Reactions of diphenyl- and diethylphosphinodithioic acids with N-alkyl-2-haloaldimines in the synthesis of new P,S- and N,P,S-containing organic compounds

Article abstract of DOI:10.1134/S1070363217100115

Diphenyl- and diethylphosphinodithioic acids, unlike the stronger О,О-dialkyl phosphorodithioic acids, react with N-alkyl-2-chloroaldimines at a 1: 1 ratio, following two pathways: nucleophilic substitution of chlorine in the primary salt by the phosphinothioylthio group and reduction of the cation of the primary salt on the C–Cl bond. Nucleophilic substitution contributes more in the case of the stronger diphenylphosphinodithioic acid, as well as in the case of a large excess of the starting chlorimine. N-Alkyl-2-bromoaldimines react only by a single pathway, specifically, reducing the cation of the primary iminium salt on the C–Br bond. New iminium salts were synthesized and converted into the corresponding aldehydes and imines. The aldehydes synthesized were converted into acetals and five-membered heterocyclic compounds.

Full text of DOI:10.1134/S1070363217100115

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 10, pp. 2313–2319. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © R.A. Khairullin, M.B. Gazizov, Yu.S. Kirillina, N.Yu. Bashkirtseva, 2017, published in Zhurnal Obshchei Khimii, 2017, Vol. 87,
No. 10, pp. 1653–1659.
Reactions of Diphenyl- and Diethylphosphinodithioic Acids
with N-Alkyl-2-haloaldimines in the Synthesis
of New P,S- and N,P,S-Containing Organic Compounds
R. A. Khairullin, M. B. Gazizov*, Yu. S. Kirillina, and N. Yu. Bashkirtseva
Kazan Research Technological University, ul. K. Marksa 68, Kazan, Tatarstan, 420015 Russia
*
e-mail: mukattisg@mail.ru
Received May 22, 2017
Abstract—Diphenyl- and diethylphosphinodithioic acids, unlike the stronger О,О-dialkyl phosphorodithioic
acids, react with N-alkyl-2-chloroaldimines at a 1 : 1 ratio, following two pathways: nucleophilic substitution
of chlorine in the primary salt by the phosphinothioylthio group and reduction of the cation of the primary salt
on the C–Cl bond. Nucleophilic substitution contributes more in the case of the stronger diphenylphos-
phinodithioic acid, as well as in the case of a large excess of the starting chlorimine. N-Alkyl-2-bromo-
aldimines react only by a single pathway, specifically, reducing the cation of the primary iminium salt on the
C–Br bond. New iminium salts were synthesized and converted into the corresponding aldehydes and imines.
The aldehydes synthesized were converted into acetals and five-membered heterocyclic compounds.
Keywords: diphenyl- and diethylphosphinodithioic acids, N-alkyl-2-chloroaldimines, iminium salts, aldehydes,
imines, acetals, five-membered heterocycles
DOI: 10.1134/S1070363217100115
Previously we showed [1–5] that О,О-dialkyl phos-
phorodithioic acids 1 react with N-tert-butyl-2-halo-2-
methylpropanimines 2 to form primary salts, viz. with
N-tert-butyl-2-halo-2-methylpropanimiminium О,О-di-
alkyl phosphorodithioates 3 (Scheme 1). Further trans-
formations of salts 3 depend on the nature of the
halogen. In the case of Cl-substituted salts 3a and 3b at
a 1 : 1 reagent ratio, nucleophilic substitution of Cl by
the dialkoxyphosphinothioylthio group occurs to form
N-tert-butyl-2-(dialkoxyphosphinothioylthio)-2-methyl-
propaniminium chlorides 4а and 4b (Scheme 1, path-
way а). Br-Substituted salts 3c and 3d react with one
more acid molecule to give C–Br bond reaction product
5b and bis(dialkoxyphosphinothioyl) disulfide 6 (path-
way b). When the 1 : 2а ratio is 2 : 1, both pathway a and
pathway b are realized, the former pathway prevailing [2].
Scheme 1.
RO) PSSH + Me CХCH NBu-t Me CХCH N HBu-t (RO) P(S)S
_
+
(
2
2
2
2
1
2
3
а
_
+
Me C CH N HBu-t Х
2
SP(S)OR2
4
b
_
+
1
Me CHCH N HBu-t Х
+ [(R O) P(S)S]
2
2
2
6
5
1
, 6; R = i-Pr (a), Et (b); 2, 5: X = Cl (a), Br (b); 3, 4: X = Cl, R = i-Pr (a) Et (b); X = Br, R = i-Pr (c), Et (d).
