Synthesis and X-ray Characterization of Alkali Metal 2-Acyl-1,1,3,3-tetracyanopropenides

Article abstract of DOI:10.1021/acs.joc.6b01040

A novel route for synthesis of 2-acyl-1,1,3,3-tetracyanopropenides (ATCN) salts in high yields and excellent purities starting from readily available methyl ketones, malononitrile, bromine, and alkali metal acetates is reported. The starting aryl(heteroaryl) methyl ketones were oxidized to the corresponding α-ketoaldehydes by new a DMSO-NaBr-H₂SO₄ oxidation system in yields up to 90% within a short reaction time of 8-10 min. The subsequent stages of ATCN preparation are realized in aqueous media without use of any toxic solvents, in accordance with principle 5 of "green chemistry". Lithium, sodium, potassium, rubidium, and cesium 2-benzoyl-1,1,3,3-tetracyanopropenides were characterized by X-ray diffraction analysis. These salts show a good potential for synthesis of five- and six-membered heterocycles and may serve as potentially useful ligands in coordination and supramolecular chemistry.

Full text of DOI:10.1021/acs.joc.6b01040

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Article
Synthesis and X-ray characterization of alkali
metals 2-acyl-1,1,3,3-tetracyanopropenides
Sergey Vladimirovich Karpov, Arthur Alexandrovich Grigor\'ev, Yakov Sergeevich
Kayukov, Irina Valer\'evna Karpova, Oleg Evgen\'evich Nasakin, and Victor A. Tafeenko
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01040 • Publication Date (Web): 06 Jul 2016
Downloaded from http://pubs.acs.org on July 7, 2016
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The Journal of Organic Chemistry
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Synthesis and X-ray characterization of alkali metals 2-acyl-1,1,3,3-
tetracyanopropenides
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Sergey V. Karpov*†, Arthur A. Grigor'ev†, Yakov S. Kayukov†, Irina V. Karpova†, Oleg E. Nasakin†,
Victor A. Tafeenko‡
†I.N. Ul’yanov Chuvash state University, Moskovskii pr. 15, Cheboksary, 428015, Russia
‡Lomonosov Moscow State University, Leninskiye Gory 1ꢀ3, Moscow, 119991, Russia
ABSTRACT: A novel route for synthesis of 2ꢀacylꢀ1,1,3,3ꢀtetracyanopropenides (ATCN) salts in high yields and excellent purities
starting from readily available methylketones, malononitrile, bromine and alkali metals acetates is reported. The starting arꢀ
yl(heteroaryl)methylketones were oxidized to corresponding αꢀketoaldehydes by new DMSOꢀNaBrꢀH2SO4 oxidation system in
yields up to 90% within a short reaction time of 8ꢀ10 min. The subsequent stages of ATCN preparation are realized in aqueous meꢀ
dia without use of any toxic solvents in accordance with principle 5 of "green chemistry". Lithium, sodium, potassium, rubidium
and caesium 2ꢀbenzoylꢀ1,1,3,3ꢀtetracyanopropenides were characterized by Xꢀray diffraction analysis. These salts show a good
potential for synthesis of fiveꢀ and sixꢀmembered heterocycles and may serve as potentially useful ligands in coordination and suꢀ
pramolecular chemistry.
INTRODUCTION
Currently, a salts containing tetracyanoallyl (TCA) anion (Figure 1) have received considerable attention. This is due to the TCA
anions have a variable denticity and might be used as bridging ligands for construction of various 1D, 2D and 3D coordination polꢀ
ymeric frameworks.1
NC
NC
CN
CN
O-
CN
NC
CN
NC
CN
CN CN
TCNO2-
CN CN
PCNP-
CN CN
TCPD2-
O(CH2)nOH
CN
O(CH2)nCH3
CN
NC
NC
CN CN
CN CN
TCNOMe- (n = 0),
TCNOEt- (n = 1), etc
TCNOMeOH- (n = 1),
TCNOEtOH- (n = 2), etc
Figure 1. TCA ligands family portrait
TCA salts can be applied for creating materials with potentially useful properties, such as magnetic,2 thermoꢀ and photochromic,3
semiconducting4 and photomagnetic.5 The spinꢀcrossover (SCO) materials based on TCA ligands are also described.6 Moreover,
these salts have received interest as components of new propellants,7 ionic liquids8 and burningꢀrate catalysts.9
We previously described a some chemical properties of new 2ꢀacylꢀ1,1,3,3ꢀtetracyanopropenides (ATCN) salts 1 containing a
carbonyl group in position 2 of TCA anion.10 The carbonyl oxygen can form an additional coordination bonds with cation. Moreoꢀ
ver, ATCN are prospective precursors for synthesis of fiveꢀ and sixꢀmembered heterocycles (Figure 2). Consequently, these comꢀ
pounds might be of interest as new building blocks in design of coordination polymers and as precursors for heterocyclic synthesis.
