US3387036A - Production of benzyl alcohol and benzaldehyde - Google Patents

Production of benzyl alcohol and benzaldehyde Download PDF

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US3387036A
US3387036A US367225A US36722564A US3387036A US 3387036 A US3387036 A US 3387036A US 367225 A US367225 A US 367225A US 36722564 A US36722564 A US 36722564A US 3387036 A US3387036 A US 3387036A
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toluene
benzaldehyde
benzyl alcohol
oxidation
mixture
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Bonnart Jacques
Poilane Georges
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • C07C409/08—Compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C07C407/003—Separation; Purification; Stabilisation; Use of additives
    • C07C407/006—Stabilisation; Use of additives
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups

Definitions

  • the present invention relates to the oxidation of toluene to benzyl alcohol and benzaldehyde.
  • the most widely used industrial process for the preparation of benzyl alcohol and benzaldehyde consists in chlorinating toluene to a mixture of benzyl chloride and benzylidene chloride, which are then saponified.
  • the process of the invention comprises oxidizing liquid toluene at 220 C. with gaseous oxygen in the presence of an inert gaseous diluent in amount such that the gaseous mixture contains not more than 21% of oxygen, the oxidation being discontinued when at most 10% of the toluene has been oxidized.
  • the diluted oxygen preferably air of reduced oxygen content, is passed through the liquid toluene at a temperature between 170 and 220 C.
  • This mixture is then ordinarily de-peroxidized, for example by catalytic hydrogenation or by heating in an inert atmosphere to 180-280 C., or to a lower temperature if the de-peroxidation is accelerated by the use of a de-peroxidation catalyst, such as a cobalt salt or a derivative of boric acid (eg the anhydride, an acid, or an ester).
  • a de-peroxidation catalyst such as a cobalt salt or a derivative of boric acid (eg the anhydride, an acid, or an ester).
  • the de-peroxidation treatment may optionally be omitted, since adequate deperoxidation generally takes place in the separation of the constituents of the mixture.
  • stabilizing agent for organic hydroperoxides so that the decomposition of the benzyl hydroperoxide, which is a primary product of the oxidation, is inhibited.
  • the mixture obtained is then subsequently de-peroxidized and separated as already described.
  • stabilizing agent the products known for stabilizing hydrogen peroxide may be used, e.g. those appearing in the list given in R. E. Kirk and D. F. Othmer (Encyclopedia of Chemical Technology, Interscience Encyclopedia, New York, vol. 7, p. 730 (1951)). More especially, sodium pyrophosphate and sodium fluoride may be used.
  • the proportion of stabilizing agent to be employed is conveniently between 0.01% and 0.5% by weight of the toluene employed.
  • the process of the invention gives a mixture of benzyl alcohol and benzaldehyde in yields from 50% when no stabilizer is employed, to 70% when a stabilizer is used.
  • EXAMPLE 1 Into a stainless steel autoclave having a capacity of 3.6 litres and provided with a stirring system are introduced 2000 g. of toluene, and a pressure of 10 bars is established with a gas mixture consisting of 10% of oxygen and 90% of nitrogen. After heating to 165 C., when the pressure reaches 12 bars, a current of the same gas mixture is introduced into the reaction mass at a rate of 350 litres per hour, the heating being continued until the temperature reaches -190 C. At the end of one hour, the heating and the passage of the gas mixture are stopped.
  • the percentage by weight of the oxidation products is determined on an aliquot fraction of the reaction product by evaporation of the toluene in vacuo, followed by determination of the benzyl hydroper-oxide by iodometry and of the acid products (expressed as benzoic acid) by alkali titration. From the difference, the percentage of the oxidation products other than hydroperoxides and acids is obtained.
  • Table I The results are set out in Table I below.
  • Example 2 The procedure of Example 1 is followed, but 0.1% by Weight of sodium pyrophosphate is added to the toluene. Analyses, carried out as in Example 1, give the results shown in Table I.
  • the benzyl alcohol and the benzaldehyde are then separated from the other oxidation products, by fractional distillation under a vacuum of 7 mm. Hg, the aldehyde passing over at 4950 C. and the alcohol at 8283 C.
  • the yields obtained are set out in Table II.
  • Example 3 The procedure of Example 1 is followed, but 0.1% by weight of sodium fluoride is added to the toluene.
  • the composition of the mixture after oxidation, determined as indicated in Example 1, is given in Table I.
  • Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at 170 C.220 C. with a mixture of gaseous oxygen and an inert gaseous diluent such that the said mixture contains not more than 21% of oxygen, until at most 10% of the toluene has been oxidized, decomposing the hydroperoxides formed to benzyl alcohol and benzaldehyde by catalytic hydrogenation and separating the benzyl alcohol and benzaldehyde produced.
  • Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at C.220 C. with a mixture of gaseous oxygen and an inert gaseous diluent such that the said mixture contains not more than 21% of oxygen, until at most 10% of the toluene has been oxidized, decomposing the hydroperoxides formed to benzyl alcohol and benzaldehyde by heating in an inert atmosphere, and separating the benzyl alcohol and benzaldehyde produced.
  • Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at 170-220 C. with air of reduced oxygen content in the presence of 0.01 to 0.5% by weight of the toluene of sodium pyrophosphate until 4 to 7% by weight of the toluene has been oxidized, decomposing the benzoyl hydroperoxide formed by heating in an inert atmosphere in the presence of a cobalt salt, and isolating benzyl alcohol and benzaldehyde from the product by fractional distillation.
  • Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at 170-220 C. with air of reduced oxygen content in the presence of 0.01 to 0.5% by weight of the toluene of sodium fluoride until 4 to 7% by weight of the toluene has been oxidized, decomposing the benzoyl hydroperoxide formed by heating in an inert atmosphere in the presence of a cobalt salt, and isolating benzyl alcohol and benzaldehyde from the product by fractional distillation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Description

