WO1983003412A1 - Process for the preparation of the potassium salt of phosphoenolpyruvic acid - Google Patents

Process for the preparation of the potassium salt of phosphoenolpyruvic acid Download PDF

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Publication number
WO1983003412A1
WO1983003412A1 PCT/US1982/000402 US8200402W WO8303412A1 WO 1983003412 A1 WO1983003412 A1 WO 1983003412A1 US 8200402 W US8200402 W US 8200402W WO 8303412 A1 WO8303412 A1 WO 8303412A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
fact
phosphite
potassium salt
preparation
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1982/000402
Other languages
English (en)
French (fr)
Inventor
Institute Of Technology Massachusetts
S.A. Firmenich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Firmenich SA
Massachusetts Institute of Technology
Original Assignee
Firmenich SA
Massachusetts Institute of Technology
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
Application filed by Firmenich SA, Massachusetts Institute of Technology filed Critical Firmenich SA
Priority to DE8282901458T priority Critical patent/DE3271625D1/de
Priority to EP82901458A priority patent/EP0107648B1/en
Priority to PCT/US1982/000402 priority patent/WO1983003412A1/en
Priority to US06/416,391 priority patent/US4478762A/en
Priority to JP57501503A priority patent/JPS59500515A/ja
Publication of WO1983003412A1 publication Critical patent/WO1983003412A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols

Definitions

  • This invention relates to organic chemical synthesis and, in particular, synthesis of phosphorlyating agents.
  • Phosphoenolpyruvic acid represents a particularly efficient phosphorylation agent, especially for organic syntheses promoted by enzymatic catalysis in which it is desired to regenerate the ATP or adenosine triphosphate. It thus constitutes a useful alternative to acetyl phosphate (AcP), over which it has a number of advantages. In fact, PEP is recognized as a more powerful phosphorylation agent than AcP, it is more stable in solution, and it, therefore, is used more easily, particularly in semiindustrial applications.
  • This invention concerns a process of the preparation of phosphoenolpyruvic acid in the form of its potassium salt, or PEP-K. Since the potassium is inert towards most enzymatic systems, and its presence is even necessary, for example, to release the activity of pyruvic kinase, the salt thus obtained can be used directly in phosphorylation processes.
  • the process of the invention consists of two steps carried out consecutively, as follows: a. The treatment of a halopyruvic acid with a trialkyl phosphite to provide a dialkyl phosphate of enolpyruyic acid of the formula
  • the potassium salt thus obtained insoluble in the reaction medium, can easily be separated from the reaction mixture by simple filtration and can thus be used directly as a phosphorylation reagent.
  • a sample of the product prepared by the process of the invention was used to synthesize glucose-6-phosphate. The method followed is specified in detail below.
  • the substituents R can represent either a lower alkyl radical, preferably methyl or ethyl, or a bivalent alkylenyl radical, such as -CH 2 -CH 2 -, for example.
  • a lower alkyl radical preferably methyl or ethyl
  • a bivalent alkylenyl radical such as -CH 2 -CH 2 -, for example.
  • trimethyl phosphite, tri-ethyl phosphite, or methyl ethylene phosphite can be used as the trialkyl phosphite, with trimethyl phosphite being preferred.
  • halopyruvic acid chloropyruvic or bromopyruvic acid
  • a solvent such as an ether, diethyl ether, for example, an ester such as ethyl acetate, or an aromatic hydrocarbon, for example, toluene or benzene.
  • diethyl ether for example, an ester such as ethyl acetate
  • aromatic hydrocarbon for example, toluene or benzene.
  • the yields of the following step which consists of the hydrolysis of the phosphate obtained, depend to a great extent on the quantity of potassium hydroxide used.
  • the optimal value of the pH is approximately 1.7-2.8, which corresponds to a quantity of potassium hydroxide equal to approximately 0.70-0.90 equivalents based on the initial quantity of halopyruvic acid used.
  • the potassium phosphoenolpyruvate obtained by the process of the invention is present in the form of a non-hygroscopic crystalline product. It is stable and of high purity, and it can be used directly in enzymatic syntheses without prior purification.
  • the process of the invention accordingly offers definite advantages over the known methods of preparation of PEP.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
PCT/US1982/000402 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid Ceased WO1983003412A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE8282901458T DE3271625D1 (en) 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid
EP82901458A EP0107648B1 (en) 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid
PCT/US1982/000402 WO1983003412A1 (en) 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid
US06/416,391 US4478762A (en) 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid
JP57501503A JPS59500515A (ja) 1982-03-29 1982-03-29 フオスフオエノ−ルピルビン酸のカリウム塩の製造法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1982/000402 WO1983003412A1 (en) 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid

Publications (1)

Publication Number Publication Date
WO1983003412A1 true WO1983003412A1 (en) 1983-10-13

Family

ID=22167904

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1982/000402 Ceased WO1983003412A1 (en) 1982-03-29 1982-03-29 Process for the preparation of the potassium salt of phosphoenolpyruvic acid

Country Status (5)

Country Link
US (1) US4478762A (enExample)
EP (1) EP0107648B1 (enExample)
JP (1) JPS59500515A (enExample)
DE (1) DE3271625D1 (enExample)
WO (1) WO1983003412A1 (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239357A3 (en) * 1986-03-25 1989-03-15 Ube Industries, Ltd. Process for preparing monosodium phosphoenolpyruvate and use of the same as visceral function improver
CN101250198B (zh) * 2008-04-01 2012-06-20 华东理工大学 一种磷酸烯醇式丙酮酸钾盐的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685552A (en) * 1952-02-29 1954-08-03 Shell Dev Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate
DE1151794B (de) * 1959-04-07 1963-07-25 Dr Friedrich Cramer Verfahren zur Herstellung des Mononatriumsalzes der Phospho-enolbrenztraubensaeure
FR3246M (fr) * 1964-02-06 1965-04-12 Pharmacodynamie Et Metabolisme Médicaments a base d'acide phospho-énol-pyruvique.

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6041674B2 (ja) * 1979-12-19 1985-09-18 花王株式会社 リン酸エステル塩乾燥物の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685552A (en) * 1952-02-29 1954-08-03 Shell Dev Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate
DE1151794B (de) * 1959-04-07 1963-07-25 Dr Friedrich Cramer Verfahren zur Herstellung des Mononatriumsalzes der Phospho-enolbrenztraubensaeure
FR3246M (fr) * 1964-02-06 1965-04-12 Pharmacodynamie Et Metabolisme Médicaments a base d'acide phospho-énol-pyruvique.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Biochem. J., Vol. 155, 1976, Great Britain, WEBSTER, et al, pp. 433-441 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239357A3 (en) * 1986-03-25 1989-03-15 Ube Industries, Ltd. Process for preparing monosodium phosphoenolpyruvate and use of the same as visceral function improver
CN101250198B (zh) * 2008-04-01 2012-06-20 华东理工大学 一种磷酸烯醇式丙酮酸钾盐的合成方法

Also Published As

Publication number Publication date
US4478762A (en) 1984-10-23
EP0107648A1 (en) 1984-05-09
JPS59500515A (ja) 1984-03-29
DE3271625D1 (en) 1986-07-17
EP0107648B1 (en) 1986-06-11
EP0107648A4 (en) 1984-08-10
JPH0251917B2 (enExample) 1990-11-08

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