New convenient method for preparation of amides of 1-adamantylthioacetic acids

Article abstract of DOI:10.1134/S107042801108015X

The reaction of 4-(1-adamantyl)-1,2,3-thiadiazole with potassium tert-butylate followed by treating with acetyl chloride and amine results in the formation of 1-adamantylthioacetic acid amides in moderate or good yields.

Full text of DOI:10.1134/S107042801108015X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1209−1213. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.A. Shchipalkin, M.L. Petrov, V.A. Kuznetsov, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8, pp. 1191−1195.
New Convenient Method for Preparation of Amides
of 1-Adamantylthioacetic Acids
A. A. Shchipalkin, M. L. Petrov, and V. A. Kuznetsov
St. Petersburg State Technological Institute, St. Petersburg,190013 Russia
e-mail: mlpetrov@lti-gti.ru
Received December 28, 2010
Abstract—The reaction of 4-(1-adamantyl)-1,2,3-thiadiazole with potassium tert-butylate followed by treating with
acetyl chloride and amine results in the formation of 1-adamantylthioacetic acid amides in moderate or good yields.
DOI: 10.1134/S107042801108015X
Amides of 1-adamantylthioacetic acids are known
to exhibit the antiviral activity [1, 2]. However only
three 1-adamantylthioacetamides are known, and they
all have been obtained by different methods: 1-Ada-
mantylthioacetamide has been prepared by treating with
hydrogen sulfide of 1-adamantylacetonitile [1], 1-ada-
mantylthioacetic acid piperidylamide, by the reaction of
1-adamantylacetic acid piperidylamide with Lawesson’s
reagent [3], 1-adamantylthioacetic morpholinamide, by
the reaction of acetylthiomorpholide anion with 1-iodoa-
damantane [4].
easily available 4-(1-adamantyl)-1,2,3-thiadiazole syn-
thesized from commercial 1-adamantyl methyl ketone
through the formation of the corresponding ethoxycar-
bonylhydrazone followed by the treatment with thionyl
chloride [5].
4-(1-Adamantyl)-1,2,3-thiadiazole (I) under the ac-
tion of the strong base like potassium tert-butylate in
anhydrous THF readily decomposed with nitrogen lib-
eration and the formation of potassium 2-(1-adamantyl)
ethynethiolate (II) [5].At further treatment of the reaction
mixture with excess secondary amine we obtained the
corresponding 1-adamantylthioacetic acid dialkylamides
Va–Vd [6]. The presumed intermediate compound in this
We recently developed a method of preparation of
1-adamantylthioacetic acids dialkylamides from the
Scheme 1.
NR1R2 = (CH2CH2)2NPh (a), (CH2CH2)2O (b), (CH2Ph)2 (c), (CH2CH2)2CH2 (d).
1209

SHCHIPALKIN et al.
1210
13C nuclei are present belonging to groups NR1R2. This is
process was 1-adamantylthioketene (IV).
due to the lack of the free rotation around the C(S)–NR1R2
bond that is characteristic of thioamides [8] and appears
in the 1H NMR spectra [9]. For instance, in the spectrum
of amide of 1-adamantylthioacetic acid Vj the protons
of the group C(S)NH2 were observed as two singlets
[δ 8.83 + 9.26 ppm]. In the spectrum of 1-ada-
mantylthioacetic acid morpholinamide (Vb) the proton
signal of the C(S)NCH2 group gave rise to two multiplets
[δ 3.82 + 4.26 ppm], and signals of 13C nuclei of the
same NCH2 group, to two singlets [δ 49.58 + 51.27 ppm].
In the spectrum of 1-adamantylthioacetic acid diben-
zylamide (Vc) the proton signal of the C(S)NCH2 group
appeared as two singlets [δ 4.82 + 5.23 ppm], and
signals of 13C nuclei of the same NCH2 group, as two
singlets [δ 54.79 + 55.25 ppm].
