WO2013105117A1 - Cu-MEDIATED ANNULATION FOR THE PRODUCTION OF 1-AMINO-2-NAPHTHALENECARBOXYLIC ACID DERIVATIVES - Google Patents

Cu-MEDIATED ANNULATION FOR THE PRODUCTION OF 1-AMINO-2-NAPHTHALENECARBOXYLIC ACID DERIVATIVES Download PDF

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Publication number
WO2013105117A1
WO2013105117A1 PCT/IN2013/000019 IN2013000019W WO2013105117A1 WO 2013105117 A1 WO2013105117 A1 WO 2013105117A1 IN 2013000019 W IN2013000019 W IN 2013000019W WO 2013105117 A1 WO2013105117 A1 WO 2013105117A1
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WO
WIPO (PCT)
Prior art keywords
carboxylate
ethyl
amino
formula
group
Prior art date
Application number
PCT/IN2013/000019
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English (en)
French (fr)
Inventor
Santhosh Rekula REDDY
Kishore Prasad PRAGATI
Brij Bhushan AHUJA
Arumugam Sudalai
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Council Of Scientific & Industrial Research
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.)
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Publication date
Application filed by Council Of Scientific & Industrial Research filed Critical Council Of Scientific & Industrial Research
Priority to US14/371,059 priority Critical patent/US9233911B2/en
Publication of WO2013105117A1 publication Critical patent/WO2013105117A1/en

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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
    • C07C227/12—Formation of amino and carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/68—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/68—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C229/70—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/68—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C229/72—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the carbon skeleton being further substituted by doubly-bound oxygen atoms
    • C07C229/74—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the carbon skeleton being further substituted by doubly-bound oxygen atoms the condensed ring system being formed by at least three rings, e.g. amino anthraquinone carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/70—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with ring systems containing two or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes

