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Патент USA US3090833

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d grates .iiatent @tiice
1
F.
Patented May 21, 1963
1
2
3,999,819
In addition, these prior metalation processes are gen
erally deemed unsuitable for commercialization due to
the dif?culties and 'high costs connected with their use.
TRANSMETALATKUN PROCEEéS
Walter E. Foster, Baton Rouge, La, assignor to Ethyl
Corporation, New York, N.Y., a corporation of
Virginia
N0 Drawing. Filed Feb. 24, 1959, Ser. No. 794,817
12 Claims.
(Cl. 269-665)
This invention relates to ‘a method of preparing organic
compounds and more particularly to the preparation of
aliphatic polyole?n hydrocarbons and organo alkali metal
compounds.
Further, the prior processes require many separate proc
ess steps as well as long periods for appreciable reaction
which at best converts only half of the reactants, e.~g.,
toluene ‘and sodium, to the desired product and com
pletely degrades the chlorine values to sodium chloride.
The above objectionable features of the prior art mate
rialiy increase the overall costs of the desired end prod
uct, and make its manufacture by these processes com
mercially unattractive.
Aliphatic polyole?n hydrocarbons are extremely inter
It is accordingly an object of the present invention to
esting chemical compounds which are readily converted
provide a process for the manufacture of aliphatic poly
into valuable industrial materials by processes well known 15 ole?n hydrocarbons. Another object is to provide a proc
to those skilled in the ‘art. Of particular interest are
ess of the above type which is suitable for manufacturing
those long chain aliphatic polyole?n compotmds Where
a very wide variety of aliphatic polyole?n hydrocarbons,
in the unsaturation is located near the terminal carbons
of the molecular chain. These compounds can easily
be processed to form long chain (4 or more carbons)
polycarboxylic ‘acids, esters, polyglycols, polyaldehydes,
polyketones, polyacetals, polyethers and other polyfunc
including many which were heretofore unknown or not
capable of preparation by prior methods. Still another
object of this invention is to provide for the conjoint
manufacture of an aliphatic polyole?n hydrocarbon and
a metalated organic compound. Another object is to
tional compounds which are of great industrial value.
provide a process of the above character which can be
For example, octa-2,6-diene can be oxidized easily to form
conducted over a relatively broad temperature range. An
succinic acid. Or, if desired, the octadiene can be treated 25 other object is to provide a simpler, more economical
chemically to form the heretofore unavailable 2,3,6]
process of the above type. Other objects and advantages
octatetrol. Heretofore, there has been no known method
of the invention will be apparent from the following
for manufacturing many other similar compounds and the
description and appended claims.
manufacture of numerous known compounds of this type
It has now been found that a wide variety of valuable
has been limited to the use of di?icult and expensive 30 aliphatic polyo-le?n hydrocarbons and organo alkali metal
processes, thereby increasing their cost and limiting their
compounds, which in some cases were previously un
commercial utilization.
known, can be simultaneously prepared by reacting an
The transmetalation of aryl compounds is ‘a well known
organic compound, particularly one having an active hy
chemical process which can be employed to convert rela
drogen, with an alkali metal aliphatic polyole?n com
tively inexpensive and available hydrocarbons into valu 35 pound. Both of these valuable co-product-s have par
ticular utility as intermediates in the production of a
able derivatives, i.e., carboxylic acids and their esters,
polycarboxylic acids and their esters, alcohols, etc. Typi
very wide variety of commercial chemicals and some
cal examples are the formation of phenylacetic acid or
heretofore unavailable chemicals, particularly, certain
phenylmalonic acid and their derivatives from toluene
mono and polycarboxylic acids, esters, alcohols, aldehydes,
and the formation of phenylenediacetic acid from Xylene. 40 nitriles, etc.
These conversion processes are not used presently be
cause of the many disadvantages inherent in their opera
tion. Thus, prior metalation reactions [Industrial and En_
gineering Chemistry 46 No. 3, page 539 (1954)] were
conducted by ?rst chlorinating an aromatic compound,
such as benzene or toluene, to produce the corresponding
chloroaromatic compound i.e. chlorobenzene or chloro
toluene. The chloroaromatic compound was then re
acted with sodium or ‘another alkali metal to form the
More particularly, the process of this invention can
be conducted by initially contacting an organic com
pound containing an active hydrogen, such as aryl,
acetylenic, nitrile, aliphatic carboxylic acid salt or cyclo
dienyl compounds, with an alkali metal aliphatic polyole
?n compound, e.g., disodio octadiene, at a temperature
not greater than about 40° C. in the presence of an ac
tive solvent. If desired, the reaction can be completed
at a temperature below about 40° C. However, in a pre
aromatic alkali metal compound, i.e., phenylsodium. The 50 ferred embodiment of this invention, following the initial
low temperature contact period, substantially all of the
so~formed aromatic alkali metal compound can then be
reacted with substances containing reactive groups, such
as carbon dioxide, sulfur dioxide, nitriles, alkyl halides,
active solvent is removed at a temperature below about
40° C. and the reaction is completed at an elevated tem
perature in the range between about 50° C. and 250° C.
aromatic nitro compounds, acid anhydrides and com
pounds containing reactive hydrogen atoms which are able 55
As a variation in the process, the transmetalation re‘
to be replaced by an alkali metal. For example, reacting
action noted above can be conducted simultaneously with
phenylsodium with toluene and carbonating the product
the formation of the alkali metal aliphatic polyole?n. In
so-formed, results in the formation of the sodium salt
one such method, an active solvent and an alkali metal
of phenylacetic acid which can be hydrolyzed, if desired,
dispersion are added to a reactor equipped with a stirrer
to the free acid. Alternatively, aliphatic halides were re 60 and re?ux condenser. The alkali metal can be dispersed
acted with sodium and the so-formed alkyl sodium com
in an inert solvent, such as isooctane, or, if desired, in
pounds were heated with ‘aromatic compounds to form
the organic compound to be trausmetalated in the process.
