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Chlorosulfenylated Carbonic Acid Derivatives.

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with suitable vinyl compounds to form sulfinic acids,
and if the reaction mixture still contains activated
vinyl compounds, sulfones are very rapidly formed.
High molecular weight polysulfones can thus be
readily prepared by polyaddition reactions with sulfoxylic acid if suitable divinyl compounds are used as
acceptors.
B
?
o n nitrous gases, dinitrogen trioxide, and nitrous acid. It is
difficult to isolate intermediates of the reduction. The utmost
care is necessary in the treatment of even small reaction mixtures from the reduction of potassium and sodium nitrites,
since violent decompositions have sometimes been observed.
5. Addition Compounds Containing Activated
Formic Acid as Formylating Agents and as Solvents
x CH~=CH-C-NH-CH~-NH-C-CH=CHZ
I
- ( C H ~ - C H ~ - C - N H - C H ~ - N - -Cc H ~ - c H ~ - s o ~ ) ~ II
II
0
insoluble, x
H ~ =HC-oc
C
0
=
unknown
- N-N-
co-C H = C H ~
(61
CO-CH=CHz
insoluble, three dimensionally
crosslinked polysulfone
With introduction of sulfur dioxide at a suitable rate
during the preparation of polysulfones, water-soluble
polysulfones with sulfinic acid end groups can also be
prepared by this method.
Many of the liquid adducts, particularly those of one
mole of trimethylamine or triethylamine with three
moles of formic acid can be used as formylating agents
for N- and 0-formylations, since the addition compounds are generally good solvents for high molecular
weight polyols and polyamines, and the formylations
are accelerated in these solvents. Reductive degradations of natural polymers such as cellulose and polypeptides proceed particularly readily.
I am grateful to Professor Dr. Holtschmidt for the use
of his unpublished experimental results on the hexamethylenetetramine-formic acid cleavage reaction, to
Professor Dr. Pestemer for spectroscopic studies, to
Dr. Joop for N M R measurements, to Dr. Fauss for
osmotic molecular weight deterniinations, and to Dr.
Klauke for the preparation of par f l yfluorinated ketones.
Received May 30, 1969
[A 736 IE]
German version Angew Chem 82, 73 (1969)
Translated by Express Translation Service. London
The results obtained in the reduction of sulfur dioxide have
led t o the investigation of the action of activated formic acid
Chlorosulfenylated Carbonic Acid Derivatives
By G. Zumach and E. KuhIe[*J
Dedicated to Professor K . Hansen on the occasion of his 60th birthday
The present article deals first with the synthesis of chlorocarbonylsu(fenyI chloride and its
imino analogs. The chemical behavior of these bifunctional compounds is illustrafed for
selected examples. Special attention is given to the syntheses of jive-membered heterocycles containing sulfur, oxygen, andlor nitrogen.
1. Introduction
The present article deals with compounds that can be
regarded both as carbonic acid derivatives and as
sulfenic acid derivatives. Two compounds of this series,
i.e. trichloromethanesulfenyl chloride ( 1 ) and N-dichloromethylenesulfenylamide chloride (Z), have been
known for a long time.
Trichloromethanesulfenyl chloride { I ) consists formally of
a n orthocarbonyl trichloride group and a sulfenyl chloride
[*I Dr. G. Zumach and Dr. E. Kiihle
Wissenschaftliches Hauptlaboratorium
der Farbenfabriken Bayer AG
509 Leverkusen-Bayerwerk (Germany)
54
group. It was first synthesized more than 100 years ago by
Rathke[ll by chlorination of carbon disulfide in the presence
of iodine, and is still produced on the large scale by the same
method.
s=c=s + 3CIz
-+
C13C-SCI
12
+ SCl2
(1)
In 1924, Kuufmann and Liepe 121 obtained “thiocyanogen trichloride” by chlorination of thiocyanogen; this product was
later found to be (2)[31.
[l] B. Rathke, Ber. dtsch. chem. Ges. 3 , 858 (1870).
[2] H. P . Kuufmann and J . Liepe, Ber. dtsch. chem. Ges. 57, 923
(1924).
[3] E. Kiihle, B . Anders, and G . Zumach, Angew. Chem. 79, 663
1967; Angew. Chem. internat. Edit. 6, 649 (1969).
Angew. Chem. internut. Edit.
1 Vol. 9 (1970)
NO. I
NCS--SCN
+ 3 Cl2
+ 2 ClSN=CClp
Alkyl-0-C-SCH3
CIz
----+
Whereas (2) behaves in most reactions as a masked sulfur
dichloride, with elimination of cyanogen chloride, the chlorosulfenylated carbonic acid derivatives to be described here are
derived from trichloromethanesulfenyl chloride ( I ) :
X
'I
CI-C-s-CI
(I),
x
(7),
(3),
x
x
191, X
(4), x
=
CI, CI
=
0
=
=
=
s
N-R
CI, SCI
We shall now consider chlorocarbonylsulfenyl chloride
(7), the iminochloromethanesulfenyl chloride (9) [43,
chlorothiocarbonylsulfenylchloride (3), and dichloromethanebis(sulfeny1 chloride) ( 4 ) . Chlorothiocarbonylsulfenyl chloride (3), which should occur as an intermediate in the chlorination of carbon disulfide, has
not yet been prepared so far as we know, but was
described by Klason 151 as the product of the thionation
of thiophosgene.
