Reaction of N-Nonaflylbenzotriazole with silyl enol ethers

Article abstract of DOI:10.1055/s-0028-1083371

N-Nonaflylbenzotriazole reacts with trimethylsilyl enol ethers in tetrahydrofuran at room temperature under tetrabutylammonium fluoride catalysis to afford o-(nonafluorobutylsulfonamido) phenylhydrazones in 19-82% yield. N-Nonaflylbenzotriazole reacts twi

Full text of DOI:10.1055/s-0028-1083371

1190
PAPER
Reaction of N-Nonaflylbenzotriazole with Silyl Enol Ethers
Reactionof
N
-Nonafly
o
lbenzotriazo
r
w
ithS
i
ilyl
E
n
t
ol
E
the
z
rs Uhde, Thomas Ziegler*
Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Fax +49(7071)295244; E-mail: thomas.ziegler@uni-tuebingen.de
Received 9 October 2008; revised 20 November 2008
(Scheme 1). For example, treatment of 1 with phenolates
and naphtholates gave regioselectively 2-(2- and 4-hy-
droxyphenylazo)- and 2-(2- and 4-hydroxy-1-naphthyl-
azo)anilines in high yields.16–19 Likewise, a monotriazole-
Abstract: N-Nonaflylbenzotriazole reacts with trimethylsilyl enol
ethers in tetrahydrofuran at room temperature under tetrabutylam-
monium fluoride catalysis to afford o-(nonafluorobutylsulfonami-
do)phenylhydrazones in 19–82% yield. N-Nonaflylbenzotriazole
reacts twice with the less sterically demanding silyl enol ethers to fused phthalocyaninato–zinc complex gave the corre-
afford the corresponding o-(nonafluorobutylsulfonamido)phenyl-
azo enols in 41–75% yield.
sponding 2-hydroxy-1-naphthylazo-substituted phthalo-
cyaninato zinc–complex with strong solvatochromic
properties.20 This novel ring-opening reaction of 1 has
Key words: benzotriazole, hydrazones, ring opening, silyl enol
ether
been further extended to a new variation of the Japp–
Klingemann reaction by treatment of 1 with CH-acidic
compounds affording hydrazones in high yield.21 Similar-
Benzotriazole has gained wide applications in organic ly, Wittig reagents react with 1 to afford triphenyl[(phenyl-
synthesis as an activating auxiliary for numerous reac- azo)methylene]phosphoranes and [bis(phenylazo)methyl-
tions.1–6 Benzotriazole is a stable, inexpensive, and bio- ene]triphenylphosphoranes.22 Furthermore, we could re-
logically innocuous compound that is usually stable under cently show that 1 and 1-cyanobenzotriazole also react
a wide variety of reaction conditions. Under more drastic smoothly with enamines to give {[o-(nonafluorobutylsul-
conditions, namely pyrolysis and photolysis, however, fonamido)phenyl]azo}-substituted enamines, 4H-pyri-
benzotriazoles decompose via extrusion of nitrogen giv- dazines, and imidazo[1,2-b][1,2,4]triazines.23,24 Recently,
ing complex reaction mixtures. Nevertheless, some useful Katritzky observed a similar 1,2,3-triazole ring-opening
synthetic applications, such deazotations and dediazota- reaction when treating 1,1¢-sulfonylbis(benzotriazole)
tions, of benzotriazoles are known. For example, in the with secondary amines.25 Scheme 2 gives an overview of
classical Graebe–Ullmann reaction, 1-phenylbenzotriaz- the ring-opening reactions of benzotriazoles observed so
ole affords carbazole upon pyrolysis7,8 or photolysis.9,10 far. Here, we now report on the reaction of 1 with tri-
Other ring-cleavage reactions of benzotriazoles are methylsilyl enol ethers.