United States Patent 15 Claims. (Cl. 260599) ABSTRACT OF THE DISCLGSURE Benzyl alcohol and benzaldehyde are produced by oxidizing liquid toluene at 170 C.220 C. with gas containing less than 21% of oxygen until not more than of the toluene has been oxidized, then preferably decomposing the hydroperoxides formed, and isolating the benzyl alcohol and benzaldehyde produced.
The present invention relates to the oxidation of toluene to benzyl alcohol and benzaldehyde.
The most widely used industrial process for the preparation of benzyl alcohol and benzaldehyde consists in chlorinating toluene to a mixture of benzyl chloride and benzylidene chloride, which are then saponified. The
benzyl alcohol and the benzaldehyde thus obtained con tain chlorinated impurities, the elimination of which by distillation, or chemically, is always difficult, but is also essential when these products are intended for use in perfumery, as pharmaceutical products, or as intermediates in organic syntheses. Moreover, these chlorinated impurities are liable to cause corrosion, which necessitates the use of special materials.
It is possible to prepare benzaldehyde by catalytically oxidizing toluene in the vapour phase at temperatures from 300 to 500 C. The yields do not exceed 30-50% (see Ullmanns Enzyklopaedie, vol. 4, 238 (1953)). The process is dangerous to perform industrially because the mixture of toluene vapour and air used is explosive.
In addition, the oxidation of toluene in the liquid phase has been described. It is known that when hydrocarbons are oxidized, the first stage of the oxidation is the formation of hydroperoxides and that first alcohols and then aldehydes (or ketones) are formed from the hydroperoxides, both of which may subsequently be oxidized to the corresponding acids. In the liquid phase oxidation of toluene, all the oxidation stages have been observed. The problem is therefore to control the oxidation in such a manner as to obtain the maximum yield of benzyl alcohol and benzaldehyde, or of their precursor benzyl hydroperoxide, which can be readily converted into benzyl alcohol and benzaldehyde in a subsequent operation.
The previously described processes for oxidizing toluene in the liquid phase have given only negligible yields of benzyl alcohol and benzaldehyde. While. the preparation of benzyl hydroperoxide from toluene has been described, it has only been possible to obtain this hydroperoxide in the presence of a considerable quantity of a peroxidic initiator, viz, cumene hydroperoxide (see United States patent specification No. 2,683,751). The separation of benzyl hydroperoxide, or of benzyl alcohol and benzaldehyde, from the product of this reaction is very ditficult because of the presence of the cumene hydroperoxide or its reduction and degradation products. If the oxidation of toluene is carried out in the presence of catalysts such as heavy metals, substantially only benzoic acid is ob tained.
It has now been found that toluene may be oxidized in the liquid phase under certain specific conditions in 3,387,036 Patented June 4, 1968 good yields to a mixture of benzyl alcohol and benzaldehyde. The process of the invention comprises oxidizing liquid toluene at 220 C. with gaseous oxygen in the presence of an inert gaseous diluent in amount such that the gaseous mixture contains not more than 21% of oxygen, the oxidation being discontinued when at most 10% of the toluene has been oxidized. In this process the diluted oxygen, preferably air of reduced oxygen content, is passed through the liquid toluene at a temperature between 170 and 220 C. under a pressure sufficient to maintain the toluene in the liquid state, in the absence of any metallic catalyst or peroxidic initiators, other than those formed from the toluene, and the oxidation is stopped at a degree of conversion of the toluene at most equal to 10%. A mixture of toluene, benzyl hydroperoxide, benzyl alcohol, benzaldehyde, benzoic acid and a few other by-products is thus obtained. This mixture is then ordinarily de-peroxidized, for example by catalytic hydrogenation or by heating in an inert atmosphere to 180-280 C., or to a lower temperature if the de-peroxidation is accelerated by the use of a de-peroxidation catalyst, such as a cobalt salt or a derivative of boric acid (eg the anhydride, an acid, or an ester). When the peroxide has been decomposed, the acid products are eliminated by washing with an aqueous alkali metal hydroxide solution, and the residual organic layer is then fractionally distilled.
When the crude oxidation product contains only a small proportion of hydroperoxide, the de-peroxidation treatment may optionally be omitted, since adequate deperoxidation generally takes place in the separation of the constituents of the mixture.
It is preferred to oxidize the liquid toluene in the presence of a stabilizing agent for organic hydroperoxides so that the decomposition of the benzyl hydroperoxide, which is a primary product of the oxidation, is inhibited. The mixture obtained is then subsequently de-peroxidized and separated as already described. As stabilizing agent, the products known for stabilizing hydrogen peroxide may be used, e.g. those appearing in the list given in R. E. Kirk and D. F. Othmer (Encyclopedia of Chemical Technology, Interscience Encyclopedia, New York, vol. 7, p. 730 (1951)). More especially, sodium pyrophosphate and sodium fluoride may be used. The proportion of stabilizing agent to be employed is conveniently between 0.01% and 0.5% by weight of the toluene employed.
The process of the invention gives a mixture of benzyl alcohol and benzaldehyde in yields from 50% when no stabilizer is employed, to 70% when a stabilizer is used.
The following examples illustrate the invention and show how it can be put into practice:
EXAMPLE 1 Into a stainless steel autoclave having a capacity of 3.6 litres and provided with a stirring system are introduced 2000 g. of toluene, and a pressure of 10 bars is established with a gas mixture consisting of 10% of oxygen and 90% of nitrogen. After heating to 165 C., when the pressure reaches 12 bars, a current of the same gas mixture is introduced into the reaction mass at a rate of 350 litres per hour, the heating being continued until the temperature reaches -190 C. At the end of one hour, the heating and the passage of the gas mixture are stopped.