313
2

2
314
KHAIRULLIN et al.
Scheme 2.
R P(S)SH + Me C(Cl) CH NR2
1
Me C(Cl) CH N HR2 R P(S)S
1
2
2
2
2
7
8
9
a
2
Me C CH N HR Cl
2
SP(S)R1
2
10
b
2
Me CH CH N HR Cl + [(RO) P(S)S]2
2
2
12
1
1
1
1
2
1
2
2
2
7
1
, R = Ph (a), Et (b); 8, R = t-Bu (a), i-Pr (b); 10, R = Ph, R = t-Bu (a), i-Pr (b); R = Et, R = t-Bu (c); 11, R = t-Bu;
1
2, R = Ph (a), Et (b).
The reason for the different reaction pathways for
pathways а and b are related as 4.6 to 1.0. In the
reactions of acid 7а with chlorimines 8а or 8b in a
1.0 : 1.2 ratio substituted iminium salts 10a or 10b
were isolated individually in yields of 91 and 81%, and
the mother liquor contained disulfide 12а ( P NMR
data). No products formed by pathway b could be
isolated individually.
Cl and Br derivatives was revealed by dynamic
3
1
1
P–{ H} spectroscopy [2, 3]: in the case of chlorimine
2
а, the equilibrium acid 1–chloriminium salt 3а or 3b
31
is strongly shifted to the right, and the system contains
no free acid, whereas in the case of bromimine 2b, the
equilibrium is shifted to the left, the system contains a
lot of free acid, and it is involved in the reduction of
iminium salt 3c or 3d cation on the C–Br bond.
The replacement in dithio acid 7 of the acceptor
phenyl substituents by more donor ethyl substituents
changed the relative contributions of pathways a and b.
The reactions of compounds 7b and 8b were per-
formed at 1 : 1 and 1 : 3 reagent ratios. With the 1 : 1
ratio, nucleophilic substitution (10c) and reduction
Diphenyl- and diethylphosphinothioic acids are
weaker acids than О,О-dialkyl phosphorothioic acids
we have studied previously [6]. We considered it of
interest to find out how the substituents on the P(IV)
atom affect the reaction pathways and to what extent
each reaction pathway contributes to the overall reac-
tion. Therefore, in the present work we set ourselves
the goal to determine the pathways of the reaction of
diphenyl- and diethylphosphinodithioic acids with
N-alkyl-2-haloaldimines and the contribution of each
pathway to the overall process, and to use the reaction
products in the synthesis of new P,S- and N,P,S-
containing compounds.
(
11) products were isolated individually in yields of 32
and 26%, respectively. The contribution ratio of path-
ways a and b is 1.2 : 1.0, i.e. much smaller compared
with 2.3 : 1.0 in the case of acid 7а. Disulfide 12b was
also isolated. With a large excess of 8а, namely, at the
7
b : 8a ratio of 1 : 3, compounds 10c and 11 were
obtained in yields of 65 and 8%, the S /Red ratio was
N
8
.1 : 1.0, i.e. pathway b was strongly suppressed.
To compare the reactivities of acids 7а and 7b
3
1
The P NMR spectrum of the reaction mixture of
diphenylphosphinothioic acid 7а with chlorimine 8а
revealed the presence of primary salt 9а (Scheme 2).
According to the NMR data, 5 min after compounds
toward chlorimine 8а, we performed a competitive
reaction: a solution of acids 7a and 7b was added
dropwise to a solution of compound 8а in CH Cl
2
2
(
reagent ratio 1 : 1 : 1) at 0–5°С, the mixture was
7
а and 8а have been mixed in a 1 : 1 ratio at room
temperature, the reaction mixture contained 28.0% of
31
stirred for 3 h at room temperature, after which its P
NMR spectrum was measured. As judged from the
signal intensities, first, acids 7а and 7b have reacted by
primary salt 9а (δ 60.3 ppm), 4.7% of disulfide 12
Р
(
δР 69.5 ppm), 8.2% of nucleophilic substitution
7
8 and 37%, second, acid 7а predominantly formed
product 10а (δ 57.9 ppm), 59.1% of starting acid 7а
Р
substitution product 10а, and the S : Red ratio for acid
N
(
δР 55.9 ppm). In 23 h at room temperature the
spectrum of the mixture showed two strong signals
7
b was 1.2 : 1.0.
from disulfide 12 and substitution product 10а in a
Thus, acid 7а is much more reactive toward
1
.0 : 2.3 ratio, respectively. Thus, the contributions of
chlorimine 8а compared to a weaker acid 7b and is
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

REACTIONS OF DIPHENYL- AND DIETHYLPHOSPHINODITHIOIC ACIDS
2315
Scheme 3.
