Addition of acetylacetone and ethyl acetoacetate to carbodiimides promoted by nickel acetylacetonate

Article abstract of DOI:10.1023/B:RUCB.0000035656.94284.ee

The addition reactions of acetylacetone and ethyl acetoacetate with diphenylcarbodiimide and dicyclohexylcarbodiimide in the presence of nickel acetylacetonate afforded N,N′-substituted α,α-dioxoketene aminals. Adducts of acetylacetone with carbodiimides

Full text of DOI:10.1023/B:RUCB.0000035656.94284.ee

676
Russian Chemical Bulletin, International Edition, Vol. 53, No. 3, pp. 676—680, March, 2004
Addition of acetylacetone and ethyl acetoacetate to carbodiimides
promoted by nickel acetylacetonate
V. A. Dorokhovꢀ and A. V. Komkov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. Eꢀmail: vador@ioc.ac.ru
The addition reactions of acetylacetone and ethyl acetoacetate with diphenylcarbodiimide
and dicyclohexylcarbodiimide in the presence of nickel acetylacetonate afforded N,N´ꢀsubstiꢀ
tuted α,αꢀdioxoketene aminals. Adducts of acetylacetone with carbodiimides are readily
deacetylated with MeONa in MeOH to form acetylketene aminals. Ketene aminals were used
for the synthesis of functionalized 1,2,3ꢀtriazoles.
Key words: carbodiimides, acetylacetone, ethyl acetoacetate, addition to the C=N bond,
catalysis, nickel acetylacetonate, deacetylation, α,αꢀdioxoketene aminals, 1ꢀRꢀ4ꢀacetylꢀ
5ꢀ(Rꢀamino)ꢀ1,2,3ꢀtriazoles, biheterocycles.
α,αꢀDioxoketene aminals are convenient starting comꢀ
of the adducts formed.16,17 The reactions of DCC, which
is less electrophilic than DPC, even with malonic ester or
indaneꢀ1,3ꢀdione in the presence of EtONa do not give
ketene aminals, and only the reaction with Meldrum's
acid affords the corresponding adduct.18 Meldrum's acid
reacts also with some other carbodiimides.19
We found that acetylacetone and ethyl acetoacetate
readily added to DPC on refluxing in THF in the presꢀ
ence of catalytic amounts of Ni(acac)2 to form ketene
aminals 1a,b, which were isolated in 70% and 75% yields,
respectively (Scheme 1).* In the case of less reactive DCC,
the addition of acetylacetone proceeded not so readily.
To achieve the best results, a large excess of diketone and
an equivalent amount of Ni(acac)2 (with respect to DCC)
are required. Under these conditions, ketene aminal 1c
was prepared in 67% yield with respect to DCC. In the
reaction with the use of a ten times smaller amount of
Ni(acac)2, the yield of adduct 1c decreased to 40% in
spite of substantially more prolonged heating of the reacꢀ
tion mixture.
pounds for the construction of heterocyclic systems.1—6
In continuation of our investigations on the synthesis of
this type of reagents from cyanamides,7—10 we studied the
reactions of acetylacetone and ethyl acetoacetate with
diphenylcarbodiimide (DPC) and dicyclohexylcarboꢀ
diimide (DCC) catalyzed by nickel acetylacetonate
Ni(acac)2.
It is known that βꢀdiketonates of a number of transiꢀ
tion metals catalyze the addition of methyleneꢀactive
βꢀdiketones and ethyl acetoacetate to the C=N bond of
isocyanates.11—14 This fact gives grounds to expect that
analogous reactions of βꢀdicarbonyl compounds with
carbodiimides will afford N,N´ꢀdisubstituted α,αꢀdioxoꢀ
ketene aminals.
Examples of the addition of methyleneꢀactive comꢀ
pounds to carbodiimides in the presence of basic catalysts
have been described earlier. More than a hundred years
ago, an adduct was prepared by the reaction of malonic
ester with DPC.15 Much more later, this adduct was
demonstrated3 to be dianilinomethylenemalonic ester.
