WO2007049148A2 - Methodes de preparation de l'acide phenylacetique - Google Patents

Methodes de preparation de l'acide phenylacetique Download PDF

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Publication number
WO2007049148A2
WO2007049148A2 PCT/IB2006/003240 IB2006003240W WO2007049148A2 WO 2007049148 A2 WO2007049148 A2 WO 2007049148A2 IB 2006003240 W IB2006003240 W IB 2006003240W WO 2007049148 A2 WO2007049148 A2 WO 2007049148A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
sodium
phenylacetic acid
tetra
ammonium
Prior art date
Application number
PCT/IB2006/003240
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English (en)
Other versions
WO2007049148A3 (fr
Inventor
Elmira Mamedemin Ramazanova
Alimamed Latif Shabanov
Original Assignee
Property Development Corporation International; Ltd., Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US11/177,893 external-priority patent/US20070010696A1/en
Application filed by Property Development Corporation International; Ltd., Inc. filed Critical Property Development Corporation International; Ltd., Inc.
Priority to CA002656354A priority Critical patent/CA2656354A1/fr
Publication of WO2007049148A2 publication Critical patent/WO2007049148A2/fr
Publication of WO2007049148A3 publication Critical patent/WO2007049148A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the present invention relates to methods of preparing phenylacetic acid.
  • the purity of the product obtained is not high due to the formation of byproducts (phenylmalonic acid, etc.), which requires supplementary purification. This creation of byproducts reduces output to 65-70%.
  • current processes are environmentally unfriendly and are not capable of being carried out in a stainless steel reactor. Thus, the current processes for the production of phenylacetic acid are not economically expedient and fail to be useful as continuous methods of phenylacetic-acid industrial production.
  • Embodiments of the present principles realize a number of significant advantages. Among other things, application of these principles advantageously reduces process time and the formation of byproducts, and increases the phenylacetic acid yield.
  • FIGURE 1 is a block diagram of a representative system embodying the principles of the present invention
  • FIGURE 2 is a schematic flow diagram illustrating an exemplary process embodying the principles of the present invention.
  • FIGURE 3 is a schematic flow diagram illustrating another exemplary process embodying the principles of the present invention. DETAILED DESCRIPTION OF THE INVENTION
  • FIGURE 1 there are four basic steps to the inventive phenylacetic acid production process. Some of the basics of the process can be found in Gilman, Henry, et al, "Benzylalkali Compounds," J. Am. Chem. Soc, Vol. 62, 1514 (1940); Nobis, John, et al, "Phenylsodium Route to Phenylacetic Acid and Dimenthyl Phenylmalonate,” Indus. Eng. Chem. Vol. 46, No.
  • an alkali metal, a phenyl halide, a solvent, and a catalyst are combined.
  • An example of this is combining sodium, chlorobenzene, toluene, and a catalyst.
  • the sodium and chlorobenzene react to form phenylsodium.
  • this reaction mixture is boiled, which causes the phenylsodium and toluene to react and form benzylsodium.
  • the reaction mixture is carbonized, preferably over dry ice, hydrolyzed, and acidified, which leads to the formation of phenylacetic acid.
  • the phenylacetic acid is crystallized and recovered from the reaction mixture.
  • metallic sodium and toluene are added to a preliminary reactor 1 for sodium disintegration.
  • a special-purpose, highspeed mixer 12 preferably capable of achieving at least 10,000 revolutions per minute, is switched on to crush the sodium and to produce a sodium-in-toluene suspension.
  • the mixer need only be used for around 1-1.5 minutes.
  • the suspension is then cooled down to around 25-30 0 C.
  • a solution containing equivalent amounts of chlorobenzene and dry toluene with around 0.0005-0.001% catalyst calculated on sodium are contained in a chlorobenzene tank 11.
  • Effective catalysts are cryptands and crown compounds, such as crown ethers.
  • the macrocyclic-catalyst will have a cavity size which corresponds to the ion radius of sodium.
  • the preferred catalysts are cryptand [2,2,2] and 16-crown-5.
  • An equivalent amount of the solution from the chlorobenzene tank 11 is added to and mixed with the preliminarily prepared suspension of metallic sodium in toluene in the preliminary reactor 1. This mixture is transferred to a phenylsodium-conversion reactor 3 with the sodium particle size not to exceed 20-25 microns.
  • the solution from the chlorobenzene tank 11 can be added directly to the phenylsodium-conversion reactor 3 without premixing the solution with the suspension in the preliminary reactor 1.
  • Another alternative is to add the chlorobenzene and catalyst to the preliminary reaction mixture in the preliminary reactor 11 prior to initial mixing.
  • the feed rate of the reagents to the phenylsodium-conversion reactor should be around 4.3 mol/hr.
  • the reactor can have an external cooling jacket.
  • the temperature in the phenylsodium-conversion reactor 3 is maintained in the range of around 27-40 0 C by regulating the reagent feed rates and the external cooling of the phenylsodium-conversion reactor 3.
  • the preferred amount of catalyst is 0.001% based on sodium. More than 0.001% catalyst can be used, but the economics for larger amounts of catalyst are not as good as for the preferred amount. All process steps should be carried out in an inert atmosphere such as nitrogen. Generally, any dry gas may be used in this process.
  • the suspension in the reserve tank 6 is transferred to a benzylsodium-conversion reactor 7.
  • the suspension is boiled in the benzylsodium-conversion reactor 7. Boiling is maintained for approximately 0.5-1.5 hours, preferably for 1.0-1.5 hours.
  • the prepared benzylsodium suspension is transferred to a cooling tank 9 where the benzylsodium suspension is cooled to 25 0 C. Following cooling in the cooling tank 9, the benzylsodium suspension is discharged by jet onto disintegrated dry ice in the carbonation reactor 10 and slowly mixed. Alternatively, liquid CO 2 may be used.
  • the dry ice in the carbonation reactor 10 is in an amount of 20 fold mole excess based on benzylsodium.
  • the residue is hydrolyzed with water by mixing and cooling in the carbonation reactor 10.
  • the volume of water used for hydrolysis is equal to 25-35% of the toluene volume.
  • the aqueous layer is then separated from the toluene layer and is acidified, preferably with hydrochloric acid.
  • the pH is preferably lowered to a pH of approximately pH 2.
  • the phenylacetic acid is then crystallized and separated from the water.
  • the phenylacetic acid prepared by the invented process has a melting temperature of 75-76 0 C.
  • the contents of the reserve tank are placed into a benzylsodium-conversion reactor, where the suspension boils for 1-1.5 hours. While boiling, the solution's color gets brick-red and then black again.
  • Table 1 shows that including a catalyst greatly increases phenylacetic- acid yield. The highest yield of the product is observed when the time of boiling in toluene equals 1 hour time. Further increase in boiling time causes a decrease in desired product yield. Also, the application of a catalyst improves the stability of the results.
  • the principles of the present invention are also embodied in methods for forming phenylacetic acid using phase transfer techniques, particularly to the phase-transfer catalytic carboxylation of benzyl-sodium in toluene / benzene in presence of a salt such as [N(C 4 H 9 ) 4 ]x .
  • Carboxylation of benzyl-sodium in solid-liquid phase-transfer catalysis condition realizes many advantages. For example, carboxylation processes using the phase-transfer catalysis techniques of the present inventive principles consume less dry ice. Further, these phase-transfer catalysis techniques prevent minor byproduct formation reactions. Additionally, phase-transfer catalysis techniques also the simplify phenylacetic acid preparation process.
  • a carboxylation reaction 1 , 2 and 3 is carried out by mixing a toluene/benzene suspension of benzyl- sodium with a toluene solution of the tetra-ethyl-ammonium-chloride and adding the prepared mixture to crushed dry ice.
  • Another important advantage of this system is the possibility of achieving selective carboxylation of benzyl-sodium yield of phenylacetic acid, and a carboxylation yield to 96-98%.
  • An important practical aspect of this process is the continuous separation of the product from the catalyst, which in effect heterogenizes the homogenous catalyst. This point accounts for the high catalyst turnover, the selectivity encountered in the carboxylation of benzyl-sodium and the high activity of the catalyst.
  • Table 2 summarizes experimental results demonstrating carboxylation processes using the phase-transfer catalysis techniques of the present inventive principles.

