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Патент USA US2410553

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2,410,553
MANUFACTURE 0F ALKYLATED ABOMATHC
COWGUNDS
Louis Schmerling, Riverside, and Vladimir N.
Ipatieff, Chicago, Ill., assignors to Universal 0H
Products Company, Chicago, Ill., a corporation
of Delaware .
No Drawing. Application November 24, 1944,
Serial No. 565,050
_ 14 Claims.
1
(Cl. 260-671)
This invention relates to reactions of ketones I activated clay, alumina, etc. The catalyst may be
with aromatic compounds and particularly with - used in the form of granules, shaped particles, or
aromatic hydrocarbons.
/
powder; although'the granular material is gen- ‘
'
_An object of this invention is to-produce alkyl
erally preferred in certain continuous types of
operation wherein the reacting aromatic com
pound and ketone are passed simultaneouslyv
through a heated reactor'vcontaining catalytic
awd aromatic compounds by reacting an arc
matic compound and a ketone in the presence of
a‘ catalyst.
‘
'
Another object of this invention is the produc
packing material. 'The process may also be car
tion of isopropyl benzene and tertiary-butylben
- ried out batchwise in suitable reactors capable
zene by reacting acetone and benzene in the pres 10 of withstanding a pressure generally of not more
ence of a zinc chloride. catalyst.
than about 100 atmospheres. Addition to the re-'
One speci?c embodiment of the present inven
action mixture of hydrogen and/or of hydrogen
tion comprises the treatment of a ketone having ,
chloride is sometimes advantageous,
an a-hydrogen atom with an aromatic compound
Theproduction of. alkylated aromatic hydro
in the presence of a zinc chloride catalyst at a 15' carbons and alkylated halo-aromatics by the in
temperature su?icient to cause the formation of
teraction of an aromatic compound with a ketone
alkylated aromatic compounds.
-
in the presence of’ a zinc chloride catalyst is un
A‘ further embodiment of the present invention
comprises the treatment of a ketone having hy-,
expected, particularly since the prior art discloses
the production of ?-phenylisobutyl methyl ketone
\drogen attached to a carbon atom adjacent to 20 by interaction of benzene and mesityl oxide in‘
the carbonyl carbon atom and an alkylatable ben
the presence of aluminum chloride. When ben
zene hydrocarbon in the presence of a zinc chlo
_ zene and mesityl ‘oxide were interacted according
ride catalyst at a-temperature of from about 150°
to the process of our invention in the presence of
to about 450° C.
our zinc chloride catalyst, the reaction product
-
h
)
Ketones utilizable in our process comprise ali
25
contained tertiary-butylbenzene, isopropyl ben
phatic and cyclic ketones containing hydrogen
zene, and acetic acid, but no ?-phenylisobutyl
attached to a carbon atom in alpha position to
methy1ketone. Other ketones and aromatic com
the carbonyl group. The aliphatic ketones in
pounds react similarly in the presence of our cat
alyst to give alkylated and polyalkylated aromatic clude alkyl ketones and ole?nic ketones, the latter
including unsaturated condensation products of 30 compounds.
alkyl ketones having hydrogen attached to an
I The process of our invention and its commer- ‘
alpha carbon atom‘. The process is particularly - 'cial value are indicated further by the following
applicable to the treatment of acetone andits
examples which are not introduced with the in
condensation product, mesityl oxide. The cyclic
tention of unduly limiting the broad scope of our
ketones utilizable in the process contain a cyclo
invention.
,para?in group or aryl group._
Example I .
Aromatic compounds which are reacted with
ketones as herein set forth include particularly
- 30 grams of acetone, 80 gramsof benzene, and
aromatic hydrocarbons and halo-aromatic hy
drocarbons. 'Thus, benzene, toluene, Xylenes,
15 grams of a pelleted zinc chloride-alumina cat
40
alyst containing 25% by weight of zinc chloride
propyl benzene, butyl benzene, and other alkylat
were placed in a glass-lined autoclave, hydrogen
able benzene hydrocarbons of higher molecular
weight as well as polycyclic aromatic hydrocar
bone and alkyl polycyclic aromatic hydrocarbons
maybe utilized in ‘our process’. Mono-halogen
was introduced to a pressure of 100 atmospheres
and thereaction mixture was rotated and heated
at 250° C. for four hours. After the autoclave
ated aromatic hydrocarbons which are sometimes
had cooled to‘about 20° C., the products which
were removed therefrom consisted of 98 grams of
referred to as aryl halides and particularly aryl
deep yellow liquid having the odor of acetic acid
chlorides and aryl bromides are converted'into
and 20 grams of used catalyst having a tan color.
