US3795708A - Process for preparing 2,3,6-trimethylhydroquinone - Google Patents

Process for preparing 2,3,6-trimethylhydroquinone Download PDF

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Publication number
US3795708A
US3795708A US00049193A US3795708DA US3795708A US 3795708 A US3795708 A US 3795708A US 00049193 A US00049193 A US 00049193A US 3795708D A US3795708D A US 3795708DA US 3795708 A US3795708 A US 3795708A
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United States
Prior art keywords
trimethylhydroquinone
mol
trimethylphenol
oxidation
dissolved
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Expired - Lifetime
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US00049193A
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English (en)
Inventor
W Orth
M Maurer
L Rappen
W Fickert
H Miele
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Rain Carbon Germany GmbH
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Ruetgerswerke AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/08—Dihydroxy benzenes; Alkylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring

Definitions

  • the main object of the present invention is to pro vide a process for preparing 2,3,G-trimethylhydroquinone which is advantageous technically as well as economically, from 2,3,6-trimethylphenol.
  • This object was attained by a process of preparing 2,3,6-trimethylhydroquinone by sulfonation of 2,3,6-trimethylphenol, oxidation of the 2,3,6-trimethylphenol-4- sulfonic acid formed and immediate reduction in aqueous solution of the trimethylqninone obtained to 2,3,6-trimethylhydroquinone; sulfonation is carried out in an organic solvent which is inert to the sulfonation agent, oxidation in the aqueous phase is likewise carried out in an organic solvent which is inert to the oxidizing agent, the quinone formed being soluble in said solvent, while the hydroquinone formed by the immediately subsequent reduction is insoluble therein.
  • the use of a solvent'results in essential advantages The sulfonic acid formed yields with the solvent a mixture which can be easily stirred, so that the sulfonation can be carried out--dependi.ng on the specific sulfonating agent-at a temperature at which the best yield is obtained.
  • a solvent always higher temperatures are necessary in order to obtain a mass which can be well stirred, but at such higher temperatures the yields are 20-50% lower or a high excess of the sulfonating agent must be used. However, such excess renders the subsequent dilution with water-due to the considerable heat of dilutionrather difficult.
  • the oxidation is carried out in the process of invention preferably at reflux temperature and this additionally contributes to the removal of the heat of oxidation, puts an upper limit on the oxidation temperature and assures that the oxidation can be carried out in the shortest possible period of time.
  • the solvent dissolves the quinone formed so that it is protected from further oxidation.
  • the use of solvent during oxidation renders distillation with steam, or a subsequent extraction of the quinone unnecessary.
  • the solvent acts simultaneously as a transporter for the 2,3,6-trimethylenequinone from the oxidation phase to the reduction phase.
  • aromatic hydrocarbons e.g. benzene and toluene
  • halogenated derivatives e.g. chlorobenzene
  • aliphatic and cycloaliphatic hydrocarbons can be used individually or in mixture with each other, for example n-hexane, ligroin, cyclohexane and halogenated hydrocarbons, such as carbontetrachloride or ethylenechloride.
  • Solvents which are inert to the sulfonating agents, e.g. concentrated sulfuric acid, oleum and chlorosulfonic acid, as well as to oxidizing agents e.g. chromic acid, manganese dioxide or mangan-IV-sulfate, are preferred.
  • Trimethylhydroquinone is an important intermediate product in the preparation of tocopherol (Vitamin E).
  • EXAMPLE 1 4.08 kg. (30 mol) of 2,3,6-trimethylphenol are dissolved in 7.5 l. toluene. To the solution under vigorous stirring 9.6 kg. (5.35 1.) (94.8 mol) of concentrated sulfuric acid are dropwise added (3.16 mol/ phenol). Thereby the temperature rises to about 60 C. Soon after starting introduction of the sulfuric acid, phenolsulfonic acid separates in the form of small balls. Stirring is continued for /2 hour and the phenolsulfonic acid formed is then dissolved by adding 18 1. water, to which 2.58 kg. (1.44 1.) (25.4 mol) concentrated sulfuric acid have been added. To the reaction mixture within 2 hours a solution of 6.57 kg.
  • EXAMPLE 3 13.6 kg. (100 mol) 2,3,6-trimethylphenol are dissolved in 25 l. benzene. To the solution 19.6 1. oleum of 15% (3.92 mol tota1-SO /mol phenol). The temperature is allowed to rise up to a maximum of 60 C. The phenolsulfonic acid which separates in the shape of small balls, is dissolved in 80 1. water and oxidized within 2 hours under stirring with a solution of 21.9 kg. (74 mol) sodium dichromate in 14.7 1. of water. Further processing takes place in the manner described in the above Example 1 with consideration of the proportions described in Example 1. In this example 13.1 kg. 2,3,6-trimethylhydroquinone are obtained as a light yellow powder, having a melting point of 170172 C. in a yield of 86.2% of the theory.
  • EXAMPLE 4 27.2 kg. (200 mol) of 2,3,6-trimethylphenol are dissolved in 50 l. of ethylene chloride. T o the solution 13.7 1. chlorosulfonic acid (206 mol) are added dropwise with vigorous stirring. Gaseous HCl gators and phenolsulfonic acid separates in fine-grained form. After further stirring for /2 hour the sulfonic acid is dissolved in 160 1. water, to which 20.4 kg. (200 mol) sulfuric acid of 96% have been added. The sulfonic acid solution is oxidized with 38.7 kg. (400 mol) of manganese dioxide of 90%, in the manner described in the above Example 2.
  • 2,3,6-trimethylhydroquinone is thus obtained as a light beige powder, having a melting point of 170 to 172 C. in a yield of 28.5 kg, i.e. 93.8% of the theory.
  • EXAMPLE 5 54.4 kg. (400 mol) of 2,3,6-trirnethylphenol dissolved in 100 l. of chlorobenzene are processed with consideration of the proportions and in the manner described in the above Example 1. The yield of 2,3,6-trimethylhydroquinone amounts to 51.9 kg., i.e. 84% of the theory, and its melting point is 170172 C.
  • EXAMPLE 6 8.16 kg. (60 mol) of 2,3,6-trimethylphenol are dissolved in 14 l. of n-hexane and treated in the manner described in the above Example 4. 2,3,6-trimethylhydroquinone is obtained in a yield of 8.52 kg., i.e. 92% of the theory, having a melting point of 170-172 C.
  • EXAMPLE 7 4.08 kg. (30 mol) of 2,3,6-trimethylphenol are dissolved in 7.5 1. of cyclohexane and treated in the manner 4 described in the above Example 1. 3.84 kg. of 2,3,6-trimethylhydroquinone having a melting point of 170-172 C. are obtained. This corresponds to a yield of 82.5% of the theory.
  • EXAMPLE 8 13.6 kg. mol) of 2,3,6-trimethylphenol are dissolved in 25 l. ligroin and processed with consideration of the proportions and in the manner described in the above Example 2. 13.85 kg. of 2,3,6-trimethylhydroquinone, corresponding to 91.2% of the theory are thus obtained, having a melting point of -172 C.
  • EXAMPLE 9 13.6 kg. (100 mol) of 2,3,6-trimethylphenol are dissolved in 25 l. of benzene and sulfonated in the manner described in the above Example 2.
  • the trimethylphenolp-sulfonic acid is dissolved in 60 l. of water and to the solution dropwise 49.4 kg. (200 mol) of manganese-IV- sulfate dissolved in 801. of sulfuric acid of 55% are added. Stirring is continued for /2 hour, the phases are separated and the organic phase is treated in the manner described in the previous examples with consideration of the proportions.
  • 12.9 kg. of 2,3,6-trimethylhydroquinone corresponding to 84.6% of the theory and having a melting point of 170-172 C. are thus obtained.
  • the chlorobenzene used in the above Example 5 has the formula C H Cl and the sodium dithionite mentioned in the specification has the formula Na S O
  • the recitation hydroquinone formed by directly subsequent reduction is to indicate that said reduction takes place immediately after oxidation.
  • oxidizing said phenol sulfonic acid by adding thereto an oxidizing agent selected from the class consisting of sodium dichromate, manganese dioxide and manganese-IV-sulfate whereby a temperature not exceeding reflux temperature is reached,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00049193A 1969-06-26 1970-06-23 Process for preparing 2,3,6-trimethylhydroquinone Expired - Lifetime US3795708A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691932362 DE1932362A1 (de) 1969-06-26 1969-06-26 Verfahren zur Herstellung von 2,3,6-Trimethylhydrochinon

