Boron difluoride acetylacetonate sulfenyl(selenyl) halides

Article abstract of DOI:10.1134/S1070363210120054

By cleavage of disulfide and diselenide derivatives of the boron difluoride acetylacetonate the previously unknown sulfenyl(selenyl) chlorides and bromides were prepared. It was shown that these compounds could be involved into the substitution and addition reactions characteristic of sulfenyl(selenyl) halides. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210120054

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 12, pp. 2430–2437. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.V. Svistunova, N.P. Shapkin, M.Yu. Zyazeva, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 12, pp. 1968–1975.
Boron Difluoride Acetylacetonate Sulfenyl(Selenyl) Halides
I. V. Svistunova, N. P. Shapkin, and M. Yu. Zyazeva
Far Eastern State University, ul. Oktyabr’skaya 27, Vladivostok, 690950 Russia
e-mail: irasvist@gmail.com
Received February 9, 2010
Abstract―By cleavage of disulfide and diselenide derivatives of the boron difluoride acetylacetonate the
previously unknown sulfenyl(selenyl) chlorides and bromides were prepared. It was shown that these
compounds could be involved into the substitution and addition reactions characteristic of sulfenyl(selenyl)
halides.
DOI: 10.1134/S1070363210120054
Recently the we [1] described acetylacetonate
complexes containing two boron chelate complexes
bound through the disulfide and diselenide bond:
[F2B(acacS)]2 I and [F2B(acacSe)]2 II. Broad range of
the reactions involving the disulfide and diselenide
groups, and also their availability make these
compounds convenient starting substances for pre-
paring new substituted boron difluoride acetylaceto-
nates. First of all our interest was attracted by the
possibility of converting the compounds I, II into the
corresponding sulfenyl and selenyl halides and their
further use in the substitution and addition reactions.
Sulfenyl chloride derivatives of acetylacetone series
were prepared recently from some metal complexes by
treating the unsubstituted chelates with sulfur
dichloride [2]. F2B(acacSCl) cannot be prepared by
this way because the boron difluoride acetyl-acetonate
unlike metal chelates does not enter the elec-trophilic
substitution reactions [3].
For the cleavage of compounds I, II and prepara-
tion of the sulfenyl chloride (selenyl chloride) deriva-
tives of the boron difluoride acetylacetonate we used
the classic reaction with sulfuryl chloride [4].
O
F
O
F
B
X
+ SO2Cl2
B
XCl
F
F
O
O
2
I, II
III, IV
X = S (I, III), Se (II, IV).
Sulfuryl chloride is an effective reagent for the
cleavage of disulfides, but simple addition of this
reagent to a solution of compound I in chloroform (or
carbon tetrachloride and benzene) does not lead to the
formation of sulfenyl chloride. The analogous result
was obtained previously. In [5] we failed to split the
disulfide group in the dimeric acetylacetonate (Hacac)2·
Cr(acacS-Sacac)Cr(acacH)2.
amounts of triethylamine. The reaction is completed
within 3–4 h and proceeds with almost quantitative
yield. Using of the amine excess for acceleration the
reaction is undesirable because bases destroy the boron
difluoride chelates.
Another catalyst of this process is THF. Performing
the reaction in pure THF is inconvenient. At room
temperature the reaction completes in several minutes
which may be concluded from the change of the color
of the reaction mixture from colorless to intensely
The formation of sulfenyl chloride III takes place
after the addition in the reaction mixture of small
2430

2431
BORON DIFLUORIDE ACETYLACETONATE SULFENYL(SELENYL) HALIDES
yellow caused by the formation of sulfenyl chloride.
But the reaction mixture soon became colorless again,
and we failed to isolate from it any individual product.
Using a mixture of chloroform or benzene with 10 vol %
of THF proved to be more convenient. The sulfenyl
chloride obtained along this pathway is contaminated
with the products of THF chlorination.
with total intensity up to 10% of the intensity of the
main signal.
The use of diethyl ether as a solvent or the an-
hydrous aluminum chloride as a catalyst was in-
effective. The reaction proceeded slower and not to the
completion.
The synthesis of sulfenyl chlorides by chlorination
of aryl benzyl sulfudes was described in [4]. We tried
to apply this reaction to the acetylacetone deriva-tives.