known to occur upon treatment of benzotriazoles with
Compound 1 was prepared from commercially available
Grignard reagents affording phenylenediamines in low to
benzotriazole and nonafluorobutanesulfonyl fluoride as
medium yield.11–13 Katritzky also described domino reac-
previously described.16 Table 1 summarizes the results of
tions of some benzotriazole derivatives that proceeded via
the reaction of 1 with various silyl enol ethers 2. Treat-
ment of 1 with 1-(trimethylsiloxy)cyclohexene (2a) at
room temperature in tetrahydrofuran did not result in a
spontaneous reaction as was previously observed with the
a ring-opening–ring-closure sequence to afford 1,2,4-tri-
azolo[1,5-a]quinoxaline14 and benzo[c]tetrazolo[1,5-
e]triazepine.15
corresponding enamine derivative, i.e. pyrrolidinocyclo-
Nu
hexene.23 The failure of the reaction between 1 and 2a
N
N
N
N
NuH
while the corresponding enamines react smoothly with 1
can be explained by the fact that typical silyl enol ethers
are seven-to-nine orders in magnitude less reactive than
the analogously substituted enamines.26,27 Accordingly,
tetrabutylammonium fluoride was added to the reaction
mixture in order to generate in situ a more nucleophilic
enolate species from 2a. However, when an equimolar
amount of tetrabutylammonium fluoride was added in one
portion to a solution of 1 and 2a in tetrahydrofuran, exten-
sive decomposition was detected by TLC and only benzo-
triazole could be isolated from the complex reaction
mixture (details are not shown in the experimental part).
Obviously, fluoride acted as a competitive nucleophile
cleaving off the nonaflyl group in Nf-Bt 1. Indeed, treat-
ment of 1 alone with tetrabutylammonium fluoride in tet-
rahydrofuran gave benzotriazole in a fast reaction and in
N
NH
Nf
Nf
1
Nf = SO2C4F9 NuH = carbon nucleophile
Scheme 1
Recently, we found a rather surprising ring-opening reac-
tion of the triazole moiety upon reaction of soft nucleo-
philes with 1-(nonafluorobutylsulfonyl)-1H-benzotri-
azole (Nf-Bt, 1) affording high yields of azo compounds
SYNTHESIS 2009, No. 7, pp 1190–1194
Advanced online publication: 11.02.2009
DOI: 10.1055/s-0028-1083371; Art ID: T17808SS
x
x
.
x
x
.2
0
0
9
© Georg Thieme Verlag Stuttgart · New York

PAPER
Reaction of N-Nonaflylbenzotriazole with Silyl Enol Ethers
1191
R2
R3
R12N
HO
N
N
N
N
N
N
OH
NH
NH
86–94% Nf
NH
Nf
ref. 16
Nf 47–92%
43–84%
X = Nf
ref. 23
X = Nf
naphthol
ref. 16
X = Nf
phenol
NR1
2
Z
ref. 21
R3
H
X = Nf
R2
N
N
N
Z
N
Z-CH2-Z
N
N
ref. 23
X = CN
R2,R3 = -(CH2)3-
N
N
X
N
NH
Nf
43%
72–89%
Z = Ac, COOEt, CN, NO2
ref. 22
X = Nf
H2C=PPh3
ref.22
ref. 25
X = SO2Bt
HNR2
X = Nf
PPh3
H(R)C=PPh3
PPh3
NR2
N
N
N
N
R
N
N
N
N
NH
NH
Nf
NH
Nf
HN
Nf
63–83%
SO2NR2
55–75%
44%
R = aryl, COOEt
Scheme 2
virtually quantitative yield. The observation that fluoride zones 3 or bis(arylazo) derivatives 4 were formed was
does not induce ring opening of the triazole ring in 1 is only dependent on sterical factors. Silyl enol ethers with
most likely due to the fact that it is a hard nucleophile an unsubstituted methylene group like 2b and 2c can at-
whereas attack at N2 of the triazole moiety occurs by soft tack Nf-Bt 1 twice to form bis(arylazo) adducts 4, while
nucleophiles like phenolates, mesomerically stabilized all other silyl enol ethers cannot. Similar bis(arylazo) ad-
carbanions, and Wittig reagents only (see Scheme 2). A ducts were also obtained previously from sterically less
smooth reaction between 1 and various silyl enol ethers 2 demanding primary Wittig reagents22 (see also
was finally obtained by slow dropwise addition of a solu- Scheme 2). The hydrazone structure of compounds 3 and
tion of an equimolar amount of tetrabutylammonium the bis(arylazo) structure of compounds 4 was also evi-
fluoride in tetrahydrofuran to a solution of 1 and 2.
dent from the UV-Vis absorption spectra of those com-
pounds. Typically, compounds 3 show absorption
maxima of 323–376 nm, with the exception of 3d, which
shows a maximum at 424.8 nm. Bis(arylazo) compounds
4b and 4c have a maximum absorption of 438 and 453.7
nm, respectively.
