Application of alkoxy-λ6-sulfanenitriles as strong alkylating reagents

Article abstract of DOI:10.1002/hc.20006

Alkoxy-λ⁶-sulfanenitriles were found to be versatile alkylating reagents toward various nucleophiles bearing at least one proton such as methanol, phenol, thiophenols, carboxylic acids, ptoluenesulfonic acid, hydrochloric acid, and primary and secondary amines. Reactivity of the alkoxy group of the λ⁶-sulfanenitriles showed an opposite trend to the usual S_N2 character, i.e. Me (la), Pr (1b), and Bu (1d) ? i-Pr (1c). In the presence of p-TsOH, alkyl tosylates were predominantly formed instead of the alkylation products of nucleophiles. In addition, even a sterically hindered substrate, neopentyloxy-λ⁶-sulfanenitrile, was found to undergo an S_N2 reaction toward thiophenol without any rearrangement product to give neopentyl phenyl sulfide in good yield.

Full text of DOI:10.1002/hc.20006

Heteroatom Chemistry
Volume 15, Number 3, 2004
6
A
pplication of Alkoxy-λ -sulfanenitriles
as Strong Alkylating Reagents
Wei Hao, Takayoshi Fujii, Tiaoling Dong, Youko Wakai,
and Toshiaki Yoshimura
Department of Material Systems Engineering and Life Science, Faculty of Engineering,
Toyama University, Gofuku, Toyama 930-8555, Japan
Received 12 December 2003; revised 15 December 2003
known and their chemistry has been developed by
6
ABSTRACT: Alkoxy-ꢀ -sulfanenitriles were found
Glemser et al. [2] in the field of inorganic or flu-
orine chemistry. Meanwhile, we have explored the
to be versatile alkylating reagents toward various
nucleophiles bearing at least one proton such as
methanol, phenol, thiophenols, carboxylic acids, p-
toluenesulfonic acid, hydrochloric acid, and primary
and secondary amines. Reactivity of the alkoxy group
of the ꢀ -sulfanenitriles showed an opposite trend to
the usual S 2 character, i.e. Me (1a), Pr (1b), and
Bu (1d) ꢀ i-Pr (1c). In the presence of p-TsOH,
alkyl tosylates were predominantly formed instead of
the alkylation products of nucleophiles. In addition,
even a sterically hindered substrate, neopentyloxy-ꢀ -
sulfanenitrile, was found to undergo an S 2 reac-
tion toward thiophenol without any rearrangement
product to give neopentyl phenyl sulfide in good
yield. ꢁC 2004 Wiley Periodicals, Inc. Heteroatom Chem
6
chemistry of organic ꢀ -sulfanenitriles since our first
6
preparation of methoxydiphenyl-ꢀ -sulfanenitrile in
6
1
989 [3] without use of trifluoro-ꢀ -sulfanenitrile as
the starting material.
6
In recent years, we have prepared a series of or-
N
6
ganic ꢀ -sulfanenitriles [4,5], and have reported the
6
X-ray structural analysis of some ꢀ -sulfanenitriles
[
4c,4d,5]. In our previous paper [5], it was reported
6
that alkoxy-ꢀ -sulfanenitriles [5] exceptionally un-
dergo a facile Ei reaction, although ꢀ -sulfanenitriles
6
6
N
are tetracoordinated hexavalent sulfur compounds
like sulfones and sulfoximides. Furthermore, dur-
ing the synthesis and the assignment of the struc-
6
ture of these alkoxy-ꢀ -sulfanenitriles [5,6], it was
1
(
5:193–198, 2004; Published online in Wiley InterScience
www.interscience.wiley.com). DOI 10.1002/hc.20006
found that they undergo acid-catalyzed hydrolysis
readily, even under slightly alkaline conditions, to
yield the corresponding sulfoximide [2] and alco-
hols. Moreover, we reported that methoxydiphenyl-
6
INTRODUCTION
ꢀ
-sulfanenitrile reacts with thiols to give methyl
ꢀ6
sulfides and diphenyl sulfoximide, and clarified the
mechanism that involves an initial equilibrated pro-
tonation of the ꢀ -sulfanenitrile by thiols followed
-Sulfanenitriles (thiazynes) [1a,1b] are relatively
unusual compounds bearing a sulfur-nitrogen triple
bond and three ligands on the sulfur atom. Only a
few inorganic ꢀ -sulfanenitriles, such as F
6
6
by nucleophilic attack of the thiolate anions on the
methyl group in the rate-determining step [7]. Both
the acid-catalyzed hydrolysis and the reaction with
thiols show that the sulfoximide moiety of proto-
3
SN, are
Correspondence to: Toshiaki Yoshimura; e-mail: yosimura@eng.
toyama-u.ac.jp.
