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Патент USA US3059040

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United States Patent O? ice
Patented Oct. 16, 1962
or carbon monoxide is vented to the atmosphere at the
end of the reaction.
The essential catalyst used in the processes of this in
vention comprises at least one halide of a group VI-III
noble metal of an atomic number 44 to 78. By the term
Thomas Alderson, Wilmington, DeL, assignor to E. I.
du Pont de Nemours and Company, Wilmington, Del,
a corporation of Delaware
“halide” is meant to include the chlorides, bromides, and
iodides. The group VIII noble metals of atomic numbers
44 to 78 are ruthenium, rhodium, palladium, osmium,
No Drawing. Filed Jan. 18, 1960, Ser. No. 2,840
2 Claims. (Cl. 260-597)
This invention relates to new and valuable procedures
iridium and platinum. Examples of halides of such
for the preparation of pentanone-3 employing group VIII 10 noble metal include ruthenium dichloride, ruthenium tetra
noble metal halides as catalysts.
There are many known methods for preparing ketones.
chloride, ruthenium triiodide, platinum tetrachloride,
platinum tetraiodide, palladium dibromide, osmium di
chloride, osmium trichloride, iridium tetrachloride, irid
Among such are acylation of hydrocarbons, oxidation of
secondary alcohols, catalytic dehydrogenation of second
ium tetrabrornide, iridum triiodide, and the like. The
ary alcohols, ozonolysis of ole?ns, thermal decarboxyla 15 preferred catalysts, because of their general availability
tion of acids, interaction of anhydrides with organometal
and solubility in water, are the noble metal bromides and
lic reagents, interaction of organometallic reagents with
ethers, hydrolysis of ketone derivatives, etc. Some of
these methods are of laboratory interest only, and others
are of limited applicability.
Because of the great ex
The valence of the noble metal in the halide catalyst
is not critical. Thus, the valence of the noble metal
20 can be in its highest state or in _a lower state.
Instead of
pansion in the industrial use of protective coatings based
on cellulose derivatives which has taken place during the
using a noble metal halide in which the noble metal is in
last few years, the demand for pentanone-3 for use as a
noble metal halides, in which the noble metal is in dif
only one state of oxidation, a mixture of one or more
solvent in preparing and using such compositions has in
ferent valence states, can be used. Similarly, the noble
creased greatly. This has stimulated interest in the dis 25 metal halide need not be in an'anhydrous form. In fact,
covery of a new and different route for cheaply mak
the hydrated forms are preferred, particularly because
ing this important chemical from readily accessible and
they are commercially available and because the reaction
relatively inexpensive intermediates. This invention pro
is carried out in an aqueous medium.
vides such a route.
As actually used in the processes of the invention,‘ the
According to the methods of this invention, penta 30 group VIII noble metal halide is initially in aqueous
none-3 is produced by reacting ethylene with carbon
solution. The amount of water used with the reactants,
monoxide and water at temperatures above 100° C. and
pressures of at least 100 atmospheres in the presence of
as indicated above, is suf?cient to dissolve at least 0.00001
mole of at least one group VIII noble metal halide, as
a catalyst composed of at least one halide of a group
is desired in order to practice the present invention.
VIII noble metal of atomic number 44 to 78.
35 Naturally, it is preferred to use halides having a ?nely
To practice this invention, one employs as essential
divided physical form to permit them to go into solution
reactants a mixture of water, carbon monoxide, and
rapidly, as a matter of convenience.
ethylene. This mixture consists of ethylene, carbon
:It has been found that the ellectiveness of the noble
monoxide and water in such proportions that the
metal halide catalyst is enhanced by including in the noble
40 metal halide an organic derivative of a group V element
of atomic number 7 to 83, in the trivalent state. Such
group V elements include nitrogen, phosphorous, arsenic,
antimony, and bismuth. Thus, such organic derivatives
include compounds of the general formula
and CO under the process conditions of this invention
react in a 2:1 mole ratio. At least su?icient Water is
present in the reactant mixture to provide 1 mole of
45 (2)
hydrogen per mole of ethylene.
