WO2006100731A1 - Procede d'acetylation d’un derive acide 5-amino-2,4,6-triiodoisophtalique - Google Patents

Procede d'acetylation d’un derive acide 5-amino-2,4,6-triiodoisophtalique Download PDF

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Publication number
WO2006100731A1
WO2006100731A1 PCT/JP2005/004992 JP2005004992W WO2006100731A1 WO 2006100731 A1 WO2006100731 A1 WO 2006100731A1 JP 2005004992 W JP2005004992 W JP 2005004992W WO 2006100731 A1 WO2006100731 A1 WO 2006100731A1
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WO
WIPO (PCT)
Prior art keywords
group
acid
amino
triodoisophthalic
organic solvent
Prior art date
Application number
PCT/JP2005/004992
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English (en)
Japanese (ja)
Inventor
Ryuji Takata
Original Assignee
Manac 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
Application filed by Manac Inc. filed Critical Manac Inc.
Priority to JP2007509085A priority Critical patent/JP4801661B2/ja
Priority to PCT/JP2005/004992 priority patent/WO2006100731A1/fr
Publication of WO2006100731A1 publication Critical patent/WO2006100731A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Definitions

  • the present invention relates to a method for producing a 5-acetamido-2,4,6-triodoisophthalic acid derivative, which comprises acetylating a 5-amino-2,4,6-triodoisophthalic acid derivative.
  • 5-Amino-2,4,6-triodoisophthalic acid or a derivative thereof is particularly used as a nonionic contrast medium or an intermediate for producing the same. Since the production of non-ionic contrast agents involves a number of processes, the yield and purity at each process greatly affect the quality and yield of the final product.
  • 5-acetoamide-2,4,6-triodoisophthalic acid or derivatives thereof is an important intermediate between nonionic contrast agents. It is desirable to produce a good and efficient product that is often used as a body.
  • Patent Document 1 a salty acetyl which is used as a force acetylating agent in which acetylacetyl is used in a dimethylacetamide solvent under relatively mild reaction conditions. Is water-free and requires special chemical drums that are difficult to transport and store for industrial use.
  • dipolar aprotic solvents such as dimethylacetamide and dimethylformamide have a high boiling point and require a great deal of time and effort to remove the high boiling energy. For this reason, if the removal becomes insufficient, there is a concern that it may become a residual solvent in the product.
  • Patent Document 2 Patent Document 3, and Non-Patent Document 1
  • acetylic acid is added to acetic anhydride.
  • Addition of acetylic acid by adding acetic anhydride serves as a acetylating agent and a solvent.
  • sulfuric acid is added after mixing raw materials and acetic anhydride, the reaction proceeds explosively with intense heat generation. For this reason, there is a risk that the accident may become a serious accident that is difficult to control.
  • wastewater containing a large amount of acetic anhydride and acetic acid and sulfuric acid must be treated for industrial use. However, it is difficult because a lot of costs are incurred for processing.
  • Patent Literature 1 Japanese Translation of Special Publication 2000-505820
  • Patent Document 2 British Patent Specification No. 785670
  • Patent Document 3 Japanese Patent Publication No. 56-54310
  • Non-Patent Document 1 J. Haavaldsen et.al, Acta Pharm. Suec, 20, 219 (1983).
  • An object of the present invention is to produce 5-acetoamide-2,4,6-triodoisophthalic acid or a derivative thereof more easily and safely in a high yield.
  • the present inventor has obtained a 5-amino-2,4,6-triodoisophthalic acid derivative as an organic solvent using acetic anhydride in the presence of an acid catalyst.
  • the present inventors have found a method of acetylene cake that can be obtained in high yield and high quality by carrying out acetylene in a simple manner with few steps.
  • X and X are the same or different, a hydroxyl group or a halogen atom.
  • R and R may be the same or different
  • a straight or branched lower alkyl group of up to 115 hydrogen or carbon atoms (wherein The alkyl group is a hydroxyl group, an amino group, a thiol group, a nitro group, a nitrile group, a carbonyl group, and an acyloxy group, which may be substituted with one or more selected substituents.
  • the acid catalyst is sulfuric acid, (1) one (5) method according to any one of the above;
  • the amount of the acid catalyst is 1 to 2 mol% with respect to the compound represented by formula 1, (1) one (6)! The method according to item 1
  • the reaction is usually carried out by dissolving the 5 amino-2,4,6-triodoisophthalic acid derivative represented by the formula 1 in an organic solvent.