the desired aromatic alkali metal compounds by trans
An aliphatic conjugated polyole?n is then added with
metalation.
agitation as a dilute feed stream (usually as a dilute gas
65
These prior metalation processes, however, give as a by
stream) over a period of time to form initially the alkali
product equal molar quantities of (l) the hydrocarbon
metal aliphatic polyole?n, preferably the dimetalated
which was chlorinated in the ?rst reaction of the process
derivative. The organic compound to be transmetalated
and (2) the desired metalated product. The process,
therefore, requires preparation of the desired product from
can be added to the reaction either in whole or in part,
before or during the addition of the conjugated poly
one half can be recovered as a valuable material.
and/or as a diluent for the active solvent. The reaction
large quantities of the ‘starting material and requires 70 ole?n. In some cases, the organic compound can be
employed as the dispersing medium for the alkali metal
handling large quantities of materials, of which only about
3,090,819
4
3
For example, octa-1,6-diene ‘can be reacted with an oxi
dizing agent, such as cold potassium permanganate to
form 1,2,6,7 octanetetrol. Further, octa-1,6-diene can be
reacted with a halogen to produce the corresponding
polyhalide or contacted with carbon monoxide and hydro
gen under certain process conditions to produce Z-methyl
azelaic dialdehyde which can then be oxidized to Z-methyl
then proceeds for a period of time with rapid stirring
until complete. In the preferred embodiment of this
invention, substantially all of the active solvent is re
moved at a temperature below 40° C. following the
addition of at least a part of the organic compound to
the reactor containing the alkali metal aliphatic poly
ole?n compound and the active solvent. The reaction
temperature is then raised to between about 50° and
250° C. in order to complete the transmetalation reaction.
azelaic acid. Similarly, otherpolyfunctional compounds
without prior separations. These subsequent chemical
acid, 3-phenyl pimelic acid, 3,4-diphenyl adipic acid, 4,5
reactions can be conducted in the reaction mixture in
which the organo alkali metal compounds were formed,
diphenyl suberic acid and other similar alcohols, alde
hydes and acids.
Some typical examples of halogenated materials which
can be prepared from the aliphatic polyole?ns obtained'
in this invention are 2,3,6,7 tetrachlorooctane, 1,2,6,7
can be prepared by subjecting the polyole?ns to other
The aliphatic polyole?n hydrocarbon and the organo al 10 well known reactions and further reacting, the’ products
so-formed. Typical examples of other such polyfunc
kali metal compound formed by this reaction can there
tional compounds formed from the polyole?n products
after ‘be separately recovered. If desired, these materials
of the present invention are 2,3,6,7-octanetetrol, 1,2,7,8
can be further reacted chemically to convert them'into
octanetetrol, 2,7-octanediol, adipic acid, Z-methylglutarie,
other valuable materials. Since the organo alkali metal
compounds, formed by this process tend to be unstable 15 acid, 1,2-dimethyl glutaric acid, 2,5-dimethyl adipic acid, ,
2,3,6,7-tetramethyl suberic acid, 3,4-dimethyl pimelic
and di?icult to handle when exposed to air, it is frequent
acid, 4,5-dimethyl suberic acid, 2,3,4,5-tetramethyl adipic
ly desirable to subject them to further chemical reactions
thereby forming other valuable materials whose physical
and chemical properties are such as to facilitate their
separation from the reaction mixture. For example, the
organo alkali metal compound can be reacted in typical
tetrachlorooctane, 3,4,7,8 tetrachlorodecane, 2,3,6,7 tetra
Grignard type reactions with carbon dioxide to give car 25 chloro-4,5 dimethyloctane, 2,3,6,7 tetrachloro-2,3,6,7
tetramethyloctane, 2,3,6,7 tetrach1oro-1,4,5,8 tetraph'enyl
boxylicacids, with sulfur dioxide to give sul?nic acids,
with formaldehyde, epoxides or oxygen to give alcohols,
with cyanogen chloride to give nitriles or used generally
as a Grignard type reagent in reactions with esters, acid
anhydn'des, aldehydes, ketones, halides and nitriles. 'I‘he 30
duces organo alkali metal compounds as valuable co
aliphatic polyole?n hydrocarbons formed in this reaction
products of the above-mentioned aliphatic polyole?n
octane, the corresponding bromo and iodo compounds
and=the like.
As described above, the present invention also pro-7
hydrocarbons. In general, alkali metal substitution com
pounds of an organic compound having an active hydro
and the like.