C I - c - CI
+ s ----+
CI -C-SCI
130-150°C
S
(3)
The very high boiling point of 140 "C at about 15 torr
given by Klason cannot be correct for this compound,
since thiophosgene boils at 73-74 "C under normal
pressure.
Dichloromethanebis(sulfeny1 chloride) (4), which is
also an intermediate of the chlorination of carbon disulfide, has however been obtained in this way in the
presence of U V light as a compound that can be isolated only in the cold, and that has an extrapolated
boiling point of 183 "C 161:
2. Syntheses
2.1. Syntheses of Chlorocarbonylsulfenyl Chloride
Chlorocarbonylsulfenyl chloride (7) (b.p. = 98 OC,
= 1.5165) was first obtained by thermolysis of
alkoxydichloromethanesulfenyl chlorides (6) a t 60 t o
70 "C 171. Since the required starting compounds are
obtainable only from alkyl S-methyl dithiocarbonates
( 5 ) 181, this synthesis is of little preparative value.
[4] Formerly known as "mustard oil chlorides".
[5] P . Klason, Ber. dtsch. chem. Ges. 20, 2376 (1887).
[61 H. M. Pitf and H . Bender, US-Pat. 3331 872 (April 13,1964),
Stauffer Chem. Comp.
[7] B. Freedman, DAS 1203 742 (Oct. 26, 1963), California Res.
Comp.
[8] I. B. Douglass and C . E. Osborne, J. Amer. chem. SOC.75
4582 (1953).
Angew. Chem. internat. Edit. J Vol. 9 (1970)
60-70 "C
---+
O=C-SCI
+ Alkyl-CI
c1
I 7)
Chlorocarbonylsulfenyl chloride (7) is now obtainable
on the industrial scale by a simple process that proceeds smoothly. This process makes use of trichloromethanesulfenyl chloride ( I ) , which is subjected to
partial hydrolysis with sulfuric acid 191. Concentrated
sulfuric acid is used with the quantity of water required
for the hydrolysis, and the components are heated at
45 to 50 "C. Chlorocarbonylsulfenyl chloride (7)
separates out as an oil that is immiscible with sulfuric
acid.
C13C-SCI
CIC-SCI
H20HzS04
___
11
(1)
+ 2 HCI
0
(7)
2.2. Syntheses ofIminochloromethanesulfenyl Chlorides
Iminochloromethanesulfenyl chlorides (9) always
occur as intermediates in the chlorination of isothiocyanates (8) to form isocyanide dichlorides (10) 131.
~
S
(6)
+ CH3S-CC13
Alkyl-O-CCI~-SCI
1 No. I
Whereas aliphatic compounds (9) are mostly unstable
and can be handled only with special precautions (disCI
R-N=C=S
R-N=C:
c1
c1>
sc1
R-N=CCl,
Table 1. Iminochloromethanesulfenyl chlorides (9) [ a ] .
R
B.p. ("Cltorr)
(M.P. ( " 0
Yield
38/12
63-65/22
80-81.5/11
76-7810.2
84-86/0.15
109-1 1210.25
(91-92)
(1 15- 116)
(189- 190)
104- l05/0.075
31
54
54
61
97
73
12
70
(%I b l
[cl
[a] Arylenedi(iminochloromethanesulfeny1 chlorides)
CIS-C(CI)=N-R-N=C(CI)-SCI:
R = p-C6H4 m.p.
82-83°C 1111; R = 4-CH3-1,3-C6H3, m.p. 75-75.5"c [ I 11;
R = p-C6H4-N=N-CsH4(p),
m.p. 158--160°C [3].
[ c ] Characterized as a derivative.
[bl Yields not optimized.
[9] W. Weiss, German Pat. 1224720 (Nov. 11, 1964), Farbenfabriken Bayer AG.
[lo] G. Zumach, unpublished.
[ l l ] G . Ottmann and H . Hooksjr., Angew. Chem. 77,427 (1965);
Angew. Chem. internat. Edit. 4, 432 (1965).
[12] Z. M. Ivanova, N . A . Kirsanova, and G. I. DerkaE, 2. org.
Chim. I, 2186 (1965).
[13] R. Neidlein and W. Haussmann, Arch. Pharmaz. 300, 609
(1967).
[14] G. I. DerkaP and N. A . Kirsanova,
(1967).
2. org. Chim. 3, 1144
55
Table 3. Chlorocarbonyl alkyl disulfides (12).
tillation under nitrogen), the aromatic and acylated
compounds are fairly stable (Table 1).
Proof of the structure of the compounds (9) is provided
by their synthesis from sulfur dichloride and from isocyanides, e.g. from cyclohexyl isocyanide.
NzC
+
ClSCl
R
N= C,
-+
[a] Yields not optimized
3. Reactions of Chlorocarbonylsulfenyl Chloride
The structure of the compounds (12) is shown by the carbonyl band, which occurs at a relatively low wavelength (5.6 pm),
and from the reaction with an amine e.g.
3.1. Open-Chain Reaction Products
C4Hs-S-S-CCI
(12a)
6
Both the chlorosulfenyl and the chlorocarbonyl grouping of chlorocarbonylsulfenyl chloride (7) are available
for nucleophilic substitutions e.g. with alcohols, thiols,
and amines. These reactions can also be carried out
selectively in some cases. The action of alcohols on
chlorocarbonylsulfenyl chloride (7) in a molar ratio
of 1 : 1 leads to alkoxycarbonylsulfenyl chlorides
(11) "51 (Table 2).
