Unexpected water addition to fluorinated 1,3λ4δ2,2,4-benzodithiadiazines with the formation of 2-amino-N-sulfinylbenzenesulfenamides

Article abstract of DOI:10.1070/MC2003v013n01ABEH001700

Fluoro-containing 1,3λ⁴δ²,2,4-benzodithiadiazines 2-4 unexpectedly add water to give previously unknown 2-amino-N-sulfinylbenzenesulfenamides 5-7 as the first derivatives of still undescribed 2-aminobenzenesulfenamide 10.

Full text of DOI:10.1070/MC2003v013n01ABEH001700

, 2003, 13(1), 19–21
Unexpected water addition to fluorinated 1,3λ4δ2,2,4-benzodithiadiazines with the
formation of 2-amino-N-sulfinylbenzenesulfenamides†
Alexander Yu. Makarov, Irina Yu. Bagryanskaya, Yuri V. Gatilov, Makhmut M. Shakirov
and Andrey V. Zibarev*
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090
Novosibirsk, Russian Federation. Fax: + 7 3832 34 4752; e-mail: zibarev@nioch.nsc.ru
10.1070/MC2003v013n01ABEH001700
4
2
Fluoro-containing 1,3λ δ ,2,4-benzodithiadiazines 2–4 unexpectedly add water to give previously unknown 2-amino-N-sulfinyl-
benzenesulfenamides 5–7 as the first derivatives of still undescribed 2-aminobenzenesulfenamide 10.
4
2
Hyperelectronic (π- and σ-excessive) 1,3λ δ ,2,4-benzodithia-
diazine1 1 and its derivatives2–5 exhibit a nontrivial combination
of antiaromaticity6,7 with moderate thermal stability and photo-
stability.1–5,8–15
F
C(3)
C(4)
C(5)
R
C(6)
F
The chemistry of these compounds is imperfectly under-
stood.1–5,8–16 Since both π-excessiveness and antiaromaticity are
destabilising factors, one can believe that the heteroatom reac-
tivity of 1 and its derivatives is high, and various new structural
types can be observed among the reaction products.
F
C(2)
C(1)
S(7)
N(11)
O(10)
N(8)
F
F
R1
F
S
R1
F
SNH2
NH
S
S(9)
or
N
H
N S O
O
Figure 1 X-ray structures for the molecules of 5 (R = F) and 7 (R = H).
Selected bond lengths (Å) and bond angles (°). 5: S(7)– C(1) 1.756(4), S(7)–
N(8) 1.676(3), N(8)– S(9) 1.529(3), S(9)– O(10) 1.454(3); C(1)– S(7)– N(8)
110.4(2), S(7)– N(8)– S(9) 121.5(2), N(8)– S(9)– O(10) 117.2(2). 7: S(7)– C(1)
1.748(3), S(7)– N(8) 1.665(2), N(8)– S(9) 1.524(2), S(9)– O(10) 1.466(3);
C(1)– S(7)– N(8) 100.2(1), S(7)– N(8)– S(9) 121.6(2), N(8)– S(9)– O(10)
116.7(2).
R2
R2
F
8
9
R1
F
S
N
S
H2O
N
F
R2
R1
F
S N S O
cally unfavourable reaction conditions prevent compounds 5– 7
from further hydrolysis. The homogeneous hydrolysis of 2 and
other partially fluorinated compounds of this type in organic
solvents gives corresponding 2,2'-diaminodiphenyl disulfides.3
According to the ∆H0f PM3 calculations, compound 5 is
less stable than its heterocyclic isomer 8 (Scheme 1) by
–
2 4
2,5,8,9 R1 = R2 = F
R1 = R2 = H
NH2
5– 7
R2
,
3 6
4,7 R1 = H, R2 = F
‡
S
S
Syntheses. Compounds 5– 7, 12. Under vacuum, 9 mg (0.5 mmol) of
N
S
N
water was condensed into a 500 ml flask containing 0.5 mmol of corre-
sponding 2– 41–5 as solids. After storage for 30 days at ambient tempera-
ture, the solid products were dissolved in CCl4, the solution was filtered,
the filtrate was evaporated under reduced pressure, and the residue (con-
sisted of unreacted starting materials 2– 4 and corresponding final pro-
ducts 5– 7) was fractionally sublimed in a vacuum and recrystallised
from hexane. Compounds 5– 7 were obtained as colourless (5) or yellow
(6,7) crystals.
S
N
F
N
1
11
12
SNH2
NH2
S
F
NH2
Compound 5, 25 % (45% conversion of 2), mp 97–98 °C. 1H NMR
(CDCl3), d: 4.47. 19F NMR (C6F6) d: 29.7, 11.9, 1.8, – 9.5. 13C NMR, d:
147.1, 143.7, 136.2, 134.3, 132.7, 100.5. 14N NMR [NH3 (liq.)], d: 336,
45. UV (heptane) lmax/nm (log e): 314 (3.96), 257 (3.57), 252 (3.59),
232 (3.84). MS, m/z: 257.9537 (M+; calc. for C6H2F4N2OS2: 257.9545).
2
10
Scheme 1
Indeed, we found that individual fluorine-containing com-
pounds 2– 4 (which are solids under normal conditions) unex-
pectedly add water to give previously unknown 2-amino-N-
sulfinylbenzenesulfenamides 5– 7 (Scheme 1)‡ as the first
derivatives of still undescribed 2-aminobenzenesulfenamide 10.
Taking into account high volatility of the title compounds,8–10,15
it is believed that under macroscopically heterogeneous con-
ditions the addition of water actually proceeded in a gas phase
followed by the precipitation of products 5– 7 as solids on the
walls of the reaction vessel.‡ Generally, the formation of 5– 7
from 2– 4 under the action of water is paradoxical since it is
well known that RNSO derivatives are highly unstable toward
hydrolysis to give corresponding RNH2.17 Seemingly, the kineti-
1
Compound 6, 28% (35% conversion of 3), mp 102– 104 ° C. H NMR
(CDCl3) d: 6.27, 6.27, 4.64. 19F NMR (C6F6) d: 61.8, 60.0. 13C NMR, d:
166.3, 163.3, 150.7, 99.4, 97.7, 94.0. 15N NMR [NH3 (liq.)] d: 341.0,
64.3. UV (heptane) lmax/nm (log e): 313 (3.88), 242 (3.86), 219 (4.20).
MS, m/z: 221.9732 (M+; calc. for C6H4F2N2OS2 221.9733).
Compound 7, 64% (83% conversion of 4), mp 88– 90 ° C. 1H NMR
(CDCl3) d: 6.37, 4.71. 19F NMR (C6F6) d: 54.8, 31.1, – 0.5. 13C NMR, d:
157.9, 152.8, 139.5, 135.9, 100.5, 93.5. 15N NMR [NH3 (liq.)] d: 337.5,
54.0 (t, J 88 Hz). UV (heptane) lmax/nm (log e): 312 (3.93), 219 (4.18).
MS, m/z 239.9638 (M+; calc. for C6H3F3N2OS2: 239.9639).
Only 4,4'-difluoro-2,2'-diaminodiphenyl disulfide 123 was obtained
from 113 under the same conditions (13%; 41% conversion of 11). After
the sublimation of unreacted 11, compound 12 was isolated as a salt by
treatment of the residue with HCl. After conversion into a free base, 12
was identified by a comparison of its mp and H and 19F NMR spectra
1
†
Names. According to the IUPAC rules, compounds 5– 7 should be named
with data for an authentic3 sample. In the case of 1,1 the reaction resulted
in unidentified tar containing no 2,2'-diaminodiphenyl disulfide (com-
parison with an authentic sample).22
2-[(sulfinylamino)sulfanyl]anilines or 2-[(sulfinylamino)sulfanyl]phenyl-
amines. This information was obtained using the ACD/IUPAC Lab Web
service (ACD/IUPAC Name Free 6.04).
– 19 –