The percentage by weight of the oxidation products is determined on an aliquot fraction of the reaction product by evaporation of the toluene in vacuo, followed by determination of the benzyl hydroper-oxide by iodometry and of the acid products (expressed as benzoic acid) by alkali titration. From the difference, the percentage of the oxidation products other than hydroperoxides and acids is obtained. The results are set out in Table I below.
The crude mixture is washed with 200 cc. of aqueous sodium hydroxide solution, the aqueous layer is separated, the toluene is driven oif from the organic fraction, and the residue is distilled. Benzyl alcohol, benzaldehyde and by-products are obtained in the yields shown in Table II below.
EXAMPLE 2 The procedure of Example 1 is followed, but 0.1% by Weight of sodium pyrophosphate is added to the toluene. Analyses, carried out as in Example 1, give the results shown in Table I.
0.001% of cobalt in the form of cobalt Z-ethylhexanoate is added to the crude oxidation mixture, the autoclave is purged with nitrogen and the product is rapidly heated to 165 C., While the inert atmosphere is maintained by bubbling nitrogen through the mixture. At the end of minutes it is found by titration of an aliquot portion that no peroxide remains in the reaction mass. The latter is washed with 200 cc. of a 5% aqueous sodium hydroxide solution, the acqueous layer is decanted, and the organic layer is concentrated by distillation of the toluene in vacuo. The benzyl alcohol and the benzaldehyde are then separated from the other oxidation products, by fractional distillation under a vacuum of 7 mm. Hg, the aldehyde passing over at 4950 C. and the alcohol at 8283 C. The yields obtained are set out in Table II.
EXAMPLE 3 The procedure of Example 1 is followed, but 0.1% by weight of sodium fluoride is added to the toluene. The composition of the mixture after oxidation, determined as indicated in Example 1, is given in Table I.
TABLE I lizer (Example 2) Benzyl alcohol percent 30. 2] 38 l B enzaldehydcjpercent 19. 2f 4 32. 3 J 3 Benzoic acid 16 14. 5 Non-recoverable lay-products. 34
Although the foregoing examples describe a batch-wise process, the process may also be carried out continuously.
We claim:
1. Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at 170 C.220 C. with a mixture of gaseous oxygen and an inert gaseous diluent such that the said mixture contains not more than 21% of oxygen, until at most 10% of the toluene has been oxidized, decomposing the hydroperoxides formed to benzyl alcohol and benzaldehyde by catalytic hydrogenation and separating the benzyl alcohol and benzaldehyde produced.
2. Process according to claim 8 in which, after the oxidation, the hydroperoxides in the oxidized toluene are decomposed by heating in an inert atmosphere in the presence of a cobalt salt.
3. Process according to claim 1 in which the gaseous mixture is air of reduced oxygen content.
4. Process according to claim 1 in which the oxidation is discontinued when 4% to 7% of the toluene has been oxidized.
5. Process according to claim 1 in which the oxidation is carried out in the presence of a stabilizing agent for organic hydroperoxides.
6. Process according to claim 5 in which the stabilizing agent is sodium pyrophosphate used in amount of 0.01 to 0.5% by weight of the toluene.
7. Process according to claim 5 in which the stabilizing agent is sodium fluoride used in amount of 0.01 to 0.5% by Weight of the toluene.
8. Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at C.220 C. with a mixture of gaseous oxygen and an inert gaseous diluent such that the said mixture contains not more than 21% of oxygen, until at most 10% of the toluene has been oxidized, decomposing the hydroperoxides formed to benzyl alcohol and benzaldehyde by heating in an inert atmosphere, and separating the benzyl alcohol and benzaldehyde produced.
9. Process according to claim 8 in which the gaseous mixture is air of reduced oxygen content.
10. Process according to claim 8 in which the oxidation is discontinued when 4% to 7% of the toluene has been oxidized.
11. Process according to claim 8 in which the oxidation is carried out in the presence of a stabilizing agent for organic hydroperoxides.
12. Process according to claim 11 in which the stabilizing agent is sodium pyrophosphate used in amount of 0.01 to 0.5 by weight of the toluene.
13. Process according to claim 11 in which the stabilizing agent is sodium fluoride used in amount of 0.01 to 0.5% by Weight of the toluene.
14. Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at 170-220 C. with air of reduced oxygen content in the presence of 0.01 to 0.5% by weight of the toluene of sodium pyrophosphate until 4 to 7% by weight of the toluene has been oxidized, decomposing the benzoyl hydroperoxide formed by heating in an inert atmosphere in the presence of a cobalt salt, and isolating benzyl alcohol and benzaldehyde from the product by fractional distillation.
15. Process for the production of benzyl alcohol and benzaldehyde which comprises oxidizing liquid toluene at 170-220 C. with air of reduced oxygen content in the presence of 0.01 to 0.5% by weight of the toluene of sodium fluoride until 4 to 7% by weight of the toluene has been oxidized, decomposing the benzoyl hydroperoxide formed by heating in an inert atmosphere in the presence of a cobalt salt, and isolating benzyl alcohol and benzaldehyde from the product by fractional distillation.
References Cited UNITED STATES PATENTS 1,902,550 3/1933 Forrest et a1 260599 X 2,199,585 5/1940 Bone 260599 2,347,434 4/1944 Reichert et al. 260-610X BERNARD HELFIN, Primary Examiner.
US367225A 1963-05-22 1964-05-13 Production of benzyl alcohol and benzaldehyde Expired - Lifetime US3387036A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523978A (en) * 1967-01-19 1970-08-11 Rhone Poulenc Sa Process for the purification of benzyl alcohol
US6590129B2 (en) * 1996-05-17 2003-07-08 Toray Industries, Inc. Method for preparing aromatic carboxylic acids, aromatic aldehydes, and aromatic alcohols
CN106831521A (en) * 2017-03-07 2017-06-13 湖北科林博伦新材料有限公司 A kind of method that toluene liquid-phase air oxidation process prepares benzyl peroxide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE799083A (en) * 1973-05-04 1973-08-31 Labofina Sa DIETHYLBENZENES OXIDATION PROCESS,