The reaction can be also carried out in the excess of
sulfuryl chloride using it as a solvent. But in this case
it proceeds slower than the catalyzed process, and the
1
The treating of sulfide V with sulfuryl chloride
yields sulfenyl chloride II in small yield.
final product is less pure. H NMR spectrum of the
product besides the singlet of β-methyl groups
(2.80 ppm) contains also some non-identified groups
O
F
O
F
(1)
B
S
CH2C6H5 + SO2Cl2
B
SCl + ClCH2C6H5
F
F
O
O
V
III
The GC–MS analysis showed that the reaction mix-
ture contained benzyl chloride, the products of its further
chlorination (dichlorotoluene, p-chlorobenzyl chloride),
and also the compound which according to its mass spec-
trum was identified as F2B(acacSCH2C6H4Cl). That means
that along with reaction (1) process (2) takes place.
O
F
O
F
B
S
CH2C6H5 + SO2Cl2
B
SCH2C6H4Cl
(2)
F
F
O
O
V
VI
Benzyl sulfide VI can be split by sulfuryl chloride
but only in the presence of basic catalysts. That is why
treating compound V with sulfuryl chloride in the
presence of the catalytic amounts of amine permits to
prepare sulfenyl chloride III in a satisfactory yield.
The reaction proceeds at room temperature to form
1
the products in quantitative yield. H NMR spectra of
the compounds obtained after evaporation of reaction
mixtures contain only the signals attributed to β-
methyl groups of complexes VII, VIII.
The chlorination of diselenide II occurs without
catalyst in an inert solvent to give pure product in a
quantitative yield.
We hoped that treating complexes I, II with iodine
would give sulfenyl (selenyl) iodides. This reaction
was carried out in THF and chloroform in the presence
of triethylamine. But in all cases the starting com-
pounds were recovered. Meanwhile, performing the
reaction in the presence of cyclohexene yielded
F2B(acacS-C6H10I). On the basis of the data obtained it
may be presumed that iodine reacts reversibly with the
formation of small amount of sulfenyl iodide which is
captured with cyclohexene. This reaction irrevers-ibly
shifts the Eq. (3).
Treating compounds I, II with bromine gave
sulfenyl bromide VII and selenyl bromide VIII.
O
O
O
O
F
F
F
F
B
X
+ Br2
B
X
Br
2
I, II
X = S (I, VII), Se (II, VIII).
VII, VIII
Diselenide complex II does not enter this reaction.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2432
SVISTUNOVA et al.
+ I2
O
O
O
O
F
F
F
F
B
S
B
S
I
2
O
O
F
F
F
F
B
S
+
I
B
S
I
O
O
IX
Complexes III, IV, VII, VIII are colored crys-
talline substances well soluble in chloroform, benzene,
ether, and acetic acid. They are insoluble or poorly
soluble in hexane and react with THF, DMF, and
acetone. We failed to find the conditions for
crystallization of complexes III, IV because they de-
compose during the procedure. Compounds VII, VIII
sulfuryl chloride can be stored at room temperature for
several weeks without noticeable decomposition.
Sulfenyl bromide VII is significantly more stable.
After storage for 6 months at 0°C the sample of this
compound according to 1H NMR data contains 50% of
disulfide I. Selenium-containing analogs are more
stable. After storage for 5 months at 0°C they only
slightly decomposed.
1
can be crystallized from hexane, but according to H
NMR data the samples obtained are more cont-
aminated than the starting substances.
Unlike the previously studied substituted boron di-
fluorideacetylacetonates [1] sulfenyl(selenyl) halides
III, IV, VII, VIII cannot be subjected to gas chro-
matography because they decompose in the injector of
the chromatograph.
Among complexes III, IV, VII, VIII sulfenyl
chloride III is the least stable. Even at –10°C it
completely decomposes to disulfide I in the course of
several days. Therefor for the preparative purpose
compound III should better be prepared directly before
use. Besides it is convenient to chlorinate large amount
of disulfide I at once and to isolate sulfenyl chloride
formed from the reaction mixture if necessary. A
solution of complex III containing an excess of
We have involved compounds III, IV, VII, VIII in
several reactions typical of sulfenyl(selenyl) halides.
The addition of ethylene and cyclohexene proceeds
under usual conditions to give the expected products.
