Sulfochlorination of β-aminopropioamidoximes
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
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analysis was performed on a CE-440 elemental analyzer (Exeter
Analytical, Inc., China). The melting points were measured on
a TPL melting-point apparatus (Khimlabpribor, Russia). The
course of reactions was monitored by TLC on Sorbfil plates
(Sorbpolymer, Russia) pre-coated with STKh-1A silica gel with
a particle size of 5—17 μm using a fluorescent indicator UV-254.
A 1 : 3 benzene—EtOH mixture was used as the eluent.
The starting β-(morpholin-1-yl)propioamidoxime (1) was
prepared in the following two steps: 1) the reaction of morpholine
with acrylonitrile, which were distilled before use (EtOH as the
solvent); 2) the resulting aminopropionitrile was distilled in vacuo
and introduced into the reaction with commercial hydroxylamine
hydrochloride, which was used as received (EtOH as the solvent).
β-(Morpholin-1-yl)propioamidoxime (1) that was isolated from
the reaction mixture was recrystallized from PriOH (benzene as
the solvent for the extraction of amidoxime 1).16
NH2); 7.48 (d, 2 H, CHsp2, J = 7.0 Hz). 13C NMR, δ: 21.25
(CH3), 31.43 (CCH2CH2N+), 62.02 (CCH2CH2N+), 62.42
(N+(CH2)2), 63.23 (O(CH2)2), 125.95 (2 C); 128.55 (2 C), 138.13
(1 C), 146.16 (1 C), 169.10 (C=N). Found (%): C, 51.81; H, 6.59;
N, 13.25; S, 9.37. C14H21N3O4S. Calculated (%): C, 51.36;
H, 6.47; N, 12.83; S, 9.79.
2-Amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-5-ammonium
benzenesulfonate (3c). The reaction time was 4 days. The yield
of 3c was 0.37 g (42.5%); m.p. 192—195 C, Rf 0.75. IR, /cm–1
:
3326 as(NH2), 3176 s(NH2), 1656 (C=N), 1604 (C=C), 1220
as(SO2), 1181 as(SO2). 1H NMR, δ: 3.13 (t, 2 H, CCH2CH2N+,
J = 7.0 Hz); 3.40, 3.65 (both m, 2 H each, Hax and Heq
,
N+(CH2)2); 3.92 (m, 6 H, CCH2CH2N+);*2 3.92 (m, 6 H,
O(CH2)2);*2 7.48—7.61 (m, 5 H, CH ); 7.48 (br.s, NH2). 13
C
2
sp
NMR, δ: 31.43 (CCH2CH2N+), 62.08 (CCH2CH2N+), 62.08
(N+(CH2)2), 63.23 (O(CH2)2), 125.93 (2 C); 128.10 (2 C), 128.84
(1 C), 148.87 (1 C), 169.10 (C=N). Found (%): C, 49.29; H, 5.97;
N, 13.87; S, 9.91. C13H19N3O4S. Calculated (%): C, 49.83;
H, 6.11; N, 13.41; S, 10.23.
β-(Morpholin-1-yl)propioamidoxime (1) was subjected to
arylsulfochlorination with substituted arylsulfonyl chlorides,
which were purchased from Sigma-Aldrich and used as received
(chloroform as the solvent, triethylamine distilled before use as
the base).
2-Amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-5-ammonium
4-bromobenzenesulfonate (3d). The reaction time was 4 days. The
yield of 3d was 0.58 g (53.2%); m.p. 230—232 C, Rf 0.30. IR,
/cm–1: 3392 as(NH2), 3336 s(NH2), 1646 (C=N), 1609
(C=C), 1225 as(SO2), 1191 s(SO2). 1H NMR, δ: 3.16 (t, 2 H,
CCH2CH2N+, J = 7.0 Hz); 3.40, 3.67 (both m, 2 H each, Hax
and Heq, N+(CH2)2); 3.87—3.98 (m, 6 H, CCH2CH2N+);*
3.87—3.98 (m, 6 H, O(CH2)2);* 7.50 (d, 2 H, CHsp2, J = 7.0 Hz);
7.39 (br.s, 2 H, NH2); 7.54 (d, 2 H, CHsp2, J = 7.0 Hz). 13C NMR,
δ: 31.48 (CCH2CH2N+), 62.07 (CCH2CH2N+), 62.46 (N+(CH2)2),
63.34 (O(CH2)2), 122.00 (1 C); 128.23 (2 C), 131.04 (2 C), 148.33
(1 C), 169.11 (C=N). Found (%): C, 40.25; H, 4.85; Br, 19.89;
N, 10.28; S, 8.17. C13H18BrN3O4S. Calculated (%): C, 39.80;
H, 4.63; Br, 20.37; N, 10.71; S, 8.17.
2-Amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-5-ammonium
4-chlorobenzenesulfonate (3e). The reaction time was 6 days. The
yield of 3e was 0.36 g (37%); m.p. 160—162 °C, Rf 0.19. IR,
/cm–1: 3405 as(NH2), 3305 s(NH2), 1647 (C=N), 1596 (C=C),
1220 as(SO2), 1191 s(SO2). 1H NMR, δ: 3.17 (t, 2 H,
CCH2CH2N+, J = 7.0 Hz); 3.40, 3.67 (both m, 2 H each, Hax
and Heq, N+(CH2)2); 3.88—3.98 (m, 6 H, CCH2CH2N+);*
3.88—3.98 (m, 6 H, O(CH2)2);* 7.37 (d, 2 H, CHsp2, J = 7.0 Hz);
7.44 (br.s, 2 H, NH2); 7.61 (d, 2 H, CHsp2, J = 7.0 Hz).