ROH
30-60 "C
+ CIC-SCI
+ RO-C-SCI+
~
-N(C2H&
(13) 0
Butyl N,N-diethylcarbamoyl disulfide (13) gives a carbonyl
band (at 6.0 pm) and yields tetraethylurea, dibutyl disulfide
and dibutyl trisulfide in the mass spectrometer 1171.
Some other reactions of the alkoxycarbonylsulfenyl
chlorides (11) and alkyl chlorocarbonyl disulfides (12)
are shown in Scheme 1.
C2HsOC(O)SCI iKSC(S)OCzHs
(Ira)
-+
----
-KCI
C?HjOC(O)-S -S-C(S)OCZHS
b.p.
HCI
II
II
-t HN(C2Hj)z + C4H9-S-S-C
0
0
CH30C(O)SCI
(7)
(11)
(lib)
+ (CH&N -C(S)OC4Hg
CH30C(O)SCI
95 "CiO.3 torr 1201
- --C4H9CI
+
~
CH3OC(O)-S-S-C(O)N(CH3)2
b.p.
Very good yields are obtained in this reaction if the
alcohol is added to the chlorocarbonylsulfenyl chloride
a t 30-60°C, care being taken to ensure that a little
chlorocarbonylsulfenyl chloride is still present at the
end of the reaction.
=
+ CH,SC(S)OCH,
__-
-CH3CI
lllb)
120-122 "C/0.3 torr
=
+
CH30C(0)- S -S-C(0)SCH3
b.p.
=
86-88 T j 0 . 2 tom
n
Table 2.
CH3
I
1 1
73-74/100
74
nc-)c?Li ;iii:'15-16
n-CsH1,
0
Alkoxycarbonylsulfenyl chlorides ( 1 I)
::.5
89-93/0.3
ClCHzCH2
CsHx-CHzCHz
CHsOCHzCH2
1
99-104/19
155-159/14
93-96/20
69
63
56
C2HS-S-S-C(0)CI
+ NaOCzHS
-NaCI
C~H~-S-S-C(O)OC~HS
(126j
b.p. = 94-98 "C/14-19 torr
[a] Yields not optimized.
C2Hj-S-S-C(0)C1+
In contrast with the alcohols, aliphatic thiols react
with chlorocarbonylsulfenyl chloride in equimolar
quantities on the chlorosulfenyl residue with formation
of the alkyl chlorocarbonyl disulfides (12) [161. This
NaOC6Hj
-4
-NaCI
(12b)
CZH~-S-S-C(O)OC~H~
b.p.
C~HS-S-S-C(O)CI
+ NaSCzHS
&
0-30 "C
~
3
R-S-S-CCI
(12)
-NaCl
reaction is so selective that it stops at the disulfide
stage (12) even when the thiol is used in excess
(Table 3).
[15] E . Miihlbauer and W. Weiss,German Pat. Appl.PI568633.5
(Dec. 2, 1966), Farbenfabriken Bayer AG.
1161 E. Miihlbauer and W. Weiss, German Pat. 1219925 (March
20, 1965), Farbenfabriken Bayer AG.
[17] Studies by Dr. W. Meise, Leverkusen
56
CZH~-S-S-C(O)SC~H~
+ HCI
b.p.
C4H9-S-S-C(O)CI+
l2OoC/1.9 torr
-+
(126)
RSH+ CIS-CCI
(7)
=
=
69 Y70.12 torr
HN(CsH7)z -4
-HCI
C4H9-S -S -C(O)N(C~H~)Z
(12a)
b.p. = 125-127 oCjO.l torr
CZHS-S-S-C(O)Cl+
HSCsH5
-+
-HCI
(126)
[C~HS-S-S-C(O)SC~HS]
-cos
b.p.
C~HS-S-S-C~HS
=
82-84 "C/0.9 torr
Scheme 1.
Angew. Chern. internat. Edit.
/
Vol. 9 (1970)
1 No. I
Thiophenols are oxidized by chlorocarbonylsulfenyl
chloride (7) to diary1 disulfides (14).
-
2 C ~ H I S Ht CIC-sCI
chlorocarbonylsulfenyl chloride (7) reacts practically
quantitatively with N-methylaniline to give N-methylbenzothiazolone (21) 1201, b.p. = 140 ' C / 2 torr.
C~HS-S-S-C~HY
-2 HCI; -COS
0
7H3
(14)
I 7)
QJNH
Aryl chlorocarbonyl disulfides can also be prepared by
another route. The action of chlorocarbonylsulfenyl
chloride (7) on an S-aryl ester of thiocarbamic acid,
r .g. (I5), leads to elimination of carbamoyl chloride
and formatlon of an aryl chlorocarbony] disulfide c.g.
(16) [181, b.p. = 86-88 "C/0.7 torr.
Chlorocarbonylsulfenyl chloride (7) reacts in the cold
with aliphatic amines, as with alcohols, on the chloro-
+
(7)
-
CH3
y 3 3
* ONFo
[@;c=o]
S
c1
(21)
Primary and secondary amines react smoothly with
chlorocarbonylsulfenyl chloride (7) in a molar ratio of
2 : 1 to give the stable carbamoylsulfenylamides (19)
(Table 4).