In other words the quantities of respective starting
materials used is always su?ioient to produce pentanone-3,
in which M is the group V element and R, R’, and R”
as schematically shown below:
are monovalent hydrocarbon radicals such as aryl, cyclo
021850 02H,
(from water)
50 alkyl, and alkyl radicals, preferably of 1 through 18 car
Thus, the Water is used in amounts su?'icient to provide
at least 1 mole of hydrogen per mole of ethylene. There
is no critical upper limit on the amount of H20 which 55
can be present.
‘In fact the water can be used as a pre
bons with the proviso that when M is nitrogen, the R’s
can form a heterocyclic structure with such nitrogen.
Examples of such compounds are tricresylphosphine, tri
tolylphosphine, trixylylphosphine, dimethylphenylarsine,
imethyldioctylarsine, dirnethylethylamine, triphenylamine,
dimethylcyclohexyla-mine, pyridine, quinoline and the
ferred reaction medium in which to effect contact be
Preferred compounds of Formula 2 are those Where
tween the ethylene and carbon monoxide in the presence
the aryl group is phenyl or tolyl; the cycloalkyl group is
of the group VIII noble metal halide catalyst.
Broadly, there is no critical or necessary relationship 60 lmethylcyclohexyl, cyclohexyl, cyclopentyl, or cyclobutyl;
between respective quantities of CH2=CH2 and CO
which must be present in the initial charge to the reactor
and the alkyl group is methyl, ethyl, propyl, butyl, decyl
or octadecyl. A preferred heterocyclic compound is pyri
dine. Most preferred organic derivatives of Formula 2
to make the processes of the present invention operative.
are pyridine, quinoline, and triphenylphosphine.
However, a practical and preferred way for attaining
the theoretical mole ratios of ethylene and carbon mon 65 The amount of group VIII noble metal halide catalyst
used is generally at least about 0.00001 mole per mole
oxide necessary for obtaining pentanone-3, according to
of ethylene reactant. In general also, one will usually not
this invention, is by using a mixture of ethylene and car
employ more than 0.1 mole of group VIII halide catalyst
bon monoxide in 1:1 mole ratio. Alternatively, the
per mole of ethylene, although the upper limit is not sig
CHFcHz or CO can be charged individually or sep
arately into the reactor, and an initial excess of one or 70 ni?cant.
the other of these reactants (with respect to the other)
When the catalyst isra mixture of halides of group VIII
can be charged to the reaction. Any unreacted ethylene
noble metals and organic derivatives of group V elements,
13:3 L‘
.312 .
. . weight” the. volumev .o? ..the..reactor.
the amount of groupvlmlnoblemetal halideswillbeatv
least 0.00001 mole per mole of ethylene and the amount
of organic vderivatives of group V element will be at least
the gas as in 1:1 mole ratiofunless otherwise speci?ed.
0.00001 moleper‘m'ole of ethylene; : Inthecatalyst mix.
Example 571
. ture the mole ratio of halide of groupVHl noble metal
This’ illustrates the inoperativenesslof a group VI-II base
‘metal halide‘ as a catalyst for the reaction of- ethylene, car
to' organic derivative ‘of group N" element iszfrom ‘about
‘bon‘monoxide', and' water 'to producepentanoneé} ‘
.§.-1Breferred catalyst combinations, r as: indicated, > are .the
group-‘VIII metalichlorides and-bromides'?with pyridine,
quinoline, and-triphenylphosphine.1v 1.
400 .mL, . and the
7 ethylene-carbon monoxide gas mixture employed contains
A pressure reactoris charged with. 125' parts of‘water
10 and" 0.91 part ot‘lniqlgelchloridekhexahydfate. ‘ time re
actor is cooled, evacuated, pressured with a 1:11 ethylene
.. Compounds;of:-Formula- 2' are sut?ciently solublein
carbon» , monoxide , mixture, _ and heated .at. 1 1805200 >": C.
water that-“using the indicated mole ratiotof group- VIII
and 750<1000.,atm,1for 10, :hours..-; A pressure, drop of 10
noblenmetalz-ihalideto the saidiorganic'derivatives, the
atm. is recorded during this'period.» There, is recovered
combination is soluble in the starting water to the desired
15 from: ‘the . reactor ' 115 parts ; of clear, . light, yellow liquid;
extent) of {at least-0.00001 mole 'pervmole- of ethylene.