N,N´ꢀSubstituted aminals were synthesized analogously
from dibenzoylmethane and benzoylacetic ester.3
However, the reactions in the presence of bases are
often accompanied by undesirable side processes due to
instability of the starting compounds or final products
with respect to the catalysts used. Presumably, that is the
reason why data on the reactions of acetylacetone or ethyl
acetoacetate with diphenylcarbodiimide are lacking in the
literature, since the expected ketene aminals can be subꢀ
jected to deacetylation in the presence of a base. For
example, it is known that the reactions of acetylacetone
with trihaloacetonitriles resulted finally in deacetylation
Colorless crystalline compounds 1a,b are readily
soluble in acetone, benzene, and chloroform but are poorly
soluble in ethanol and light petroleum. The structures of
1a,b were confirmed by physicochemical methods and
elemental analysis. The mass spectra of ketene aminals
1a,b are characterized by the presence of molecular ion
peaks. In the 1H NMR spectrum of compound 1a in
CDCl3, both Me groups give a singlet at δ 2.50. The
1
results of IR and H NMR spectroscopy are also indicaꢀ
* We chose Ni(acac)2 as the catalyst because it showed the highꢀ
est efficiency compared to acetylacetonates of other metals in
the reaction of acetylacetone with phenyl isocyanate.13
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 645—649, March, 2004.
1066ꢀ5285/04/5303ꢀ0676 © 2004 Plenum Publishing Corporation

Addition of acetylacetone to carbodiimides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
677
Scheme 1
Scheme 3
R1 = Ph (a), cycloꢀC6H11 (c)
Compounds 2a,c are colorless crystalline compounds,
which are readily soluble in acetone, ethanol, chloroꢀ
form, and benzene. Their structures were confirmed by
spectroscopic methods (IR, 1H NMR, and mass spectra).
The 1H NMR spectra (in CDCl3) of ketene aminals 2a,c
are characterized by the presence of a singlet of HC=C at
δ 4.91 and 4.54, respectively. According to the IR and
1H NMR spectroscopic data, one of the NH groups is
involved in an intramolecular N—H...O hydrogen bond.
Earlier,21 compound 2a has been synthesized by the
reaction of aniline with β,βꢀdichlorovinyl methyl ketone.
Ketene aminals prepared from carbodiimides can be
used as chelating ligands and starting compounds for the
construction of heterocyclic compounds. Earlier, we have
demonstrated22 that monoacylketene aminals containing
the unsubstituted NH2 group can be involved in the
1,3ꢀdipolar addition to tosyl azide.22 The subsequent
Dimroth rearrangement and elimination of TsNH2 afford
4ꢀacylꢀ5ꢀaminoꢀ1,2,3ꢀtriazole derivatives. Analogously,
compounds 2a,c are smoothly transformed into the corꢀ
responding 1,2,3ꢀtriazoles 3 and 4 (Scheme 4).
R1 = Ph, R2 = R3 = Me (a); R1 = Ph, R2 = Me, R3 = OEt (b);
R1 = cycloꢀC6H11, R2 = R3 = Me (c)
tive of the formation of intramolecular N—H...O hydroꢀ
gen bonds in solutions, which is typical of diacylketene
aminals.8,9
The crystalline product prepared from DCC is poorly
soluble in organic solvents (including DMSO), but the
results of mass spectrometry and IR spectroscopy (in KBr)
are in complete agreement with structure 1c.
The role of Ni(acac)2 in promotion of the reactions
of acetylacetone with carbodiimides is illustrated in
Scheme 2, which is analogous to the scheme of catalysis
of the addition of acetylacetone to benzoylcyanamide proꢀ
posed earlier.8
Scheme 2
Acetyltriazoles can react with DMF dimethylacetal
(DMF DMA) to give condensation products at the meꢀ
thyl group of the acetyl fragment.22 Correspondingly, reꢀ
fluxing of triazole 3 with DMF DMA in toluene afforded
enaminone 5. Its treatment with hydrazine hydrate in
boiling THF gave rise to 1ꢀphenylꢀ5ꢀphenylaminoꢀ4ꢀ
(pyrazolꢀ5ꢀyl)ꢀ1,2,3ꢀtriazole (7).
