gem-dichlorocyclopropanes containing acetylacetone fragment in the side chain

Full text of DOI:10.1134/S1070363216090255

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 9, pp. 2126–2128. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Yu.G. Borisova, G.Z. Raskildina, S.S. Zlotskii, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 9, pp. 1564–1566.
LETTERS
TO THE EDITOR
gem-Dichlorocyclopropanes Containing Acetylacetone Fragment
in The Side Chain
Yu. G. Borisova, G. Z. Raskildina*, and S. S. Zlotskii
Ufa State Petroleum Technical University, ul. Kosmonavtov 1, Ufa, 450062 Russia
*
e-mail: graskildina444@mail.ru
Received April 14, 2016
Keywords: gem-dichlorocyclopropane, 2,4-pentanedione, trans-1,3-dichloropropene, C-alkylation, carbenation
DOI: 10.1134/S1070363216090255
Previously we have described a method for prepara-
tion of substituted malonates and their derivatives by
C-alkylating malonic ester with chloromethyl-gem-
dichlorocyclopropanes [1, 2]. In continuation of these
studies we performed the reactions of chloromethyl-
cyclopropanes 1a–1c with pentane-2,4-dione 2.
O
O
OH
O
H
Practically quantitative output of carbenation of
alkenylketones 5a–5c makes it possible to consider a
method of producing cyclopropane diketones 3a–3c
via intermediate alkylation of CH-acid 2 with the
corresponding olefins 4a–4c more efficient.
Chloromethyl derivatives 1a and 1b reacted with
diketone 2 in the presence of sodium butoxide under
microwave irradiation to form the corresponding
monoadducts 3a and 3b. Compound 1c was found to
be inactive in this reaction (Scheme 1).
Olefin 5c and cyclopropane 3c which are
derivatives of trans-1,3-dichloropropene 4c retain the
trans-configuration. This was indicated by the
presence of the signals of the double bond protons in
the NMR spectrum of compounds 5c appeared at 5.80
Reactivity of unsubstituted (1a) and substituted
(
1b) cyclopropanes in this reaction was virtually
identical (see the table).
3
and 6.06 ppm as doublets of triplets with J = 13.3 Hz,
An alternative way to produce the desired sub-
stituted gem-dichlorocyclopropanes included C-alkyla-
tion of diketone 2 with chloroolefins 4a–4c followed
by dichlorocarbenation of unsaturated monoadducts
whereas the analogous protons in cis-isomer resonated
in a stronger field with the coupling constant J =
3
7.3 Hz [3]. The NMR spectrum of compound 3c had
8
the signal of the proton at C atom of the cyclopropane
5
[
a–5c under phase-transfer catalysis as described in
1]. Thus, olefins 4a and 4b reacted to form the
corresponding mono- (5a, 5b) and bisadducts (6a, 6b)
ring at 3.20 ppm as a doublet with a coupling constant
Scheme 1.
(
Scheme 2, table).
O
O
The bisadduct yields rose with increasing chloro-
R1
olefin activity. Note that in the case of less active trans-
1
O
O
H
R2
,3-dichloropropene 4c the bisadduct was not formed.
R1
ClCH2
+
It should be noted that monosubstituted diketones
a, 3b, 5a–5c are in an equilibrium with enol forms in
Cl
Cl
H
Cl
Cl
3
a ratio of 95 : 5 → 90 : 10, respectively. This was
H
indicated by the integral signal intensity of hydroxyl
1а−1c
2
3а, 3b
(
16.76 ppm) and CH proton (3.72 ppm) adjacent to
1
2
R = H (1а, 3а); CH
Cl (1c).
3
(1b, 3b); R = H (1а, 1b, 3а, 3b);
two keto groups.
2
126

gem-DICHLOROCYCLOPROPANES CONTAINING ACETYLACETONE FRAGMENT
2127
Scheme 2.
R2
R2
H
R2
R1
H
H
R1
ClCH2
H
R1
O
2
+
+
R1
R2
O
O
O
4а−4c
5а−5c
6а, 6b
:CCl2
3
а−3c
1
2
R = H (4а, 4c, 5а, 5c, 6а, 6c); CH
3
(4b, 5b, 6b); R = H (4а, 4b, 5а, 5b, 6а, 6b); Cl (4c, 5c).