Definitions

  • This invention relates to cheaper and practical protocol for the construction of ,a wide variety of 1 -Amino-2-naphthalenecarboxylic acid derivatives and their structural analogues that proceeds with high yields in a single step via intramolecular cascade cyano ene reaction.
  • 1 -Amino-2-naphthalenecarboxylic Acid Derivatives are the intermediates of Dyes and Pigments useful in Peptide Synthesis. There is less literature available on preparation of 1 -Amino-2-naphthalenecarboxylic Acid Derivatives. An article titled “Efficient Synthesis of 1 -Amino-2-naphthalenecarboxylic Acid Derivatives via a Sequential Michael Addition/Enolate-Nitrile Coupling Route and Its Application to Facile Preparation of 9-Amino Analogues of Arylnaphthofuranone Lignans" by Kazuhiro Kobayashi et al, published in J. Org.
  • the dihydronaphthalenecarboxylic acid derivatives were converted, to the corresponding 1 -amino-2-naphthalenecarboxylic acid derivatives in 43-99% yields on dehydrogenation with palladium on activated carbon in refluxing p-cymene.
  • Main object of the present invention is to provide an effective synthesis for the preparation of 1 -Amino-2-naphthalenecarboxylic acid and its derivatives with quantitative yields.
  • present invention provides a one pot process for the preparation of compound of formula (A) and their structural analogues comprising reacting compound of formula (B) with CuCN in solvent at a temperature in the range of 145 ° -155 °C for time period in the range of 10 to12 hours;
  • R 1 ,R 2 ,R 3 , R A are selected independently from the group consitsitng of hydrogen, alkyl, alkoxy, halo, N0 2 or CN;
  • R 5 is sleeted independently from the group consitsitng of H, CH 3 , C 2 H 5 , Ph or
  • R 6 is selected independently from the group consitsitng of C0 2 Et, C0 2 Me, C0 2 Ph, COMe, COPh, CN, S0 2 Ph, CONH 2 or N0 2 ;
  • R 7 is selected independently from the group consitsitng of H, CH3 of Ph; and X represents halo group.
  • the polar aprotic solvent is preferably DMF.
  • the halo group is preferably bromo.
  • compound of formula (B) is selected from the group consisting of
  • present invention provides a compound of formula (A)
  • R 1 , R 2 , R 3 , R 4 are selected independently from hydrogen ,
  • R 5 is sleeted independently from H, CH3, C2H5, Ph, CH3C6H/1;
  • R 6 is selected independently from C0 2 Et, C0 2 Me, C0 2 Ph, COMe, COPh, CN, S0 2 Ph, CONH 2) N0 2 and
  • R 7 is selected independently from H, CH 3 , Ph.
  • representative compounds of formula A comprising:
  • Present invention provides a facile, cost-effective method involving one-pot CuCN-mediated cyano ene reaction of the compound of formula (B) for the construction of a wide variety of 1 -Amino-2-naphthalenecarboxylic acid derivatives of formula (A) and their structural analogues that proceeds with high yields in a single step via intramolecular cascade cyano ene reaction.
  • CuCN is very cheap, easy to perform at higher scales, showed remarkably broad substrate scope and good functional group tolerance and not much effluent is generated.
  • the one-pot CuCN-mediated cyano ene reaction typically requires substantially similar conditions of Rosenmund-von Braun Reaction .
  • This novel transformation involves cascade reaction sequence, first substitution of bromo with CN and followed by an intramolecular cyano ene reaction to access 1 -Amino-2- naphthalenecarboxylic acid derivatives with quantitative yields.
  • the procedure tolerates a series of functional groups, such as methoxyl, fluoro and chloro groups. Otherwise synthesis of 1 -Amino-2 -naphthalenecarboxylic acid derivatives requires multiple steps.
  • 1 -Amino-2-naphthalenecarboxylic acid derivatives of formula (A) is represented as enlisted herein.
  • R 1 , R 2 , R 3 , R 4 are selected independently from the group consitsitng of hydrogen, alkyl, alkoxy, halo, N0 2 or CN;
  • R 5 is sleeted independently from the group consitsitng of H, CH 3 , C 2 H 5 , Ph or
  • R 6 is selected independently from the group consitsitn of C0 2 Et, C0 2 Me, C0 2 Ph, COMe, COPh, CN, S0 2 Ph, CONH 2 or N0 2 ;
  • R 7 is selected independently from the group consitsitng of H, CH3 of Ph; and X represents halo group.
  • Present invention provides a one pot synthesis of various 1 -Amino-2- naphthalenecarboxylic acid derivatives of formula (A) and their structural analogues which includes reacting a compound of formula (B) with CuCN in polar aprotic solvent and refluxing the mixture at a temperature in the range of 145- 1 55 ° C for 10-1 2 hours.
  • the compound of formula (B) is
  • R 1 , R 2 , R 3 , R 4 are selected independently from the group consitsitng of hydrogen, alkyl, alkoxy, halo, N0 2 or CN;
  • R 5 is sleeted independently from the group consitsitng of H, CH3, C2H5, Ph or CH3C H ;
  • R 6 is selected independently from the group consitsitng of C0 2 Et, C0 2 Me, C0 Ph, COMe, COPh, CN, S0 2 Ph, CONH 2 or N0 2 ;
  • R 7 is selected independently from the group consitsitng of H, CH3 of Ph; and X represents halo group.
  • the process steps involve tandem reaction sequence where in the first step substitution of bromo with CN and followed by an intramolecular cyano ene reaction to access 1 -Amino-2-naphthalenecarboxylic acid derivatives with quantitative yields.
  • the halo group is preferably bromo.
  • the polar aprotic solvent is selected preferably DMF.
  • 1 -(2-bromo-4,5-dimethoxyphenyl)but-2-ene derivatives are subjected to one-pot CuCN-mediated cyano ene reaction to obtain corresponding 6,7-dimethoxy-1 -aminonaphthalene-3-substituted compounds in good yield.
  • the reaction of the present invention may be carried out at 120 to 160 ° C in DMF for a period of 10 to 20hrs to achieve the product in good yields in the range of 75 to 90%.
  • the products may be isolated using column chromatography and further may be purified by crystallization techniques known in the art.
  • the present invention discloses compound of formula A
  • R 1 , R 2 , R 3 , R 4 are selected independently from hydrogen, alkyl, alkoxy, halo, N0 2 , CN;
  • R 5 is sleeted independently from H, CH 3 , C 2 H 5 , Ph, CH3C6H4;
  • R 6 is selected independently from C0 2 Et, C0 2 Me, C0 2 Ph, COMe, COPh, CN, SOzPh, CONHz, N0 2 and
  • R 7 is selected independently from H, CH 3 , Ph.
  • 1 -Amino-2-naphthalenecarboxylic acid derivatives of formula (A) encompasses Ethyl 1 -aminonaphthalene-2-carboxylate, Ethyl 1 - amino-6-methoxynaphthalene-2-carboxylate, Ethyl 1 -amino-6,7- dimethoxynaphthalene-2-carboxylate, Ethyl 1 -amino-7, 8- dimethoxynaphthalene-2-carboxylate, Ethyl 1 -amino-6-(benzyloxy)-7- methoxynaphthalene-2 -carboxylate, Ethyl 1 -amino-6-methylnaphthalene-2- carboxylate, Ethyl 1 -amino-6-fluoronaphthalene-2-carboxylate, Ethyl 1 -amino- 6-nitronaphthalene-2-carboxylate, Ethyl 5-a
  • R 1 , R 2 , R 3 , R 4 are selected independently from hydrogen, alkyl, alkoxy, halo, N0 2 , CN;
  • R 5 is sleeted independently from H, CH3, C2H 5 , Ph , CH C6H4;
  • R 6 is selected independently from C0 2 Et, C0 2 e, C0 2 Ph, COMe, COPh, CN, S0 2 Ph, CONH 2 , N0 2 ;
  • R 7 is selected independently from H, CH 3 , Ph ;
  • X represents halo group
  • the compound of formula (B) according to the invention is selected from the group consisting of
  • Example 1 is given by way of illustration and therefore should not be construed to limit the scope of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/IN2013/000019 2012-01-10 2013-01-10 Cu-MEDIATED ANNULATION FOR THE PRODUCTION OF 1-AMINO-2-NAPHTHALENECARBOXYLIC ACID DERIVATIVES WO2013105117A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/371,059 US9233911B2 (en) 2012-01-10 2013-01-10 Cu-mediated annulation for the production of 1-amino-2-naphthalenecarboxylic acid derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN83/DEL/2012 2012-01-10
IN83DE2012 IN2012DE00083A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2012-01-10 2013-01-10

