Note: Descriptions are shown in the official language in which they were submitted.
~L~l'75~55
Quite a number of processes directed to the epoxy-
dization of olefins are known, although the greatest part
oE them are methods which either did not find a prac-tical
industrial application or are now of no interest because not
possessing, to a sufficient extentt all of the requisites of
an applicable and economical character and, lately, also of
ecological acceptability, etc., necessary or rendering them
entirely acceptable for industrial use.
/
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~17~il355
. .
Even at the present time, besides the direct oxidation
of ethylene to ethylene oxide, the propylene oxide, and at any
rate the epoxides in general, are obtained almost exclusively
by the known chlorohydrin process.
Schematically, that process consis s in reacting an
olefin with chlorine water obtaining théreby the chlorohydrin
which is trea$ed successively with alkalis (lime) thereby
obtaining the corresponding epoxide. However, the process is
subject to ever-increasing difficulties ~rom the industrial
point of view as well as on the economical plane, and with
respect to environmental compatibility. In fact, the chloro-
hydrin process leads to the contemporaneous, more or less
abundant and dificult to control, production of both mineral
as well as organic chlorinated by-products which, while not
useful, present major problems in the qualitative and quantita-
tive disposal thereo~.
To this must be added the growing cost of the chlorine,
strictly bound to energy consumption, and other factors.
Therefore, quite recently interest was aroused in the
epoxydization of an olefin by a process conducted in an anhy-
drous organic phase with an organic hydroperoxide and in the
presence of catalysts based on molybdenum, tungsten or
vanadium, of which there have been some actual industrial
applications.
However, that process has the disadvantage that
production of the epoxide is accompanied by the production of
the alcohol corresponding to the hydroperoxide, in quantities
equivalent to or even greater than the epoxide. Exploitation
of the alcohol as such, or recycie thereof, represents serious
economical burdens which substantially affect commercial use
of this process.
' ! l
ll~S~5S
Research has been directed, also, to more direct
oxidation methods.
Thus, epoxydization processes by means of molecular
oxygen with silver catalysts, etc., have been proposed. Those
processes had only limited success in the case of ethylene. The
techniques proved to be not extendible to other olefins of
significant interest, e.g., propylene~
Hydrogen peroxide, due to its oxidizing action assoc-
iated with the absence of en~ironmental problems, problems of
pollution, etc., has been suggested as suitable for a certain
number of epoxidizakion processes.
According to those proc~esses, since ~he activity of
the hydrogen peroxide toward the olefins as such is rather
limited or altogether absent, it is necessary to use activating
agents, in general organic acids such as for instance formic
acid, acetic acid, etc., in organic solvents, which acids, in
the form of peracids, form "in situ" the reactive epoxidizing
agent.
Those processes, also, do not seem to have achieved
any real success, both because of the difficulty of obtaining
peracids as well as because of the instability of the epoxides
in an acid medium which makes necessary rather burdensome
operating conditions.
Other processes have been described as applicable
selectively to the preparation of epoxy-alcohols (glycydGls) by
an epoxidization of hydrosoluble olefins with hydrogen peroxide,
in an aqueous solution containing primary or secondary alcohols,
and in the presence of catalysts based on: Mo, V, W.
In this last-mentioned case, it is a question of a
technique substantially directed towards glycydols only,
compounds that are of a limited commercial interest. On the
` `` ! ,,
. 11~5~55
other hand, the epoxidization xeaction of the olefins with
hydrogen peroxide leads to the ~ormation of water which,
expecialIy when metal catalysts are used in the form of per- ¦
oxides inhibits, with its accumulations, the reaction itself,
a drawback which it was attempted to obviate by the use of
concentrated solutions of hydrogen peroxide, as well as by
using potentiated catalytic systems.
Thus, there have been described olefins oxidizable by
reaction with highly concentrated hydrogen peroxide in a homo- !
geneous, essentially organic liquid phase, in the presence of
catalytic systems soluble in the organic li~uid and based on
elements of the IV, V and VI B (Ti, V, Mo, W) groups, of the
¦ Periodic Classification OfElements associated with elements
selected from Pb, Sn, As, Sb, Bi, Hg, and so on.
- The results did not meet expectations on the practical !
level because of the slowness o the reaction and o~ the
expensiveness of the catalytic system consisting, in general,
of very sophisticated organometallic compounds, necessary for
their solubility in the organic medi~lm.
Moreover, the use of hydrogen peroxide of high concen-
tration t,70%) involves some risks from the point of view of
safety, not easily economically surmountable.
Improvements have been described as achievable ~y the
use, in the above-mentioned technique, of catalysts based on
tungsten or molybdenum or of arsenic or boron with an excess
of olefin, in general, in combination with continuous distilla-
tion of the interfering water.