It appeared that triazole 4 did not react with DMF
DMA under analogous conditions and even on refluxing
in xylene. We succeeded in preparing the corresponding
enaminone 6 in good yield from compound 4 only with
the use of a stronger electrophilic reagent, viz., bis(diꢀ
methylamino)methoxymethane.23 Subsequent cyclization
with hydrazine hydrate in EtOH afforded biheterocycle 8.
Crystalline 1,2,3ꢀtriazole derivatives 3—8 were isoꢀ
lated in 70—90% yields. Compounds 3, 4, 7, and 8 are
readily soluble in organic solvents (triazoles 3, 7, and 8
are poorly soluble only in light petroleum, and triazole 7
is poorly soluble also in MeCN). The spectroscopic charꢀ
acteristics of heterocycles 3—8 are in agreement with their
structures (for pyrazolyltriazoles 7 and 8, the most probꢀ
able position of the proton of NH in the pyrazole ring is
presented).
Ethyl acetoacetate adds to carbodiimides as its Ni cheꢀ
late formed from Ni(acac)2 in the presence of an excess of
the ester. As expected (see above), ketene aminals 1a,c
are readily deacylated with MeONa in boiling MeOH to
give monoacetylketene aminals 2a,c (Scheme 3) (cf. also
deacetylation of diacylketene aminals derived from cyanꢀ
amides20).

678
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
Dorokhov and Komkov
Scheme 4
R1 = Ph (2a, 3, 5, 7), cycloꢀC6H11 (2c, 4, 7, 8)
Found (%): C, 70.44; H, 6.19; N, 9.02. C19H20N2O3. Calcuꢀ
Compounds 7 and 8 are of interest as potential chelatꢀ
ing ligands.
lated (%): C, 70.35; H, 6.21; N, 8.64. IR (CHCl3), ν/cm–1
:
3300—3040 (NH, CH); 1625, 1597, 1585 (CO, C=C). 1H NMR
(CDCl3), δ: 1.39 (t, 3 H, Me, J = 6.8 Hz); 2.51 (s, 3 H, MeCO);
4.31 (q, 2 H, CH2, J = 6.8 Hz); 6.80—7.05 (m, 10 H, Ph); 12.60
(br.s, 2 H, NH). MS, m/z: 324 [M]+.
Experimental
The 1H NMR spectra were recorded on a Bruker WMꢀ250
instrument. The 13C NMR spectra were measured on a Bruker
AMꢀ300 spectrometer. The IR spectra were recorded on a
Specord Mꢀ80 instrument. The mass spectra were obtained on a
Kratos MSꢀ30 instrument (EI, 70 eV, the temperature of an
ionization chamber was 250 °C, a direct inlet system). Diphenylꢀ
carbodiimide was synthesized by dehydration of diphenylurea.24
Tosyl azide25 and bis(dimethylamino)methoxymethane23 were
prepared according to known procedures.
3ꢀ(Dicyclohexylaminomethylene)pentaneꢀ2,4ꢀdione (1c).
A mixture of DCC (1.2 g, 5.8 mmol), Ni(acac)2 (0.75 g,
2.9 mmol), and acetylacetone (10 mL, 97.5 mmol) in dry THF
(9 mL) was refluxed for 13—14 h and cooled to ~20 °C. The
precipitate that formed was filtered off and washed with THF
(10 mL) and EtOH (10 mL). Ketene aminal 1c was obtained in a
yield of 1.2 g (67%), m.p. 263—265 °C. Found (%): C, 70.39;
H, 9.75; N, 9.17. C18H30N2O2. Calculated (%): C, 70.55;
H, 9.87; N, 9.14. IR (KBr), ν/cm–1: 3300—3100 (NH, CH);
1630, 1560 (CO, C=C). MS, m/z: 306 [M]+.
