EP0163635A4 - Process for preparing substituted benzyl malonic acid esters. - Google Patents
Process for preparing substituted benzyl malonic acid esters.Info
- Publication number
- EP0163635A4 EP0163635A4 EP19840900178 EP84900178A EP0163635A4 EP 0163635 A4 EP0163635 A4 EP 0163635A4 EP 19840900178 EP19840900178 EP 19840900178 EP 84900178 A EP84900178 A EP 84900178A EP 0163635 A4 EP0163635 A4 EP 0163635A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- butyl
- hydride
- ester
- reaction
- malonic acid
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
Definitions
- This invention relates to 3, 5-dihydrocarbyl-4- hydroxybenzylmalonic acid esters and the preparation and uses thereof as antioxidants for oxidizable organic materials when such materials are exposed to oxidative degradative conditions.
- the materials of the invention are prepared by reacting a 2,6-dihydrocarbyl-4-substituted-methylphenol with an ester of a 1,3-dicarboxylic acid in the presence of an alkali metal hydride or an alkaline earth metal hydride.
- a novel process for the preparation of 3, 5-dihydrocarbyl-4-hydroxybenzylmalonic acid esters which comprises reacting a 2, 6-dihydrocarbyl-4-hydroxy or -halogen substituted-methylphenol with an ester of a 1,3-dicarboxylic acid in the presence of an alkali metal hydride or an alkaline earth metal hydride.
- R 1 and R 2 are the same or different and are hydrogen or hydrocarbyl radicals having up to at least 40 carbon atoms with the provision that at least one of R 1 or R 2 must be other than hydrogen;
- R 3 and R 4 are the same or different and are linear or branched alkyl radicals having up to at least 20 carbon atoms with the provision that at least one of R 3 or R 4 must be other than hydrogen and
- Y is hydroxy or halogen.
- radicals described above are secondary radicals such as secondary butyl, secondary amyl, secondary octyl; tertiary radicals such as tertiary butyl, tertiary hexyl and tertiary decyl; alkyl radicals such as methyl, ethyl, propyl, butyl, nonyl, decyl, tetradecyl, hexadecyl, nonadecyl; aralkyl radicals such as methyl phenyl and pentyl phenyl, and cycloalkyl radicals such as cyclopentyl, cyclohexyl and cycloheptyl radicals.
- secondary radicals such as secondary butyl, secondary amyl, secondary octyl
- tertiary radicals such as tertiary butyl, tertiary hexyl and tertiary decyl
- Group II esters ofarboxylic acid compounds are malonic acid, dimethyl ester, malonic acid, diethyl ester, malonic acid, diisopropyl ester, malonic acid, di-n-hexyl ester, malonic acid, dioctyl ester, malonic acid, didodecyl ester, malonic acid, ethyl, methyl diester, malonic acid, ethyl, isopropyl diester, malonic acid, n-butyl, ethyl diester, malonic acid, n-butyl, dodecyl diester, malonic acid, octyl, ethyl diester, malonic acid, ethyl monoester, malonic acid, n-propyl monoester
- Group III benzylated malonic acid esters functioning as antioxidants are 3, 5-di-t-butyl-4-hydroxybenzylmalonic acid, dimethyl ester, 3, 5-di-t-butyl-4-hydroxybenzylmalonic acid, diethyl ester, 3, 5-di-t-butyl-4-hydroxybenzylmalonic acid, diisopropyl ester,
- any of the alkali metal hydrides or alkaline earth metal hydrides may be used in the practice of the present process. These include sodium hydride, potassium hydride, lithium hydride, magnesium hydride, calcium hydride, and the like. Sodium hydride is preferred.
- the process of the invention is carried out by reacting the 2,6-dihydrocarbyl-4-hydroxymethylphenol or the 2, 6-dihydrocarbyl-4-halomethylphenol starting material with at least 1 molar equivalent of malonic acid ester reactant although an excess of ester reactant can be used.
- a preferred range of malonic acid ester reactant to halomethylphenol reactant or hydroxymethylphenol reactant is from about 1 to 10 moles of ester per mole of halomethylphenol or hydroxymethylphenol reactant.
- At least 1 mole of hydride per mole of halomethylphenol or hydroxymethylphenol reactant should be used in the process of the invention, although an amount of hydride up to about 50 moles of hydride per mole of the substituted methylphenol reactant can be used, if desired.
