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Short Note

tert-Butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate

1
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospekt, Moscow 119991, Russia
2
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350, China
3
State Key Laboratory of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center (RECAST), Nankai University, Tianjin 300071, China
*
Author to whom correspondence should be addressed.
Molbank 2023, 2023(2), M1614; https://doi.org/10.3390/M1614
Submission received: 9 March 2023 / Revised: 27 March 2023 / Accepted: 28 March 2023 / Published: 30 March 2023
(This article belongs to the Collection Heterocycle Reactions)

Abstract

:
Non-fullerene acceptors have recently attracted much attention as components of organic solar cells. 1H-indene-1,3(2H)-dione is a key compound for the synthesis of the end-capping component of non-fullerene acceptors. In this communication, an intermediate for the synthesis of this compound, tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate, was prepared by the reaction between phthalic anhydride and tert-butyl acetoacetate. Further treatment with sodium methoxide in methanol led to the formation of 1H-indene-1,3(2H)-dione in a high yield. The structure of the newly synthesized compound was established by means of elemental analysis, high-resolution mass spectrometry, 1H, 13C NMR, IR spectroscopy, mass spectrometry and X-ray analysis.

Graphical Abstract

1. Introduction

Organic solar cells (OSCs) have made significant progress over the past decades due to the urgent need to replace exhaustible energy sources with renewable and clean solar energy. Among them, bulk heterojunction solar cells are of particular interest because of their remarkable flexibility, semi-transparency, and high potential for large-scale production and achieved power-conversion efficiency of more than 17% [1,2]. One of the key parts of organic solar cells are acceptors, including the rapidly developing non-fullerene ones (NFAs) [3,4,5]. The most frequently studied NFA structure is the A-D-A, where 1H-indene-1,3(2H)-dione derivatives play the role of end-capping acceptors with activated methylene group [6,7,8]. However, despite its simplicity, the synthesis of 1H-indene-1,3(2H)-dione acceptors often proceeds with low yields (20–30%) [9,10,11,12], and the procedure for preparing these compounds needs to be improved. Typically, this protocol involves the reaction of phthalic anhydride and its derivatives with a compound containing an activated CH2 group in acetic anhydride and triethylamine. The mechanism of this multi-step transformation has not been studied in detail, but it seems to involve Knoevenagel condensation, elimination of the acetyl and ester groups to form isobenzofuranone, and rearrangement to indanedione (Scheme 1). The most commonly used CH2 component is tert-butyl acetoacetate [9,11,12,13,14,15].
Herein, we report the synthesis of tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1 and its conversion to 1H-indene-1,3(2H)-dione.

2. Results and Discussion

tert-Butyl-(E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1 was obtained using a simple and convenient procedure, which included the reaction of phthalic anhydride and tert-butyl acetoacetate in acetic anhydride in the presence of triethylamine at room temperature for 20 h (Scheme 2). The reaction proceeded with high yield (83%) and regioselectivity. It is interesting to note that in the reaction between phthalic anhydride and silylenol ether, obtained from tert-butyl acetoacetate, product 1 was not isolated [16]. To confirm the possibility of using product 1 as an intermediate in the synthesis of 1H-indene-1,3(2H)-dione, it was shown that the reaction of ester 1 with sodium methoxide in methanol at room temperature for 20 h, followed by treatment with hydrochloric acid, produced 1H-indene-1,3(2H)-dione in a high yield (80%).
The structure of tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1 was confirmed by means of elemental analysis, high-resolution mass spectrometry, 1H, 13C NMR, IR spectroscopy as well as mass spectrometry. The configuration of the double bond of ether 1 was established on the basis of NOESY experiments (Figure 1). The singlet corresponding to the hydrogen atoms of tert-butyl (1.18 ppm) correlates with aromatic protons (8.26 ppm), while the methyl singlet (3.14 ppm) does not correlate with aromatic protons of the system, which proves the existence of a single isomer 1 of the proposed compound. The structure of compound 1 was also unambiguously confirmed using an X-ray diffraction analysis (Figure 2). X-ray diffraction analysis in combination with NOESY NMR spectra showed the presence of only one E-regiomer in the structure, in which the bulky tert-butyloxycarbonyl group is closer to the aromatic ring.
In conclusion, it was shown that the reaction of phthalic anhydride with tert-butyl acetoacetate is regioselective and led to tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1, which is an intermediate in the synthesis of 1H-indene-1,3(2H)-dione from phthalic anhydride.

