WO2002055461A1 - Process for the c-alkylation of aromatic hydroxyl compounds - Google Patents
Process for the c-alkylation of aromatic hydroxyl compounds Download PDFInfo
- Publication number
- WO2002055461A1 WO2002055461A1 PCT/US2001/000710 US0100710W WO02055461A1 WO 2002055461 A1 WO2002055461 A1 WO 2002055461A1 US 0100710 W US0100710 W US 0100710W WO 02055461 A1 WO02055461 A1 WO 02055461A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hydroquinone
- sulfonic acid
- sulfuric acid
- acid
- moles
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- 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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
Definitions
- This invention pertains to a novel process for the preparation of dialkyl aromatic hydroxyl compounds such as dialkylphenols, dialkyl- benzenediols, dialkylnaphthols and dialkylnaphthalenediols. More specifically, this invention pertains to a process for the preparation of dialkylbenzenediols, especially 2,5-dialkylhydroquinone, by contacting a benzenediol with an olefin in the presence of a sulfonic acid and sulfuric acid.
- British Published Patent Application GB 1,469,896 described a process for the synthesis of a hydroxy-(1 ,1 ,3,3-tetramethylbutyl)benzene by the reaction of a hydroxybenzene having one or more hydroxyl groups and optionally substituted, in particular hydroquinone, and a 2,2,4-trimethylpentene, i.e., one of its isomers: ⁇ -diisobutylene and ⁇ -diisobutylene, or a mixture of the two, in the presence of highly concentrated sulfuric acid and ethylene glycol.
- highly concentrated sulfuric acid means a concentration in water that is greater than 90%, preferably in the range of 95+3%.
- Japanese Kokai 04-103,550 discloses the preparation of dialkylhydroquinones by treating hydroquinone with an olefin containing 6-30 carbon atoms using a strongly acidic polystyrene sulfonic acid-type cation resins wherein the resin preferably consists of particles having a particle diameter of not greater than 0.2 mm.
- 2,5-Bis(1 ,1 ,3,3- tetramethylbutyl)hydroquinone was prepared in a yield of 81% by the reaction of diisobutylene with hydroquinone at 125°C for 6 hours in the presence of ⁇ .05mm diameter particles of a strongly acidic polystyrene sulfonic acid resin.
- Japanese Kokai 04-103,550 also discloses the ( preparation of 2,5-bis(1 ,1 ,3,3-tetramethylbutyl)hydroquinone in a 40% yield by the reaction of diisobutylene with hydroquinone at 35°C for 6 hours in the presence of acetic, phosphoric and sulfuric acids.
- Patent Document WO 97/16402 discloses a process for the C-alkylation of a hydroxylated aromatic compound having at least one ortho or para hydrogen atom with respect to the hydroxyl group wherein the hydroxylated aromatic compound is contacted with a strong proton acid and a compound which forms a carbocation in the presence of the acid and in the presence of a solvent consisting of a water.alcohol couple.
- 2,5-di-tert- octylhydroquinone is prepared by contacting hydroquinone with diisobutylene in the presence of water, methanol and benzenesulfonic acid over a period of 8.5 hours to obtain a reaction yield of 74% with an 88% conversion of the hydroquinone.
- dialkyl aromatic hydroxyl compounds such as dialkylphenols, dialkylbenzenediols, naphthols and dialkylnaphthalenediols.
- the present invention provides a process for the preparation of dialkyl aromatic hydroxyl compounds such as benzenediols, especially 2,5-dialkylhydroquinone, which comprises contacting an aromatic hydroxyl compounds with an olefin in the presence of a sulfonic acid and sulfuric acid wherein the sulfonic acid:sulfuric acid molar ratio is in the range of 0.3:1 to 3:1.
- Our novel process provides dialkyl aromatic hydroxyl compounds in good yields over shorter reaction periods.
- the product is of high purity, avoiding complex work-up such as alkali washes, thereby increasing product shelf-iife.
- the product precipitates cleanly from the reaction mixture facilitating application in a continuous reactor system.
- the reaction proceeds readily in a temperature range which minimizes contaminant build-up and avoids the requirement of specialized pressure equipment. Low cost, readily available catalysts are utilized. No organic alcohol or alkane cosolvent is required beyond the reacting olefin itself.