R1
R2
O
O
F
F
F
B
X
Y
+
B
X
Y
F
O
O
R1
R2
X_XVII
III, IV, VII, VIII
R1 = R2 = H, X = S, Y = Cl (X); X = S, Y = Br (XI); X = Se, Y = Cl (XII); X = Se, Y = Br (XIII); R1 = R2 = (CH2)4, X = S,
Y = Cl (XIV); X = S, Y = Br (XV); X = Se, Y = Cl (XVI); X = Se, Y = Br (XVII).
Sulfenyl(selenyl) bromides react with olefins
significantly slower than the corresponding chlorides.
Treating compound III or VII with potassium cyanide
in acetic acid gave thiocyanate derivatives as it was shown
by the chromatomass spectrometry. But the attempts to
prepare F2B(acacSCN) XVIII in individual state failed
because of their low yield. Studying the reaction
mixtures by means of semiquantutative TLC permitted
to evaluate the yield of thiocyanate XVIII at 5–8%.
Our attempt to prepare sulfenyl amide by treating
complex III with diethylamine failed because the
chelate completely decomposes which is typical of the
boron difluoride complexes.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2433
(3)
BORON DIFLUORIDE ACETYLACETONATE SULFENYL(SELENYL) HALIDES
O
O
O
O
F
F
F
F
B
+ HCN
B
XCN
XCl
III, IV
XVIII, XIX
X = S (III, XVIII), Se (IV, XIX).
O
O
O
O
F
F
F
F
B
XCl
+ HP(O)(OEt)2
B
(4)
XP(O)(OEt)2
III, IV
XX, XXI
X = S (III, XX), Se (IV, XXI).
Considering that bases decompose the boron
complexes, we have used acidic agent for performing
the substitution reactions.
column used. Besides, the decomposition increases
with the molecular mass of the chelate. On the
chromatogram of complex XIII intensity of the
diketone peak is approximately equal to that of the
chelate. Adduct XVII having the highest molecular
mass decomposes completely in the evaporator of the
chromatograph which makes it impossible to study this
product by GLC.
Reaction of sulfenyl chloride III with hydro-cyanic
acid proceeds with a high yield, but thiocyanate XVIII
obtained contains an admixture of non-identified violet
compound which we could not remove from the
preparation.
EXPERIMENTAL
The formation of compounds X–XVII is not
accompanied by side processes, and the reactions (4)
and (5) can be regarded as a convenient synthetic
method for preparing these substances.
IR spectra were registered on an Infralum FT-801
apparatus in KBr pellets in the range 4000–550 cm–1.
1H NMR spectra were taken on an ADVANCE 400
MHz spectrometer in CDCl3 against TMS. Mass
spectra were obtained on a gas chromatograph with the
mass-selective detector. GLC studies were carried out
on a Agilent 6890N cromatograph with flame ioniza-
tion detector and an Agilent 5973N instrument with
mass-selective detector. Cromatography studies were
carried out on a HP-5MS (HP-5) 30000×0.250 mm ×
0.25 μm column, carrier gas helium was used for the
mass-selective detector and argon for the flame
ionization one, constant flow regime with the volume
rate by the column 0.7 ml min–1 was maintained. The
injector temperature 250°C, flow division 1:30.
Temperature program: 1 min at 50°C with the
subsequent growth of temperature at a rate 10 deg min–1
up to 280°C and the subsequent maintenance at 280°C
for 20 min. The regime of the flame ionization
detector: detector temperature 290°C, hydrogen flow
rate 40 ml min–1, air flow rate 300 ml min–1, heaving
argon flow 30 ml min–1. The operating regime of the
mass-selective detector: conjugation unit temperature
The products of olefins addition to X-XVII as well
as to selenocyanate XIX are stable colorless crystalline
substances. Crystals of the selenium-containing com-
plexes have high refraction index. The iodine-con-
taining complex IX slightly decomposes at the
recrystallization and storage to give disulfide I. Thio-
phosphate XX while storing at –10°C fairly quickly
decomposed to give the non-identified red products.
Selenophosphate XXI is significantly more stable,
though while storage it also acquires red coloration.
Compounds IX–XVI and XVIII–XXI can be sub-
jected to gas chromatography though they partially
decompose in the course of these studies. Alongside
the peak of chelate the chromatograms contain also a
peak of the corresponding diketone with the intensity
2–5% of that of chelate. Besides, the decomposition
products give a broad peak before the chelate peak.
