Condensation of chloromethyl propargyl ether with nitriles

Article abstract of DOI:10.1134/S1070428017020269

Reactions of aromatic and aliphatic nitriles with chloromethyl propargyl ether in the presence of activated zinc followed by treatment with water in the presence of H₃PMo₁₂O₄₀ afforded β-oxoethers.

Full text of DOI:10.1134/S1070428017020269

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 2, pp. 296–298. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © G.M. Talybov, 2017, published in Zhurnal Organicheskoi Khimii, 2017, Vol. 53, No. 2, pp. 295–296.
SHORT
COMMUNICATIONS
Condensation of Chloromethyl Propargyl Ether with Nitriles
G. M. Talybov
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
pr. Khodzhaly 30, Baku, AZ 1025 Azerbaijan
e-mail: ahmed_adna@rambler.ru
Received July 29, 2016
Abstract—Reactions of aromatic and aliphatic nitriles with chloromethyl propargyl ether in the presence of
activated zinc followed by treatment with water in the presence of H PMo12O40 afforded β-oxoethers.
3
DOI: 10.1134/S1070428017020269
One of important methods of building up a С–С
bond is Blaise reaction [1] that up till now is widely
used in the synthesis of various organic compounds
the formation of side products [2, 4]. In the course of
the reaction chloromethyl propargyl ether adds to the
cyano group forming an intermediate organozinc
compound [6–9]. Both aliphatic and aromatic nitriles
enter this reaction.
[2–9]. The reaction consists in the interaction of
nitriles with esters of haloorganic acids in the presence
of zinc to obtain the corresponding β-ketoesters.
The structure of synthesized ketoethers 1–6 was
confirmed by spectral methods.
We studied for the first time the reaction of organic
nitriles with α-haloether (chloromethyl propargyl
ether) on activated zinc with subsequent treatment with
water in the presence of phosphomolybdic heteropo-
lyacid H PMo O of Keggin structure resulting in the
formation of ketoethers 1–6. Applying the asymmetric
reduction they can be used in the synthesis of chiral β-
oxyethers.
2
-[(Prop-2-yn-1-yl)oxy]-1-phenylethan-1-one(1).
Under inert atmosphere (nitrogen) to 0.1 g of copper
bromide and 9.7 g (0.15 g-atom) of freshly cleaned zinc
foil was charged in a three-neck flask and 300 mL of
dry diglyme was added. Then quickly 10.3 g (0.1 mol)
of benzonitrile and 20.8 g (0.2 mol) of chloromethyl
propargyl ether were charged in the flask. The reaction
mixture was boiled for 45 min, then cooled for 15 min
with an ice bath, 0.018 g (0.01 mol) of H PMo O
was added, and the mixture was stirred for 45 min at
room temperature. After separating the layers the water
layer was diluted with water and extracted with
diglyme. The combined organic solutions were washed
with water, with saturated solution of sodium
hydrogen carbonate, and again with water. The extract
was dried with sodium sulfate, the solvent was
removed, the residue was distilled in a vacuum. Yield
3
12 40
The reaction proceeding in a nitrogen atmosphere
excludes the hydrolysis of α-haloether, which easily
suffers decomposition by moist air, and the high yields
3
12 40
(
up to 68%) of target compounds 1–6 are attained at
elevated temperature, in particular, by using diglyme
as solvent.
As known, the first stage of Blaise reaction is the
formation on the zinc surface of Reformatsky reagent
in the form of a solvate complex, same as in the case
of α-halosubstituted esters [10, 11]. This complex is
surrounded with a dense solvate shell thus impeding
20
20
10.5 g (61%), bp 86–88°С (2 mmHg), d4 1.007, nD
–
1
1.5141, MR 52.04, calc. 51.36. IR spectrum, ν, cm :
D
NaHCO3,
Zn, Δ
R
H PMo12O40
R
3
RC N + Cl
O
O
O
Diglyme
H O
2
NZnCl
O
1_
6
R = Ph (1), 4-MeС
6
H
4
(2), 3-MeС
6
H
4
6 4 5 8
(3), 2-MeС H (4), C H11 (5), C H17 (6).
2
96