Distillation of the liquid product‘separated a mix
50 ture of acetic acid and mesityl oxide from about
18 grams of alkylated benzene hydrocarbons con
alkylated aryl halides by treatment with ketones
in the presence of a zinc chloride catalyst as here
in' set forth.
'
.
Although zinc chloride may be used as such to
taining mono-isopropyl benzene, mon0~tertiary~
catalyze the process of our invention, it'is pref!
butylbenzene, and polyalkylated benzene‘ hydro
.erable to support this catalytic material by a suit
carbons. The yield of mono~alkylated benzene
able carrier such as silica, diatomaceous earth, 55 hydrocarbons was about 40% of the theoretical
2,410,503
4 ,
based upon the amount of acetone charged while the yield of polyalkylated benzenes-was about 32% ‘
having hydrogen, attached to a carbon atom ad
lacent to the carbonyl group and an alkylatable
of the theoretical.
aromatic compound selected from the group con
sisting of aromatic hydrocarbons and aryl halides '
in the presence of a zinc chloride catalyst.
-
'In a similar run in which acetone alone‘ was
heated at 250° C. under hydrogen pressure in the
presence of the zinc chloride catalyst, no alkyl_
2. A- process for producing alkylated aromatic
hydrocarbons which comprises reacting an alkyl
benzenes were formed and the reaction product
consisted of water, acetic acid, and high boiling
condensation products consisting mainly of
mesityloxide, phorene, etc.
atable aromatic hydrocarbon and a ketone hav
ing hydrogen attached to acarbon atom adja
10 cent to the carbonyl carbon atom in the pres
ence of a zinc chloride catalyst.
. Example-II
3. A process for producing alkylated benzene
30 grams of acetone, 80 grams of benzene, and
hydrocarbons which comprises reacting an al
15 grams of zinc chloride-silica catalyst, the lat
kylatable benzene hydrocarbon and a ketone hav
ter consisting of 25%v by weight of zinc chloride 15 in‘; hydrogen attached to a carbon atom adja
deposited upon celite spheres, were placed in ‘a
cent to the carbonyl carbon atom in the pres
glass-lined autoclave to which hydrogen was
ence of a zinc chloride catalyst.
'
,
.added to 100 atmospheres pressure. The charged
4. A process for producing alkylated benzene
autoclave was then rotated and heated at 300°
hydrocarbons which comprises reacting an al
C. for 4 hours. After the autoclave and contents
kylatable benzene hydrocarbon and an aliphatic
had cooled to about 25° C., 93 grams of liquid
ketone having hydrogen attached to a carbon
product and 25 grams of used catalyst in the
atom adjacent to'the carbonyl carbon atom in the
form of tan spheres were‘ removed therefrom.
presence of a zinc chloride catalyst.
' The liquid product was washed with water be
5. A process for producing alkylated benzene
'_fore distillation. Neutralization or the washed 25 hydrocarbons which comprises reacting an al
water with caustic soda solution followed ‘by
kylatable benzene hydrocarbon and an alkyl ke
evaporation yielded sodium acetate which was
tone having hydrogen attached to a carbon atom
identi?ed by its reaction with parabromophenacyl
adjacent to the carbonylcarbon atom in the pres
bromide which gave parabromophenacyl acetate
ence of a zinc chloride catalyst.
melting at 84-85° C. Distillation‘ of the washed 30. r - 6. A process for producing alkylated benzene
liquid product gave the following fractions:
hydrocarbons which comprises reacting an al
I
kylatable benzene hydrocarbon and an ole?nic
Fraction No. '
n. P.,'° c. - Distillate,cc.
ketone having hydrogen attached to a carbon
11D”
atom adjacent to the carbonyl carbon atom in
1..
.
e4
______ ._
35 the presence of a zinc chloride catalyst.
2.
5.2
1. 4909
3..
5.5
1.4877
4 ..... ..
5.2
1.4881
hydrocarbons‘ which comprises reacting acetone
5..
6..
7...-
5.2
2.5
as
1. 4898
1. 4900
1. 4905
catalyst.