The degree of decomposition depends on the purity of
chromatographic system and the prehistory of the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2434
SVISTUNOVA et al.
Table 1. Yields, physical and analytical characteristics of compounds F2B(acacR) III, IV, VII–XVII, XIX–XXI
Comp.
no.
Yield,
%
Calculated
C, %
R
mp, °С
Solvent
Found C, %
Formula
IIIа
IV
SCl
97–100
100
99–100
100
35
82–90
103–110
69–72
–
–
–
–
28.21
22.95
23.49
19.59
34.17
34.51
29.22
28.89
25.11
44.64
38.56
38.30
34.15
28.62
34.12
29.89
C5H6BClF2O2S
C5H6BClF2O2Se
C5H6BBrF2O2S
C5H6BBrF2O2Se
C11H16BF2IO2S
C7H10BClF2O2S
C7H10BBrF2O2S
C7H10BClF2O2Se
C7H10BBrF2O2Se
C11H16BClF2O2S
C11H16BBrF2O2S
C11H16BClF2O2Se
C11H16BBrF2O2Se
C6H6BF2NO2Se
C9H16BF2O5PS
C9H16BF2O5PSe
28.01
22.98
23.20
19.64
34.05
34.67
29.30
29.05
25.19
44.55
38.74
38.47
34.06
28.61
34.20
29.78
SeCl
SBr
VII
VIII
IX
SeBr
97.5–99.5
SC6H10I
73–76 (decomp.) Ether–hexane
78b
Ether–pentane
45–46
SC2H4Cl
X
SC2H4Br
79
75.5–76.5
71–72
Hexane
XI
Ether–pentane
SeC2H4Cl
SeC2H4Br
SC6H10Cl
SC6H10Br
SeC6H10Cl
SeC6H10Br
SeCN
70b
83
XII
XIII
XIV
XV
XVI
XVII
XIX
XX
XXI
82–84
Hexane
Hexane
Hexane
Hexane
79
80–82
78–80
85
87–89
99–101
92–98 c (decomp.) Hexane
66
48b
Ether–pentane
146–148
42–45
Ether–pentane
Ether–pentane
b
SP(O)(OEt)2
SeP(O)(OEt)2
40–45
42
39.5–41
a
For the compound obtained according to the procedure a. Overall yield considering additional portions of substance obtained after
1–2 evaporations of mother liquor. c mp 98–99°C after repeated crystallization.
200°C, electron impact ionization 70 eV, complete
scanning regime in the m/z range 250–450, detection
delay 3 min. TLC was carried out on Sorbfil PTSKh-
A-UF plates, elution with 10:5:0.5 benzene-hexane-
acetic acid. Development by UV irradiation (254 nm).
Method b. A mixture of 300 mg of compound I,
6 ml of dry benzene, 600 μl of dry THF, and 300 μl of
SO2Cl2 was stirred for 5 h and then evaporated in a
vacuum at room temperature. Dry residue containing
yellow crystals covered with black tarnish was
dissolved in dry ether. The solution obtained was
evaporated in a vacuum at room temperature. Yield of
compound III 95–98%, mp 84–90°C.
Method c. A mixture of 300 mg of F2B
(acacSCH2Ph), 6 ml of dry chloroform, 600 μl of
SO2Cl2, and 25 μl of a catalyst (see method a) was
stirred for 5 h. After that the solvent was removed in a
vacuum at room temperature. Dry residue was washed
on a filter with hexane and dried in air. Yield of
compound III 60–64%, mp 82–88°C.
Boron difluoride 3-acetylacetonatoselenyl chloride.
A mixture of 300 mg of finely powdered compound II,
3 ml of dry chloroform or benzene, and 300 μl of
SO2Cl2 was stirred for 3 days. Red solution obtained
was evaporated in a vacuum at room temperature until
the complete removing of solvent. Residual yellow-
orange crystals are pure compound IV.
Compounds I, II, V, XVIII were prepared accord-
ing to the reported procedures [1].
Yields, main analytical and spectral characteristics
are presented in Tables 1, 2.