3
J = 6.2 Hz. The same proton signal in cis-isomer
3-[(2,2-Dichloro-1-methylcyclopropyl)methyl]-
3
appeared in a weak field (3.57 ppm, J = 8.0 Hz) [3].
pentane-2,4-dione (3b). Yield 70% (a), 95% (b), bp
1
1
1
(
41°C (3 mmHg). H NMR spectrum, δ, ppm (J, Hz):
Synthesis of dichlorocyclopropylacetylacetones
3a–3c). a. A mixture of 0.01 mol (1.0 g) of pentane-
,4-dione, 0.001 mol (0.1 g) of sodium butoxide, 0.01 g
1
0
8
2
.20 s (3Н, С Н ), 1.60 d (2Н, С Н , J = 7.5), 2.40 s
3
2
(
2
1
5
6
6Н, С Н , С Н ), 2.30–2.60 m (2Н, С Н ), 3.55–3.60
3 3 2
3
13
m (1Н, С Н). C NMR spectrum, δ , ppm: 18.19
С
catamine AB, and 60 mL of anhydrous acetonitrile was
under microwave irradiation at constant stirring for
3
1
0
1
5
6
8
(
6
С Н ), 24.80 (С Н , С Н ), 32.58 (С Н , С Н ),
3 3 3 2 2,
3
9
2
4
6.53 (С Н, С Cl ), 191.17 (С =О, С =О). Mass
2
0 min. The mixture was then cooled to room
spectrum, m/e (I , %): 144 (20), 123 (7), 109 (13), 43
rel
temperature and was charged with 0.015 mol of the
corresponding dichlorocyclopropane 1. Next, the
mixture was irradiated with stirring for 4–6 h. After
completion of the reaction (GLC monitoring), the
resulting mixture was cooled to room temperature,
washed with water, and extracted with chloroform.
The organic layer was dried with potassium carbonate
and evaporated. The residue was distilled in a vacuum.
(
100).
3-[(2,2,3-Trichloro-1-methylcyclopropyl)methyl]-
pentane-2,4-dione (3c). Yield 85% (b), bp 149°C
1
(2 mmHg). H NMR spectrum, δ, ppm (J, Hz): 2.05–
7
1
5
2.10 m (1Н, С Н), 2.30 s (6Н, С Н , С Н ), 2.70–2.80
3
3
6
8
3
m (2Н, С Н ), 3.20 d (1Н, С Н J = 6.2), 4.30 d.d (1Н,
2
,
3
3
2
13
С Н, J = 7.5, J = 9.5). C NMR spectrum, δ , ppm:
С
1
5
6
7
8
2
6
4.79 (С Н , С Н ), 30.85 (С Н , С Н), 40.39 (С Н),
3 3 2
b. A mixture of 0.01 mol of the corresponding ester
, 30 mL of chloroform, 32 g of a 50% solution of
3
9
2
4
8.55 (С Н, С Cl ), 191.17 (С =О, С =О). Mass
2
5
spectrum, m/e (I , %): 131 (40), 133 (6), 135 (1), 97
rel
NaOH, and 0.001 mol (0.23 g) of triethylbenzyl-
ammonium chloride was stirred at 0–5°C for 6–9 h
until complete conversion of the substrate. After the
reaction was completed (GLC monitoring) the mixture
was washed with water until neutral. The organic layer
was dried with calcium chloride and evaporated. The
residue was distilled in a vacuum.
(
10), 43 (100).
