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Патент USA US2115332

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' 2,115,332‘
' Patented Apr. 26, 193sv
UNITED STATES21,115,332PATENT OFFICE
METHOD OF PRODUCING- PHENOLIC COM
POUNDS
Charles G. Grosscup, Philadelphia, Pa., assignor Y
to The Sharples Solvents Corporation, Phila
delphia, Pa, a corporation of Delaware ~
_No Drawing. Application March 24, 1933,
.
~
Serial No. 662,528
9 Claims. (01. 260-154)
, The present invention relates to the production
_ of- alkyl derivatives of, phenolic compounds by
the condensation of ole?ns with phenol or one?of
its derivatives in the presence of an acid catalyst.
5 It comprises an improvement over the process
de?ned and claimed in‘ the co-pending applica
tion of William M. Lee and Lee H. Clark, Serial
No. 623,486, ?led July 20, 1932. '
'
'
such phenol, and it also results in the undesired
formation of phenol acids. Thus, where sul
phuric acid is used as a catalyst, phenol sulphonic
acids are formed. Difficulty is also encountered
in the practice of the process of the Lee and 5‘
Clark application in an attempt to separate the‘ '
oily layer formed by the treatment'of the acid
liquor with phenol from acid formed during such
-
In the above identi?ed application, a method‘
By the practice of the present invention all'of 10
10 of producing phenolic derivatives was described, the above mentioned di?iculties are avoided. The
which involves the selective absorption of a de
initial acid absorption step is entirely eliminated,
sired ole?n compound or mixture of ole?n com
and there is accordingly no loss of hydrocarbon
pounds from a mixture containing a larger num
due to polymerization. Furthermore, in the
ber of such compounds. In the preferred m'ethé practice of the invention, only ‘a very small 15
16 0d of procedure, in accordance with that appli-' amount of acid is used and the di?iculties en
cation, the absorption of the desired ole?ne is countered in the practice of the Lee and Clark
obtained by a-succession of counter-current batch process in connection with the solution of phenol,
contacts, in which a given batch of acid succes
and the formation of phenol acids and the di?i
sively contacts ole?n mixtures containing pro
culty of separating the acid catalyst from the '20
20 'gressively larger proportions of the ole?n mate
oily layer are accordingly obviated.
treatment.
rial which it is desired to absorb.
At the com
pletion of this absorption operation, the acid liq-.
uor formed by the absorption of the desired ole-i
?n in the acid is contacted with an equimolecular
25 proportion of phenol, the agitation being main
tained for approximately one hour. The mixture
so obtained is next subjected to a settling opera
tion, and gradually separated into an acid layer
and a supernatant oily layer, which is believed
30 to consist principally of alkyl phenyl ether. The
acid layer is thereafter drawn o? from the oily
layer, and the oily layer is subjected to re?ux
for a period of several hours, at a temperature
between 110° (and 135° C. to produce the desired
alkyl phenolic derivative.
While the process described above constitutes
a satisfactory method of producing alkyl deriva
tives of phenolic compounds, it possesses a num
ber of serious disadvantages.v In the ?rst place,
40 the selective absorption of. the desired ole?n
material from the mixture of ole?n material in
the acid is a di?icult and time-consuming oper
ation. This operation is also objectionable be
' cause of the fact that it necessarily involves a
45 certain amount of undesired polymerization of
the ole?ns under treatment. In the practice of
.
d
4
a
In the practice of the invention a mixture of
ole?ns is ?rst treated with the phenolic com
pound to be condensed at substantially normal
temperature. A very small trace of an acid 25
adapted to act as a‘ catalyst is added to the mix
ture‘ of phenol and hydrocarbon, and intimately
mixed therewith, the mixture being re?uxed to
cause a preliminary reaction to take place be
tween the olefin and the phenolic compound. 30
This treatment is carefully controlled to prevent
the reaction of the phenolic compound with ole?n
material in the mixture other than that which
it is desired to condense.
Y
'
The practice of the invention thus involves a 35
treatment of the mixture of hydrocarbon,
phenolic compound and catalyst to cause a selec
tive condensation of desired ole?n material with
the phenol to the exclusion of other ole?n mate-,
‘rial
present.
-
_
>
40
,
The mixture of reacted and unreacted material
is next distilled and the heads passing o? at a
temperature within the boiling range of the ole
?n are separately collected. The residue is
thereafter digested by heating it to a teinpera- 45
ture adapted to cause a conversion of the reac- .
'tion product of the ole?n and phenol, this treat- .
the Lee and Clark application, an adequate sepa
ment being continued for a considerable period of
ration of unreacted acid from the acid liquor - time in order to effect a substantially complete
produced by the absorption treatment is never conversion of the in'tial condensation product.