- the reaction is advantageously conducted at a temperature of from 50°C. to 500°C. While lower temperatures can be used, the reaction rates are generally correspondingly lower. Temperatures above 500°C. can be used, but excessive decomposition of the reaction components can occur. Reflux temperature at atmospheric pressure is effective and preferred. Typically, the reaction can be conducted at atmospheric pressure. However, higher pressures up to about 1000 psig may be used, if desired.
- a solvent for the reaction mixture is not generally required, especially if an excess of malonic acid ester reactant is used.
- a solvent which is inert under the reaction conditions i.e., those solvents which do not enter into the reaction, may be added to the reaction vessel.
- Useful solvents comprise aprotic solvents which include ethers such as diethyl ether, dibutyl ether, 1-ethoxyhexane, tetrahydrofuran, 1,4-dioxane, 1, 3-dioxolane, diglyme, 1,2-diethoxyethane, and tertiary amines such as pyridine, N-ethylpiperidine, triethylamine, tributylamine, N,N-diphenyl-N-methylamine, N,N-dimethylalanine, etc.
- ethers such as diethyl ether, dibutyl ether, 1-ethoxyhexane, tetrahydrofuran, 1,4-dioxane, 1, 3-dioxolane, diglyme, 1,2-diethoxyethane, and tertiary amines such as pyridine, N-ethylpiperidine, triethylamine, tribut
- Especially useful solvents are dipolar aprotic solvents such as dimethyl sulfoxide, N,N-dimethylforma mide, N.N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone, acetonitrile and like materials.
- Other solvents which are inert under the reaction conditions may be used: for example, low boiling hydrocarbons, halogenated hydrocarbons, examples of which are benzene, toluene, tetrachloroethane, the chlorinated benzenes, the chlorinated toluenes, etc., and lower alkanols having up to about 6 carbon atoms.
- the amount of solvent can be expressed as a volume ratio of solvent to halomethylphenol reactant or hydroxymethylphenol reactant.
- Suitable volume ratios of solvent to halomethylphenol reactant or hydroxymethylphenol reactant can be from 0/1 to 500/1 and preferably from 1/1 to 300/1.
- the mode of addition in the process is not particularly critical. Accordingly, it is convenient to add the halomethylphenol reactant or the hydroxymethylphenol reactant to a mixture of the other materials, add the malonic acid ester compound to a mixture of the other materials, add the reactants to a mixture of the substituted methylphenol and solvent, introduce all ingredients simultaneously into the reaction zone, or the like.
- the process should be carried out for the time sufficient to convert substantially all of the halomethylphenol reactant or the hydroxymethylphenol to the corresponding benzylated malonic acid ester.
- the length of time for optimum yield will depend primarily upon the reaction temperature and the particular solvent, if any, used in the reaction. In general, excellent yields of the benzylated malonic acid ester are obtained in from about two to twenty-four hours.
- substantially anhydrous is meant a reaction system wherein the total amount of water present is no more than about 5 percent by weight, based on the reaction mixture. When the amount of water in the system exceeds this, both reaction rate and yield of product decrease.
- the process may readily be conducted in a batchwise, semi-batch or continuous manner and in conventional equipment. Under the reaction conditions, elimination of the hydroxyl group or halide occurs yielding a quinone methide intermediate which undergoes nucleophilic attack by the malonic acid ester reactant to form the desired benzylated malonic acid ester product. Some bis (hydroxyphenyl)methane and benzyl ether by-products may also be formed.
- the benzylated malonic acid ester product is easily separated from the reaction mixture by such means as distillation, extraction, crystallization and other methods obvious to those skilled in the chemical processing art.
- the benzylated malonic acid ester products prepared by the process of this invention have antioxidant properties and are capable of stabilizing polymers normally subject to oxidative degradation when incorporated into the polymers using conventional techniques such as by addition to polymer lattices; or by addition to solid polymers on a mill or in a Sanbury.
- the novel compounds of this invention are effective antioxidants in both unleaded and leaded gasolines made from a wide variety of base stocks and for engine and industrial oils which are derived from crude petroleum or produced synthetically.
- Example I A dimethylformamide solution (25 mmols) of diethyl sodiomalonate (generated by treating a dimethylformamide solution of 2.4 g; 15 mmols diethyl malonate with 0.72 g; 30 mmols oil-free sodium hydride) was added with stirring under a nitrogen atmosphere to a dimethylformamide solution (25 mLs) of 2,6-di-t-butyl-4-chloromethylphenol (2.49 g; 10 mmols).