,nD25, 1.3359 (water, nD2°~,-1.3329.), which whenanalyzed
processes ofdtheinvention can,"-in general, ‘be con
by. gas chromatography; shows only one peak on analu
any conventional pressure apparatus; 1+ - .
mina-packed column at 6.5 minutes. Thus, this product
7 ' This inventionican be practiced by heating the reactant
is -.,not: .pentanone-3,1 especially becausexdistilledrwater
batchwis'e, semi-continuously, or continuously =in~>any suit‘
shows. av peak at26.5 minutes on the .samejcolumn. 1 ._
able pressure resistant vessel, e.g., an autoclave, or tubular
converter preferablyllined with an inert material such as
glass, porcelain,vsil'ver, stainless steel, ‘etc. ‘ Iniacontinu
' ousprocessythe-reactants may v‘be introduced: at one or ' ‘
more points within- the 'reaction-vesseL- -'In‘ certain in
stances, it£is=better to employ a tubular reactor in'which
temperature; and pressure are‘ not uniform throughout'the
length of the'vvessel.
' ~This example illustrates that‘pyridine is ineffective in
activating. a group
base metal as: acatalyst .for .the
formation of pentanone-S fromOHF-OHR, O0; and H20.
- The above; wprocedureisnrepeatedi using 130 parts of
water, alongr- with 0.91 ~ part --of-' ‘nickels: chloride’ hexa
hydrate and 1.‘5~lparts~of_ pyridine;v Again apressure
drop of __10.atm. visobserved- during thereaction period.
There are recovered-fromthei reactor 127= parts of: clear
liquid,- 7711325,, 1.3400, andlapproximatelysthree parts of
brown, sticky oil, 111,25 1.5025.’ The clear liquid is anal
!In the stoichiometrywif ‘the ‘reaction of formation of "
pentanone-3, the ethylene and carbon monoxide appear
to react in 2:1 mole ratio; " In‘th‘e overall reaction, how- '
ever, additional carbon monoxidemay be required to react
with‘thel water-'Etogive carbon dioxide ‘and-the vneeded
yzed by ‘gas chromatography- onWan alumina-packed ‘col
hydrogen. ' i'l'he‘plausibility of thellatte'r ‘reaction as :the ‘
11mm»: A?single absorptionlpeakiis observed-at 67.5 min.
sourcezo'f the hydrogen-in thisv synthesis is indicatedjby'the
utes. ~Distilledwaterishowsasingle peak at 6.5 ‘minutes
identi?cation of; carbon “dioxide; in‘ the'bleedgases - from
when ‘analyzed on this -c01umn.'~-.This"r'esult shows that
the "reactorfwhemcarbon- 'monoxide‘- is heated with water
pyridine has. noie?ect- in 'promoting'the catalytic prop
erties of nickel chloride in the reaction vof ethylene,'car
'in' the presence’of say' iridium*trichloride trihydr'atel-l In
practice their'eiactorcantbe charged‘withlwater Y'andj-the‘n '
hon-monoxide,‘ and :water to-produce pentanone-3. -
pressured-witha? :-1 mole ratio or 'ethyle'neécarbon‘mom
oxide gas mixture in tsuche‘anio‘unt‘ that the internal ‘pres;
‘sure-‘is at Vleasti100'atmo‘spheres,’ preferably'at least 200
V A pressure reactor is charged with-100 partseot Water,
‘ atmospherés?-As a‘rul'e,'thereis'ndpracticaP advantage
1.04 parts of a commericallmixture of ruthenium chlo
in'o‘peratin‘g rfat 'lpfess'ures'above 3000-‘ atmospheres: ‘-_' "°'
rides containing 81% RuCl4-H2O and 19% RuCl3-3H2O,
45 and; 1.2 parts OfpPy-Iidine-ZSIIhe'IeKCtOLjS cooled, evacu
ated,;~and;pres_sureduwith a 1:1: carbon; monoxide-ethyl
temperatures ‘which are ‘at least 100°C. “Generally,- there
ene; mixtures {The reactants.v are; heated; at‘ 195420", ~- C,
is no practical merit-in-'usingitemperatures above 350°-'C. _
under 550-650 atm. pressureior; 10 hours.-;;During,this
'and this represents the practical operating'temperatur'e.