'
gen, particularly aryl, acetylenic, nitrile aliphatic car
\A wide variety of aliphatic polyole?n hydrocarbons can
be produced by the present invention. Typical examples 35 boxylic acid salt and cyclodienyl compounds or the mono
or polysubstituted derivatives of aryl compounds, can be
of such hydrocarbons are the octadienes, such as octa
can be converted to aldehydes, alcohols, carboxylic acids
1,6-diene, octa-l,7-diene and octa-2,6—diene; the substi
prepared by the process of this invention. These aryl
tuted octadienes, such as 4,5 dimethylocta1,6-diene, 4,5
derivatives, however, should not contain any functional,
groups such as the hydroxy, carboxyl, nitro, halide (other
than ?uoride) and the like groups which are reactive
towards alkali metals. Aryl compounds which are suit
able for forming alkali metal substitution compounds in
dimethylocta-2,6-diene, 2,7 dimethylocta-1,6-diene, 2,7
dimethylocta-2,6-diene, 2,7 dimethylocta-1,7~diene, 3,6 di
methylocta-1,6-diene, 3,6 dimethylocta-2,6-diene, 3,6 di
methylocta-3,6-diene, 2,6 dimethylocta-lJ-diene, 2,6 di
methylocta-2,6-diene, 3,7 dimethylocta-1,6-diene, 2,3,6,7
tetramethylocta - 1,6 - diene, 2,3,6,7 tetramethylocta-1,7
diene, 2,3,6,7 tetramethylocta—2,6-diene 2,3,6,7-tetra-t
butylocta-1,6-diene, 2,3,6,7 - tetra - t - butylocta-1,7-diene,
2,3,6,7-tetra-t-butylocta-2,6-diene,
diene, 1,8 diphenylocta-2,6—diene,
diene, 1,5 diphenylocta-2,6-diene,
diene, 1,5 diphenylocta-l,7-diene,
diene, 4,5 diphenylocta-1,6-diene,
1,8
1,8
1,5
4,5
4,5
dipheny1octa—1,6
diphenylocta-l,7
diphenylocta-1,6
diphenylocta-2,6
diphenylocta-l,7~
diene, 1,4,5,8 tetraphenylocta-1,6-diene, 1,4,5,8 tetra
phenylocta—1,7-die-ne, , 1,4,5,8
tetraphenylocta-2,6‘diene,
45
clude benzene, diphenyl methane, triphenylmethane,
phenylacetylene, acenaphthene, retene, indene, aryl ethers
as, for example, anisole, aryl carboxylic acid salts, aryl
sulfonic acid salts, aryl ?uorides, furan, ?uorene, thio
phene, pyr-role, pyrazole, imidazole, triazoles, tetrazoles,
oxazole, thionaphthene, indole, couman'n, quinoline, cin
noline, naphthyrid-ine, carbazole, thioanthrene, racridine,
50 phenazine ‘and the mono and poly-alkyl derivatives of
these aryl compounds.
Other organic compounds which can be metalated in
this improved process are acetylene and homologues of
acetylene, acetonitr-ile and its homologues, cyclopenta
1,6-diene, 2,3,6,7 tetraphenylocta-l,7—diene, and the like. 55 diene, Z-methylcyclopentadiene, 3-methy1cyclopentadiene,
2,3-dimethylcyclopentadiene, l-methylcyclopentadiene, 3.
Other typical examples of the type of aliphatic polyole?n
2,3,6,7 tetraphenylocta-2,6-diene, 72,3,6,7 tetraphenylocta
hydrocarbons formed by the present invention are 4~
methylnona-2,6-diene, 4-methylnona-l,6-diene, deca—2,7
diene, deca-2,8-diene, deca-3,7-diene, 5,6 dimethyldeca
2,8-diene, 5,6 dimethyldeca-2,7-diene, 5,6 dimethyldeca
3,7-diene, 3,4,5,6,7,8 hexamethyldeca-2,7-diene, 3,4,5,6,7,8
hexamethyldeca-2,8-diene, 3,4,5,6,7,8 hexamethyldeca
3,7-diene, dodeca-2,4,8,10-tetrene, dodeca-l,3,9,1l-tetrene,
dodeca-2,4,9,l1-tetrene, 4 ethenedeca-1,6,8-triene, 4,5 di
etheneocta-1,7-diene, 4 ethenedeca-l,5,7,9-tetrene and
other polyole?ns belonging to the group having a gen
eral formula of CnH2n_2 which heretofore have been
either extremely di?icult and costly to prepare or which
are unknown at the present time.
;Ehylcyclopentadiene, 3-propylcyclopentadiene land the
.
e.
The aliphatic carboxylic acid salts, suitable for use in
60 the process of this invention, are preferably alkali metal
salts ‘and contain from 2 to 20 carbon atoms.
Best re
sults are obtained ‘with monocarboxylic acid salts. Typi
cal examples of alkali metal aliphatic salts are sodium
acetate, sodium propionate, sodium butyrate, sodium hex
anoate, the corresponding lithium and potassium salts
and other alkali metal salts containing up to 20 carbon
atoms.
Typical examples of transmetalated alkali metal com
pounds which can be prepared by the process of this in
The aliphatic polyole?n hydrocarbons prepared by the 70 vention are phenyl sodium, phenyl lithium, benzylsodium,
benzyl potassium, diphenylmethyl sodium, o-anisylsodi
um, p-rnethylbenzylsodium', xylylene disodium, pyrryl
‘ functional compounds such as polycarboxylic acids, poly
sodium, a-naphthobenzyl sodium, sodium acetylide, po
aldehydes, polyketones, polyacetals, polyethers, poly
tassium acetylide, a-sodio acetonitrile, cyclopentadienyl
alcohols, polyhalides, polynitriles, polyamides, polyesters,
polyurethans, polynitro compounds, polyepoxides, etc. 75 sodium, cc-SOdlO sodium acetate, OL-POtBSSllII'l’l potassium '
present invention can be converted to long chain poly
‘spacers
S
5
‘acetate, OL-SOdlO sodium propionate, a-SOdiO sodium cap
‘roate, a-sodio sodium palmitate, a-lithio lithium stearate,
a temperature above about 50° C. in order to complete
etc.
ployed with the higher boiling organic compounds and
the reaction.
In general, higher temperatures are em
temperatures between about '50” .and 250° C. can be
These alkali metal compounds can thereafter be further
reacted to form other valuable materials, as for example, C11 satisfactorily employed, although temperatures between
about 80° and 150° C. are preferred.
phenylacetic acid, p-phenylene diacetic acid, terephthalic
acid, .trimesic acid, and other aryl carboxylic acids.
