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Патент USA US2404120

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Patented July 16, .1946 l
'- 2,404,120
William N. Axe, Bartlesville, Okla, assignor to
Phillips Petroleum Company, a corporation of
No Drawing. Application July 3, 1944,
Serial No. 543,421
12 Claims. ~ (01. zed-e71)
This invention relates to derivatives of aro~ '‘
matic compounds. In one modi?cation it relates
to alkenyl derivatives of aromatic compounds.
In another ‘modi?cation it relates to normal al
kyl derivatives of aromatic compounds. As spe~
ci?c modi?cations it relates to the alkenylation
of aromatic hydrocarbons and to the production '
of normal alkyl derivatives of aromatic hydro
carbons. This application is a continuation-in
part of my copending application Serial No. 433, 10
192, ?led March 3, 1942.
boiling normal l,3-tdiole?nys to produce normal
monoalkenyl derivatives of said aromatic hydro
Still another‘ object of this invention is to pro
duce normal butyl benzene.
Further objects and advantages of my inven
tion will become apparent to one skilledin the
art from the accompanying disclosure and dis
I have now found that aromatic compounds,
includingr aromatic hydrocarbons, phenols, naph
Normal alkenyl aromatic compounds and nor
mal alkyl aromatic compounds are’ valuable in
thols, and aromatic halides, can be reacted with
normal 1,3-diole?ns to produce alkenyl deriva
termediate compounds both in their own rights
tives of said aromatic compounds. I have. fur
and as intermediates in organic syntheses. They 15 ther found that such alkenyl ‘derivatives include
may be used for the production of normal ali
normal monoalkenyl derivatives whichcanv ‘be
phatic derivatives of such compounds as amino
successfully subjected. to nondestructive , hydroqe
benzenes, aminonaphthalenes, phenols, naph-v
thols, aminophenols, aminonaphthols, quinolines,
genation to produce thecorrespondingnormal
alkyl derivatives. 1 have .further discovered. that
and the like. These materials can be used in the
such derivatives can be‘produced in extremely
highyields ,and can be recovered in substantial
quantities in a condition of high purity. As the
aromatic reactant of my process I prefer to use
preparation of oxidation inhibitors, pharmaceu
ticals, dyestuffs, and explosives. ‘The develop
ment of the full potentialities of normal aliphatic
derivatives of such compounds has been preclud
benzene, naphthalene, simple alkyl derivatives of
ed by the absence of suitable sources of such 225 these hydrocarbons such as toluene, ethylben
compounds. Thus, when ole?ns are used to al
zene, xylenes, and'the like, phenol, naphthols, ~
kylate aromatic compounds the normal alkyl de
and simple alkyl derivatives of these materials,
rivative is produced only in the case of ethylene
and aromatic halides such as phenyl chloride,
and with other ole?ns it is impossible to produce
phenyl bromide, one of the naphthyl chlorides.
a normal alkyl derivative by catalytic alkylation. 30 and the like, although other alkenylatable aro
Synthetic methods for the production of normal
matic compounds are notto be excluded from the
alkyl derivatives have been limited heretofore to
broad concept of my invention.‘ As the diole?n
reactions of the Wurtz-Fittig type in which aro~
reactant I prefer to use a low-boiling normal, ‘1,3
matic halides have been condensed, in the .pres
diole?n such as 1,3-butadiene, l,_3-pentadiene,
ence of a metal such as sodium, with normal a1 35 1,3-hexadiene, and the like. Although it is a pri
kyl halides. The best yields reported for such re
mary object of my invention to produce normal
actions have not exceeded about 30‘per cent of
aliphatic derivatives by the use of normal l,3-di_
the theoretical yield and more often actual
ole?ns, it is to be understood that alkyl deriva
_ yields are from about 10/to 20 percent of the
tives of normal 1,3-diole?ns, such as S-methyl
theoretical yields. Other disadvantages of such 40 l,3-hexadiene and 6-methyl-l,3-heptadiene, to
synthesis operations include the use of large
produce aromatic derivatives such ‘as l-phenyl
quantities of metals ‘such as sodium with appre
G-methyl heptylene, andthe like, are not to be
ciable attendant hazards, the employment of ex
excluded from the broad concepts of my inven
pensive intermediate compounds, the necessity of
special solvents, and the relatively di?icult pro 45 ~ Broad'features of this process may be more
duction of. normal alkyl halides
readily understood by considering a typical pro
An object of this invention is to produce nor
cedure. A blend of butadiene in benzene, in
mal aliphatic derivatives of aromatic compounds.
