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Патент USA US2134102

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:Patented Oct.25, 1938 j
2,134,102 '
pnnrnnoonnoams'rrowor 1,1,2-rm
Oliver W. Cass, lViagai-a Falls, N. Y., assignor to '
E. ‘I. du Pont de Nemours & Company, Wil
mington,‘ DeL, a corporation of Delaware
No Drawing. Application May 13, 1935,
Serial No: 21,300.
5 Claims. (01. mill-654) I,
This application relates to the preparation of
unsaturated chlorhydrocarbon derivatives from
and CHa.CCl_=CHCl are not present in any ap- ‘ _ ‘
, saturated chlorhydrocarbons by treatment with
a basic material. More particularly it relates .pre‘ciable amounts and that. 1,1-dichlorpropene— '
5 to the preparation oi, 1,1-dichlorpropene~l, .
produced‘ in practically quantitative yields.
by reacting 1,1,2 trichlorpropane,
10 with a base.‘
1, the isomer which from theoretical considera- ‘5
, tions would be believed leastlikely to result, is
. have found that, the 1,1-dichlorpropene-2 and
the 1,2-dichlorpropene-1, isomers arenot pro
In a copending patent application, Ser. No.
19,954 ?ied May 6, 1935 by Arthur A. Levine and
Oliver W. Cass, a process is disclosed for the
15 preparation of isomeric mixtures consisting es-'
sentially oi 1,1,2 triehlorpropane and 1,2,3 tri
duced since they are not fiound in ‘recoverable 1o
amounts in the‘ reaction product and the 1,1‘
chlorpropene-l isomer is formed in yields which
are' normally well over 90%.
As a basic material I have used aqueous solu
tions of sodium and potassium hydroxide vand 15
aqueous solutions of the alkali earth metal hy
chlorpropane by chlorinating propylene dichlo "droxides such as calcium hydroxide. Any basic
ride. ‘In that application separation of the two material is suitable. Thus I have used with
isomers by distillation and condensation is also complete success, alcoholic solutions of caustic
” disclosed. This application relates to the ‘fur-. soda and caustic potash. I prefer,‘ however, ior 20
ther treatment oi'the 1,1,2 trichlorpropane iso
mer to prepare a chemical compound which is
valuable for various purposes. ,
The compound 1,1,2 trichlorpropane,’
most purposes. to use one of the relatively less'
expensive alkali metal bases dissolved in some
suitable solvent such as alcohol or water. Bolu-4
tions of soda ash (sodium carbonate) in various ‘
media will also be iound'entirely satisfactory for 25
the purposes oi’ the process.
when pure, is a colorless liquid having an at
mospheric boiling pointooi approximately 132'
C. One of the objects. oi.’ this invention is to
” react this liquid with'basic material at a tem
perature belowkthe boiling point of the trichlor-
' _
While the process of this reaction'is best car
ried out in the liquid-‘phase, it is also possible
to remove an atom of chlorine and one atom
01' hydrogen from 1,1,2 trichlorpropane and con- 30 '
vert it to an unsaturated compound by the use
propane so ~that an atom of hydrogen and one of a gas phase reaction. Thus by vaporizing the
.0! chlorine are split oil, thereby resulting in an . 1,1,2 ' trichlorpropane and passing the vapors
unsaturated compound having one atom less of
Prom considerations of theoretical chemistry,
any one of three isomers might result by the
over a catalyst comprising any .01’ the common
hydrogen chloride-removing catalysts. such as 35,
barium chloride on‘ charcoal, commercially im
portant yields of 1,1-dichlorpropene-l have been
removal oi.’ hydrogen chloride from the trichlor- ' obtained. Other suitable catalysts are the hal
- ides particularly the chlorides of various metals
Propane. These threeisomers are
such as those of Ni, 'Cu,‘Pb, Cd and Fe. When 40
using barium chloride on charcoal the process-is‘
v A consideration of chemical0 principles would
best carried out at an elevated temperature of
about 300° C. or ‘one within the’ temperature
range 250 to 350° C. vIn this reaction, as con;
trasted with the liquid phase reaction,‘the chlo- 45 '
rine is removed as hydrogen chloride and not as,
a salt of the base, as when utilizing a liquid
also indicate that presumably‘ a mixturev of all
three isomers in various proportions and
amounts might result. Of the three possible
But little need be said about the precise de
50 isomers, 1,1-dichlorpropene-1, CHaCH=CCh, is tails of the process, other than that it is pre- so
_ the one which might be, considered'least likely ierred that it becarried out in the ‘liquid phase.
to result since it is a derivative of methyl ketene, The ‘1,1,2 trichlorpropane is introduced into a
CH:.CH=CO, which“ is an extremely ' unstable vessel containing a ‘strong solution of the base
phasev process.
compound. Surprisingly enough, however, ithas
“ been discovered that the isomers
dissolved in a suitable solvent such as water or.
