Synthesis of acyloxyalkyl esters of thiocarbonic and dithiocarbamic acids

Article abstract of DOI:10.1134/S1070428013020048

Reactions of acyloxyalkyl chloride with alkaline salts of alkylxanthic, butyltrithiocarbonic, and diethyldithiocarbamic acids afforded a series of acyloxyalkyl esters of various nature and positions of the acyl groups in the molecule.

Full text of DOI:10.1134/S1070428013020048

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 2, pp. 198−203. © Pleiades Publishing, Ltd., 2013.
Original English Text © N.P. Mustafaev, M.A. Kulieva, K.N. Mustafaev, T.N. Kulibekova, G.A. Kakhramanova, M.R. Safarova, N.N. Novotorzhina, N.V. Zyk,
2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 2, pp. 210−214.
Synthesis of Acyloxyalkyl Esters of Thiocarbonic
and Dithiocarbamic Acids
N. P. Mustafaev, M. A. Kulieva, K. N. Mustafaev, T. N. Kulibekova,
G. A. Kakhramanova, M. R. Safarova, and N. N. Novotorzhina
Institute of Additives Chemistry, National Academy of Sciences of Azerbaijan, Baku, 1029 Azerbaidjan
e-mail: aki05@mail.ru
Received April 17, 2012
Abstract—Reactions of acyloxyalkyl chloride with alkaline salts of alkylxanthic, butyltrithiocarbonic, and
diethyldithiocarbamic acids afforded a series of acyloxyalkyl esters of various nature and positions of the acyl
groups in the molecule.
DOI: 10.1134/S1070428013020048
synthesis of a series of acyloxyalkyl esters of alkylxanthic,
butyltrithiocarbonic, and diethyldithiocarbamic acids
with a different nature and the place of the acyl group in
the molecule.
Derivatives of thiocarbonic acids are extensively used
in various fields of the national economy, for example,
as additives to lubricating oils, flotators, pesticides,
vulcanization accelerators, stablizers and additives to the
polymeric compositions [1].
Acyloxyalkyl esters of thiocarbonic and diethyl-
dithiocarbamic acids were obtained from the acyloxyalkyl
chlorides and the alkaline salts of appropriate acids.
In extension of our research in the field of the synthesis
and investigation of thiocarbonic acids derivatives [2] we
planned to synthesize a series of derivatives of these acids
containing in the molecule a carboxy group to improve
their lubricity.
The initial acyloxymethyl chlorides Iа–Id were ob-
tained in a 80–85% yield from carboxylic acids chlorides
and paraformaldehyde in the presence of zinc chloride at
45–50°С by procedure [3].
We report here the results of the studies on the
S
S
R'O
SK
R'O
BuS
S(CH2)nOC(=O)R
IIа_IIl
S
S
S
BuS
SNa
RCOO(CH2)nCl
S(CH2)nOC(=O)R
IIIа_IIId
Iа_Ij
S
Et2N
SNa
Et2N
S(CH2)nOC(=O)R
IVа_IVe
I, n = 1: R = Me (а), Et (b), C7H15 (c), Ph (d); n = 2: R= Me (e), Et (f), Bu (g), Vin (h), HSCH2 (i), Ph (j); II, n = 1: R = Me, R′ = Et (а),
i-Pr (b), Bu (c); R′ = i-Pr, R = Et (d), C7H15 (e), Ph (f); n = 2: R′ = i-Pr, R= Me (g), Et (h); R = Bu, R′ = Et (i), i-Pr (j); R′ = i-Pr, R = Vin
(k), HSCH2 (l); III, n = 1: R= Me (а), Ph (b); n = 2: R = Me (c), Ph (d); IV, n = 1: R = Me (а), Ph (b); n = 2: R = Me (c), Bu (d), Vin (e).
198

SYNTHESIS OF ACYLOXYALKYL ESTERS
199
presence of triethylamine.
RCOOCH2Cl
ZnCl2
+
RCOCl HCHO
For this reaction in their turn the starting S-hydroxy-
methyl derivatives of xanthic acids were obtained by the
treatment with hydrochloric acid of the water solutions
of the equimolar amounts of potassium alkylxanthate and
formaldehyde by the procedure [5].
Iа_Id
R = Me (а), Et (b), C7H15 (c), Ph (d).
The initial acyloxyethyl chlorides Ie–Ij were syn-
thesized by the esterification of carboxylic acids with
ethylenechlorohydrin in the presence of KU-2 catalyst.
