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Desulfuration of Thio-Acids with Dimethyl Sulfoxide.

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8-Chlorinated cis-2,4-pentadienoyl chlorides (1) with R = H
or CsHs and R’ = CI react in the same way but more slowly
(reaction time: 4 days).
Monothioacetic acid is also desulfurated by dimethyl sulfoxide; the yield is 70% after one week at 2OoC.
Received: February 7th, 1966
[Z 154/987 IE]
German version: Angew. Chem. 78, 393 (1966)
Alkylation of Amine Oxides with Sultones
By Dr. W. D. Willmund
I
I
I
I
I
I
Wissenschaftliches Laboratorium, Henkel & Cie.,
Diisseldorf (Germany)
Decomp. p.
1 i:;1
1 55- 1 60
177-183
176-180
Alkoxyammonium halides are formed on reaction of tertiary
amine oxides with alkyl halides [I].
We have found that alkylation of tertiary amine oxides with
1,3-propanesultone ( I ) in acetone or ethanol leads to alkoxyammonium sulfobetains (2). Reaction conditions : dropwise
addition of a n equimolar amount of sultone to a boiling
solution of the amine oxide in acetone, removal of the crystalline sulfobetaine after 2 hr, washing with acetone and
vacuum drying. For pyridine oxide: reaction in the melt or
in a little ethanol.
[a1
[a]
[bl
118-120
219-222
I 28.9 I [a1
128-133
?’
+ H2C-CH2
O\s,C
I
I HZ
R-N-o
I
0 2
( 2 ) . Yield
The pyrylium salts can be stored only if completely free from
solvent and with rigid exclusion of air and moisture. The
tetrachloro derivatives (R = C1) are particularly sensitive.
They decompose rapidly in moist air with formation of the
corresponding 2-pyrones.
[%I
Ci2H2s
C14Hz9
Ci6H13
Ci8H37
Benzyl
Cyclohexyl
Phenyl
Received: February 3rd. 1966
[ Z 156/989 I€]
German version: Angew. Cbem. 78, 448 (1966)
[l] A . Roedig and G. Murkl, Liebigs Ann. Chem. 659, 1 (1962);
A . Roedig, R . Kohlhaupt, and G. Markl, Chem. Ber. 99,698 (1966).
[2] A . Roedig, Angew. Chem. 76, 216 (1964); Angew. Chem.
internat. Edit. 3, 317 (1964).
[3] The trans-ketone (R = C1, R’ = CsH5) does not react with
SnC14 in CS2.
CH3
CH3
CHI
CH3
CHI
CH3
CH3
R‘
R - Ago- ~3
Institute of Organic Chemistry of the Polish Academy of
Sciences, Lodz (Poland)
It was found that 0,O-diethyl hydrogen thiophosphate ( I )
and 0-ethyl hydrogen ethylthiophosphonate (2) are converted into the sulfur-free analogues when allowed to stand
with an equimolar amount of dimethyl sulfoxide for one week
at 20 “C. Yields are about 75-80%. After reaction thedimethy1 sulfide formed is distilled off and the residue is dissolved
in methanol and filtered from sulfur.
9
R,P
+ (CH3)2S +
S
R‘ \OH
= OC2H5,
-soy
(3)
A 2
R
R2
R3
Paste
42-43
149
86
71
69.4
Alkoxyammonium sulfobetaines are stable in neutral or acidic
aqueous solution. In a n alkaline medium (pH 12) they are
cleaved at the N-0 bond, yielding the tertiary amines and
a-formylsulfonates.
Received: February 7th, 1966
[Z 151/984 IE]
German version: Angew. Chem. 78, 391 (1966)
( I ) , R = R‘= O C ~ H S
(Z), R
64.6
79
70.3
79
29.3
36.6
45
54.4
61.3
[a] Very violent reaction; the oily product was not obtained pure.
[ b l Contains 1 mole of water of crystallization.
By Dr. M. Mikotajczyk
-+
172
174
175.5
178
I74
155
[a1
194.5- I95
182 [ b l
The reaction is not confined to 1,3-propanesuItone. Butanesultone (1,2-0xathiane 2,2-dioxide), o-toluenesultone [the
sultone from o-(hydroxymethy1)benzenesulfonic acid], and
tridecanesultone (formed o n reaction of SO3 with l-tridecene [21 with amine oxides afford similar 0-alkylation
products of type (3).
Desulfuration of Thio-Acids with
Dimethyl Sulfoxide
+ (CH3)fi0
10
R-N-o-(cH~)~-so,O
R2
[a] From aldehyde or ketone
[b] From acid chloride.
[cl From the chloroferrate with NaC104 in acetonitrile
R, H
P
d ‘OH
R’
-+
R‘= C2H5
~
Diphenyldithiophosphinic acid (3) undergoes a strongly exothermic reaction with 2 moles of dimethyl sulfoxide, yielding
similarly (up to 90%) the sulfur-free acid.
(C6H&PS2H-!- 2 (CH3)2SO
-->
(C~H~)ZPO
I ~
2 (CH3)2S
H
i2S
(3)
Angew. Chem. internat. Edit. 1 Vol. S (1966)
/ No. 4
[ I ] W. R . Dunstan and E. Goulding, J. chem. SOC.(London) 75,
792 (1899); J. Meisenheimer, Liebigs Ann. Chem. 397, 273 (1913);
K . B. .4ugustinsson and H. Hasselqrrist, Acta chem. scand. I S , 8 17
(1961).
[2] German Patent Application 1159430 (Aug. 9th, 1962/Dec.
19th, 1963); Henkel & Cie., inventors: H . Baumann, W. Stein,
and M . Voss.
419
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