GB2026479A - Process for preparing hindered phenolic aldehydes - Google Patents
Process for preparing hindered phenolic aldehydes Download PDFInfo
- Publication number
- GB2026479A GB2026479A GB7923460A GB7923460A GB2026479A GB 2026479 A GB2026479 A GB 2026479A GB 7923460 A GB7923460 A GB 7923460A GB 7923460 A GB7923460 A GB 7923460A GB 2026479 A GB2026479 A GB 2026479A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hindered phenolic
- hydrogen
- phenolic aldehyde
- process according
- hindered
- 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.)
- Granted
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- -1 phenolic aldehydes Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000000526 short-path distillation Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 abstract description 5
- 239000011368 organic material Substances 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IQRXEGCBJWNCHY-UHFFFAOYSA-N 2,6-dihydroxyheptan-4-one Chemical compound CC(O)CC(=O)CC(C)O IQRXEGCBJWNCHY-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- AKGIGSUIOWBKLL-UHFFFAOYSA-N 4-(3,5-ditert-butyl-4-hydroxyphenyl)butan-2-one Chemical compound CC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 AKGIGSUIOWBKLL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GAGNIIQUGIBVSU-UHFFFAOYSA-N CC(CC(=O)CC(C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C Chemical group CC(CC(=O)CC(C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C GAGNIIQUGIBVSU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000006423 Tishchenko reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SMTUJUHULKBTBS-UHFFFAOYSA-N benzyl(trimethyl)azanium;methanolate Chemical compound [O-]C.C[N+](C)(C)CC1=CC=CC=C1 SMTUJUHULKBTBS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003555 thioacetals Chemical class 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/26—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups
- C07C47/27—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/002—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by transformation of a functional group, e.g. oxo, carboxyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Novel hindered phenolic aldehydes of formula <IMAGE> wherein R and R<1> are alkyl, cycloalkyl or aralkyl, R<2> is alkyl or hydrogen, and R<3> is methyl or hydrogen, are prepared by the reaction of a hindered phenol with acrolein or methacrolein. The hindered phenolic aldehydes are important intermediates in the preparation of organic compounds which are useful as stabilizers for organic materials subject to oxidative deterioration.
Description
SPECIFICATION
Process for preparing hindered phenolic aldehydes
This invention relates as indicated to a process for preparing hindered phenolic aldehydes. More particularly, it relates to such a process which is conveniently carried out at relatively low temperatures and which produces good yields of the desired product.
The hindered phenolic aldehydes which are produced by this process are useful in the preparation of a certain type of compound which is in turn useful as an oxidation inhibitor. These compounds are characterized by a chemical structure containing a 3,5-dialkyl-4-hydroxyphenylalkyl group, viz.,
where Rand R1 are lower alkyl, cycloalkyl or aralkyl groups, i.e., alkyl, cycloalkyl or aralkyl groups of 3-10 carbon atoms, R2 is a lower alkyl group or hydrogen, R3 is methyl or hydrogen.They are said to be useful not only as oxidation inhibitors but also as stabilizers for oganic material normally subject to deterioration caused by heat, light, oxygen, ozone and other physical and/or chemical forces tending to cause degradation, embrittlement, gum or sludge formation, discoloration and other undesirable effects in a variety of organic materials, e.g., lubricating oils and fuel oils, and in general, oils of animal, vegetable or mineral origin, waxes, soaps, greases, gasolines, natural and synthetic rubbers, resins and plastics such as olefin polymers, e.g., polyethylene and polypropylene. Compounds of this type are shown in U.S. Patents 3,226,443; 3,242,240; 3,285,855; 3,531,483; 3,644,482; 3,923,735; 4,081,475; Re. 27,004; and U.K. 1,355,109.
The preparation of 4-(3',5'-ditertiarybutyl-4'-hydroxyphenyl) butan-2-one by the reaction of 2,6ditertiarybutylphenol with methylvinyl ketone is shown in U.S. Patent 3,226,443. Potassium t-butoxide is a catalyst for the reaction which is carried out at 50-650C for over 16 hours.
A similar reaction usng methyl methylacrylate instead of methylvinyl ketone, to prepare methyl-3-(3'5'ditertiarybutyl-4-hydroxyphenyl) propionate, is shown in U.S. Patents 3,247,240; 3,644,482; and Re. 27,004.
Although potassium t-butoxide is shown as the catalyst, benzyltrimethylammonium methoxide and sodamide are said to be effective catalysts also.
U.S. Patent 3,923,735 shows a somewhat similar reaction involving a 2,6-ditertiarybutylphenol and methylhydroxyethyl ketone. Sulfuric acid is the catalyst. The product is methyl-2-(3',5'-ditertiarybutyl-4'hydroxyphenyl)ethyl ketone. No reaction conditions are given.
