SYNTHESIS AND CRYSTAL STRUCTURE OF DIPOTASSIUM SALTS
383
disappearance of the 31Р NMR signals of the dialkyl
phosphite (about 7 ppm). The solvent was removed
under vacuum, and the obtained alkylaminomethyl
phosphonate 2 was dissolved in 20 mL of ethanol; 6.0 g
of potassium hydroxide and 2 mL of water were added,
the mixture was refluxed during 4 h until hydrolysis
was complete (disappearance of the 31Р NMR signal of
the alkylaminomethyl phosphonate 2 at 18–20 ppm),
and ethanol was removed under vacuum. The mixture
was cooled on an ice bath, 6.0 g of KOH and 40 mL of
water were added at temperature not exceeding 10°C
with stirring during 1 h, 6.54 mL (0.11 mol) of freshly
distilled carbon sulfide was added, and the mixture was
stirred during 4 h at room temperature. Water and other
volatile substances were removed under reduced pressure
and the residue was dried in a vacuum dessicator over
calcined CaCl2. The product was recrystallized from a
1,4-dioxane–ethanol mixture (4a, 4b, 4d) or ethanol (4c)
and dried in a vacuum oven at 60°C (5 mmHg)
Dipotassium ethyl{[(carbodithioato)cyclo-
hexylamino]methyl}phosphonate (4c). Yield 31.37 g
1
(84%), white crystals, decomp. 213°С (ethanol). H
NMR spectrum (D2O), δ, ppm (J, Hz): 0.78‒1.06 m (5H,
CHaHe), 0.92 t (3H, CH3CH2O,3JHH = 7.1), 1.16–1.58 m
(5H, CHaHe), 3.65 d. t (2H, OCH2CH3,3JHP = 14.2, 3JHH
=
7.0), 4.17 d (2H, PCH2N, 2JHP = 10.8), 5.14 m (1H,
cyclo-C1H). 13С{1H} NMR spectrum (D2O), δС, ppm (J,
Hz): 16.1 d (CH3CH2O, 3JCP = 6.1), 25.0 (cyclo-C2H2,
cyclo-C6H2), 25.5 (cyclo-C3H2, cyclo-C5H2), 29.9 (cyclo-
C4H2), 47.2 d (PCH2N, 1JCP = 148.4), 60.9 d (POCH2,
2JCP = 5.7), 63.5 (cyclo-C1H), 208.7 (CSSK). 31Р{1H}
NMR spectrum (D2O): δР 18.2 ppm. Found K, %: 20.82.
C10H18K2NO3PS2. Calculated K, %: 20.93.
Dipotassium butyl{[(carbodithioato)(2-
methoxyethyl)amino]methyl}phosphonate (4d).
Yield 28.31 g (75%), white crystals, decomp. 177°С
(dioxane–ethanol). 1H NMR spectrum (CD3CN), δ, ppm:
0.89 m (CH3CH2CH2), 1.34 m (CH3CH2CH2), 1.56 m
(CH3CH2CH2), 3.38 s (CH3O), 3.82 m (POCH2), 4.37 m
(OCH2CH2N), 4.65 m (OCH2CH2N), 4.75 m (PCH2N).
13С{1H} NMR spectrum (CD3CN), δС, ppm (J, Hz): 13.6
(CH3CH2CH2), 19.1 (CH3CH2CH2), 33.1 (CH3CH2CH2),
51.7 d (PCH2N, 1JCP = 143.4), 52.3 (OCH2CH2N), 58.5
(OCH2CH2N), 64.6 d(POCH2, 2JCP = 6.2), 69.9 (CH3O),
212.5 (CSSK). 31Р{1H} NMR spectrum (CD3CN): δР
16.8 ppm. Found K, %: 20.80. C10H18K2NO3PS2.
Calculated K, %: 20.71.