‘ which the benzene is present in substantial mo
Another object of this invention is to produce
lar'excess, serves asthe primary feed stock. The
normal alkyl derivatives,v of aromatic compounds.
blend is charged to a reaction zone at moderate
A further objectyof this invention is to produce
temperatures and pressures where it is intimate
normal alkenyl derivatives of. aromatic com
ly commingled with a’ liquid complex compound
of boron fluoride such as those to be hereinafter
A still further object of this invention is to re
described. The e?'luent is preferably continuous
act low-boiling aromatic hydrocarbons-with 10w:
ly removed from the reaction zone and afterpme:
chanical separation of the catalyst phase, the
preferable not to use a granular material contain
hydrocarbon stream is washed free of dissolved
ing appreciable amounts of silica.
boron ?uoride and the excess benzene is recoV-.
In the alkenylation step the reaction appears
to be primarily mono-alkenylation to form mono
alkenyl derivatives of the aromatic compound.
It also appears that secondary reactions take place
ered by fractional distillation. The debenzenized
product is further fractionally distilled to sepa-‘
rate a main product (normal butenyl benzene, or.
phenyl butene) boiling at about 365‘to about 370°
to certain extents,‘ including cyclization and/or
polymerization of the resulting monoalkenyl
F., and a higher-boiling kettle product. The ‘
main product fraction may be hydrogenated over
derivatives. This conclusion is based on the ob
servation that the aromatic compound reacted is
a conventional hydrogenation catalyst such as‘
molecularly equivalent to the diole?n reacted. If
extensive polyalkenylation occurred, to form di
;or tri-alkenyl aromatic derivatives, the amount
Raney nickel, platinum or any of the .morerugged
industrial hydrogenation catalysts to yieldln-bu-l
tylbenzene, which ordinarily requires ‘no further
of aromatic hydrocarbon reacted would be sub
I have found that efficient catalysts for such 15 stantially less than the molecular equivalent'of
the diole?n, while if the monoalkenyl derivative
alkenylation reactions can be prepared by sub-v
entered into reaction with the aromatic hydro
stantially saturating water with a boron trihalide.
carbon, to form the corresponding di-substituted
A preferred boron trihalide is boron trifluoride,
para?in hydrocarbon, the amount of aromatic hy
although I do not intend to exclude other boron
trihalides, particularly ‘boron trichloride and 20 drocarbon reacted would be substantially greater
than .a molecular equivalentof the diole?n. No
boron tribromide which are low-boilingmaterials.
appreciable polymerization of- the diole?n is be
A preferred catalyst for use in myprocess is con
lieved to take place under preferred conditions
veniently prepared bypassing gaseous boron ?uo
ride into water until the desired hydrate concen
tration is realized. The resulting hydrate is aliq
uid of relatively high speci?c gravity and sub
stantially immiscible with hydrocarbons. . Dur
ing this reaction considerable heat is evolved and
suitable means for cooling should be provided.
Since the speci?c gravity of a completely satu
rated solutionis approximately 1.77, convenient,
control of concentration can'be effected by means
of hydrometer determinations. Means for‘ me
» chanicalagitation of the absorbent liquid may be
used, andIhaJyefouhd that such means are often
helpful in obtaining some of the higher concentra- ' '
,tions of the hydrate used in the process. In the
vpreparation of the catalyst, the gaseous boron
?uoridemay be passed into waterwhilethe tem
of operation, a conclusion deducedfrom a con
sideration of. the relativeamounts of reactants
which undergo reaction and from the characteris
tics of such ‘high-boiling products. Such results
contrast with the results obtained when catalysts
such as sulfuric acid are used with the same re
actants. Thus, when benzene and 1,3-butadiene
are reacted in the presence of sulfuric acid it has
been reported that the product is diphenylbutane
' and that no phenylbutene is produced.