The process here makes available a compound having the above-indicated 3,5-dialkyl-4hydroxyphenylalkyl group. It comprises reacting acrolein or methacrolein with a hindered phenol having the structure:
where Rand R1 are alkyl, cycloalkyl or aralkyl groups of 3-10 carbon atoms and R2 is a lower alkyl group or hydrogen.
In a preferred instance, R and R1 in the above hindered phenol reactant preferably, in one instance, are the same and, still more preferably, they are tertiary alkyl groups. A particularly preferred phenolic reactant, because of its ready availability and the efficacy of stabilizer products prepared therefrom, is 2,6ditertiarybutylphenol. In another preferred instance one of R and R1 is a blocking group such as tertiary butyl, amethylstryryl or cyclohexyl, and the other is methyl or ethyl, and R2 is methyl. The term "lower alkyl" means an alkyl group having 1-4 carbon atoms.
The two reactants are used in approximately stoichiometric quantities, i.e., one mol of acrolein per mol of dialkylphenol. Large excessive amounts of acrolein should be avoided so as to minimize the formation of undesirable by-products. The reaction is slightly exothermic and external cooling is required if the temperature of the reaction mixture is to be maintained at a constant level. Ordinarily, the temperature should be maintained within the range of from about -10 C to about 60"C.
Because of the sensitivity of acrolein to polymerization under a wide variety of conditions, it is desirable to add to it in very small portions to the reaction mixture. Otherwise there is a considerable risk that the ultimate yield of the desired product will be diminished by the formation of undesirable by-products as above. One very effective way to add the acrolein to the reaction mixture is to evacuate a closed system to a pressure of 20 mm. Hg and permit the acrolein to vaporize (at room temperature) into the reaction mixture from a separate flask.
The hindered phenolic aldehyde product which results may be purified by distillation. The product mixture is not entirely stable at high temperatures and it is desirable to conduct the distillation quickly and at reduced pressure, e.g., in a short-path distillation apparatus. Also, because of the relatively high temperatures at which the hindered phenolic aldehydes distill, it is helpfu I to add a very low vapor pressure oil such as peanut oil or mineral oil to the product mixture just prior to distillation to serve as a carrier. The distilled product tends to decompose on standing with the formation of higher molecular weight materials and, unless it is to be used promptly, it is advisable to purify it further as by crystallization from heptane. The crystallized product is relatively stable.
The reaction is carried out in the presence of a basic catalyst such as an alkali metal oxide, hydroxide, alcoholate, carbonate or bicarbonate. Alkali metal alcoholates of lower alcohols, i.e., 1-8 carbon atoms, are preferred. Illustrative species include sodium or potassium methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, t-butoxide, n-hexoxide, t-pentoxide, etc. Sufficient catalyst should be used to insure the alkalinity of the process mixture throughout the time of reaction. An amount within the range of from about 0.001 to about 0.25 mol of catalyst per mol of hindered phenol reactant is desirable for this purpose.
A solvent ordinarily is used. It facilitates temperature control and also insures intimate contact of the reactants. Any inert, low-boiling (below 150"C) solvent is suitable. Alcohols, ethers, hydrocarbons, ketones, etc. are illustrative of solvents that are contemplated.
The hindered phenolic aldehyde product may, as indicated, be used to prepare compounds which are useful as stabilizers for organic materials which are subject to oxidative (or other) deterioration. Thus, it may be reduced to the corresponding alcohol, as below:
which may, in turn, be esterified with any of the various mono- or poly-carboxylic acids to form stabilizeers of the type shown in U.K. Patent 1,355,109. Also, the hindered phenolic alehyde may be reacted with alcohols or mercaptans to form acetals or thioacetals; or they may be converted to the corresponding esters via the
Tishchenko reaction. All of these and other such products are effective stabilizers for organic materials and, in particular, for polymers.
An illustrative example of the process herein is as follows:
Example
To a stirred solution of 206 g. (1.0 mol) of 2,6-ditertiarybutylphenol in 200 ml. of 2-ethylhexanol containing 0.5 ml. of a 30% solution of postassium tertiary-pentoxide in tertiarypentyl alcohol, at a pressure of about 20 mm. Hg. there is added 68 ml. (53 g., 1.0 mol) of acrolein. The acrolein is added portionwise, as a vapor over a period of one hour, with external cooling of the reaction mixture so as to maintain the temperature at 20-25"C. The reaction mixture is stirred until a gas chromatogram shows 85-90% conversion. The product mixture is neutralized with carbon dioxide and then diluted with 100 g. of peanut oil. The resulting mixture is distilled rapidly in a short-path distillation apparatus; a film still wherein the wall temperature is 275-300"C is suitable. The distillation is carried out at 0.1-0.5 mm. Hg within an hour. The yield is 185-215 g. of a product containing 92-97% of the desired phenolic aldehyde. The distilled product can be purified by crystallization from a 40-50% heptane solution, M.P., 70-73"C.
