ppg Industries, Inc. Peroxide composition containing phenolic antioxidant
EP0589069A1 (en) * 1992-09-18 1994-03-30 Nippon Hypox Laboratories Incorporated Hydroquinone derivatives and antioxidants and tumor inhibitors containing them
US5847224A (en) * 1995-06-23 1998-12-08 Global Octanes Corporation Method for improving the color of MTBE, ETBE and TAME

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2031069A (en) * 1931-05-12 1936-02-18 Swift & Co Stabilization of oils and fats
US2138924A (en) * 1936-05-27 1938-12-06 Goodrich Co B F Antioxidant
US2235884A (en) * 1937-07-01 1941-03-25 Merck & Co Inc Ethers of trimethyl-hydroquinone and process of preparing the same
US2247364A (en) * 1937-06-04 1941-07-01 Merck & Co Inc Alkyl ethers of duro-hydroquinone and process for producing the same
US2280814A (en) * 1937-06-03 1942-04-28 Merck & Co Inc Ethers of durohydroquinone and process of preparing same
US2310710A (en) * 1939-09-18 1943-02-09 Universal Oil Prod Co Inhibitor for gasoline

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2031069A (en) * 1931-05-12 1936-02-18 Swift & Co Stabilization of oils and fats
US2138924A (en) * 1936-05-27 1938-12-06 Goodrich Co B F Antioxidant
US2280814A (en) * 1937-06-03 1942-04-28 Merck & Co Inc Ethers of durohydroquinone and process of preparing same
US2247364A (en) * 1937-06-04 1941-07-01 Merck & Co Inc Alkyl ethers of duro-hydroquinone and process for producing the same
US2235884A (en) * 1937-07-01 1941-03-25 Merck & Co Inc Ethers of trimethyl-hydroquinone and process of preparing the same
US2310710A (en) * 1939-09-18 1943-02-09 Universal Oil Prod Co Inhibitor for gasoline

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2942033A (en) * 1960-06-21 Stabilization of polyoxyalkylene
US2833634A (en) * 1953-01-26 1958-05-06 Ethyl Corp Synergistic antioxidants and their use
US2836568A (en) * 1955-12-02 1958-05-27 Ethyl Corp Stabilized fuel antiknock
US2888503A (en) * 1955-12-29 1959-05-26 Universal Oil Prod Co 2, 6 dialkoxy, 4 alkyl phenol antiozidants
US2888502A (en) * 1955-12-29 1959-05-26 Universal Oil Prod Co Antiozidation of rubber with 2, 6 dialkoxy-4-allyl phenol
US3017443A (en) * 1957-12-30 1962-01-16 Universal Oil Prod Co Method of incorporating a mixture of 2, 6-dialkoxy-4-alkylphenol and 2, 2'-alkylene-bis-(4, 6-dialkylphenol) in rubber, and resulting product
US2957903A (en) * 1959-03-24 1960-10-25 Du Pont Stabilization of organic isocyanates
US3271456A (en) * 1962-03-26 1966-09-06 Exxon Research Engineering Co Oxygenated organic compounds of improved odor
US3423469A (en) * 1962-04-30 1969-01-21 Monsanto Co Polyphenyl ether compositions
US3415891A (en) * 1964-02-07 1968-12-10 Takeda Chemical Industries Ltd Stabilization of polyoxyalkylene polyols with ascorbic acid type stabilizer
US3409683A (en) * 1967-06-07 1968-11-05 Union Carbide Corp Stabilization of alkylidenebicycloheptenes
US3873466A (en) * 1971-09-17 1975-03-25 Ici Ltd Stabilisation of fats and oils with phenolic antioxidants
US3969383A (en) * 1974-01-07 1976-07-13 Ciba-Geigy Corporation Fat compositions stabilized with esters of fatty acids and tertiary lower alkyl substituted hydroquinones and method therefrom
US4552682A (en) * 1982-09-30 1985-11-12 Ppg Industries, Inc. Peroxide composition containing phenolic antioxidant
EP0589069A1 (en) * 1992-09-18 1994-03-30 Nippon Hypox Laboratories Incorporated Hydroquinone derivatives and antioxidants and tumor inhibitors containing them
US5847224A (en) * 1995-06-23 1998-12-08 Global Octanes Corporation Method for improving the color of MTBE, ETBE and TAME

Similar Documents

Publication Publication Date Title
US2679459A (en) Stabilization of organic compounds
US3644278A (en) Substituted hydroxylamine stabilizers
US2962531A (en) 3, 5-dialkyl-4-hydroxy benzylamines
US2279973A (en) Stabilization of organic substances
US2479948A (en) Stabilized composition
US2553441A (en) Stabilization of organic materials
US2591651A (en) Stabilized organic compositions containing bis (hydroxy alkoxy phenyl) alkanes
US3367870A (en) Method of stabilization with carbonbonded phosphorus derivatives and compositions stabilized thereby
US3579582A (en) Hydroxy and/or hydrocarbyloxy and amino substituted tetrahydronaphthalenes
US2633425A (en) Stabilization of organic compounds
US3345327A (en) Stabilization of propylene
CN102492524A (en) Synthesis method for liquid phenolic ester type antioxidants
US2771368A (en) Stabilization of organic compounds
US2668768A (en) Stabilization of edible fats and oils
US2959550A (en) Nonvolatile organic compositions stabilized by nu-alkyl p-hydroxybenzamide
US2864676A (en) Stabilization of organic compounds
US2554687A (en) Stabilization of organic compounds
US2771367A (en) Stabilization of organic compounds
US3867445A (en) Substituted hydroxylamine anti-oxidants
US2698247A (en) Stabilization of organic compounds
US2770545A (en) Stabilization of organic compounds
US2633415A (en) Stabilization of organic compounds
US3493616A (en) Hydroxy and/or hydrocarbyloxy and amino-alkano-tetrahydronaphthalenes
US2801926A (en) Stabilization of organic compounds
US3010812A (en) Stabilization of organic compounds