4,4ꢀ(Dianilino)butꢀ3ꢀenꢀ2ꢀone (2a). A mixture of ketene
aminal 1a (10 g, 34 mmol) and MeONa (34 mmol, from 0.78 g
of Na) in MeOH (300 mL) was refluxed for 3—4 h (TLC conꢀ
trol), cooled to ~20 °C, acidified with AcOH to pH ~7, and
concentrated in vacuo. Chloroform (50 mL) was added to the
residue, AcONa was filtered off, the filtrate was concentrated,
and the residue was recrystallized from a benzene—hexane mixꢀ
ture. Compound 2a was obtained in a yield of 6.30 g (73%), m.p.
114—115 °C (cf. lit. data21: 116—117 °C). 1H NMR (CDCl3), δ:
2.00 (s, 3 H, Me); 4.91 (s, 1 H, CH=); 6.19 (br.s, 1 H, NH);
7.12—7.50 (m, 10 H, Ph); 12.90 (br.s, 1 H, NH).
3ꢀ(Dianilinomethylene)pentaneꢀ2,4ꢀdione (1a).* A mixture
of DPC (12.25 g, 63 mmol), acetylacetone (7.7 mL, 75 mmol),
and Ni(acac)2 (1.67 g) in dry THF (30 mL) was refluxed for 12 h
(TLC control), cooled to ~20 °C, and kept for 16 h. The precipiꢀ
tate that formed was filtered off and ketene aminal 1a was obꢀ
tained in a yield of 11 g. The filtrate was concentrated and the
residue was recrystallized from EtOH to obtain additionally 2 g
of compound 1a, the total yield was 70%, m.p. 154—156 °C.
Found (%): C, 73.56; H, 6.03; N, 9.88. C18H18N2O2. Calcuꢀ
lated (%): C, 73.45; H, 6.16; N, 9.51. IR (CHCl3), ν/cm–1
:
3300—3040 (NH, CH); 1615, 1595, 1570 (CO, C=C). 1H NMR
(CDCl3), δ: 2.50 (s, 6 H, Me); 6.80—6.90 (m, 6 H, Ph); 7.00
(m, 4 H, Ph); 12.95 (br.s, 2 H, NH). MS, m/z: 294 [M]+.
Ethyl 2ꢀ(dianilinomethylene)ꢀ3ꢀoxobutanoate (1b). A mixꢀ
ture of DPC (4.47 g, 23 mmol), ethyl acetoacetate (2.9 mL,
23 mmol), and Ni(acac)2 (0.4 g, 1.6 mmol) in dry THF (10 mL)
was refluxed for 6—8 h (TLC control). The solvent was evapoꢀ
rated in vacuo and the residue was chromatographed on a colꢀ
umn with SiO2 (CHCl3 as the eluent). After evaporation of the
solvent, the residue was recrystallized from EtOH to prepare
ketene aminal 1b in a yield of 5.6 g (75%), m.p. 107—108 °C.
4,4ꢀ(Dicyclohexylamino)butꢀ3ꢀenꢀ2ꢀone (2c). Compound 2c
was synthesized analogously to ketene aminal 2a from ketene
aminal 1c (11.4 g, 37 mmol) and MeONa in MeOH. The reacꢀ
tion was completed in 6—8 h (TLC control) to give an oil, which
was crystallized by trituration with a mixture of hexane and
diethyl ether and recrystallized from a mixture of hexane
and benzene. The yield was 8.4 g (85%), m.p. 154—155 °C.
Found (%): C, 72.63; H, 10.65; N, 10.28. C16H28N2O. Calcuꢀ
lated (%): C, 72.67; H, 10.67; N, 10.59. IR (CHCl3), ν/cm–1
:
3448 (NH); 3300—3100 (NH, CH); 1605, 1570 (CO, C=C).
* A. V. Zubarev participated in the synthesis of compounds 1a—c.