, 2003, 13(1), 19–21
gonal to an aromatic ring [the dihedral angle is 83.9(1)° for 5
or 97.5(1)° for 7].
Although the molecules of 5 and 7 are structurally similar,
their crystal packings exhibited different supramolecular motifs
(Figure 2). In the case of 5, a hydrogen-bonded 1D network was
observed as infinite zigzag chains along the crystallographic
axis b featured a shortened18 N– H···O contact of 2.31(4) Å and
an N– H···O angle of 157(4)° . For 7, 0D network was found
as hydrogen-bonded centrosymmetric dimers with an N– H···O
distance of 2.50(4) Å and an N– H···O angle of 163(4)°. Addi-
tionally, the molecules of neighbouring hydrogen-bonded dimers
of 7 demonstrated a parallel-slipped arrangement of aromatic
rings with an interplanar separation of 3.43 Å and a distance
between ring centroids of 4.10 Å, thus forming pseudo-π-stacked
centrosymmetric dimers. It is well known that weak non-cova-
lent interactions19 play significant roles in controlling molecular
conformations, packing structures in crystals, and molecular
recognition. In particular, both π-stacking interactions and hydro-
gen bonds are known to be general supramolecular synthons
of significant importance with regard to new developments in
crystal engineering.18– 20
b
c
0
a
a
Thus, first derivatives 5– 7 of unknown 2-aminobenzene-
sulfenamide 10 were prepared by unusual water addition to
4
2
1,3λ δ ,2,4-benzodithiadiazines 2– 4 and structurally charac-
terised. Significantly, neither 10 (a priori useful synthon) nor
its derivatives can be prepared in an obvious way, for example,
by the reduction of 2-nitrobenzenesulfenamides or 1,2,3-benzo-
thiadiazoles, due to the well-known instability of sulfenamide
S– N linkages under the mildest reductive conditions.21
b
0
c
This work was supported by the Russian Foundation for Basic
Research (grant nos. 99-03-33115 and 01-03-06190). The access
to the Cambridge Structural Database (grant no. 99-07-90133)
and to the STN International databases (grant no. 00-03-32721)
are acknowledged. A.M. is also grateful to the Russian Academy
of Sciences for the State Scientific Scholarship and to the Siberian
Branch of the Russian Academy of Sciences for the N. N. Vorozhtsov
Award for young scientists.
Figure 2 Molecular packing of compounds 5 (upper) and 7 (lower) in
crystals.
20– 24 kcal mol– 1 (for various conformations of 8) and more
stable than acyclic isomer 9 by ~4 kcal mol– 1. We can speculate
that the transformation of 2 into 5 is kinetically controlled and
does not include the intermediate participation of 8.
In contrast to 2– 4, parent compound 1 and its derivative 11
give only unidentified tar and disulfide 12, respectively, under
the same conditions.‡ Intermediate compounds were neither
isolated nor detected in the reaction mixtures by GC-MS or
1H and 19F NMR spectroscopy. The reason for this difference
between 1, 11 and 2– 4 is unclear. For example, the ∆∆H0f
(PM3) for the hydrocarbon analogues of compounds 5, 8 and 9
is almost the same as that for 5, 8 and 9 themselves.
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= 9.3840(6), c = 9.8699(7) Å, b = 104.855(5), U = 873.3(1) Å3, space
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– 21 –