  • the 5-amino 2,4,6-triodoisophthalic acid derivative does not dissolve in the organic solvent, both of them react in a solid-liquid two-phase system. It is particularly preferable to suspend the 5-amino-2,4,6-triodoisophthalic acid derivative of 1 in an organic solvent, add an acid catalyst, and add acetic anhydride dropwise to the slurry.
  • both X and X are particularly preferable as the compound represented by Formula 1.
  • 1 2 represents a hydroxyl group
  • X and X both represent a halogen atom
  • X and X Are compounds in which both represent NHR, and both X and X represent OR.
  • R and R in formula 1 are each hydrogen or a carbon atom.
  • alkyl group is a group consisting of a hydroxyl group, an amino group, a thiol group, a nitro group, a nitrile group, a carbonyl group, and an acyloxy group
  • Force is substituted with one or more selected substituent (s).
  • substituent of the alkyl group a hydroxyl group is particularly preferable.
  • the acyl of the acyloxy group has 1 to 15 carbon atoms.
  • Hydroxyl group, amino group, thiol group, nitro group, carbonyl group, and acyloxy group group force Selected straight or branched lower chain up to 5 carbon atoms substituted with one or more selected substituents
  • alkyl group examples include -CH CH (OH) CH OH
  • the organic solvent in the present invention is preferably an organic solvent that does not react with acetic anhydride.
  • organic solvents include halogenated hydrocarbon solvents such as methane tetrachloride, chloroform, methylene chloride, dichloroethane, and chloroform, dimethyl ether, and jetyl.
  • halogenated hydrocarbon solvents such as methane tetrachloride, chloroform, methylene chloride, dichloroethane, and chloroform, dimethyl ether, and jetyl.
  • aliphatic ether solvents such as ether, methyl ethyl ether, and tetrahydrofuran
  • organic solvents having a tolyl group such as acetonitrile, propio-tolyl, and petit-tolyl.
  • the amount of the organic solvent used in the present invention is not particularly limited, but it is 1 to 5 times by weight, preferably 1.5 to 2 times by weight of 5-amino-2,4,6 tolyoisophthalic acid derivative. It is.
  • the acid catalyst used in the present invention is not particularly limited, but specific examples thereof include hydrochloric acid, sulfuric acid, hydrobromic acid, p-toluenesulfonic acid, methanesulfonic acid, etc., preferably sulfuric acid. It is.
  • the amount of the acid catalyst is not particularly limited, 5-amino-2, 4 of the formula 1, 6-preparative RHO de isophthalic acid derivatives 0.5 1 5 mole 0/0, preferably 1 one 2 mole 0/0 is there.
  • the amount of acetic anhydride used in the present invention is 1 to 12 molar equivalents, preferably 1.0 to 1.2 molar equivalents, of the 5 amino-2, 4, 6, 6 triode isophthalic acid derivative represented by Formula 1.
  • the reaction temperature in the present invention is not particularly limited, but is preferably 0 to 100 ° C. It is preferably 10-50 ° C.
  • reaction time in the present invention is not particularly limited, but is preferably 0.5 hours or more.
  • 5-acetoamide-2,4,6-triodoisophthalic acid derivatives can be obtained.
  • the filtered mother liquor can be easily discarded by neutralizing with a small amount of caustic soda or its aqueous solution.
  • Sample preparation The sample was dissolved in a developing solvent at a rate of 1 mg, ml to obtain a sample solution.
  • a 5-acetamido-2,4,6-triodoisophthalic acid derivative can be safely obtained in a high yield, high purity and by a simple operation of filtration.
  • the derivative can be easily dried and eliminates the need for a large amount of waste liquid treatment.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L’invention décrit un procédé de production d’un dérivé 5-acétamide-2,4,6-triiodoisophtalique comprenant l’acétylation d’un dérivé acide 5-amino-2,4,6-triiodoisophtalique dans un solvant organique en présence d’un catalyseur acide et au moyen d’anhydride acétique. Ce procédé pratique permet de fournir un dérivé acide 5-acétamide-2,4,6-triiodoisophtalique avec un rendement et une qualité élevés.
PCT/JP2005/004992 2005-03-18 2005-03-18 Procede d'acetylation d’un derive acide 5-amino-2,4,6-triiodoisophtalique WO2006100731A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2007509085A JP4801661B2 (ja) 2005-03-18 2005-03-18 ５−アミノ−２，４，６−トリヨードイソフタル酸誘導体のアセチル化方法
PCT/JP2005/004992 WO2006100731A1 (fr) 2005-03-18 2005-03-18 Procede d'acetylation d’un derive acide 5-amino-2,4,6-triiodoisophtalique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2005/004992 WO2006100731A1 (fr) 2005-03-18 2005-03-18 Procede d'acetylation d’un derive acide 5-amino-2,4,6-triiodoisophtalique