Here, also, the use of concentrated solutions (~70~) 1
of hydrcgen peroxide is practically required, with the corres-
ponding handling problems connected with it as already mentioned
with regard to the safety of the installations. Moreover, the
_~_ ~
~.'75~S~i
continuous removal of the reaction water, besides that intro~
duced by the hydrogen peroxide itself, an operation that ma~es
the high M202 concentrations practically necessary from the
start, proves particularly economically burdensome.
On the other hand, the oxidization of the olefins
with hydrogen peroxide involves an intrinsic contradiction
resulting from the operating conditions which require at best
an aqueous medium, possibly acid, as far as the catalytic
system and the hydrogen peroxide are concerned, while the
oxidization reaction and the stability of the epoxi.de require
preferably a neutral organic medium.
All of the prior processes discussed above, and which
involve the use of hydrogen peroxide, substantially tend to
make the reaction medium homogeneous in some way and also tend
to avoid the inhibiting accumulation of H20, with rather
uncertain results, at least from the point of view of the
actual industrial feasibility of such processes.
It is known from the litexature to conduct chemical
reactions in general substantially based on the ionic exchange,
accoraing to the so-called "double phase" technique.
There has also been described the possibility of
epoxydizing olefins with hydrogen peroxide, in a doub1e phase,
in the presence of mineral derivatives based on tungsten and
molybdenum. We are not aware of any practical interest in the
method because of the poor efficiency of the catalyst, also
verified by us, and therefore the double-phase technique has
not appeared to be at all convenient or commercially feasible.
_5_
~L175055
THE PRESENT INVENTION
One object of this invention is to provide a process
for the catalytic epoxidization of olefins, uSing hydrogen
peroxide, as an oxidizing agent, which process is relatively
simple, economical, and free of the drawbacks o the processes
known heretofore.
A partiaular object of this invention is to provide
a process for the catalytlc epoxidization of olefins with
diluted hydrogen peroxide, characterized in having a high
degree of selectivity for the desired epoxide which is obtained
by means of an efficient long-life catalytic system, without
requiring a burdensome continuous distillation of the reaation
water. .
In the process of this invention, the contradiction
inherent in the usual operating conditions is effectively
overcome by the use of the reaction technique conducted in a
double, aqueous-oryanic liquid phase.
Said technique involves the use of two unmixable or
hardly mixable reaction means o difering polarity, so that
both the pH control, as well as the concentration of the
hydrogen peroxide and the elimination of the reaction water,
are substantially less constrictive of the practical effective-
ness o the process~
We have found that the epoxydization reaction of .
olefins with hydrogen peroxide catalyzed by compounds based on
transition metals, can be made`both con~enient and practical by
the use of a particular catalytic system which, unexpectedly
exhalting the epoxydization reaction, permits of conducting the
the epoxydization reaction of the olefins in an economical,
hand-operational and easy way, according to the "double-phase"
technique.
~;t5~55
Summing up, the present invention represents the
surprising overcoming of a prejudice existing in the prior art,
according to which the epoxydlzation rieaction of olefins with
hydrogen peroxide, in the presence.of catalysts, and conducted
according to the double-phase technique would.not lead to
- practical results. This situation appears to have deterred
the skilled in the art Erom further research in the Eield and
from expecting the surprisingly better results obtained by the
present process.
The present invention is thus concerned with a process
for the catalytic epoxidation of olefins by reaction with-
hydrogen peroxide according to the double phase technique
with onium~> salts, characterized in that the reaction is
conducted in an aqueous-organic liquid two-phase system,
consisting of:
~a) an organic phase substantially containing the
olefin having the formula:.
Rl / R3
C = C
R2 R4
wherein Rl, R2, R3 and R4, which may be subistituted with
functional groups inert to the reaction conditions, represent
hydrogen atoms or hydrocarbyl groups selected from alkyls and
alkenyls having up to 30 carbon atoms.j~ cycloalkyls and cyclo-
alkenyls having from 3 to 12 carbon atoms, and which may be
branched; aryls, alkyl-aryls and alkenyl-aryls having from 6
to 12 carbon atoms; or wherein an Rl, R2, R3, R4 group taken
together with an adjacent group represents alkyl or alkenyl
groups having up to 12 carbon atoms in the resulting cycle;
and
(b) an aqueous acidic phase substantially containing
the hydrogen peroxide;
- 7 -
i. .