time a pressure drop of 705;,31111-318 or‘t>,serv.ed;.v -_§There is
Since outstanding resultsare realized using temperatures
o£>150° to-300° (2., the process is most generallyoperated 50 recqveredlfroml thezreactoni? 1: parts of liquid; consisting
Thereaction of ethylene, carbon monoxide, and water
is conducted‘ in the presenc'e'ofit-he aforesaid ‘catalysts at
in this’ran'ge.
of a clear red-brown top phase;and;>aclear colorless. bot
tom phase. ‘This product'is distilled through a 12-inch
' '
“The noblem'etal
water,‘ 'and'c-a'rbon
niqué Tmonoxideto'
duce' pentanon'eQBi. ,‘Ihps, 'ifjthé' nQBIe‘InetaI'fLaLide 'is
replaced by a’halide of'a base metalibf group VH1 ‘alone
or jaf?xtur‘e with‘an organic derivative‘ o‘f-a group'V
reaction pfdductf 2'. "
distilling column and a total of 136 parts, of distillate,
boiling at 30+64° C./ 3 immrpressure; and v7» parts of black
residue is obtained. The distillate is Washed with two
times its .volume ; of 1 concentrated. aqueous calcium chlo
ride solution and; 69 pa11s...of.-organic; P11886518 recovered.
Thiszmaterial isiractionallyzdistilled to ,yieldAO parts of
product boiling. at 9.9e-102“ :C.~,~,n 25=1.3901, ~. and: with
""In‘oiie embodiment "or ‘this’ inven'uema pressure ‘rel
actor. is charged with water 'and- catalyst.,_ fIhe reactor 60 the characteristic, infrared, absorption] vspectrum -of penta
none-3_. This structuredist con?rmed 'by preparing the
is then cooledv to 0°C. or lower, evacuated, and 1:1‘ mole
ratio ethylene-'carbon'monoxide' mixedfgasds‘lthe‘n "in_- I 2,4-dinitrophenylhydrazone, MP; 156'’ C., and making
jected'in amount such‘ that am’oof’ ‘C; the *pr‘essure'within
the reactoris'at least 100 atmospheres.‘ The charge is’agi
a' mixed meltingpoint determination with the 2,4:dinitro
phenylhydrazonepf.authentic;pentanone-3;l “There is no‘
65 depression in themeltingpoint; 3. There is also obtained
tatedjandi maintained '- at 'the'ftemperature ‘selected for re
25 'parts, .of product, B.P.~ .85-..-919.C;/,.which, has
7 action with periodic mamas-er ethylene-carbon monoxide
mixed gas :toi'c'ompensatei ‘for
consumed‘ the‘ reac . the characteristic int'r'a'redv absorptionlspectrum of .pro
tion: “"i'l‘hese‘conditions are‘ maintained
there'is no ":7 pionic acid, and. 5. parts of higher boiling organic mate
,furtheripressure drop; Thereafter, the reaction mixture
is allowed to fcooljthe reactor ‘is vopened;andthe contents 70 »" 'Re‘petition'i of. the -'above procedure" ‘using triphenyl
are" discharged-‘The desired {pentagon-3- i's'isolated by 7 sti'binein‘nplace'of pyridine gives similar results. a
distillation ‘of Qrhernie'ans'know? to'those Iskill‘ed'in the _’
and valuable advantages ‘ofi'this "'v'e'ntionli?
i, >Q;Exqmple 41,...“
; l.
7 The procedure'o'f Example 3 is followed with a ‘charge
are by 75 consisting of 1'00'parts' of water,“ ‘1.0215 parts" of rhodium
'(Ihe' examples
_.which. follow‘furt"
- I xh‘er illustrate
l.the :unique
trichloride trihydrate, and 1.5 parts of pyridine. The
and pressured with a 1:1 carbon monoxide-ethylene mix
reactor is cooled, evacuated, and pressured with a 1:1
carbon monoxide-ethylene mixture. The reactants are
heated at 174-200" C. and 500—600 atm. for 1.5 hours.
