메뉴 건너뛰기




Volumn 14, Issue 1, 2010, Pages 180-187

Sonogashira reactions with propyne: Facile synthesis of 4-Hydroxy-2-methylbenzofurans from Iodoresorcinols

Author keywords

[No Author keywords available]

Indexed keywords


EID: 77149164764     PISSN: 10836160     EISSN: 1520586X     Source Type: Journal    
DOI: 10.1021/op900263b     Document Type: Article
Times cited : (29)

References (59)
  • 2
    • 77149153589 scopus 로고    scopus 로고
    • Complications were caused by the need to purge unreacted and polymerized succinate residues
    • Complications were caused by the need to purge unreacted and polymerized succinate residues.
  • 3
    • 77149164002 scopus 로고    scopus 로고
    • McKerrecher, D.; Rayner, J. W. WO Patent 046139 A1, 2004
    • McKerrecher, D.; Rayner, J. W. WO Patent 046139 A1, 2004.
  • 9
    • 23744473269 scopus 로고    scopus 로고
    • For representative Suzuki reactions of allylboronic acids and boronate esters, see
    • For representative Suzuki reactions of allylboronic acids and boronate esters, see: (a) Kotha, S.; Behera, M.; Shah, V. R. Synlett 2005, 1877.
    • (2005) SynLett. , pp. 1877
    • Kotha, S.1    Behera, M.2    Shah, V.R.3
  • 15
    • 0033750821 scopus 로고    scopus 로고
    • (d) Bunz, U. H. F. Chem. Rev. 2000, 100, 1605-1644.
    • (2000) Chem. Rev. , vol.100 , pp. 1605-1644
    • Bunz, U.H.F.1
  • 29
    • 77149139995 scopus 로고    scopus 로고
    • When investigating a Sonogashira approach to 1, our initial concerns centered on the cost and handling of propyne. While somewhat costly on research scale, propyne (which is isolated in pure form by distillation of MAPP gas) is readily available on scale from several suppliers at low cost (less than $150/kg or $6/mol). MAPP gas is composed of propyne, allene, propane, and propene
    • When investigating a Sonogashira approach to 1, our initial concerns centered on the cost and handling of propyne. While somewhat costly on research scale, propyne (which is isolated in pure form by distillation of MAPP gas) is readily available on scale from several suppliers at low cost (less than $150/kg or $6/mol). MAPP gas is composed of propyne, allene, propane, and propene.
  • 30
    • 77149171918 scopus 로고    scopus 로고
    • Hong, Y.; Kania, R. S. U.S. Patent 0137395 A1, 2005. One use of propyne in the synthesis of indoles via a Sonogashira-cyclization reaction has been reportEd.
    • (a) Hong, Y.; Kania, R. S. U.S. Patent 0137395 A1, 2005. One use of propyne in the synthesis of indoles via a Sonogashira-cyclization reaction has been reported:
  • 32
    • 77149171641 scopus 로고    scopus 로고
    • A SciFinder search revealed over 2000 unique 2-methylbenzofuran- containing compounds prepared over the past 30 years and one compound (trioxysalen) in clinical use
    • A SciFinder search revealed over 2000 unique 2-methylbenzofuran- containing compounds prepared over the past 30 years and one compound (trioxysalen) in clinical use.
  • 33
    • 77149179968 scopus 로고    scopus 로고
    • 4) of commercial 4-bromo-3,5-dihydroxybenzoic acid (Sigma- Aldrich). Iodoresorcinols were prepared by iodination of commercial methyl 3,5-dihydroxybenzoic acid with I2. See the experimental section for details
    • 4) of commercial 4-bromo-3,5-dihydroxybenzoic acid (Sigma- Aldrich). Iodoresorcinols were prepared by iodination of commercial methyl 3,5-dihydroxybenzoic acid with I2. See the experimental section for details.
  • 34
    • 77149129159 scopus 로고    scopus 로고
    • 2NEt as base in DME was chosen as a reference starting point for reaction exploration based on literature precedent
    • 2NEt as base in DME was chosen as a reference starting point for reaction exploration based on literature precedent.
  • 41
    • 77149169597 scopus 로고    scopus 로고
    • Primary resorcinol-based impurities are enyne products derived from alkynylation of the intermediate alkynylresorcinol prior to cyclization. These include adduct i and lesser amounts of higher order enynes ii
    • Primary resorcinol-based impurities are enyne products derived from alkynylation of the intermediate alkynylresorcinol prior to cyclization. These include adduct i and lesser amounts of higher order enynes ii.
  • 42
    • 77149171336 scopus 로고    scopus 로고
    • When running on the Endeavor system, 100 g tanks of propyne were attached to the secondary gas port. Each reaction was purged with N2 and then placed under a propyne blanket. No propyne purges were carried out
    • When running on the Endeavor system, 100 g tanks of propyne were attached to the secondary gas port. Each reaction was purged with N2 and then placed under a propyne blanket. No propyne purges were carried out.
  • 43
    • 77149128532 scopus 로고    scopus 로고
    • Temperature-dependent activity coefficient data are frequently obtained from binary VLE measurements. Measurement of VLE data in the laboratory can be time consuming; therefore, computational methods accounting for functional group contributions or molecular interaction potential are used to estimate composition and temperature dependent activities of components in a mixture of interest
    • Temperature-dependent activity coefficient data are frequently obtained from binary VLE measurements. Measurement of VLE data in the laboratory can be time consuming; therefore, computational methods accounting for functional group contributions or molecular interaction potential are used to estimate composition and temperature dependent activities of components in a mixture of interest.