~ alcohol, While the reaction will proceed at room?“
temperature, it is preferable to maintain a some
what elevated temperature,"one somewhere be
tween the boiling point of 1,1-dichlorpropene-1
. (which is 77-78° C.) and‘ the boiling point of the
1,1,2 trichlorpropane (132° 0.). However, since
5 liter ?ask."I‘he ?ask was equipped with a
stirrer and a re?ux condenser. Into the ?ask
1475 grams of. 1,1,2 trichlorpropane was then
The mixture was thoroughly stirred and heated
until an oil began to re?ux back in the con
pene-l-will steam distill at a temperature below denser, the mixture in the reaction vessel being
77° C., it is not necessary to maintain a temper- ‘ maintained at a temperature of about 75° C.
ature that high. 'Ihere \are two procedures of The elevated temperature in the reaction vessel
10 value in carrying out this liquid phase reaction. was maintained for three hours during which
A re?ux condenser may be attached to the vessel period the mixture was stirred constantly. At
in which the reaction is carried out, in which the end of this period the oil was separated from
there is water present and ‘the 1,1-dichlorpro
case the 1,.l-dichlorpropene-i, which is distilled
off, will be condensed and ?ow back into the ves
ll sel. Or, it is possible to attach to the vessel
a fractionation column in which ‘the 1,1-dichlor
propene-l will be distilled o?', ‘condensed, and
recovered as a liquid outside of the reaction
vessel. Yields of about the same uniformly high
the slightly basic aqueous solution, dried, and
carefully fractionated.
The product was 953 grams of 1,1-dichlor
propene-l, which has a boiling point of about
“Fl-78° C. 94 grams of the residue consisted of
unreacted 1,1,2 trichlorpropane. Based upon the
quantity of sodium hydroxide consumed, the
yield of 1,1 chlorpropene-i was 94% theoretical. 20
Example 2
_ In practice, as I have indicated, the 1,1,2 tri-v
chlorpropa-ne is preferably added to the basic
In these operations a ?ask equipped with a
percentages are obtained by the use of either
material dissolved in a solvent. Heat is then stirrer and “a short fractionation column was
applied and the mixture is thoroughly stirred. used. .The same weights of materials indicated
The elevated temperature is maintained for about in Example 1 were reacted, i. e. 400 grams of 95%
three hours during which time the agitationv is sodium hydroxide in 2500v cc. of water and 1475
continuous. At the end of this period, if a re?ux - grams of the trichlorpropane. A condenser was
condenser has been used, the oil may be readily placed incommunication with the fractionation
separated from the basic material since it will column so that material passing thru the column
rise to the top of the vessel. On the other hand, - and condenser would flow into‘ a receiving vessel. ‘
if a fractionation column has been used, the
The reaction vessel and its contents were heat
1,1-dichlorpropene-l will be found in the re
ed with constant stirring to a temperature “of
ceiver attached to the condenser of the frac
about 78°-85° C. at which temperature liquid
‘ionation column.
began to pass through the fractionation column
1,i,-dichlorpropene-1 is readilyseparated from and condenser to the receiving vessel. After‘
unreacted 1,1,2 trichlorpropane and any other ‘about three hours no more oily material re
by-products. in the reaction mixture since it has mained in the reaction vessel. The oil was sepa
a boiling point of 77-78. C. while the boiling point rated from the aqueousj layer in the receiver,
of 1,1,2 trichlorpropane‘is 132' C. High yields dried and fractionated.
are obtained by the process, the yields being in
The product consisted of 908 grams of 1,1-di
the neighborhood of 90% or over. 1
chlorpropene-l boiling at 77-78° C. and 114 grams
The reaction occurring, using sodium hy
of unreacted 1,1,2 trichlorpropane. The yield of
1,1-dlchlorpropene-l, based upon the amount of
sodium hydroxide consumed, was 89% of the
- 'droxide as a typical basic material, may be ex
pressed as follows:
When using a catalytic material such as BaCl:
on a charcoal carrier, the reaction occurring is
probably as follows:
It is thus evident that a saturated chlorinated
55 hydrocarbon is converted into an unsaturated
chlorinated hydrocarbon containing one atom
- In this example the ‘reaction was carried out
at room temperature and without external heat
ing. A solution of 56 grams of potassium hy
droxide in 800 cc. of ethyl alcohol was placed in
a 1-liter ?ask. To the potassium hydroxide was
then added 147.5 grams of 1,1,2 trichlorpropane.
A rise in temperature of the ?ask contents was 56
evident 'at once and a white'precipitate of po
less of chlorine by the removal of hydrogen chlo
tassium chloride immediately formed.
ride in the process disclosed.