_ In order to favor the desired ‘primary reaction
I prefer to use moderate reaction temperatures,
relatively short reaction periods, .and relatively
high molar ratios of aromatic compoundto diole
?n reactant. The reaction maybe satisfactorily
and conveniently conducted ata temperature -be-'
peraturei's maintained below 150° F._, and prefer-‘
ablyabove-75" F., untilthe water is saturated
tween about '70 and about 150° F., with a tem
usingv'boron tri?uoride~containing complexes it is
5 amount of catalyst present should not exceed that
perature between about'SO to 90° F. and about v1.10 '
to 120° F. being preferred; Temperatures above
and boron ?uoride passes through'unabsorbed.
150° F., or below 70° F;, arejnot ‘tob'e. excluded,
At this point a water-boroni?uoride mol ratio of
approximately 1:1 is ordinarily obtained. The 45 however. The. average'reaction ‘time may be be
tween a few minutes and a few hours, with satis-.
catalyst may be, used in this form, or water may
factory results being obtained with a reaction time
be added until a desired higher mo'l ratio is .ob-‘
between about 5 and about 20 minutes. “The molar
tained; alternately, the addition of boron fluoride
ratio of aromatic compounds to diole?n in the feed
may be halted at the desired hydrate concentraé
tion by determination of the increase in weight 60 to a continuous reaction :step may be between
about 2:1 and about lozlwith satisfactory opera
or speci?c gravity of the liquid. Preferably, the
tion generally being obtained with aratio between
alkenylation catalyst of this invention comprises
about 47:1 and about 6: 1. vIntimate mixing of the
a hydrated boron fluoride containing from about
reaction mixture, accompanied. by recirculation,
1.0 to about 1.5 mole of water per mol of- :boron
?uoride; This catalyst preparation reaction may 55 will generally result in higher effective ratios. in
the reaction .zone.- In some instances it is- desir
be ‘conducted, if desired, under pressure, partic
able to use moderate superatmospheric pressures,
' ularly when using boron trifluoride or boron tri
particularly with the lower boiling reactants, but
chloride. ‘When an active catalyst of this inven-‘
generally the pressure need not be appreciably
tion ‘loses appreciable quantities of‘ boron tri
above that which will insure that the reactants
?uoride or other boron trihalide during use, its 60 are present in liquid phase and to insure that the
activity decreases and‘for this reason it is desir
catalyst is adequately saturated with the boron
able to add during a continuous process small
trihalide. As previously stated it is preferred that
amounts’of boron trihalide initially used to pre
the reacting mixture and, the catalyst be in
fpare the catalyst, continuously or intermittently,
timatelyadmixed. This may be accomplished by
in order that the activity of the catalyst will .re-;
efficient stirring mechanism, by continuously re
main or be maintained substantially constant. In
circulating in a closed cycle a substantial amount
most instances the resulting active‘catalytic ma
of the reaction mixture comprising. reactants,
teriiall is a liquid and can be readily employed as
products and catalyst, by pumping such. a re
such, preferably with intimate mixing with the
action mixture through a long tube .coil at. a rate
reaction mixture. If ity is "desired to use such a
such that conditions of turbulent ?ow exist, or by
catalyst vin the solid form it may beiused' in ad,
other means well known to those skllledin the
m'ixture with porous granular catalyst'supports
art of hydrocarbon alkylations. It is preferred
such as activated charcoal, activated alumina,
that the reaction mixture contain at least about
5 . activated bauxite, and the like, although when
5 per cent by volume off-the catalyst and that. the
which will permit a continuous phase of reacting
materials when the reaction mixture is intimately
admixed. Thus it is desired that the. catalyst
phase not be the continuous phase when a liquid
catalyst is used. Inert materials may be present
during the reaction, such ‘as relatively nonre
active impurities normally accompanying the re
actants, added low-boiling, para?in hydrocarbons
‘ thatlspeci?c limitations expressed in such ex
amples-are not ‘to be. used to restrict my inven
tion unduly. v
‘ ‘I
‘g 1‘
Example I
of ‘catalyst of composition comprising
, 1.5 mols ‘of water to one mol of boron ?uoride
was‘suspended in 312 grams of benzene by agi
tation. Butadiene was introduced at a ?ow rate
such as a parai?nic naphtha fraction,or“the like.‘
When 1,3-butadiene is the diolefi'n- reactant 10 of 15 grams per houruntill50 grams had been
absorbed. The reaction was carried out at 89 to
the monoalkenyl product is substantially com
95° F. The alkylate was processed as‘ above
pletely the normal alkenyl derivative. 'With di-i
and the benzene-free alkylate was fractionated
ole?n reactants containing [a liigherinumber 'of
to yield 300 grams (85% yield) of phenyl-butenes
carbon atoms per molecule-‘suchhighi'yields" of
the normal derivative will often notbe obtained 15 boiling between 356 to ‘365° F. (uncorr.).
but it will still be possible to obtain quite sub;
Example II
stantial yields of the normal alkenyl derivative.
