Are a-Oxothioacyl Chlorides Formed in the /.?

I R-C-C-Cl R-C-CH3 /I/

u s U
Reaction of Methyl Ketones with Thionyl 0 s 0
Chloride?[''I
By Gunadi Adiwidjaja, Horst Giinther, and Jiirgen Voss"'
Oka and Hara12]recently reported that they had prepared
a-oxothioacyl chlorides (2) from methyl ketones (I) as well
iCI
I
SOCl2
Pyridine

CI
as from the a-chlorosulfenyl chlorides (3) formed in the * R-C -C- S3-C-C-R
I I I I
same reaction. Proof of the structure of (2) was based merely o u C I O
on rather uninformative 'H-NMR spectra, a C-S band at
1230 cm ~(arising, however, from thionyl chloride) and a
peak at m / e = 184 in the mass spectrum of the product mix-
ture obtained from acetophenone (Ib), and its subsequent
reaction to give the a-oxothioamide (5b).-With exception
R- C -C-N( CH3& R-C-C-OCH) R-C-CI ( * R-C-C-CI)
of the oxamide derivative R2N-CO-CS-Cli31, com- U I r i Y II 1
I
'pounds of type (2) have so far not been described in the liter- 0 s 0 s 0 0 0
ature and their existence is highly questionable (cf. 14]).We /5J 161 171 181
obtained other results, both on exact repetition as well as on
slight modification of the procedure given in (see Scheme
Scheme 1
1).

Table 1. Primary and secondary products of the reaction of methyl ketones (I) with thionyl chloride

Cpd. R Yield M.p. ["C] 'H-NMR "C-NMR

[a1 [%I B.p. ["C/torr] 6 values 6 values

(3a) tBu 50 [bl 1.28 (s, tBu). 6.08 (s, CH) 204.5 (CO), 65.5 (CCI)
(36) Ph 45 P I 6.64 (s, CH), 7.45-8.35 (m, Ph) 189.0 (CO), 65.7 (CCI)
(4a) rBu 40 [b] 72.5 1.50 (s, tBu) 198.2 (CO), 94.1 (CC12)
/46) Ph 40IbJ 106 7.32-8.22 (m, Ph) 184.6 (CO), 93.8 (CCM
(5u) tBu 96 [c] 40.5 1.27 (s, tBu), 3.10 (s, NMe). 3.32 (s. NMe) 207.3 (CO). 198.1 (CS)
(5b) Ph 78 [d] 84.5 [el 3.13 (s, NMe), 3.44 (s. NMe). 7.28-7.43 (m. 3H). 7.73-7.93 188.4 (CO), 196.6 (CS)
(m, 2H)
15c) p-tBu-C6H4 69 [d] 116 1.37 (s, rBu), 3.23 (s. NMe), 3 57 (s, NMe), 7.35-8.19 (m,
4 H)
(Sd] 3,5-tBuI-C,H1 47 [d] 162 1.39 (s, 2tBu). 3 25 (s. NMe), 3.58 (s, NMe). 7.55-7.77 (m.
3 H)
(5e) p-Me2N-CS-CO-CoHa [fl 85 202
1 3 Me2N-CS [g] 5 118
(5g) 3.5-(Me2N-CS-CO),C,H3 [h] 3 226 3.25 (s, 3 NMe). 3.56 (s, 3 NMe). 8.69 (s, 3H) 184.5 (CO), 194.2 (CS)
(6u) tBu [i] 79 [d] 68-69/9 1.25 (s. rBu), 4.13 (s, OMe) 203.2 (CO), 214.3 (CS)
/rib] Ph [kl 56 [d] 86.5/0.2 4.22 (s. OMe), 7.33-7.52 (m. 3H). 7.80-7.97 (m, 2H) 187.2 (CO), 212.9 (CS)
(6c) p-tBu-C,H, 40 [d] 114/0.2 1.30 (s. tBu), 4 27 (s. OMe). 7.40-7.98 (m, 4 H )
16d) 3.5-tBu2-C,H1 51 [d] 37.5-39 1.33 (s. 2 tBu). 4 25 (s. OMe). 7.60-7.72 (m, 3 H)
(IOU) tBu 77 [I] 77.5 1.55 (s. tBu). 3 20 (s, NMe), 3.49 (s. NMe) 201.7 (NCS). 258.8 (CS)

[a] (40). (4b1, 15) and (6) gave correct elemental analyses. (3~).(3d). ( 4 ~ )and
. (4d) were not characterized; the mixtures obtained from ( l c ) and from (Id] on reaction with
thionyl chloride were allowed to react directly with nucleophiles. [b] Determined NMR spectroscopically. [c] Referred to (3u): [(3u] + (4u)l gave 85% /5u]. [d] From [/3) +
V)], referred to (11. [el M p- (literature) 84-85 "C [2]. [q From IA-diacetylbenzene. [g] From acetone. [h] From 1.3.5-triacetylbenzene. [i] ,,A (isooctane) = 392 (log
~=1.6X).309(225),260(3-39)~,220(3.94)nm; NCO)=1705cm '.[k]A,,.(isooctane) = 398(logt.=1.97),338(2.39),251 (4.17),218(3.54)s; u(CO)=1665cm ' . [ I ] Re-
ferred to 150).