Publications (1)

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US3795708A true US3795708A (en) 1974-03-05

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US (1) US3795708A (de)
CH (1) CH524556A (de)
DE (1) DE1932362A1 (de)
FR (1) FR2051407A5 (de)
GB (1) GB1249760A (de)
NL (1) NL7007689A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927045A (en) * 1973-01-15 1975-12-16 Rhone Poulenc Sa Process for the preparation of trimethyl-para-benzaquinone
US3954891A (en) * 1971-12-07 1976-05-04 Rutgerswerke Aktiengesellschaft Method of making substituted hydroquinones
US3956346A (en) * 1974-01-21 1976-05-11 Rhone-Poulenc Industries Process for the preparation of trimethyl-benzoquinone
US8226850B1 (en) * 2009-09-22 2012-07-24 Clemson University Research Foundation Thermally enhanced oxygen scavengers including a transition metal and a free radical scavenger

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954891A (en) * 1971-12-07 1976-05-04 Rutgerswerke Aktiengesellschaft Method of making substituted hydroquinones
US3927045A (en) * 1973-01-15 1975-12-16 Rhone Poulenc Sa Process for the preparation of trimethyl-para-benzaquinone
US3956346A (en) * 1974-01-21 1976-05-11 Rhone-Poulenc Industries Process for the preparation of trimethyl-benzoquinone
US8226850B1 (en) * 2009-09-22 2012-07-24 Clemson University Research Foundation Thermally enhanced oxygen scavengers including a transition metal and a free radical scavenger

Also Published As

Publication number Publication date
NL7007689A (de) 1970-12-29
CH524556A (de) 1972-06-30
FR2051407A5 (de) 1971-04-02
GB1249760A (en) 1971-10-13
DE1932362A1 (de) 1971-01-07

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