In any case a fraction’ containing, or "comprising
Operating under conditions similar to those
given in Example I, toluene may be reacted with
essentially, the desired normal alkenyl deriva
tive may be readily separated from the reaction 20 piperylene (1,3-pentadiene) to produce n
pentenyltoluene. In this instance, the toluene
eiliuents, generally by passing the effluents to a
free product is subjected to a preliminary frac
settling chamber wherein the catalyst separates
from a liquid phase containing unreacted charge
tionation under 10 mm. pressure to ‘effect a
rough separation of higher-boiling products
stock and reaction products, and separating
from this liquid phase, as by fractional distilla 25 from the pentenyltoluene. Final puri?cation
involves fractional distillation at atmospheric
tion, a fraction of any desired purity.‘ ‘
pressure to give a product boiling at about
As will be appreciated the normal alkenyl de
430-440° F. amouning to about 60 per cent of
rivative may, in many instances, be a desired
the total alkenylate. Analytical data and oxida
product of the process. However, I have found
that this material may be readily converted to 30 tion reactions indicate this materialto be essen
tially 1 - (p-tolyl)-2-pentene. Nondestructive
the normal alkyl derivative by nondestructive
hydrogenation results in quantitative reductions
hydrogenation. This hydrogenation will most
to 1emethyl-4rn-pentylbenzene having substan
often be conducted. in a manner such that the
tially the same boiling range as the original
alkenyl group is saturated by hydrogen. How
ever, it will be appreciated that, particularly 35 alkenyl derivative.
Although I have described my invention in
when aromatic hydrocarbons are reacted in ac
cordance with my invention, not only may nor
considerable detail, with the inclusion of cer
mal alkyl derivatives thereof be produced by such
tain speci?c embodiments, it is not intended that
a nondestructive hydrogenation, but the hydro
genation may be extended to include partial or
complete saturation of the aromatic nucleus.
Thus it is possible to react a benzene with a low
boiling 1,3-diole?n to produce a normal alkenyl
derivative of said benzene, ‘and subsequently to
the scope of the invention be limited unduly by '
such details.
I claim:
1. A process for the production of normal ali
phatic derivatives of aromatic compounds, which
comprises reacting an aromatic compound with’
hydrogenate this product, in one or more steps, 45 a normal 1,3-diole?n in the presence of a com
to produce a normal alkyl derivative or a corre
plex catalyst resulting from substantially satu
sponding normal alkyl cyclohexane.
a naphthalene may be converted to a normal
rating water with a boron trihalide.
2. A process for the production of normal
alkenyl derivative, and this product may sub
alkyl derivatives of aromatic compounds, which
, sequently be hydrogenated, in one or more steps, 50 comprises reacting an aromatic compound with
to produce a normal alkyl derivative, a normal
alkyl tetralin, or a normal alkyl decalin. For
-a normal 1,3-diole?n in the presence of a com
plex catalyst resulting from substantially satu
such hydrogenations any suitable known nonde
rating Water with a boron trihalide to form .a
structive hydrogenation catalyst may be em
normal alkenyl derivative of said aromatic com- I
ployed which is capable of effecting saturation
of the alkenyl group without saturation of the
pound, separating from e?luents of said alkenyla
tion a fraction comprising said normal alkenyl
derivative, and subjecting said fractionto non
destructive hydrogenation to form a normal al
kyl derivative of said aromatic compound.
aromatic nucleus or without reaction of any
other reactive group in the alkenyl compound.