+
H O, H
2
Me C CHO
2
_
+
−
t-BuN H Cl
3
SP(S)R2
Me C CH NHBu-t Cl
2
15a, 15b
Et N
3
SP(S)R2
Me C CH=NBu-t
2
_
.
Et N HCl
10a, 10c
3
SP(S)Ph2
1
6a
C H
6
6
1
5a + RNH2
Me C CH=NR
MS 3 A°
2
SP(S)Ph2
17
16b, 16c
R = Ph (10a, 15a), Et (10c, 15b), i-Pr (16b), p-tolyl (16c).
Scheme 4.
2
+
(
R O) CH, C H , H
3
6
6
Me C CH(OR2)2 + HCOOR2
2
SP(S)Ph2
18а, 18b
15
Bn
N
CH2
CH2
1
9, C H
Δ
6
6,
Me C CH
2
N
SP(S)R2
Bn
20а, 20b
R = Me (18a), Et (18b, 20b), Ph (20a).
also involved in the preferential formation of
substitution product 10а (pathway а). In the case of
acid 7b at a 1 : 1 reagent ratio, the contribution of
pathway b much increases. However, when imine 8а is
present in a large excess (reagent ratio 1 : 3), the
contribution of pathway a considerably increases.
As would be expected, acid 7b reacted with 2-bromo-
aldimine 8b exclusively along the scheme involving
reduction of the primary salt cation Me C(Br)·
2
+
–
CH=N HBut-Et P(S)S 13 to form a salt with the
2
reduced cation, specifically, N-tert-butyl-2-methylpro-
+
–
paniminium bromide Me CHCH=N HBut-Br 14 and
2
disulfide 12.
The results of the experiment can be interpreted as
follows.
To confirm the structure of new-type iminium salts
10 and synthesize previously unknown polyfunctional
organic compounds, we studied some properties of the
latter. Because hydrolysis of iminium salts is one of
accessible methods of synthesis of aldehydes [7], the
reaction mixture of compounds 8а and 7а in a ratio
1.2 : 1.0, which contained iminium salt 10 as the
principal component, was hydrolyzed with excess
water with 2 drops of conc. HCl (Scheme 3). The com-
position and structure of organophosphorus aldehydes
of new types, 1,1-dimethyl-2-oxoethyl diphenyl- (15а)
In the case of the stronger acid 7а, the acid–
chloriminium salt 9 equilibrium is strongly shifted to
the right, the system contains no free acid, and the
primary salt undergoes nucleophilic substitution to
form iminium salt 10. In the case of the weaker acid
7
b, this equilibrium is shifted to the left, and the
system contains a lot of free acid which takes part in
the reduction reaction. Excess chlorimine 8а decreases
the сoncentration of acid 7b in the system and
decreases the contribution of pathway b.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

2
316
KHAIRULLIN et al.
and diethylphosphinodithioates (15b), were confirmed
by elemental analysis and H and P NMR spectroscopy.
(400.13 and 100.61 МHz) spectrometers in СDCl3.
The chemical shifts were referensed to TMS using the
signals for residual protons or carbon nucleus of the
1
31
N-Alkylimines are important derivatives of alde-
hydes [7]. New organophosphorus imines 16 were
synthesized in two ways: reaction of aldehyde 15а
with primary amines 17 and treatment of iminium salt
3
1
deuterated solvent . The Р NMR spectra were
registered on AVANCE 400 WB (162.0 МHz) and
Bruker MSL-400 (162.0 МHz) spectrometers, the δР
values were referenced to external 85% Н РО .
3
4
1
0а with triethylamine (Scheme 3).