In this way, 1-(trimethylsiloxy)cyclohexene (2a) reacted
with 1 to afford hydrazone 3a in 82% yield (Table 1, entry
1). 2-(Trimethylsiloxy)propene (2b), however, afforded
only 22% of the corresponding hydrazone 3b while the
bis-adduct 4b was obtained in 75% yield (entry 2). Simi-
larly, a-(trimethylsiloxy)styrene (2c) gave 30% of the hy- The reaction of 1 with the trimethylsilyl enol ether of (+)-
drazone 3c along with 41% of the bis-adduct 4c (entry 3). camphene 2e afforded the two isomeric hydrazones 3e
The formation of the bis-adducts 4b and 4c can be inter- and 3e¢ (entry 5). In general, all hydrazones described
preted in terms of a keto–enol equilibrium between the here, except hydrazone 3e¢, exhibit the Z-configuration at
initially formed amide A and the corresponding enolate B
(Scheme 3). The latter enolate B reacts as a strong nucleo-
phile with a second molecule Nf-Bt 1 to give the bis-
O
N
R
O
N
R
SiMe3
R
adducts 4. The formation of the bis-adducts 4 resembles,
to some extent, the formation of formazanes from b-dike-
tones and diazonium salts under basic conditions,28 al-
though compounds 4 were isolated as bis(arylazo)
tautomers. The bis(arylazo) tautomeric structures of com-
pounds 4 were clearly evident from their NMR spectra
which showed sharp singlets at d = 5.10 and 4.56 for the
hydroxy groups in 4b and 4c, respectively.
O
N
N
1, Bu4NF
– Me3SiF
NH
Nf
N
2b R = Me
2c R = Ph
B
Nf
A
H2O
1
4b R = Me
4c R = Ph
3b R = Me
3c R = Ph
Silyl enol ethers 2d–f gave solely the monohydrazones
3d–f, respectively (entries 4–6). Whether monohydra-
Scheme 3
Synthesis 2009, No. 7, 1190–1194 © Thieme Stuttgart · New York

1192
M. Uhde, T. Ziegler
PAPER
Table 1 Reaction of 1 with Various Silyl Enol Ethers 2
the C=N bond, although simple hydrazones of aldehydes
and ketones usually form E-isomers.29 Most likely, the
preferred Z-configuration in the case of hydrazones 3 is
due to a hydrogen bond between the NH group and the
carbonyl group that stabilizes the Z-configuration. A sim-
ilar observation, i.e. the stabilization of the Z-isomer
through a hydrogen bond, has previously been observed
for b-keto enamines and vinamidine.30 As was also ob-
served in these cases, the 1H NMR spectra of compounds
3a–f show the NH group resonating at lower field be-
tween d = 12 and 14 while the proton of the NH group in
E-isomer 3e¢ is found at d = 7.96. Therefore, 3e¢ was as-
signed the E-configuration. It is noteworthy though, that
3e and 3e¢ could not be interconverted by heating. No re-
action of silyl enol ethers 2 was observed with 1-cyano-
and 1-nitrobenzotriazole.
Entry Silyl enol ether
Product
3,4
Yield
O
N
H
N
OSiMe3
1
2a
3a 82%
H
N
Nf
O
N
H
N
3b 22%
4b 75%
H
N
OSiMe3
Nf
2
2b
O
H
N
N
N
H
N
H
All reagents were commercially obtained at highest commercial
quality and used without further purification. Air- and moisture-
sensitive liquids and solutions were transferred via syringe or stain-
less steel cannula. Organic solutions were concentrated by rotary
evaporation below 45 °C. Reactions were carried out under anhy-
drous conditions using dry glassware within an argon atmosphere in
dry, freshly distilled solvents, unless otherwise noted. Yields refer
to chromatographically and spectroscopically (1H NMR, 13C NMR)
homogeneous and recrystallized materials. Analytical TLC was
performed on glass plates precoated with a 0.25 mm thickness of
Macherey & Nagel Polygram® SIL G/UV254. Silica gel 60 (particle
size 0.040–0.063 mm) was used for flash chromatography. NMR
spectra were recorded on a Bruker Advance 250 spectrometer (at
250 MHz for 1H, and at 62.9 MHz for 13C NMR spectra) and cali-
brated using the CDCl3 as an internal reference. Melting points were
determined on a Büchi B-540 and are uncorrected. Specific rota-
tions were recorded with a Perkin Elmer polarimeter model 341 at
589 nm and 20 °C in a quartz cuvette of 10 cm length. Elemental
analysis was performed on Hekatech GmbH Euro EA 3000 analyz-
er. FAB-MS were measured on a Finnigan MAT TSQ 70 spectrom-
eter, MALDI-TOF-MS were measured on a Bruker Autoflex
spectrometer, and HRMS were measured on a Bruker Apex II FT-
ICR spectrometer.