The best yields were obtained at the ratio carboxylic
acid–ethylenechlorohydrin 1.2:1 and the amount of KU-2
catalyst of 10% calculated on the acid.
CH2O,
S
S
HCl
H
R'O
SK
R'O
SCH2O
H
The identical refraction indices and IR spectra of
acyloxymethyl xanthates with the same substituents prove
the identity of compounds obtained by both methods.
KU-2
RCOOH + ClCH2CH2OH
RCOOCH2CH2Cl
Ie_Ij
R = Me (e), Et (f), Bu (g), Vin (h), HSCH2 (i), Ph (j).
Acyloxyethyl esters of thiocarbonic and diethyl-
dithiocarbamic acids were synthesized in more severe
conditions. Due to the lower reactivity of the chlorine
atom in the acyloxyethyl chlorides their reactions
with the thioacid salts was performed in polar solvents
(2-propanol, DMF) at higher temperature, 70–75°С, over
4–5 h. The yield of the target products attained 80–90%.
The xanthates and diethyldithiocarbamate employed
as the initial compounds are freely available reagents
manufactured by the chemical industry. The sodium
butyltrithiocarbonate necessary for the synthesis of the
trithiocarbonic acids esters was obtained from sodium
butylmercaptide and carbon disulfide in DMF by the
known method [4] and was used further without the
isolation from the solution.
The synthesized derivatives of thiocarbonic and
diethyldithiocarbamic acids are light-yellow fluids, well
soluble in organic solvents and mineral oils.
S
The composition and structure of esters synthesized
were confirmed by the elemental analysis, IR and
1Н NMR spectra.
BuSH + NaOH + CS2
BuS
SNa
Acyloxymethyl chlorides fairly easily react with the
alkaline salts of thioacids, and the nature of the substituent
at the thiocarbonyl group virtually does not affect the du-
ration of the reaction and the yield of the target compound.
Because of the hydrolysis of the acyloxymethyl chlorides
in water and the reactions with the other hydroxyl-con-
taining compounds the reaction with the alkaline salts of
thioacids was carried out in aprotic solvent, benzene. At
the vigorous stirring of equimolar amounts of the initial
substances at 40–45°С within 2–3 h the yield of target
compounds reached over 85%.
The IR spectra of all acyloxyalkyl esters of thiocarbonic
acids contain strong absorption bands in the region 1750–
1740 cm–1 characteristic of the C=O group.
The other specific groups of the acyl fragment give
rise to absorption bands in their appropriate frequency
regions [6]: The double bond absorption of the acryloyl
group is observed in the region 1650–1620 cm–1, the
vibrations of the aromatic ring of the benzoyl group
appear as a strong band at 1600–1590 cm–1, to the S–H
bond of the sulfhydryl group belongs a weak band in the
region 2600–2550 cm–1.
Acyloxymethyl esters of xanthic acids unlike the other
target compounds were also synthesized by an alternative
procedure: by the reaction of carboxylic acids chlorides
with hydroxymethyl esters of the xanthic acids in the
The characteristic functional group of all synthesized
derivatives of thiocarbonic acids is the C=S group
whose stretching vibrations appear in the xanthate
spectra as strong bands at 1060–1030 cm–1, in those of
trithiocarbonates at 1058–1053 cm–1, of dithiocarbamates,
at 990 cm–1 in agreement with the published data [6,
7]. The other characteristic absorptions of the xanthate
fragments are strong bands in the regions 1250–1235 and
RCOCl,
Et3N
S
S
HOH2CS
OR'
RCOOCH2S
OR'
IIa, IIb
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MUSTAFAEV et al.
200
1150–1090 cm–1 belonging to ester bonds.
and 1.5 cm. Silica gel ACK was used as sorbent, eluent
benzene–2-propanol, 4 : 1. Eluates were evaporated
in a vacuum. Reaction product was controlled by the
refraction index.
The bands characteristic of amide bonds of
dithiocarbamates, often called NCS-bands [6–8] were
observed at 1570–1395 and 1420–1260 cm–1.
Acyloxymethyl chlorides Iа–Id were obtained
by adding gradually at room temperature 0.2 mol of
paraformaldehyde and 0.4 g of zinc chloride to 0.2 mol of
carboxylic acid chloride. The reaction mixture was stirred
at 45–50°С till paraformaldehyde completely dissolved,
the precipitate of zinc chloride was filtered off, and the
filtrate was distilled in a vacuum.