S05S
in the presence of a catalytic system consisting of two compo- .
nents, the first being at least..one compound selected Erom W,
Mo in the metal state, tungs~ic, molybdic acids and the
corresponding neutral alkaline salts, the metal-carbonyls
W~CO).6 and Mo(CO~6; the oxides MoO2, MozO5, Mo2O3, MoO3,
WO2, W2O5, WO3; sulphides WS2 and WS3; oxychlorides and chlori-
.des of tungsten and molybdenum, and the second being at leastone derivative selected from phosphoric, polyphosphoric, pyro-
phosphoric, arsenic acids and their alkaline saIts, -the oxides
P2O5 and As2O5 and chlorides and oxychlorides PC15, AsC15,
POC13 and AsOC13.
The reaction may be represented by the following scheme:.
>C = C< + H202' > >C - C< -~ H20
' O
The reaction is conducted in the double-phase, aqueous-
organic system, under vigorous stirring, in the presence o the
above-defined catalytic system. The organic phase consists o
the olefin and possibly of an organic solvent and the aqueous
phase of the hydrogen peroxide.
The temperature and the operating pressure are practi-
cally determined by the reactivity and by the nature of the
olefin, by the stability of the hydrogen peroxide and.of the
" onium 1I salts used in the organic medium.
Temperatures comprised between 0C and 120C and
pressures between atmospheric pressure and about 100 atmospheres
are, in general, sufficient.
Substituent groups, inert under the reaction conditions,
are, for instance: hydroxyl groupsr halogens (Cl, Br, F~ I),
nitro-, alkoxyl, amine, carbonyl, carboxyl, ester, amide, or
nitrile groups, and the like.
,. ~ .
~17S055
The Rl, R2, R3 and R4 groups may also be alkenyls, in
other words, the process according ko this invention is appli-
cable also to polyolefins such as dienes, trienes, conjugated
or not
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~ . I 1~L75(~55
.,
. Olefins suited for the epoxydization according tothis invention include, by way of examplés: alkylic, alicyclic,,
alkylarylic unsaturated hydrocarbons such as: propylene,
. butenes, pentenes, and in general the linear or branched mono- I
¦ and di-olefins having up to 20 carbon atoms, cyclohexene/ nor- ¦
¦ bornene, limonene, camphene, vinyl-cyclohexene, styrene, indene,,
¦ stilbene, etc., unsaturated alkyl halides such as: allyl . ¦
¦ halides; unsaturated acids and theix esters such as: acrylic,
. ¦ methacrylic, crotonic, oleic acid, etc.; unsaturated alcohols
10. . ¦ and their esters, such as: allyl alcohol, etc., unsaturated
¦ aldehydes and ketones such as: methylallyl acetone, etc.
¦ Definitely acid pH values increase the stability of
¦ the hydrogen peroxide, but make the epoxide unstable. Thus,
convenient pH values are those comprised between abbut 2 and 6.
Said range of pH values is obtained in practice directly by the
presence of the system consisting of the xeactants and of the
catalyst used, or, i~ ne~essary, the pH may be adjusted by
means o mineral acids (HCl, etc.).
. On the other hand, as alread.y indicated herein, the
double-phase react.ion technique renders the operation of the
process.less sensitive to occasional variations in the pH
value.
The duration of the reaction depends on the nature and
. on the quantity of the catalyst, on the solvent medium and on
the olefin used in the process. In general, times comprised
between just a few minutes and several hours will be sufficient
for completing the reaction.
The quaternary "onium" salts used in the process are
known salts that are comprised in the formula:
(R'l, R'2, R'3~ R'~M) X ,
wherein M is chosen between N and P; X is a stable anion such
^,:,
;,, ' , ~9_
~l~S~5~
as Cl,Br, HSO~ , N03 , etc., R'l, R' 2 ~ R ' 3 and R14 represent
monovalent hydrocarbyl groups having a total number oE carbon
atoms of up to 70, but preferably comprised between 25 and 40.
Depending on whether M is an atom of N or P, one
obtains the corresponding " onium" salt, i.e., the ammonium
(N) or phosphonium (P) salt.
The two or more element components of the catalytic
system used in this process may belong to di-fferent molecules
or they may be part o the same complexed molecule comprising
the two or more element components.
In that case, there may be used heteropolyacids known
as: phosphotungstic, arsenotungstic, phosphomolybdic,
heteropolyacids, etc., or their alkaline or alkaline earth
salts.
They may easily be obtained by heating and acidifying
a solution consisting, Eor instance, of a tungstate, and of a
salt of the central atom of the complex in the appropriate
state of oxidization, according to known methods.
. .
11~75~5S
. The two or more components o the catalytic system ~re
used according to a mutual a~tomic ratio, expressed aB the total
o the metals belonging to the ~irst with respect to the total
......... of those belonging to the second group of the above-de~ined
elements, and comprised between 12 and 0.1, but.preferably
. . between.about 1.5 and 0.25.