The precipitated potassium chloride was re
moved by ?ltration and the alcoholic filtrate was
diluted with water. The oily layer which sepa
rated was removed, washed with water, dried and
distilled. A fraction of 51 grams boiling at
75-85° C. was secured. The greater portion of
As previously sug- I
gested, it is indeed surprising that the 1,1-di
chlorpropene-l isomer is produced in substantial
quantitative yields and that the two other isomers
CH==CH.CHC12 and CH.1.CC1=CKCi are practi
cally completely absent. Moreover ‘when it is
considered that the 1,1-dichlorpropene-1 isomer
CH.1.CH=CClz is a derivative of methyl ketene,
CH1.CH=CO, and would normally be expected
propane is indeed remarkable.
As ‘illustrative examples of the process the fol
lowing may be given:
this fraction was 1,1-dichlorpropene-l, boiling
at 77.5. C. The yield was 67% ‘of the theoreti
cal based on the quantity of potassium hydroxide
used. up in the reaction.
to be unstable, the preparation of this product
by removal of hydrogen chloride from trichlor
Emmple 3‘
Example 4
In this example 590 grams of 1,1,2 trichlorpro 70
pane were stirred for six hours in a flask fitted
with a re?ux condenser vat a temperature of
85° C. with a 20% excessv of a 20% calcium oxide
A solution of 400
or‘ 95% sodium hy-_ suspension in water. At ‘the end of this period
droxide and 2500 cc. of water was 91min a the oil was removed by steam distillation, sepa
rated from the aqueous layer, dried and frac
ting 01! hydrogen chloride irom the trichlorpro
pane by a catalytic process utilizing a hydrogen ‘
The product consisted 01-195 gramsof 1,1-di
chlorpropene-l and 253 grams of unreacted 1,1,2
ed to the speci?c times, temperatures, conditions,
pene-l, based upon the amount of 1,1,2 trichlor
chemical agents,'or amounts which have been dis
closed as illustrative in the preceding typical
examples. Various modi?cations of the inven
tion may come within its purview and the-scope
Example 5
In this example hydrogen chloride was re
moved from the 1,1,2 trichlorpropane by the use i
of the hydrogenchloride-removing catalyst bari
um chloride.
A tube was packed with charcoal on which the
15 barium chloride was retained. The tube was
?tted at the upper end with an inlet bulb which
could be ?lled with the trlchlorpropane. A stop
cock at the lower end of this bulb could be ad
chloride-removing catalyst. The invention is one
of broad general utility and is not to be restrict
'trichlorpropane. ‘ The yield of 1,1-dichlorpro
propane used up in the reaction was 77% of the
justed to regulate the ?ow of the liquid through
the tube.
The tube was heated to a temperature of 300
350° C. and the 1,1,2 trichlorpropane permitted to
?ow at a relatively slow rate through the tube.
Hydrogen chloride gas was evolved and passed.
25 out through a ventin the upper end of the col
umn. The lower end of the tube, which was in
_ communication with a condenser, served to col
lect the reaction product.
In the condenser at the lower end of the heat
30 ed tube an oil separated which was washed with
thereofis to be determined solely in‘ accordance 10
with the appended claims.
I claim:
1. A process of preparing 1,1-dichlorpropene-1
which comprises reacting 1,1,2 trichlorpropane
with a basic compound of a metal of the group 15
consisting of the alkali metals and the alkaline
earth metals.
2. A process of preparing 1,1-dichlorpropene-1
which comprises reacting 1,1,2 trichlor'propane
with a basic compound of a metal of the group 20
consisting of the alkali metals and the alkaline
earth metals at a temperature below the boiling
point of 1,1,2 trichlorpropane.
3. A process for “preparing 1,1-dichlorpropene-1
whichv comprises reacting 1,1,2 trichlorpropane 25
in the liquid phase with a basic compound of a
metal of the group consisting of the alkali metals
and the alkaline earth metals.
4. A process for preparing 1,1-dichlorpropene-1
which comprises reacting 1,1,2 trlchlorpropane in 30
the liquid state with a solution of sodium hy
water and distilled. From this product 30 grams
of 1,1-dichlorpropene-1 boiling at a temperature droxide.
5. A process for preparing 1,1-dichlorpropene-1
of 77-78 C. was obtained. The isomers 1,1 di-‘ which comprises reacting 1,1,2 trichlorpropane in
chlorpropene-Z and 1,2 dichlorpropene-1 'could the liquid state at an elevated temperature with 35
35 not be found in the reaction product.
a basic compound of a metal of the group con
It is thus evident that the invention resides in sisting of the alkali metals and the alkaline earth
the prepaartion of 1,1 dichlorpropene-i in sub
stantially quantitative yields by reacting 1,1,2 tri
chlorpropane with a basic material or by split
metals dissolved in a suitable solvent.
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