Ali parts and percentages herein are by weight unless otherwise expressly stated.
Claims (12)
1. A hindered phenolic aldehyde of the general formula:
wherein R and R1, which may be the same or different, each represent alkyl, cycloalkyl or aralkyl groups of 3 to 10 carbon atoms, R2 represents an alkyl group of 1 to 4 carbon atoms or hydrogen, and R3 is methyl or hydrogen.
2. A hindered phenolic aldehyde according to claim 1 wherein R and R1 are the same and R2 is hydrogen.
3. A hindered phenolic aldehyde according to claim 1 or 2 wherein Rand R1 are tertiary alkyl groups and
R2 is hydrogen.
4. A hindered phenolic aldehyde according to claim 3 wherein R and R1 are tertiary butyl groups and R2 is hydrogen.
5. A process for the preparation of a hindered phenolic aldehyde as claimed in any one of the preceding claims which process comprises reacting acrolein or methacrolein with a hindered phenol of the general formula:
where R, R1 and R2 are as defined in any one of the preceding claims.
6. A process according to claim 5 wherein the acrolein or methacrolein is added portionwise to the hindered phenol.
7. A process according to claim 5 or 6 wherein the temperature is maintained at from 10"C to 60"C.
8. A process according to any one of claims 5 to 7 wherein the reaction is catalyzed by a basic catalyst.
9. A process according to claim 8 wherein the basic catalyst is a basic alkali metal catalyst.
10. A process according to claim 8 or 9 wherein the product mixture is distilled through a short-path distillation apparatus.
11. A process according to claim 5 substantially as described in the Example.
12. Oxidation inhibitors containing a 3,5-dialkyl-4-hydroxyphenylalkyl group of the formula
wherein R, R', R2 and R3 are as defined in any one of claims 1 to 4, when prepared from a hindered phenolic aldehyde as claimed in any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92854878A | 1978-07-27 | 1978-07-27 | |
| US4640279A | 1979-06-06 | 1979-06-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2026479A true GB2026479A (en) | 1980-02-06 |
| GB2026479B GB2026479B (en) | 1982-09-29 |
Family
ID=26723877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7923460A Expired GB2026479B (en) | 1978-07-27 | 1979-07-05 | Process for preparing hindered phenolic aldehydes |
Country Status (5)
| Country | Link |
|---|---|
| CA (1) | CA1108185A (en) |
| DE (1) | DE2930603C2 (en) |
| FR (1) | FR2433503A1 (en) |
| GB (1) | GB2026479B (en) |
| IT (1) | IT1165266B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568819A1 (en) * | 1992-04-25 | 1993-11-10 | BASF Aktiengesellschaft | Process for the preparation of 3-(hydroxyphenyl)-propionaldehydes and optionally the preparation of 3-(hydroxyphenyl)-propanols |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3247240A (en) * | 1962-01-05 | 1966-04-19 | Geigy Ag J R | Process for the preparation of carbonyl compounds containing a hindered phenol group |
-
1979
- 1979-07-05 GB GB7923460A patent/GB2026479B/en not_active Expired
- 1979-07-18 CA CA332,057A patent/CA1108185A/en not_active Expired
- 1979-07-25 IT IT24662/79A patent/IT1165266B/en active
- 1979-07-26 FR FR7919361A patent/FR2433503A1/en active Granted
- 1979-07-27 DE DE2930603A patent/DE2930603C2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568819A1 (en) * | 1992-04-25 | 1993-11-10 | BASF Aktiengesellschaft | Process for the preparation of 3-(hydroxyphenyl)-propionaldehydes and optionally the preparation of 3-(hydroxyphenyl)-propanols |
| US5304685A (en) * | 1992-04-25 | 1994-04-19 | Basf Aktiengesellschaft | Preparation of 3-(hydroxyphenyl)propionaldehydes and their hydrogenation to 3-(hydroxyphenyl)propanols |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2433503B1 (en) | 1983-10-28 |
| GB2026479B (en) | 1982-09-29 |
| DE2930603A1 (en) | 1980-02-21 |
| CA1108185A (en) | 1981-09-01 |
| DE2930603C2 (en) | 1985-01-17 |
| FR2433503A1 (en) | 1980-03-14 |
| IT7924662A0 (en) | 1979-07-25 |
| IT1165266B (en) | 1987-04-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940705 |