Publications (1)

Publication Number Publication Date
WO2006100731A1 true WO2006100731A1 (fr) 2006-09-28

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Application Number Title Priority Date Filing Date
PCT/JP2005/004992 WO2006100731A1 (fr) 2005-03-18 2005-03-18 Procede d'acetylation d’un derive acide 5-amino-2,4,6-triiodoisophtalique

Country Status (2)

Country Link
JP (1) JP4801661B2 (fr)
WO (1) WO2006100731A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014527510A (ja) * 2011-06-24 2014-10-16 ホビオネ インテル リミテッド トリヨード造影剤の製造
FR3062851A1 (fr) * 2017-02-10 2018-08-17 Guerbet Procede de preparation monotope de composes organo-iodes
US11472767B2 (en) 2018-08-02 2022-10-18 Guerbet Process for the monotopic preparation of intermediate organo-iodinated compounds for the synthesis of ioversol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5654310B2 (fr) * 1976-06-11 1981-12-24
GB2142009A (en) * 1983-06-22 1985-01-09 Dagra Nv N,n,n',n'-tetra (hydroxyethyl)-5-acetylamino-2,4,6-triidoisophthaloyldiglycinamide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB994215A (en) * 1960-08-25 1965-06-02 Mallinckrodt Chemical Works Isophthalic acid derivatives and process for preparing same
FR2511871A1 (fr) * 1981-08-28 1983-03-04 Guerbet Sa Procede pour augmenter la tolerance des produits opacifiants et produits opacifiants ainsi obtenus
FR2512014A1 (fr) * 1981-08-28 1983-03-04 Guerbet Sa Composes bromes utilisables dans des produits opacifiants

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5654310B2 (fr) * 1976-06-11 1981-12-24
GB2142009A (en) * 1983-06-22 1985-01-09 Dagra Nv N,n,n',n'-tetra (hydroxyethyl)-5-acetylamino-2,4,6-triidoisophthaloyldiglycinamide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014527510A (ja) * 2011-06-24 2014-10-16 ホビオネ インテル リミテッド トリヨード造影剤の製造
FR3062851A1 (fr) * 2017-02-10 2018-08-17 Guerbet Procede de preparation monotope de composes organo-iodes
US10836711B2 (en) 2017-02-10 2020-11-17 Guerbet Method for the one-pot production of organo-iodinated compounds
US11472767B2 (en) 2018-08-02 2022-10-18 Guerbet Process for the monotopic preparation of intermediate organo-iodinated compounds for the synthesis of ioversol

Also Published As

Publication number Publication date
JPWO2006100731A1 (ja) 2008-08-28
JP4801661B2 (ja) 2011-10-26

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