- diethyl sodiomalonate generated by treating a dimethylformamide solution of 2.4 g; 15 mmols diethyl malonate with 0.72 g; 30 mmols oil-free sodium hydride
- reaction mixture was heated to a temperature of 125°C and held at that temperature for 3 hours and then poured into cold 2N hydrochloric acid (100 mLs) .
- the aqueous reaction slurry was extracted with diethyl ether (3 x 30 mLs).
- the combined organic extract was dried (MgSO 4 ) and concentrated to give 2.44 g; 39% by VPC of 3,5-di-t-butyl-4-hydroxybenzylmalonic acid, diethyl ester.
- Example II To an ethanol solution (10 mLs) of 2,6-di-t-butyl-4-hydroxymethylphenol (2.63 g; 10 mmols) and ethanol solution (15 mmols) of diethyl sodiomalonate (generated by treating an ethanol solution of 1.6 g; 10 mmols diethyl malonate with 0.48 g; 20 mmols oil-free sodium hydride) was added with stirring under a nitrogen atmosphere. The reaction mixture was heated at reflux for 16 hours and then poured into cold 2N hydrochloric acid (100 mLs) . The aqueous reaction slurry was extracted with diethyl ether (3 x 30 mLs). The combined organic extract was dried (MgSO 4 ) and concentrated to give 1.42 g; 39% by VPC of 3,5-di-t-butyl-4-hydroxybenzylmalonic acid, ethyl ester.
- diethyl sodiomalonate generated by treating an ethanol solution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1983/001817 WO1985002182A1 (en) | 1983-11-15 | 1983-11-15 | Process for preparing substituted benzyl malonic acid esters |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0163635A1 EP0163635A1 (en) | 1985-12-11 |
EP0163635A4 true EP0163635A4 (en) | 1986-04-02 |
Family
ID=22175590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19840900178 Pending EP0163635A4 (en) | 1983-11-15 | 1983-11-15 | Process for preparing substituted benzyl malonic acid esters. |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0163635A4 (en) |
JP (1) | JPS61500546A (en) |
WO (1) | WO1985002182A1 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2352107A1 (en) * | 1973-04-26 | 1974-11-14 | Socechim | NEW CHEMICAL COMPOUNDS, THEIR PRODUCTION METHODS AND APPLICATIONS OF THESE COMPOUNDS, IN PARTICULAR TO THE SYNTHESIS 2,4-DIAMINO- (3 ', 4', 5'-TRIMETHOXY-) 1-BENZYL-PYRIMIDINE |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2161213A (en) * | 1939-06-06 | Substituted malonig esters | ||
AT61183B (en) * | 1911-03-10 | 1913-09-10 | Farbenfab Vorm Bayer F & Co | Process for the preparation of ethyl aryl malonic esters and ethyl aryl cyano acetic esters. |
US1984283A (en) * | 1931-02-05 | 1934-12-11 | Du Pont | Ester of polycarboxylic acids |
GB653319A (en) * | 1947-01-18 | 1951-05-16 | Abbott Lab | Improvements in or relating to the manufacture of malonates and cyanoacetates |
-
1983
- 1983-11-15 EP EP19840900178 patent/EP0163635A4/en active Pending
- 1983-11-15 WO PCT/US1983/001817 patent/WO1985002182A1/en not_active Application Discontinuation
- 1983-11-15 JP JP84500143A patent/JPS61500546A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2352107A1 (en) * | 1973-04-26 | 1974-11-14 | Socechim | NEW CHEMICAL COMPOUNDS, THEIR PRODUCTION METHODS AND APPLICATIONS OF THESE COMPOUNDS, IN PARTICULAR TO THE SYNTHESIS 2,4-DIAMINO- (3 ', 4', 5'-TRIMETHOXY-) 1-BENZYL-PYRIMIDINE |
Non-Patent Citations (1)
Title |
---|
See also references of WO8502182A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1985002182A1 (en) | 1985-05-23 |
JPS61500546A (en) | 1986-03-27 |
EP0163635A1 (en) | 1985-12-11 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB LI LU NL SE Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB LI LU NL SE |
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Effective date: 19851115 |
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A4 | Supplementary search report drawn up and despatched |
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17Q | First examination report despatched |
Effective date: 19870611 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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REG | Reference to a national code |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: ROPER, JERRY, MONROE Inventor name: EVERLY, CHARLES, RAY |