1H NMR (CDCl3), δ: 1.10—1.95 (m, 20 H, CH2); 2.00 (s, 3 H,

Addition of acetylacetone to carbodiimides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
679
Me); 3.10—3.38 (m, 2 H, CH); 4.00 (br.s, 1 H, NH); 4.54 (s,
1 H, CH=); 11.12 (br.s, 1 H, NH). MS, m/z: 264 [M]+.
(12 Torr) at ~100 °C. Benzene (2 mL) and light petroleum
(3 mL) were added to the residue and the precipitate that formed
was filtered off. The yield of triazole 7 was 0.133 g (88%), m.p.
192—193 °C (from MeCN). Found (%): C, 67.28; H, 4.81;
N, 27.99. C17H14N6. Calculated (%): C, 67.53; H, 4.67; N, 27.80.
IR (KBr), ν/cm–1: 3360—3120 (NH); 1615, 1598, 1520.
1H NMR (CDCl3), δ: 6.60—6.72 (m, 3 H, Ph and H(4) Pyr);
6.82 (m, 1 H, Ph); 6.93 (br.s, 1 H, NH); 7.10 (m, 2 H, Ph);
7.30—7.50 (m, 3 H, Ph); 7.52—7.75 (m, 3 H, Ph and H(3) Pyr).
MS, m/z (Irel (%)): 302 [M]+ (63), 274 [M – N2]+ (87),
77 [Ph]+ (100).
4ꢀAcetylꢀ1ꢀphenylꢀ5ꢀphenylaminoꢀ1,2,3ꢀtriazole (3). A mixꢀ
ture of ketene aminal 2a (1.01 g, 4 mmol) and TsN3 (0.79 g,
4 mmol) in THF (15 mL) was stirred at ~20 °C for 24 h. The
solvent was removed in vacuo, the residue was extracted with
heptane heated to boiling (4×15 mL), the mixture was concenꢀ
trated, and triazole 3 was obtained in a yield of 0.94 g (85%),
m.p. 112—113 °C (from heptane). Found (%): C, 69.18; H, 5.24;
N, 20.06. C16H14N4O. Calculated (%): C, 69.05; H, 5.07;
N, 20.13. IR (KBr), ν/cm–1: 3270—3250 (NH); 1640 (CO),
1595, 1575, 1515. 1H NMR (CDCl3), δ: 2.75 (s, 3 H, Me); 6.70
(m, 2 H, Ph); 6.90 (m, 1 H, Ph); 7.00 (m, 2 H, Ph); 7.12—7.38
(m, 5 H, Ph); 8.78 (br.s, 1 H, NH). MS, m/z: 278 [M]+.
1ꢀCyclohexylꢀ5ꢀcyclohexylaminoꢀ4ꢀ(pyrazolꢀ5ꢀyl)ꢀ1,2,3ꢀ
triazole (8). A mixture of triazole 6 (0.173 g, 0.5 mmol) and
hydrazine hydrate (0.1 mL, 2 mmol) in EtOH (4 mL) was reꢀ
fluxed for 1.5 h. The solvent and an excess of hydrazine were
removed in vacuo (12 Torr) at ~100 °C. The residue was exꢀ
tracted with heptane (9 mL) heated to boiling, the extract was
cooled, and the precipitate that formed was filtered off (opꢀ
erations were repeated five more times using the filtrate).
Pyrazolyltriazole 8 was obtained in a yield of 0.11 g (72%), m.p.
127—128 °C. Found (%): C, 64.55; H, 8.20; N, 26.80. C17H26N6.
4ꢀAcetylꢀ1ꢀcyclohexylꢀ5ꢀcyclohexylaminoꢀ1,2,3ꢀtriazole (4).
A mixture of ketene aminal 2c (1.06 g, 4 mmol) and TsN3
(0.79 g, 4 mmol) in THF (15 mL) was stirred at ~20 °C for 24 h.
The solvent was removed in vacuo and light petroleum (20 mL)
was added to the residue. The mixture was heated to boiling and
cooled to ~20 °C. Then TsNH2 that precipitated was filtered off,
the filtrate was concentrated, and triazole 4 was obtained in a
yield of 0.98 g (85%). An analytical sample was purified from a
small amount of a TsN3 impurity by column chromatography
on SiO2 (C6H6 and CHCl3 were used successively as the eluꢀ
ents), m.p. 62—63 °C. Found (%): C, 66.20; H, 8.86; N, 19.23.