N-tert-Butyl-2-(diphenylphosphinothioylthio)-2-
methylpropan-1-iminium chloride (10a). Acid 7а,
Acetals as aldehyde derivatives easily react with
both electrophiles and nucleophiles, as well as with
bifunctional compounds, and, therefore, they are
widely used in organic synthesis [8]. To synthesize
new organophosphorus acetals 18, aldehydes 15 were
treated with an excess of trialkyl orthoformate in
benzene in the presence of catalytic amounts of H SO
1
0.53 g (0.042 mol), was added in portions with
stirring under dry argon to a solution of 8.17 g
0.05 mol) of imine 8a in 60 mL CCl , maintaining the
(
4
temperature at 0–3°С. The reaction mixture was then
let to warm up to 20°С, stirred for 6 h, and allowed to
stand at a room temperature for 48 h. The solvent and
excess chlorimine were removed in a vacuum, the
residue was treated with diethyl ether and cooled
down. The crystals were filtered off. Yield 15.8 g (91%),
2
4
(
Scheme 4).
One of the important methods of the synthesis of
five-membered cyclic compounds with two hetero-
atoms is the reaction of aldehydes with bifunctional
nucleophiles, in particular, alkane-1,2-diamines. To
synthesize five-membered heterocycles containing
phosphorus in the side chain, aldehydes 15 were
reacted with N,N'-dibenzylethane-1,2-diamine 19. The
reaction was performed in benzene in the presence of
Å molecular sieves (Scheme 4). In this way, we
synthesized 1-(1,3-dibenzyl-1,3-diazolidin-5-yl)-1-methyl-
ethyl diphenyl- (20а) and diethylphosphinodithioates (20b).
1
mp 124°С. Н NMR spectrum, δ, ppm: 1.62 s (9H,
CMe ), 1.86 s (6H, CMe ), 7.90 d.d (4H, ortho-CH ,
3
2
Ar
3
3
JHH = 7.0, J = 14.4 Hz), 7.36–7.54 m (6H,
meta,para-CH ), 8.87 s (1H, CH=N ), 14.81 br.s (1H,
N H). Р NMR spectrum: δ 57.63 ppm. Found, %: C
PH
+
Ar
+
31
P
5
8.48; H 6.71; P 7.43; S 15.10. C H NClPS .
20 27 2
3
Calculated, %: C 58.31; H 6.61; P 7.52; S 15.57. The
3
1
Р NMR spectrum of the mother liquor showed a
signal at δ 69.5 ppm corresponding to disulfide 12а.
Р
In conclusion, it can be noted that diphenyl- and
diethylphosphinodithioic acids react with N-alkyl-2-
chloraldimines along two pathways: the nucleophilic
substitution of chlorine in the primary iminium salt by
the phosphinothioylthio group and the reduction of the
cation of the primary salt on the C–Cl bond. The
contributions of the two pathways depend on the strength
of the acid and the reagent ratio: nucleophilic substi-
tution prevails in the case of the stronger diphenyl-
phosphinodithioic acid and at a 1 : 3 acid : imine ratio.
N-Alkyl-2-bromoaldimines react with diphenyl- and
diethylphosphinodithioic acids exclusively via reduc-
tion of the cation of the primary iminium salt on the
C–Br bond. New types of organophosphorus iminium
salts were obtained and converted into new types of
organophosphorus aldehydes. The latter were further
converted into imines, acetals, and five-membered
heterocycles containing phosphorus in the side chain.
N-Isopropyl-2-(diphenylphosphinothioylthio)-2-
methylpropan-1-iminium chloride (10b) was pre-
pared in a similar way from 4.67 g (0.032 mol) of
imine 8b and 6.15 g (0.025 mol) of acid 7а. Yield 7.9 g
1
(
1
81%), mp 102–103°С. Н NMR spectrum, δ, ppm:
3
.52 d (6H, CHMe , J
= 6.4 Hz), 1.79 s (6H,
2
HH
CMe ), 4.09 m (1H, NCH), 7.87 d.d (4H, ortho-CH ,
2
Ar
3
3
JHH = 7.2, J = 14.4 Hz), 7.47–7.53 m (6H, meta,para-
PH
+
+
CH ), 8.83 br.s (1H, CH=N ), 15.22 br.s (1H, N H).
Ar
31
Р NMR spectrum: δ 56.33 ppm. Found, %: C 57.21;
P
H 6.47; P 7.57; S 16.24. C H NClPS . Calculated, %:
1
9
25
2
C 57.34; H 6.33; P 7.78; S 16.11.
Reaction of acid 7b with imine 8а. a. Ratio 1 : 1.