Further, these alkali metal compounds can be reacted with
The reaction time required to complete the transmetala
tion reaction, while not too critical, is an important factor
in the present invention. Satisfactory yields of the ali
formaldehyde to form primary alcohols, with other alde
hydes to form secondary alcohols, ‘with ketones and 10 phatic polyole?n products are obtained only when the
transmetalation reaction is allowed su?‘icient time to pro
esters to form tertiary alochols, with nitriles to form
ceed to completion. From the chemistry of the trans
ketones and with halogenated compounds to undergo a
metalation reaction, a transfer of two atoms of the alkali
condensation reaction.
metal per molecule of aliphatic polyolefln hydrocarbon
The alkali metal aliphatic polycle?n compounds em
ployed in the practice ‘of the present invention can be 15 formed is involved. it appears that an incomplete trans
metalation reaction normally results in the formation of a
prepared by a variety of processes. As pointed out
monoalkali metal aliphatic polyole?n compound and a
above, in one method of preparing these alkali metal
decreased yield of the desired polyole?n hydrocarbon.
aliphatic polyole?n compounds, a dilute stream of a
This situation is particularly disadvantageous when the
conjugated aliphatic polyene is permitted to react with
?nely dispersed alkali metal in the presence of an active 20 combined reaction product is to be further reacted, e.g.,
by a carbonation reaction. In such cases, not only does
solvent. The alkali metal dispersion is generally pre
the transmetalated compound react with the carbon di
pared by rapidly stirring and then cooling a mixture of
oxide :but any co~present monoalkali metal aliphatic poly
the molten metal and an inert solvent containing from
oleiin undergoes the same reaction to form a product con
1 to 50 percent, and preferably from 5 to 35 percent by
weight of the metal, based on the total weight of the 25 sisting of the alkali metal salt of a complicated mixture
dispersion, thereby solidifying the metal to form particles
having a size generally less than about 50 microns,
preferably less than about 10 microns. Dispersing
known to the art, e.g., oleic acid, dilinoleic acid,
quently can be used. The so-formed alkali metal
persion, consisting principally of the metal dispersed
within an inert solvent, is then mixed with the active
solvent to be used in the polyole?n addition reaction. In
some cases the reaction can be conducted’ in the presence
of a polynuclear aromatic hydrocarbon, such as naph
thalene .or terphenyl, as a catalyst.
The reaction tem
perature is maintained below 40° C. and usually below
0° C.
of carboxylic acids.
When practicing the preferred embodiment of the in
and
vention wherein the reaction is completed at a tempera
aids
ture above 50° C., it is desirable to contact the alkali
fre
dis 30 metal aliphatic polyole?n ‘with the other reactants for a
The reaction proceeds smoothly as the conju
reaction period of not less than about one half hour at a
temperature below about 40° C. followed by a reaction
period of not less than about one hour at a temperature
above 50° C. In the event that it is desired to practice
the low temperature embodiment of this invention, where
in the transmetalation reaction occurs concurrently with
the formation of the alkali metal polyole?n compound,
it is generally desirable and frequently necessary to allow
gated aliphatic polyole?n is added slowly and the alkali
metal aliphatic polyole?n compound usually separates as
the reaction to continue for at least an additional one half
a solid phase. Still another method for preparing these
polyole?n compound, particularly if this reaction period
alkali metal compounds is by reacting the conjugated
aliphatic polyole?n with dispersed alkali metal in the
is less than about 7 hours. This additional reaction
period is particularly desirable if the combined reaction
products are to be subjected to a subsequent reaction,
e.g., carbonation, sulfonation, etc.
Pressure is not too ‘critical in the practice of this in
presence of a mixture of an active solvent and the com
pound containing an active hydrogen with which the
alkali metal aliphatic polyole?n compound is to be re
acted. By this method, the transmetalation reaction of
the present invention can be carried out concurrently
hour following the complete formation of the alkali metal
vention. Pressures above atmospheric can be used if
desired or when necessary to con?ne the solvents when
with the formation of the alkali metal aliphatic polyole?n
compound. In both methods, effective agitation of the
reaction mixture is desirable.
While it is usually preferred ‘to employ sodium or
particularly when it is desired to remove the active sol
vent prior to completing the reaction at an elevated tem
potassium as the alkali ‘metal component of the organo
perature. Generally, however, it is preferred to operate
metallic compound used in the present invention, all of
temperatures above their atmospheric boiling point are
employed. Subatmospheric pressures can also be used,
at atmospheric
ressure primarily ‘as a matter of con
the other alkali metals are suitable. Thus, lithium, 55 venience and ease of operation.
rubidium, cesium and francium can be employed in the
The active solvents suitable for use in the present in
preparation of the alkali metal aliphatic polyole?n com
vention can be selected from the group consisting of
pounds with ‘equally good results.
Mixtures or alloys
of alkali and alkaline earth metals also may be used.
The use of sodium is preferred, however, primarily be
cause of cost and availability.
Although the present invention can be carried out over
a wide range of temperature, the initial reaction temper
ature employed is of importance. Generally, satisfactory
others, acetals and tertiary amines.
A preferred group of others for use in the present in
60 vention include both aliphatic mono- and polyethers. The
preferred monoethers have a CH3-O— group and have
an oxygenzcarbon ratio not less than 1:4. Typical exam
ples of these preferred monoethers are dimethyl ether,
methyl ethyl ether, methyl isopropyl ether, methyl n
results are obtained when temperatures up to about 40° C.
65 propyl ether or mixtures of these ethers. The above
are maintained during the initial stages of the reaction
although it has been found that reaction temperatures
below about 0° C. are preferred and give the best re
sults. Satisfactory results have also been obtained when
operating at temperatures as low as —80° C. In the
preferred embodiments of this invention where it is de
sired to operate at higher temperatures after the initial
reaction period, .the active solvent is removed at a tem
others can also be mixed with hydrocarbon solvents, if
desired.