N
N
Nf
Nf
O
H
N
3c 30%
4c 41%
N
Me3SiO
H
N
3
2c
Nf
O
H
N
N
N
H
N
H
N
N
Nf
Nf
O
Me3SiO
H
N
4
2d
3d 70%
N
H
N
Nonafluorobutane-1-sulfonamides 3; General Procedure
1-(Nonafluorobutylsulfonyl)-1H-benzotriazole16 (1, 1.0 g, 2.5
mmol) and trimethylsilyl enol ether 2 (2.75 mmol) were dissolved
under argon in abs THF (50 mL). A soln of TBAF·3 H2O (0.59 g,
2.5 mmol) in THF (50 mL) was pre-dried with 3 Å molecular sieves
and slowly added dropwise at r.t. to the stirred soln of 1 and 2 over
the course of 30 min. The resulting soln was stirred at r.t. for an ad-
ditional 15 min and diluted with EtOAc (100 mL). H2O (50 mL)
was added followed by concd aq HCl soln until the aqueous phase
became colorless. The organic phase was separated, dried (anhyd
Na2SO4), filtered, and concentrated under reduced pressure. The
residue was purified by chromatography (silica gel, n-hexane–
EtOAc, 4:1) and recrystallization of the solids after evaporation of
the eluent afforded compounds 3 and 4.
Nf
O
H
N
N
H
3e 35%
3e¢ 34%
N
Nf
5
2e
O
O
N
Me3Si
NH
Nf
N
H
(Z)-Nonafluoro-N-{2-[2-(2-oxocyclohexylidene)hydrazi-
nyl]phenyl}butane-1-sulfonamide (3a)
Following the general procedure using 1-(trimethylsil-
oxy)cyclohexene31 (2a, 0.47 g) gave 3a (1.02 g, 82%) as light yel-
low crystals; mp 160–161 °C (EtOH).
1H NMR (CDCl3): d = 1.77–1.83 (m, 4 H, 2 CH2), 2.46–2.52 (m, 2
H, CH2), 2.58–2.63 (m, 2 H, CH2), 6.87–6.97 (m, 2 H, Harom), 7.05–
O
H
N
O
N
H
6
2f
3f 74%
Me3Si
N
Nf
Synthesis 2009, No. 7, 1190–1194 © Thieme Stuttgart · New York

PAPER
Reaction of N-Nonaflylbenzotriazole with Silyl Enol Ethers
UV-Vis: lmax (e) = 375.9 nm (177,823 dm3 mol–1 cm–1).
1193
7.12 (m, 1 H, Harom), 7.51–7.55 (m, 1 H, Harom), 10.74 (s, 1 H,
SO2NH), 13.73 (s, 1 H, NH).
13C NMR (CDCl3): d = 22.4 (1 C, CH2), 23.4 (1 C, CH2), 32.2 (1 C,
CH2), 40.4 (1 C, CH2), 117.7, 123.8, 132.6, 133.0, 123.5, 124.8,
127.2 (7 C, Carom, C=N), 198.7 (1 C, C=O).
Anal. Calcd for C18H12F9N3O3S (521.05): C, 41.47; H, 2.32; N,
8.06. Found: C, 41.37; H, 2.42; N, 8.71.
Bis(butane-1-sulfonamide) 4c
Mp 164–165 °C (EtOH).
MS (FAB): m/z = 500.0 [M + H]+, 217.2 [M + H – Nf]+.
UV-Vis: lmax (e) = 356.7 nm (12,709 dm3 mol–1 cm–1).
