Synthesis of Diazonaphthoquinones from Naphthols by Diazo-Transfer Reaction with 2-Azido-1,3-dimethylimidazolinium Chloride

Abstract

An efficient synthetic method for the synthesis of diazo­naphthoquinones from naphthols is described. A variety of diazo­naphthoquinones were synthesized from the corresponding naphthols by the diazo transfer with 2-azido-1,3-dimethylimidazolinium chloride prepared by the reaction of 2-chloro-1,3-dimethylimidazorinium chloride and sodium azide.

azides - diazo compounds - diazonaphthoquinone - diazo transfer - quinone diazide

References and Notes

For a review, see:

1a Ershov VV. Nikiforov GA. de Jonge CRHI. Quinone Diazides   Elsevier; Amsterdam: 1981. 

1b Zollinger H. Diazo Chemistry   VCH; Weinheim: 1994. 

2a Ried W. Appel H. Justus Liebigs Ann. Chem.   1961,  646:  82 

2b Figueiredo LJO. Kascheres C. J. Org. Chem.  1997,  62:  1164 

3 Colas C. Goeldner M. Eur. J. Org. Chem.  1999,  1357 

4a Yagihara M. Kitahara Y. Asao T. Chem. Lett.  1974,  1015 

4b Hacker NP. Turro NJ. Tetrahedron Lett.  1982,  23:  1771 

4c Bucher G. Sander W. J. Org. Chem.  1992,  57:  1346 

4d Almstead J.-IK. Urwyler B. Wirz J. J. Am. Chem. Soc.  1994,  116:  954 

4e Qiao GG. Andraos J. Wentrup C. J. Am. Chem. Soc.  1996,  118:  5634 

4f de Lucas NC. Netto-Ferreira JC. Andraos J. Lusztyk J. Wagner BD. Scaiano JC. Tetrahedron Lett.  1997,  38:  5147 

4g Murata S. Kobayashi J. Kongou C. Miyata M. Matsushita T. Tomioka H. J. Org. Chem.  2000,  65:  6082 

4h Kirmse W. Eur. J. Org. Chem.  2002,  2193 

4i Urdabayev NK. Popik VV. J. Am. Chem. Soc.  2004,  126:  4058 

For reviews, see:

5a Reiser A. Shih H.-Y. Yeh T.-F. Huang J.-P. Angew. Chem., Int. Ed. Engl.  1996,  35:  2428 

5b Reiser A. Huang JP. He X. Yeh TF. Jha S. Shih HY. Kim MS. Han YK. Yan K. Eur. Polym. J.  2002,  38:  619 

5c Fukukawa K.-i. Ueda M. Polym. J.  2008,  40:  281 

6a Anderson LC. Roedel MJ. J. Am. Chem. Soc.  1945,  67:  955 

6b Anderson JDC. Le Fevra RJW. Wilson IR. J. Chem. Soc.  1949,  2082 

6c Tedder JM. Webster B. J. Chem. Soc.  1960,  4417 

6d Sander W. Bucher G. Wandel H. Kraka E. Cremer D. Sheldrick WS. J. Am. Chem. Soc.  1997,  119:  10660 

7a Cava MP. Litle RL. Napier DR. J. Am. Chem. Soc.  1958,  80:  2257 

7b Ried W. Dietrich R. Chem. Ber.  1961,  94:  387 

7c Trost BM. Kinson PL. J. Am. Chem. Soc.  1975,  97:  2438 

7d Hacker NP. Turro NJ. Tetrahedron Lett.  1982,  23:  1771 

7e Hacker NP. Kasai PH. J. Am. Chem. Soc.  1993,  115:  5410 

7f Brown PJN. Cadogan JIG. Gosney I. Johnstone A. Paton RM. Wilson NH. J. Chem. Soc., Perkin Trans. 2  1996,  2303 

7g Ferreira VF. Jorqueira A. Leal KZ. Pimentel HRX. Seidl PR. da Silva MN. da Souza MCBV. Pinto AV. Wardell JL. Wardell SMSV. Magn. Reson. Chem.  2006,  44:  481 

For reviews, see:

8a Regitz M. Angew. Chem., Int. Ed. Engl.  1967,  6:  733 

8b Regitz M. Synthesis  1972,  351 

8c Doyle MP. Chem. Rev.  1986,  86:  919 

8d Padwa A. Austin DJ. Angew. Chem., Int. Ed. Engl.  1994,  33:  1797 

8e Ye T. McKervey MA. Chem. Rev.  1994,  94:  1091 

8f Doyle MP. Ye T. McKervey MA. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds   John Wiley and Sons; New York: 1998. 

