REACTIONS OF 2-ACYL-1,3-INDANDIONES WITH NITROGEN NUCLEOPHILES

Full text of DOI:10.1135/cccc19942734

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Hrnciar, Svanygova:
REACTIONS OF 2-ACYL-1,3-INDANDIONES WITH NITROGEN
NUCLEOPHILES
Pavel HRNCIAR and Eva SVANYGOVA
Department of Organic Chemistry,
Comenius University, 842 15 Bratislava, The Slovak Republic
Received September 12, 1994
Accepted October 11, 1994
Dedicated to Professor Milan Kratochvil on the occasion of his 70th birthday.
It is known that 2-acyl-1,3-hexanediones react with nitrogen nucleophiles selectively at
carbonyl carbon of acyl group. Many derivatives prepared in this manner showed sig-
nificant herbicide efficiency1–4
.
Reactions of 2-acyl-1,3-indandiones with nitrogen nucleophiles were studied rarely.
The question, if they react with carbonyl carbon of acyl group or indandione skeleton,
has not been answered unambiguously. Vanag et al.5 stated that 2-diphenylacetyl-1,3-
indandione reacted with ammonia at carbonyl carbon of acetyl group. On the contrary,
Braun and Mosher6 pointed out that the same reaction yielded the product of reaction at
carbonyl carbon of indandione skeleton. Similar discrepancy occurred at the course of
reaction with hydrazine5,6. Later, Mosher has changed his opinion by publishing the
conclusion that nitrogen nucleophiles react with carbonyl carbon of acyl group7–10
.
To make clear the question which carbonyl carbon of 2-acyl-1,3-indandiones enters
the reaction with nitrogen nucleophiles we carried out the reactions with 2-acetyl- (Ia),
2-propionyl- (Ib), 2-pivaloyl- (Ic), and 2-benzoyl-1,3-indandione (Id). We used differ-
ent 2-acyl-1,3-indandiones with the aim to find out if the character of acyl group affects
the course of reaction. We used ethoxyamine, primary amines, phenylhydrazine, hydra-
zine and methylhydrazine as nucleophile reactants. The reactions were carried out in
methanol at reflux at 10% excess of nitrogen base. The reactions with phenylhydrazine,
hydrazine and methylhydrazine were performed with twofold excess of nitrogen base.
The separation of reaction products was carried out by chromatography on silica gel.
We found that 2-acyl-1,3-indandiones I react with ethoxyamine both at the acyl-
carbonyl carbon to produce 2-(1-ethoxyiminoalkyl)-1,3-indandiones II and the carbonyl
carbon of indandione skeleton to give rise 3-(ethoxyimino)-2-acyl-1-indanones III. In
all cases, the carbonyl carbon of acyl group was preferred (the observed ratio of products II
to III was 6 – 8 : 1). From the reaction of 2-acyl-1,3-indandiones with primary amines
only the products IV of reaction with the acylcarbonyl carbon were isolated.
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The hydrazines used reacted with 2-acyl-1,3-indandiones also at carbonyl carbon of
acyl group in the first step to produce hydrazones. However, the products isolated in
most cases were formed by the attack of hydrazone nitrogen at carbonyl carbon of
indandione skeleton giving rise to derivatives of indeno[2,3-d]pyrazole-4-one V. It is
interesting that 2-acetyl-1,3-indandione and 2-propionyl-1,3-indandione, reacting with
phenylhydrazine and hydrazine, yielded only corresponding hydrazones VI.
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Hrnciar, Svanygova:
An attempt to convert the hydrazones VI to the indeno[2,3-d]pyrazole-4-ones V by
refluxing in methanol for 12 h failed.
The structure of isolated products was assigned on the basis of elemental analysis,
1H NMR and IR spectra. The structure assignment was supported by comparison of
chemical shift and multiplet shape of starting 2-acyl-1,3-indandione skeleton at enol
acyl group11. Similar arrangement of chemical shifts of aromatic hydrogens have also
products II and IV. This fact sustains our assignment of the structure of these com-
pounds which means that the reactions of 2-acyl-1,3-indandiones with nucleophiles
took place at the acylcarbonyl carbon.