The absorption bands of the ordinary C–S bonds are
known to be weak [6] and due to the uncertainty of their
position are as a rule seldom used for the identification.
Yet in the spectra of trithiocarbonates beside the
absorption band of the C=S group another strong band is
observed in the range of 825–790 cm–1. The appearance
of this band cannot be ascribed to the vibrations of the
bonds C–C, C–H or C–O whose spectral range is well
known. It can be positively stated that this band originates
just from the structure of the fragment –SC(=S)S– since
in the xanthate sperctra where this structure is lacking the
band does not appear.
1H NMR spectra of acyloxyalkyl esters of thiocarbonic
acids were studied by the examples of acetyloxyalkyl
esters of isopropylxanthic IIb, IIg, butyltrithiocarbonic
IIIа, IIIc, and N,N-diethyldithio-carbamic IVа, IVc
acids. The acetyl protons in the spectra of all six
compounds appear as a singlet at 2.0 ppm.
Acetoxymethyl chloride (Iа). Yield 18.5 g (85%), bp
102–103°С (760 mm Hg), d420 1.2010, nD20 1.4210. MRD
22.92, calculated 22.57. Found, %: Cl 32.56. C3H5ClO2.
Calculated, %: Cl 32.71.
Propionyloxymethyl chloride (Ib). Yield 20.8 g
(85%), bp 106–107°С (760 mm Hg), d420 1.1481 (1.1824
[3]), nD20 1.4221 (1.4295 [3]). MRD 27.12, calculated
27.19. Found, %: Cl 29.01. C4H7ClO2. Calculated, %:
Cl 28.98.
Octanoyloxymethyl chloride (Ic). Yield 31.2 g
(81%), bp 114–115°С (760 mm Hg), d4 1.0109, nD20
20
1.4330. MRD 49.55, calculated 50.28. Found, %: Cl 18.32.
The methylene protons of the OCH2S fragment of
the acetyloxymethyl esters of thiocarbonic acids IIb,
IIIа, IVа also give rise to singlets, but in a weaker field,
around 5.65 ppm. The protons of the methylene group in
the acetoxyethyl esters of the thiocarbonic acids IIg, IIIc,
IVc are observed at 4.13–4.19 (OCH2) and 3.25–3.55 ppm
(SCH2). The proton signals of O, S , and N-substituents
C9H17ClO2. Calculated, %: Cl 18.44.
Benzoyloxymethyl chloride (Id). Yield 27.3 g (80%),
bp 92–93°С (760 mm Hg), d420 1.2342, nD20 1.5276. MRD
42.54, calculated 42.06. Found, %: Cl 20.20. C8H7ClO2.
Calculated, %: Cl 20.82.
Acyloxyethyl chlorides Ie–Ij were obtained by
esterification of 0.24 mol of carboxylic acid with 0.2 mol
of ethylenechlorohydrin in boiling benzene in the
presence of cation exchanger KU-2 taken in amount of
10% with respect to the acid. The reaction was stopped
after the theoretical quantity of water was azeotropically
distilled. Then the reaction mixture was washed in
succession with a solution of NaHCO3 and with water till
neutral washings, filtered, benzene was distilled off, and
the residue was subjected to vacuum distillation.
1
in the H NMR spectra of the derivatives of xanthic,
butyltrithiocarbonic, and diethyldithiocarbamic acids
appear in the following regions (δ, ppm): OPr-i: 1.42 d
(6H, 2CH3), 5.45 m (1H, CH); SBu: 0.99 t (3H, CH3),
1.50 m (4H, CH2CH2), 3.22 t (2H, SCH2); NEt2: 1.30 t
(6H, 2CH3), 3.80 m (4H, 2CH2).
EXPERIMENTAL
2-(Acetoxy)ethyl chloride (Ie). Yield 19.8 g (81%),
bp 43°С (10 mm Hg), d420 1.1553 (1.1700 [9]), nD20 1.4240
(1.4247 [9]). MRD 27.07, calculated 27.19. Found, %:
Cl 22.85. C4H7ClO2. Calculated, %: Cl 23.58.
IR absorption spectra were recorded on a
spectrophotometer Specord 75IR from thin film. H
1
NMR spectra were registered on a spectrometer Varian
Т-60 (60 MHz) in CCl4, internal reference TMS. The
purification and isolation of compounds synthesized was
commonly performed by vacuum distillation, and the
compounds decomposing at the distillation were purified
by absorption column chromatography on a column 1.5
m high consisting of three sections of diameters 4, 3,
2-(Propionyloxy)ethyl chloride (If). Yield 21 g
(77%), bp 59°С (10 mm Hg), d420 1.0824, nD20 1.4205.