That a mixture of (3) and the trisulfane (4) is formed on
reaction of ( I ) with thionyl chloride in pyridine follows from
the spectroscopic data (Table I), and especially from the "C-
NMR spectra. (4a), which crystallizes from the crude prod-
uct at - 20 "C in yields of up to 25%, was characterized, inter
aka, by X-ray structure analysis (Fig. 1). (46) could be iso-
lated by column chromatography (SO2, CH2C12/CC1, (1: I),
5% yield).
Both the mixture [(3)+ (4)] as well as pure (4) afford a-ox-
othioamides (5) almost quantitatively on reaction with dime-
[*] Prof. Dr. J . Voss, DipLChem. H. Giinther
Institut fur Organische Chemie und Blochemie der Universitat
Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (Germany)
Dr. G. Adiwidjaja
Mineralogisch-PetrographrschesInstitut der Universitat
Hamburg (Germany)
["I Activated Thiocarboxylic Esters, Part 7. This work was supported by the
Deutsche Forschungsgemeinschaft (Project Vo I80/5) and the Fonds der Che-
mischen lndustrie We thank Chemischen Werken Hiils for supplying us with
1.3.5-triacetylbenzene.-Part 6: [I].
thylamine. This reaction can also be carried out with other
secondary aliphatic or araliphatic amines and tert-butylam-
ine.
Reaction with methanol in the presence of bases affords
the previously unknown a-oxothionic esters (6) (see Table l),
which represent a further type of esters containing adjacent
C -0-and C=-S-groups. In contrast to the blue a-thioxo
esters R-CS-CO-OR, which tend to dimerizeIs1, the
orange-colored isomers (6) are stable.
Surprisingly, we also obtained 85% 1,4-benzenebis(N,N-
dimethyl-a-oxothioacetamide) (54 from 1,4-diacetylben-
zene, and even from the very complex mixtures which are
formed on reaction of SOCl2 with acetone or 1,3,5-triacetyl-
benzene we were able to isolate 5% N,N,N',N'-tetramethyI-
mesoxaldithioamide (5fl[61and 3% of the tristhioamide (5g),
respectively, in analytically pure form by column chromatog-
raphy (see Table 1).-2,4,6-Tri-tert-butylacetophenone, on
the other hand, does not give the corresponding thioamide.
The a-oxothioamides (5) can be sulfurized with the dimer-
ic phosphane sulfide (9)['1 in good yields to the red to green-