The attempts to carry out this reaction with primary
amines, aromatic amines, and ammonia failed. The main
reaction product under these conditions after the final
treatment of the reaction mixture with water was the
protonation product of the potassium 2-(1-adamantyl)
ethynethiolate (II), 2-(1-adamantyl)methylene-4-(1-
adamantyl)-2H-1,3-dithiol (VI) [7].
The mass spectra of thioamides Va–Vl contained
sufficiently intense peaks of the molecular ions. The
isotopic composition of these molecular ions was in
agreement with the calculations. Further fragmenta-
tion of the molecular ions also confirms the structure of
obtained thioamides Va–Vl. The main direction of the
fragmentation of the molecular ions of thioamides Va–Vl
is the rupture of the Ad–CH2C(S)NR1R2 bond with the
formation of a stable adamantyl ion [Ad]+ of m/z 135 and
of high intensity as is characteristic of the mass spectra
of adamantine derivatives [10].
We developed a new convenient method of the
preparation of 1-adamantylthioacetamides from the
4-(1-adamantyl)-1,2,3-thiadiazole.After the decomposi-
tion of 4-(1-adamantyl)-1,2,3-thiadiazole (I) by treating
with potassium tert-butylate in anhydrous THF to the
obtained potassium 2-(1-adamantyl)ethynethiolate (II)
acetyl chloride was added, and further treatment with
excess amine led to the formation of 2-(1-adamantyl)
thioacetamides Va–Vl. The presumed intermediate com-
pound in this process was 1-(1-adamantyl)-2-acetylsul-
fanylacetylene (VII).
Thus we developed a new simple method for prepa-
ration of 1-adamantylthioacetamides independent of the
amine nature and did not requiring the isolation of the
intermediate products.
The structure of thioamides Va–Vl was proved by 1H,
13C NMR, and mass spectra and by comparison with the
EXPERIMENTAL
1
known published data. In the H, 13C NMR spectra of
thioamides Va–Vl with R1=R2 alongside the characteristic
Melting points were measured on a Boёtius heating
block. 1H and 13C NMR spectra were registered on a spec-
trometer Bruker AMX-400 (400 and 100 MHz respec-
13
signals of protons and C nuclei of the adamantyl and
CH2C(S)N moieties the doubled signals of protons and
Scheme 2.
S
NHR1R2
R1
O
CH3COCl
N
R2
S
II
_CH3CONHR1R2
VII
Vа_Vl
NR1R2 = (CH2CH2)2NPh (a), (CH2CH2)2O (b), (CH2Ph)2 (c); H, CH(CH2)2 (d); H, CH(CH3)2 (e); H, CH2CH=CH2
(f); H, CH2CH2OH (g); H, Ph (h); H, CH2Ph (i); H2 (j); (CH2CH2)2NCH3 (k); (CH2CH2)2CH2CH3 (l).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

NEW CONVENIENT METHOD FOR PREPARATION OF AMIDES
1211
tively), as internal references served the residual protons
(1H) and carbon nuclei (13C) of deuterated solvents. Mass
spectra were measured on a mass spectrometer Finnigan
INCOS 50 with a direct admission of the sample into the
ion source, the energy of ionizing electrons 70 eV, the
temperature of the ionizing chamber 200°C. The reaction
progress was monitored by TLC on Silica Gel 60 F254
plates, development under UV irradiation and in iodine
vapor. All reaction products were chromatographically
pure (eluents chloroform–hexane, 1 : 1; ethyl acetate–hex-
ane, 1 : 10). All solvents used in the study were purified
and dried by standard procedures.
(DMSO-d6), δ, ppm: 1.64 m (12HAd), 1.94 m (3HAd),
2.76 s (2H, CH2CS), 3.61 m, 3.66 m (4H, CSNCH2CH2),
3.82 m, 4.26 m (4H, CSNCH2). 13C NMR spectrum
(DMSO-d6), δ, ppm: 28.03 (CHAd), 34.23 (C1Ad), 36.29,
42.32 (CH2Ad); 49.58, 51.27 (CH2N), 54.70 (CH2CS),
65.94 (CH2O), 198.82 (CS). Mass spectrum, m/z (Irel, %):
279 (43) [M]+, 278 (42) [M – H]+, 246 (12) [M – H – S]+,
192 (9) [M – H – N(CH2CH2)2O]+, 144 (92) [M – Ad]+,
135 (70) [Ad]+, 110 (31), 86 (77), 67 (31), 55 (44), 41
(100). Mcalc 279.44.
