Electron Deficient Dienes. 4. [1] A Synthetic Equivalent of 4-Methylene­glutaconic Acid, its Mono and Diethyl Esters and their Use in a Concise General Synthesis of Isophthalic Acids and Isophthalates

Abstract

Reaction of a series of 2′-hydroxybenzophenone-3-carboxylic acid ethyl esters under Dakin reaction conditions affords isophthalic acid monoethyl esters, which can be converted into the corresponding diethyl isophthalates (6 examples) and isophthalic acid (1 example) by esterification and hydrolysis, respectively. This transformation renders the direct precursor of the benzophenones a synthetic equivalent of 4-methyleneglutaconic acid (4-methylenepent-2-enedioic acid) and its mono and diethyl esters.

Dakin reaction - Diels-Alder - inverse electron demand - isophthalates - isophthalic acids

References

1 Part 3 in this series: Bodwell GJ. Hawco KM. da Silva RP. Synlett  2002,  179 

See for example:

2a Finelli L. Lotti N. Munari A. J. Appl. Polym. Sci.  2002,  84:  2001 

2b Lodefier P. Jonas AM. Legras R. Macromolecules  1999,  32:  7135 

2c Liu AS. Liau WB. Chiu WY. Macromolecules  1998,  31:  6593 

See for example:

3a Parker D. Feast WJ. Macromolecules  2001,  34:  5792 

3b Parker D. Feast WJ. Macromolecules  2001,  34:  2048 

3c Magnusson H. Malmström E. Hult A. Macromol. Rapid Commun.  1999,  20:  453 

See for example:

4a Yamakawa Y. Ueda M. Takeuchi K. Asai M. Macromolecules  1999,  32:  8363 

4b Leon JW. Kawa M. Fréchet JMJ. J. Am. Chem. Soc.  1996,  118:  8847 

See for example:

5a Moulton B. Lu J. Hajndl R. Hariharan S. Zaworotko MJ. Angew. Chem. Int. Ed.  2002,  41:  2821 

5b Hamilton AD. Choi K. J. Am. Chem. Soc.  2001,  123:  2456 

5c Ohata N. Masuda H. Yamauchi O. Angew. Chem. Int. Ed.  1996,  35:  531 

5d Zafar A. Yang J. Geib SJ. Hamilton AD. Tetrahedron Lett.  1996,  37:  2327 

5e Yang J. Marendaz J.-L. Geib SJ. Hamilton AD. Tetrahedron Lett.  1994,  35:  3665 

5f Valiyaveettil S. Enkelmann V. Müllen K. J. Chem. Soc., Chem. Commun.  1994,  2097 

See for example:

6a Yang SY. Long LS. Huang RB. Zheng LS. Chem. Commun.  2002,  472 

6b Tan XS. Sun J. Xiang DF. Tang WX. Inorg. Chim. Acta  1997,  255:  157 

See for example:

7a Fyles TM. Knoy R. Müllen K. Sieffert M. Langmuir  2001,  17:  6669 

7b Reb P. Margarit-Puri K. Klapper M. Müllen K. Macromolecules  2000,  33:  7718 

7c Pathare PM. Wilbur DS. Hamlin DK. Heusser S. Quadros EV. McLoughlin P. Morgan AC. Bioconjugate Chem.  1997,  8:  161 

See for example:

8a Bodwell GJ. Miller DO. Vermeij RJ. Org. Lett.  2001,  3:  2093 

8b Bodwell GJ. Fleming JJ. Miller DO. Tetrahedron  2001,  57:  3577 

8c Bodwell GJ. Fleming JJ. Mannion MR. Miller DO. J. Org. Chem.  2000,  65:  5360 

8d Bodwell GJ. Bridson JN. Houghton TJ. Kennedy JWJ. Mannion MR. Chem.-Eur. J.  1999,  5:  1823 

8e Bodwell GJ. Bridson JN. Houghton TJ. Kennedy JWJ. Mannion MR. Angew. Chem., Int. Ed. Engl.  1996,  35:  1320 