C16H26N4O. Calculated (%): C, 66.17; H, 9.02; N, 19.29.
IR (KBr), ν/cm–1: 3305 (NH); 1645 (CO); 1575. 1H NMR
(CDCl3), δ: 1.20—2.15 (m, 20 H, CH2); 2.60 (s, 3 H, Me); 3.29
(m, 1 H, CH); 4.02 (m, 1 H, CH); 6.42 (d, 1 H, NH, J =
9.8 Hz). 13C NMR (CDCl3), δ: 24.14, 24.87, 25.16, 25.52, 32.44,
Calculated (%): C, 64.94; H, 8.33; N, 26.73. IR (KBr), ν/cm–1
:
1
3298, 3200—3120 (NH); 1607, 1545, 1505. H NMR (CDCl3),
δ: 1.00—2.20 (m, 20 H, CH2); 2.83—3.05 (m, 1 H, CH);
4.05—4.25 (m, 1 H, CH); 4.44 (br.s, 1 H, NH); 6.76 (d, 1 H,
H(4) Pyr, J = 1.7 Hz); 7.61 (d, 1 H, H(3) Pyr, J = 1.7 Hz).
13C NMR (CDCl3), δ: 24.87, 25.19, 25.60, 25.77, 32.93, 33.95
(CH2); 56.95, 57.29 (CH); 102.45 (dd, C(4) Pyr, 1J = 178 Hz,
2J = 8 Hz); 129.98 (C(4)); 131.24 (d, C(3) Pyr, 1J = 185 Hz);
138.56 (C(5)); 143.03 (C(5) Pyr). MS, m/z (Irel (%)): 314 [M]+
(62), 55 (100).
3
33.82 (CH2); 54.10, 58.28 (CH); 131.55 (q, C(4), J = 3.2 Hz);
144.98 (C(5)); 193.86 (q, CO, 2J = 6.0 Hz). MS, m/z: 290 [M]+.
4ꢀ[3ꢀ(Dimethylamino)acryloyl]ꢀ1ꢀphenylꢀ5ꢀphenylaminoꢀ
1,2,3ꢀtriazole (5). A mixture of triazole 3 (0.278 g, 1 mmol) and
DMF DMA (0.20 mL, 1.5 mmol) in toluene (7 mL) was reꢀ
fluxed for 4 h and cooled to ~20 °C. Light petroleum (10 mL)
was added and the precipitate that formed was filtered off to
obtain triazole 5 in a yield of 0.23 g (70%), m.p. 201—202 °C.
Found (%): C, 68.27; H, 5.82; N, 21.03. C19H19N5O. Calcuꢀ
lated (%): C, 68.45; H, 5.74; N, 21.01. 1H NMR (CDCl3), δ:
2.98 and 3.12 (both s, 6 H, NMe2); 6.15 (d, 1 H, CH=, J =
13 Hz); 6.68 (m, 2 H, Ph); 6.82 (m, 1 H, Ph); 6.95 (m, 2 H, Ph);
7.12—7.30 (m, 3 H, Ph); 7.40—7.50 (m, 2 H, Ph); 7.88 (d, 1 H,
CH=, J = 13 Hz); 9.17 (br.s, 1 H, NH).
References
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1ꢀCyclohexylꢀ5ꢀcyclohexylaminoꢀ4ꢀ[3ꢀ(dimethylamiꢀ
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and CH); 3.95—4.12 (m, 1 H, CH); 6.10 (d, 1 H, CH=, J =
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1ꢀPhenylꢀ5ꢀphenylaminoꢀ4ꢀ(pyrazolꢀ5ꢀyl)ꢀ1,2,3ꢀtriazole (7).
A mixture of triazole 5 (0.167 g, 0.5 mmol) and hydrazine hydrate
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solvent and an excess of hydrazine were removed in vacuo

680
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
Dorokhov and Komkov
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Received February 4, 2004;
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