A solution of 3.6 g (0.0235 mol) of acid 7b in 20 mL
of CCl was added dropwise to a solution of 3.8 g
4
(
0.0235 mol) of chlorimine 8а in 20 mL of CCl4,
maintaining the temperature at 0–5°C. The reaction
mixture was then let to warm up to 25°С, stirred for
5 h, and allowed to stand at a room temperature for 24 h.
The crystals were filtered off to obtain 1.0 g (26% per
imine) of 2-methylpropan-1-iminium chloride 11,
EXPERIMENTAL
1
13
The Н and С NMR spectra were recorded on
Tesla BS-567A (100 МHz) and AVANCE 400WB
1
mp 139°C. Н NMR spectrum, δ, ppm: 1.26 d (6H,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

REACTIONS OF DIPHENYL- AND DIETHYLPHOSPHINODITHIOIC ACIDS
2317
3
Me CH, J = 8.0 Hz), 1.55 s (9H, CMe ), 3.77 sextet
the formation of substituted product 10c and of
reduction product 12b in a ratio 55 : 45.
2
HH
3
+ 3
3
(
1H, J = 8.0 Hz), 7.88 d.d (1H, CH=N , J = 8.0,
HH HH
3
+
JHH = 16.0 Hz), 15.87 br.s (1H, N H). From cold
mother liquor we isolated 2.4 g (32% per imine) of
iminium chloride 10c, mp 103°C. Н NMR spectrum,
δ, ppm: 1.24 t and 1.30 t (6H, MeCH , J = 8.0 Hz)
.65 s (9H, CMe ), 2.12 s (6H, CMe ), 2.14 m (4H,
CH P), 8.69 s (1H, CH=N ), 15.17 br.s (1H, N H). Р
NMR spectrum: δ 77.2 ppm. Found, %: C 45.45; H
.55; P 9.7; N 4.22. C H NClPS . Calculated, %: C
5.62; H 8.63; P 9.86; N 4.43. The mother liquor
remaining after removal of iminium chloride 10c was
washed with two portions of water, and the organic
layer was dried over MgSO . The solvent was re-
moved, and the residue was recrystallized from isopro-
panol to obtain 1.4 g of bis(diethylphosphinothioyl)
disulfide 12b, mp 57°С. Н NMR spectrum, δ, ppm:
.31 t and 1.36 t (12H, MeCH , J = 8.0 Hz), 2.12–
Reaction of acid 7b with imine 8b. A solution of
1
1.5 g (9.7 mmol) of acid 7b in 10 mL of CCl was
4
3
added dropwise with stirring to a solution of 2.0 g
2
HH
(
9.7 mmol) of imine 8b in 10 mL of CCl , maintaining
4
1
3 2
+
+
31
the temperature at 0–5°C. The reaction mixture was
then let to warm up to 20°C and allowed to stand for
2
Р
2
4 h. The crystals were filtered off to obtain 0.85 g
8
4
12 27 2
(
85%) of N-tert-butyl-2-methylpropan-1-iminium
1
bromide 14, mp103–104°C. Н NMR spectrum, δ,
ppm: 1.30 d (6H, Me CH, J = 7.0 Hz), 1.57 s (9H,
CMe ), 3.75 m (1H, Me CH), 8.18 d (1H, CH=N , J =
8
5
3
2
HH
+
3
3
2
HH
4
+
31
.0 Hz), 14.4 br.s (1H, N H). Р NMR spectrum: δР
7.63 ppm. Found, %: C 51.74; H 8.59; N 6.86.
1
C H NBr. Calculated, %: C 51.94; H 8.72; N 6.73.
8 18
3
From the mother liquor we first removed CCl and
4
1
2
2
HH
3
1
then, in a vacuum of 0.08 mmHg, volatile products
.23 m and 2.36–2.48 m (8H, CH P). Р NMR spec-
trum: δ 91.1 ppm.
2
1
which were collected in liquid nitrogen trap. The H
Р
NMR spectrum of the condensate in the trap showed
no other signals than those of the starting bromimine
8b. From the residue we isolated 1.17 g (78%) of
b. Ratio 1 : 3. A solution of 4.6 g (0.03 mol) of acid
b в 40 mL CCl was added dropwise to a solution of
7
4
1
1
4.6 g (0.09 mol) of chlorimine 8а in 60 mL of CCl4
disulfide 12b, mp 57°C. Н NMR spectrum, δ, ppm:
3
maintaining the temperature at 0–5°С. The mixture
was then allowed to stand at a room temperaturе for 24 h.