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Figure 2. A described routes for heterocyclization of ATCNꢀ
Scheme 1. The first synthesis of ATCN12
The ATCN salts were first obtained by Bardasov et al. via a threeꢀstep synthesis using acetophenones, selenium dioxide,
malonodinitrile and brommalonodinitrile as starting compounds12 (Scheme 1). At the first stage, glyoxal hydrates 3 were obtained
by a well known method13 via oxidation of acetophenones 2 with selenium dioxide in 42ꢀ69% yields. At the second stage, the reꢀ
sulting glyoxal hydrates were reacted with mixture of equal amounts of malonodinitrile and brommalonodinitrile with formation of
the corresponding cyclopropanes 4 via Adduction and Ring Closure (ARC) process.
At the final stage of the ATCN salts synthesis, cyclopropanes 4 were being reacted with equal amount of sodium acetate in aceꢀ
tonitrile followed by solvent removing by rotary evaporation. The total yield of ATCN (based on starting acetophenones) does not
exceed 44%. In addition, this method of ATCN preparation has a number of significant disadvantages such as: a necessity of long
refluxing and the formation of fine particulate selenium which have polluted the product at oxidation stage; a necessity a prelimiꢀ
nary synthesis of unstable irritant brommalonodinitrile at stage 2 as well as a necessity of toxic acetonitrile using as solvent at final
stage.
Herein, we report a novel process version for ATCN salts preparation based on the oxidation of aryl(heteroaryl)methylketones to
aryl(heteroaryl)glyoxals by new DMSO ꢀ NaBr ꢀ H2SO4 system and subsequent ARC reaction with malonodinitrile and bromine in
water. At the final stage, the corresponding cyclopropylketones 4 were being undergo ring opening reaction under the action of
potassium acetate in ethanol. The resulting potassium ACTN salts were precipitated by saturated aqueous KCl.
The application of this method allowed us to increase ATCN salts total yields up to 80% and decrease total synthesis time to less
than 3 hours. Also, this method is not required toxic and expensive reagents, such as selenium dioxide and acetonitrile in
accordance with principle 5 of "green chemistry". In addition, lithium, sodium, potassium, rubidium and caesium 2ꢀbenzoylꢀ
1,1,3,3ꢀtetracyanopropenides were characterized by Xꢀray diffraction analysis.
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RESULTS AND DISCUSSION
Stage 1. Oxidation of aryl(heteroaryl)methylketones to glyoxales by the NaBr - DMSO - H2SO4 oxidizing system.
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Currently, a variety of methods for the oxidation of methylketones to αꢀketoaldehydes are described. One of the most applied
methods involves using of CrO3, diphenylselenoxide or selenium dioxide.13,14 More safe and accessible reagent is DMSOꢀHBr mixꢀ
ture, but this method also have a disadvantages such as a long reaction time (1ꢀ24h) and medium yields (low to 50% on average).14b
We have developed an alternative method of oxidation of aryl(heteroaryl)methylketones 2 to corresponding arꢀ
yl(heteroaryl)glyoxals 3 based on readily available reagents such as DMSO, NaBr and concentrated sulphuric acid (Scheme 2).
Scheme 2. Reaction of aryl(heteroaryl)methylketones with DMSO - NaBr - H2SO4 mixture
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This method allows obtaining glyoxal hydrates 3 significantly faster and in higher yields. The reaction process comprises heating
at 100ꢀ110 ºC a mixture of ketone 2, DMSO and an sodium bromide in the presence of sulphuric acid. When the reaction is finꢀ
ished, the formation of dimethyl sulphide bubbles have sharply reduced which is a convenient visual indication for the process
completion. The isolation of glyoxals is not required for further ARC reaction, but it can be readily carried if necessary (see Table 1
and Experimental Section for details).
Table 1. The substituents and yields of isolated glyoxal hydrates 3
Entry
R
Yield (%)
87
Ph
3a
4ꢀCH3C6H4
4ꢀBrC6H4
90
81
76
89
78
86
3b
3c
3d
3e
3f
4ꢀNO2C6H4
4ꢀCH3OC6H4
2,4ꢀCl2C6H3
3ꢀClC6H4
3g
3h
3i
3,4ꢀ(OCH3)2C6H3 90
2ꢀNaphthylꢀ
2ꢀThienylꢀ
2ꢀFurylꢀ
77
81
80
83
3j
3k
3l
5ꢀBrꢀ2ꢀthienylꢀ
Using KBr instead of NaBr leads to decreased glyoxals 3 yields of about 10ꢀ20%.
A proposed mechanism for this "oneꢀpot" reaction comprises a initial particular oxidation of bromide ion to bromine by sulphuric
acid. Subsequent bromination of aryl(heteroaryl)methylketones leads to αꢀbromoketone, which immediately oxidized with DMSO.
The forming hydrogen bromide is then particularly oxidized to bromine by sulphuric acid (Scheme 3).
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Scheme 3. A proposed mechanism for oxidation of aryl(heteroaryl)methylketones
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Stage 2. Adduction and Ring Closure (ARC) reaction
At the second stage, the resulting glyoxals were being undergo the ARC reaction under the action of a mixture of equal amounts
of malonodinitrile and brommalonodinitrile.
The outdated version12 of this synthesis requires a preliminary preparation of pure crystalline monobrommalonodinitrile via broꢀ
mination of malonodinitrile. Subsequent ARC reaction with glyoxals was realized in acetonitrile in quite good yields of resulting
tetracyanocyclopropylketones (73ꢀ82%). Our approach to reaction optimization comprises preparation of malonodinitrile and
brommalonodinitrile equimolar mixture in water and subsequent cyclopropanation under "oneꢀpot" reaction conditions (Scheme 4).