Table 4
Carbamoylsulfenylaniides R-C--SR
(/Pi
0
23.5
(CH3)zN-C -SChH.c-!- CIC SCI
[a] Yields not optimized.
+
1,
0
0
115)
171
(CH3)lN- CCI-I CIC-S-S
0
ChHc
0 (16)
carbonyl residue at first, but the resulting carbamoylsulfenyl chlorides ( 1 7) readily decompose with elimination of sulfur to form the carbamoyl chlorides (18).
Even the mild cleavage of the carbamoylsulfenylamides (19) with hydrogen chloride yields the same
products [191.
2 R2NH t- CIC-SCI
OQC
--RzNH*CI
RzN- C - SCI ->
-S
As well as substitutions, chlorocarbonylsulfenyl
chloride (7) can also undergo additions, of which two
types will be described.
The addition of compound (7) to olefins in a molar
ratio of 2 : 1 leads to elimination of phosgene and
formation of 2-chloroalkyl chlorocarbonyl disulfides.
Chlorocarbonyl 2-chlorocyclohexyl disulfide reacts
with methanol to form the compound (22), b.p. = 143
to 145 "C/1.8 torr.
c1
R2N CCI
0
( 7)
2 HCI
7
--RzNHzCI
S- S - 8 - OCH,
R2N-C -S-NRz
I,
The unstable carbamoylsulfenyl chloride (17) can
however be intercepted with cyclohexene e.g. to form
the compound (20) (R =: CH3, &' = 1.5329).
With aromatic amines, this "interception reaction"
takes place intramolecularly with cyclization. Thus
[18] G. Zumach and E . Kuhle, German Pat. Appl. P 1947952.8
(Sept. 23, 1969), Farbenfabriken Bayer AG.
[19] The dimethylthiocarbamidosulfenyl chloride formed a s an
intermediate in the chlorolysis of tetramethylthiuram disulfide
also immediately loses sulfur to form dimethylthiocarbamoyl
chloride; cf. E . J . Rifler, US-Pat. 2466276 (Feb. 2, 1946),
Sharples Chem. Inc.
Angew. Chem. internat.
Edit. J VoI. 9 (1970) J No. I
Tsothiocyanates are formed by addition of chlorocarbonylsulfenyl chloride (7) to isocyanides, again
with elimination of phosgene.
NsC
+ (7)
4
N = C,
In the reaction of chlorocarbonylsulfenyl chloride (7)
with an 0-alkyl N,N-dialkylthiocarbamate, chloroalkane is eliminated as in a reaction described by
Harris 121'. The expected chlorocarbonyl N,N-dialkylcarbamoyl disulfide, e.g. (23), decomposes even at 0 "C
[20] E . Muhlbauer, Leverkusen, unpublished.
1211 J . F. Harris, J. Amer. chem. SOC.82, 155 (1960).
57
with liberation of sulfur and carbon oxide sulfide to
give the N,N-dialkylcarbamoyl chloride, in this case
(24).
(CH&N-C--OC.+Hq -t(7)
-C,HyCI
I
Chlorocarbonylsulfenyl chloride f 7), however, does
not give (28) with R' = COCI; two moles of (7) react
instead with one mole of the monosubstituted formamide t o give the heterocycle (27) (method b in Table
5) 1241.
RNH-CHO
S
+
'I
0
123)
Table 5.
see text.
'07)
(24)
R
__f
-2HC1
I ,2,4-dithiazolidine-3,5-diones
(27). For methods a and b
It is sometimes possible to intercept the unstable intermediate (23) as an ester or amide, e.g. as the ester (25)
(b.p. = 120-122 "C/0.3 torr).
(23)
-COCIz,
(CH3)zN -CCI
0
CH3OH
+ 2 (7)
(CH3)zN-C
S-S-C-OCH3
I
0
0
M.p. ("C)
(B.p. ("Citorr))
Yield (%) [a]
Method a
Method b
38-39 (80j0.2)
(90-92/0.15)
87-88
93-94
168
109-110
166-1 68
183-184
67
83
41
35
75.5
41
79
70
I
40
-
42
-
28
-
35
39
(25)
[a] Yields not optimized.
3.2. Ring Closure Reactions
In contrast with the reaction of chlorocarbonylsulfenyl
chloride (7) with 0-esters of N,N-dialkylthiocarbamic
acids, in which the unstable intermediate (23) changes
into dialkylcarbamoyl chloride (24), the carbamoyl
chlorocarbonyl disulfides (26) formed in the reaction
of compound (7) with 0-alkyl esters of N-monosubstituted thiocarbamic acids can achieve stability by
cyclization to form 1,2,4-dithiazolidine-3,5-diones
(27) (method a in Table 5) [221.
The unsubstituted 1,2,4-dithiazolidine-3,5-dione(30),
m.p. = 142-144°C cannot be obtained by the two
methods described. It is obtained by reaction of 0ethyl thiocarbamate with (7) in the presence of triethylamine followed by hydrolysis of the intermediate
f29) with concentrated hydrochloric acid.
H2N-$-OC2H,
+ (7)
-+
S
RNH-C-S-S-CCl
II
I1
0
0
0
0
This reaction proceeds particularly smoothly with 0alkyl esters of N-arylthiocarbamic acids in the presence
of a tertiary amine as a hydrogen chloride acceptor.