So-called “Raney nickel” has been found desir3.-A process for the alkenylation of ‘an aro
able in accomplishing this result when the hy
matic hydrocarbon, which comprises reacting a
drogenation is conducted at moderate tempera
tures and pressures. More drastic hydrogena
' low-boiling normal 1,3-diolefin hydrocarbon with
a molar excess of an alkenylatable aromatic-hy
tion conditions will be necessary in order to pro
duce the more saturated products just discussed.
drocarbon under alkenylation conditions in the
Thus, in the selective hydrogenation of the 65 presence of a catalyst resulting from saturating
water with boron tri?uoride.
ole?nic linkage, the rate of absorption of hy
drogen may amount to about 1 mol per hour at
4. The process of claim 3 wherein said diole?n
is 1,3-pentadiene. '
pressures of 20 to 50 pounds per square inch and
temperatures ranging from about '75 to about
5. The process of claim 3 Whereinsaid are-'
150° F. Nuclear hydrogenation can be effected. 70 matic hydrocarbon is naphthalene" and said di
with the same catalyst at pressures of about
ole?n is 1,3-butadiene.
500 to 5000 pounds per square inch and at tem-'
6. A process for the production of a normal.
alkyl benzene, which comprises reacting a mix
peratures of about 250 to 350° F.
The following examples illustrate my inven
tion further. However, it is to be understood
ture comprising a low-boiling normal 1,3-dio1e?n
and a molar excess of benzene under alkenyla
sulting from saturating water" with‘ boron‘ trie
1;3-diole?n*at a reaction temperature between
?uoride to produce a normal monoalkenyl deriva
'tive of benzene, separating from e?iuents of said
alkenylation a fraction comprising said normal
; monoalkenyl derivative, and subjecting said _frac
about '70and about 150° F. and under a‘ pressure
su?icient to maintain the reactants in the liquid
phase, said aromatic hydrocarbon and said di
ole?n' being in a ratio of about 2:1 to 10:1 of
tion to nondestructive hydrogenation under co'n- -
aromatic hydrocarbon to diole?n, in the presence
of a catalyst comprising a liquid complex result
ditionssuch that substantially only said alkenyl
group is saturated with hydrogen. I
alkenyl'aromatic hydrocarbon, which comprises
reactinga'naromatic hydrocarbon with a normal
' , 'tion conditions in the presenceof a catalyst'rei
ing from saturating water with boron tri?uoride,
' 7. The process of claim ?wherein said. diole?n
and‘ maintaining a reaction time between about
is 1,3-butadiene and normal butylbenzene is, pro.
5 and to about 20 minutes.’
8. Theprocess of claim 6 wherein said diole?n
is 1,3-pentadiene and normal'pentylbenzene is,
9.'A process for the production of an aryl
butene, which comprises reacting an alkenylat
able; aromatic hydrocarbon'with 1,3-butadiene at
12._ A process for the ‘production of a normal
alkyl'aromatic. hydrocarbon, which comprises re
15 acting arr-aromatic hydrocarbon with a normal
1,3-diole?n at a- reaction temperature between
about 70 and, about 150° F. and under a pressure
suf?cient to maintain thereactants in the liquid
phase, said aromatic hydrocarbon and said di
a reaction temperature not greater than about
120° F., and with a substantial molar excess of 20 ole?n being in a ratio'of about 2:1 to 10:1 of
aromatic hydrocarbon to diole?n', in the presence
said aromatic hydrocarbon, in the presence, as
of a catalyst comprising a liquid'complex result
a’ catalyst, of a complex resulting from reacting
ing from saturating water with boron tri?uoride;
boron ?uoride with about 1 to about 1.5 molar
maintaining a reaction time between about 5 and
equivalents of-water.
’ '
raboutl20'minutes whereby to form an alkenyl
10. A process for the alkenylation of an arc;
matic hydrocarbon, which comprises reacting'a '
low-boiling-normal 1,3-diole?n hydrocarbon with
aromatic hydrocarbon; and non-destructively hy
drogenating ‘said alkenyl aromatic hydrocarbon
to a normal alkyl‘aromatic hydrocarbon in‘ the
a molar excess of an alkenylatable aromatic hyé
presence of a nickel hydrogenation catalyst at a
drocarbon at a temperature of about '70 to about
150? F. and under sufficient- pressure to maintain 30 pressure ‘of about 20‘ to about 50 pounds’ per
- the reactants in the liquid phase in the presence
of a- catalyst resulting from saturating Water
with boron tri?uoride.
'11.'A process for the production‘ of normal
. square inch and a temperature between about 75
and about 150°-F.
' ~
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