The crystals were filtered off to obtain 0.4 g of
-methylpropan-1-iminium chloride 10c. From cold
mother liquor we isolated an additional 6.2 g of
1
2
.16 t and 1.31 t (12H, MeCH , J = 8.0 Hz), 1.96–
2
HH
3
1
.02 m and 2.09–2.15 m (8H, CH P). Р NMR spec-
2
trum: δ 89.10 ppm. Found, %: C 31.18; H 6.71; P 20.07.
Р
2
C H P S . Calculated, %: C 31.35; H 6.58; P 20.21.
8
20 2 4
3
1
1
,1-Dimethyl-2-oxoethyl diphenylphosphinodi-
iminium chloride 10c. The Р NMR spectrum of the
thioate (15а). Acid 7а, 15 g (0.06 mol), was added in
portions under argon to a solution of 11.6 g (0.071 mol)
of imine 8а in 75 mL of anhydrous methylene chloride
maintaining the temperature of the reaction mixture at
residue after removal of the solvent contained a strong
signal at δ 90.0 ppm corresponding to disulfide 12b
Р
and a weak signal at δ 77.3 ppm corresponding to
Р
iminium chloride 11.
0
–5°С. The mixture was stirred at room temperature
Competitive reaction of acids 7а and 7b with
imine 8а. A solution of a mixture of 0.93 g (3.7 mmol)
of acid 7а and 0.57 g (3.7 mmol) of acid 7b was added
dropwise at 0–5°С to a solution of 0.6 g (3.7 mmol)
chlorimine 8а in CH Cl . The reaction mixture was
for 5 h. After 48 h, to convert iminium salt 10а into
aldehyde 15а, water, 16 mL (0.089 mol), containing 2–
3
drops of conc. HCl was added maintaining the
temperature of the reaction mixture at 10–15°С. The
mixture was stirred at room temperature for 1 h. The
organic layer was separated and dried with MgSO4.
The solvent was removed and the residue was re-
2
2
then let to warm up to 20°C and was stirred for 3 h.
3
1
The Р NMR spectrum of the reaction mixture showed
signals of compounds 10а (57.3 ppm), 12а (68.12 ppm),
crystallized from CCl . Yield 10.2 g (54%), mp 102°С.
4
1
0c (77.21 ppm), and 12b (89.25 ppm), as well аs
signals of the starting dithio acids 7а (56.55 ppm) and
b (75.46 ppm). From the integral intensities of the
1
Н NMR spectrum, δ, ppm: 1.28 s (6H, CMe ), 7.31–
2
7
.39 m (6H, meta,para-CH ), 7.83 d.d (4H, ortho-
Ar
7
3
3
CH , J = 7.0, J = 14.0 Hz), 9.65 s (1H, CHO).
Ar
HH
PH
signals it was concluded that, firstly, in the reaction
with chlorimine 8а 78% of acid 7а was consumed and
as little as 37% of acid 7b, and secondly, the reaction
of diphenylphosphinothioic acid 7а with imine 8а
resulted predominantly in the formation of substitution
product 10а, and of diethylphosphinothioic acid 7b, in
31
Р NMR spectrum: δ 56.3 ppm. Found, %: C 59.77;
P
H 5.21; P 9.73; S 19.85. C H OPS . Calculated, %: C
1
6
17
2
5
9.98; H 5.35; P 9.67; S 20.01.
1,1-Dimethyl-2-oxoethyl diethylphosphinodithioate
(15b) was prepared in a similar way from 16.2 g
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KHAIRULLIN et al.
3
31
(
0.1 mol) of imine 8а and 7.7 g (0.05 mol) acid 7b.
7.8, J = 14.0 Hz). Р NMR spectrum: δ 55.19 ppm.
PH
P
1
Yield 6.0 g (54%), bp 81–82°C (0.08 mmHg). Н
Found, %: C 58.78; H 6.27; P 8.31. C H O PS .
18 23 2 2
NMR spectrum, δ, ppm: 1.18 t and 1.24 t (6H, MeCH ,
Calculated, %: C 58.99; H 6.33; P 8.45.
