Synthesis of 2-Alkylidenethiazolidine-4,5-diones and 2-Alkylideneoxazolidine-4,5-diones by One-Pot Cyclization of Arylacetonitriles with Heterocumulenes and Ethyl 2-Chloro-2-oxoacetate

Abstract

2-Alkylidenethiazolidine-4,5-diones and 2-alkylidene­oxazolidine-4,5-diones have been prepared by one-pot cyclization of arylacetonitriles with heterocumulenes and ethyl 2-chloro-2-oxoacetate.

one-pot cyclization - arylacetonitriles - heterocumulenes

References

<A NAME="RD08604ST-1A">1a</A> Sheehan JC. Corey EJ. J. Am. Chem. Soc.  1951,  73:  4756 

<A NAME="RD08604ST-1B">1b</A> Shiozaki N. Ishida N. Iino K. Hiraoka T. Tetrahedron Lett.  1977,  4059 

<A NAME="RD08604ST-1C">1c</A> Shiozaki N. Ishida N. Iino K. Hiraoka T. Tetrahedron  1980,  36:  2735 

<A NAME="RD08604ST-2">2</A> Goerdeler J. Schenk H. Chem. Ber.  1965,  98:  2954 

<A NAME="RD08604ST-3A">3a</A> Stolle R. Luther M. Chem. Ber.  1920,  53:  314 

<A NAME="RD08604ST-3B">3b</A> Speziale AJ. Smith LR. J. Org. Chem.  1963,  28:  1805 

<A NAME="RD08604ST-4A">4a</A> Zankowska-Jasinska W. Eilmes J. Rocz. Chem.  1973,  47:  2235 

<A NAME="RD08604ST-4B">4b</A> Barnikow G. Saeling G. J. Prakt. Chem.  1974,  316 (4):  534 

<A NAME="RD08604ST-4C">4c</A> See also: Zaleska B. Pol. J. Chem.  1988,  62:  767 

<A NAME="RD08604ST-4D">4d</A> Zaleska B. Monatsh. Chem.  1986,  117:  671 

<A NAME="RD08604ST-5">5</A> Richter R. Temme G. J. Org. Chem.  1981,  46:  3015 

<A NAME="RD08604ST-6">6</A> Bergman J. Stalhandske C. Tetrahedron  1996,  52 (3):  753 

<A NAME="RD08604ST-7">7</A> Satzinger G. Liebigs Ann. Chem.  1978,  473 

<A NAME="RD08604ST-8">8</A> For one-pot reactions of N-nucleophiles and isocyanates, see: Khattak I. Ketcham R. Schaumann E. Adiwidjaja G. J. Org. Chem.  1985,  50:  3431 

For one-pot reactions of arylmethylnitriles with isothiocyanates and 1,2-dibromoethane and chloroacetic chloride, see:

<A NAME="RD08604ST-9A">9a</A> Bukowski L. Pharmazie  2001,  56:  23 

<A NAME="RD08604ST-9B">9b</A> Rudorf W.-D. Tetrahedron  1978,  34:  725 

<A NAME="RD08604ST-10A">10a</A> Böhme H. Stammberger W. Liebigs Ann. Chem.  1971,  56 

<A NAME="RD08604ST-10B">10b</A> Kondo K. Tunemoto D. Tetrahedron Lett.  1975,  17:  1397 

<A NAME="RD08604ST-10C">10c</A> Tanaka K. Matsui S. Kaji A. Bull. Chem. Soc. Jpn.  1980,  53:  3619 

<A NAME="RD08604ST-10D">10d</A> Eisch JJ. Dua SK. Behrooz M. J. Org. Chem.  1985,  50:  3676 

<A NAME="RD08604ST-10E">10e</A> Hendrickson JJ. Boudreaux GJ. Palumbo PS. J. Am. Chem. Soc.  1986,  108:  2358 

<A NAME="RD08604ST-10F">10f</A> McCrombie SW. Shankar BB. Ganguly AK. Padwa A. Bullock WH. Dyszlewski AD. Tetrahedron Lett.  1987,  28:  4127 

<A NAME="RD08604ST-10G">10g</A> Thomson MW. Handwerker BM. Katz SA. Belser RB. J. Org. Chem.  1988,  53:  906 

<A NAME="RD08604ST-11">11</A> Dilithiated benzylcyanides exist as base-associated monoanions. For a review of the structure of lithiated and dilithiated nitriles and sulfones, see: Boche G. Angew. Chem., Int. Ed. Engl.  1989,  28:  277 ; Angew. Chem. 1989, 101, 286

<A NAME="RD08604ST-12">12</A>

Typical Experimental Procedure: To a THF solution (10 mL) of 1a (0.234 g, 2.0 mmol) was added n-butyllithium (0.24 mL, 4.4 mmol, 1.6 M) at 0 °C. After stirring for 1 h, 2a (0.270 g, 2.0 mmol) was added and the solution was stirred for 1 h at 0 °C. Subsequently, 3a (0.241 g, 2.0 mmol) was added. After warming of the solution to 20 °C during 16 h, an aqueous solution of HCl (30 mL, 1 M) was added. The organic and the aqueous layer were separated and the latter was extracted with EtOAc (3 ¥ 30 mL). The combined organic layers were extracted with brine (30 mL), dried (Na₂SO₄), filtered and the solvent of the filtrate was removed in vacuo. The residue was purified by column chromatography (silica gel, n-hexane-EtOAc = 5:1) to give 4a as a yellow solid (0.358 g, 58 %). Spectroscopic data of 4a: ¹H NMR (300 MHz, CDCl₃): δ = 7.37-7.41 (m, 3 H, Ph), 7.43-7.51 (m, 4 H, Ph), 7.63-7.69 (m, 3 H, Ph). ¹³C NMR (75 MHz, CDCl₃): δ = 94.42, 113.50 (C), 126.65, 128.37, 129.37, 129.88, 130.10, 131.36 (CH), 140.43, 143.23, 156.40, 178.50 (C). IR (KBr): ν = 2193 (w), 1739 (s), 1591 (s), 1492 (s), 1444 (w) cm^-1. MS (EI, 70eV): m/z (%) = 306 (27) [M⁺], 218 (33), 159 (100), 114 (16), 88 (9). Anal. Calcd for C₁₇H₁₀N₂O₂S: C, 66.65; H, 3.29; N, 9.14. Found: C, 66.85; H, 3.02; N, 8.97.