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Short Note

Dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate)

Thimo Huber
1 and
David D. Díaz
Institut für Organische Chemie, Universität Regensburg, Universitätsstr. 31, 93040 Regensburg, Germany
ICMA, CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain
Author to whom correspondence should be addressed.
Molbank 2010, 2010(4), M701;
Submission received: 7 September 2010 / Accepted: 22 October 2010 / Published: 25 October 2010


The synthesis of dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate) (3) by an addition-elimination reaction between isophthalic dihydrazide (1) and dipropargyl dicarbonate (2) is reported. The title compound was characterized by FT-IR, 1H NMR, 13C NMR, EI-MS, elemental analysis and melting point determination.

Graphical Abstract

Substituted hydrazides have found important applications as traceless linkers for solid-phase synthesis [1] or as synthetic intermediates for the synthesis of pesticides [2], steroids [3], and antimycobacterials [4]. Taking advantage of their donor/acceptor hydrogen-bonding ability, hydrazides have been also used in the formation of molecular duplex strands via interstrand hydrogen bonds [5]. On the other hand, terminal alkynes are versatile functional groups in organic synthesis and materials science mainly due to their characteristic metal-catalyzed reactions [6]. In particular, polyvalent alkynes have emerged as valuable cross-linking agents and monomers in the renowned ‘click’ chemistry [7], with special emphasis on materials science [8,9].
Herein, we report the synthesis of dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate) (3) by an addition-elimination reaction between isophthalic dihydrazide (1) and dipropargyl dicarbonate (2) in refluxing acetonitrile (Scheme 1). Symmetrical dipropargyl dicarbonate (2) was prepared from the corresponding propargyl chloroformate [10] following the method reported by Brown and co-workers [11].

Experimental Section


1H and 13C NMR spectra were recorded at 25 °C on a Bruker Avance 300 spectrometer in CDCl3 as solvent, and chemical shifts are reported relative to Me4Si (δ = 0) [10]. The low-resolution mass spectrum was obtained using a Varian MAT 311A spectrometer. Elemental analysis was performed on a Heraeus Mikro-Rapid analyzer. The infrared spectrum was recorded using a Diamond ATR (attenuated total reflection) accessory (Golden Gate) on a Bio-Rad Excalibur FTS 3000 MX spectrophotometer. The melting point (mp) was measured in a Büchi 510 and is uncorrected. Thin-layer chromatography was carried out on Merck aluminium sheets coated with silica gel 60 F254. Compounds were visualized by use of 254 nm UV light and/or iodine as staining reagent. All solvents were of p.a. grade or purified by standard techniques [12]. Anhydrous sodium sulfate was used for drying solutions.
Synthesis of dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate) (3): Dipropargyl dicarbonate (2) (500 mg, 2.75 mmol) in CH3CN (5 mL) was added dropwise to isophthalic dihydrazide (1) (223 mg, 1.15 mmol) in CH3CN (10 mL) at 0 °C using an ice-water bath. The resulting mixture was vigorously stirred at room temperature for 12 h and further refluxed for 15 min. The solvent was evaporated under reduced pressure, and the residue was washed thoroughly with cold CH3CN (3 × 10 mL) and Et2O (3 × 10 mL). Further recrystallization from CH3CN/MeOH afforded compound 3 (276 mg, 67% yield) as an off-white hygroscopic solid: TLC Rf (CH2Cl2/MeOH 4:1) 0.70; m.p. 204–206 °C; 1H NMR (300 MHz, DMSO-d6) δ/ppm = 3.57 (s, 2 H), 4.74 (s, 4 H), 7.65 (t, J = 7.6 Hz, 1 H), 8.04 (dd, J = 8.0 Hz, 1.6 Hz, 2 H), 8.35 (s, 1 H), 9.53 (s, 2 H), 10.53 (s, 2 H); 13C NMR (75 MHz, DMSO-d6) δ/ppm = 52.3, 77.6, 78.8, 126.8, 128.8, 130.4, 132.6, 155.4, 165.4; FT-IR (ATR) νmax (cm−1) 3301, 3238, 3012, 1736, 1656, 1512; MS (ESI) m/z 359 [MH+]. Elemental analysis calculated for C16H14N4O6 • 1/3 H2O: C, 52.75; H, 4,06; N, 15.38; found: C, 52.60; H, 4.00; N, 15.62.

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3Supplementary File 4


D.D.D. thanks the Alexander von Humboldt Foundation for a research fellowship for experienced researchers.

References and Notes

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  10. See Supplementary Files.
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Scheme 1.
Scheme 1.
Molbank 2010 m701 sch001

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Huber, T.; Díaz, D.D. Dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate). Molbank 2010, 2010, M701.

AMA Style

Huber T, Díaz DD. Dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate). Molbank. 2010; 2010(4):M701.

Chicago/Turabian Style

Huber, Thimo, and David D. Díaz. 2010. "Dipropargyl 2,2'-isophthaloylbis(hydrazinecarboxylate)" Molbank 2010, no. 4: M701.

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