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WO (1) WO2013105117A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010059773A1 (en) * 2008-11-20 2010-05-27 Merck Sharp & Dohme Corp. Aryl methyl benzoquinazolinone m1 receptor positive allosteric modulators

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010059773A1 (en) * 2008-11-20 2010-05-27 Merck Sharp & Dohme Corp. Aryl methyl benzoquinazolinone m1 receptor positive allosteric modulators

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BRUNCKO M ET AL: "Naphthamidine urokinase plasminogen activator inhibitors with improved pharmacokinetic properties", BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, PERGAMON, ELSEVIER SCIENCE, GB, vol. 15, no. 1, 3 January 2005 (2005-01-03), pages 93 - 98, XP027800857, ISSN: 0960-894X, [retrieved on 20050103] *
KAZUHIRO KOBAYASHI ET AL.: "Efficient Synthesis of 1-Amino-2-naphthalenecarboxylic Acid Derivatives via a Sequential Michael Addition/Enolate-Nitrile Coupling Route and Its Application to Facile Preparation of 9-Amino Analogues of Arylnaphthofuranone Lignans", J.ORG. CHEM, vol. 62, 1997, pages 664 - 668, XP002696277, DOI: doi:10.1021/jo961744r
KAZUHIRO KOBAYASHI ET AL.: "Efficient Synthesis of 1-Amino-2-naphthalenecarboxylic Acid Derivatives via a Sequential Michael Addition/Enolate-Nitrile Coupling Route and Its Application to Facile Preparation of 9-Amino Analogues of Arylnaphthofuranone Lignans", JOURNAL ORGANIC CHEMISTRY, vol. 62, no. 3, 1997, pages 664 - 668, XP002696277 *

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IN2012DE00083A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2015-05-01
US20150011781A1 (en) 2015-01-08

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