TABLE I
Yields, analytical and spectral data of compounds II and III
Calculated/Found
M.p., °C
Yield, %
Formula
(M.w.)
Compound
1H NMR spectrum
% C
% H % N
IIa
132 – 134 C13H13NO3
62 (231.2)
67.53 5.67
67.46 5.44
6.06 1.33 t, 3 H, J = 6.5 (CH3); 2.60 s,
6.21 3 H (CH3); 4.03, 2 H, J = 7 (CH2);
7.45 – 7.68 m, 4 H (aryl)
IIb
IIc
109 – 111 C14H15NO3
52 (245.2)
68.63 6.12
68.69 6.10
5.71 1.20 – 4.96 m, 6 H (2 × CH3); 3.15 q,
5.93 2 H (CH2); 2.08 q, 2 H (CH2);
7.45 – 7.71 m, 4 H (aryl)
87 – 89 C16H17NO3
38 (273.3)
70.33 6.96
70.25 7.12
5.12 0.55 t, 3 H (CH3); 1.27 s, 9 H (CH3);
5.00 3.71 q, 2 H, J = 7 (CH2);
7.72 – 8.4 m, 4 H (aryl
IId
126 – 128 C18H15NO3
52 (293.3)
97 – 102 C13H13NO3
16 (231.2)
73.72 5.12
73.85 4.90
4.80 0.75 t, 3 H, (CH3); 4.17 q, 2 H, J = 7
4.90 (CH2); 7.26 – 7.95 m, 9 H (aryl)
IIIa
67.53 5.62
67.28 5.90
6.06 1.31 t, 3 H, J = 6.5 (CH3); 1.43 s, 3 H
6.32 (CH3); 4.31 2 H, J = 7 (CH2);
7.25 – 7.83 m, 4 H (aryl)
IIIb
IIIc
IIId
65 – 68 C14H15NO3
12 (245.2)
68.63 6.12
68.36 6.43
5.71 1.41 – 1.52 m, 6 H (2 × CH3); 2.92 q,
5.72 2 H (CH2); 4.31 q, 2 H (CH2);
7.52 – 8.24 m, 4 H (aryl)
19 – 26 C16H17NO3
traces (273.3)
70.33 6.96
78.51 6.68
5.12 0.48 t, 3 H (CH3); 1.41 s, 9 H
4.68 (2 × CH3); 3.71 q, 2 H, J = 7 (CH2);
7.72 – 8.4 m, 4 H (aryl)
87 – 93 C18H15NO3
12 (293.3)
73.72 5.12
73.56 4.73
4.80 1.14 t, 3 H (CH3); 3.5 q, 2 H, J = 6.2
4.60 (CH2); 7.49 – 8.28 m, 9 H (aryl)
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The multiplet of aromatic hydrogens has the symmetrical arrangement similarly to
starting 2-acyl-1,3-indandiones. It means that the symmetrical substitution of aromatic
part of indane skeleton remained preserved. On the other hand, the symmetry of sub-
stitution on the aromatic part of indane skeleton was affected by reaction of nitrogen
nucleophile with carbonyl carbon of indandione skeleton. The arrangement of multi-
plets of aromatic indane protons of pyrazoles V was also changed.
TABLE II
Yields, analytical and spectral data of compounds IV
Calculated/Found
M.p., °C
Yield, %
Formula
(M.w.)