The preferred polyethers are ethylene ‘glycol diethers,
such as methyl methyl, methyl ethyl, ethyl ethyl, methyl
|butyl, ethyl butyl, butyl butyl, butyl lauryl; diethylene
glycol others, such as methyl methyl, methyl ethyl, ethyl
butyl and butyl lauryl; trimethylene glycol others, such as
dimethyl, diethyl, methyl ethyl, etc; glycerol ether-s, such
perature below about 40° C. and preferably below about
0° C. and the residual reaction mixture is then heated to 75 as trimethyl, dimethyl ethyl, diethyl methyl, etc.; and
3,090,819
7..
cyclic’ ethers, such as dioxane, tetrahydrofuran, methyl,
glycerol formal, dimethylene pentaerythrite.
was quenched with 100 parts of distilled water in apnitro-p
gen atmosphere. The aqueous product solution was sep-,
arated from the isooctane solution and acidi?ed with corn-p
centrated hydrochloric acid to give .a white?occulent
A wide variety of acetals can also be used in the pres
ent invention. Typical examples of suitable acetals are
methylal, 1,1-dimethoxy ethane, 1,1-dimethoxy propane,
product containing the desired phenyl acetic acid. This,
~1,1-dimethoxy butane, methylal glycol formal, methyl
product was distilled under reduced pressure to give 48.3 _
glycerol formal, etc. The preferred iacetals are methylal,
parts of the phenylacetic acid, having a melting point of
methylal glycol formal and methyl glycerol formal.
63° to 70° C. and a neutralization equivalent of 138.
This corresponds to a yield of 71 percent, based on the
invention including both aliphatic and aromatic amines. 10 butadiene reacted. This material was recrystallized to.
The preferred tertiary amines for use in this invention
produce a product having amelting point of 76-77,‘1 C.
A wide variety of tertiary amines are suitable for tins
are trimethyl amine, dimethyl ethyl amine, tetramethyl
methylene diamine and N-methyl morpholine.
The amount of active solvent employed in the reaction"
mixture can ‘be varied considerably without departing 15
from the scope of the invention. The amounts used will
EXAMPLE II
This example illustrates the preferred embodiment of
generally depend on the particular reactants and solvent
used.
The isooctane ‘fraction, above, yielded 16.8 parts of an
isomeric mixture of octadienes with the octa-1,6-diene'
isomer being present as the, predominant isomer.
the process of this invention wherein the reaction is ini
In general, the use of from 100 to 2,000 cc. of
solvent per gram mole of alkali metal aliphatic polyole?n
compound ibeing reacted is recommended as a suitable
reaction dilution. When a diluent is used along with the
active solvent, su?icient active solvent should be present
tiated at a low temperature and completed at an elevated
temperature.
To the reactor of Example I were added 320 parts of
dimethyl ether and 25 parts of sodium having anraverage
particle size of about 10 microns and dispersed in an equal
to have an active promoting effect upon the reaction. In
the speci?c embodiment of the invention wherein the
amount of toluene. Twenty-?ve parts of butadiene were
transmetalation reaction occurs concurrently with the 25 added in a dilute gas stream over a period of 5 hours, dur
formation of the alkali metal polyole?n, it is preferred to
ing which time the reaction temperature was maintained
use a reaction medium which contains a weight of active
at —30° C. The reaction mixture was stirred for an ad!
solvent at least as great as the weight of any co-present
ditional % hour at —30° C. and 260 parts of dry toluene
diluent.
were added.
The reaction mixture was warmed over a
For those reactions in which it is desired to heat the 30 period of one half hour to remove most of the dimethyl
reaction mixture during the ?nal stages of the transmetala
ether solvent at a temperature below 20° C. and the last
tion, it is generally preferred to use a more volatile active
traces of the solvent were removed by heating the mixture ’
solvent so that it can be removed more conveniently.
to 100° C. The mixture was then heated for 2 hours at
The proportion of alkali metal aliphatic polyole?n
compound to the organic compound having an active hy
100° to 105° C. with rapid stirring to prevent charring
drogen varies. over a wide range depending on the com
and then cooled to 0° C. The cooled mxture containingv
benzyl sodium and an isomeric mixture of octadienes
pounds employed and the degree of metalation desired.
was poured on to an excess of crushed Dry Ice to convert ‘
In order to obtain ‘a satisfactory conversion of the alkali
the benzyl sodium to sodium phenyl acetate. The excess
Dry Ice was evaporated and the reaction mixture was
40 quenched with 100 parts of distilled water in a nitrogen
sirable to use at least the required theoretical amount of
atmosphere. The product was separated into an aqueous
the organic compound to be transmetalated. Generally, :
and organic phase. The aqueous phase was acidi?ed with
when monometalation of the compound to be transmeta
concentrated hydrochloric acid to give 50.7 parts of
lated is desired, at least a stoichiometric amount of this
phenylacetic acid, having a melting point of 63° to 770° C.
compound is employed, and frequently it can be present
and a neutralization equivalent of 138.‘ This corresponds
in excess of this amount. Thus, as mentioned above, it
to a yield of 80.5 percent based on the butadiene. The
metal aliphatic polyole?n component to the correspond
ing aliphatic polyole?n hydrocarbon, it is generally de
often can be used conveniently as a reaction medium dilu
ent or as the principal solvent in the latter stages of the
organic phase yielded an isomeric mixture of octa-l,6-_‘
‘diene, octa-1,7-diene and octa-2,6-diene with the octet-1,6
preferred embodiment of the transmetalation reaction
wherein the active solvent is removed prior to bringing
diene isomer largely predominating.
the reaction to completion at an elevated temperature. 50
Where it is desired to polymetalate an organic compound,
it is preferred to'employ substantially about stoichiometric
quantities of each of the reactants, i.e., the alkali metal
aliphatic polyole?n and the organic compound to be trans
metalated.
sults are obtained:
Methyl ethyl ether
Methyl isopropyl ether
Ethylene glycol dimethyl ether
1,1-dimethoxy ethane
Tetrahydrofuran
'
The following non-limiting examples illustrate the
process of the present invention.
All proportions are
given ‘by weight.