1-Adamantylthioacetic acid dibenzylamide (Vc)
was obtained from 1 g (4.5 mmol) of thiadiazole I,
0.55 g (4.7 mmol) of potassium tert-butylate, 0.42 g
(5.4 mmol) of acetyl chloride, and 8.87 g
(45 mmol) of dibenzylamine. Yield 1.7 g (70%).
Colorless crystals, mp 151–152°C [6]. 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.71 m (12HAd), 1.93 m (3HAd),
2.83 s (2H, CH2CS), 4.82 c, 5.23 c (4H, CSNCH2), 7.13 d
1-Adamantylthioacetic acid N-phenylpiperazin-
amide (Va). To a solution of 1.5 g (6.8 mmol) of thia-
diazole I in 25 ml of anhydrous THF was added 0.83 g
(7.4 mmol) of potassium tert-butylate under argon at room
temperature. The reaction mixture was stirred for 5 min
till the end of gas liberation; therewith from the reaction
mixture potassium thiolate II precipitated. Then a solu-
tion was added of 0.64 g (8.2 mmol) of acetyl chloride
in 15 ml of anhydrous THF. The reaction mixture was
kept for 10 min, cooled to 0°C, and a solution was added
of 11.03 g (68 mmol) of N-phenylpiperazine n 15 ml of
anhydrous THF. The reaction mixture was stirred for 5 h,
poured into 150 ml of water, extracted with chloroform
(3Ч15 ml). The combined extracts were dried with anhy-
drous sodium sulfate, filtered, boiled with activated car-
bon, filtered, and evaporated. The residue was recrystal-
lized from ethanol. Yield 1.5 g (62%). Colorless crystals,
5
(2H, HP h), 7.37 d (2H, HP h), 7.33 m (6H, H3Ph, H4Ph, HPh).
13C NMR spectrum (DMSO-d6), δ, ppm: 28.43 (CHAd),
34.95 (C1Ad), 36.43, 42.61 (CH2Ad), 54.79, 55.25 (CH2N),
55.87 (CH2CS), 126.64 (C4Ph), 127.61, 127.82, 127.98
(C2, C4Ph), 128.58, 129.03 (C3, C5Ph), 135.86, 136.41 (C1Ph),
202.15 (CS). Mass spectrum, m/z (Irel, %): 389 (8) [M]+,
298 (8) [M – Bn]+, 135 (47) [Ad]+, 106 (20), 91 (100)
[Bn]+, 79 (21), 65 (22). Mcalc 389.6.
2
6
1-Adamantylthioacetic acid cyclopropylamide (Vd)
was obtained from 1 г (4.5 mmol) of thiadiazole I, 0.55 g
(4.9 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
of acetyl chloride, 2.5 g (4.5 mmol) of cyclopropylamine,
10 min after amine addition the reaction mixture was
diluted with 100 ml of water, extracted with chloroform
(3 × 15 ml), the extract was evaporated, the reaction
product was crystallized from 80% aqueous ethanol.
Yield 0.5 g (49%). Colorless crystals, mp 131–132°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 0.57 m (2H, CH2,
cyclopropyl), 0.73 m (2H, CH2, cyclopropyl), 1.56 m
(12HAd), 1.65 m (1H, CH, cyclopropyl), 1.89 m (3HAd),
2.34 s (2H, CH2CS), 9.45 s (NH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 5.82 (cyclopropyl), 28.33 (CHAd),
33.06 (C1Ad); 36.33, 41.93 (CH2Ad), 59.12 (CH2CS),
200.35 (CS). Mass spectrum, m/z (Irel, %): 249 (16) [M]+,
234 (22) [M – CH2]+, 207 (15) [M – cyclopropyl]+, 174
(5) [M – cyclopropyl – S]+, 135 (69) [Ad]+, 114 (23),
93 (31), 79 (51), 55 (24), 41 (100). Found, %: C 74.37,
74.53; H 8.89, 9.12. C15H23NS. Calculated, %: C 72.24;
H 9.29. M 249.4.
