490
I. S. NIZAMOV ET AL.
where Ucor(0)—corrosion rates without inhibitor; Uinh(t)—corrosion rates in time t after
inhibitor introduction.
S-Alkyl O,O-Di-iso-butyl Dithiophosphates 5a and 6a, and O-Alkyl
O,O-Di-iso-butyl Thionophosphates 7a and 8a
The mixture of red phosphorus (0.4 g), sulfur (0.81 g), and iso-butanol (1.87 g,
25.2 mmol) was heated for 12 h at 100–110◦ with stirring. Olefins 1a–c (3.4 g, 14.3 mmol)
and anhydrous ZnCl2 (0.1 g, 0.7 mmol, 2.9 wt%) were added into the mixture and the
stirring was continued for 4 h at 80◦C. The mixture was filtered. The filtrate was evap-
orated under vacuum (0.02 mm Hg) at 60◦C for 1 h and gave 2.7 g (90%) of a mixture
20
of 5a, 6a, 7a, and 8a. nD 1.4450. Anal. Found С 62.11; Н 11.08, Р 5.86; S 12.59.
С24Н51О2РS2 and С26Н55О2РS2. Calcd. С 61.75–63.10; Н 11.04-311.23; Р 6.26–6.64;
S 12.93–13.71% (there and then elemental analysis data for minor products 7 and 8 were
not taken into account). IR: film, ν = 2957, 2924, 2854 (СН3 as, s; СН2 as, s); 1466
δ (СН3 as); 1377 δ [(СН3)2C gem. s); 999 [(P)O C]; 964 (OC C); 675 (P S); 553
(P S). 1H NMR: δ = 0.86 t (3Нxn, СН3СH2CH2, 3JНH = 7.5 Hz, 7a, 8a); 0.91 t (3Нxn,
3
3
СН3СH2CH2, JНH = 7.2 Hz, 5a, 6a); 1.00 d {12Нxn, [(СН3)2CHCH2О]2Р, JНH
=
6.8 Hz}; 1.29 br s [С(СН2)nС]; 1.39 m [1Нxn, СH(CH3)2]; 1.52 d [3Нxn, СН3С(Н)SP,
3JНH = 6.2 Hz, 6a]; 1.59 s [6Hxn, (СН3)2CSP, 5a]; 1.60 m [2Нxn, PSС(СН3)2СH2CH2,
5a, 7a]; 1.67 m [2Нxn, PSСН(СН3)СH2CH2, 6a]; 1.70 s [6Hxn, (СН3)2CSP, 7a]; 2.00 m
(2Нxn, PSС(СН3)2СH2CH2, 5a, 7a); 2.07 t (2Нxn, PSС(СН3)2СH2CH2, 3JНH = 6.8 Hz,
5a, 7a); 3.03 m [1Нxn, PSСН(СH3)CH2, 6a]; 3.87 m {4Нxn, [(СН3)2CHCH2О]2Р, 5a,
6a}; 3.97 m {4Нxn, [(СН3)2CHCH2О]2Р, 7a, 8a}. The 13C NMR (signal form in the 13C-
{ H} NMR was brought in braces): δ = 14.1 q (s) [(СН3)2CHCH2О, 1JНC = 125.0 Hz, 5a,
1
6a, 7a, 8a]; 15.8 q (s) [(СН3)2CSP, 1JНC = 124.7 Hz, 5a, 7a]; 17.9 q (s) (СН3CHSP, 1JНC
= 124.1 Hz, 6a, 8a]; 18.9 and 19.0 two q (two s) (СН3СH2CH2, 1JНC = 125.5 Hz, 5a, 6a,
7a, 8a); 22.7 t (s) (СН3СH2CH2, 1JНC = 124.1 Hz, 5a, 6a, 7a, 8a); 23.4–23.5, 24.3–24.7,
26.6–26.8 and 27.7–28.0 m (m) (СН2СH2CH2); 28.9 t (s) [PSC(CH3)2СН2СН2СH2CH2,
1JНC = 126.2 Hz, 5a); 29.2 t (s) [PSC(CH3)2СН2СH2CH2, 1JНC = 126.9 Hz, 5a); 29.4 t
(s) (СН3СH2CH2, 1JНC = 123.2 Hz, 5a, 6a, 7a, 8a); 29.6 t (s) (СН3СH2CH2CH2, 1JНC
= 128.4 Hz, 5a, 6a, 7a, 8a); 29.7 t (s) (СН2СH2CH2, 1JНC = 124.7 Hz, 6a, 8a); 31.9 t (s)
( СH2 , 1JНC = 126.2 Hz); 33.9 t (s) (СH2, 1JНC = 129.7 Hz); 36.7 t (s) (POCHСH2, 1JНC
= 120.3 Hz, 7a); 37.7 t (s) (POCСH2, 1JНC = 120.3 Hz, 8a); 39.5 m (s) (PSCHСH2, 6a);
39.8 t (s) (PSCСH2, 1JНC = 126.9 Hz, 5a); 36.7 m (d) (PSСH, 2JPC = 5.9 Hz, 6a); 41.3 m
(d) (PSС, 2JPC = 5.5 Hz, 5a); 67.4 m (s) (POСHCH2CH2, 8a); 70.0 m (s) [POС(CH3)2CH2,
7a]; 73.5 dt (d) [POСH2CH(CH3)2, 1JНC = 170.9 Hz, 2JPC = 7.7 Hz, 7a, 8a]; 73.8 dt (d)
[POСH2CH(CH3)2, 1JНC = 170.2 Hz, 2JPC = 6.6 Hz, 5a, 6a]. 31Р NMR: δР = 98.9, 90.3
and 69.0 in ratio 15:55:30. MS (ESI), m/e: 478.3 [М]+, 501.4 [М + Na]+ require 478.8
7a, 8a (from C18); 554.6 [М + Na + K]+, 1009.6 [2М + K]+ require 466.8 5a, 6a (from
C16); 1049.1 [2М + Na + K]+ requires 494.8 5a, 6a (from C18).
S-Alkyl O,O-Di-iso-octyl Dithiophosphates 5b and 6b and O-Alkyl
O,O-Di-iso-octyl Thionophosphates 7b and 8b
The mixture of red phosphorus (0.79 g), sulfur (1.59 g) and iso-octanol (6.5 g,
49.9 mmol) was heated for 10 h at 100◦C with stirring. Olefins 1a–c (6.1 g, 25.6 mmol)
and anhydrous ZnCl2 (0.15 g, 1.1 mmol, 2.5 wt%) were added into the mixture and the
stirring was continued for 4 h at 80◦C. The mixture was filtered. The filtrate was diluted