This method allows obtaining the tetracyanocyclopropylketones 4 in good yields (Table 2) and quite purities.
Table 2. The substituents and yields of 3-aroyl(heteroaroyl)cyclopropane-1,1,2,2-tetracarbonitriles 4
Entry
R
Yield (%)
79
Ph
4a
4ꢀCH3C6H4
4ꢀBrC6H4
83
75
71
86
69
73
4b
4c
4d
4e
4f
4ꢀNO2C6H4
4ꢀCH3OC6H4
2,4ꢀCl2C6H3
3ꢀClC6H4
4g
4h
4i
3,4ꢀ(OCH3)2C6H3 90
2ꢀNaphthylꢀ
2ꢀThienylꢀ
2ꢀFurylꢀ
65
93
89
90
4j
4k
4l
5ꢀBrꢀ2ꢀthienylꢀ
Scheme 4. Synthesis of 3-aroyl(heteroaroyl)cyclopropane-1,1,2,2-tetracarbonitriles 4
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Stage 3. Synthesis of ATCN salts 1 via carbanion cleavege of tetracyanocyclopropylketones 4.
At the third stage, the resulting tetracyanocyclopropylketones 4 were reacted with alkali acetates in ethanol (Scheme 5). We have
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found, that ATCN salts solubility in saturated corresponding metal chloride solutions is drastically reduced. This allowed to isolate
ATCN salts 1 in high yields (Table 3) by salting out without usage of rotary evaporator. According to H NMR data, the purity of
the crude products (after drying in vacuo) is 97ꢀ99%.
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Scheme 5. Synthesis of 2-acyl-1,1,3,3-tetracyanopropenides (ATCN) 1
Table 3. The substituents and yields of ATCN salts 1
Entrya
R
Yield (%)
Total yieldb
(%)
Ph
89 (1aLi)
91 (1aNa)
94 (1aK)
95 (1aRb)
96 (1aCs)
95
57 (1aLi)
59 (1aNa)
60 (1aK)
60 (1aRb)
61 (1aCs)
69
1a
4ꢀCH3C6H4
4ꢀBrC6H4
1b
1c
1d
90
86
58
49
4ꢀNO2C6H4
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4ꢀCH3OC6H4
2,4ꢀCl2C6H3
3ꢀClC6H4
96
83
87
93
88
95
96
93
75
48
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80
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73
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77
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1f
1g
1h
1i
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2
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4
5
6
7
8
3,4ꢀ(OCH3)2C6H3
2ꢀNaphthylꢀ
2ꢀThienylꢀ
9
1j
1k
1l
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2ꢀFurylꢀ
5ꢀBrꢀ2ꢀthienylꢀ
aCompounds 1b-l are potassium salts bTotal yield is based on the starting acetophenones without intermediate isolation of glyoxals 3 and
purification of cyclopropanes 4
X-ray characterization of alkali metals ATCN salts.
Further, we have investigated the crystal structure of alkali metals 2ꢀbenzoylꢀ1,1,3,3ꢀtetracyanopropenide salts 1a by Xꢀray difꢀ
fraction analysis, because these compounds might be of considerable interest as new ligands in coordination chemistry. The syntheꢀ
sis of lithium, sodium, rubidium and caesium salts was carried out analogously to potassium salts preparation via using appropriate
metal acetates and chlorides. CCDC 1452031ꢀ1452035 for 1aCs, 1aK, 1aLi, 1aNa and 1aRb respectively, contain the supplementary
crystallographic data for this work. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
The molecular structures of salts 1a(Li-Cs) showing the atom labelling scheme one can see on the Figures S1ꢀS5 in Supporting Inꢀ
formation. The crystal parameters and refinement metrics, to accompany the thermal ellipsoid plot are also provided in the SI (Taꢀ
bles: S1 for 1aLi, S3 for 1aNa, S5 for 1aK, S7 for 1aRb and S9 for 1aCs). Selected bond lengths and angles for 1a(Li,Na,K,Rb,Cs) are in the
tables (SI): S2, S4, S6, S8 and S10 correspondingly.
Singleꢀcrystal Xꢀray diffraction analysis reveals that lithium 2ꢀbenzoylꢀ1,1,3,3ꢀtetracyanopropenide 1aLi is a monohydrate and
crystallizes in the triclinic system with space group P-1. The coordination environment of Li, shown in Figure S1 (a), is four coorꢀ
dinate with two nitrogens N1i and N4i belonging to the two ATCNꢀ ligands, a carbonyl oxygen O1 from the third ATCNꢀ and a oxꢀ
ygen O2 from coordinated water in a slightly distorted tetrahedral geometry. Each lithium cation connect the N1 and N2 nitrogens
belonging to different ATCNꢀ anions to form a 1D chain. The carbonyl groups of ATCNꢀ connects the neighboring 1D chains to
generate a 1D ribbons (Figure S1 (b)). Moreover, the neighboring 1D ribbons are further connected through dipoleꢀdipole interacꢀ
tions between cyano groups as well as hydrogen bonds between coordinated water molecules and N2 nitrogen atoms (Figure S1
(c)).