CONDENSATION OF CHLOROMETHYL PROPARGYL ETHER WITH NITRILES
297
3
9
289, 2110 (С≡СH), 3083, 3064, 3029, 1601, 1488,
(≡СCH O), 89.0 (OCH ), 125.0 (CHarom), 126.8
(2CHarom), 127.9 (2CHarom), 128.9 (CHarom), 205.13
2
2
1
85, 700, 770 (Ph), 1725 (C=O), 1100 (С–О–С). Н
4
NMR spectrum, δ, ppm: 2.65 t (1Н, ≡СН, J 2 Hz),
(С=О). Found, %: С 76.82; Н 6.82. С Н О .
1
2
12
2
4
4
7
5
.14 s (2Н, COCH O), 4.25 d (2Н, ОСН С≡, J 2 Hz),
Calculated, %: C 76.57; H 6.43.
-[(Prop-2-yn-1-yl)oxy]heptan-1-one (5) was
obtained from hexanenitrile. Yield 68%, bp 65–66°С
2
2
1
3
.25–7.45 m (5H, Ph). С NMR spectrum, δ, ppm:
6.0 (≡СCH O), 69.0 (≡СH), 75.0 (≡СCH O), 88.0
1
2
2
(OCH CO), 126.0 (CHarom), 126.8 (2CHarom), 126.9
20
20
2
(
2 mmHg), d4 0.6608, nD 1.4089, MR 62.88, calc.
D
(
2CHarom), 129.9 (CHarom), 206.13 (С=О). Found, %: С
–1
6
3
1
2.10. IR spectrum, ν, cm : 3310, 2100 (С≡СН),
085, 3065, 3068, 1682, 1441, 985, 776, 719 (Ph),
727 (С=О), 1110 (С–О–С). Н NMR spectrum, δ,
ppm: 0.91 t (3Н, Me, J 7.5 Hz), 0.98–1.12 m [6Н,
7
5
6.02; Н 5.82. С Н О . Calculated, %: С 75.84; Н
11 10 2
.79.
Compounds 2–6 were obtained similarly.
-(4-Methylphenyl)-2-[(prop-2-yn-1-yl)oxy]ethan-
-one(2) was obtained from p-tolunitrile. Yield 63%,
1
3
4
(
СН ) ], 2.50 t (1Н, ≡СН, J 2 Hz), 3.99 t (2Н, СН О,
2
3
2
1
3
J 6.1 Hz), 4.14 s (2Н, COCH O), 4.16 d (2Н,
2
1
4
13
2
0
20
ОСН
2
С≡, J 2 Hz). С NMR spectrum, δ, ppm: 25.0
bp 92–93°С (2 mmHg), d4 1.095, nD 1.5191, MRD
5
–
1
(CH
3
), 34.0 (СН ), 36.0 (СН ), 38.0 (СН ), 39.0 (СН ),
2
2
2
2
2.14, calc. 51.36. IR spectrum, ν, cm : 3300, 2110
5
3.0 (СН ), 66.0 (СН ), 73.0 (≡С), 79.0 (COCH O),
2
2
2
(
(
С≡СH), 3043, 3074, 3034, 1611, 1498, 975, 710, 760
Ph), 1715 (C=O), 1160 (С–О–С). Н NMR spectrum,
1
81.0 (С≡), 204.0 (С=О), 210.0 (ОСH
2
О). Found, %: С
4
74.19; Н 10.42. С10Н О . Calculated, %: C 71.39; H
16 2
δ, ppm: 2.31 s (3Н, Me), 2.55 t (1Н, ≡СН, J 2 Hz),
4
9.59.
4
7
2
.14 s (2Н, COCH O), 4.08 d (2Н, ОСН С≡, J 2 Hz),
2 2
1
3
.25–7.45 m (4H, Ph). С NMR spectrum, δ, ppm:
1-[(Prop-2-yn-1-yl)oxy]decan-1-one (6) was
obtained from nonanenitrile. Yield 59%, bp 76–78°С
1.0 (Me), 57.0 (≡СCH O), 70.0 (≡СH), 74.0
2
2
0
20
(
≡СCH O), 89.0 (OCH ), 126.0 (CHarom), 126.8
(3 mmHg), d4 0.8720, nD 1.4282, MR 62.08, calc.
2
2
D
–
1
(
2CHarom), 127.9 (2CHarom), 129.9 (CHarom), 206.13
62.10. IR spectrum, ν, cm : 3310, 2110 (С≡СН),
(
С=О). Found, %: С 76.52; Н 5.42. С Н О .
3085, 3065, 3061, 1682, 1441, 985, 776, 719 (Ph),
1
2
12
2
1
Calculated, %: C 76.57; H 6.43.
1715 (С=О), 1120 (С–О–С). Н NMR spectrum, δ,
3
ppm: 0.90 t (3Н, Me, J 7.5 Hz), 0.91–1.16 m [12Н,
1-(2-Methylphenyl)-2-[(prop-2-yn-1-yl)oxy]ethan-
4
(
СН ) ], 2.41 t (1Н, ≡СН, J 2 Hz), 3.89 t (2Н, СН О,
2
6
2
1
-one(3) was obtained from o-tolunitrile. Yield 68%,
3
2
0
20
J 6.1 Hz), 4.14 s (2Н, COCH
ОСН С≡, J 2 Hz). С NMR spectrum, δ, ppm: 25.0
2
O), 4.16 d (2Н,
bp 86–88°С (2 mmHg), d4 1.0978, nD 1.5201, MRD
5
(
(
4
13
–
1
2
2.08, calc. 51.36. IR spectrum, ν, cm : 3310, 2100
(
CH ), 34.0 (СН ), 36.0 (СН ), 38.0 (СН ), 39.0 (СН ),
3
2
2
2
2
С≡СH), 3023, 3064, 3044, 1611, 1498, 975, 710, 758
1
54.0 (СН
2
), 64.0 (СН
2
), 74.0 (≡С), 77.0 (COCH
2
O),
Ph), 1713 (C=O), 1140 (С–О–С). Н NMR spectrum,
4
80.0 (С≡), 206.0 (С=О), 211.0 (ОСH
2
О). Found, %: С
74.09; Н 10.52. С13Н О . Calculated, %: С 74.24; Н
22 2
δ, ppm: 2.30 s (3Н, Me), 2.53 t (1Н, ≡СН, J 2 Hz),
4
4
7
2
(
(
.12 s (2Н, COCH O), 4.11 d (2Н, ОСН С≡, J 2 Hz),
2 2
1
3
10.54.
.21–7.43 m (4H, Ph). С NMR spectrum, δ, ppm:
1.0 (Me), 56.0 (≡СCH O), 69.0 (≡СH), 73.0
IR spectra of compounds 1–6 in tetrachloromethane
were recorded on a spectrophotometer Specord 75 IR.
NMR spectra were registered on a spectrometer Вruker
2
≡СCH O), 87.0 (OCH ), 125.0 (CHarom), 126.8
2 2
2CHarom), 128.9 (2CHarom), 129.9 (CHarom), 210.13
1
13
(
С=О). Found, %: С 76.72; Н 5.92. С Н О .
SF-300 [300.13 ( H), 75 ( C) MHz] in СDСl , internal
1
2
12
2
3
Calculated, %: C 76.57; H 6.43.
reference HMDS.
REFERENCES
1-(3-Methylphenyl)-2-[(prop-2-yn-1-yl)oxy]ethan-
1
-one(4) was obtained from m-tolunitrile. Yield 67%,
2
0
20
bp 97–99°С (2 mmHg), d4 1.1001, nD 1.5211, MRD
1. Blaise, E.E., C. R. Hebd. Seances Acad. Sci., 1901,
–
1
5
2.04, calc. 51.36. IR spectrum, ν, cm : 3300, 2110
vol. 132, p. 478.
(
(
С≡СH), 3033, 3054, 3034, 1621, 1498, 975, 710, 760
Ph), 1717 (C=O), 1150 (С–О–С). Н NMR spectrum,
2
. Lee, J.H., Choi, B.S., Chang, J.H., Lee, H.B.,
Yoon, J.-Y., Lee, J., and Shin, H., J. Org. Chem., 2007,
vol. 72, p. 10261. doi 10.1021/jo701743m
1
4
δ, ppm: 2.29 s (3Н, Me), 2.55 t (1Н, ≡СН, J 2 Hz),
4
4
7
1
.18 s (2Н, COCH O), 4.10 d (2Н, ОСН С≡, J 2 Hz),
.25–7.45 m (4H, Ph). С NMR spectrum, δ, ppm:
2
2
3. Rao, H.S.P., Rafi, S., and Padmavathy, K.,
Tetrahedron, 2008, vol. 64, p. 8037. doi 10.1016/
j.tet.2008.05.109
1
3
8.0 (Me), 56.0 (≡СH O), 72.0 (≡СH), 74.0
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017