N-monosubstituted formamides react with sulfenyl
chlorides in the presence of thionyl chloride to give the
iminocarbonic acid derivatives (28) [231.
r
-2
HCI
/SR'
R-N=C\
c1
[22] G. Zumach, W. Weiss, and E. Kiihle, Belgian Pat. 682991
(June 23, 1966), Farbenfabriken Bayer AG.
[23] E. Kiihle, Angew. Chem. 74, 861 (1962); Angew. Chem.
internat. Edit. 1, 647 (1962).
58
@+
0AN&O
H
(291
(30)
As a bifunctional compound, chlorocarbonylsulfenyl
chloride (7) can be used with other bifunctional reactants for the synthesis of heterocycles containing
sulfur. Thus primary carbonamides (31) undergo Nsulfenylation and simultaneous ring closure with (7)
to form 5-substituted 2-oxo-1,3,4-oxathiazoles
(32) 1251
These can also be obtained from the amides (31) with
trichloromethanesulfenyl chloride ( I ) 126,271.
When primary thioamides are used, the sulfenylation
with (7) takes place not on the nitrogen but on the
7
R'-SCl
(CZH33N*
s-s
s-s
C2H,0-dN&0
RNH-2-0-Alkyl
+ (7)
S
[24] G. Zumach, W. Weiss, and E. Kuhle, Belgian Pat. 682820
(June 20, 1966), Farbenfabriken Bayer AG.
[25J E. Miihlbauer and W. Weiss, Belgian Pat. 680644 (May 6,
1966), Farbenfabriken Bayer AG.
I261 a) E. Kiihle, unpublished; b) A. Sennig and P. Kelly, Acta
chern. scand. 21, 1871 (1967).
[27] Belgian Pat. 710988 (Aug. 19, 1968), Badische Anilin- und
Soda-Fabrik.
Angew. Chem. internat. Edit.
/ Vol. 9
(1970)
/ No. I
sulfur, with formation of 5-substituted 3-oxo-l,2,4dithiazoles (33) r10,281.
N,N'-Disubstituted ureas react with compound (7)
not in the enol form but in the keto form with "N,N'bridging" to form 2,4-disubstituted 1,2,4-thiadiazolidine-3,S-diones (34) 1291.
The reaction of (36) with hydrogen sulfide in aprotic
solvents leads to 3-imino-5-oxo-l,2,4-dithiazolidine
hydrochlorides (38) and the thiadiazolidines (37).
The reaction probably proceeds via the 5-0x0-3thioxo-l,2,4-thiadiazolidines(37), which rearrange
in the presence of hydrogen chloride into (38).
The salts (38) can also be obtained by the reaction of N,N'-disubstituted thioureas with chlorocarbonylsulfenyl chloride (7) in the absence of a
hydrogen chloride acceptor, whereas compound (37)
is formed in the presence of a tertiary amine. The bases
of the salts (38) are unstable and change back into
(37)
131'
As is shown by NMR spectroscopic studies and independent synthesis (see Section 4.2.3), the reaction
of N-alkyl-N'-arylureas with compound (7) leads
exclusively to 4-alkyl-2-aryl-l,2,4-thiadiazolidine-3,5diones (35). No isomers are formed.
(38)
(37)
without
H,N
R N H - C - N H R + (7)
The reversible rearrangement (37) &38) can be followed IR-spectroscopically by observation of the
appearance and disappearance of an absorption band
at 1620cm-1, which must be assigned to the C - N
double bond in (38) [321.
Another synthesis for (preferably symmetrically substituted) compounds (34) is the addition of (7) to
carbodiimides followed by hydrolysis of the intermediate
3-chloro-5-oxothiadiazolinium
chlorides
(36) [301. A number of 1,2,4-thiadiazolidine-3,5-diones
(34) are listed in Table 6 .
T h e IR spectra of t h e compounds (36) contain a split a b sorption b a n d between 1650 a n d 1750 cm-1, t h e stronger
component, situated a r o u n d 1730 cm-1, being d u e t o t h e CO
group, a n d t h e weaker component, situated a r o u n d 1680
cm-1, t o a C = N double bond.
In contrast with the reaction of N-alkyl-N'-alkylureas
with the compound (7), the reaction of N-alky1-N'arylthioureas with (7) leads to isomer mixtures in
which the component (39) generally predominates
strongly. Other examples of ring closure reactions
with (7) are listed in Table 7.
Table 7.
Reaction partner
C,H,- c - 0 l i
CFI,-Cli
Cyclizations with chlorocarbonylsulfenyl chloride (7)
Reaction product
"'x.
H3C y = O
c f i3 c - 0 i I
C,HsOOC-CH
~
R
I
R'
M.p.
Yield
( "C)
(%) [a1
65
52-54
90-91
48-49
107
114-115
154
158-1 59
179-180
44
47
15
24
52
36
35
aoH
61
44.5
[a] Yields not optimized.
[28] P. M . Hell, Dissertation, Universitat Hamburg 1968.
[291 G. Zumach, L . Eue, W. Weiss, E . Kiihle, and H . H a c k ,
Belgian Pat. 698601 (May 17, 1967); Belgian Pat. 709916 (Jan.