Sodium (1aNa) and potassium (1aK) 2ꢀbenzoylꢀ1,1,3,3ꢀtetracyanopropenides crystallize as monohydrates in monoclinic symmetry
with space group P 21/n. Xꢀray diffraction analysis demonstrates that 1aNa and 1aK crystals are isostructural and show only minor
differences in bond lengths and bond angles (Figures S2 and S3). The coordination environment of Na is six coordinate with three
cyano group nitrogens N1iii, N2i and N3ii belonging to the three ATCNꢀ ligands, a carbonyl oxygen O1 from the fourth ATCNꢀ and
a two oxygens O2 and O2i from coordinated water in a slightly distorted octahedral geometry. The two neighboring sodium or poꢀ
tassium cations are combined into pair through two water molecules as shown on Figures S2 (b) and S3 (b). Each ATCN anion
connects three sodium atom pairs to form 2D mesh structure. The 3D supramolecular structure is formed by stacking 2D layers.
Potassium salt 1aK displays similar topological structure to 1aNa.
Rubidium (1aRb) and caesium (1aCs) 2ꢀbenzoylꢀ1,1,3,3ꢀtetracyanopropenides crystallize in monoclinic symmetry with space
group P 21/c. Xꢀray diffraction analysis demonstrates that 1aRb and 1aCs crystals are isostructural and show minor differences in
bond lengths and bond angles (Figures S4 and S5).
The coordination environment of Cs comprises five cyano group nitrogens N1iii, N2i, N3vi, N4ii, N4iii belonging to the four ATCN
ligands, a carbonyl oxygen O1 from the fifth ATCNꢀ and benzene ring with minimum distances 3.882 Å (Cs…C4iv) and 3.821 Å
(Cs…C5vi) (Figure S5 (a)).
All salts 1a are yellow or yellowꢀgreen crystalline powders and have a good solubility in water and polar organic solvents. 1aLi
and 1aNa also reveals an intense yellowꢀgreen luminescence in solid state under UV lamp irradiation and have no luminescence
properties in any solutions.
In summary, we have developed the new fast, simple and efficient route for ATCN salts synthesis. All ATCN salts for the first
time were characterized by H and 13C NMR. Xꢀray diffraction analysis reveals that ATCNꢀ anion has the ability to form multiple
1
coordination bonds that makes them candidates for creation of various 1D, 2D and 3D supramolecular structures and potential funcꢀ
tional materials.
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EXPERIMENTAL SECTION
General
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All starting materials and solvents were obtained from commercial suppliers and used without further purification. Н and 13C
NMR spectra were registered at operating frequencies 500 and 121 МHz respectively, solvent DMSOꢀd6, internal reference TMS.
HRMS data were acquired with a QTOF mass spectrometer. The Xꢀray data was collected by using STOE diffractometer Pilatus
100K detector, focusing mirror collimation Cu Kα (1.54086 Å) radiation, rotation method mode. STOE XꢀAREA software was
used for cells refinement and data reduction. Intensity data were scaled with LANA (part of XꢀArea) in order to minimize differꢀ
ences of intensities of symmetryꢀequivalent reflections (multiꢀscan method). The structures were solved and refined with SHELX15a
program. The nonꢀhydrogen atoms were refined by using the anisotropic full matrix leastꢀsquare procedure. Molecular geometry
calculations were performed with the SHELX program, and the molecular graphics were prepared by using DIAMOND15b and
Mercury15c software.
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Preparation of aryl(heteroaryl)glyoxals 3 via oxidation of aryl(heteroaryl)methylketones by DMSO - NaBr - H2SO4 system (gen-
eral procedure).
Aryl(heteroaryl)methylketone (0.1 mol) and sodium bromide (5.0 g, 0.048 mol) were dissolved in DMSO (50 mL) in a 150ꢀmL
tallꢀform beaker. The mixture was heated strictly to 85 ºC under stirring and then a ~5 mL of concentrated sulfuric acid was quickly
added to the reaction. The reaction mass was foaming due to dimethyl sulfide gas formation and the reaction temperature began to
rise. It is important to maintain the temperature of the reaction mass within the range between 100 and 115 ºC. When the reaction is
finished (5ꢀ7 min), the formation of dimethyl sulphide bubbles have sharply reduced and the reacting mixture becomes viscous.
After cooling, the yellowꢀorange oil which formed was dissolved in 50 mL of ethanol, the resulting solution was then used at the
second stage of ATCN synthesis.
If necessary, aryl(heteroaryl)glyoxals might be isolated (as hydrated form). For this purpose, a 50 mL of distilled water was addꢀ
ed to the resulting yellowꢀorange oil, the resulting mixture was refluxed for 5 min under stirring. The aqueous phase was separated
then cooled to 0ꢀ5 ºC and left for 3 h or overnight. The formed white precipitate was filtered and dryed in air.
Notes: Using KBr instead of NaBr leads to decreased yields of glyoxale hydrates of about 10ꢀ20% due to gelling of the reaction
mass. Dimethyl sulfide is irritant. This reaction should be carried out in a wellꢀventilated fume hood.
Stage 2. Synthesis of 3-aroyl(heteroaroyl)cyclopropane-1,1,2,2-tetracarbonitriles 4 (general procedure).