2
98
TALYBOV
4
. Chun, Y.S., Ryu, K.Y., Ko, Y.O., Hong, J.Y., Hong, J.,
8. Sakthivel, K. and Srinivasan, K., J. Org. Chem., 2014,
Shin, H., and Lee, S.-g., J. Org. Chem., 2009, vol. 74,
vol. 79, p. 3244. doi 10.1021/jo500137m
p. 7556. doi 10.1021/jo901642t
9
. Kim, J.H., Choi, S.Y., Bouffard, J., and Lee, S.-g.,
J. Org. Chem., 2014, vol. 79, p. 9253. doi 10.1021/
jo501672c
5
. Hoang, C.T., Bouillère, F., Johannesen, S., Zulauf, A.,
Panel, C., Pouilhès, A., Gori, D., Alezra, V., and
Kouklovsky, C., J. Org. Chem., 2009, vol. 74, p. 4177.
doi 10.1021/jo900324d
. Kim, J.H., Shin, H., and Lee, S.-g., J. Org. Chem., 2012,
vol. 77, p. 1560. doi 10.1021/jo201964a
1
1
0. Zil’berman, E.N., Reaktsii nitrilov (Reactions of
Nitriles), Moscow: Khimiya, 1972.
6
1. Metody elementoorganicheskoi khimii (Methods
of Organoelemental Chemistry), Nesmeyanov, A.N.
and Kocheshkov, K.A., Eds., Moscow: Nauka,
1964.
7
. Kim, J.H., Chun, Y.S., and Lee, S.-g., J. Org. Chem.,
2
013, vol. 78, p. 11483. doi 10.1021/jo402015n
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