Angew. Chem. In[. Ed. Engl. I 9 (1980) No. 7 0 Verlug Chemie, GmbH, 6940 Weinheim, 1980 0570-0833/X0/0707-0S63 $ 02S0/0 563
ish black a-thioxothioamides (lo), a class of substances of
which only one example has hitherto been reported"].
The mixture of (3) and (4,which is also readily accessible
in larger quantities, is thus a valuable starting material for
products which presumably would be formed from the still
unknown (21.
c101@c102
Fig I . Molecular structure of the trisulfane 14a) in the crystal (ORTEP diagram):
vibration ellipsoids with 30% probability. - Space group P2,2,2,. a = 2655.6,
b = 1173.5. c=629.1 f O . l pm. Z = 4 , p= 1.48 g cm '. The intensities of the re-
flections were measured with an automated single crystal diffractometer Syntex
P2,(CuKC.radiation) and corrected in the usual way. The crystal structure was
determined on the basis of 1584 symmetric independent structure amplitudes by
the direct method using the computer program MULTAN and refined to
R=6.8% (R,=6.1%).
On heating (distillation) [(3)+ (4)] one obtains acyl chlo-
rides (7) and (Sb), but not the pure a-chlorosulfenyl chlo-
rides (3), and under no circumstances (2)lz1.Recent reports of
Pizey and SymeonidesI'l, in which only pivaloyl chloride (7a),
i. e. the thermolysis product of [(3a)+ (4a)], could be ob-
tained o n reaction of pinacolone with thionyl chloride, are to
(9) (IOa - d )
be seen in this light. The surprisingly uniform thermolysis,
however, is preparatively not without interest, for it leads
practically in one step from methyl ketones to acyl chlorides
in acceptable yields.
Experimental
(5a): A solution of (4a) (4.32 g, 10 mmol) in ether (50 ml)
is added dropwise at - 8 0 ° C to a stirred solution of
(CH,),NH (4.5 g, 100 mmol) in ether (50 ml). After warming
to room temperature, the reaction mixture is poured into 500
ml of water, neutralized with dil. HCl, the ether removed, the
aqueous phase extracted with CHC13, the organic phases
washed with water, dried with Na2S04 and evaporated to
dryness. Recrystallization of the residue from hexane affords
pale yellow crystals of (Sa).-(5b-d) are synthesized analo-
gously from [(3)+ (4)].
(6a): The mixture [(3a)+ (4a)l obtained from (la) ( 5 g, 50
mmol) is dissolved in 100 ml methanol and treated dropwise
with stirring at 0 ° C with 27.7 ml (20.2 g=200 mmol) of tri-
ethylamine. The mixture is diluted with 300 ml water, neu-
tralized with dil. HCl, extracted with ether, washed with wa-
ter, dried with Na2S0, and evaporated down. The residue is
dissolved in CHCl,, filtered over a layer of S O 2 , and dis-
tilled in a vacuum; (6a) is a n orange-yellow oil.
564 0 Verlag Chemie, GmbH, 6940 Wernheim, 1980 0570-0833/80/0707 0564
(1Oa): A solution of (5a) ( 5 g, 28.9 mmol) in toluene (60
ml) is treated with 6.5 g (15.9 mmol) of (9) and the mixture
heated under reflux for 3 h. After cooling, the mixture is
poured into 500 ml water, extracted with ether (3 x 150 ml),
the combined ether phases washed twice with water, dried
with Na2S0,, and evaporated down. The red, crystalline resi-
due is dissolved in CHC13 and filtered over a layer of S O z .
(1Oa) forms luminous carmine-red crystals.
Distillation of [(3a)+ (4a)Jat normal pressure affords (7a)
in 50% yield [based on (la)].-[(3b) + (4b)l gives a mixture of
(7b) (36% yield) and (Sb) (15% yield).
Received: May 14, 1979 [Z 507 IE]
supplemented: February 25. 1980
German version: Angew. Chem. 92. 559 (1980)
11)J. Voss. H. Gunther. Synthesis 1978, 849.
[2] K. Oka, S. Hara, Tetrahedron Lett. 1976, 2783.
[3] W. G. Phillips. K. W. Ratrs, J . Org. Chem. 37. 1526 (1972).
141 G. Seybold, Angew Chem. 87. 710 (1975); Angew. Chem. Int. Ed. Engl. 14,
703 (1975).
[S] K. Thimm, J . Voss. Tetrahedron Lett. 1975, 537: P. Metmer. J. Vialle. A. Vi-
bet. Tetrahedron 34, 2289 (1978).
161 E Campaigne, C. Skowronski. R. A. Forsch, J. C Beckman, Synth Commun.
6 , 387 (1976). have obtained (Sat via another more complicated route.
[7] B. S. Pedersen. S.Scheib.ve, N . H. Nilsson, S -0.Lawesson. Bull. SOCChim
Belg. 87, 223 (1978).
[8] P. A . Barrett, 1. Chem. SOC.1957, 2056.
[9] J. S. Pizey. K. Svmeonides. Phosphorus Sulfur 8. 1 (1980).
Aeylated Ketenimines and Allenes from Oxazol-
5(4H)-ones and Furan-2(3H)-ones~"~
By Hans-Michael Berstermann, Raymond Harder, Hans-
Wilhelm Winter, and Curt Wenimp[''
Flash vacuum pyrolysis of 4-substituted isoxazol-5(4H)-
ones results in the elimination of C 0 2 and formation of ace-
tylenes, isocyanides, or related compounds"]. Oxazol-
5(2H)-ones thermally extrude COz with formation of nitrile
ylides[2"],whereas both COz- and CO-elimination from oxa-
zol-5(4H)-ones is known[*". We now report that oxazol-
5(4H)-ones (1) and (3) and furan-2(3H)-ones (5) extrude CO
only. The reaction of (5) constitutes a useful synthesis of pro-
padienyl ketones (6).
The oxazol-5(4H)-ones (1) were prepared by standard
and subjected to flash pyrolysis'41at 500-900 "C/
ca. 10- 4 torr. Over this temperature range, the only products,
['I
Prof. Dr. C. Wentrup. Dip1 -Chem. H.-M. Berstermann, Dipl.-Chem. H:W.
Winter
Fachbereich Chemie der Universitat
Lahnberge, D-3550 Marburg (Germany)
Dr. R. Harder
Institut de Chimie Organique de I'Universite
CH-I005 Lausanne (Switzerland)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie and abstracted in part from the diploma thesis
of H.-M. Berstermann. Marburg 1979. and the doctoral thesis of R. Harder. Lau-
sanne 1976.
$ 02 S0/0 Angew. Chem. Int. Ed. Engl. 19 (1980) No 7