1
mp 152–153°C [6]. H NMR spectrum (DMSO-d6), δ,
ppm: 1.62 m (12HAd), 1.94 m (3HAd), 2.10 s (2H, CH2CS),
3.10 m (4H, CSNCH2CH2), 3.62 m (4H, CSNCH2), 6.77
t (H4Ph, J 7.6 Hz), 6.89 d (H2, H6Ph, J 10.8 Hz ), 7.18 t
(H3, H5Ph, J 8 Hz). 13C NMR spectrum (CDCl3), δ, ppm:
28.53 (CHAd), 34.34 (C1Ad), 36.40, 42.96 (CH2 Ad),
48.26, 49.46 (CH2NPh), 49.18, 50.42 (CH2NCS), 55.94
(CH2CS), 115.95 (C2, C6Ph), 120.21(C4Ph), 128.99 (C3,
C5Ph), 149.94 (C1Ph), 200.08 (CS). Mass spectrum, m/z
(Irel, %): 354 (18) [M]+, 321 (7) [M – H – S]+, 235 (11),
219 (37) [M – Ad]+, 135 (14) [Ad]+, 132 (100), 120 (25),
104 (27), 91 (21), 77 (28), 56 (11), 41 (13). Mcalc 354.55.
Compounds Vb–Vl were similarly prepared.
1-Adamantylthioacetic acid morpholinamide (Vb)
was obtained from 1 g (4.5 mmol) of thiadiazole I, 0.55 g
(4.7 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
of acetyl chloride, and 3.9 g (45 mmol) of morpholine.
Yield 0.7 g (48%). Colorless fine needle crystals, mp
1
147–148°C (mp 148–149°C [4]). H NMR spectrum
1-Adamantylthioacetic acid isopropylamide (Ve)
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SHCHIPALKIN et al.
1212
was obtained from 1 g (4.5 mmol) of thiadiazole I, 0.55 g
(4.9 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
of acetyl chloride, and 2.48 g (4.5 mmol) of isopropyl-
amine, 10 min after amine addition the reaction mixture
was diluted with 100 ml of water, extracted with chloro-
form (3 × 15 ml), dried with anhydrous sodium sulfate, the
extract was evaporated, the residue was chromatographed
on a column with silica gel (3 × 20 cm) eluting in suc-
cession with mixtures chloroform–hexane, 1 : 10, and
chloroform–hexane, 1 : 1. Yield 0.5 g (44%). Colorless
36.41, 42.39 (CH2Ad), 47.96 (CH2OH), 60.07 (CH2CS),
61.67 (CH2NH), 201.71 (CS). Mass spectrum, m/z (Irel,
%): 253 (19) [M]+, 235 (8) [M – OH]+, 220 (12) [M – S]+,
208 (6) [M – (CH2)2OH]+, 176 (5) [M – (CH2)2OH – S]+,
135 (100) [Ad]+, 117 (7), 107 (14), 91 (47), 79 (56), 55
(29), 41 (78). Found, %: C 65.87, 66.19; H 9.05, 9.39.
C14H23NOS. Calculated, %: C 66.36; H 9.15. M 253.4.
1-Adamantylthioacetic acid phenylamide (Vh) was
obtained from 1 g (4.5 mmol) of thiadiazole I, 0.55 g
(4.9 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
of acetyl chloride, and 4.19 g (4.5 mmol) of aniline.