The catalytic system is used in ~uantities comprised
between 0.0001 and I g-atom of metal or of total metals belong
. ing to the first group of elements per 1 mol.of hydrogen
10 , peroxide, but preferably comprised between 0.005 and 0.2 g-atom
. per àbout.l mole.
Mixtures o the elements and/or their derivatives may
also be used to obtain the catalytic system.
. The quantity o ~uaternary or "onium" salt present in
the heterogeneous system, may vary within wide limits. Efec-
tive results can be achieved by using rom ahout 0.01 mol to 2
mol~ of "oni~m" salt per 1 g atom of catalyst, but preferably
from 0.1 mol to 1 mol per 1 g-atom, re~er.red to the irst com-
ponent or to the sum of the first components.
. Effective '!onium" salts include dicetyldimethyl-
ammonium chloride, tricaprylmethylammonium chloride, hexade-
~yltributylphosplloniulll clllori~ an~ tl~c lilce.
The reactants are used in substantially equimolecular
. ratios,!and a limited excess or lack of the one in respect of
the other of the reactants is nok detrimental to the course of
. the reaction.
.
.. .. . .
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.. .. .. . .
' . ` !l
75~SS
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Illustratively, workable operating values may be con-
sidered ratios comprised between 0.1 mol and about 59 mols of
olefin per mol of hydrogen peroxide, but preferably values
: comprised between about 1 mol and 20 mols.
. The reaction is conducted, as previously indicated,
according to the double-phase technique. More particularly,
the organic phase ~a) may indifferently consist of the react-
ing olefin itself, used in a suitable excess, or it may consist
of the reacting olefin dissolved in appropriate extraneous
organic solvents~
As solvents for the organic phase there are used inert
solvents substantially unmixable with the aqueous phase;
effective practical results are obtained by the use of
. aliphatic, alicyclic or aromatic hydrocarbons such as: heptane r
- octane, cyclohexane, benzene, toluene, xylenes, etc., chlor-
inated hydrocarbons such as: dichloromethane, trichloromethane,
chloroethane, chloropropane, dichloroethanes, trichloroethanes,
tetrachloroethanes, di- and trichlorop.ropanes, tetrachloro-
. propanes, chlorobenzene, or by the use of alkyl esters such as:
ethyl acetate or suitable mixtures comprising the same.
The skilled in the art can choose the type of organic
. phase (a) depending, for instance, on the reactivity of the
. starting olefin and on the parameters used in each instance~.
. When inert solvents as listed above are used as solvents for
the organic phase, the concentration of the olefin in the
solvent is not critical to the performance of the process.
operating values for the olefin concentration in the
organic phase are comprised between 5% and about 95% by weight;
higher values or lower values are however compatible within the
limits of their practicability~ The concentration of hydrogen
1~ - 12 -
'- t' '` I j
. ~ 5(~S5
., . . I
peroxide in the aqueou5 phase may be maintained between 0.1
~and about 70~ by weight.
However, the process of this invention has the advan-
tage of per~itting use of low hydrogen peroxide concentrations.
Hydrogen peroxide concentrations comprised between 1% and
about 10% have proved to be effective. Concent~a~
tions below 1% are also effective. This advantage brings with
it the favorable economical aspects of the process, when com-
pared with the costly preparation of solutions with concentra-
tions greater than 70% known from the prior axt, as well as
eliminating the necessity of maintaining said high concentra-
tion during the course of the process, while satisfying the
security requirements already mentioned.
In an illustrative practical embodiment of the
process, it is conducted as follows:
Into a reactor fitted with a stirrer, a heat-control-
ling system and a reflux coolant, there are introduced in pre-
established quantities and ratios, the reactants (H2O2 and the
olefin in the solvent). Thereupon, the catalytic system and the
rest of the solvent are introduced, with the "onium" salt in
the desired quantities. Under vigorous stlrring~ the hetero-
geneous mixture is brought to the reaction temperature for the
desired time. At the end, after separation of phases and cool-
ing down, etc., the epoxide and the reactants are separated by
means of conventional methods ~e.g., distillation, etc.).
The process pxoves particularly convenient thanks to
the mild and simple operating condi~ions.
More particularly, it allows to effec-tively operate
using high olefin concentrations in a solvent medium, or also
in the absence of an extraneous solvent, thereby xealizing the
corresponding technological and economical advantages.
- 13
.'