9 Bodwell GJ. Ernst L. Hopf H. Tetrahedron Lett.  1989,  30:  6005 

10 Bodwell GJ. Frim R. Hopf H. Rabinovitz M. Chem. Ber.  1993,  126:  167 

11 Ahn K.-D. Hall HK. J. Polym. Sci., Polym. Chem.  1981,  19:  629 

12 Bodwell GJ. Pi Z. Tetrahedron Lett.  1997,  38:  309 

13 Bodwell GJ. Pi Z. Pottie IR. Synlett  1999,  477 

14a Varma RS. Naicker KP. Org. Lett.  1999,  1:  189 

14b Lee JB. Uff BC. Quart. Rev.  1967,  21:  429 

14c Hassall CH. Org. React.  1957,  9:  73 

14d Baker W. Bondy HF. Gumb J. Miles D. J. Chem. Soc.  1953,  1615 

14e Dakin HD. Org. Synth., Coll. Vol. 1   Wiley; New York: 1941.  p.149 

14f Baker W. Jukes EHT. Subrahmanyam CA. J. Chem. Soc.  1934,  1681 

14g Dakin HD. Am. Chem. J.  1909,  42:  477 

14h See also: Ogata Y. Sawaki Y. J. Org. Chem.  1969,  34:  3985 

14i Boeseken J. Cohen WD. Kip CJ. Recl. Trav. Chim. Pays-Bas  1936,  55:  815 

15

Bodwell, G. J.; Hawco, K. M. unpublished results.

16

Sample Procedure: 4,6-Indandicarboxylate Diethyl Ester ( 4): [9] [10] To a stirred suspension of NaH (60% dispersion in mineral oil, 35.2 mg, 0.88 mmol) in THF (15 mL) was added dropwise a solution of 11 (219.5 mg, 0.71 mmol) in THF (5 mL) and the resulting yellow solution was stirred for 10 min. To the resulting solution was added H₂O₂ (30% aq solution, 95.3 mg, 0.84 mmol) and the mixture was stirred for 20 h. The reaction mixture was concentrated under reduced pressure, and concentrated aq HCl solution (5 mL) was added. The resulting precipitate was collected by suction filtration and washed with a small amount of H₂O. The solid was dried in vacuo and then suspended in absolute EtOH (25 mL). To this suspension was added concentrated H₂SO₄ (0.5 mL) and the mixture was heated at reflux for 11 h. The solvent was removed under reduced pressure and H₂O (25 mL) was added. The mixture was then extracted with CH₂Cl₂ (3 × 25 mL). The combined organic layers were washed with sat. aq NaHCO₃ solution, and dried over MgSO₄. The solvent was removed under reduced pressure and the residue was subjected to silica gel column chromatography (20% EtOAc/hexane) to afford diester 4 (144.2 mg, 78%) as pale yellow crystals: Mp 43-45 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.49 (s, 1 H), 8.04 (s, 1 H), 4.390 (q, J = 7.2 Hz, 2 H), 4.384 (q, J = 7.1 Hz, 2 H), 3.32 (t, J = 7.4 Hz, 2 H), 2.97 (t, J = 7.4 Hz, 2 H), 2.13 (quint, J = 7.4 Hz, 4 H), 1.411 (t, J = 7.2 Hz, 3 H), 1.407 (t, J = 7.5 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.7, 166.5, 152.1, 146.6, 129.9, 129.1, 127.1, 61.3, 61.1, 34.3, 32.5, 25.2, 2 × 14.6. IR(nujol): ν = 1724 (s), 1299 (m), 1227 (s)cm^-1. UV/Vis (CH₂Cl₂): λ_max (log ε) = 302 (3.38) nm; MS (EI. 70 eV): m/z (%) = 262 (69) [M⁺], 233 (100), 117 (99). HRMS (EI): m/z calcd for C₁₅H₁₈O₄ [M⁺]: 262.1205. Found: 262.1223. All other products were characterized as above.

17 Brown JB. Henbest HB. Jones ERH. J. Chem. Soc.  1950,  3634