Bromine (16.0 g, 0.1 mol) was dissolved in 600 mL of distilled water under stirring. Malonodinitrile (13.2 g, 0.2 mol) was disꢀ
solved in 50 ml of EtOH and the resulting mixture was poured into bromine solution. A mixture obtained at previous stage and
containing aryl(heteroaryl)glyoxal was added dropwise to the resulting solution under vigorous stirring. After the mixture had been
stirred for 30 min, the white precipitate was filtered off, washed with ice cold ethanol and used at next stage without additional puꢀ
rification. If necessary, cyclopropylketones 4 might be recrystallized from acetone or acetic acid.
Stage 3. Synthesis of 2-aroyl(heteroaroyl)-1,1,3,3-tetracyanopropenides 1 (general procedure)
3ꢀAroyl(heteroaroyl)cyclopropaneꢀ1,1,2,2ꢀtetracarbonitrile 4 (0.05 mol) was added to a mixture of alkali metal acetate (0.07 mol)
and ethanol (20 mL) then stirred at 45ꢀ50 ºC until the solids had dissolved. The resulting darkꢀyellow solution was filtered, the filꢀ
trate allowed to cool then poured into 10% corresponding alkali metal chloride solution (75 ml) and left for 30 min at 5ꢀ10 ºC. The
resulting precipitate was filtered, washed with diethyl ester and dryed in air.
3-Benzoylcyclopropane-1,1,2,2-tetracarbonitrile (4a)
White solid 4a (19.43 g, 79% yield), m.p. 214ꢀ215 °C (Lit.12 211ꢀ212 °C) (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 8.26
3
(d, 3J (H,H) = 7.3 Hz, 2H), 7.80 (t, 3J (H,H) = 7.3 Hz, 1H), 7.65 (t, J (H,H) = 7.9 Hz, 2H), 5.67 (s, 1H); 13C NMR (125.77 MHz,
DMSOꢀd6), δ: 186.7, 136.4, 135.7, 130.5, 129.6, 111.7, 109.7, 38.2, 23.9; HRMS–ESI (m/z) [M]+ calcd for C14H6N4O 246.0542,
found 246.0543.
3-(4'-Methylbenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4b)
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White solid 4b (21.6 g, 83% yield), m.p. 209ꢀ210 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 8.17 (d, 3J (H,H) = 7.93
Hz, 2H), 7.47 (d, 3J (H,H) = 7.93 Hz, 2H), 5.64 (s, 1H), 2.46 (s, 3H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 186.0, 133.7, 130.6,
130.5, 130.2, 111.7, 109.7, 38.2, 23.7, 22.3; HRMS–ESI (m/z) [M]+ calcd for C15H8N4O 260.0698, found 260.0699.
3-(4'-Bromobenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4c)
White solid 4c (24.37 g, 75% yield), m.p. 215ꢀ217 °C (Lit.12 214ꢀ215 °C) (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 8.18
(d, 3J (H,H) = 9.16 Hz, 2H), 7.88 (d, 3J (H,H) = 9.16 Hz, 2H), 5.65 (s, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 186.2, 165.0,
135.4, 133.7, 132.6, 130.9, 111.7, 109.6, 38.0, 24.0; HRMS–ESI (m/z) [M]+ calcd for C14H5BrN4O, 323.9647, 325.9626, found
323.9649, 325.9625.
3-(4'-Nitrobenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4d)
Paleꢀyellow solid 4d (20.7 g, 71% yield), m.p. 253ꢀ254 °C (decomp.); 1H NMR (500.13 MHz, Acetoneꢀd6), δ: 8.63 (d, 3J (H,H) =
8.54 Hz, 2H), 8.50 (d, 3J (H,H) = 8.54 Hz, 2H), 5.78 (s, 1H); 13C NMR (125.77 MHz, Acetoneꢀd6), δ: 185.6, 151.7, 140.5, 131.2,
124.2, 110.7, 108.3, 38.5, 23.4; HRMS–ESI (m/z) [M]+ calcd for C14H5N5O3 291.0392, found 291.0391.
3-(4'-Methoxybenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4e)
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White solid 4e (23.7 g, 86% yield), m.p. 205ꢀ206°C (Lit.12 204ꢀ205 °C) (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 8.25
(d, 3J (H,H) = 9.16 Hz, 2H), 7.18 (d, 3J (H,H) = 9.16 Hz, 2H), 5.63 (s, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 184.6, 165.6,
133.1, 129.0, 115.0, 111.7, 109.7, 56.8, 38.3, 23.5; HRMS–ESI (m/z) [M]+ calcd for C15H8N4O2 276.0647, found 276.0649.
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3-(2',4'-Dichlorobenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4f)
Paleꢀyellow solid 4f (21.7 g, 69% yield), m.p. 228ꢀ229 °C (decomp.); 1H NMR (500.13 MHz, Acetoneꢀd6), δ: 8.23 (d, 3J (H,H) =
8.55 Hz, 1H), 7.79 (d, 4J (H,H) = 1.83 Hz, 1H), 7.69 (dd, 3J (H,H) = 6.71 Hz, 4J (H,H) = 1.83 Hz, 1H), 5.48 (s, 1H); 13C NMR
(125.77 MHz, Acetoneꢀd6), δ: 185.4, 140.0, 134.4, 134.2, 133.7, 131.2, 128.1, 110.5, 108.1, 41.0, 23.2; HRMS–ESI (m/z) [M]+
calcd for C14H4Cl2N4O 313.9762, 315.9735, found 313.9762, 315.9734.