Dipotassium ethyl{[isopropyl(carbodithioato)-
amino]methyl}phosphonate (4a). Yield 27.01 g (81%),
1
white crystals, decomp. 197°С (dioxane–ethanol). H
NMR spectrum (D2O), δ, ppm (J, Hz): 0.91 d (6H,
CH3CH, 3JHH = 6.9), 0.93 m (3H, CH3CH2O), 3.67 d. t
3
3
(2H, OCH2CH3, JHP = 14.0, JHH = 7.1), 4.14 d (2H,
PCH2N,2JHP = 13.4), 5.53 septet (1H, CH3CH,3JHH = 6.7).
13С{1H} NMR spectrum (D2O), δС, ppm (J, Hz): 16.0 d
(CH3CH2O, 3JCP = 6.3), 19.2 (CH3CH), 46.3 d (PCH2N,
Diethyl[(isopropylamino)methyl]phosphonate (2a)
was prepared as described elsewhere [17]. Yield 19.04 g
(91%) colorless oil, bp 57°С (3.7×10–3 mm Hg), nD20
1.4321. 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 0.94 d
1JCP = 148.7), 55.0 (CH3CH), 60.9 d (POCH2, 2JCP
=
5.9), 208.9 (CSSK). 31Р{1H} NMR spectrum (D2O): δР
18.3 ppm. Found K, %: 23.53. C7H14K2NO3PS2.
Calculated K, %: 23.45.
(6H, CH3CH, 3JHH = 6.5), 1.27 t (6H, CH3CH2O, 3JHH
=
7.0), 2.95 d (2H, PCH2N, 2JHP = 11.3), 3.44 septet (1H,
CH3CH, 3JHH = 6.5), 4.10 d. t (1H, CH3CH, 3JHP = 12.1,
3JHH = 7.0). 13С{1H} NMR spectrum (CDCl3), δС, ppm (J,
Hz): 16.4 d (CH3CH2O,3JCP = 6.2), 17.4 (CH3CH), 46.2 d
(PCH2N, 1JCP = 165.4), 52.0 d (POCH2, 2JCP = 11.3),
Dipotassium ethyl{[butyl(carbodithioato)amino]-
methyl}phosphonate (4b). Yield 26.76 g (77%),
1
white crystals, decomp. 195°С (dioxane–ethanol). H
NMR spectrum (D2O), δ, ppm (J, Hz): 0.83 t (3H,
CH3CH2CH2, 3JHH = 7.4), 1.15 t (3H, CH3CH2O, 3JHH
=
3
62.0 d (CH3CH, JCP = 6.7). 31Р{1H} NMR spectrum
7.1), 1.18–1.27 m (2H, CH3CH2CH2), 1.56–1.64 m (2H,
CH3CH2CH2), 3.83–3.90 m (2H, OCH2CH3), 4.09 t
(CDCl3): δР 25.2 ppm.
(2H, CH2CH2N, 3JHH = 7.1), 4.53 d (2H, PCH2N, 2JHP
=
Potassium ethyl[(isopropylamino)methyl]phos-
phonate (3a). Yield 17.56 g (88%), white hygroscopic
powder. 1H NMR spectrum (D2O), δ, ppm (J, Hz): 0.97 d
(6H, CH3CH, 3JHH = 6.4 Hz), 1.18 t (3H, CH3CH2O,
3JHH = 7.1 Hz), 2.68 d (2H, PCH2N, 2JHP = 13.4 Hz),
2.80 septet (1H, CH3CH, 3JHH = 6.3 Hz), 3.84 d. t (2H,
OCH2CH3, 3JHP = 14.2, 3JHH = 7.1 Hz). 13С{1H} NMR
spectrum (D2O), δС, ppm (J, Hz): 15.9 d (CH3CH2O,3JCP =
12.3). 13С{1H} NMR spectrum (D2O), δС, ppm (J, Hz):
13.2 (CH3CH2CH2), 16.2 d (CH3CH2O,3JCP = 5.8), 19.5
(CH3CH2CH2), 27.5 (CH3CH2CH2), 59.3 d (PCH2N,
1JCP = 144.6), 53.7 (CH2CH2N), 61.6 d (OCH2CH3,2JCP =
5.7), 208.9 (CSSK). 31Р{1H} NMR spectrum (D2O):
δР 17.5 ppm. Found K, %: 22.41. C8H16K2NO3PS2.
Calculated K, %: 22.50.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 3 2020