‘
EXAMPLE I
A stirred reaction vessel was equipped with a con
denser having a gas inlet tube reaching below the surface
of the reaction mixture. About 250 parts of dimethyl
ether and 17.2 parts of sodium dispersed in 60 parts of
toluene were then added. Twenty-seven (27) parts of
butadiene were gradually added in a dilute gas stream over
a period of 5 hours while maintaining the reaction mix
ture at a temperature of —30° C. The reaction mixture
Was stirred for an additional hour at —-30° C., to com
EXAMPLE III
When any of the following active solvents are employed
in the processes of Examples I and II, similarly good re
60
Dioxane
Methyl glycol formal
Trimethyl amine
Methyl diethyl amine
Tetramethyl methylene diamine
EXAMPLE IV
Example I is repeated except that p-xylene is metalated
instead of toluene. In this example, 26 parts of p-xylene are employed instead of the 60 parts of toluene. Similar
plete the conversion of toluene to benzyl sodium and 70 yields are obtained except that p-phenylene diacetic acid
is obtained as a product instead of the phenyl acetic acid
the formation of an isomeric mixture of octadienes. There
of Example I.
'
after, 290 parts of isooctane were added and the mixture
EXAMPLE V
was poured on to an excess of crushed Dry Ice to con
vert the benzyl sodium to sodium phenyl actate. The
The following runs are typical examples of the wide
excess Dry Ice was evaporated and the reaction mixture 75 variety of aryl compounds which can be metalated by the T I p
3,090,819
9
16
present invention. The apparatus and method of Ex
amples I and II are used except that the aryl component
is varied. Similar results to those of Examples I and
ample, 34 parts of cyclopentadiene are used. The yield
of products obtained is similar to Example XI. S-car
boxy-1,3 cyclopentadiene and an isomeric mixture of
II are obtained in each case.
octadienes are obtained as products.
When sodium is replaced with other alkali metals or
mixtures containing a major proportion of an alkali metal
Table I
Aryl compound:
Aryl acid obtained
such as lithium, potassium, cesium, rubidium, franciuni,
Benzene ____________________ _. Benzoic acid.
alloys of sodium and potassium or sodium and calcium,
Mesitylene __________________ __ Trimesic acid.
substantially identical results are obtained as in the ex
Anisole____________________ __ Anisic acid.
Indene _____________________ _- l-carboxy-indene.
10
amples given above.
Equally good results are obtained when l-methylbuta
diene, Z-methylbutadiene, 1,2-dimethylbutadiene, 1,3-di
EXAMPLE VI
Example I is repeated except that 2,3-dimethylbutadiene
methylbutadiene, 1,4 - dimethylbutadiene, 1,1,4,4 - tetra
methylbutadiene, 2,3-di-t-butylbutadiene, 1-phcnylbutadi—
is employed in place of the butadiene and in the same 15 ene, 1,2-diphenylbutadiene, 1,3-diphenylbutadiene, 1,4~
molar proportions. A similar yield of the phenylacetic
acid and the isomeric mixture of tetramethyloctadienes
is also obtained.
EXAMPLE VII
Example II is repeated except that cumene is used in
stead of toluene. In this example a total quantity of
325 parts of cumene are added to the reactor.
More
diphenylbutadiene, 1,3,5-hexatr'iene and 1,3,5-heptatriene
are employed in the above reactions as the conjugated
polyene reactant.
Similarly, when o-xylene, m-xylene, 1,2,3~trimethyl
benzene, 1,2,4-trimethylbenzene, a-methylnaphthalene, B
methylnaphthalene, diphenylmethane, acenaphthene, phe
nylacetylene, pyrrole, indole, quinoline, ?uorene, retene,
propionitrile, acetylene and Z-methyl cyclopentadiene are
over, following the removal of the active solvent, the re
employed as the reactant to be transmetalated, the corre
action mixture is heated for two hours at 140° C. instead
of the 100° to 105° C. used in Example II. A satisfac 25 sponding metalated compound or its reaction product is
tory yield of p-isopropylbenzoic acid and an isomeric
mixture of octadienes are obtained.
EXAMPLE VIII
readily recovered in good yields.
Similarly good results are obtained over a wide range
of reaction temperatures. Reaction temperatures as low
as —80° C. and as high as 40° C. give good yeilds of
Example II is repeated except that after completing the
aliphatic polyole?n hydrocarbons and transmetalated
reaction the cooled reaction mixture is contacted with a
stream of dry sulfur dioxide until the acid reaction to
compounds when employing the low temperature process
of this invention. In the preferred embodiment of the
process of the invention, wherein the solvent is removed
Congo paper disappears and the mass is further Worked
up as described in Example II. a-Toluenesul?nic acid
at a temperature below about 40° C. prior to complet
and an isomeric mixture of octadienes are obtained in 35 ing the reaction at an elevated temperature, uniformly
satisfactory yields.
good results are obtained when subsequent reaction tem
EXAMPLE IX
Example II is repeated except that upon completing the
reaction, the reaction mixture is treated with excess 40
benzonitrile. When the reaction is complete, the whole
peratures as low as 50° C. and as high as 250° C. are
employed to complete the reaction.