Yield 0.35 g (27%). Colorless crystals, mp 147– 148°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.68 m (12HAd),
1.96 m (3HAd), 2.59 s (2H, CH2), 7.16 t (H4Ph, J 5.7 Hz),
7.33 d (H3Ph, H5Ph, J 7.1 Hz), 7.74 d (H2Ph, H6Ph, J 7 Hz),
11.01 s (NH). 13C NMR spectrum (DMSO-d6), δ, ppm:
28.16 (CHAd), 33.62 (C1Ad), 36.36, 41.92 (CH2Ad), 61.22
(CH2CS), 123.15 (C2Ph, C6Ph), 125.19 (C4Ph), 127.76
(C3Ph, C5Ph), 139.43 (C1Ph), 199.49 (CS). Mass spectrum,
m/z (Irel, %): 285 (40) [M]+, 252 (100) [M – SH]+, 135 (53)
[Ad]+, 109 (8), 93 (22), 77 (31), 55 (11), 41 (20). Found,
%: C 75.47, 75.69; H 8.14, 8.37. C18H23NS. Calculated,
%: C 75.74; H 8.12. M 285.4.
1
crystals, mp 110–111°C. H NMR spectrum (CDCl3),
δ, ppm: 1.20 m (3H, CH3, J 5.3 Hz), 1.59 m (12HAd),
1.92 m (3HAd), 2.44 s (2H, CH2CS), 4.59 m (1H, CH,
J 5.1 Hz), 7.01 s (NH). 13C NMR spectrum (CDCl3), δ,
ppm: 21.12 (CH3), 28.39 (CHAd), 33.37 (C1Ad), 36.39,
42.41 (CH2Ad), 47.18 (CH), 61.93 (CH2CS), 199.30 (CS).
Mass spectrum, m/z (Irel, %): 251 (54) [M]+, 250 (58)
[M – H]+, 218 (31) [M – S]+, 208 (9) [M – (CH3)2CH]+,
176 (92) [M – (CH3)2CH – S]+, 135 (100) [Ad]+, 116 (38),
91 (36), 79 (50), 58 (63), 41 (78). Found, %: C 71.43,
71.82; H 9.87, 10.16. C15H25NS. Calculated, %: C 71.66;
H 10.02. M 251.4.
The separation and purification of compounds Vf–Vl
was carried analogously to compound Ve.
1-Adamantylthioacetic acid benzylamide (Vi) was
obtained from 1 g (4.5 mmol) of thiadiazole I, 0.55 g
(4.9 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
acetyl chloride, and 4.8 g (4.5 mmol) of benzylamine.
Yield 0.45 g (34%). Colorless crystals, mp 145–146°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.60 m (12HAd),
1.93 s (3HAd), 2.45 s (2H, CH2CS), 4.71 d (2H, CH2N,
J 5.3 Hz), 7.30 m (5H, Ph), 9.91 s (NH). 13C NMR spec-
trum (DMSO-d6), δ, ppm: 28.10 (CHAd), 33.08 (C1Ad),
36.37, 42.41 (CH2Ad), 49.89 (CH2Ph), 61.52 (CH2CS),
127.51 (C4Ph), 128.11 (C2Ph, C6Ph), 128.11 (C3Ph, C5Ph),
136.02 (C1Ph), 201.19 (CS). Mass spectrum, m/z (Irel, %):
299 (9) [M]+, 135 (11) [Ad]+, 91 (100) [Bn]+, 79 (19), 65
(13), 55 (8), 41 (13). Found, %: C 76.48, 76.73; H 8.55,
8.72. C19H25NS. Calculated, %: C 76.20; H 8.41. M 299.5.
1-Adamantylthioacetic acid allylamide (Vf) was
obtained from 1 g (4.5 mmol) of thiadiazole I, 0.55 g
(4.9 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
of acetyl chloride, and 2.47 g (0.045 mol) of allylamine.
Yield 0.47 g (41%). Colorless crystals, mp 117–118°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.62 m (12HAd),
1.96 m (3HAd), 2.52 s (2H, CH2), 4.27 t (2H, CH2C=,
J 5 Hz), 5.25 m (2H, CH2), 5.89 m (1H, CH), 7.20 s (NH).