8g Zhang Z. Wang J. Tetrahedron  2008,  64:  6577 

9 Balli H. Müller V. Sezen-Gezgin A. Helv. Chim. Acta  1978,  61:  104 

10 Kitamura M. Tashiro N. Okauchi T. Synlett  2009,  2943 

Selected synthesis of 1-diazo-2(1H)naphthalenone (3) and 2-diazo-1(2H)naphthalenone (5), see ref. 6, 7, and 9, and also see:

11a Bamberger E. Ber. Dtsch. Chem. Ges.  1894,  27:  679 

11b Süs O. Glos M. Möller K. Eberhardt H.-D. Justus Liebigs Ann. Chem.  1953,  583:  150 

12

Typical Procedure for the Preparation of 1-Diazo-2(1 H )naphthalenone (3)
[Caution: Although we have never had any trouble with azidoimidazolinium salt 4, it is potentially explosive.]
To a solution of 2-chloro-1,3-dimethylimidazolinium chloride (228 mg, 1.35 mmol) in MeCN (2 mL), NaN₃ (99.4 mg, 1.5 mmol), and 15-crown-5 ether (0.06 mL, 0.3 mmol) was added at -20 ˚C, and the mixture was stirred for 30 min. 2-Naphthol (130 mg, 0.90 mmol) and Et₃N (0.25 mL, 1.8 mmol) in THF (4 mL) was added to the mixture, which was stirred for 20 min. The reaction was quenched with H₂O, and organic materials were extracted three times with CH₂Cl₂. The combined extracts were washed with H₂O and brine, and then, dried over anhyd Na₂SO₄. The solvent was removed in vacuo to afford crude compounds. The crude materials were purified by flash column chromatography (silica gel: hexane-EtOAc = 4:1) to give diazonaphthoquinone 3 in 86% yield.

13

Spectral Data for 3
IR (ATR): 2333, 2221, 2084, 1616, 1558, 1479, 1452, 1394, 1346, 1304, 1251, 1203, 819, 613 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.62 (d, 1 H, J = 9.8 Hz) 7.57 (dd, 1 H, J = 7.8, 1.2 Hz) 7.51 (ddd, 1 H, J = 7.8, 7.8, 1.2 Hz), 7.28 (br d, 1 H, J = 7.8 Hz), 7.27 (ddd, J = 7.8, 7.8, 1.2 Hz), 6.65 (d, 1 H, J = 9.8 Hz). ^¹³C NMR (100 MHz, CDCl₃): δ = 180.2, 140.2, 130.0, 129.7, 127.1, 125.9, 125.6, 124.7, 119.6, 77.2. Anal. Calcd (%) for C₁₀H₆N₂O: C, 70.58; H, 3.55; N, 16.46. Found: C, 70.76; H, 3.70; N, 16.39. Mp 74-75 ˚C (dec.).

14

Spectral Data for 5
IR (ATR): 2917, 2850, 2348, 2113, 1689, 1619, 1562 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 8.33 (d, 1 H, J = 8.0 Hz) 7.59 (ddd, 1 H, J = 8.0, 7.2, 1.4 Hz), 7.49 (d, 1 H, J = 7.2 Hz), 7.47 (ddd, 1 H, J = 8.0, 7.2, 1.4 Hz), 6.89 (d, 1 H, J = 9.3 Hz), 6.58 (d, 1 H, J = 9.3 Hz). ^¹³C NMR (100 MHz, CDCl₃): δ = 180.2, 137.47, 132.6, 129.5, 128.2, 127.2, 125.3, 117.3, 116.2, 74.2. Anal. Calcd (%) for C₁₀H₆N₂O: C, 70.58; H, 3.55; N, 16.46. Found: C, 70.20; H, 3.68; N, 16.74. Mp 73.5-74 ˚C (dec.).