3-(3'-Chlorobenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4g)
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White solid 4g (20.4 g, 73% yield), m.p. 221ꢀ222 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 8.43 (s, 1H), 8.12 (d, 3J
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(H,H) = 7.93 Hz, 1H), 7.86 (d, 3J (H,H) = 7.93 Hz, 1H), 7.66 (t, 3J (H,H) = 7.93 Hz, 1H), 5.71 (s, 1H); 13C NMR (125.77 MHz,
DMSOꢀd6), δ: 186.0, 138.1, 135.0, 134.5, 131.4, 130.7, 128.5, 111.7, 109.6, 38.0, 24.1; HRMS–ESI (m/z) [M]+ calcd for
C14H5ClN4O 280.0152, 282.0122, found 280.0154, 282.0123.
3-(3',4'-Dimethoxybenzoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4h)
White solid 4h (27.5 g, 90% yield), m.p. 184ꢀ185 °C (Lit.12 186ꢀ187°C) (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 8.00
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(dd, 3J (H,H) = 6.71 Hz, 4J (H,H) = 1.83 Hz, 1H), 7.69 (d, 4J (H,H) = 1.83 Hz, 1H), 7.21 (d, 3J (H,H) = 9.16 Hz, 1H); 5.70 (s, 1H);
3.94 (s, 3H), 3.90 (s, 3H). 13C NMR (125.77 MHz, DMSOꢀd6), δ: 184.5, 155.6, 149.5, 128.9, 126.1, 112.2, 111.8, 111.7, 109.7,
57.0, 56.7, 38.1, 23.5; HRMS–ESI (m/z) [M]+ calcd for C16H10N4O3 306.0753, found 306.0755.
3-(1'-Naphthoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4i)
White solid 4i (19.24 g, 65% yield), m.p. 208ꢀ209 °C (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 8.69 (d, 3J (H,H) = 8.54
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Hz, 1H), 8.60 (d, J (H,H) = 7.32 Hz, 1H), 8.33 (d, J (H,H) = 8.54 Hz, 1H), 8.33 (d, J (H,H) = 8.54 Hz, 1H), 8.10 (d, J (H,H) =
8.55 Hz, 1H), 7.8 ꢀ 7.73 (m, 3H); 5.71 (s, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 188.3, 136.0, 134.1, 133.7, 132.9, 129.9,
129.6, 128.0, 127.7, 126.3, 125.4, 111.7, 109.7, 24.0; HRMS–ESI (m/z) [M]+ calcd for C18H8N4O 296.0698, found 296.0697.
3-(2'-Thienylcarbonyl)cyclopropane-1,1,2,2-tetracarbonitrile (4j)
White solid 4j (23.44 g, 93% yield), m.p. 204ꢀ205 °C (Lit.12 201ꢀ202°C) (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 8.58
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(d, J (H,H) = 3.66 Hz, 1H.), 8.29 (d, J (H,H) = 4.88 Hz, 1H), 7.42 (t, J (H,H) = 4.27 Hz, 1H), 5.57 (s, 1H); 13C NMR (125.77
MHz, DMSOꢀd6), δ: 178.9, 143.4, 139.3, 138.7, 130.2, 111.6, 109.5, 38.7, 23.5; HRMS–ESI (m/z) [M]+ calcd for C12H4N4OS
252.0106, found 252.0105.
3-(2'-Furoyl)cyclopropane-1,1,2,2-tetracarbonitrile (4k)
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White solid 4k (21.0 g, 89% yield), m.p. 215ꢀ216 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 8.25 (s, 1H), 8.12 (br. s,
1H), 6.90 ꢀ 6.93 (m, 1H), 5.32 (s, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 173.1, 151.9, 151.2, 115.4, 114.7, 111.6, 109.3, 38.7,
23.3; HRMS–ESI (m/z) [M]+ calcd for C12H4N4O2 236.0334, found 236.0333.
3-[(5'-Bromo-2'-thienyl)carbonyl]cyclopropane-1,1,2,2-tetracarbonitrile (4l)
White solid 4l (29.79 g, 90% yield), m.p. 227ꢀ228 °C (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 8.39 (d, 3J (H,H) = 4.27
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Hz, 1H), 7.60 (d, J (H,H) = 4.27 Hz, 1H), 5.52 (s, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 178.2, 144.9, 141.7, 139.2, 133.8,
126.2, 111.6, 109.4, 38.2, 23.7; HRMS–ESI (m/z) [M]+ calcd for C12H3BrN4OS 329.9211, 331.9190, found 329.9213, 331.9191.
Potassium 2-benzoyl-1,1,3,3-tetracyanopropenide (1aK)
Yellow crystalline powder 1aK (13.35 g, 94% yield), m.p. 272ꢀ273 °C (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 7.96 (d,
3J (H,H) = 7.32 Hz, 2H), 7.81 (t, 3J (H,H) = 7.32 Hz, 1H), 7.66 (t, 3J (H,H) = 7.93 Hz, 2H); 13C NMR (125.77 MHz, DMSOꢀd6), δ:
193.1, 165.7, 136.4, 133.6, 130.4, 130.4, 117.9, 115.3, 51.2; HRMS–ESI (m/z) [M]+ calcd for C14H5N4O 245.0469, found 245.0470.
