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Патент USA US2412814

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Patented Dec. 17, 1946
John David Kendall and Harry Derek Edwards,
Ilford, England, assignors to Iliord Limited,
Ilford, England, a British Company
No Drawing. Application December “(1943,
' geiiggaNo. 514,666. In Great Britain January
The‘acid condensing agent may be any strongly
' This invention relates to the production of or!
ganic compounds which are useful as interme
diates for the formation of dyestuffs, and to the ,
~ organic compoundsso produced. 1
acidic‘ substance; sulphuric acid and zinc chloride ‘
have been found very suitable.
The following examples illustrate the inven
‘According to ‘the present invention organi
tion, as applied to the production of the com- a
compounds of the general Formula I:
pound p-ethyl thio acrolein diethyi mercaptal. '
Exsuru: I
(a) Preparation of mam: aldehyde diethyl
mercaptaljrom acrolein
where R is an allq’vl group, are obtained by treat:
100 grams of acrolein was cooled to about 5° C.
ing' with an alkylmercaptan, in the presence of
an acid condensing agent, a compound of one of
and 90ccs. oi bromine added dropwise, with good '
the Formulae II, III, IV or V:
shaking, over. about 2 hours. 5 gm's. of sodium
’ bicarbonate was added and the mixture left over
. '15
night. The acrolein dibromide was ?ltered and
then added slowly to 260 gms. of ethyl mercan
tanywith stirring and cooling so that the tem
perature was kept below 10° C. The reaction
mixture was then allowed to stand for two hours
at room temperature. 5 gms..oi sodium bicar
bonate was then added and the mixture allowed
to stand overnight. A solution of 200 guns. of
caustic potash in 900 ccs. ethyl alcohol was pre
pared and the reaction mixture (now containing P
25 acrolein dibromide mercaptaD' added slowly/‘at a
> temperature of about '30~40° C. The mixture was
then boiled under re?ux for 1/2 hour. The alco
" hol was then distilled oil through a' partial con
or by treating with an alkyl mercaptan in the
presence of a basic condensing agent under pres
sure, a compound of Formula II.
Compounds of the general Formula II may be
obtained by brominating acrolein and treating
the product with an alkyl mercaptan followed by
heating with an alkali to remove bromine.‘- Com
denser, and after standing for 14 hours the resi
30 due was ?ltered from the precipitated potassium
bromide‘ and concentrated ‘further. The vpotas
sium bromide precipitate was dissolved in 1 litre
of waterand added to the concentrate from the
alcohol distillation. Oil was precipitated and was
separated off. The aqueous liquors were then ex
tracted, and the ether extracts and oil bulked and
dried over sodium carbonate. The ether was dis- -
pounds of general Formula III may be converted 1 tilled oil and the residue distilled in vacuo. . The
to compounds .of general Formula V by treating
product contained a trace of bromine which was
them with a sodium alkyl mercaptide and an 40 removed by boiling under re?ux with '5 gms. so
alkyl mercaptan under pressure._
dium mercaptide in 100 ccs. alcohol for 1/2 hour.
Beta-alkyl-thio acrolein di-alkyl mercaptais
The alcohol was distilled oil, the residue poured
can be made by treating a compound of Formula
into water, ether-extracted and distilled as be
II in which the groups R are alkyl groups with
fore, giving the product as an oil.’ 13. P, 125° C.
alkyl mercaptan in the presence of a basic con
at 10 mm. pressure.
densing agent underlpressure.
(b) Preparation of p-ethul-thio acrolein'diethul '
The most convenient compound of general For
mercaptal from proparwl aldehyde diethyl ~
'mula I to prepare is that in which the groups R
mercaptal ’
are ethyl groups since ethyl mercaptan is the
most convenient of the allq/l mercaptans to em 50 v80 gms. of propargyl aldehyde diethyl mercap
ploy. In using the compounds of general For
ta1,75 cos. of ethyl‘mercaptan and 68 guns. of an
mula I as dyestu? intermediates the condensation
hydrous zinc chloride were mixed in the cold and produce dyestu?'s may eliminate all the 3-873.
allowed to stand for two days, after which the
groups so that the nature of ‘the R group is not
mixture was poured on to cracked ice, and treated
then of importance.