EXAMPLE XIV
mass is stirred for an hour at room temperature, then
Example I was repeated except that sodium metal,
poured into water and the organic phase is separated,
boiled with dilute hydrochloric acid, cooled and extracted
with ether. On distilling the ether extract, desoxybenzoin
butadiene and sodium acetate were reacted in ethylene
glycol dimethyl ether at 50° C. The sodium acetate was
and an isomeric mixture of octadienes are obtained.
metal. The OL-SOdlO sodium acetate Was produced in 92
percent conversion. Similar results are obtained with
EXAMPLE X
Example II is repeated except that upon completing
employed in equal molar proportions with the sodium
lithium and potassium metal and with the corresponding
alkali metal salts of propionic, butyric and other acids
the reaction, the reaction mixture is treated with an
containing up to 20 carbon atoms.
excess of formaldehyde. The mixture is cooled, hy
drolyzed with dilute hydrochloric acid and the resulting
mixture is extracted with ether. On distillation of the
ethereal extract, phenethyl alcohol and an isomeric mix
As is believed apparent from the above, the present
invention provides a means of economically producing
a wide variety of aliphatic polyole?n hydrocarbons and
metalated compounds, many of which have heretofore
ture of octadienes are obtained.
been unavailable. More particularly, these aliphatic poly
EXAMPLE XI
Example I is repeated except that methylacetylene is
metalated instead of toluene. In this example, 60 parts
of isooctane are present in the reactor as the dispersion
ole?n hydrocarbons and metalated compounds can be
produced conjointly and over a relatively broad reaction
temperature range. From the above, it is apparent that
by varying the conjugated polyene or the compound to
be transmetalated in the process, a wide spectrum of
medium for the sodium and 22 parts of methylacetylene 60 aliphatic polyole?n hydrocarbons and metalated com
are employed instead the 60 parts of toluene. An equally
pounds can be produced as desired. The products can
satisfactory yield of tetrolic acid is obtained as well as
be used as important chemical intermediates in the manu
a comparable yield of the isomeric mixture of octadienes.
facture of valuable polymeric materials, plasticizers, syn
thetic detergents, anti-foaming agents, solvents, adhesives,
EXAMPLE XII
65 and many other valuable materials.
Example X1 is repeated except that acetonitrile is
This application is continuation-in-part of application
metalated instead of methylacetylene. In this example,
Serial No. 448,773 ?led August 9, 1954, now abandoned.
21 parts of acetonitrile are employed and the yield of
I claim:
products obtained are similar to those obtained in the
1. A transmetalation process for preparing aliphatic
other examples. Cyanoacetic acid and an isomeric mix
polyole?n hydrocarbons containing at least 8 carbon
ture of octadienes are recovered as products.
atoms and organo alkali metal compounds simultane
ously, which comprises reacting (a) a dialkali metal poly
EXAMPLE XIII
ole?n compound containing at least 8 carbon atoms with
Example XI is repeated except that cyclopentadiene is
(b) an active hydrogen-containing organic reagent ca
employed as the material to be metalated. In this ex
pable of forming an alkali metal derivative thereof,
3,090,819
12
11s
selected from the group consisting of (1) aryl hydrocar-p
toward alkali metals, said dialkali metal polyole?n being
bons, (2) acetylenic hydrocarbons, (3) cyclodienyl hy
drocarbons, (4) aryl ethers, (5) aryl ?uorides, (6)
an octa to dodeca polyene having an unsaturation ranging
alkali metal salts of monocarboxylic acids containing
between about 2 through 20 carbon atoms, and (7) sub
from dienes to tetraenes, said reaction being initiatedat
a temperature not greater than about 40° C. inva reaction
_ medium comprising an ether selected from the groups
' consisting of aliphatic mono ethers having a methoxy
group and an oxygen to carbon ratio of not less than 1:4,
stituted hydrocarbons, wherein the sole substituent is a
nitrilo group; which reagents are free from functional
groups which are reactive toward alkali metals, said
and polyethers derived from aliphatic polyhydric alcohols‘
having all of the hydroxyl atoms replaced by alkyl groups
dialkali metal polyole?n hydrocarbon being an octa to
dodeca polyene and having an unsaturation ranging from
and mixtures thereof.
'
'
6. A transmetalation process for the simultaneous prep
aration of an aliphatic polyole?n hydrocarbon containing
dienes to tetraenes, said reaction being initiated at a
temperature not greater than about 40° C. in a reaction
at least 8 carbon atoms and an organo alkali metal com
medium consisting essentially of a solvent selected from
pound which comprises reacting (a) a dialkali metal poly
the group consisting of ethers, acetals and tertiary
amines; and recovering said polyole?n hydrocarbon and
, ole?n with (b) an active hydrogen-containing reagent ca
an alkali metal compound of said organic reagent as
pable of forming an alkali metal derivative thereof, se
lected from the group consisting of (1) aryl hydrocarbons,
(2) acetylenic hydrocarbons, (3) cyclodienyl hydrocar
2. A transmetalation process for preparing aliphatic
bons, (4) aryl ethers, (5) aryl ?uorides, (6) alkali metal
polyole?n hydrocarbons containing at least 8 carbon atoms
and organo alkali metal compounds simultaneously, which 20 salts of monocarboxylic acids, containing between about
2 through 20 carbon atoms, and (7) substituted hydrocar
comprises reacting (a) a dialkali metal polyole?n com
bons wherein the sole substituent is a nitrilo group, said
pound with (b) an active hydrogen-containing organic
reaction being initiated at a temperature not greater than
reagent capable of forming an alkali metal derivative
about 40° C. and in dimethyl ether.
,
thereof, selected from the group consisting of (1) aryl hy
products of the reaction.
.