The HRMS, 1H NMR and 13C NMR data for lithium, sodium, rubidium and caesium salts 1a are completely analogously for 1aK.
Yellow crystalline powder 1aLi (11.2 g, 89% yield), m.p. 172ꢀ173 °C (decomp.);
Yellow crystalline powder 1aNa (12.19 g, 91% yield), m.p. 303ꢀ304 °C (Lit.12 228ꢀ229 °C) (decomp.);
Yellow crystalline powder 1aRb (15.67 g, 95% yield), m.p. 275ꢀ276 °C (decomp.);
Yellow crystalline powder 1aCs (18.2 g, 96% yield), m.p. 269ꢀ270 °C (decomp.).
Potassium 2-(4'-methylbenzoyl)-1,1,3,3-tetracyanopropenide (1b)
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Lemonꢀyellow crystalline powder 1b (13.3 g, 94% yield), m.p. 277ꢀ278 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ:
7.85 (d, 3J (H,H) = 7.32 Hz, 2H), 7.46 (d, 3J (H,H) = 7.93 Hz, 2H), 2.45 (s, 3H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 192.5,
166.0, 147.4, 131.2, 131.0, 130.5, 117.9, 115.4, 51.1, 22.3; HRMS–ESI (m/z) [M]+ calcd for C15H7N4O 259.0625, found 259.0626.
Potassium 2-(4'-bromobenzoyl)-1,1,3,3-tetracyanopropenide (1c)
Yellow crystalline powder 1c (16.65 g, 90% yield), m.p. 260ꢀ261 °C (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 7.85ꢀ7.93
(m, 4H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 192.3, 165.0, 133.7, 132.6, 132.2, 130.9, 117.8, 115.1, 51.2; HRMS–ESI (m/z)
[M]+ calcd for C14H4BrN4O 322.9574, 324.9554, found 322.9576, 324.9555.
Potassium 2-(4'-nitrobenzoyl)-1,1,3,3-tetracyanopropenide (1d)
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Orangeꢀyellow crystalline powder 1d (14.2 g, 86% yield), m.p. 253ꢀ254 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ:
8.45 (d, 3J (H,H) = 8.54 Hz, 2H), 8.25 (d, 3J (H,H) = 8.54 Hz, 2H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 192.2, 164.4, 152.1,
137.8, 131.9, 125.7, 117.7, 115.0, 51.4; HRMS–ESI (m/z) [M]+ calcd for C14H4N5O3 290.0320, found 290.0321.
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Potassium 2-(4'-methoxybenzoyl)-1,1,3,3-tetracyanopropenide (1e)
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Paleꢀyellow crystalline powder 1e (15.0 g, 96% yield), m.p. 306ꢀ308 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 7.91
(d, 3J (H,H) = 9.16 Hz, 2H), 7.17 (d, 3J (H,H) = 9.16 Hz, 2H), 3.92 (s, 3H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 191.2, 166.2,
165.7, 133.0, 126.6, 118.0, 115.8, 115.5, 56.7, 51.0; HRMS–ESI (m/z) [M]+ calcd for C15H7N4O2 275.0574, found 275.0576.
Potassium 2-(2',4'-dichlorobenzoyl)-1,1,3,3-tetracyanopropenide (1f)
Yellow crystalline powder 1f (14.65 g, 83% yield), m.p. 299ꢀ300 °C (decomp.); 1H NMR (500.13 MHz, DMSOꢀd6), δ: 7.96 (d, 3J
(H,H) = 8.54 Hz, 1H), 7.90 (d, 4J (H,H) = 1.83 Hz, 1H), 7.69 (dd, 3J (H,H) = 6.12 Hz,4J (H,H) = 1.83 Hz, 2H); 13C NMR (125.77
MHz, DMSOꢀd6), δ: 190.5, 165.0, 140.7, 135.5, 135.4, 132.5, 131.2, 129.2, 117.7, 115.3, 51.8; HRMS–ESI (m/z) [M]+ calcd for
C14H3Cl2N4O 312.9689, 314.9660, found 312.9694, 314.9661.
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Potassium 2-(3'-chlorobenzoyl)-1,1,3,3-tetracyanopropenide (1g)
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Yellow crystalline powder 1g (13.87 g, 87% yield), m.p. 320ꢀ321 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 7.95 (d,
3J (H,H) = 6.71 Hz, 2H), 7.90 (d, 3J (H,H) = 8.55 Hz, 1H), 7.71 (t, 3J (H,H) = 7.93 Hz, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ:
192.1, 164.7, 136.2, 135.4, 135.3, 132.7, 129.5, 129.1, 117.8, 115.1, 51.4; HRMS–ESI (m/z) [M]+ calcd for C14H4ClN4O 279.0079,
281.0050, found 279.0081, 281.0052.