Compound
1H NMR spectrum
% C % H % N
IVa
149 – 150 C14H15NO2 73.36 6.55 6.11 1.32 t, 3 H (CH3); 2.82 s, 3 H (CH3);
71
(229.2)
73.12 6.45 6.43 3.62 q, 2 H, J = 6.5 (CH2); 7.41 – 7.73 m,
4 H (aryl)
IVb
IVc
IVd
157 – 159 C14H15NO2 73.36 6.55 6.11 0.81 t, 3 H (CH3); 1.21 q, 6 H, J = 3.5
63
(229.2)
73.71 6.50 6.00 (2 × CH3); 2.91 s, 3 H (CH3); 3.51 q,
J = 6.8 (CH2); 7.43 – 7.71 m, 4 H (aryl)
169 – 171 C15H17NO2 74.01 6.99 5.76 0.79 t, 3 H (CH3); 1.46 – 1.91 m, 4 H
68
(243.2)
73.92 7.12 5.63 (CH2); 3.46 q, 2 H, J = 7 (CH2);
7.48 – 7.81 m, 4 H (aryl)
74 – 75 C15H17NO2 74.07 6.99 5.76 0.79 – 1.24 m, 6 H (2 × CH3);
62
(243.2)
74.14 6.83 5.93 1.34 – 1.86 m (aryl); 2 H (CH2); 3.05 q,
2 H, J = 7 (CH2); 3.4 q, 2 H, J = 7 (CH2);
7.51 – 7.90 m (aryl)
IVe
63 – 65 C15H17NO2 74.07 6.99 5.76 0.81 t, 3 H, 1.80, 3 H (2 × CH3); 1.23, 3 H
60
(243.2)
74.10 6.81 5.93 (CH3); 2.77 q, 2 H, J = 7 (CH2);
3.29 – 3.47 m, 1 H (CH); 7.37 – 7.51 m,
4 H (aryl); 8.1 s, 1 H (OH)
IVf
137 – 139 C18H15NO2 77.98 5.42 5.13 0.92 t, 3 H (CH3); 3.62 q, 2 H, J = 7
71 (277.3) 77.90 5.63 5.25 (CH2); 7.43 – 7.95 m, 9 H (aryl)
174 –175 C17H21NO2 75.30 7.83 5.21 0.9 t, 3 H (CH3); 1.49 m, 9 H (CH3);
IVg
63
(271.3)
75.40 7.61 4.92 1.68 – 1.86 m, 3 H (CH3); 3.41 q, 2 H,
J = 7 (CH2); 7.45 – 7.72 m, 4 H (aryl)
IVh
170 – 172 C19H17NO2 78.31 5.81 4.81 1.28 s, 3 H, 1.31 s, 3 H (CH3); 3.22 –3.47 m,
(291.4) 78.49 5.78 4.93 1 H (CH); 7.32 – 7.64 m, 9 H (aryl)
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The structure of products of nucleophilic substitution of 2-acyl-1,3-indandiones was
further confirmed by IR study of their spectra in the range of symmetrical and asymme-
trical vibration of β-dicarbonyl part of indandione skeleton. Within the range of valence
C=O vibrations, the compounds prepared have absorption bands. On the basis of
our previous experience12–14, we are able to find out if these compounds have the
coupled indandione cyclic β-dicarbonyl skeleton (the validity of equation νs(CO) =
0.78 νas(CO) + 412.8 needed). Such a relationship between νs and νas was found only
for compounds II and IV and not for the compounds III and V.
TABLE III
Yields, analytical and spectral data of compounds V
Calculated/Found
M.p., °C
Yield, %
Formula
(M.w.)
Compound
1H NMR spectrum
% C % H % N
Va
Vb
139 – 142 C12H10N2O
43 (198.1)
72.73 5.05 14.14 2.33 s, 3 H (CH3); 3.95 s, 3 H (CH3);
72.76 5.01 13.90 7.18 – 7.59 m, 4 H (aryl)
81 – 82 C13H12N2O
51 (212.2)
73.58 5.66 13.20 1.35 t, 3 H (CH); 2.68 q, 2 H (CH);
73.57 5.68 13.21 3.93 s, 3 H (CH3); 7.2 – 7.4 m,
4 H (aryl)
Vc
Vd
Ve
Vf
195 – 198 C14H14N2O
46 (226.2)
74.34 6.19 12.39 1.39 s, 9 H (CH3); 7.23 – 7.69 m,
74.16 6.31 12.13 4 H (aryl)
147 – 148 C15H16N2O
32 (240.2)
75.00 6.67 11.67 1.37 s, 9 H (3 × CH3); 3.95 s, 3 H
75.11 6.66 11.64 (CH3); 7.32 – 7.71 m, 4 H (aryl)
145 – 148 C20H18N2O
43 (302.3)
79.47 5.96 9.27 1.44 s, 9 H (3 × CH3); 7.11 – 7.71 m,
79.51 5.85 9.25 9 H (aryl)
265 – 267 C16H10N2O
43 (246.3)
78.04 4.05 11.38 7.48 – 8.3 m, 9 H (aryl)
77.76 3.96 11.35
Vg
Vh
195 –198 C17H12N2O
42 (260.3)
78.46 4.62 10.77 4.04 s, 3 H (CH3); 7.23 – 7.32 m,
78.58 4.68 10.74 9 H (aryl)
206 – 208 C22H14N2O
43 (322.4)
81.99 3.73 8.69 7.43 – 8.40 m, 14 H (aryl)
82.10 3.71 8.58
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EXPERIMENTAL
1
The H NMR spectra of CDCl3 solutions (δ, ppm; J, Hz) were measured at 80 MHz TESLA E S 587
instrument, the IR spectra of chloroform solutions were recorded with Spectra 75 JR (Zeiss, Jena)
apparatus. Starting materials (2-acyl-1,3-indandiones Ia – Id) were prepared according to the de-
scribed procedure15.