13C NMR spectrum (CDCl3), δ, ppm: 28.40 (CHAd), 33.38
(C1Ad), 36.40, 42.41 (CH2Ad), 48.28 (CH2C=), 61.77
(CH2CS), 118.06 (CH2=), 131.88 (CH=), 201.54 (CS).
Mass spectrum, m/z (Irel, %): 249 (11) [M]+, 234 (76)
[M – CH2], 135 (47) [Ad]+, 107 (11), 93 (23), 79 (42), 55
(21), 41 (100). Found, %: C 72.49, 72.67; H 9.01, 9.41.
C15H23NS. Calculated, %: C 72.24; H 9.29. M 249.4.
1-Adamantylthioacetic acid amide (Vj) was ob-
tained from 1 g (4.5 mmol) of thiadiazole I, 0.55 g
(4.9 mmol) of potassium tert-butylate, 0.42 g (5.4 mmol)
of acetyl chloride. The reaction mixture was kept for
10 min, then it was cooled to –20°C, and at this tem-
perature ammonia was bubbled through the solution for
30 min, then the solvent was evaporated, the residue was
washed with 100 ml of water, extracted with chloroform
(3 × 15 ml), dried with anhydrous sodium sulfate, the
extract was evaporated, the residue was chromatographed
1-Adamantylthioacetic acid N-ethylhydroxylamide
(Vg) was obtained from 1 g (4.5 mmol) of thiadiazole
I, 0.55 g (4.9 mmol) of potassium tert-butylate, 0.42 g
(5.4 mmol) of acetyl chloride, and 2.7 g (4.5 mmol) of
ethanolamine. Yield 0.5 g (43%). Colorless crystals,
1
mp 156–157°C. H NMR spectrum (CDCl3), δ, ppm:
1.62 m (12HAd), 1.95 m (3HAd), 2.52 s (2H, CH2), 3.02 s
(OH), 3.80 m (4H, OCH2CH2), 7.78 s (NH). 13C NMR
spectrum (CDCl3), δ, ppm: 28.42 (CHAd), 33.37 (C1Ad),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

NEW CONVENIENT METHOD FOR PREPARATION OF AMIDES
1213
spectrum (CDCl3), δ, ppm: 11.62 (CH3), 28.50 (CHAd),
34.53 (C1Ad), 36.37, 42.86 (CH2Ad), 49.57 (CH2CH3),
51.40, 51.78 (NCH2), 52.04, 52.41 (CSNCH2), 55.84
(CH2CS), 199.56 (CS). Mass spectrum, m/z (Irel, %): 306
(11) [M]+, 273 (7), 234 (6), 171 (18), 135 (11) [Ad]+, 113
(6), 97 (85), 91 (25), 84 (100), 79 (35), 72 (48, 56 (60), 42
(56). Found, %: C 70.43, 70.78; H 9.31, 9.52. C18H30N2S.
Calculated, %: C 70.54; H 9.14. M 306.5.
on a column with silica gel (3 × 20 Cm) eluting with
a mixture chloroform–hexane, 1 : 1. Yield 0.4 g (42%).
Colorless crystals, mp 175–176°C (mp 174–175°C [1,
1
2]). H NMR spectrum (DMSO-d6), δ, ppm: 1.59 m
(12HAd), 1.91 m (3HAd), 2.31 s (CH2), 8.83 br.s (NH2),
9.26 br.s (NH2). 13C NMR spectrum (DMSO-d6), δ, ppm:
28.14 (CHAd), 32.81 (C1Ad), 36.43, 42.06 (CH2Ad), 59.15
(CH2CS), 204.26 (CS). Mass spectrum, m/z (Irel, %):
208 (73) [M]+, 176 (10) [M – S]+, 135 (100) [Ad]+, 118
(8), 107 (25), 91 (58), 79 (78), 67 (32), 60 (51), 53 (34),
41 (97). M 209.4.