4.5
______ .r
Residue ..... _.
7. A process for producing alkylated benzene
and benzene in the presence of a zinc chloride
40
i
8. A process -for producing alkylated benzene ,
hydrocarbons which comprises reacting mesityl
Fractions 1 and 2 consisted mainly of uncon
verted benzene. Fractions 3 and 4 consisted
chie?y of isopropyl-benzene and some tertiary
butylbenzene. Fractions 5 and 6 consisted chiefly 45
of tertiary-butylbenzene. Fraction 7 and the ~
residue contained polyalkylbenzene hydrocar-~
bons including di-isopropylbenzene. Based upon
the amount of acetone charged, the yield of
mono-alkylbenzene hydrocarbons was about 55% 50
of the theoretical while the yield of_ polyalkyl
benzenes' was about 34% of the theoretical.
oxide and benzene in the presence of a zinc chlo- ,
ride catalyst.
,9. A process for producing alkylated benzene
hydrocarbons which comprises reacting an al-.
kylatable benzene hydrocarbon and an aliphatic
ketone'having hydrogen attached to a‘ carbon
atom adjacent to the carbonyl carbon atom at a
temperature of from-about 150° to about 450° C.
and’ at a pressure of from substantially atmos
pheric to about 200 atmospheres in the presence
of hydrogen and of a zinc chloride catalyst.
10. A process for producing alkylated benzene
Example‘ III
hydrocarbons which comprises reacting an al
In a run similar to that described in Example 55 kylatable benzene hydrocarbon and an aliphatic
ketone having hydrogen attached to a carbon
I, 30' grams of mesityl oxide, 79 grams of ben
, atom adjacent to the carbonyl carbon atom at a
zene, 15 grams of the zinc chloride-alumina cat
temperature of from about 150° to about 450° C.
alyst were placed in an autoclave ,to which hy
and at a pressure of from substantially atmos
drogen was added-to 100 atmospheres pressure
and then heated at 250° C. for 4 hours. The 95 60 pheric to about 200 atmospheres in the presence
of hydrogen and of a solid composite of zinc chlo
grams of reddish-brown liquid product which
ride and a carrier.
‘
was recovered from this treatment contained
11. A'process for producing alkylated benzene
hydrocarbons which comprises reacting an al-‘
benzene was about 26% of the theoretical based 65 kylatable benzene hydrocarbon and an alkyl ke
tone having hydrogen attached to a carbon atom
upon the amount of mesityl oxide charged-while
adjacent to the carbonyl carbonatom at a tem-v
the yield of polyalkylated benzenes was about
acetic acid, tertiary-butylbenzene,. and polyal
kylated benzenes. The yield of tertiary-butyl
perature of from about 150° to about 450° C. and
at a pressure of‘fro/m substantially atmospheric
invention and particularly its- commercial value 70 to about 200 atmospheres in the presence of hy
drogen and of a solid composite of zinc chloride
are evident from the preceding speci?cation and
40% of the theoretical.
»
The character of the process of the present
numerical data presented.
We claim as our invention:
_
»
l. A process for producing alkylated aromatic
and a carrier.
.
_
12. A process for producing alkylated benzene
hydrocarbons which comprises reacting an .al
compounds which comprises reacting 9, ketonev l?/kylatable benzene hydrocarbon and an .ole?nic
2,410,558
ketone having hydrogen attached to a carbon
in the presence of hydrogen and of a solid‘ com
atom adjacent to the carbonyl‘ carbon atom at a \
posite of zinc chloride and a carrier.
temperature of from about 150° to about 450° C.
and at- a pressure of from substantially atmos
pheric to about 200 atmospheres in the presence
of hydrogen and of a solid composite of zinc chlo
-
ride and a carrier.
13. A process for producing alkylated benzene v
” hydrocarbons which comprises reacting acetone
and benzene at a temperature of from about 150° 10
to about 450° C.’ and at a pressure of from sub
stantially atmospheric to about 200 atmospheres
-
14. A process for producing alkylated benzene
hydrocarbons which comprises reacting mesityl oxide and benzene at a temperature of from about
150° to about 450‘0 C. and ata- pressure of from
substantially?atmospheric to about 200 atmos
vpheres in the presence of hydrogen and of a solid
composite of zinc chlorideand a carrier. .
LOUIS scmmmncl
VLADIMIR. N. IPATIEFF.
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