Synthesis of compounds 5 and 6. A mixture of
.01 mol (1.0 g) of pentane-2,4-dione, 0.001 mol
0
a
Alkylation of pentane-2,4-dione 2
Substrate (А)
Time, h
Adduct (yield, %)
3а (65%)
3
-[(2,2-Dichlorocyclopropyl)methyl]pentane-2,4-
b
1
а
4
dione (3a). Yield 65% (a), 90% (b), bp 139°C
(
С Н), 1.30–1.36 m (2Н, С Н ) 1.60–1.65 m (2Н,
С Н ), 2.40 s (6Н, С Н , С Н ), 3.55–3.60 m (1Н,
С Н). C NMR spectrum, δ , ppm: 24.80 (С Н), 27.11
(
С Cl ), 191.17 (С =О, С =О). Mass spectrum, m/e (I ,
%
1
b
4 mmHg). H NMR spectrum, δ, ppm: 0.90 m (1Н,
1b
4
3b (70%)
7
8
2
4
а
2
5а (75%) 6а (10%)
5b (80%) 6b (20%)
6
1
5
2
3
3
3
13
7
4
b
3
С
6
1
5
8
3
С Н ), 30.78 (С Н , С Н ), 32.15(С Н ), 58.57 (С Н,
1.5
5c (50%)
–
2
3
3
2
4c
9
2
4
a
2
rel
Molar reagents ratio А : 2 : BuONa = 1.5 : 1 : 0.1, acetonitrile,
b
): 143 (10), 130 (40), 109 (10), 111 (4), 113 (1), 95
26), 43 (100).
microwave irradiation. Catalyst catamine AB, 10 wt % relative
(
to diketone 2.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 9 2016

2
128
BORISOVA et al.
7
10
8
11
2
(
0.1 g) of sodium butylate, and 60 mL of anhydrous
acetonitrile was irradiated at constant stirring for
0 min. The mixture was then cooled to room
(С Н, С Н), 133.04 (С Н, С Н), 206.95 (С =О,
4
С =О). Mass spectrum, m/e (I , %): 138 (9), 123 (9),
97 (24), 79 (6), 43 (100).
rel
2
temperature and was charged with 0.015 mol of the
corresponding alkene 4. Next, irradiation was continued
for 2 h to complete conversion of pentane-2,4-dione.
Upon completion of the reaction (GLC monitoring) the
mixture was cooled to room temperature, washed with
water, and extracted with chloroform. The organic
layer was dried with potassium carbonate and
evaporated. The residue was distilled in a vacuum.
3
,3-Bis(2-methyl-2enyl)pentane-2,4-dione (6b).
1
Yield 20%, bp 137°C (3 mmHg). H NMR spectrum,
δ, ppm (J, Hz): 1.60 s (6Н, С Н С Н ), 2.15 s (6Н,
9
13
3
,
3
1
5
6
10
2
С Н , С Н ), 2.80 d (4Н, С Н , С Н , J = 2.0), 4.60–
3
3
2
13
2
8
12
4
.80 m (4Н, С Н , С Н ). C NMR spectrum, δ ,
2 2 С
9
13
1
5
ppm: 24.15 (С Н , С Н ), 27.01 (С Н , С Н ), 38.24
3
3
3
3
6
10
3
8
12
(
(
(
С Н , С Н ), 70.38 (С ), 114.00 (С Н , С Н ), 140.92
2 2 2 2
7
11
2
4
С , С ), 206.81 (С =О, С =О). Mass spectrum, m/e
Irel, %): 112 (17), 98 (20), 85 (45), 43 (100).
2
-Allylpentane-2,4-dione (5a). Yield 75%, bp 81°C
1
(
(
(
10 mmHg). H NMR spectrum, δ, ppm (J, Hz): 2.15 s
6Н, С Н , С Н ), 2.60 t (2Н, С Н , J = 7.2), 3.70 t
1Н, С Н, J = 7.0), 5.00–5.10 m (1Н, С Н), 5.55–5.65
m (1Н, С Н), 5.75–5.85 m (1Н, С Н). C NMR
Chromatographic analysis of the reaction products
1
5
6
3
3
3
2
was performed on a chromatograph HRGS 5300 Mega
Series Carlo Erba equipped with a flame ionization
detector (carrier gas helium, flow rate 30 mL/min,
column length 25 m, ramp 50–280°C, heating rate
3
3
8
8
7
13
1
5
6
spectrum, δ , ppm: 31.08 (С Н , С Н ), 32.13 (С Н ),
С
3
3
2
3
8
7
6
(
[
7.90 (С Н), 117.43 (С Н ), 134.02 (С Н), 203.57
2
8
deg/min, detector temperature 250°C, evaporator
2
4
С =О, С =О). Mass spectrum, m/e (I , %): 140 (1)
rel
temperature 300°C). GC-MS spectra were recorded on
a Fisons (quartz capillary column DB 560, 50 m) and
Focus instrument equipped with Finnigan DSQII mass
spectrometric detector (ion source temperature 200°C,
direct input temperature 50–270°C, heating rate
10 deg/min, column ThermoTR-5MS, 50 × 2.5 × 10 m, a
helium flow rate 0.7 mL/min). Mass spectra were
recorded in an electron impact ionization mode. NMR
spectra were registered on a Bruker AVANCE-400
spectrometer in CDCl3.