MRD 31.93, calculated 31.81. Found, %: Cl 26.10.
C5H9ClO2. Calculated, %: Cl 26.00.
2-(Valeroyloxy)ethyl chloride (Ig). Yield 25 g (76%),
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SYNTHESIS OF ACYLOXYALKYL ESTERS
201
bp 72°С (10 mm Hg), d420 1.0284, nD20 1.4180. MRD
40.34, calculated 41.05. Found, %: Cl 21.62. C7H13ClO2.
Calculated, %: Cl 21.58.
C 42.98; H 6.28; S 28.69. C8H14O3S2. Calculated, %:
C43.24; H 6.36; S 28.82.
Propionyloxymethyl ester of isopropylxanthic acid
(IId). Yield 38.2 g (86%), bp 98–101°С (0.5 mm Hg),
d420 1.1293, nD20 1.5150. MRD 59.37, calculated 59.60.
Found, %: C 43.02; H 6.23; S 28.34. C8H14O3S2.
Calculated, %: C 43.24; H 6.36; S 28.82.
2-(Acryloyloxy)ethyl chloride (Ih). Yield 18.2 g
(68%), bp 60°С (10 mm Hg), d420 1.1491, nD20 1.4490.
MRD 31.41, calculated 31.34. Found, %: Cl 26.27.
C5H7ClO2. Calculated, %: Cl 26.39.
Octanoyloxymethyl ester of isopropylxanthic acid
(IIe). Yield 50.2 g (86%). The compound was purified
by chromatography. d420 1.0506, nD20 1.5025. MRD 82.20,
calculated 82.68. Found, %: C 53.14; H 8.17; S 21.70.
C13H24O3S2. Calculated, %: C 53.42; H 8.22; S 21.91.
2-(Mercaptoacetoxy)ethyl chloride (Ii). Yield 23.2 g
(75%), bp 70°С (10 mm Hg), d420 1.3099, nD20 1.5000.
MRD 34.72, calculated 35.00. Found, %: Cl 22.91;
S 20.68. C4H7ClSO2. Calculated, %: Cl 23.05; S 20.71.
2-(Benzoyloxy)ethyl chloride (Ij). Yield 27.7 g
(75%), mp 107°С (from isooctane). Found, %: Cl 18.91.
C9H9ClO2. Calculated, %: Cl 19.24.
Benzoyloxymethyl ester of isopropylxanthic acid
(IIf). Yield 47.00 g (87%). The compound was purified
by chromatography. d420 1.1911, nD20 1.5778. MRD 75.28,
calculated 74.46. Found, %: C 53.10; H 5.02; S 22.93.
C12H14O3S2. Calculated,%: C 53.33; H 5.17; S 23.70.
Acyloxymethyl esters of alkylxanthic acids IIа–
IIf. To a slurry of 0.2 mol potassium alkylxanthate in
benzene at room temperature was added 0.2 mol of
acyloxymethyl chloride, and the mixture was stirred for
2–3 h at 40–45°С. The reaction mixture was washed with
water, filtered, benzene was distilled off, and the residue
was subjected to vacuum distillation.
Acyloxyethyl esters of alkylxanthic acids IIg–IIl.
To a mixture of 0.2 mol potassium alkylxanthate in 50 ml
of isopropyl alcohol was added 0.2 mol of acyloxyethyl
chloride, the reaction mixture was stirred for 4 h at
70–75°С, washed with water, filtered, and the filtrate was
subjected to vacuum distillation.
Acetoxymethyl ester of ethylxanthate (IIа). Yield
35 g (90%), bp 77–78°С (0.4 mm Hg), d420 1.2089, nD20
1.5252. MRD 49.26, calculated 49.78. Found, %: C 36.84;
H 5.69; S 32.45. C6H10O3S2. Calculated, %: C 37.11; H
5.15; S 32.99.
2-(Acetoxy)ethyl ester of isopropylxanthic acid
(IIg). Yield 39 g (88%), bp 100–100.5°С (0.4 mm Hg),
d420 1.1450, nD20 1.5228. MRD 59.29, calculated 59.58.
Found, %: C 42.85; H 6.76; S 28.78. C8H14O3S2.
Calculated, %: C 43.22; H 6.35; S 28.85.