55 with a little dilute acid. The oil obtained was
‘ 3
‘separated from the aqueous liquors, which were
tracted'with ether. The oil and the ether ex.
extracted with ether. The oil and ether extracts
were bulked'and well washed with water, fol
tracts were bulked and washed with water and
lowed by sodlum carbonate solution, and ?nally
over potassium carbonate. The ether solution
was filtered and the solvent distilled oil‘. The
product was obtained by distillation of the re-'
sidual oil in vacuo, as a yellow oil, B. P. 190“ C. at
10% sodium carbonate solution, and ?nally dried
dried over potassium carbonate. The solution '
was ?ltered and the ether distilled off. The re
sidual oil was distilled in vacuo, collecting frac
10 mm. pressure.
tions (1) up to 120° C., (2) 120-160° C., (3) 160'
Exmm III
195” C. Distillates (2) and (3) were redistilled
fractionally from a sulphuric acid bath to give 10 Preparation of p-ethyl-‘thio acrolein diethyl
the product boiling at 185-192° C. at 6 mm.‘
mercaptal from propargyl aldehyde diethyl
0(0) Alternative preparation of p-ethyl-thio acro
lein- diethyl mercaptal from propargyl aldehyde
25 gms. of propargyl aldehyde diethyl acetal,
15 60 ccs. of ethyl .mercaptan‘and 3.5 cos. of 50%
diethyl mercaptal
aaueous'sulphuric ‘acid (by volume) were mixed
and allowed to stand for 12 days. At the end of
this period ether was added and‘the ‘solution
53 gms. of propargyl aldehyde diethyl mercap
tal, 50ccs. of ethyl mercaptan and 5 drops of con
washed with water and sodium carbonate solu
and allowed to stand for a week. The acid layer 20 tion and dried over potassium carbonate. I The
. ether extracts were ?ltered and the solvent dis
was then separated off and the oil well washed
tilled off. Distillation of the residue under re
' with water and dried over potassium carbonate.
duced pressure gave the required product and,
After ?ltering, the excess ethyl mercaptan was
centrated sulphuric acid were mixed in the cold
as a low boiling fraction, some s-ethyl-thlo acro
distilled 01f from a water bath and the residue dis
~lein diethyl acetal.
tilled in vacuo, separating into three fractions
which were redistilled to give the product boiling
at 168-190“ C. at 6 mm. pressure.
Preparation of ?-ethul-thio acrolein diethyl
mercaptal from ,a-ethoxu acrolein diethyl ace
.(a) Preparation of p-ethyl-thio acrolein diethyl
acetal from propargyl aldehyde diethyl acetal
128 gms. of propargyl aldehyde diethyl acetal,
16.8 gm's. of sodium mercaptide and 15 cos. of '
ethyl mercaptan were heated together in a sealed
7.2 ms. of p-ethoxy acroleinacetal were mixed
with 12 cos. of ethyl mercaptan and 1 cc. of a 50%
aqueous sulphuric acid solution was added. The
reaction mixture, which grew hot‘, was cooled and
then allowed to stand at room temperature ‘for
tube, the temperature being raised to 120° C. 35 10 days. Ether was then added, the acid layer
over 31/2 hours and maintained at 115° C.-120° C.
- separated oil. and the ether extract, after wash
for four hours. 'When cool the reaction mixture
ing with _10% sodium. carbonate solution, was
was poured on to crushed ice and the oil sepa
dried over anhydrous potassium carbonate. The
rated by extraction with ether. The ether ex
ether was distilled on‘ and the residual oil dis
tracts were dried over potassium carbonate, the 40 tilled in vacuo, and the following fractions col
solution ?ltered and the ether distilled oil. The
lected: (1) -80° C., (2) 80-120° C., (3) 120-160° '
residual oil was distilled twice under reduced
0., (4) 160-200" C. Fraction (4) was redistlllecl
pressure to yield the product boiling at 105° C.
to, yield the required product.
at 6mm. pressure.
What we claim is:
(12) Preparation of p-ethyl-thio acrolein diethyl?
mercaptal from p-ethyl-thio acrolein diethyl
1. Compounds of the general formula:
, Rs-o_H=cH-c§
33 gms. of s-ethyl-thio acrolein diethyl acetal,
40 gms. of ethyl mercaptan and 13 grns. of an 50
where the groups R are alkyl groups.
hydrous zinc chloride were employed. The zinc
2. The compound of the general formula: V
\ chloride was added carefully to the cooled solu
tion of the p-ethyl-thio acrolein diethyl acetal in
th ,’ ethyl mercaptan. _The reaction mixture was
allowed to stand for 6 days and then poured’ into 55
ice water containing a small amount of dilute '
‘ i
‘ c,H|s—‘cH=cn—-o11
\SC:Hs _
hydrochloric acid. The oil which precipitated
was separated off and the aqueous liquors ex
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