WO2011098386A1 - Procédé pour la préparation d'un dérivé de l'acide anthranilique - Google Patents

Procédé pour la préparation d'un dérivé de l'acide anthranilique Download PDF

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Publication number
WO2011098386A1
WO2011098386A1 PCT/EP2011/051535 EP2011051535W WO2011098386A1 WO 2011098386 A1 WO2011098386 A1 WO 2011098386A1 EP 2011051535 W EP2011051535 W EP 2011051535W WO 2011098386 A1 WO2011098386 A1 WO 2011098386A1
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WO
WIPO (PCT)
Prior art keywords
compound
formula
weight
concentration
sodium hydroxide
Prior art date
Application number
PCT/EP2011/051535
Other languages
English (en)
Inventor
Vikrant Murudi
Ashok Shankarappa Shyadligeri
Brijnandan Premnath Mishra
Markus Adolf Luginbuehl
Maren Fuerst
Original Assignee
Syngenta Participations Ag
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 Syngenta Participations Ag filed Critical Syngenta Participations Ag
Publication of WO2011098386A1 publication Critical patent/WO2011098386A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters

Definitions

  • the present invention relates to the selective preparation of 6-nitro-anthranilic acid.
  • 6-Nitro-anthranilic acid is a valuable intermediate for the preparation of benzonorbornene fungicides, as described for example in WO 2007/048556.
  • 6-nitro-anthranilic acid (A) can be prepared according to the following scheme:
  • 3-Nitro-phthalimide (E) is a useful starting material for the preparation of 6-nitro-anthranilic acid, in particular for large scale manufacturing which requires high safety standards.
  • 6-nitrophthalamic acid (D) is then converted to 6-nitro-anthranilic acid (A).
  • 6-nitrophthalamic acid may be reacted first with aqueous base, such as, for example, aqueous sodium hydroxide, and sodium hypochlorite, and then with aqueous acid, such as, for example, aqueous hydrochloric acid.
  • aqueous base such as, for example, aqueous sodium hydroxide, and sodium hypochlorite
  • aqueous acid such as, for example, aqueous hydrochloric acid.
  • the disadvantage of this prior art process is the relatively low yield in each of the two steps (70-73%). Further, isolation is required to enrich the desired isomer with additional filtration which leads to high waste generation and higher cycle time (energy inefficient). Also, a two step synthesis is undesired for large scale production.
  • the aim of the present invention is therefore to provide a novel process for the selective production of 6-nitro-anthranilic acid that avoids the disadvantages of the known process and makes it possible to prepare 6-nitro-anthranilic acid in high yields and good quality in an economically and ecologically advantageous way in a one-pot process with a high safety standard.
  • the concentrated hydrochloric acid used in the process according to the invention has a concentration of 30 - 38 % by weight, preferably 30 - 35 % by weight.
  • the reaction mass is acidified at a temperature of 5 to 10°C with concentrated hydrochloric acid to a pH of 1.5 to 2.0.
  • the suspension of the compound of formula I I in sodium hydroxide can be prepared by charging an aqueous solution of sodium hydroxide (2 to 3 mol), cool the solution to a temperature of 20 to 30°C, in particular 25°C, and add portionwise 1 mol of the compound of formula II under stirring.
  • the suspension of the compound of formula II in sodium hydroxide can be advantageously prepared by charging an aqueous solution of sodium hydroxide (preferably 2 mol), at a temperature of 5 to 60 °C, in particular 5 to 40°C, preferably of 25 to 30 °C, keep the temperature of the solution at 20 to 40°C, in particular 20 to 25°C, and add portionwise 1 mol of the compound of formula I I under stirring.
  • concentration of sodium hydroxide is preferably 5 to 25%, more preferably 5 to 20%, in particular 15% by weight.
  • the sodium hypochlorite (preferably in an amount of 1 .1 to 1 .2 mol) is added portionwise, preferably during 20 to 45 minutes.
  • a preferred temperature range for the addition is from 5 to 60°C, in particu lar 5 to 40° C, preferably 25 to 30 ° C .
  • the sodium hypochlorite concentration is preferably 8% to 15%, in particular 10 - 12 % by weight. It is preferred to stirr the reaction mass for 1 to 2 hours for complete conversion of the compound of formula II to the compound of formula I. It is advantageous to cool the reaction mass to a temperature from 5 to 10 °C before acidification to pH 1 .5 - 2.0 using concentrated HCI.
  • a significant advantage of the process of this invention is the overall yield which is between 70% and 90%. Further, the process is carried out as a one-pot synthesis without isolation of intermediates. This qualifies the process of this invention in particular for large scale manufacturing of the compound of formula I.
  • a further significant of the invention is the safety of the process (inherently safe process) due to the presence of a nitro group.
  • alkaline solution of compound of formula II into NaOCI solution results in an accumulation and generation of the N-halo compound which is very high energetic and explosive compound.
  • a lower mole ratio of NaOH as claimed with respect to compound of formula II results in undesired excessive gas evolution during acidification.
  • Example 1 (best mode): A solution of NaOH (2.0 mole) having a strength of 1 5% by weight was cooled to a temperature of 25°C. Then 1 .0 mole of 3-nitro-phthalimide was added portionwise under stirring. While maintaining the temperature at 25-30°C, 1 .2 mole solution of 12% strength sodium hypochlorite was added portionwise. During addition, the pH of the reaction mass was kept at pH 12.0 with aqueous sodium hydroxide with a concentration of of 15% by weight. After stirring for 2 hours, the reaction mass was cooled down to 5-10 °C and acidified with 32% hydrochloric acid to a pH value of 1 .8. After stirring for another hour, the reaction mass was filtered with a suction filter. Then the cake was washed with cold water (8-10 °C) and dried under vacuum to yield 6-nitro-anthranilic acid in an amount of 88% of theory.