Ester IIа was obtained also by an alternative method:
To 30.4 g (0.2 mol) of hydroxymethyl ester of ethylxanthic
acid in 100 ml of benzene at 5°С was added 20.2 g (0.2
mol) of triethylamine, then 15.7 g (0.2 mol) of acetyl
chloride. The reaction mixture was stirred for 30 min at
20°С and 2 h at 35°С. The precipitate was filtered off,
the filtrate was washed with water, filtered, benzene was
distilled off, and the residue was subjected to vacuum
distillation. Yield 34.9 g (90%).
2-(Propionyloxy)ethyl ester of isopropylxanthic
acid (IIh). Yield 40.6 g (86%), bp 110–111°С (0.4 mm
Hg), d4 1.1287, nD20 1.5220. MRD 63.86, calculated
20
64.21. Found, %: C 45.20; H 7.07; S 27.78. C9H16O3S2.
Calculated, %: C 45.76; H 6.78; S 27.11.
2-(Valeroyloxy)ethyl ester of ethylxanthic acid
(IIi). Yield 42.5 g (85%), bp 116–117°С (0.4 mm Hg),
d420 1.1075, nD20 1.5128. MRD 68.92, calculated 67.82.
Found, %: C 47.79; H 7.31; S 25.78. C10H18O3S2.
Calculated, %: C 48.00; H 7.20; S 25.60.
The physical constants and the data of the elemental
analysis showed the identity of compounds obtained by
two methods.
2-(Valeroyloxy)ethyl ester of isopropylxanthic
acid (IIj). Yield 46.4 g (84%), bp 129°С (0.4 mm
Hg), d420 1.0833, nD20 1.5040. MRD 72.27, calculated
72.26. Found, %: C 49.25; H 7.78; S 23.98. C11H20O3S2.
Calculated, %: C 49.97; H 7.63; S 24.26.
Acetoxymethyl ester of isopropylxanthic acid (IIb).
Yield 37 g (89%), bp 96–98°С (0.5 mm Hg), d420 1.1624,
nD20 1.5250. MRD 54.91, calculated 54.97. Found, %:
C 40.21; H 5.65; S 29.98. C7H12O3S2. Calculated, %:
C 40.28; H 5.77; S 30.77.
2-(Acryloyloxy)ethyl ester of isopropylxanthic
acid (IIk). Yield 38.4 g (82%), bp 121°С (0.45 mm Hg),
d420 1.1609, nD20 1.5337. MRD 62.70, calculated 63.74.
Acetoxymethyl ester of butylxanthic acid (IIc).
Yield 39 g (88%), bp 102–103°С (0.5 mm Hg), d420 1.1384,
nD20 1.5152. MRD 58.89, calculated 58.60. Found, %:
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MUSTAFAEV et al.
202
Found, %: C 46.28; H 5.88; S 27.22. C9H14O3S2.
Calculated, %: C 46.15; H 5.98; S 27.34.
reaction mixture was washed with water, filtered, ben-
zene was distilled off, and the residue was subjected to
vacuum distillation. Yield 37.6 g (85%), bp 130–131°С
(0.6 mm Hg), d420 1.1646, nD20 1.5567. MRD 61.12,
calculated 60.98. Found, %: C 43.31; H 7.32; N 6.30
S 28.90. C8H15NO2S2. Calculated, %: C 43.42; H 6.80;
N 6.33; S 28.95.
2-(Mercaptoacetoxy)ethyl ester of isopropyl-
xanthic acid (IIl). Yield 36.8 g (83%), bp 176°С
(0.45 mm Hg), d420 1.2570, nD20 1.5740. MRD 66.77,
calculated 67.40. Found, %: C 37.83; H 6.18; S 37.65.
C8H14O3S3. Calculated, %: C 37.78; H 5.56; S 37.82.
Benzoyloxymethyl ester of diethyldithiocarbamic
acid (IVb) was obtained similarly. Yield 48.7 g (86%),
white crystals, mp 39–40°С (from heptane). Found,
%: C 55.18; H 6.20; N 4.90; S 22.59. C13H17NO2S2.
Calculated, %: C 55.12; H 6.00; N 4.94; S 22.61.