- the compounds which may be prepared according to the present invention are useful as antioxidants and stabilizers in a variety of products such as oils and fats and petroleum products and as industrial intermediates for the production of surface active agents, coating materials and plastics.
- the process of our invention comprises contacting an aromatic hydroxyl compound such as a benzenediol with an olefin in the presence of a sulfonic acid and sulfuric acid wherein the sulfonic acid:sulfuric acid molar ratio is in the range of 0.3:1 to 3:1 to produce a dialkyl aromatic hydroxyl compound such as a dialkylbenzenediol.
- a sulfonic acid:sulfuric acid molar ratio is in the range of 0.3:1 to 3:1 to produce a dialkyl aromatic hydroxyl compound such as a dialkylbenzenediol.
- the olefin reactant employed in the process may contain from 3 to 30 carbon atoms, preferably ⁇ -olefins containing from 3 to 12 carbon atoms.
- Examples include, but are in no way are limited to, isobutylene, isoamylene, 1-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 1-octene, diisobutylene, 1-decene, 1-dodecene, 2-dodecene, 1-tetradecene, 2-tetra- decene, 1-hexadecene, 1-eicosene, ⁇ -pinene, camphene, limonene and styrene.
- Olefin precursors which dehydrate or in some other way eliminate or rearrange under the reaction conditions to form an olefin also may be employed as the olefin source.
- the olefin-generating feedstock should be chosen judiciously to insure that its reactivity or bulk does not slow the conversion, generate contaminants or otherwise affect detrimentally the desired alkylation reaction.
- Isobutylene and diisobutylene are particular preferred olefin reactants, e.g., for the production of
- the olefin:aromatic hydroxy compound mole ratio normally should be at least 2:1 and typically is in the range of 3:1 up to 9:1 , preferably 4:1 to 6:1. Since the reaction mixture contains two distinct phases, the reaction of the olefin with the aromatic hydroxy compound is influenced by a variety of factors.
- the alkylation reaction is carried out in the presence of at least one sulfonic acid and sulfuric acid.
- the sulfonic acid may be selected from a wide variety of halosulfonic acids and aliphatic, cycloaiiphatic and aromatic sulfonic acids.
- sulfonic acids include fluorosulfonic acid; chlorosulfonic acid; alkane mono- and di-sulfonic acids containing up to 6 carbon atoms such as methanesulfonic acid, ethanesulfonic acid, ethanedisulfonic acid and trifluoromethanesulfonic acid; aryl mono- and di- sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, benzenedisulfonic acid, naphthalenesulfonic acid, napthalenedisulfonic acids, camphorsulfonic acid and xylenesulfonic acid.
- Benzenesulonic acid and the toluenesulfonic acids represent the preferred sulfonic acids.
- the amount of sulfonic acid employed normally is in the range of 0.3 to 8 moles of sulfonic acid, preferably 1 to 4 moles sulfonic acid, per mole of hydroquinone.
- the amount of sulfuric acid used may be 0.1 to 5 moles sulfuric acid, preferably 0.8 to 4 moles sulfuric acid, per mole of hydroquinone reactant.
- the mole ratio of the sulfonic acid:sulfuric acid typically is in the range of 0.3:1 to 3:1 , preferably 0.5 to 2:1 , most preferably 1:1.
- the process or reaction mixture includes water in a sufficient amount to maintain the sulfonic acid in solution. The use of a substantial excess of water can be detrimental to reaction rate and therefore should be avoided. Although it normally is desirable to minimize the amount of water used, amounts of water slightly greater than that required to maintain the sulfonic acid in solution may be beneficial to separating the phases, e.g., by decantation, of the reaction mixture in product recovery.
- the water concentration preferably is in the range of 10 to 20 weight percent, based on the total weight of the process or reaction mixture, i.e., the aromatic hydroxy compound and olefin reactants, the sulfonic and sulfuric acids and the water.
- An advantage of the present process is that the presence of an alkanol such as methanol is not an essential feature of the process and, therefore, the reaction mixture involved in the process preferably is free essentially free of any alkanol.