Contract grant sponsor: Ministry of Education, Culture, Sports,
Science and Technology.
6
nated alkoxy-ꢀ -sulfanenitriles is a very good leav-
6
ing group and thus alkoxy-ꢀ -sulfanenitriles are very
effective alkylating reagents. As an application of
this reaction, the scope and limitations of the use
Contract grant numbers: 13029039 and 14044032.
ꢁ
c 2004 Wiley Periodicals, Inc.
1
93

1
94 Hao et al.
6
of alkoxy-ꢀ -sulfanenitriles as alkylating agents were
OR
O
examined.
Ph
S
Ph + NuH
NuR
+
Ph
S
Ph
N
NH
2
1
a-e
RESULTS AND DISCUSSION
i
6
(1a: R = Me, 1b: R = Pr, 1c: R = Pr, 1d: R = Bu, 1e: R = Neopentyl )
Reaction of Alkoxy-ꢀ -sulfanenitriles with
Various Nucleophiles
SCHEME 1
In order to study these alkylation reactions for
various nucleophilic agents, the alkylation reac-
tion of various nucleophiles with these alkoxy-ꢀ -
isopropyl methyl ether quantitatively. Meanwhile,
phenol and thiols were more easily alkylated than al-
cohols. The reaction of the alkoxy-ꢀ -sulfanenitriles
with primary and secondary amines also gave the
corresponding N-alkylated amines. Structural ef-
fect of the alkyl group showed an opposite trend
6
6
sulfanenitriles was carried out in an NMR tube. The
products were identified by comparing their IR and
NMR spectra with those of the authentic samples
6
or the reported data. These alkoxy-ꢀ -sulfanenitriles
gave the corresponding alkylation products in high
yields toward oxygen (alcohol, carboxylic, sulfonic
acids), nitrogen (amines), and sulfur (thiols) nucle-
ophiles, as shown in Scheme 1 and Tables 1–3.
Alcohols were relatively hard to be alkylated
to the usual S 2 character, i.e., primary (1a, 1b,
N
1d) ꢀ secondary (1c), as shown in the reaction
with phenol. This tendency is the same as the ki-
netic results in the hydrolysis we reported previ-
ously [6]. Meanwhile, methyl phenyl sulfide and
6
in chloroform. But the reaction of isopropoxy-ꢀ -
Et N as nucleophiles could not be alkylated, so that
3
sulfanenitrile (1c) with MeOH as solvent afforded
an active proton on the reagents is required for
6
a
TABLE 1 Alkylation Products by Reactions of Alkoxy-λ -sulfanenitriles with Nucleophiles
Substrates
Nucleophile
NuH
Conditions
Time
Products Yield (%)b
NuR (2)
◦
1
1
a–d (R)
a (Me)
Eq.
Temp ( C)
Solvent
c
PhSH
PhSCH3
2.0∼3.0
2.0∼3.0
30
50
10 h
3 days
C H
95
0
96
0
6
6
c
CHCI
3
-
---------------------------------------------------------------------------------------------------------------------------
CH OH
20
20
2.0
1.3
80
r.t.
45
r.t.
r.t.
40
40
40
r.t.
r.t.
r.t.
r.t.
72 h
114 h
336 h (78 h)
2 h
CDCI
0
0
1
3
3
3
CH OH
CH OH
3
3
PhOH
PhSH
CDCI3
CDCI3
89 (15)
99
91 (16)
99
1b (Pr)
CIC H CH NH
24 h
24 h
50 h
15 min
1 h
1 h
0.5 h
CIC H CH NH
2
20
96
22
98
6
4
2
2
6
4
2
Piperidine
Alanine
AcOH
85
Piperidine
2.0
1.3
1.0
1.3
1.5
CD CN
0
89
0
92
3
CDCI3
CDCI3
CDCI3
CF COOH
99
98
99
99
3
p-TsOH
HCI
CD CN
98
99
3
-
---------------------------------------------------------------------------------------------------------------------------
CH OH
20
20
200
2.0
1.3
80
r.t.