1H NMR (DMSO-d6): d = 4.56 (s, 1 H, OH), 7.27–7.31 (m, 2 H,
HPh), 7.34–7.38 (m, 2 H, HPhenylene), 7.56–7.60 (m, 4 H, HPhenylene),
7.66–7.70 (m, 1 H, HPh), 7.73–7.75 (m, 2 H, HPh), 7.94–7.96 (m, 2
H, HPhenylene).
Anal. Calcd for C16H14F9N3O3S (499.06): C, 38.48; H, 2.83; N,
8.41. Found: C, 38.35; H, 2.85; N, 8.09.
13C NMR (DMSO-d6): d = 119.2, 126.6, 133.2 (3 C, CPh) 125.7,
128.96, 130.0, 130.72 (4 C, CPhenylene), 115.8, 133.0, 138.4, 141.0, (4
C, CPh/Phenylene, C=COH), 189.3 (COH).
MS (FAB): m/z = 944.8 [M + Na]+, 923.0 [M + H]+.
MS (MALDI-TOF): m/z = 945.05 [M + Na]+.
(Z)-Nonafluoro-N-{2-[2-(2-oxopropylidene)hydrazinyl]phe-
nyl}butane-1-sulfonamide (3b) and N,N¢-[2,2¢-(1E,1¢E)-(2-Hy-
droxyprop-1-ene-1,1-diyl)bis(diazene-2,1-diyl)bis(2,1-phenyl-
ene)]bis(nonafluorobutane-1-sulfonamide) (4b)
Following the general procedure using 2-(trimethylsil-
oxy)propene31 (2b, 0.36 g) gave first 3b (0.25 g, 22%) as light yel-
low crystals and then 4b (0.81 g, 75%) as deep red crystals.
UV-Vis: lmax (e) = 453.7 nm (15,165 dm3 mol–1 cm–1).
(Z)-Nonafluoro-N-(2-{2-[1-oxo-3,4-dihydronaphthalen-2(1H)-
ylidene]hydrazinyl}phenyl)butane-1-sulfonamide (3d)
Following the general procedure using 1-(trimethylsiloxy)-3,4-
dihydronaphthalene32 (2d, 0.60 g) gave 3d (0.96 g, 70%) as orange
crystals; mp 156–157 °C (EtOH).
1H NMR (CDCl3): d = 2.88–2.91 (m, 2 H, CH2), 3.03–3.06 (m, 2 H,
CH2), 6.94–7.01 (m, 2 H, HPhenylene), 7.11–7.15 (m, 1 H, HPhenylene),
7.24–7.26 (d, 1 H, HNaphthyl), 7.30–7.34 (t, 1 H, HNaphthyl), 7.46–7.50
(m, 1 H, HNaphthyl), 7.55–7.58 (m, 1 H, HPhenylene), 7.97–7.99 (m, 1 H,
HNaphthyl), 10.76 (s, 1 H, SO2NH), 14.00 (s, 1 H, NH).
Butane-1-sulfonamide 3b
Mp 104–105 °C (n-hexane–EtOAc, 9:1).
1H NMR (CDCl3): d = 2.32 (s, 3 H, CH3), 6.95–7.02 (m, 1 H, Harom),
7.19–7.22 (m, 1 H, Harom), 7.29–7.36 (m, 1 H, Harom), 7.59–7.59 (m,
2 H, Harom, N=CH), 10.74 (s, 1 H, SO2NH), 13.93 (s, 1 H, NNH).
13C NMR (CDCl3): d = 21.0 (1 C, CH3), 115.4, 121.6, 128.4, 129.0,
137.1, 120.6, 140.1 (7 C, Carom, C=N), 171.9 (1 C, C=O).
MS (FAB): m/z = 460.0 [M + H]+, 177.2 [M + H – Nf]+.
HRMS (ESI): m/z [M + H]+ calcd for C13H11F9N3O3S: 460.03719;
found: 460.03714.
UV-Vis: lmax (e) = 330.4 nm (27,974 dm3 mol–1 cm–1).
13C NMR (CDCl3): d = 29.1 (1 C, CH2), 31.6 (1 C, CH2), 117.5,
123.6, 123.8, 127.4 (4 C, CPhenylene), 127.7, 128.3, 128.8, 134.3 (4 C,
CNaphthyl), 124.4, 133.1, 133.2, 134.5, 143.0 (5 C, CPhenylene/Naphthyl,
C=N), 184.9 (1 C, C=O).