- an alkanol e.g., an alkanol containing from 1 to 3 carbon atoms, diol, e.g., a diol containing 2 to 4 carbon atoms, or other water-misicle solvent
- the reaction mixture may contain up to 75 weight percent of an alkanol, such as methanol, based on the weight of the water present.
- the water may be replaced entirely with such an alkanol, diol or other water miscible solvent which is capable of maintaining the sulfonic acid in solution.
- the process may be carried out over relatively wide range of temperatures depending, for example, upon the particular reactants employed, the amounts of acids employed, the particular sulfonic acid employed and other process variables.
- the process most frequently is operated at temperatures in the range of 35 to 75°C although solubility problems may occur at lower temperatures and impurity formation and/or slow reaction rates may occur at higher temperatures.
- the process preferably is carried out at a temperature in the range of 50 to 70°C, most preferably 55 to 65°C.
- the process may be carried out under atmospheric (ambient) pressure or elevated pressure.
- the process may be operated as a batch process or it may be carried out in a continuous or semi-continuous manner.
- one mode of continuous operation may comprise continuously feeding in a stream of dissolved aromatic hydroxy compound and a stream of olefin in proportion to the amount of solid product being continuously filtered out.
- the key is not necessarily to retain an exact level of the sulfonic acid/sulfuric, acid/water mixture, but to keep the ratio of the three components relatively constant.
- the solid product can be removed and the filtrate can be used directly as the media for conversion of a second batch of olefin and aromatic hydroxy compound.
- a second batch-like process may involve recycling of the sulfonic acid/sulfuric acid/water phase to the next reaction and recharging only the olefin and aromatic hydroxy compound.
- the reaction is not dependent as much on the exact amounts of the sulfonic acid, sulfuric acid and water as it is on the relative proportion of these three components. Therefore, the sulfonic acid/ sulfuric acid/ water phase can be recycled numerous times without adding small quantities of sulfonic acid, sulfuric acid and/or water to compensate for transfer losses.
- the excess olefin and olefin side- products also can be recycled in a sense in that they can serve as an effective recrystallization solvent.
- Conversion levels were determined by the following liquid chromatography test method: A 500 mg sample of the reaction mixture is pipetted from a rapidly stirring reactor and diluted in 50 mL of high-purity acetonitrile. After appropriate instrument/method calibration, the sample is injected into a reverse-phase liquid chromatographic column (Supelco LC-8 15 cm x 4.6 mm 5 ⁇ m) using a 0.1 M NaOAc buffer/acetonitrile mobile phase with a PE Binary LC pump 250. The concentration of acetonitrile eluent is increased from 70% - 100% over 15 minutes. An ultra-violet detector (Applied Biosystems 757 Abs. Detector), set at 280 nm, is used to monitor the component elution. The peak area is recorded relative to the peak area of all the components in the sample.
- the product is isolated after five hours via filtration from the reaction mixture.
- the solids are recrystallized from 150 mL heptane and isolated to obtain 2,5-bis(1 ,1 ,3,3-tetramethyl- butyl)hydroquinone having a purity of greater than 98.5% in a 72% yield.
- Diisobutylene (500 g) and water (70 g) were added and the lower aqueous phase (containing PTSA, sulfuric acid, hydroquinone, mono-(1 ,1,3,3-tetra- methylbutyl)hydroquinone and small amounts of other polar side products) is decanted and transferred into another reactor.
- the diisobutylene phase is washed with 1500 g water two times at 50°C and once at 85°.
- the remaining clear organic phase at 85°C is cooled to 70°C and eventually to 0-10°C and the 2,5-bis(1,1 ,3,3-tetramethylbutyl)hydroquinone product which crystallizes is collected by filtration.
- the product is washed with 600 g cold diisobutylene and dried at room temperature overnight. The product was obtained in a yield of 75% and a purity of greater than 98.5%.
- hydroquinone 200 g, 1.8 moles
- diisobutylene 1018 g, 9.1 moles
- This mixture is heated under a nitrogen blanket with stirring to 58°C.
- approximately 87-94 mole percent ratio of the hydroquinone has been consumed.