45
r.t.
r.t.
r.t.
40
40
40
40
r.t.
r.t.
r.t.
19 h
114 h
2 h
78 h
2 h
24 h
24 h
50 h
72 h
CDCI
18
99
99
98
99
95
69
0
20
99
99
99
99
97
75
0
3
3
CH OH
CH OH
3
3
CD OD
CD OD
3
3
PhOH
PhSH
CDCI3
CDCI3
1c (i -Pr)
CIC H CH NH
CIC H CH NH
6
4
2
2
6 4 2 2
Piperidine
Alanine
85
Piperidine
2.0
2.0
1.3
1.3
1.5
CD CN
3
Et N
CDCI3
CDCI3
CDCI3
0
0
3
AcOH
p-TsOH
HCI
5 min
15 min
15 min
99
99
99
99
99
99
CD CN
3
-
1
---------------------------------------------------------------------------------------------------------------------------
d (Bu)
PhOH
AcOH
2.0
1.3
r.t.
r.t.
336 h (78 h)
15 min
CDCI
91 (16)
99
92 (17)
99
3
CDCI3
a
Substrates.
b
c
1
The yields and purity were determined by H NMR analysis.
Ref. [7].

6
Application of Alkoxy-ꢀ -sulfanenitriles as Strong Alkylating Reagents 195
6
a
TABLE 2 Alkylation Products by Reactions of Alkoxy-λ -sulfanenitrile with Nucleophiles in the Presence of Acid
Substrates
Nucleophile
NuH
Conditions
Acid (eq).
Products and Yield (%)b
1
b,c (R)
Eq. Temp. Time (h)
Solvent NuR (2)
Others
1
1
1
1
b (Pr)
c (i -Pr)
b (Pr)
PhOH
Menthol
Geraniol
Piperidine
2.0
2.0
2.0
1.0
r.t.
r.t.
r.t.
r.t.
24
0.5
1
p-Ts OH (1.0)
p-Ts OH (1.0)
p-Ts OH (1.0)
NH2OTs(1.0)
CDCI3
CDCI3
CDCI3
12
0
0
99
99
99
99
p-TsOPr (71)
p-TsO-i -Pr (99)
p-TsOPr (99)
c (i -Pr)
0.5
CD CN
0
p-TsO-i -Pr (99)
3
+
−
1b (Pr)
Benzylamine 1.0
r.t.
1
PhCH NH OTs (1.0) CD CN
0
99
p-TsOPr (99)
2
3
3
a
Substrates.
b
1
The yields and purity were determined by H NMR analysis.
these reactions. We have reported the importance
of the initial protonation of the nitrogen atom of
tively. Piperidine and benzylamine in the presence of
their p-toluenesulfonate salts did not afford the alky-
lated amines but gave alkyl p-toluenesulfonates. In-
terestingly, even weaker nucleophiles, anions of the
stronger acid, showed a higher reactivity than the
neutral stronger nucleophiles.
6
alkoxy-ꢀ -sulfanenitriles in both the hydrolysis and
6
the reaction of methoxy-ꢀ -sulfanenitrile with thiols
[7]. Therefore, the alkylations were examined under
acid-catalyzed conditions.
Unexpectedly, the presence of acid was found
to reduce the yield of the alkylation products (Ta-
ble 2). In the presence of p-toluenesulfonic acid
Then the reactions of compound 1 with acetic,
trifluoroacetic, p-toluenesulfonic, and hydrochloric
acids were carried out in CDCl . As shown in Table 1,
3
in CDCl
3
, phenol was alkylated in a rather lower
even a strong acid, whose conjugate base is a very
weak nucleophile, p-TsOH, gave the correspond-
ing ester quantitatively. These reactions reveal that
yield, and menthol and geraniol were not alkylated
at all, while p-TsOH was instead alkylated quantita-
6
a
TABLE 3 Reactions of Neopentyloxy-λ -sulfanenitrile (1e) with Nucleophiles
Nucleophile
NuH
Conditions
Products Yield (%)b
◦
Entry
Eq.