2-(1-Ethoxyiminoalkyl)-1,3-indandiones IIa – IId and 3-Ethoxyimino-2-acyl-1-indanones IIIa – IIId
2-Acyl-1,3-indandione (0.01 mol) and ethoxyamine (0.012 mol) were heated in methanol (100 ml) at
30 °C (at reflux in the case of 2-pivaloyl-1,3-indandione) for 5 h. The solvent was evaporated, the
residue dissolved in a small volume of chloroform and the reaction mixture was separated chromato-
graphically on silica gel (elution with heptane–chloroform 10 : 1), the compounds IIa – IId were
eluted as first. The analytical data of prepared compounds are summarized in Table I.
2-(1-N-R2-Iminoalkyl)-1,3-indandiones IV
2-Acyl-1,3-indandione (0.01 mol) and primary amine (0.012 mol) were heated in methanol at reflux
for 3 h. Methanol was evaporated and the crude product dissolved in a small volume of chloroform
and purified by chromatography on silica gel (elution with heptan–chloroform 5 : 1). The analytical
data of compounds IV are summarized in Table II.
1-R3-3-R1-Indano[2,3-d]pyrazol-4-ones V
2-Acyl-1,3-indandione (0.01 mol) and the corresponding hydrazine (0.012 mol) was stirred in 100 ml
of methanol at 30 °C for 4 h. The solvent was evaporated and the crude product was purified by
TABLE IV
Yields, analytical and spectral data of compounds VI
Calculated/Found
M.p., °C
Yield, %
Formula
(M.w.)
Compound
1H NMR spectrum
% C
% H % N
VIa
VIb
VIc
237 – 239 C11H10N2O2 65.35 4.95 13.86 1.33 t, 3 H (CH3); 4.12 s, 2 H (NH);
65 (202.3) 65.32 5.05 13.79 7.41 – 7.62 m, 4 H (aryl)
186 – 189 C17H14N2O2 73.38 5.04 10.07 1.39 t, 3 H (CH3); 4.36 s, 1 H (NH);
61 (278.4) 73.43 5.12 9.93 6.52 – 7.69 m, 9 H (aryl)
210 – 212 C12H12N2O2 66.67 5.55 12.96 1.12 t, 3 H (CH3); 3.72 q, 2 H (CH2);
53
(216.3)
66.58 5.41 13.10 4.81 s, 1 H (NH); 7.42 – 7.62 m,
4 H (aryl)
VId
159 – 162 C18H16N2O2 73.97 5.48
51 (292.4) 74.13 5.36
9.59 1.21 t, 3 H (CH3); 3.83 q, 2 H (CH2);
9.48 6.58 – 7.65 m, 9 H (aryl)
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Hrnciar, Svanygova:
chromatography on silica gel (elution with heptane–chloroform 8 : 1). The analytical data of com-
pounds V are summarized in Table III.
The reaction conditions used for the reaction of 2-acetyl- and 2-propionyl-1,3-indandiones with
hydrazine and/or phenylhydrazine yielded the corresponding hydrazones VI. Their analytical data are
summarized in Table IV.
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