Boron
difluoride
3-acetylacetonatosulfenyl
chloride. Metod a. The catalyst, 100 μl of triethyl-
amine, was diluted with 1 ml of dry chloroform, and
100 μl of the solution obtained was diluted with 1 ml
of chloroform. A mixture of 300 mg of finely
powdered compound I, 3 ml of chloroform. 300 μl of
SO2Cl2, and 12 μl of the catalyst was stirred for 5 h
(reaction mixture was stirred for no less than 4 h after
the complete dissolution of disulfide). The solvent was
removed in a vacuum from the obtained yellow
solution at room temperature to give compound III as
the yellowish orange crystals.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2435
BORON DIFLUORIDE ACETYLACETONATE SULFENYL(SELENYL) HALIDES
Table 2. Spectral characteristics of boron difluoride β-diketonates F2B(acacR)
ν, cm–1
R
δ, ppm
m/z (intensity %, [ion]+)
C=O
C=C
1555
1467
B–F
B–O
another
bands
SCl
1205 1420, 1353,
2.80 s (6H; СН3 chelate)
–
1119
1047
SeCl
1551
1461
1188 1415, 1365,
1115 1169, 1100,
1042, 1021
2.87 s (6H; СН3 chelate)
–
SBr
1555
1467
1205 1420, 1355,
1119 1185, 1048
2.79 s (6H; СН3 chelate)
2.84 s (6H; СН3 chelate)
–
–
SeBr
1551
1461
1185 1413, 1369,
1115 1168, 1099,
1042, 1019
2.66 s (6H; СН3 chelate), 1.45 m 388 (1, [M]+); 369 (2, [M – F]+); 261 (8, [M – I]+);
(3Н), 1.66 m (1Н), 1.83 m (1Н), 209 (49, [C6H10I]+); 179 (13, [M – C6H10I]+); 81
2.08 m (2Н), 2.43 m (1Н), 2.98 t.d (100, [C6H9]+)
SC6H10I
1551
1473
1179 1408, 1364,
1146 1346, 1146,
1053, 977
(J 8.46, 3.93 Hz, 1Н; CHS), 4.21
t.d (J 8.63, 3.93 Hz, 1Н; CHI)а
2.68 s (6H; CH3 chelate), 2.93 t 244 (37); 242 (100, [M]+); 225 (8); 223 (19, [M – F]+);
SC2H4Cl
1553
1467
1206 1416, 1352,
1116 1239, 1045
(J 6.83 Hz, 2H; CH2S), 3.62 t 207 (27, [M – Cl]+); 206 (21); 180 (27, [M –
(J 6.83 Hz, 2H; CH2Cl)
CH2=CHCl]+); 179 (29); 173 (27); 160 (16); 145
(33); 87 (32)
2.72 s (6H; CH3 chelate), 2.99 t 292 (45); 290 (100); 288 (50, [M]+); 273 (8); 271
SeC2H4Cl
1552
1467
1193 1419, 1346,
1116 1321, 1193,
1089, 1042,
(J 7.71 Hz, 2H; CH2Se), 3.71 t (15); 269 (7, [M – F]+); 255 (11, [M – Cl]+); 228
(J 7.71 Hz, 2H; CH2Cl)
(28); 227 (42); 226 (31, [M – C2H4Cl]+); 219 (17);
208 (33, [M – C2H4Cl–F]+); 192 (19); 173 (13); 135
(20); 133 (26)
1025, 708
2.68 s (6H; CH3 chelate), 3.01 t 288 (40); 286 (39, [M]+); 269 (9); 267 (8, [M – F]+);
SC2H4Br
1561
1463
1180 1347, 1232,
(J 7.52 Hz, 2H; CH2S), 3.46 t 217 (5); 215 (5); 207 (100, [M – Br]+); 206 (27); 179
1118
1251, 944,
621
(J 7.52 Hz, 2H; CH2Br)
(48, [M – CH2CH2Br]+); 160 (30); 145 (52); 109
(27); 107 (27)
2.72 s (6H; CH3 chelate), 3.09 t 338 (8); 336 (55); 334 (71); 332 (34, [M]+); 317 (10);
(J 7.85 Hz, 2H; CH2Se), 3.56 t 315 (12, [M – F]+); 306 (4); 265 (7); 263 (9); 257 (7);
(J 7.85 Hz, 2H; CH2Br)
SeC2H4Br
1551
1460
1186 1415, 1370,
1115 1347, 1168,
1100, 1056,
255 (42); 253 (22, [M – Br]+); 229 (19); 227 (100);