~s~ss
t'
In the known processes which do not describe the use
of solvents and which are conducted in a homogeneous phase with
concentrated H2~J, there are prescribed large excesses of the
starting olefin, necessary for ensuring reasonable margins of
operational safety. This circumstance is not relevant in the
case of the present process, in which, on the~ontrary, the
difficulty concerning an aspect as important as is that of
safety, is overcome by means of the double-phase technique.
Still other advantages are the possibility of using
hydrogen peroxide at a low concentration, which may easily and
economically be bought on the market or may be readily prepared
without involving operational security risks.
Lastly, the high yields and high selectivity that
are obtainable together with the other advantages noted, ensure
a considerably interest in the industrial application of the
process.
The compounds obtained, epoxides of ole~ins, are
chemical products of a considerable industrial importance. In
factt they represent products that find interesting applications
in industry, also on a high qualitative scale, within a wide
range of uses well known to the skilled in general.
As a matter of fact, besides as useful intermediates
in organic synthesis, amongst the main uses there may be listed
those in which they are employed as intermediates in the produc-
tion of urethanes, in the industry of blown or foamed products,
of glycols for lubricants, surfactants, esters for plasticizers,
polyester resins, etc.
The following further enabling examples are given for
illustrative and not limiting purposes.
Examples 4, 6, 18 and 19 are given for comparative
purposes in order to compare results under conditions of the
Prior Art.
- 14 -
,
~L~3L75(~55
r
The symbol w/v stands for weight/volume.
EXAMPLE 1
Into a four-necked flask, fitted with a stirrer, a
thermometer and provided with a reflux~coolant, there were in-
troduced 22.1 g of octene-l (0.197 mol), 0.8 g of tricaprylme-
thylammonium chloride ~0.002 mol?, 40 ml of H2'O, 165 g of
Na2WO~.2H2O ~0.005 mol), 0.83 g of NaH2PO4.H2O ~0.006 mol~,
2 ml of a 14.7~ by w/v (0.003 mol~ o~ H3PO4, 10.96 g of a
38.2% H2O2 (0.123 mol?, 16 cc of 1.2 dichloroethane. Thereupon
the
.
- 15 -
s~s~
mixture was additioned with 1.30 cc o H~S04 at 31.7~ concen-
tration, and, under vigorous stirring the mixture was rapidly
brought up to 70~C and maintained at that temperature for ~5
minutes. At the end, into the reaction medium there were dosed
off, by the iodometric method, 0.0023 mol of unreacted H2O2
and by gas-chromatography (GLC) 0.102 mol of epoxyoctane, which
corresponded to a conversion of the H2O2 equal to 98.1% with a
selectivity in epoxyoctane of 84.5~.
. .
EXAMPLE 2
Into a four-necked ~lask, fitted with a stirrer and
provided with a thermometer and reflux-coolant, there were
introduced 35.61 g of octene-l (0.318 mol), 60 ml of benzene,
1.2 g of dicetyldimethylammonium chloride (0.002 mol), 40 ml of
water, 3.3 g of Na2WO4.2H2O ~0.010 mol), 7.0 ml of H3PO4 at
i 14.7% by w/v (0.0105 mol) and 11.47 g of H2O2 at a 38.2% con-
centration (0.129 mol). This rnixture was thereupon rapidly
brought up to 70C, ~ der vigorous st.irring, and was then
maintained at that temperature for 2 hours. At the end of the
. reaction, from the reaction mass were dosed off, by -the
) iodometric method, 0.0097 mol of unreacted H2O2, and by gas-
chromatography 0.1014 mol of epoxyoctane, which corresponded to
a conversion of hydrogen peroxide of 92.4%, with a selectivity
for epoxyoctane of 86.4%.
EXAMPLE 3
i Into a four-necked flask, fitted w.ith a stirrer, a
thermometer and a reflux-coolant, there were introduced 22.1 g
of l-octene (0.197 mol), 1.2 g of dicetyldimethylammonium
chloride (0.002 mol), 40 ml of H2O, 165 g of Na2WO4.2H2O
~' 11'75055
(0.005 mol), 0.83 g of NaH2PO4~H2O (0~006 mol), 2 ml of H3PO4
at 14.7% w/v (0.003 mol and 10.96 g of H2O2 at 38.2% (0.123
mol). Thereupon there were added 0.95 ml of H2SO4 at 31.7%
concentration and, under vigorous stirring, the mixture was
brought rapidly up to 70C and was then maintained at that
temperature for 45 minutes. At the end o~ the reaction, from
the reaction mass, by the iodometric method, there were dosed
off 0.006 mol of unreacted H2O2 and by li~uid gas chromatog-
raphy (LGC) 0.0936 mol of epoxyoctan~, corresponding to a con-
version of the H2O2 of 95%, with a selectivity in epoxyoctane
of 80~.