3. Materials and Methods

The solvents and reagents were purchased from commercial sources and used as received. Elemental analysis was performed on a 2400 Elemental Analyzer (Perkin ElmerInc., Waltham, MA, USA). 1H and 13C NMR spectra were taken with a Bruker AM-300 machine (Bruker AXS Handheld Inc., Kennewick, WA, USA) (at frequencies of 300 and 75 MHz) in CDCl3 solution, with TMS as the standard. J values are given in Hz. MS spectrum (EI, 70 eV) was obtained with a Finnigan MAT INCOS 50 instrument (Hazlet, NJ, USA). High-resolution MS spectrum was measured on a Bruker micrOTOF II instrument (Bruker Daltonik Gmbh, Bremen, Germany) using electrospray ionization (ESI). IR spectrum was measured with a Bruker “Alpha-T” instrument in KBr pellet.
X-ray diffraction data were collected at 100 K on a four-circle Rigaku Synergy S diffractometer equipped with a HyPix600HE area-detector (kappa geometry, shutterless ω-scan technique), using graphite monochromatized Cu Kα-radiation. The intensity data were integrated and corrected for absorption and decay using the CrysAlisPro program [17]. The structure was solved with direct methods using SHELXT [18] and refined on F2 using SHELXL-2018 [19] in the OLEX2 program [20]. All non-hydrogen atoms were refined with individual anisotropic displacement parameters. All hydrogen atoms were placed in ideally calculated positions and refined as riding atoms with relative isotropic displacement parameters. The Mercury program suite [21] was used for molecular graphics. Cambridge Crystallographic Data Centre contains the supplementary crystallographic data for this paper No. CCDC 2247414. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (accessed on 7 March 2023) (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44-1223-336033; e-mail: [email protected]).
Synthesis of tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1 (Supplementary Materials).
Triethylamine (0.7 mL, 4.7 mmol) was added dropwise with vigorous stirring to a solution of phthalic anhydride (200 mg, 1.35 mmol) and tert-butyl acetoacetate (490 mg, 2 mmol) in acetic anhydride (1.3 mL, 13.7 mmol). The mixture was stirred overnight at room temperature, poured into cold water (5 mL) and the crude product was collected using filtration and washed with water. Yield 324 mg (83%), white solid, mp 150–152 °C. Rf = 0.8 (CH2Cl2). 1H NMR (300 MHz, CDCl3): 8.26 (d, J = 6.3, 1H), 8.02 (d, J = 5.1, 1H), 7.81 (td, J = 5.7, J = 0.9, 1H), 7.74 (td, J = 5.4, J = 0.6, 1H), 2.64 (s, 3H), 1.62 (s, 9H). 13C NMR (75 MHz, CDCl3): 195.6, 164.4, 163.4, 152.0, 136.7, 135.3, 132.7, 126.0, 125.9, 125.4, 117.8, 83.7, 31.8, 28.0 (3 CH3). MS (EI, 70 eV), m/z (I, %): 288 (7), 232 (8), 217 (20), 190 (15), 173 (100), 57 (33), 43 (36). HRMS-ESI (m/z): calcd. for (C16H17O5) 289.1071, found m/z 289.1074. IR, ν, cm−1: 3433, 3092, 2986, 1814, 1726, 1640, 1472, 1372, 1254, 1160, 1056, 997, 837, 691. Anal. calcd. For C16H16O5 (288.2952): C, 66.66; H, 5.59. Found: C, 66.84; H, 5.72%.
Synthesis of 1H-indene-1,3(2H)-dione from tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1 (Supplementary Materials).
A 5.4 M solution of sodium methoxide in MeOH (0.04 mL, 1.1 mmol) was added to a solution of tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1 (200 mg, 0.7 mmol) in dry methanol (7 mL), and the mixture was stirred overnight at room temperature. The solvent was evaporated under reduced pressure and the residue was treated with a mixture of hydrochloric acid (3 mL) and ice-water (4 mL). The resulting mixture was refluxed for 1 h, cooled to room temperature, diluted with water (3 mL) and extracted with CH2Cl2 (3 × 10 mL). The combined organic extracts were dried over MgSO4 and evaporated under reduced pressure. The residue was purified using column chromatography on silica gel (Silica gel Merck 60, eluent dichloromethane). Yield 82 mg (80%), pale yellow solid, mp 128–131 °C (lit. mp 130–132 °C [22]). Rf = 0.5 (dichloromethane). The data on the 1H and 13C NMR spectra correspond to data in the literature [23].
Crystallographic data of the compound 1 are given in Table 1.