13C NMR, δ: 31.49 (CCH2CH2N+), 62.04 (CCH2CH2N+),
62.46 (N+(CH2)2), 63.33 (O(CH2)2), 127.93 (2 C); 128.11 (2 C),
133.38 (1 C), 147.89 (1 C), 169.11 (C=N). Found (%): C, 44.68;
H, 5.47; Cl, 10.47; N, 12.50; S, 8.85. C13H18ClN3O4S. Calculat-
ed (%): C, 44.89; H, 5.22; Cl, 10.19; N, 12.08; S, 9.22.
2-Amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-5-ammonium
4-nitrobenzenesulfonate (3f). The reaction time was 3 days. The
yield of 3f was 0.49 g (48.5%); m.p. 192—195 °C, Rf 0.17. IR,
/cm–1: 3405 as(NH2), 3305 s(NH2), 1664 (C=N), 1601
(C=C), 1204 as(SO2), 1120 s(SO2). 1H NMR, δ: 3.14 (t, 2 H,
CCH2CH2N+, J = 7.0 Hz); 3.41, 3.64 (both m, 2 H each, Hax
and Heq, N+(CH2)2); 3.88—3.99 (m, 6 H, CCH2CH2N+);*
3.88—3.99 (m, 6 H, O(CH2)2);* 7.29 (br.s, 2 H, NH2); 7.85
(d, 2 H, Csp2H, J = 7.0 Hz); 8.19 (d, 2 H, Csp2H, J = 7.0 Hz).
13C NMR, δ: 31.47 (CCH2CH2N+), 62.13 (CCH2CH2N+),
62.44 (N+(CH2)2), 63.35 (O(CH2)2), 123.71 (2 C); 127.39 (2 C),
147.79 (1 C), 155.00 (1 C), 169.09 (C=N). Found (%): C, 43.96;
H, 5.29; N, 16.01; S, 9.28. C13H18N4O6S. Calculated (%):
C, 43.57; H, 5.06; N, 15.63; S, 8.95.
The solvents for the synthesis, recrystallization, extraction,
and TLC (EtOH, PriOH, benzene, chloroform) were purified
according to standard procedures described for each solvent.17
Synthesis of 2-amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-
5-ammonium arylsulfonates (3a—f) (general procedure). Triethyl-
amine (0.28 g, 0.0028 mol) was added to a solution of β-(morph-
olin-1-yl)propioamidoxime (1) (0.5 g, 0.0028 mol) in chloroform
(10 mL). The reaction mixture was cooled to 0 C. A solution of
arylsulfonyl chloride (0.55 g, 0.0028 mol) in chloroform (2 mL)
was added dropwise with stirring. Then the reaction mixture was
allowed to warm to room temperature and stirred for several days
until the completion of the reaction. The course of the reaction
was monitored by TLC. The resulting white precipitates of aryl-
sulfonates 3a—f were filtered off and recrystallized from PriOH.
2-Amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-5-ammonium
4-methoxybenzenesulfonate (3a). The reaction time was 2 days.
The yield of 3a was 0.4 g (41.4%); m.p. 225—227 C, Rf = 0.16.
IR, /cm–1: 3377 as(NH2), 3312 s(NH2), 1650 (C=N), 1597
(C=C), 1205 as(SO2), 1119 s(SO2). 1H NMR, δ: 3.14 (t, 2 H,
CCH2CH2N+, J = 7.0 Hz); 3.41, 3.64 (both m, 2 H each, Hax
and Heq, N+(CH2)2); 3.75 (s, 3 H, OCH3); 3.93 (m, 6 H,
CCH2CH2N+);* 3.93(m, 6 H, O(CH2)2);* 6.84 (d, 2 H, CHsp2
,
J = 7.0 Hz); 7.30 (br, 2 H, NH2); 7.53 (d, 2 H, CHsp2, J = 7.0 Hz).
13C NMR, δ: 31.47 (CCH2CH2N+), 55.64 (CH3O), 62.02
(CCH2CH2N+), 63.35 (N+(CH2)2, 62.42 (O(CH2)2), 113.20
(2 C); 127.51 (2 C), 141.89 (1 C), 159.65 (1 C), 169.10 (C=N).
Found (%): C, 48.75; H, 5.93; N, 12.70; S, 9.02. C14H21N3O5S.
Calculated (%): C, 48.97; H, 6.16; N, 12.24; S, 9.34.
2-Amino-8-oxa-1,5-diazospiro[4.5]dec-1-ene-5-ammonium
4-tosylate (3b). The reaction time was 2 days. The yield of
2-aminospiropyrazolylammonium tosylate (3b) was 0.44 g
(47.8%); m.p. 220—222 C, Rf 0.14. IR, /cm–1: 3422 as(NH2),
3367 s(NH2), 1654 (C=N), 1601 (C=C), 1195 as(SO2), 1120
s(SO2). 1H NMR, δ: 3.14 (t, 2 H, CCH2CH2N+, J = 7.0 Hz);
3.36 (s, 3 H, CH3); 3.40, 3.65 (both m, 2 H each, Hax and Heq,
N+(CH2)2); 3.93 (m, 6 H, CCH2CH2N+);* 3.93 (m, 6 H,
O(CH2)2);* 7.11 (d, 2 H, CHsp2, J = 7.0 Hz); 7.35 (br.s, 2 H,
* Hereinafter, the overlapping signals of protons in the 1H NMR
spectra of compounds 3a—f are marked with an asterisk.