EX~LE 4 (Comparative Example)
Exa~ple 2 was repeated, except that the H3PO4 was sub-
stituted with an equivalent quantity of H2SO4. After 2 hours
of reaction, from the reaction product were dosed of~ 0.0986
mol of unreacted hydrogen peroxide and 0.007 mol of epoxyoctane,
which corresponded to a conversion of hydrogen peroxide of
23.5%, with a selectivity in epoxyoctane of 23.2%.
EXAMPI.E 5
Into a four-necked flask, fitted with a stirrer, a
thermometer and a reflux-coolant, there were introduced 22.1 g
of l-octene (0.197 mol3, 0.8 g (0.002 mol) of tricaprylmethyl-
ammonium chloride, 40 ml of H2O, 165 g of Na2WO~.2R2O ~0.005
mol3, 3.12 g (0.010 mol) of Na2HAsO4.7H2O, 10.96 g (0.123 mol)
of a 38.2% H2O2 and 16 ml of 1,2-dichloroethane.
Thereupon about 3 ml of a 31.7% H2SO4 were added and,
under viyorous stirring, the mixture was rapidly brought up to
70C and maintained there for 45 minutes. At the end of the
-17-
'7~ 5
reaction, from the reaction mixture were dosed off 0.0047 mol
of unreacted H2O2 ~conversion 96.2%? and 0.0978 mol of epoxy-
octane (selectivity 82.6~).
,,~
EXAMPLE 6 (Comparative Example)
Proceeding as in Example 5, but in the complete
absence of tungstates and using 240 ml of a 31.7% H2SO4, after
6Q minutes of reaction, from the reaction mass there was dosed
off a quantity of H2O2 equal to that introduced inltially. The
¦ LGC did not reveal the presence of any epoxyoctane.
EXAMPLE 7
¦ Operations were as in Example 1, but using 0.93 g of
¦ hexadecyltributylphosphonium chloride (0.002 mol) instead of
¦ the quaternary ammonium salt. After 60 minutes of reaction,
¦ from the reaction mass there were dosed off 0.0051 mol of
¦ unreacted H2O2 (conversion = 95.9%) and 0.0892 mol of epoxy-
¦ octane (selectivity = 75.6).
` EXPMPLEa ~
Example 2 was repeated, using as a catalyst 2.46 g of
sodlum phosphotungstate (0.010 g-atom of Wj and by adding to
the reaction system 1.9 ml of NaOH at a 35% concentration.
After 2 hours of reaction, as in Example 1, from the reactiQn
product were dosed off 0.0376 mol of unreacted hydrogen per-
oxide and 0.0568 mol of epoxyoctane, whlch corresponded to a
conversion of the hydrogen peroxide of 70.8% r with a selec-
tivity for epoxyoctane of 62.1%.
~ 1175055
EXP~LE 9
Into a four-necked flask, fitted with a st~rrer, a
thermometer and a reflux-coolant, there were introduced 31.1 g
~0.379 mol) of cyclohexene, 0.6 g (0.001 mol) o~ dicetyldi-
methylammonium chloride, 40 ml of H2O, 0.66 g (0.002 mol) of
Na2WO4.2H2O, 1.1 ml (0.0015 mol) of a 14.7% H3PO4, 10.96 g
~0.123 moL~ of 38.2% H2O2 and 40 cc of benzene.
The mixture, subjected to vigorous stirring, was
rapidly brought up to 70C and maintained ak that temperature
for 15 minutes. At the end of this period~ from the reaction
mixture there were dosed off 0.009 mol of unreacted H2O2 and
0.096 mol of epoxycyclohexane, which corresponded to a conver-
sion of the hydrogen peroxide of 92.6%, with a seIectivity in
epoxycyclohexane of 84%.
. ~ , . .
EXAMPLE 10
Into a four-necked flask, fitted wi~h a stirrer, a
thermometer and a reflux-coolant, there were introduced 16.2 g
of cyclohexene (0.197 mol), 60 ml of benzene, 102 g of dicet~l-
dimethylammonium chloride (0.002 mol), 40 ml of water, 3.3 g
(0.010 mol) of Na2WO~.2H2O, 4.62 ml (0.0069 mol) of H3PO4 at
14.7% w/v and 11.47 g (0.129 mol~ of H2O2 at 38.2% concentra-
tion.
This mixture was rapidly brought up to 70C, under
vigorous stirring, and was then maintained at that temperature
for 30 minutes.
At the end of the reaction, ~rom the reaction product
were dosed off 0.015 mol of unreacted H2O2 and 0.099 mol of
epoxycyclohexane, which corresponded to a conversion of the
l hydrogen peroxide of 88.4~ with a selectivity in epoxycyclo-
I ¦ hexane of 86~8~.