26,1968), both Farbenfabriken Bayer AG.
1301 P. Fischer and W . Weiss, German Pat. Appl. P 1670917.4
(Sept. 4, 1967), Farbenfabriken Bayer AC.
Angew. Chem. internat. Edit.
1 Vol. 9 (1970) / No. I
[31] The bisaromatic compounds, for which the form of the
thiadiazolidine (37) is unknown, represent an exception.
[32] C. K . Bradsher, F. C. Brown, E. F. Sinclair, and S. T . Websrer, 3. Amer. chem. Soc. 80, 414 (1958).
[33] E . Muhfbauer and W . Weiss, German Pat. 1233882 (March
18, 1965), Farbenfabriken Bayer AG.
59
S
S
Aryl-NH-C-NH-Alkyl
II
+ (7)
Aryl-yKF-Alkyi
-+
(39)
In the presence of isocyanides, the iminochloromethanesulfenyl chlorides, e.g. (Sa), lose chlorine with
regeneration of the isothiocyanates from which they
are derived, while the isocyanides are converted into
isocyanide dichlorides e.g. (IOa).
S
+ Aryl-N K r - A l k y l
2-s
0
+
~ W = C C l z
4. Reactions of Iminochloromethanesulfenyl
Chlorides
4.1. Open-Chain Reaction Products
As sulfenyl chlorides, the compounds (9) also add to
olefinic double bonds (3,361.
The principal reactants for reactions of iminochloromethanesulfenyl chlorides (9) to give open-chain
products are primary and secondary aliphatic and
aromatic amines. The reaction with two moles of
amine yields S-aminoisothioureas (40), the stability
of which depends on the substituents (Table 8).
Hydrolysis of the adducts (41) leads to the 5'-esters of
thiocarbamic acids (42), which, when R' is an electronegative residue (e.g. phenyl), can sometimes
cyclize to give 2-oxo-l,3-thiazolidines (43) [361.
S
0
R-N=CCl-SCI
+4
- -\
,NH
R"
-
,--
1
(41)
I1
RNH-C-S-CHz-CHC1-R'
+
OA&R1
R
R-N=C-S-N,
R"
( 9)
(43)
(40)
+
2
R'\
Rl
4.2. Ring Closure Reactions
,hTHzCI
I'
4.2.1. R e a c t i o n w i t h Vinyl E t h e r s
Table 8.
S-Arninoisothioureas (40) 1351.
1 1
R
R'
R"
M.p. ("C)
(B.P.
( "Citorr))
150-150.5
(88j0.015)
102-103
215-216
[a] Yields optimized.
A special case of the reaction of iminochloromethanesulfenyl chlorides (9) with olefins is the addition of (9)
to vinyl alkyl ethers. The resulting adducts (44) lose
chloroalkane and hydrogen chloride even at room
temperature to give 2-0xo-l,3-thiazolines (45) (Table
9) 110, 371.
CHz=CH-O-A1kyl
(9)
7Hz
S-
Cl-C,,
,CH-0-Alkyl
N C1
I
(44)
Delocalization of the double bond in (40) can be
detected in certain cases by NMR spectroscopy 1341.
Selective reaction of iminochloromethanesulfenyl
chlorides (9) with only one mole of amine is also
possible; the products are sulfenylamide derivatives.
23
-Alkyl-CI
- 0
-HCI
i?
k
(45)
C~HS-C-N=CCL-S-NH-C~H~ C6Hs-N=CCI-S-N(CH3)2
I/
N-C~HS
Table 9.
M.p. ( "C)
(B.p. ( "C/torr))
m.p. 219-220 "C [14]
The reaction of the compounds (9) with alkoxides
leads to elimination of sulfur 1141, whereas with sodium
thiolates they give isothiocyanates and diary1 disulfides [341.
1341 G. Ottmann and H. Hooks j r . , Angew. Chem. 79, 1062
(1967); Angew. Chem. internat. Edit. 6, 1072 (1967).
[35f Cf. also X. Ley ard U. Eholzer, Angew. Chem. 78, 6 7 2
(1966); Angew. Chem. internat. Edit. 5, 674 (1966).
60
2-Oxo-1,3-thiazolines (45).
b.p. 88-90 "C/0.2 torr
CH,
C4H9
C6HS
46-47
(65-67/0.15)
(81-83/0.15)
70-71
1
Ref.
I
(%) [a1
[lo]
51
1101
1371
49
81
[a] Yields not optimized.
1361 G. Ottmann and H . Hooksjr.,Angew. Chem. 78,210 (1966);
Angew. Chem. internat. Edit. 5, 250 (1966).
I371 G . Ottmann, H . Hoberecht, and H . Hooksjr., Angew. Chem.
79, 1063 (1967); Angew. Chem. internat. Edit. 6, 1073 (1967).
Angew. Chem. internat. Edit. / Vol. 9 (1970)
/ No. I
4.2.2. R e a c t i o n w i t h K e t o n e s a n d A l d e h y d e s
The first step in the reaction of compounds (9) with
ketones is probably the addition of the SCI grouping
to the enolized form of the ketone[381. The hypothetical intermediate (46) is stabilized by ring closure
and intramolecular neutralization of the hydrogen
chloride to form the salt (47), from which the base
(49) can be liberated with tertiary amines even below
0 "C. With another mole of tertiary amine, (49) can be
converted into the oxathiole (50) (Table 10). The
compounds (47) and (49) rearrange instantaneously
on contact with water or alcohol into the 4,Sdisubstituted 2-0xo-l,3-thiazolines (48) (Table 11).