225 (51, [M – C2H4Br]+); 208 (90); 206 (44, [M –
C2H4Br–F]+); 193 (35)
1019
2.67 s (6H; CH3 chelate), 1.38 m 298 (4); 296 (12, [M]+); 277 (1, [M – F]+); 180 (9,
(3H), 1.76 m (3H), 2.08 m (1H), [M – C6H9Cl]+); 179 (4); 117 (6); 81 (100, [C6H9]+);
2.31 m (1H), 2.80 t.d (J 9.67, 79 (10)
4.10 Hz, 1H; CHS), 3.84 t.d (J 9.48,
4.10 Hz, 1H; CHCl)
SC6H10Cl
1560
1463
1195 2946, 2857,
1119 1348, 1339,
1237, 1187,
1052, 1035,
1004
2.71 s (6H; CH3 chelate), 1.40 m 346 (3); 344 (6); 342 (3, [M]+); 325 (1, [M – F]+);
(2H), 1.51 m (1H), 1.78 m (3H), 228 (3); 227 (3, [M – C6H9Cl]+); 210 (3); 208 (12);
2.11 m (1H), 2.32 m (1H), 3.12 t.d 206 (6, [M – C6H10Cl–F]+); 117 (4); 81 (100, [C6H9]+)
(J 9.62, 4.01 Hz, 1H; CHSe), 4.04
SeC6H10Cl
1551
1460
1184 2946, 2851,
1090 1335, 1231,
1044, 1030,
999, 685,581
t.d (J 9.33, 4.01 Hz, 1H; CHCl)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2436
SVISTUNOVA et al.
Table 2. (Contd.)
ν, cm–1
B–F
R
δ, ppm
m/z (intensity %, [ion]+)
C=O
C=C
another
bands
B–O
2.67 s (6H; CH3 chelate), 1.42 m 342 (2); 340 (2, [M]+); 323 (1); 321 (1, [M – F]+);
(3H), 1.78 m (2H), 1.91 m (1H), 180 (3, [M – C6H9Br]+); 179 (4); 163 (12); 161 (13);
2.12 m (1H), 2.42 m (1H), 2.92 t.d 81 (100, [C6H9]+); 79 (4)
(J 8.97, 4.27 Hz, 1H; CHS), 4.04
SC6H10Br
SeC6H10Br
SeCN
1561
1462
1196
1118
2944, 2855,
1349, 1237,
1186, 1075,
1052, 1033,
1000, 571
t.d (J 9.05, 4.27 Hz, 1H; CHBr)
1551
1460
1186
1090
2944, 2849,
1343, 1335,
1233, 1177,
1115, 1042,
1028, 997,
664
2.70 s (6H; CH3 chelate), 1.46 m
(2H), 1.58 m (1H), 1.73 m (1H),
1.82 m (1H), 1.95 m (1H), 2.17 m
–
(1H), 2.39
m (1H), 3.30 t.d
(J 8.54, 4.10 Hz, 1H; CHSe), 4.23
t.d (J 8.20, 4.10 Hz, 1H; CHBr)
255 (10); 253 (59); 251 (27, [M]+); 234 (22, [M – F]+);
227 (16, [M – CN]+); 207 (25, [M – CN–HF]+); 184
(100); 162 (32); 136 (95); 117 (31); 107 (28); 93
(25)
1547
1472
1169
1088
2161, 1416,
1347, 1210,
1021, 1007,
949, 623
2.80 s (6H; CH3 chelate)
2.65 s (6H; CH3 chelate), 1.37 t.d 316 (2, [M]+); 296 (50, [M – HF]+); 203 (41); 186
SP(O)(OEt)2 1563
1476
1185
1113
2989, 1418,
1368, 1357,
1254, 1036,
1003, 982,
963,780, 600
2988, 1348,
1252, 1026,
1003, 972,
571
[J 7.02, 0.73 Hz, 6H; CH3 (OEt)], (4); 175 (14); 160 (23, [M – P(O)(OEt)2–F]+); 147
4.23
m
[J 9.06×1, 7.02×3, (21); 114 (100); 109 (20); 81 (21); 72 (28)
2.05×1 Hz, 4H; CH2 (OEt)]
2.71 s (6H; CH3 chelate), 1.38 t.d 366 (1); 364 (4); 362 (2, [M]+); 344 (70, [M – HF]+);
[J 7.03, 0.39 Hz, 6H; CH3(OEt)], 208 (69, [M – P(O)(OEt)2–F]+); 203 (41); 175 (32);
4.23 t.d [J 7.03, 9.18 Hz, 4H; 162 (81); 160 (40); 147 (59); 128 (34); 109 (100);
SeP(O)(OEt)2 1553
1474
1165
1092
CH2 (OEt)]
91 (35); 81 (78)
a
1H NMR spectrum always contains a signal of the methylene protons of disulfide I (2.62 ppm) with the intensity 3–5% with respect to
the intensity of the main signal.