During this period, a pressure drop of 840 atm. is ob
served. From this reaction there is obtained 200 parts
ture. The reactants are heated at 160—180“ C./ 500-600
atm. for 10 hours, during which period a pressure drop
in excess of 1040 atm. is observed.
There is removed
from the reactor 203 parts of two-phase liquid consisting
of a dark red-brown top phase and clear colorless bot
of products consisting of a clear red-brown top phase
tom phase. This two-phase liquid is distilled through a
and a clear colorless bottom phase. The product is dis
12-inch distilling column to yield 179 parts of two-phase
tilled through a 12-inch distilling column to yield 182
distillate, boiling range 30-76“ C./ 3 mm. The aqueous
parts of distillate, boiling range 20—68° C./ 3.5 mm. and 10 phase is saturated with sodium chloride and 125 parts of
7 parts of black viscous residue' From the distillate there
organic phase, nD25=1.3982, is separated. A residue
is separated 116 parts of organic phase which is dried
of 10 parts of tar is also obtained. The organic phase is
over anhydrous magnesium sulfate and fractionally dis
again fractionally distilled to yield 80 parts of pentanone
tilled. ‘From this distillation there is obtained 93 parts
3, B.P. 100-102° C., nD25=1.3903, identi?ed by its in
of pentanone-3, B.P. 100° C., nD25=l.3889. This struc 15 ‘frared absorption spectrum. There is also obtained 18
ture is con?rmed by preparing the 2,4-dinitrophenylhy
drazone, M.P. 156° C.
parts of propionic acid, identi?ed by infrared analysis,
and 15 parts of higher boiling carbonyl compounds.
There is no depression in a
mixed melting point determination with the 2,4-dinitro
phenylhydrazone of authentic pentanone-3. There is
also obtained 15 parts of 3,6-octanedione which is identi 20
?ed by ‘boiling point (61° C./2 mm.), melting point (34—
36° C.), and by elemental analysis (percent C=67.28,
percent H=9.84; empirical formula C4H-7O).
Repetition of the above procedure substituting triphen
ylphosphine and quinoline, respectively, for the pyridine
yields similar results.
Example 5
Example 8
A pressure reactor is charged with 100 parts of Water
and 0.8 part of the commercial mixture of ruthenium
chlorides of Example 3. The reactor is cooled, evacuated,
and pressured with a 1:1 carbon monoxide-ethylene mix
The reactants are heated at 188-196° C. and
25 750-1000 atm. for 10 hours, during which time a pres
sure drop of 1425 atm. is observed.
There is obtained
173 parts of a two-phase product, the top phase being
clear deep red in color, and the bottom phase clear and
A pressure reactor is charged with 100 parts of water,
colorless. The two-phase product is distilled through a
2 parts of a one molar solution of palladous chloride in
12 N hydrochloric acid and 7 parts of pyridine. The 30 12-inch distilling column to yield 157 parts of two
reactor is cooled, evacuated, and pressured with a 1:1
carbon monoxide-ethylene mixture. The reactants are
heated at 250° C. and 1000 atm. pressure for 10 hours,
phase distillate, boiling range 25—76° C./ 2 mm. The dis
tilla-te is saturated with sodium chloride and 113 parts
of organic phase is separated. This material has a refrac
tive index of 1.3939. It is dried over anhydrous mag
during which period a pressure drop of 935 atm. is ob
served. There is removed from the reactor 162 parts 35 nesium sulfate and fractionally distilled to yield 80 parts
of pentanone-3, B.P. 100-102° C., nD25=\1.3900", and 20
of two-phase liquid which is distilled through a 12-inch
parts of higher vboiling carbonyl-containing compounds.