Time
Temp. ( C)
Solvent
NuCH C(CH )
(2)
Others
2
3 3
1
2
3
4
5
6
7
8
9
CH OH
20
65
2.0
56
2.0
61
2.0
1.3
1.3
5.0
1.3
80
80
85
85
2
24 h
114 h
240 h
114 h
144 h
114 h
1 h
8 h
8 h
2 h
48 h
24 h
114 h
24 h
114 h
50 h
r.t.
45
r.t.
45
r.t.
45
r.t.
40
40
r.t.
r.t.
40
45
40
45
40
CDCI3
0
0
0
0
0
0
1
2
1
98
3
99
99
99
88
99
99
6
15
20
43
1
–
–
–
3
CH OH
CH OH
3
3
p-TolOH
p-TolOH
PhOH
PhOH
PhOH
PhSH
PhSH
AcOH
p-TsOH
CDCI3
p-TolOH
CDCI3
c
–
–
c
PhOH
–
–
+
d
g
e
c
CDCI (H )
Trace
98
85
0
12
0
0
0
3
f
CDCI3
–
–
+
f
CDCI (H )
3
c
10
11
12
13
14
15
16
AcOH
CDCI3
–
–
c
h
CIC H CH NH
CIC H CH NH
10
67
6
4
2
2
2
6
4
2
2
2
h
CIC H CH NH
CIC H CH NH
6
4
2
6
4
2
Piperidine
Piperidine
Alanine
Piperidine
Piperidine
(CH ) CCH O (18)
(CH ) CCH O (49)
3 3
3 3
0
0
CD CN
–
3
a
Substrate.
b
c
d
e
f
1
Yields and purity were determined by H NMR analysis.
Complex mixture of rearranged products (NuC(CH CH
.05 eq. p-TsOH.
TsOCH C(CH
Ref. [8].
3
)
2
2 3 3 3 2 3 2 3 2
CH , CH CH C(CH ) , CH CH C(CH ) CH , etc.).
0
2
3 3
) .
g
h
0
.06 eq. p -TsOH.
CIC CH N CHC(CH ) .
6
H
4
2
3 3

1
96 Hao et al.
6
alkoxy-ꢀ -sulfanenitriles serve as strong alkylating
agents toward acids and actual nucleophiles are their
conjugate bases. However, in the case of the reaction
with piperidine and p-chlorobenzylamine, the pro-
ton transfer from the amines to the nitrogen atom of
responding neopentylamines, but afforded thermal
decomposition product 2,2-dimethylpropanal (en-
tries 14 and 15) and its condensation product 2,2-
dimethylpropylidene-p-chlorobenzylamine (entries
12 and 13), respectively. However, the reaction with
phenol, p-cresol, and AcOH afforded only complex
rearranged products and no Ei products even at
6
the ꢀ -sulfanenitrile is unlikely because of too much
difference of the pK
-sulfanenitriles and the unprotonated amines. The
reactions with piperidine and p-chlorobenzylamine
may proceed by their direct attack or by a general
base catalysis.
a
values between the protonated
6
◦
ꢀ
45 C (entries 6, 4, and 10). We reported previously
6
that alkoxy-ꢀ -sulfanenitriles undergo facile Ei reac-
tion in refluxing benzene to afford the corresponding
elimination products and N-unsubstituted diphenyl-
sulfilimine [5]. Ei reactions of sulfoxides and sulfil-
imines in protic solvents are known to undergo rate
retardation [9,10], which is attributable to the result
of no Ei reaction of 1e in phenol and p-cresol.
From these findings, it is suggested that the re-
activity depends on both the position of the equilib-
rium of the initial protonation and the nucleophilic-
ity of the counter anion. The fact that alanine is not
alkylated may be interpreted as follows. In the sec-
ond step the reaction involves the protonated cation
One-Pot Reaction
6
of the ꢀ -sulfanenitrile and the carboxylate counter
anion whose nucleophilicity is similar to acetate an-
ion. But the initial equilibrium constant is consid-
ered to be much smaller than that of acetic acid from
One-pot alkylation of nucleophiles by sodium alkox-
ide using fluoro(diphenyl)-ꢀ -sulfanenitrile was also
carried out. Alcohols were first converted to sodium
alkoxide in DMSO (method A) or alcohols (method
B) using sodium hydride or metallic sodium, re-
6
the pK
acetic acid (pK
a
difference between alanine (pK
a
= 9.69) and
a
= 4.8). Thus the reaction with ala-
nine must be very slow.