Boron
difluoride
3-acetylacetonatosulfenyl
removing the solvent the residue was crystallized from
the solvent indicated in Table 1.
bromide. A mixture of finely powdered compound I,
300 mg, 6 ml of dry chloroform (or benzene), and
162 mg of bromine (20% excess) was stirred for 2 h
and then evaporated in a vacuum at room temperature.
Residual orange crystals are pure compound VII.
Reaction with cyclohexene. This reaction was
carried out analogously at the addition of 0.6 ml of
cyclohexene.
Boron difluoride 3-(2-iodocyclohexenylthio)acetyl-
acetonate. A mixture of 300 mg of compound I,
220 mg of iodine, 3 ml of dry THF, and 400 μl of
cyclohexene was stirred for 2 days. Light brown
solution obtained was evaporated in a vacuum at room
temperature. Dry residue was extracted with 2:1 ether–
hexane mixture. After removing the solvent the residue
was crystallized from the solvent indicated in Table 1.
Boron difluoride 3-acetylacetonatoselenyl bromide.
This compound was prepared analogously using
130 mg of bromine (20% excess). Reaction time 1 h,
brown crystals.
Reaction with ethylene. Through a solution of
sulfenyl chloride (bromide) or selenyl chloride
(bromide) prepared from 300 mg of disulfide I or
diselenide II in 10 ml of dry chloroform ethylene was
bubbled until the decoloration of solution. After
Boron difluoride 3-(thiocyano)acetylacetonate.
To a solution of 550 mg of sulfenyl chloride III in
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2437
BORON DIFLUORIDE ACETYLACETONATE SULFENYL(SELENYL) HALIDES
5 ml of dry chloroform 0.6 ml of hydrocyanic acid was
added at room temperature in one portion. After 0.5 h
the solution get colorless, and the solvent was removed
in a vacuum at room temperature. The crystallization
of dry residue from ether gave violet crystals. Ac-
cording to the IR, mass spectral data, and the retention
time (gas chromatography) the substance obtained was
F2B(acacSCN) [1], mp 95–111°C (reported data 133–
142°C [1]). According to the semiquantative TLC
yield of the compound synthesized was 55–65%.
in 6 ml of dry chloroform 250 mg of diethyl hydrogen
phosphite was added (10% excess); 3–4 h after the
complete decoloration the reaction mixture was
evaporated in a vacuum at room temperature. The
residual colorless oil with the red hue was crystallized
from the solvent indicated in Table 1.
Boron difluoride 3-(diethoxyphosphorylseleno)-
acetylacetonate was prepared analogously.
REFERENCES
1. Svistunova, I.V. and Fedorenko, E.V., Zh. Obshch.
Khim., 2008, vol. 78, no. 8, p. 1280.
Boron difluoride 3-(thioselenylcyano)acetyl-
acetonate. This compound was prepared analogously
from 400 mg of selenyl chloride IV, 5 ml of chloro-
form, and 0.4 ml of hydrocyanic acid. Reaction
mixture was evaporated after 10 min. After crystal-
lization from ether colorless crystals were obtained.
2. Kluiber, R., J. Am. Chem. Soc., 1961, vol. 83, no. 14,
p. 3030.
3. Guhman, E.V. and Reutov, V.A., Zh. Obshch. Khim.,
2003, vol. 73, no. 10, p. 1671.
4. Koval’, I.V., Usp. Khim., 1995, vol. 64, no. 8, p. 781.
Boron difluoride 3-(diethoxyphosphorylthio)-
acetylacetonate. To a solution of 350 mg of disulfide I
5. Svistunova, I.V., Shapkin, N.P., and Nikolaeva, O.V.,
Zh. Obshch. Khim., 2005, vol. 75, no. 3, p. 367.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010