drocarbons, (2) acetylenic hydrocarbons, (3) cyclodienyl
hydrocarbons, (4) aryl ethers, (5) aryl ?uorides, (6) al
kali metal salts of monocarboxylic acids containing be
tween about 2 through 20 carbon atoms, and (7) sub
stituted hydrocarbons wherein the sole substituent is a
25
7. A transmetalation process for the simultaneous prep
aration of an aliphatic polyole?n hydrocarbon containing
at least 8 carbon atoms and an organo alkali metal com
pound which comprises reacting (a) a dialkali metal poly-~
ole?n hydrocarbon compound with (b) an active hydro
nitrilo group; which reagents are free from functional 30 gen-containing reagent capable of forming an alkali metal
derivative thereof, selected from the group consisting of
groups which are reactive toward alkali metals, said di
(l) aryl hydrocarbons, (2) acetylenic hydrocarbons, (3)
alkali metal polyole?n being an octa to dodeca polyene
cyclodienyl hydrocarbons, (4) aryl ethers, (5) aryl ?uo
and having an unsaturation ranging from dienes to tet
rides, ( 6) alkali metal salts of monocarboxylic acids con-_
raenes, said reaction being initially carried out at a tem
perature not greater than about 40° C. in a reaction 35 taining between about 2 through 20 carbon atoms, and
( 7) substituted hydrocarbons wherein the sole substituent
medium consisting essentially of a solvent selected from
is a nitrilo group, said reaction being initiated at a temper
the group consisting of ethers, acetals and tertiary amines,
ature not greater than about 0° C. and in a reaction me
removing substantially all of said solvent at a temperature
dium comprising an ether selected from the groups con
below about 40° C. and thereafter increasing the reaction
sisting of aliphatic mono ethers having a methoxy group
temperature to between about 50° C. and 250° C. to com
and an oxygen to carbon ratio of not less than 1:4 and
plete the said transmetalation reaction.
3. A transmetalation process for preparing aliphatic
polyole?n hydrocarbons containing at least 8 carbon atoms
and organo alkali metal compounds simultaneously, which
comprises reacting (a) a dialkali metal polyole?n com
pound with (b) an active hydrogen-containing organic re
agent capable of forming an alkali metal derivative there
of, selected from the group consisting of (l) aryl hydro
polyethers derived from aliphatic polyhydric alcohols hav
aration of an aliphatic polyole?n hydrocarbon containing
reacting in approximately equimolar proportions disodium
at least 8 carbon atoms and an organo alkali metal com
octadiene with sodium acetate in an ethylene glycol di
ing all of the hydroxyl hydrogen atoms replaced by alkyl '
groups and mixtures thereof.
8. A process for the simultaneous preparation of octa-'
diene and benzyl sodium which comprises reacting diso
dium octadiene with toluene in a dimethyl ether reaction
medium, said reaction being initiated at a temperature not
greater than about 40° C. and thereafter recovering octa
carbons, (2) acetylenic hydrocarbons, (3) cyclodienyl hy
drocarbons, (4) aryl ethers, (5) aryl ?uorides, (6) alkali 50 diene and benzyl sodium as products of the reaction.
9. An improved process for the preparation of benzyl
metal salts of monocarboxylic acids containing between
sodium comprising reacting disodium octadiene with at
about 2 through 20 carbon atoms, and (7) substituted
least a stoichiometric quantity of toluene in a reaction me
hydrocarbons wherein the sole substituent is a nitrilo
dium consisting essentially of a solvent selected from the
group, said reaction being initiated at a temperature not
group consisting of ethers, acetals and tertiary amines, said
greater than about 40° C. in a reaction medium consist—
reaction being initiated at a temperature not greater than
ing essentially of a solvent selected from the group con
about 40° C., completing said reaction to form benzyl
sisting of ethers, acetals and tertiary amines; and recover
sodium.
ing said polyole?n hydrocarbon and alkali-metal com
10. The process of claim 9 wherein the solvent is di
pound of said organic reagent as products of the reaction.
4. The process of claim 3 further de?ned wherein the 60 methyl ether.
11. A process for the simultaneous preparation of octa
dialkali metal polyole?n is disodiumoctadiene.
diene and alpha-sodio-sodium acetate which comprises
5 . A transmetalation process for the simultaneous prep
pound which comprises reacting (a) a dialkali metal poly 65 methyl ether reaction medium at a temperature of about
50° C., and thereafter recovering octadiene and alpha
ole?n compound containing at least 8 carbon atoms with
sodio-sodium acetate as products of the reaction.
(b) an active hydrogen-containing organic reagent ca
pable of forming an alkali metal derivative thereof, se
lected from the group consisting of (1) aryl hydrocarbons,
12. A transmetalation process for simultaneously pre
paring octadiene and an alpha-sodio-alkali metal salt of an
(2) acetylenic hydrocarbons, (3) cyclodienyl hydrocar
aliphatic monocarboxylic acid which comprises reacting
bons, (4) aryl ethers, (5) aryl ?uorides, (6) alkali metal
disodium octadiene with an alkali metal salt of an ali
phatic monocarboxylic acid in an active solvent selected
from the group consisting of ethers, acetals and tertiary
amines, and thereupon recovering the octadiene and the
bons wherein the sole substituent is a nitrilo group; which
reagent is free from functional groups which are reactive 75 alpha-sodio~alkali metal salt of an aliphatic monocar
salts of monocarboxylic acids containing between about
2 through 20 carbon atoms, and (7) substituted hydrocar
"3,090,819
13
14
boxylic acid as products of the reaction; said reaction
being initiated at a temperature not greater than about
2,171,867
2,171,871
2,773,092
2,816,917
2,881,209
40° C., said alkali metal salt of an aliphatic monocar
boxylic acid containing from 2 to about 20 carbon atoms
in the molecule and said disodiurn octadiene being formed
by reacting butadiene with sodium in an active solvent as
hereinabove de?ned.
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,934,123
2,023,793
Hoffman et a1 __________ __ Dec. 7, 1933
Scott ________________ __ Dec. 10, 1935
‘
_
_'
Scott et a1 _____________ .__ Sept. 5, 1939
Walker _______________ __ Sept. 5, 1939
Carley et a1 ____________ __ Dec. 4, 1956
Hansley et a1. _., ____ __'___ Dec. 17‘, 1957
Nobis et a1. ___________ __ Apr. 7, 1959
OTHER REFERENCES
Morton et al.: “Jour. Am. Chem. Soc.,” vol. 69, pp. 160
(1947).
10
Coates: “Quart. Reviews” (London), vol. 4, pp. 217
235 (1950), p. 220 only needed.
Hansley: “Ind. & Eng. Chem,” vol. 43, No. 8, August
1951, pp. 1759 to 1766.
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