Bis(butane-1-sulfonamide) 4b
Mp 190–191 °C (EtOH).
MS (FAB): m/z = 548 [M + H]+, 265.1 [M + H – Nf]+.
UV-Vis: lmax (e) = 424.8 nm (15,375 dm3 mol–1 cm–1).
1H NMR (DMSO-d6): d = 2.61 (s, 3 H, CH3), 5.10 (s, 1 H, OH),
7.25–7.38 (m, 4 H, Harom), 7.56–7.60 (m, 2 H, Harom), 7.92–7.95 (m,
2 H, Harom).
13C NMR (DMSO-d6): d = 27.1 (1 C, CH3), 119.9, 125.1, 126.2,
130.2, 133.5, 140.5, 142.4 (7 C, Carom, C=COH), 193.9 (1 C, COH).
MS (FAB): m/z = 861.0 [M + H]+, 577.1 [M – Nf]+.
MS (MALDI-TOF): m/z = 883.02 [M + Na]+.
UV-Vis: lmax (e) = 438.0 nm (13,048 dm3 mol–1 cm–1).
Anal. Calcd for C20H14F9N3O3S (547.06): C, 43.88; H, 2.58; N,
7.68. Found: C, 43.88; H, 2.32; N, 7.70.
(1S,4R)-(Z)-Nonafluoro-N-{2-[2-(4,7,7-trimethyl-3-oxobicy-
clo[2.2.1]heptan-2-ylidene)hydrazinyl]phenyl}butane-1-sulfon-
amide (3e) and (1S,4R)-(E)-Nonafluoro-N-{2-[2-(4,7,7-trimethyl-
3-oxobicyclo[2.2.1]heptan-2-ylidene)hydrazinyl]phenyl}butane-
1-sulfonamide (3e¢)
Following the general procedure using (1S,4R)-1,7,7-trimethyl-2-
(trimethylsiloxy)bicyclo[2.2.1]hepta-2-ene33 (2e, 0.62 g) gave first
3e (0.48 g, 35%) as yellow crystals followed by 3e¢ (0.47 g, 34%)
as light yellow crystals.
(Z)-Nonafluoro-N-{2-[2-(2-oxo-2-phenylethylidene)hydrazi-
nyl]phenyl}butane-1-sulfonamide (3c) and N,N¢-[2,2¢-(1E,1¢E)-
(2-Hydroxy-2-phenylethene-1,1-diyl)bis(diazene-2,1-
diyl)bis(2,1-phenylene)]bis(nonafluorobutane-1-sulfonamide)
(4c)
(Z)-Isomer 3e
Mp 97.5–98.5 °C (n-hexane–EtOAc, 9:1).
[a]D20 +161.3 (c 1, CHCl3).
Following the general procedure using a-(trimethylsiloxy)styrene31
(2c, 0.53 g) gave first 3c (0.39 g, 30%) as neon yellow crystals fol-
lowed by 4c (0.47 g, 41%) as deep red crystals.
1H NMR (CDCl3): d = 0.89 (s, 3 H, CH3), 0.99 (s, 3 H, CH3), 1.03
(s, 3 H, CH3), 1.47–1.62 (m, 2 H, CH2), 1.77–1.90 (m, 1 H, CHH),
2.07–2.21 (m, 1 H, CHH), 2.62–2.64 (m, 1 H, CH), 6.90–7.00 (m,
2 H, Harom), 7.13–7.20 (m, 1 H, Harom), 7.55–7.59 (m, 1 H, Harom),
11.9 (s, 1 H, NNH).
13C NMR (CDCl3): d = 8.7 (1 C, CH3), 18.3 (1 C, CH3), 20.5 (1 C,
CH3), 25.7 (1 C, CH2), 30.2 (1 C, CH2), 47.9 [1 C, C(CH3)2], 50.8
(1 C, CH), 59.8 (1 C, CCH3), 116.2, 122.5, 125.0, 127.8, 122.6,
134.7, 143.6 (7 C, Carom, C=N), 205.2 (1 C, C=O).
Butane-1-sulfonamide 3c
Mp 191–192 °C (CHCl3).