Supplementary Materials

The following are available online: copies of 1H, 13C NMR, IR, LR and HR mass-spectra for the compound 1.

Author Contributions

Conceptualization, E.A.K.; methodology, O.A.R. and B.K.; software, E.A.K.; validation, O.A.R. and T.D.; formal analysis, investigation, A.S.C. and T.D.; resources, O.A.R.; data curation, E.A.K.; writing—original draft preparation, O.A.R.; writing—review and editing, B.K. and T.D.; visualization, O.A.R.; supervision, O.A.R.; project administration, O.A.R.; funding acquisition, O.A.R. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Not applicable.

Acknowledgments

Crystal structure determination was performed in the Department of Structural Studies of N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences.

Conflicts of Interest

The authors declare no conflict of interest.

Sample Availability

Samples of the compound 1 are available from the authors.

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Scheme 1. The mechanism of the formation of 1H-indene-1,3(2H)-dione via tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate.
Scheme 1. The mechanism of the formation of 1H-indene-1,3(2H)-dione via tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate.
Molbank 2023 m1614 sch001
Scheme 2. Synthesis of 1H-indene-1,3(2H)-dione via tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1.
Scheme 2. Synthesis of 1H-indene-1,3(2H)-dione via tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1.
Molbank 2023 m1614 sch002
Figure 1. A key NOE interatomic interaction in tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1.
Figure 1. A key NOE interatomic interaction in tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1.
Molbank 2023 m1614 g001
Figure 2. X-Ray structure (ORTEP at 50% level) of tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1.
Figure 2. X-Ray structure (ORTEP at 50% level) of tert-butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate 1.
Molbank 2023 m1614 g002
Table 1. Crystal data and structure refinement for compound 1.
Table 1. Crystal data and structure refinement for compound 1.
Empirical FormulaC16H16O5
Formula weight288.29
Temperature99.9(2) K
Wavelength1.54184 Å
Crystal systemMonoclinic
Space groupP 21/c
Unit cell dimensionsa = 6.68587(5) Å a = 90°
b = 10.54420(10) Å b = 94.2747(7)°
c = 20.48957(18) Å g = 90°
Volume1440.44(2) Å3
Z4
Density (calculated)1.329 g/cm3
Absorption coefficient0.824 mm−1
F(000)608
Crystal size0.4 × 0.16 × 0.03 mm3
Theta range for data collection4.328 to 77.931°.
Index ranges−7 <= h <= 8, −13 <= k <= 13, −25 <= l <= 25
Reflections collected16,388
Independent reflections3062 [R(int) = 0.0234]
Observed reflections2878
Completeness to theta = 67.684°100.0%
Absorption correctionGaussian
Max. and min. transmission1.000 and 0.434
Refinement methodFull-matrix least-squares on F2
Data/restraints/parameters3062/0/194
Goodness-of-fit on F21.055
Final R indices [I > 2sigma(I)]R1 = 0.0338, wR2 = 0.0874
R indices (all data)R1 = 0.0356, wR2 = 0.0890
Largest diff. peak and hole0.194 and −0.230 e.Å−3
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MDPI and ACS Style

Chechulina, A.S.; Knyazeva, E.A.; Kan, B.; Duan, T.; Rakitin, O.A. tert-Butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate. Molbank 2023, 2023, M1614. https://doi.org/10.3390/M1614

AMA Style

Chechulina AS, Knyazeva EA, Kan B, Duan T, Rakitin OA. tert-Butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate. Molbank. 2023; 2023(2):M1614. https://doi.org/10.3390/M1614

Chicago/Turabian Style

Chechulina, Alexandra S., Ekaterina A. Knyazeva, Bin Kan, Tainan Duan, and Oleg A. Rakitin. 2023. "tert-Butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate" Molbank 2023, no. 2: M1614. https://doi.org/10.3390/M1614

APA Style

Chechulina, A. S., Knyazeva, E. A., Kan, B., Duan, T., & Rakitin, O. A. (2023). tert-Butyl (E)-3-oxo-2-(3-oxoisobenzofuran-1(3H)-ylidene)butanoate. Molbank, 2023(2), M1614. https://doi.org/10.3390/M1614

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