11 ~5055
EX~MPLE 11
Into a four necked flask, fitted with a stirrer, a
thermometer and a reflux-coolant, there were introduced 30.2 g
(0.368 mol) of cyclohexene, 0.6 g (0.001 mol) of dicetyl-
dimethylammoniumchloride,.40 cc of H2O, 0.66 g (0.002 mol) of
Na2WO4.2H2Oi 1.1 ml of a 14.7% w/v H3PO4 (0.0015 mol), and 11-2
g (0.126 mol) of a 38.2% H2O2.
Under vigorous stirring, the mixture was then brought
up to 70C and maintained at that temperature for 15 minutes
(initially the reaction was exothermic). At the end, from the .
reaction mixture were dosed off 0.0057 mol of unreacted H2O2
(con~ersion = 95.5%) and 0.0985 mol of epoxycyclohexane
(selectivity: 81.9~ on H2O2). .
EXAMPLE 12
Into a four-necked flask, fitted with a stirrer, a
thermometer and a reflux-coolant, there were introduced 29.1 g
(0.355 mol) o cyclohexene, 20 ml of 1~2-dichloroethane, 0.4 g
~0.001 mo].) of tricaprylmethylammonium chloride, 40 ml of water,
0.66 g (0.002 mol) of Na2WO4.2H2O, 1.1 ml (0.0015 mol) of a
14.7% w/v H3PO4 and 10.96 g to.l23 mol) of a 38.2% H2O2.
The reaction mixture was then rapidly brought up to
70C and maintained at that temperature for 45 minutes. At
the end of this period, rom the reaction mèdium were dosed off
0.004 mol of unreacted ~22 and 0.099 mol of epoxycyclohexane,
which corresponded to a conversion of the hydrogen peroxide of
96.7~, with a selectivity in epoxycyclohexane of 83%.
!
. .
~ 75~:)55
EXAMPLE 13
-Ex~nple 10 was repeated, using 4.9 ml of H3PO4 at
; 14.7% w/v (0.0074 mol) and operating at 50C. After a reaction
of 30 minutes, from the reaction mass there were dosed off
0.037 mol of unreacted H2O2 and 0~0848 mol of epoxycyclohexane, .
which corresponded to a conversion of the hydrogen peroxide of
71.3%, with a selectivity for epoxycyclohexane of 92.1~.
EXAMPLE 14
. '
Example 13 was repeated, bringing the reaction time to
1 hour. From the reaction product were then dosed off 0.0122
¦ mol of unreacted hydrogen peroxide and 0.0951 mol of epoxy-
¦ cyclohexane, which corresponded to a conversion of the hydrogen
¦ peroxide of 90.5%, with a selectivity in epoxycyclohexane equal
to 81.4%.
EXAMPLE 15 .
¦ Example 10 was repeatedj using 3.96 g of WC16 ~0.010
¦ mol) instead of Na2WO~.2H2O and 3.58 g (0.010 mol) of
¦ Na2HPOq.12~l2O instead of H3POq. To this reaction mass were .
¦ then additioned ~.5 ml of a 35% NaOH. Af~er 30 minutes of
¦ reaction there were then dosed off 0.01057 mol of unreacted
¦ hydrogen peroxide and 0.0688 mol of epoxycyclohexane, which
¦ corresponded to a conversion of hydrogen peroxide of 91.6%,
¦ with a selectivity for epoxycyclohexane of 55.9%.
¦ EXAMPLE 16
.
Example 10 was repeated, but using 3.52 g of ~7(CO~6
(0.010 mol) instead of Na2WO4.2H2O and 3.58 g (0.010 mol.~ of
Na2HPO4.12H2O instead of H3PO4. To this mixture were then
-21-
.
~ 1175055
added 2 ml of H2SO4 at a concentration of 31.7~. After 30
minutes of reaction, there were dosed off ~.00506 mol o
unreacted hydrogen peroxide and 0.0565 mol of epoxycyclo-
hexane, which corresponded to a conversion of the hydrogen
peroxide of 96.1~, with a selectivity for epoxycyclohexane of
43.6%.
.
~ EXAMPLE 17
. '
Example 10 was repeated, using however 4.4 ml of
H3PO4 at a 14.7% w/v concentration, (0.0066 mol), operating at
a temperature of 50C and by prolonging the reaction time to 1
hour. Thereupon, there were dosed off 0.0407 mol of unreacted .
hydrogen peroxide and 0.0805 mol of epoxycyclohexane, which
corresponded to a conversion of the hydrogen peroxide of
68.4~, with a selectivity for the epoxycyclohexane of 91ol~
`EXAMPLE 18 (Comparative Example)
The procedure was as in Example 17, but substituting
the phosphoric acid with an equivalent ~uantity of H~SO~.