  • 44
    • 77149136934 scopus 로고    scopus 로고
    • COSMOthermX, version C21-0108, software for technical computation; COSMOlogic GmbH & Co. KG: Leverkusen, Germany, 2008
    • COSMOthermX, version C21-0108, software for technical computation; COSMOlogic GmbH & Co. KG: Leverkusen, Germany, 2008.
  • 45
    • 0004119654 scopus 로고    scopus 로고
    • The non-random two-liquid (NRTL) solution model was chosen as a descriptor for mixture activity coefficients. COSMOtherm data was regressed into NRTL binary interaction parameters for each solvent pairing with propyne, which were then transferred into an Aspen Plus databank. Reference for NRTL: Wiley: New York
    • The non-random two-liquid (NRTL) solution model was chosen as a descriptor for mixture activity coefficients. COSMOtherm data was regressed into NRTL binary interaction parameters for each solvent pairing with propyne, which were then transferred into an Aspen Plus databank. Reference for NRTL: Seader, J. D.; Henley, E. J. Separation Process Principles; Wiley: New York, 2006; pp 55-56.
    • (2006) Separation Process Principles , pp. 55-56
    • Seader, J.D.1    Henley, E.J.2
  • 46
    • 77149160799 scopus 로고    scopus 로고
    • Aspen Plus, version 7.1 software for technical computation; Aspen Technology: Burlington, MA, 2008
    • Aspen Plus, version 7.1 software for technical computation; Aspen Technology: Burlington, MA, 2008.
  • 47
    • 77149123815 scopus 로고    scopus 로고
    • Complete descriptions and data on solubility calculations can be found in the supporting information
    • Complete descriptions and data on solubility calculations can be found in the supporting information.
  • 48
    • 77149173630 scopus 로고    scopus 로고
    • The 600 mL Parr reactor used for these experiments has a dip tube for subsurface gas delivery
    • The 600 mL Parr reactor used for these experiments has a dip tube for subsurface gas delivery.
  • 49
    • 77149151080 scopus 로고    scopus 로고
    • The mass flow device installed in our kilo facility pressure reactor is calibrated for hydrogen delivery and provided incorrect information during propyne charging operations
    • The mass flow device installed in our kilo facility pressure reactor is calibrated for hydrogen delivery and provided incorrect information during propyne charging operations.
  • 50
    • 77149145386 scopus 로고    scopus 로고
    • Palladium levels dropped somewhat with silica gel chromatography (3% after aqueous work up to 0.5-1.0% after chromatography)
    • Palladium levels dropped somewhat with silica gel chromatography (3% after aqueous work up to 0.5-1.0% after chromatography).
  • 51
    • 77149165614 scopus 로고    scopus 로고
    • On the basis of our dissolution studies, we anticipated that propyne concentrations could be as high as 13 wt%
    • On the basis of our dissolution studies, we anticipated that propyne concentrations could be as high as 13 wt%.
  • 52
    • 77149166495 scopus 로고    scopus 로고
    • Water and saturated ammonium chloride were introduced in a 1:1 volume ratio. On scale, water was added first followed by the ammonium chloride solution
    • Water and saturated ammonium chloride were introduced in a 1:1 volume ratio. On scale, water was added first followed by the ammonium chloride solution.
  • 53
    • 77149167978 scopus 로고    scopus 로고
    • As a result of the rapid degassing, when running on larger scale, the water and ammonium chloride solution should be added slowly with aN2 purge. Both the degassing and the heat increase related to the dissolution of DMAc in water were roughly dose controllEd.
    • As a result of the rapid degassing, when running on larger scale, the water and ammonium chloride solution should be added slowly with aN2 purge. Both the degassing and the heat increase related to the dissolution of DMAc in water were roughly dose controlled.
  • 54
    • 77149162881 scopus 로고    scopus 로고
    • This solvent system was chosen to maximize extraction of propyne related impurities and to minimize loss of benzofuran 1 from the aqueous phase
    • This solvent system was chosen to maximize extraction of propyne related impurities and to minimize loss of benzofuran 1 from the aqueous phase.
  • 55
    • 77149158334 scopus 로고    scopus 로고
    • If the aqueous solution is stored at or below 20 °C, the product will crystallize and hold on to a large amount of dark nonpolar impurities
    • If the aqueous solution is stored at or below 20 °C, the product will crystallize and hold on to a large amount of dark nonpolar impurities.
  • 57
    • 77149132634 scopus 로고    scopus 로고
    • The procedure was modified to accommodate solvent restrictions in our scaleup facilities and to improve robustness
    • The procedure was modified to accommodate solvent restrictions in our scaleup facilities and to improve robustness.
  • 58
    • 77149159927 scopus 로고    scopus 로고
    • An ∼7 mL disposable glass tube purchased from Biotage for use on the Endeavor system
    • An ∼7 mL disposable glass tube purchased from Biotage for use on the Endeavor system.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.