distilling column to give 133.5 parts of two-phase distil
late, boiling range 20-46° C./ 3 mm., and 21 parts of non
Eample 9
volatile viscous residue. The distillate is washed with
calcium chloride, the organic phase is separated, dried 40 A pressure reactor is charged with 100 parts of water,
1.045 parts of rhodium trichloride trihydrate, and 1.5
over anhydrous magnesium sulfate, and then fractionally
parts of pyridine. The reactor is cooled, evacuated, and
distilled. There is thus isolated 28 parts of pentanone-3,
pressured with a 1:1 carbon monoxide-ethylene mix
B.P. 99-105 ° C., nD25=1.3905, whose 2,4-dinitrophenyl
ture. The reactants are heated at 100-190° C. under
hydrazone melts at 156° C. Its mixed melting point
with the 2,4-dinitrophenylhydrazone of authentic pen 45 100-200 atm. pressure for 10 hours, during which period
a pressure drop somewhat in excess of 10 atm. is observed.
tanone-3 is 156° C. From this distillation there is also
There is obtained 116 parts of two-phase liquid which
is distilled rapidly through a 12-inch distilling column
to yield 111 parts of clear colorless two-phase distillate,
Repetition of the above procedure using tricyclohexyl
50 boiling range 20-30° C./ 3 mm. The distillate is separated
amine in place of pyridine gives similar results.
and dried over anhydrous magnesium sulfate. The
Example 6
product is fractionally distilled to yield 18 parts of
A pressure vessel is charged with 100 parts of water,
pentanone-3, B.P. 98-110" 0., nD25=1.3895, identi?ed by
0.5 part of iridium trichloride trihydrate, and 1.5 parts
its infrared absorption spectrum.
of pyridine. The reactor is cooled, evacuated‘, and pres 55 The above procedure is repeated using triethylbis
sured with a 1:1 carbon monoxide-ethylene mixture.
muthine in place of pyridine with similar results.
obtained 7 parts of higher boiling aldehydes and alcohols,
as identi?ed by infrared analysis.
The reactants are heated at 250° C. and 1000 atm. for
Pentanone-3 is a valuable chemical which ?nds wide
10 hours, during which time a pressure drop of 635 atm.
application as a solvent and diluent in the formulation
is observed. There is recovered from the reactor 108
of lacquers based on cellulose derivatives, plastics, and the
parts of two-phase liquid consisting of a clear brown 60 like.
top phase and a clear colorless bottom phase. This ma
The process of this invention in employing water as
terial is distilled through a 12-inch distilling column to
the hydrogen donor in the synthesis of pentanone-3 differs
yield 96 parts of clear colorless two-phase distillate and
from previously known methods which use hydrogen in
7 parts of sticky residue. Sodium chloride is added and
the initial charge. It is economical and e?icient, and
the organic phase is separated and fractionally distilled. 65 therefore represents a step forward in the synthesis of
From this distillation there is obtained 18 parts of pen
this valuable chemical.
tanone-3, B.P. 100-102° C., nD25=1.3905, identi?ed by
The foregoing detailed description has been given for
its infrared absorption spectrum.
clearness of understanding only and no unnecessary
Repetition of the above procedure using triphenylarsine
limitations are to be understood therefrom. The inven
in place of pyridine gives similar results.
70 tion is not limited to the exact details shown and described,
for obvious modi?cations will occur to those skilled in
Example 7
the art.
A pressure reactor is charged with 100 parts of water
and one part of the commercial mixture of ruthenium
This application is a continuation-in-part of my earlier
application Serial No. 712,303, ?led January 31, 1958
chlorides of Example 3. The reactor is cooled, evacuated, 75 now abandoned.
chlorides 'ana iodides "endisaid catalyst being presentiin
The embodiments of the invention in whichv an ex
amount of at least 0.00001 mole per mole Qf'eth'yIen‘eI
elusive property or privilege is claimed arede?ned' as
, 1. ‘A process for preparing pentanone-3 comprising con‘
tacting reactants‘ consisting essentially of ethylene,‘ carbon
monoxide and water at a temperature abovelOO” O. and
a' pressure above “100 atmospheres‘in the‘ presence fof a
catalyst consistingessentiallyof ‘at ‘least 'onehalide of a‘
group V111 ‘noble metal’ of"atomic' number 44-78, said
' halide being selected irom'thecless consisting of bromides;
5- atmosphe'res énilsiaid'_hialide" is"; chlericleifr' _ '
‘References2 Cited inmthe ?le o‘fthis' patent
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