+ (9)
R'- CH
II
S-
-+
[R-N=YI
R"-C - OH
CH-R'
I+
',.-
C1 HO
c1
K'-CH2
I
CHO
Table 11.
hydes.
I R
2-0~0-1,3-thiazolines(48) and (51) f r o m ketones and alde-
I
R'
I
R"
1
"1.
M.p. ("C)
Yield
(B.P. ( "Ctorr)) (%) [a1
103.5- 104.5
115-116
83.5-84.5
(94/0.4)
26
[a] Yields not optimized
4.2.3. R e a c t i o n w i t h C o m p o u n d s
Containing C-N Multiple Bonds
I
HC1
R
(47)
Possibly the most interesting property of the iminochloromethanesulfenyl chlorides (9) is their ability to
react with certain compounds containing C-N
multiple bonds. With isothiocyanates, for example,
they form sparingly soluble unstable products that
(48)
Table 10. 2-Imino-1,3-oxathioles (SO).
(53)
I
I
I
I
(54)
have been known for a long time as "mustard oil
monochlorides", and for which we 131 have proposed
the polar structures (53) and (54) [38al.
Reaction of (9) with aliphatic primary aldehydes C6H~-NH-C-NH-C6H5
I1
S
yields 2-oxo-1,3-thiazolines (51) [ EE (48), R" = HI
that are monosubstituted in position 5 (Table 11). The
(61)
isomeric iminooxathioles (52) are not formed 1371.
Scheme 2.
~~
1381 G . Ottmann, G . D. Vickers, and H. Hooksjr., J. heterocyclic
Chem. 4, 527 (1967).
Angew. Chem. internat. Edit.
1 Vol. 9 (1970) No. I
[38a] In view of the differences in the nucleophilic strengths of
N, 0, and S, we favor type (54) in the case of the isothiocyanate
adducts and type (53) for the isocyanate adducts.
61
The salt character of the compounds explains their sparing
solubility in organic solvents. The hydrolysis of the "mustard
oil monochlorides", e.g. (55), to give the "mustard oil oxides"
e.g. (57), can be similarly explained [391.
The structure of (57) can be proved by degradation with
aniines to form N,N',N"-trisubstituted monothiobiurets [40,41J
as well as by independent synthesis (see Scheme 2).
We have obtained similar results in the hydrolysis of ( S S ) ,
with CH3 instead of C6H5. In principle, mixed aromaticaliphatic compounds (57) can also be prepared by themethods
described, but the products are usually mixtures of isomers
that are difficult to separate.
formation of the nitriles. (62) reacts with hydrogen
sulfide, or preferably with phosphorus pentasulfide,
to give 3-oxo-5-thioxo-1,2,4-thiadiazolidines (63)
(Table 12).
The aminolysis of (62) with primary aliphatic and
aromatic amines leads to 5-imino-3-0~0-1,2,4-thiadiazolidines (64) (Table 13) [45,461.
(62)
0
R'-N%-R
R"-NH
- R'
Isocyanates, like isothiocyanates, can also react with
the compounds (9)[421, and the products are again
sparingly soluble, salt-like substances, which we
believe to be 3-oxothiadiazolinium chlorides (62) L38al.
The synthesis described proceeds particularly easily
and in high yields when the chlorination of isothiocyanates is carried out in the presence of isocyanates [431.
(64)
Table 13. 5-1rnino-3-0~0-1,2,4-thiadiazolidines
(64).
76.5
81
51
6
Hydrolysis of the very reactive compounds (62) with
water [42,441 yields 1,2,4-thiadiazolidine-3,5-diones
(34), which are also obtained from N,N'-disubstituted
ureas with chlorocarbonylsulfenyl chloride (7) or
from carbodiimides with (7) (see Table 6). (34) is also
obtained in the reaction of (62) with alcohols, which
is accompanied by elimination of chloroalkane, or
with primary amides, which is accompanied by the
A special case of the addition of iminochloromethanesulfenyl chlorides (9) to isocyanates is the addition to
silyloxysulfonyl isocyanates (65) or the corresponding
chlorination of isothiocyanates in the presence of (65).
These reactions lead to elimination of thechlorosilanes,
again with formation of sparingly soluble products,
for which we propose the structure of inner salts (66).
Their hydrolysis yields 1,2,4-thiadiazolidine-3,5-diones
(67) with no substituent in position 2 (Table 14)[47J.
R'.$i-O-SO,-N=C=O
+ (9)
-
(65)
0
G03S-N'%N-R + R',Si-CI
b.4c1
(63)
HN
x
N-R
(67)
Table 14. 1,2,4-Thiadiazolidine-3,5-diones(671.
Table 12. 3-0~0-5-thioxo-l,2,4-thiadiazolidines
(63j.
R'
CH3
CH3
C6HS
3,4-Cfz-CaH,
CH3
CH,
CHj
60
142-143
170
I
60
56
63
E:iB-CH,
I I :: 1
149-150
64-65
67-68
46.5
C-C~HI~
1
128-130 73.5
218-220 79.5
5~H~12-CaH3 225-2271 61.5
[a] Yields not optimized.