,2-Diethoxy-1,1-dimethylethyl diphenylphosphino-
dithioate (18b) was prepared in a similar way from
.41 g (0.0169 mol) of aldehyde 15a and 5 g
0.0338 mol) of triethyl orthoformate. Yield 5.2 g
2
3
JHH = 8.0 Hz), 1.53 s (6H, CMe ), 1.98–2.10 m (4H,
2
2
3
1
CH P), 9.64 s (1H, CHO). Р NMR spectrum: δР
2
7
5.9 ppm. Found, %: C 42.71; H 7.49; P 13.71.
5
(
C H OPS . Calculated, %: C 42.83; H 7.64; P 13.81.
8
17
2
1
2
-(tert-Butylazanylidene)-1,1-dimethylethyl di-
phenylphosphinodithioate (16а). Triethylamine, 1.88 g
0.0186 mol), was added dropwise to a solution of
(79%), mp 102°С. Н NMR spectrum, δ, ppm: 1.19 t
3
(6H, CH Me, J = 7.2 Hz), 1.41 s (6H, CMe ), 3.62
2
HH
2
3
(
q and 3.79 q (4H, OCH , J = 7.2 Hz), 4.86 s (1H,
CH), 8.0 d.d (4H, ortho-CH , J = 7.2, J = 14.0
Ar HH PH
Hz), 7.48–7.55 m (6H, meta,para-CHAr). Р NMR
2 HH
3
3
7
0
.4 g (0.0186 mol) of salt 10c in 40 mL of CH Cl at
–5°C. The reaction mixture was then let to warm up
2
2
3
1
to 20°C and was stirred for 3 h. Triethylamine hyd-
rochloride was filtered off, the solvent was removed,
and the residue was recrystallized from petroleum ether.
spec-trum: δ 54.74 ppm. Found, %: C 60.81; H 6.79;
P
P 8.01; S 16.13. C H O PS . Calculated, %: C 60.89;
2
0
27
2
2
H 6.90; P 7.85, S 16.25.
-(1,3-Dibenzyl-1,3-diazolidin-5-yl)-1-methylethyl
diphenylphosphinodithioate (20а). A solution of 1.6 g
0.005 mol) of aldehyde 15a, 1.2 g (0.005 mol) of
1
Yield 4.6 g (69%), mp 62°С. Н NMR spectrum, δ,
1
3
ppm: 1.04 d (6H, CHMe , J = 6.0 Hz), 1.55 s (6H,
2
HH
3
CMe ), 3.15 quintet (1H, CHMe , J = 6.0 Hz), 7.40–
2
2
HH
(
7
7
.50 m (6H, meta,para-CH ), 7.92 s (1H, CH=N),
Ar
N,N'-dibenzylethanediamine, and 3 g of 3 Å molecular
sieves in 35 mL of benzene was heated for 5 h at 50°C.
Molecular sieves were filtered off, the solvent and
3
3
.97 d.d (4H, ortho-CH , J = 6.8, J = 14.0 Hz).
Ar
HH
PH
3
1
Р NMR spectrum: δ 54.46 ppm. Found, %: C 62.96;
P
H 6.81; P 8.73; N 3.69. C H NPS . Calculated, %: C
19
24
2
volatile substances were removed in a vacuum
6
3.13; H 6.69; P 8.57; N 3.87
,1-Dimethyl-2-[(4-methylphenyl)azanylidene]-
ethyl diethylphosphinodithioate (16c). A mixture of
.2 g (0.01 mol) of aldehyde 15а, 1.08 g (0.01 mol)
p-toluidine 17c, and 3 g of molecular sieves 3 Å in
0 mL of benzene was refluxed for 6 h with a Dean–
1
(
0.02 mmHg). Yield 2.5 g (93%). Н NMR spectrum,
1
δ, ppm: 1.42 s (6H, CMe
2
), 2.49 q and 2.78 q (4H,
3
CH CH , J = 6.0 Hz), 3.61 d and 4.29 d (2H,
2
2
HH
2
3
PhCH , J = 14.0 Hz), 4.43 s (1H, CHN ), 7.13 m
2 HH 2
(6H, meta,para-CH , C H ), 7.30 m (10H, CH Ph),
Ar
6
5
2
3
3
3
7.81 d.d (4H, ortho-CH , C H , J = 7.6, J
14.0 Hz). Р NMR spectrum: δ 55.51 ppm. Found,
=
Ar
6
5
HH
PH
3
1
Stark trap. The molecular sieves were then filtered off,
the solvent was removed, and the residue was re-
P
%: C 70.63; H 6.41; P 5.53; S 11.67. C H N PS .