Potassium 2-(3',4'-dimethoxybenzoyl)-1,1,3,3-tetracyanopropenide (1h)
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White crystalline powder 1h (15.99 g, 93% yield), m.p. 331ꢀ332 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ: 7.56 (dd,
3J (H,H) = 8.54 Hz, 4J (H,H) = 1.83 Hz, 1H), 7.42 (d, 4J (H,H) = 1.83 Hz, 1H), 7.20 (d, 3J (H,H) = 8.54 Hz, 1H), 3.93 (s, 3H), 3.87
(s, 3H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 191.1, 166.2, 155.8, 150.2, 127.1, 126.5, 118.1, 115.5, 112.3, 110.4, 56.9, 56.5,
51.2; HRMS–ESI (m/z) [M]+ calcd for C16H9N4O3 305.0680, found 305.0681.
Potassium 2-(1'-naphthoyl)-1,1,3,3-tetracyanopropenide (1i)
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Brownꢀyellow crystalline powder 1i (14.69 g, 88% yield), m.p. 218ꢀ220 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ:
9.00 (d, 3J (H,H) = 8.55 Hz, 1H), 8.38 (d, 3J (H,H) = 7.93 Hz, 1H), 8.24 (d, 3J (H,H) = 6.71 Hz, 1H), 8.13 (d, 3J (H,H) = 7.93 Hz,
1H), 7.74 ꢀ 7.82 (m, 2H), 7.70 (t, 3J (H,H) = 7.93 Hz, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 194.5, 166.9, 137.4, 135.8, 134.6,
131.0, 130.4, 129.9, 129.2, 128.0, 126.2, 126.1, 118.1, 115.5, 51.9; HRMS–ESI (m/z) [M]+ calcd for C18H7N4O 295.0625, found
295.0623.
Potassium 2-(2'-thienylcarbonyl)-1,1,3,3-tetracyanopropenide (1j)
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Greenꢀyellow crystalline powder 1j (13.77 g, 96% yield), m.p. 256ꢀ257 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ:
8.27 (d, 3J (H,H) = 5.87 Hz, 1H), 7.96 (d, 3J (H,H) = 5.14 Hz, 1H), 7.35 (t, 3J (H,H) = 5.14 Hz, 1H); 13C NMR (125.77 MHz,
DMSOꢀd6), δ: 184.9, 165.1, 140.3, 139.8, 138.5, 130.6, 117.9, 115.4, 51.4; HRMS–ESI (m/z) [M]+ calcd for C12H3N4OS 251.0033,
found 251.0032.
Potassium 2-(2'-Furoyl)-1,1,3,3-tetracyanopropenide (1k)
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Greenꢀyellow crystalline powder 1k (13.15 g, 96% yield), m.p. 292ꢀ923 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ:
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8.23 (s, 1H), 7.71 (d, 3J (H,H) = 3.66 Hz, 1H), 6.87 (dd, J (H,H) = 3.66 Hz, J (H,H) = 1.22 Hz, 1H); 13C NMR (125.77 MHz,
DMSOꢀd6), δ: 179.3, 164.1, 151.9, 149.8, 125.1, 117.9, 115.4, 114.7, 51.5; HRMS–ESI (m/z) [M]+ calcd for C12H3N4O2 235.0261,
found 235.0260.
Potassium 2-[(5'-bromo-2'-thienyl)carbonyl]-1,1,3,3-tetracyanopropenide (1l)
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Greenꢀyellow crystalline powder 1l (17.16 g, 93% yield), m.p. 276ꢀ278 °C (decomp.); H NMR (500.13 MHz, DMSOꢀd6), δ:
7.88 (d, 3J (H,H) = 4.27 Hz, 1H), 7.53 (d, 3J (H,H) = 4.26 Hz, 1H); 13C NMR (125.77 MHz, DMSOꢀd6), δ: 184.0, 163.9, 141.7,
139.5, 134.4, 127.0, 117.8, 115.2, 51.6; HRMS–ESI (m/z) [M]+ calcd for C12H2BrN4OS 328.9138, 330.9118, found 328.9140,
330.9119.
ASSOCIATED CONTENT
Supporting Information
1
Supporting Information contains H and 13C NMR spectra graphics for all synthesized compounds and Xꢀray characterization data for
compounds 1a(Li-Cs). This material is available free of charge via the Internet on the ACS Publications website. CCDC 1452031ꢀ1452035
for 1aCs, 1aK, 1aLi, 1aNa and 1aRb respectively, contain the supplementary crystallographic data for this work. These data can be obtained
free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
AUTHOR INFORMATION
Corresponding Author
*Corresponding Author: *Eꢀmail: serg31.chem@mail.ru
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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This work was supported by RFBR, research project 16ꢀ33ꢀ60135 "мол_a_дк". The XꢀRay study was supported in part by M. V. Lomonoꢀ
sov Moscow State University Program of Development.
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Page 11 of 11
The Journal of Organic Chemistry
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new oxidation
system
O
O
O
4
R
R
CH3
5-8 min
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up to 90%
O
1 eq.Br2
M+
"one-pot"
synthesis
O
CN
CN
R
NC
MOAc
EtOH
CN
CN
R
CN
NC CN
65-93%
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NC CN
1:1 mixture of
malononitrile and
bromomalononitrile
2 eq.
Total yield
48-80%
M = Li, Na, K, Rb, Cs
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