spectively, and to this was added fluorodiphenyl-
6
ꢀ
-sulfanenitrile to give the corresponding alkoxy-
-sulfanenitriles and then various nucleophilic
6
ꢀ
Reaction of Neopentyloxydiphenyl-ꢀ6-
sulfanenitrile (1e) with Various Nucleophiles
reagents (NuH) to afford the corresponding alkyla-
tion products (Scheme 2). These methods are effec-
tive to avoid the accompanying hydrolysis of alkoxy-
6
Since the structural effect of the alkoxy group shows
ꢀ -sulfanenitriles during their separation. As some
an opposite trend to the usual S
teresting to examine how this reaction overcomes
the steric effect. As a sterically hindered alkoxy
N
2 reaction, it is in-
examples shown in Table 4, PhSH, AcOH, and p-
TsOH were successfully alkylated in good yields. The
one-pot reaction is especially useful to obtain an acid
ester of inverted alcohols like the Mitsunobu reaction
[11–13].
6
derivative, neopentyloxy(diphenyl)-ꢀ -sulfanenitrile
(1e) was examined as the alkylating agent (Table 3).
It is interesting that the reaction of 1e with
thiophenol gave neopentyl phenyl sulfide in good
yield without any rearrangement (entry 8), since
there are only a few examples of substitution reac-
tion on the neopentyl carbon atom. The presence of
p-toluenesulfonic acid only lowered the yield like
Discussion
According to our previous mechanistic investiga-
tion of the hydrolysis of alkoxy(aryl)(phenyl)-ꢀ -
6
sulfanenitriles and the reaction of methoxydiphenyl-
6
6
other alkoxy-ꢀ -sulfanenitriles (entry 9). The reac-
ꢀ
-sulfanenitrile with thiols [6,7], the present re-
tion with p-TsOH in CDCl at room temperature
3
action is considered to proceed via an initial pro-
tonation of the nitrogen atom of the alkoxy-ꢀ -
sulfanenitrile by the conjugate acid (NuH) of the nu-
cleophiles (Nu ) followed by a nucleophilic attack
6
also afforded neopentyl tosylate in 12% yield to-
gether with a complex mixture of rearranged prod-
ucts which are considered to be formed via rear-
rangement of neopentyl cation (entry 11). However,
the reaction with methanol, p-cresol, and phenol at
room temperature did not afford any product with-
out rearrangement (entries 1, 3, and 5). The reaction
−
of the counter anions at the alkoxy carbon probably
F
S
OR
O
with phenol in the presence of p-TsOH in CDCl
3
gave
+
NuH
Ph
Ph + RO Na
Ph
S
N
1
Ph + NaF
NuR + Ph
S
Ph
a trace amount of neopentyl tosylate and the similar
complex mixture (entry 7). On the other hand, the
reaction with piperidine and p-chlorobenzylamine
without solvents by warming did not afford the cor-
N
NH
2
1
0
SCHEME 2

6
Application of Alkoxy-ꢀ -sulfanenitriles as Strong Alkylating Reagents 197
6
a
TABLE 4 Alkylation Products from Diphenylfluoro-λ -sulfanenitrile
Products and
b
Substrate
Nucleophile
Eq.
Conditions
Yield (%)
−
+
◦
10
(1)RO Na
(2) NuH
Eq.
Method
Temp ( C)
Time
NuR
(2)
−
+
i
i
i
PrO Na
1.1
1.1
1.1
PhSH
AcOH
1.3
1.3
1.3
A
B
B
r.t.
r.t.
r.t.
