Classifications

• • 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

• the present invention relates to substituted hydroquinone compounds and, more particularly, it relates to the synthesis of (1-phenyleth ⁇ l) hydroquinone.
• (1-phenylethyl) hydroquinone is synthesized by reacting styrene with hydroquinone in the presence of an organic diluent and in the presence of effective reaction stimulating amounts of a Lewis acid.
• the crude (1- ⁇ henylethyl) hydroquinone reaction product and unreacted reactants are then vacuum distilled to obtain a fraction consisting primarily of the (1-phenylethyl) hydroquinone.
• the vacuum distillation is done in the presence of an organic diluent which co-distills with unreacted hydroquinone under the conditions of vacuum distillation.
• suitable Lewis acids are: para-toluene sulfonic acid, sulfuric acid, boron trifluoride, hydrofluoric acid, stannic chloride and aluminum trichloride.
• the diluent is an ether, for example, a lower (C-.-C-.) alkyl ether including, for example, ethyl ether and tetrahydrofuran, and most desirably, a liquid polyether like the dialkoxy tetraglycols wherein the alkoxy group contains up to four carbon atoms, other diluents include halogenated benzenes, for example, tribromobenzene, hexadecane, pentadecane and octylether.
• halogenated benzenes for example, tribromobenzene, hexadecane, pentadecane and octylether.
• the diluent employed during the reaction will be a solvent for the reactants and the products, and as indicated above, preferably will be an ether. Desirably, the material has a boiling point in excess of about 135 ⁇ C.
• reaction diluent By performing the reaction in a reaction diluent, good yields are obtained.
• a desired organic diluent during distillation distillation diluent
• the distillation diluent is selected to co-distill with hydroquinone so as to allow for the recovery of substantial amounts of the monosubstituted material and at the same time prevent plugging of the distillation column by the hydroquinone.
• the reaction is done at a suitable temperature and for a suitable time effective to form the product and preferably is conducted at approximately 135°C to about 145°C for several hours.
• the crude product is purified by high vacuum batch distillation.
• the organic diluent employed during distillation will have a boiling point in the range of about 270-290°C and it is generally preferred to use as the reaction diluent material that will function as the distillation diluent.
• the diluent will be tetraethyleneglycol dimethylether, that is, a material of the formula CH- (OCH-CH-).
• OCH- also known as dimethoxytetraglycol
• Tetraglyme material also known as dimethoxytetraglycol
• the preferred Lewis acid is para-toluene sulfonic acid, and, in this case, it is preferred to purify the crude (1-phenylethyl) hydroquinone product by distillation employing sodium hydrogen sulfite, or other alkali metal hydrogen sulfite, to neutralize the para-toluene sulfonic acid catalyst and prevent oxidation of hydroquinone and the synthesized (1-phenylethyl) hydroquinone to quinones.
• an object of the present invention is to form the monosubstituted i.e., (1-phenylethyl) hydroquinone in high yields
• the stoichiometry employed will generally be about an equimolar amount of hydroquinone to styrene and preferably a slight molar excess of hydroquinone to styrene. Accordingly, desirable molar ratios of hydroquinone to styrene will be about 1:1 to about 1.20:1 or even 1.25:1 if desired.
• the (1-phenylethyl) hydroquinone produced in accordance with the present invention is ideally suited as a reactant for a wide variety of chemical reactions wherein the mono substituted diol is needed.
• the crude product has the appearance of a heavy motor oil both in relative viscosity and color, and it is homogeneous and free of suspended solids. The yield is about 19.316 Kg.
• the crude product is purified by high vacuum batch distillation employing a 12 liter flask reboiler with agitator and vacuum, a 4 ft.
• the (1-phenylethyl) hydroquinone product generally may be described as a glassy material.
• PEHQ (1-Phenylethyl)hydroquinone
• DPEHQ Di(phenylethyl)hydroquinone - probably a mixture of 2,5-DPEHQ and 2,6-DPEHQ
• distillation diluent and the reaction diluent were the same as this is generally the preferred technique for practicing the present invention. If, however, it is desired to use different diluents, obviously the reaction diluent can be removed from the reaction mixture prior to purifying the crude product. Another suitable diluent can be added and the distillation effected in the presence of this distillation diluent.
• the present process provides for a high yield of the monosubstituted material i.e., (1-phenylethyl) hydroquinone relative to any di-substituted material.
• the ratio of monosubstituted material to di-substituted material in the crude product will be at least about 1.8:1 (weight basis) and typically in excess of about 2.3:1.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
• Manufacturing Of Magnetic Record Carriers (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Compounds Of Unknown Constitution (AREA)

Priority Applications (5)

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Publications (1)

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Citations (3)

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• 1986
  • 1986-03-06 US US06/836,902 patent/US4661645A/en not_active Expired - Fee Related
• 1987
  • 1987-02-24 WO PCT/US1987/000359 patent/WO1987005290A1/en not_active Ceased
  • 1987-02-24 CA CA000530508A patent/CA1250861A/en not_active Expired
  • 1987-02-24 AU AU70870/87A patent/AU7087087A/en not_active Abandoned
  • 1987-02-24 JP JP62501614A patent/JPS63502283A/ja active Granted
  • 1987-02-24 DE DE8787901909T patent/DE3774222D1/de not_active Expired - Lifetime
  • 1987-02-24 AT AT87901909T patent/ATE69042T1/de not_active IP Right Cessation
  • 1987-02-24 EP EP87901909A patent/EP0260300B1/en not_active Expired
  • 1987-03-05 ES ES8700606A patent/ES2005110A6/es not_active Expired
  • 1987-11-03 NO NO874574A patent/NO167085C/no unknown
  • 1987-11-03 FI FI874845A patent/FI874845A0/fi not_active Application Discontinuation
  • 1987-11-05 DK DK580887A patent/DK170155B1/da not_active IP Right Cessation

Patent Citations (3)

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