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

Abstract

L'invention porte sur une méthode de préparation de l'acide phénylacétique, cette méthode comprenant la carboxylation par transfert de phase du sodium benzylique en présence d'un catalyseur de sel.
PCT/IB2006/003240 2005-07-08 2006-07-10 Methodes de preparation de l'acide phenylacetique WO2007049148A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA002656354A CA2656354A1 (fr) 2005-07-08 2006-07-10 Methodes de preparation de l'acide phenylacetique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11/177,893 US20070010696A1 (en) 2005-07-08 2005-07-08 Method of preparation of methyl-benzyl-ketone
US11/177,893 2005-07-08
US11/325,856 2006-01-05
US11/325,856 US20070010686A1 (en) 2005-07-08 2006-01-05 Method of preparing phenylacetic acid

Publications (2)

Publication Number Publication Date
WO2007049148A2 true WO2007049148A2 (fr) 2007-05-03
WO2007049148A3 WO2007049148A3 (fr) 2007-07-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2006/003240 WO2007049148A2 (fr) 2005-07-08 2006-07-10 Methodes de preparation de l'acide phenylacetique

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WO (1) WO2007049148A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354528A (zh) * 2021-06-07 2021-09-07 李乾华 一种苯乙酸生产方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GILMAN, H.; PACEVITZ, H, A. AND BAINE, O: "Benzylalkali Compounds" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 62, 1940, pages 1514-1520, XP002427994 cited in the application *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354528A (zh) * 2021-06-07 2021-09-07 李乾华 一种苯乙酸生产方法

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Publication number Publication date
WO2007049148A3 (fr) 2007-07-19

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