50
attained.
As a consequence of this fact, an un
The practiceof the invention will be better
desirably large quantity of acid remains in the I understood by reference to the following illus- “
acid liquor when it is mixed with th‘ phenolic trative examples of the production of tertiary
compour :1 which is to be condensed with the amyl phenol by the condensation of iso-amylene'
Ole?nj This results in an undesired solution of with phenol:
\
55
inherit,‘ in the acid, and the' consequent loss of
2
.
2,1 15,332
Ezample 1
140 grams'of mixed amylenes, comprising ap
proximately 50% normal amylenes and 50% iso-_
amylenes, were agitated together with 188 grams ~
of‘ phenol, and 1.96 grams of 98% ‘sulphuric acid.
of the hydroxy-aromatic material or substantial
‘ ' '
reaction between the 'hydroxy-aromatic material ~
and the normal ole?ns, separating the normal
ole?ns from the initial reaction. product so
formed, and thereafter subjecting the initial re-,
were then added to the mixture and the entire action product to conditions of increased tem
mass was thoroughly agitated and re?uxed for perature to cause nuclear alkylation of the aro
approximately one hour, at a temperature of-42° ~matic material to ‘take place, to form a. tertiary
10 C. By this treatment the iso-amylene of the
mixture was condensed with the phenol, whereas
only a very small proportion of the normal
amylene was so condensed. The unreacted
amylene, consisting principally of normal
my amylene, was then removed by distillation of the
mixture up to 60° C. The residue, comprising
260 grams of material, was digested for a period‘
of _four hours, at a temperature of-l35° C.
The
_
'
' ~
‘
3. A process of preparing tertiary alkyl hy
droxyparomatic compounds that comprises sub
jecting, in the. presence of an acid catalyst,.a mix
ture of hydroxy-aromatic material and ole?ns,
some of which ole?ns are-normal oleiins and
some of which are iso-ole?ns, to reaction condi 15
tions oi_time and temperature su?lcient to cause
only a preliminary-reaction to take place be
crude amyl phenol so obtained was then washed
and neutralized and purified by fractional dis
tillation under reduced pressure. 110 grams of
material, comprising principally
alkyl hydroxy-aromatic compound.
tween the hydroxy-aromatic material and the
iso-ole?ns, but which conditions are less severe
tertiary amyl ,
than are necessary to cause substantial-nuclear 20
alkylation of the hydroxy-aromatic material or
phenol, and having a melting range from 60-72°
substantial reaction between the hydroxy-aro-'
C. was obtained.
matic material and the normal ole?ns, separating the normalole?ns from the initial reaction prod- ,
.
Example 2
188 grams: of'phenol' were mixed with 140 grams
of amylene mixture in the same manner as‘ de
scribed in connection with Example 1, above.
3.16 grams of 62% ‘sulphuric acid were added to
the mixture and thoroughly agitated therewith.
_ The entire mixture was‘ then re?uxed for a pe
riod of two hours at a temperature of 43° C. and
the unreacted amylene removed by distillation, as
in Example 1, above.‘ The remaining mixture
was then digested, washed, neutralized and puri
?ed, as in Example 1, and yielded 70 grams of
tertiary amyl phenol cut, melting from 69
not so formed‘, and thereafter subjecting the ini
tial reaction product to conditions of increased
temperature to cause nuclear alkylation’ of the
aromatic material to take place, to ‘form a ter
tiary alkyl hydroxy-aromatic compound.
.
4. A process for preparing tertiary amyl phenol 30
which comprises subjectinga mixture 01' a'myl- .
enes containing both normal and iso-amylenes
and phenol to reaction conditions of'time and
temperature su?‘icient to cause only a preliminary
reaction to take place between the phenol and 35
the iso~amylenes but which conditions are less
severe than are necessary to cause substantial
nucleart alkylation of the phenol or substantial
'
Example 3
reaction between the phenol and the normal
188 grams of phenol were mixed with 140 grams amylenes, separating the normal amylenes from 40
of mixed amylenes, as vin Example 1, above. ‘the initial - reaction product so formed and
.89 grams of a mixture of equal parts by volume thereafter subjecting the initial reaction prod
of glacial acetic and sulphuric acids were added Hot to conditions of increased temperature to
to the mixture and intimately agitated therewith. ‘cause nuclear alkylation of the phenol to take
place to form tertiary amyl phenol;
'
The material was then re?uxed, distilled, digest
5. A process for preparing tertiary amyl phenol
ed and puri?ed, as in connectionv with Example
2, above, and yielded 106 grams of ya tertiary amyl which comprises subjecting, in the presence of an
phenol out, having a melting range from 74-84° C. acid catalyst, a mixture of amylen'es containing
both‘ normal and ,iso-amylenes and phenol to
50 ' Modi?cations of the invention will be obvious
. to those skilled in the art and I do not, therefore, reaction conditions of time and temperature will
wish to be limited except by the scope of the cient to cause only a preliminary reaction to take
sub-joined claims, as interpreted in the light of,‘ place between the phenol‘ and the iso-amylenes
79.5“ C.
the spirit of the invention.