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1902550A (en) * 1930-01-31 1933-03-21 Nat Synthetic Corp Process of oxidizing cyclic organic compounds
US2199585A (en) * 1935-07-15 1940-05-07 Ici Ltd Production of oxygenated organic compounds
US2347434A (en) * 1941-06-30 1944-04-25 Du Pont Stabilization of peracid solutions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1902550A (en) * 1930-01-31 1933-03-21 Nat Synthetic Corp Process of oxidizing cyclic organic compounds
US2199585A (en) * 1935-07-15 1940-05-07 Ici Ltd Production of oxygenated organic compounds
US2347434A (en) * 1941-06-30 1944-04-25 Du Pont Stabilization of peracid solutions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523978A (en) * 1967-01-19 1970-08-11 Rhone Poulenc Sa Process for the purification of benzyl alcohol
US6590129B2 (en) * 1996-05-17 2003-07-08 Toray Industries, Inc. Method for preparing aromatic carboxylic acids, aromatic aldehydes, and aromatic alcohols
CN106831521A (en) * 2017-03-07 2017-06-13 湖北科林博伦新材料有限公司 A kind of method that toluene liquid-phase air oxidation process prepares benzyl peroxide
CN106831521B (en) * 2017-03-07 2018-08-21 湖北科林博伦新材料有限公司 A kind of method that toluene liquid-phase air oxidation process prepares benzyl peroxide

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JPS495324B1 (en) 1974-02-06
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FR1366078A (en) 1964-07-10
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NL128577C (en)

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