Abstract

La présente invention a pour objet un nouveau procédé pour la préparation d'un composé de formule (I), lequel procédé comprend l'ajout de 1 à 2 moles d'hypochlorite de sodium ayant une concentration de 8 % à 15 % en poids à une suspension du composé de formule (II) dans de l'hydroxyde de sodium aqueux à une température de 5 à 60 °C, la concentration de l'hydroxyde de sodium dans la suspension étant de 5 à 25 % en poids ; et l'acidification de la masse réactionnelle avec de l'acide chlorhydrique concentré jusqu'à un pH de 1,5 à 2,0, ledit procédé étant mis en œuvre sous forme d'une synthèse « one-pot » sans isolement des intermédiaires.
PCT/EP2011/051535 2010-02-09 2011-02-03 Procédé pour la préparation d'un dérivé de l'acide anthranilique WO2011098386A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN276DE2010 2010-02-09
IN276/DEL/2010 2010-02-09

Publications (1)

Publication Number Publication Date
WO2011098386A1 true WO2011098386A1 (fr) 2011-08-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/051535 WO2011098386A1 (fr) 2010-02-09 2011-02-03 Procédé pour la préparation d'un dérivé de l'acide anthranilique

Country Status (4)

Country Link
AR (1) AR080142A1 (fr)
TW (1) TW201136873A (fr)
UY (1) UY33220A (fr)
WO (1) WO2011098386A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11560384B2 (en) 2017-05-04 2023-01-24 University Of Utah Research Foundation Benzonorbornadiene derivatives and reactions thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007031323A1 (fr) 2005-09-16 2007-03-22 Syngenta Participations Ag. Procédé de production d'amides
WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007031323A1 (fr) 2005-09-16 2007-03-22 Syngenta Participations Ag. Procédé de production d'amides
WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HEINRICH SEIDEL, J. C. BITTNER: "Über Derivate der Nitrophtalsäuren", MONATSHEFTE FÜR CHEMIE, vol. 23, 1902, pages 415 - 436, XP002638261, DOI: 10.1007/BF01527262 *
ROBERT A SNOW ET AL: "Analysis of bridging regioselectivity operative in photorearrangement of ortho-substituted benzonorbornadienes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC; US, vol. 99, no. 11, 25 May 1977 (1977-05-25), pages 3734 - 3744, XP002271785, ISSN: 0002-7863, DOI: DOI:10.1021/JA00453A036 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11560384B2 (en) 2017-05-04 2023-01-24 University Of Utah Research Foundation Benzonorbornadiene derivatives and reactions thereof

Also Published As

Publication number Publication date
AR080142A1 (es) 2012-03-14
TW201136873A (en) 2011-11-01
UY33220A (es) 2011-09-30

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