55
I claim:
‘
but which conditions are less severe than are
,
e
-
1.' A process of making alkyl derivatives of
phenols that comprises mixing at least one phenol
with a hydrocarbon material including at least
one ole?n, and with a condensation catalyst com
prising a mixture of sulphuric and acetic acids,
regulating the temperature and concentration of
necessary to cause substantial nuclear alkylation
of the phenol or substantial reaction between the
phenol and the normal ole?ns, separating the
normal ole?ns from the initial reaction product
‘so formed and thereafter subjecting the initial
reaction product to conditions of increased tem
perature to cause nuclear alkylation of the phenol
the catalyst so that the phenol and ole?n react to take place to form tertiary amyl phenol.‘
6. A process of preparing tertiary alkyl hy
but the remainder of the hydrocarbon material
substantially does not, and thereafter removing ’ droxy-aromatic compounds that comprises sub
jecting, in the presence of a catalytic amount 01’
- the unreacted hydrocarbon material.
2. A process of preparing tertiary alkyl hy- ' sulphuric acid, a mixture of hydroxy-aromatic
material and ole?ns, some of which ole?ns are
droxy-aromatic compounds that comprises sub
jecting a mixture of-hydroxy-aromatic material normal olefins and some of which are iso-olefins,
and ole?ns, some of which are normal ole?ns and to reaction conditions ‘of time and temperaturev
su?icient to cause only a preliminary reaction
some of which are iso-ole?ns, to reaction condi
tions of time and temperature su?icient to cause to take place between the hydroxy-aromatic ma 70
only a preliminary reaction to take place between terial and the iso-ole?ns, but which conditions
are less severe than are necessary to cause sub—v
the hydroxy-aromatic material and the iso-ole_
?ns, but which conditions are less severe than are
75 necessary to cause substantial nuclear alkylation
,
stantial nuclear alkylation of the hydroxy-aromatic material or substantial reaction between
the hydroxy-aromatic material and the normal
2,115,332
ole?ns, separating the normal ole?ns from the
initial reaction product so formed and thereafter
subjecting the initial reaction product to condi
tions of ‘increased temperature to cause nuclear
alkylation ‘of the hydroxy-aromatic material to
take place, to'form a tertiary alkyl hydroxy-aro
matic compound.
7. A process of preparing tertiary alkyl hy
droxy-aromatic compounds that comprises sub
10 jecting a mixture of hydroxy-aromatic material
and ole?ns, some ofv which ole?ns are normal
ole?ns and some of which are iso-ole?ns, to a
‘temperature of around 42° C. to cause a prelimi
nary reaction to take place between the hydroxy
15 aromatic material and the iso-ole?ns, separat
3
terial and ole?ns, some of which ole?ns are nor
mal ole?ns and some of which are iso-ole?ns, to
a temperature of around 42° C. for about one to
two hours to cause a preliminary reaction to take
place between the hydroxy-aromatic material and
the iso-ole?ns, separating the normal ole?ns from
the initial reaction product so formed, and there
after subjecting the initialvreaction product to a '
temperature between about 110° C. and about
135° C. to cause nuclear alkylation of the hy 10
droxy-aromatic material to take place, to form a
tertiary alkyl hydroxy-aromatic compound.
9. A process for preparing tertiary amyl phenol
which comprises subjecting'in the presence of a
catalytic amount of sulphuric acid a mixture of 16
ing the normal ole?ns from the initial reaction
product so formed, and thereafter subjecting the
initial reaction product to a temperature between
vamylenes containing both normalv and iso-amyl
about 110° C. and about 135° C. to cause nuclear
reaction to take place between the phenol and
the iso-amylenes, separating the normal amylenes 20
from the initial reaction product so formed and
thereafter subjecting the initial reaction product
20 alkylation of the hydroxy-aromatic material to
take place, to form a tertiaryalkyl hydroxy-aro
matic compound.
.
8. A process of preparing tertiary alkyl hy
droxy-aromatic compounds that comprises sub
25 jecting in the presence of a catalytic amount of
sulphuric acid a mixture of hydroxy-aromatic ma
enes and phenol to a temperature of about 42° C.
for about one to two hours to cause a preliminary
to a temperature between about 110° C: and about
135° C. to‘cause nuclear alkylation of the phenol
to take place to form tertiary amyl phenols.
25
CHARLES G. GROSSCUP.
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