+
М] , 98 (13), 97 (20), 83 (11), 43 (100).
3
-(2-Methylprop-2-enyl)pentane-2,4-dione (5b).
1
Yield 80%, bp 91°C (6 mmHg). H NMR spectrum, δ,
ppm (J, Hz): 1.72 s (3Н С Н ), 2.05 s (6Н, С Н ,
9
1
3
3
–4
5
6
3
С Н ), 2.50 d (2Н, С Н , J = 7.5), 3.88–3.92 m (1Н,
3
2
3
8
13
С Н), 4.60–4.80 m (2Н, С Н ). C NMR spectrum,
2
9
1
5
δ , ppm: 24.19 (С Н ), 27.04 (С Н , С Н ), 38.24
С
3
3
3
6
3
8
7
(
2
1
С Н ), 70.38 (С Н), 114.30 (С Н ), 140.92 (С ),
2
2
2
4
06.87 (С =О, С =О). Mass spectrum, m/e (I , %):
12 (13), 97 (20), 85 (10), 43 (100).
rel
ACKNOWLEDGMENTS
3
-(2E)-(3-Chloroprop-2-enyl)pentane-2,4-dione
1
(
5c). Yield 50%, bp 135°C (7 mmHg). H NMR
spectrum, δ, ppm (J, Hz): 2.15–2.20 s (6Н, С Н ,
This work was supported by the Russian Science
Foundation (project no. 15-13-10034) and the President
of the Russian Federation in the framework of the
support program for young scientists and post-graduate
students (SP-1960.2015.4, 2015–2017).
1
3
5
6
3
3
С Н ), 2.60 t (2Н, С Н , J = 7.4), 3.70 t (1Н, С Н,
3
2
7
3
3
3
J = 7.2), 5.80 d.t (1Н, С Н, J = 13.3, J = 7.4), 6.06 t
1Н, С Н, J = 13.3). C NMR spectrum, δ , ppm:
8
3
13
(
2
(
С
1
5
6
3
2.87 (С Н , С Н ), 28.79 (С Н ), 67.33 (С Н), 120.11
3 3 2
7
8
2
4
С Н), 129.18 (С Н), 202.75 (С =О, С =О). Mass
REFERENCES
spectrum, m/e (I , %): 131 (38), 133 (12), 135 (4), 97
rel
1
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no. 1, p. 200. doi 10.1134/S1070363215010351
(15), 43 (100).
Diallylpentane-3,3-2,4-dione (6a). Yield 10%, bp
1
1
2
7
(
(
32°C (3 mmHg). H NMR spectrum, δ, ppm (J, Hz):
2. Borisova, Yu.G., Raskil’dina, G.Z., and Zlotsky, S.S.,
Russ. J. Gen. Chem., 2016, vol. 86, no. 8, p. 1954. doi
10.1134/S1070363216080296
1
5
6
9
3
.05 s (6Н, С Н , С Н ), 2.60 d (4Н, С Н , С Н , J =
.3), 5.10 d.d (4Н, С Н, С Н, J = 9.5), 5.50–5.60 m
С Н, С Н). C NMR spectrum, δ , ppm: 25.70
С Н , С Н ), 35.14 (С Н , С Н ), 63.50 (С ), 117.95
3
3
2
2
7
10
3
7
10
13
3. Shiriazdanova, A.R., Kazakova, A.N., and Zlotsky, S.S.,
С
1
5
6
9
3
Bash. Khim. Zh., 2009, vol. 16, no. 4, p. 102.
3
3
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 9 2016