2 h
78
86
88
83
90
93
−
+
Ph S(F)N
PrO Na
10 min
20 min
2
−
+
PrO Na
p-TsOH
a
Substrate.
b
1
The yields and purity were determined by H NMR analysis.
through an S
N
2 transition state. The opposite trend
Alkylation of Various Nucleophiles with
Alkoxy-ꢀ -sulfanenitriles
6
of the structural effect of the alkyl group shows a
carbocation-like loose transition state like their hy-
drolysis mechanisms [6]. The tendency that the more
acidic conjugate acids are more reactive suggests
that the initial protonation is more important than
the next step as reported previously [7]. The exclusive
formation of the alkyl tosylate from the alkylamine
A typical example is as follows: to a 5-ml solution of
6
−3
alkoxydiphenyl-ꢀ -sulfanenitrile (ca. 7.0 × 10 mol
−
3
dm ) in CDCl , CD CN, CD OD, or no solvent in an
3
3
3
NMR tube, was added an appropriate amount of nu-
1
cleophile, and H NMR was taken immediately and at
1
appropriate time intervals. After H NMR signals of
6
in the reaction of isopropoxy-ꢀ -sulfanenitrile with
6
the alkoxy-ꢀ -sulfanenitriles disappeared or showed
piperidine in the presence of piperidinium tosy-
late suggests that the counter anion is more nucle-
ophilic than the amine in an organic solvent, proba-
bly because of stronger ion-pair interaction than ion-
molecule interaction in the second step nucleophilic
reaction.
The present reaction is similar to esterification
of carboxylic acids by diazomethane in view of in-
volvement of the initial protonation and the follow-
ing facile alkylation. But the present system is avail-
able to a wide variety of alkylation and is safer. Our
method is also similar to the Mitsunobu reaction
no further change, the products were analyzed by
comparing their IR and NMR spectra with those
of the authentic samples or the reported data. The
1
yields of the products were determined by H NMR
from the integral ratios of the products to the sum
6
of 2 and the alkoxy-ꢀ -sulfanenitriles as shown in
Tables 1–3. The by-product S,S-diphenylsulfoximide
(2) was obtained in almost quantitative yield.
One-Pot Reaction
[
11–13], because alcohols are first activated and var-
Method A. A typical example is as follows: to
a 30-ml Erlenmeyer flask was added 100 mg (2.3
mmol) of 55% dispersion of sodium hydride in
mineral oil. The sodium hydride was washed sev-
eral times by decantation with dry ether. To this
was added 6 ml of DMSO to dissolve sodium hy-
dride with stirring at room temperature under an
argon atmosphere. After 1 h, 0.2 ml (2.6 mmol) of
dry isopropanol was added into the reaction solu-
tion and was allowed to react by stirring for 1 h
ious nucleophiles having an active proton can eas-
ily be alkylated at the second step. Though the yield
of the alkylation of alcohols using primary alkoxy-
6
ꢀ
-sulfanenitriles is low compared to the Mitsunobu
reaction, the alkylation of even strong acids is an im-
portant feature at the present reaction.
EXPERIMENTAL
Reagents and Instruments
to give a sodium alkoxide solution. A solution of
6
Reagents and solvents were obtained commercially
and were further purified by general methods when
necessary. IR spectra were taken on a Horiba FT-710
spectrometer, H NMR and C NMR spectra were
obtained on a JEOL-JNM 400 NMR spectrameter in
fluorodiphenyl-ꢀ -sulfanenitrile 1
0
(438 mg, 2 mmol)
in DMSO (6 ml) was added to the stirred solution
of sodium alkoxide. After stirring for 10 min, 0.268
ml (2.6 mmol) of thiophenol was added and stirring
was continued for 2 h. The reaction mixture was
poured into ice water and extracted with chloroform
(5 × 5 ml). The combined organic extract was dried
over anhydrous sodium sulfate and concentrated un-
der reduced pressure to give isopropyl phenyl sul-
fide in 78% yield and S,S-diphenylsulfoximide (2) as
1
13
CDCl
3
, CD
3
CN, or CD OD with TMS as an internal
3
standard. Elemental analyses were performed on a
Yanaco MT-5 CHN CORDER. Fluoro- and alkoxy-ꢀ -
sulfanenitriles were prepared according to the meth-
ods reported in our previous papers [5,6].
6

1
98 Hao et al.
shown in Table 4. The products were identified by
comparing their IR and NMR spectra with those of
the authentic samples.
Chem Int Ed Engl 1980, 19, 883–899 and references
therein.
3] Yoshimura, T.; Tsukurimichi, E.; Kita, H.; Fujii,
[
H.; Shimasaki, C. Tetrahedron Lett 1989, 30, 6339–
6
340.