ACKNOWLEDGMENTS
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant
no. 08-03-00383-a).
1-Adamantylthioacetic acid N-methylpiperazi-
nylamide (Vk) was obtained from 1 g (4.5 mmol) of
thiadiazole I, 0.55 g (4.9 mmol) of potassium tert-bu-
tylate, 0.42 g (5.4 mmol) of acetyl chloride, and 4.47 g
(4.5 mmol) of N-methylpiperazine. Yield 0.4 g (30%).
REFERENCES
1
Colorless crystals, mp 117–118°C. H NMR spectrum
1. Aigami, K., Inamoto, Y., Takaishi, N., Nattori, K., Takat-
suki, A., and Tamura, G., J. Med. Chem., 1975, vol. 18,
p. 713.
2. Aigami, K. and Inamoto, Y., US Patent 396228, 1976.
3. Klimko, Yu.E., Isaev, S.D., and Yurchenko, A.G., Zh. Org.
Khim., 1995, vol. 31, p. 191.
4. Murguia, M.C. and Rossi, R.A., Tetrahedron Lett., 1997,
vol. 38, p. 1355.
5. Petrov, M.L., Shchipalkin, A.A., and Kuznetsov, V.A., Zh.
Org. Khim., 2007, vol. 43, p. 631.
(CDCl3), δ, ppm: 1.65 m (12HAd), 1.95 m (3HAd), 2.35 s
(3H, CH3N), 2.48 m (4H, CH2N), 2.82 s (2H, CH2CS),
3.80 m, 4.40 m (4H, CSNCH2). 13C NMR spectrum
(CDCl3), δ, ppm: 28.53 (CHAd), 34.09 (C1Ad), 36.40,
45.19 (CH2Ad), 49.58 (CH3N), 49.97, 50.65 (CSNCH2),
54.05, 54.53 (CH2N), 55.90 (CH2CS), 199.88 (CS). Mass
spectrum, m/z (Irel, %): 292 (7) [M]+, 259 (5), 234 (4), 157
(11), 135 (11) [Ad]+, 99 (8), 91 (10), 83 (70), 70 (100),
58 (16), 42 (22). Found, %: C 70.07, 70.24; H 9.87, 9.91.
C17H28N2S. Calculated, %: C 69.81; H 9.58. M 292.5.
6. Petrov, M.L., Shchipalkin, A.A., and Kuznetsov, V.A., Zh.
Org. Khim., 2008, vol. 44, p. 774.
1-Adamantylthioacetic acid N-ethylpiperazinyl-
amide (Vl) was obtained from 1 g (4.5 mmol) of thia-
diazole I, 0.55 g (4.9 mmol) of potassium tert-butylate,
0.42 g (5.4 mmol) of acetyl chloride, and 4.5 g (4.5 mmol)
of N-ethylpiperazine. Yield 0.3 g (21%). Colorless crys-
tals, mp 104–105°C. 1H NMR spectrum (CDCl3), δ, ppm:
1.02 t (3H, CH3, J 7 Hz), 1.63 m (12HAd), 1.98 m (3HAd),
2.39 q (2H, CH2CH3, J 7.1 Hz), 2.44 m (4H, CH2N), 2.80 s
(2H, CH2CS), 3.77 m, 4.18 m (4H, CSNCH2). 13C NMR
7. Petrov, M.L., Shchipalkin, A.A., and Kuznetsov, V.A., Zh.
Org. Khim., 2010, vol. 46, p. 1212.
8. Gordon, A.J. and Ford, R.A., The Chemist’s Companion,
New York: Wiley, 1972.
9. Petrov, M.L., Kupin, B.S., and Petrov,A.A., Zh. Org. Khim.,
1971, vol. 7, p. 1120.
10. Bagrii, E.I., Adamantany: poluchenie, svoistva, primenenie
(Adamantanes: Synthesis, Properties, Application),
Moscow: Nauka, 1989, p. 34.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011