Acetoxymethyl ester of butyltrithiocarbonic acid
(IIIа). To 18 g (0.2 mol) of butylmercaptane in 50 ml
of DMF was slowly added 8 g (0.2 mol) of sodium
hydroxide, and the mixture was stirred for 2.5 h at
60–70°С. Then at 20–25°С 19 g (0.25 mol) of carbon
disulfide was added, 21.7 g (0.2 mol) of acetoxymethyl
chloride was added by portions, and the mixture was
stirred for 2–3 h at 40–45°С. The reaction mixture was
washed with water, filtered, the solvent was distilled
off, and the residue was distilled in a vacuum. Yield
40 g (85%), bp 129–130°С (0.5 mm Hg), d420 1.1648,
nD20 1.5652. MRD 66.68, calculated 66.62. Found, %:
C 40.32; H 5.93; S 40.38. C8H14O2S3. Calculated, %:
C 40.33; H 5.92; S 40.33.
Acyloxyethyl esters of diethyldithiocarbamic
acid IVc–IVe were obtained in the same way as the
acyloxymethyl esters, but the reaction was carried out in
DMF at 75–80°С over 4–5 h.
Acetoxyethyl ester of diethyldithiocarbamic acid
(IVc). Yield 41.3 g (88%), bp 128°С (0.5 mm Hg),
d420 1.1346, nD 1.5518. MRD 66.25, calculated 65.60.
20
Found, %: C 45.79; H 7.39; N 6.12; S 26.9. C9H17NO2S2.
Calculated, %: C 45.95; H 7.23; N 5.95; S 27.23.
Benzoyloxymethyl ester of butyltrithiocarbonic
acid (IIIb) was obtained similarly. Yield 51.6 g (86%).
The compound was purified by chromatography.
d420 1.1729, nD20 1.5940. MRD 86.83, calculated 86.11.
Found, %: C 51.75; H 5.15; S 31.10. C13H16O2S3.
Calculated, %: C 52.00; H 5.33; S 31.96.
2-(Valeroyloxy)ethyl ester of diethyldithiocarbamic
acid (IVd). Yield 47.6 g (86%), bp 154°С (0.4 mm Hg),
d420 1.0784, nD 1.5338. MRD 79.93, calculated 79.45.
20
Found, %: C 51.83; H 8.49; N 5.15; S 22.95. C12H23NO2S2.
Calculated, %: C 51.98; H 8.33; N 5.05; S 23.10.
2-(Acryloyloxy)ethyl ester of diethyldithiocarbamic
acid (IVe). Yield 42 g (85%). The compound was purified
by chromatography. d420 1.1395, nD20 1.5645. MRD 70.65,
calculated 69.75. Found, %: C 48.67; H 6.79; N 5.55;
S 25.81. C10H17O2S2. Calculated, %: C 48.57; H 6.88;
N 5.66; S 25.91.
Acyloxyethyl esters of butyltrithiocarbonic acid
IIIc, IIId were obtained and isolated analogously to the
acyloxymethyl esters with the only difference that after
the addition of the acetoxyethyl chloride the reaction
mixture was stirred for 4–5 h at 75–80°С.
2-(Acetoxy)ethyl ester of butyltrithiocarbonic
acid (IIIc). Yield 43.8 g (87%), bp 105–106°С (0.45
mm Hg), d420 1.1507, nD20 1.5600. MRD 70.91, calculated
71.24. Found, %: C 42.38; H 6.77; S 37.52. C9H16O2S3.
Calculated, %: C 42.85; H 6.35; S 38.09.
REFERENCES
1. Kuliev, A.M., Khimiya i tekhnologiya prisadok k maslam
i toplivam (Chemistry and Technology of Additives to
Oils and Fuels), Leningrad: Khimiya, 1985, pp. 102, 136;
Vinogradova, I.E., Protivoiznosnye prisadki k maslam
(Antiwear Additives to Oils), Moscow: Khimiya, 1972, p.
66; Mel’nikov, N.N., Khimiya pestitsidov (Chemsitry of
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Kulieva, M.A., Ramazanova, Yu.B., and Shikhaliev, Sh.M.,
Zh. Prikl. Khim., 1988, vol. 61, p. 1590.
2-(Benzoyloxy)ethyl ester of butyltrithiocarbonic
acid (IIId). Yield 54 g (86%). The compound was purified
by chromatography. d420 1.1759, nD20 1.5900. MRD 90.26,
calculated 90.72. Found, %: C 53.90; H 5.62; S 29.80.
C14H18O2S3. Calculated, %: C 53.50; H 5.73; S 30.57.
Acetoxymethyl ester of diethyldithiocarbamic
acid (IVа). To a mixture of 45 g (0.2 mol) of sodium
diethyldithiocarbamate trihydrate in 50 ml of benzene
was added 21.7 g (0.2 mol) of acetoxymethyl chloride,
and the mixture was stirred for 2–3 h at 40–45°С. The
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