After 30 minutes of reaction, from the reaction mass there
were dosed off 0.00413 mol of epoxycyclohexane.
,
l EXAMPLE 19 ~Comparative Example)
_
Operations were as in Example 17, but in the absence
of Na2WO4~2H2O and by substituting H3PO4 with 0.9 g (0.006
mols) of NaH2PO4.H2O. After 30 minutes of reaction, the
hydrogen peroxide was found to have remained unaltered and no
i presence o~ epoxycyclohexane was detected by LGC.
-22-
. ,
5055
~ ' ,. .'
EXAMPLE 20
Example 13 was repeated, but using 2.42 g (0.010 mol)
¦ of Na2MoO4.2H2O instead of Na2WO4.2H2O, and S.l g (0.0077 mol)
of H3PO4 at 14.7~ w/v. ~
. ¦ After 30 minutes of reactlon, from the reaction mass
¦ there were dosed off 0.1088 mol of unreacted h~drogen peroxide
and 0.0010 mol of epoxycyclohexane, which corresponded to a
conversion of the hydrogen peroxide of 15.6% with a selectivity
. for the epoxycyclohexane of 49.5%.
EXAMPLE 21
Example 10 was repeated, but usiny, instead of
¦ Na2WO4.2H2O and H3PO4~ 2-46 g of 2Na3PQ4.24WO3.H2O (sodium
phosphotungstate) equal to 0.010 g-atom of W and to 0.0008 g-
. ¦ atom of P. To this mixture were then added 1.9 ml of a 35
; ¦ NaOH.
. ¦ After 30 minutes of reaction, from the reaction mass
. ¦ were dosed off 0.0877 mol of unreacted hydroyen peroxide and
. ¦ 0.0245 mol of epoxycyclohexane, which corresponded to a conver-
. ¦ sion of the hydrogen peroxide of 32.1~, with a selectivity for
) j the epoxycyclohexane of 59.3%.
¦ EXAMPLE 22
¦ Example 2 was repeated but using 2.42 g (0.010 mol) of
¦ Na2MoO4.2H2O instead of Na2WO4.2H2O and uslng 1,2-dichloro-
¦ ethane (60 ml) instead of benzene as a solvent.
; ¦ After 2 hours of reaction, from the reaction product
were dosed off, iodometrically, 0.1105 mol of unreacted hydro-
gen peroxide and 0.0081 mol of epoxyoctane, which corresponded
to a conversion of the hydrogen peroxide of 14.3~, with a
selectivity for the epoxyoctane of 43.8%.
1:1750S5
. , ,
EXAM*L~ 23 ~
. .
Example 1 was repeated, but substituting the l-octene
with 33.35 g (0.1985 mol~ l-dodecene. Ater 1 hour, rom the
- reaction product were dosed o~f 0.0059 mol of hydrogen peroxide
and 0.0958 mol of 1,2-epoxydodecane, which corresponded to a
conversion of th~ hydrogen p~eroxide of 91.9%, with a selec-
tivity for the epoxydodecane of 80.7%.
. , . , .
EXAMPLE 24
' ~ ' ' ' ,'
Into an autoclave of 1 Liter holding capacity, l~ned
) with glass and provided with a magnetic stirrer, there were
introduced 2.48 g ~o.bo7s mo}) of Na2WO4.2H2O, 1.25 g (0.009
mol) of NaH~PO4.H2O, 2.9 ml (0.0044 mol) of H3PO4 at 14.7~ w/v,
0.25 ml of H2SO4 at 31.7% concentration, sb ml of 1,2 dichloro-
ethane, 1.3 g (0.0032 mol) of tricapryl-methylammonium chloride,
32.35 g (0.363 mol) of H2O2 at 38.2% concentration.
After removal of the air from the autoclave, 72 g of
propylene (1.714 mol) were loaded into the autoclave. The
reaction mass was thereupon heated up to 60C under vigorous
stirring, thereby attaining a pressure of 18 atmospheres. The
D reaction mixture was then maintained at this temperature for 1
hour. At the end of this period, after cooling down, there
were dosed off 6.32 g (0.186 mol) of unreacted H2O2 and 6.73 g
(0.116 mol) of propyléne oxide, which corresponded to a conver-
stion of the hydrogen peroxide of 48.76%, with a selectivity
for the propylene~oxide of 65.5%. Moreover 0.63 g (0.008 mol~
of propylene glycol was also obtained.