Method B. Typical examples are as follows: to a
[4] (a) Yoshimura, T.; Kita, H.; Takeuchi, K.; Takata,
E.; Hasegawa, K.; Shimasaki, C.; Tsukurimichi, E.
Chem Lett 1992, 1433–1436; (b) Yoshimura, T.;
Takata, E.; Miyake, T.; Shimasaki, C.; Hasegawa, K.;
Tsukurimichi, E. Chem Lett 1992, 2213–2216; (c)
Yoshimura, T.; Hamata, K.; Imado, M.; Hamata, K.;
Tomoda, K.; Fujii, T.; Morita, H.; Shimasaki, C.; Ono,
S.; Tsukurimichi, E.; Furukawa, N.; Kimura, T. J Org
Chem 1997, 62, 3802–3803; (d) Ohkubo, M.; Fujii, T.;
Ono, S.; Morita, H.; Yoshimura, T.; Horn, E.; Sato, S.
Chem Lett 1997, 153–154.
3
0 ml Erlenmeyer flask was added 26 mg (1.1 mmol)
of sodium and 8 ml dry isopropanol to dissolve the all
metallic sodium. To this was added fluorodiphenyl-
6
ꢀ
0
-sulfanenitrile 1 (219 mg, 1 mmol) in 8 ml of dry
isopropanol at room temperature under an argon
atmosphere. After stirring for 10 min, the reaction
mixture was condensed to afford a slurry which was
dissolved in 2 ml of CDCl
canted to 0.075 ml (1.3 mmol) of AcOH or 224 mg
1.3 mmol) of p-TsOH for 10 min or 15 min, respec-
3
. The supernatant was de-
[
5] Yoshimura, T.; Ohkubo, M.; Fujii, T.; Kita, H.; Wakai,
Y.; Ono, S.; Morita, H.; Shimasaki, C.; Horn, E. Bull
Chem Soc Jpn 1998, 71, 1629–1637.
(
tively, to give the corresponding isopropyl ester and
S,S-diphenylsulfoximide (2) as shown in Table 4.
[
6] Yoshimura, T.; Dong, T.; Fujii, T.; Ohkubo, M.; Sakuta,
M.; Wakai, Y.; Ono, S.; Morita, H.; Shimasaki, C. Bull
Chem Soc Jpn 2000, 73, 957–965.
REFERENCES
[7] Yoshimura, T.; Tsukurimichi, E.; Sugiyama, Y.; Kita,
H.; Shimasaki, C.; Hasegawa, K. Bull Chem Soc Jpn
1991, 64, 3176–3178.
[8] Pierini, A. B.; Penenory, A. B.; Rossi, R. A. J Org Chem
1985, 50, 2739–2742.
[9] Oae, S.; Furukawa, N. Tetrahedron 1977, 33, 2359–
2367.
[
1] (a) This type of compound was first named as “thi-
azyne” by Clifford et al. [b] previously, and we have
also used this name. But, in order to avoid confusion
with heterocyclic didehydrothiazine etc., the name
6
“
ꢀ -sulfanenitrile” is used in this paper based on IU-
PAC recommendation; (b) Clifford, A. F.; Howell, J.
L.; Wooton, D. L. J Fluorine Chem 1978, 11, 433–439.
2] (a) Glemser, O.; Schroder, H.; Haeseler, H. Z Anorg
Allg Chem 1955, 279, 28–37; (b) Glemser, O.; Richert,
H. Z Anorg Allg Chem 1961, 307, 313–327; (c) Richert,
H.; Glemser, O. Z Anorg Allg Chem 1961, 307, 328–
[10] Yoshimura, T.; Tsukurimichi, E.; Iizuka, Y.; Mizuno,
H.; Isaji, H.; Shimasaki, C. Bull Chem Soc Jpn 1989,
62, 1891–1899.
[11] Mitsunobu, O. Synthesis 1981, 1–28.
[12] Castro, B. R. Org Reactions; John Wiley & Sons, Inc.;
New York, 1983, 29, Chapter 1.
[
3
1
44; (d) Glemser, O.; Meyer, H.; Haas, A. Chem Ber
964, 97, 1704–1709; (e) Glemser, O.; Mews, R. Angew
[13] Hughes, D. L. Org Reactions; John Wiley & Sons, Inc.;
New York, 1992, 42, Chapter 2.