1H NMR (CDCl3): d = 7.03–7.09 (m, 2 H, Harom), 7.17–7.21 (m, 1
H, Harom), 7.46–7.50 (m, 2 H, Harom), 7.55–7.62 (m, 2 H, 2 Harom),
7.69 (s, 1 H, N=CH), 7.94–7.96 (m, 2 H, Harom), 10.21 (s, 1 H,
SO2NH), 14.53 (s, 1 H, NH).
13C NMR (CDCl3): d = 113.0, 117.6, 119.2, 119.5, 119.6, 122.4,
123.3, 124.1, 127.8, 128.7, 131.8 (11 C, Carom, C=N), 182.2 (1 C,
C=O).
MS (FAB): m/z = 554.1 [M + H]+.
HRMS (ESI): m/z [M + Na]+ calcd for C20H20F9N3NaO3S:
MS (FAB): m/z = 522.0 [M + H]+, 239.1 [M + H – Nf]+.
576.09739; found: 576.09711.
Synthesis 2009, No. 7, 1190–1194 © Thieme Stuttgart · New York

1194
M. Uhde, T. Ziegler
PAPER
UV-Vis: lmax (e) = 362.0 nm (10,500 dm3 mol–1 cm–1).
(3) Katritzky, A. R.; Denisko, O. V. Pure Appl. Chem. 2000, 72,
1597.
(E)-Isomer 3e¢
Mp 161–162 °C (n-hexane–EtOAc, 9:1).
(4) Donghi, M.; Habermann, J.; Ley, S. V. Chemtracts 2002, 15,
751.
(5) Katritzky, A. R. J. Heterocycl. Chem. 1999, 36, 1501.
(6) Katritzky, A. R.; Qi, M. Collect. Czech. Chem. Commun.
1998, 63, 599.
(7) Graebe, C.; Ullmann, F. Justus Liebigs Ann. Chem. 1896,
291, 16.
(8) Ullmann, F. Justus Liebigs Ann. Chem. 1904, 332, 82.
(9) Mehta, L. K.; Parrick, J.; Payne, F. J. Chem. Soc., Perkin
Trans. 1 1993, 1261.
[a]D20 +163.3 (c 1, CHCl3).
1H NMR (CDCl3): d = 0.90 (s, 3 H, CH3), 1.04 (s, 3 H, CH3), 1.06
(s, 3 H, CH3), 1.45–1.65 (m, 2 H, CH2), 1.78–1.89 (m, 1 H, CHH),
2.04–2.16 (m, 1 H, CHH), 2.91–2.93 (m, 1 H, CH), 6.95–7.01 (m,
1 H, Harom), 7.22–7.25 (m, 2 H, Harom), 7.40–7.43 (m, 1 H, Harom),
7.96 (s, 1 H, NNH), 8.81 (s, 1 H, SO2NH).
13C NMR (CDCl3): d = 9.1 (1 C, CH3), 18.1 (1 C, s, CH3), 20.6 (1
C, CH3), 23.8 (1 C, CH2), 31.3 (1 C, CH2), 45.7 (1 C, CH), 46.1 [1
C, C(CH3)2], 58.3 (1 C, CCH3), 116.9, 122.7, 127.2, 129.0, 121.3,
137.3, 148.7 (7 C, Carom, C=N), 203.6 (1 C, C=O).
(10) Burgess, E. M.; Carithers, R.; McCullagh, L. J. Am. Chem.
Soc. 1968, 90, 1923.
(11) Katritzky, A. R.; Rachwal, S.; Offerman, R. J.; Najzanek, Z.;
Yagoub, A. K.; Zhang, Y. Chem. Ber. 1990, 123, 1545.
(12) Katritzky, A. R.; Rachwal, S.; Rachwal, B. J. Org. Chem.
1989, 54, 6022.
MS (FAB): m/z = 554.1 [M + H]+, 271.2 [M + H – Nf]+.
UV-Vis: lmax (e) = 336.4 nm (26,703 dm3 mol–1 cm–1).
(13) Katritzky, A. R.; Hughes, C. V.; Rachwal, S. J. Heterocycl.
Chem. 1989, 26, 1579.
(14) Katritzky, A. R.; Huang, T.-B.; Denisko, O. V. J. Org.
Anal. Calcd for C20H20F9N3O3S (553.11): C, 43.40; H, 3.67; N,
7.59. Found: C, 43.13; H, 2.70; N, 7.12.
Chem. 2002, 67, 3118.