32
35
2
2
crystallized from octane. Yield 3.07 g (75%), mp 87°C.
Calculated, %: C 70.82; H 6.41; N 5.16; P 5.71; S
11.82.
1
Н NMR spectrum, δ, ppm: 1.73 s (6H, CMe ), 2.73 s
2
3
(
3H, CH ), 6.90 d and 7.09 d (4H, C H , J
=
3
6
4
HH
1
-(1,3-Dibenzyl-1,3-diazolidin-5-yl)-1-methylethyl
diethylphosphinodithioate (20b). A mixture of 1.5 g
6.6 mmol) of aldehyde 15b and 1.66 g (6.6 mmol) of
8
.0 Hz), 7.44–7.53 m (6H, meta,para-CH ), 8.03 d.d
Ar
3
3
(
(
4H, ortho-CH , J = 8.0, J = 14.0 Hz), 8.20 s
1H, CH=N). Р NMR spectrum: δ 53.89 ppm.
Ar HH PH
(
31
P
N,N'-dibenzylethanediamine in 30 mL of benzene was
refluxed for 4 h with a Dean–Stark trap. The solvent
was removed, and the residue was recrystallized from
Found, %: C 67.56; H 5.80; N 3.57; P 7.70. C H NPS .
23
24
2
Calculated, %: C 67.45; H 5.91; N 3.42; P 7.56.
1
2
,2-Dimethoxy-1,1-dimethylethyl diphenylphos-
alcohol. Yield 2.3 g (79%). Н NMR spectrum, δ, ppm:
3
3
phinodithioate (18а). Sulfuric acid, 2 drops, was
1.06 d.t (6H, CH CH , J = 7.6, J = 21.0 Hz),
2 3 HH PH
added to a solution of 1.74 g (0.0054 mol) of aldehyde
1.60 s (6H, CMe ), 1.94 m (4H, CH P), 2.63 q and
2 2
2
3
1
5а and 1.44 g (0.0136 mol) of trimethyl orthoformate
2.93 q (4H, CH CH , J = 10.4, J = 6.0 Hz), 3.60
2 2 HH HH
2
in 15 mL of benzene. The mixture warmed up slightly.
It was allowed to stand for 2 days, the solvent and
excess ortho ester were removed, and the residue was
d and 4.25 d (4H, CH Ph, J = 13.6 Hz), 4.37 s (1H,
2 HH
3
CH), 7.10 d (2H, para-CH , C H , J = 7.2 Hz),
Ar
6
3
5
HH
3
7.17 d.d (4H, meta-CH , C H , J = J = 7.2 Hz),
7.27 d (4H, ortho-CH , C H , J = 7.2 Hz).
Ar
6
5
HH
HH
3
31
recrystallized from CCl . Yield 1.54 g (78%), mp 113°C.
Р
4
Ar
6
5
HH
1
Н NMR spectrum, δ, ppm: 1.40 s (6H, CMe ), 3.43 s
NMR spectrum: δ 72.52 ppm. Found, %: C 64.71; H
2
P
(
6H, OCH ), 4.91 s (1H, CH), 7.41–7.50 m (6H,
8.03; N 6.27; P 6.83. C H N PS . Calculated, %: C
64.54; H 7.90; N 6.27; P 6.93.
3
24 35
2
2
3
meta,para-CH ), 7.98 d.d (4H, ortho-CH , J =
Ar
Ar
HH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

REACTIONS OF DIPHENYL- AND DIETHYLPHOSPHINODITHIOIC ACIDS
2319
ACKNOWLEDGMENTS
p. 1175. doi 10.1016/j.tetlet.2015.01.104
4
. Khairullin, R.A., Gazizov, M.B., Aksenov, N.G., and
Khayarov, Kh.R., Russ. J. Gen. Chem., 2015, vol. 85,
no. 9, p. 2099. doi 10.1134/S1070363215090133
The work was financially supported by the Ministry
of Education and Science of the Russian Federation in
the framework of the base part of the state contract for
scientific research (project no. 4.5348.2017/8.9).
5. Gazizov, M.B., Khairullin, R.A., Perina, A.I., Min-
nikhanova, A.A., Aksenov, N.G., Gnezdilov, O.I.,
Il’yasov, A.V., and Khayarov, Kh.R., Russ. J. Gen.
Chem., 2016, vol. 86, no. 3, p. 499. doi 10.1134/
S1070363216030014
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017