- Diisobutylene 500 g is added and the lower aqueous phase is transferred to another reactor for further recycles.
- the diisobutylene phase is washed with 1500 g water two times at 50°C and once at 85°.
- the remaining clear organic phase at 85°C is cooled to 70°C and eventually to 0-10°C and the 2,5-bis(1 ,1 ,3,3-tetramethylbutyl)- hydroquinone product which crystallizes is collected by filtration.
- the product is washed with 600 g cold diisobutylene and dried at room temperature overnight.
- the product is obtained in a yield of 86-91%, based on the weight of the hydroquinone reactant, with a purity greater than 98.5%.
- the PTSA-containing layer can be recycled and used as described in this example until a substantial, e.g., >80%, hinders agitation of the reaction mixture and/or the time and temperature to achieve the desired conversion.
- a substantial, e.g., >80%, hinders agitation of the reaction mixture and/or the time and temperature to achieve the desired conversion has not been observed, formation of such by-products also would limit the extent to which the PTSA-containing layer can be recycled advantageously
- EXAMPLE 5 To a 500 mL, 3-neck, round-bottom flask equipped with a stirrer, thermocouple and nitrogen are added 67 weight percent p-toluenesulfonic acid (PTSA) in water (33.5 g), hydroquinone (20.0 g, 0.18 moles), diisobutylene (101.8 g, 0.91 moles) and 95% aqueous sulfuric acid (11.2 g, 0.112 moles). This mixture is heated to 58°C under a nitrogen blanket with stirring.
- PTSA p-toluenesulfonic acid
- diisobutylene 50 g is added and the lower aqueous phase (containing PTSA, sulfuric acid, hydroquinone, mono-(1 ,1 ,3,3-tetramethyibutyl)hydroquinone and small amounts of other polar side products) is transferred to another reactor.
- the diisobutylene phase is washed with 150 g water two times at 50°C and once at 85°.
- the remaining clear organic phase at 85°C is cooled to 70°C and eventually to 0-10°C and the 2,5-bis(1,1,3,3-tetramethylbutyl)- hydroquinone product which crystallizes is collected by filtration.
- the product is washed with 60 g cold diisobutylene and dried at room temperature overnight.
- the 2,5-bis(1 , 1 ,3,3-tetramethylbutyl)hydroquinone product is obtained in a yield of 73% product and a purity greater than 98.5%.
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01900977A EP1349821A1 (en) | 2001-01-09 | 2001-01-09 | Process for the c-alkylation of aromatic hydroxyl compounds |
PCT/US2001/000710 WO2002055461A1 (en) | 2001-01-09 | 2001-01-09 | Process for the c-alkylation of aromatic hydroxyl compounds |
JP2002556141A JP2004517867A (en) | 2001-01-09 | 2001-01-09 | Method for C-alkylation of aromatic hydroxyl compounds |
Applications Claiming Priority (1)
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PCT/US2001/000710 WO2002055461A1 (en) | 2001-01-09 | 2001-01-09 | Process for the c-alkylation of aromatic hydroxyl compounds |
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WO2002055461A1 true WO2002055461A1 (en) | 2002-07-18 |
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PCT/US2001/000710 WO2002055461A1 (en) | 2001-01-09 | 2001-01-09 | Process for the c-alkylation of aromatic hydroxyl compounds |
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JP (1) | JP2004517867A (en) |
WO (1) | WO2002055461A1 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1997016402A1 (en) * | 1995-10-31 | 1997-05-09 | Rhodia Chimie | Method for c-alkylating hydroxylated aromatic compounds |
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2001
- 2001-01-09 EP EP01900977A patent/EP1349821A1/en not_active Withdrawn
- 2001-01-09 WO PCT/US2001/000710 patent/WO2002055461A1/en not_active Application Discontinuation
- 2001-01-09 JP JP2002556141A patent/JP2004517867A/en not_active Ceased
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Publication number | Priority date | Publication date | Assignee | Title |
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WO1997016402A1 (en) * | 1995-10-31 | 1997-05-09 | Rhodia Chimie | Method for c-alkylating hydroxylated aromatic compounds |
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EP1349821A1 (en) | 2003-10-08 |
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