(15) Katritzky, A. R.; Fan, W.-Q.; Greenhill, J. V. J. Org. Chem.
1991, 56, 1299.
(Z)-Nonafluoro-N-{2-[2-(1-formylpropylidene)hydrazinyl]phe-
nyl}butane-1-sulfonamide (3f)
Following the general procedure using 1-(trimethylsiloxy)but-1-
ene (2f, 0.39 g) gave 3f (0.88 g, 74%) as yellow-orange crystals; mp
68.5–69.5 °C (n-hexane–EtOAc, 9:1).
1H NMR (DMSO-d6): d = 1.03 (t, 3 H, CH3), 2.48 (q, 2 H, CH2),
7.00–7.04 (m, 1 H, Harom), 7.29–7.35 (m, 2 H, Harom), 7.55–7.57 (m,
1 H, Harom), 9.09 (s, 1 H, SO2NH), 9.32 (s, 1 H, O=CH), 13.58 (s, 1
H, NNH).
13C NMR (CDCl3): d = 9.2 (1 C, CH3), 15.1 (1 C, CH2), 117.4,
123.9, 128.4, 130.1, 121.2, 138.3 (6 C, Carom), 149.2 (1 C, C=N),
192.1 (1 C, C=O).
(16) Micó, X. A.; Ziegler, T.; Subramanian, L. R. Angew. Chem.
Int. Ed. 2004, 43, 1400; Angew. Chem. 2004, 116, 1424.
(17) Micó, X. A.; Richter, M.; Schwarz, S.; Strähle, J.; Ziegler,
T.; Subramanian, L. R. Z. Kristallogr. NCS 2003, 218, 547.
(18) Micó, X. A.; Richter, M.; Schwarz, S.; Strähle, J.; Ziegler,
T.; Subramanian, L. R. Z. Kristallogr. NCS 2003, 218, 549.
(19) Subramanian, L. R.; Micó, X. A.; Ziegler, T. DE
102004005316, 2005; Chem. Abstr. 2005, 143, 268286.
(20) Micó, X. A.; Vagin, S. I.; Subramanian, L. R.; Ziegler, T.;
Hanack, M. Eur. J. Org. Chem. 2005, 4328.
(21) Anwar, M. U.; Tragl, S.; Ziegler, T.; Subramanian, L. R.
Synlett 2006, 627.
MS (FAB): m/z = 473.9 [M + H]+, 191.1 [M + H – Nf]+.
UV-Vis: lmax (e) = 323.3 nm (21,429 dm3 mol–1 cm–1).
(22) Micó, X. A.; Bombarelli, R. G.; Subramanian, L. R.; Ziegler,
T. Tetrahedron Lett. 2006, 47, 7845.
(23) Uhde, M.; Anwar, M. U.; Ziegler, T. Synth. Commun. 2008,
38, 881.
Anal. Calcd for C14H12F9N3O3S (473.05): C, 35.53; H, 2.56; N,
8.88. Found: C, 35.39; H, 2.52; N, 8.25.
(24) Ziegler, T.; Uhde, M.; Kirchmann, M. Z. Kristallogr. NCS
2008, 223, 31.
(25) Katritzky, A. R.; Khelashvili, L.; Le, K. N. B.; Mohapatra,
P. P.; Steel, P. J. J. Org. Chem. 2007, 72, 5805.
(26) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33,
938; Angew. Chem. 1994, 106, 990.
Acknowledgment
We thank Professor K. Albert for measuring the NMR spectra, Pro-
fessor K. P. Zeller for performing the mass spectrometry, and P.
Krüger for doing the elemental analyses. This work was financially
supported by the Deutsche Forschungsgemeinschaft (grant ZI 338/
6-1) and the Fonds der Chemischen Industrie.
(27) Kempf, B.; Hampel, N.; Ofial, A. R.; Mayr, H. Chem. Eur.
J. 2003, 9, 2209.
(28) Yao, H. C. J. Org. Chem. 1964, 29, 2959.
(29) Benassi, R.; Taddei, F. J. Chem. Soc., Perkin Trans. 2 1985,
1629.
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Tetrahedron 2005, 61, 2555.
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Synthesis 2009, No. 7, 1190–1194 © Thieme Stuttgart · New York