[a] Yields not optimized.
[39] E. Fromm and R . Heyder, Ber. dtsch. chem. Ges. 42, 3800
(1909).
1401 M . G. Paranjpe, Indian J. Chem. 5,21 (1967).
[41] M . Freund and G . Bachrach, Liebigs Ann. Chem. 285, 198
(1895).
[42] G.Ottmann and H . Hooksjr., Angew. Chem. 78,681 (1966);
Angew. Chem. internat. Edit. 5,672 (1966).
[43] H . Holtschmidt, G. Zumach, F. Doring, and E. Kiihle,
Belgian Pat. 712734 (March 25, 1968), Farbenfabriken Bayer
AG.
[44] G. Ottmann and H . Hooks j r . , US-Pat. 3374240 (June 29,
1965), Olin Mathieson Chem. Corp.
The reaction of alkyloxymethyliminochloromethanesulfenyl chlorides (68) with isocyanates follows an unexpected course. It is possible that the expected but
___1451 G . Ottmann and H . Hooks j r . , J. heterocyclic Chem. 4 , 365
(1967).
[46]According to G. Ottmann and H . Hooksjr. [45],theaminolysis of the compounds (62), which they formulate as
R-N=CCI-S-NR'-COCI,
yields an isomer mixture. However,
they describe only one type of compound in their patent (USPat. 3282950 (Jan. 21, 1965), Olin Mathieson Chem. Corp.).
[47] G. Zumach, H . Holtschmidt, E . Kiihle, and J . Pedain,
Belgian Pat. 728853 (Feb. 24, 1969), Farbenfabriken Bayer AG.
Angew. Chem. internat. Edit. Vol. 9 (1970) / No. I
unisolable salts (69) lose the chloromethyl ether to
give the 2-substituted 5-chloro-3-oxo-1,2,4-thiadiazolines (70) (Table 15) 1481, whose chlorine on C-5 is accessible to the usual nucleophilic substitution reactions.
Table 16.
1,2,4-Thiadiazolinederivatives (72) and (73).
I X
Alkyl- 0-CH, - N=CC1- SC1
[a] Yields not optimized
+
R -N= C=0
1
C-3. On aminolysis of (71) with primary aliphatic or
aromatic amines, imino derivatives (73) are formed
(Table 16).
A
4.2.4. O t h e r R e a c t i o n s
O°C -ClCH2-O-Alkyl
R-N
N
kqc1 (70)
It is even possible in some cases to obtain compounds
(70) by chlorination of carbamoyl isothiocyanates and
cyclization of the intermediate, unisolated carbamoyliminochloromethanesulfenyl chlorides with tertiary
amines, e.g.:
SH
0
0
II
Cl
A
C,H,-NH-C-N=C= S
Table 15.
Thioureas react smoothly with the compounds (9) in
the presence of a tertiary amine to form diiminodithiazolidines. For example, N , N'-diphenylthiourea
reacts with N-phenyliminochloromethanesulfenyl
chloride (74) to form 3,5-bis(phenylimino)-4-phenyl1,2,4-dithiazolidine (75).
CsH5- NH - C -N= CC1- SCI
&BH5
5-Chloro-3-oxo-1,2,4-thiadiazolines
(70).
(75)
M.p.
("C)
(%) 1 4
40
187-188
66
72
53
118-119
37.5
R
99-100
71-72
132-133
204-206
Yield
[a] Yields not optimized.
Another example of the addition of compounds (9)
to C-N multiple bonds is their reaction with cyanates.
The products are again sparingly soluble, very reactive
substances, which probably have the structure (71) 1491.
Hydrolysis of these products yields 5-0~0-1,2,4-thiadiazolines (72) with an aryloxy or alkoxy residue on
0-R'
(71)
0-R'
(72), X = 0
(73), x = N-R"
-~
[48] G. Zumach, H . Holtschmidt, and E. Kiihle, German Pat.
App. P 1907116.0 (Feb. 13, 1969), Farbenfabriken Bayer AG.
1491 G. Zumach, H . Holtschmidt, and E. Kiihle, Belgian Pat.
725054 (Dec. 6, 1968), Farbenfabriken Bayer AG.
Angew. Chem. internat. Edit.
c1s
II
Yol. 9 (1970)
1 No. I
The reaction of chlorocarbonylsulfenyl chloride (7)
with primary amides (Section 3.2) cannot be applied
to the compounds (9)- Whereas aliphatic compounds
(9) give compounds such as (58) with primary amides
(cf. Section 4.2.3), the aromatic compounds, e.g. f74),
give the 2-imino-5-oxo-1,3,4-oxothiazolidines,
e.g.
(76), m.p. - = 112°C.
0
II
2 R-C-NHz + 2 (74)
- 4 HCI
2 R-C-N
+0
N
C6H5
(76)
W e are grateful to Prof. Dr. Holtschnzidt for his
valuable suggestions. Dr. Heitzer kindly recorded a
large number of I R and N M R spectra and contributed
fo the progress of the investigations by discussion, while
we are indebted to Dr. Weiss, Inorganic Section of
Farbenfabriken Bayer A C , for providing the chlorocarbonylsulfenyl chloride.
Received: July 3, 1969
[A 738 IE]
German version: Angew. Chem. 82, 63 (1970)
Translated by Express TransIation Service, London
63
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