Note: Descriptions are shown in the official language in which they were submitted.
H.28239 /287Lr~
3U~ J~L
THIS INVENTION relates to organic nitriles, more
speci~ically to dicyanobutene and to a method for its
manufacture from butadiene.
It has already been proposed to manufacture dicy-
anobu-tene from butadiene by a two-s-tage process in which
butadiene is chlorinated to give dichlorobutene, and -the
dichlorobutene is then reacted with hydrogen cyanide or
an alkali metal cyanide to give dicyanobu-tene. Apart
from the fact that two stages are involved, the me-thod
involves the introduc-tion of chlorine and its subsequent
removal. It has also been proposed to react butadiene
with hydrogen cyanide in presence of a catalyst, for
example a zerovalent nickel catalyst, as described, for
example, in British P~tent Specification No. 1,104,140,
but commercially known methods introduce only one cyano
group to give a mixture of pentene-nitriles and me-thyl-
butenenitriles. The pentenenitriles may subsequently be
reacted with ~urther hydrogen cyanide in a separate stage
to give adiponitrile, but the latter compound cannot be
obtained by this method from butadiene in a single stage
in significant yield.
We have now found a method by which two cyano groups
may be introduced into the molecule of butadiene in a
single stage to give dicyanobutene.
Our invention provides a process for the manufacture
of dicyanobutene which comprises reacting butadiene with
hydrogen cyanide an(i oxygen or an oxygen-containing gas
in the presence of a catalyst comprising copper ions and
,. ~
: . . . . . . .
... .. . . . . .
H,2~239 /28748
:1~8~Z2~
halide ions and of a solvent for -the ca-talyst.
The copper ions in the catalyst used in the
process of our invention may be added in the cuprous
or cupric form. Under the influence of the oxygen
used in the process cuprous ions tend to be oxidised
to cupric, whereas the hydrocyanation reaction tends
to cause the cupric ions to be reduced to cuprous.
The copper may be added to the reaction mixture as a
halide, for example as cuprous or cupric chloride,
bromide or iodide (or as any mixture thereof) since
this will ensure the presence of halide in addition
to copper, but this is not essential. Other copper
salts may be used, especially the salts o~ organic
acidsj more especially the sal-ts of aliphatic
carboxylic acids and particularly the salts of alkane
carboxylic acids having from 2 to 6 carbon atoms. As
examples of such copper salts there may be mentioned
copper formate, acetate, propionate, bu-tyrate, lactate,
l~;lycollate, acetylacetonate, naphthenate, stearate and
benzoate. Moreover, other sources of halide ion may
be used for example alkali metal and ammonium chloride,
bromide and iodide as well as hydrogen chloride,
bromide ~nd iodi~le and chlorine, bromine and iodine
themselves. ~ur-ther, organic chlorine, bromine and
iodine compounds may be used as the halide source, for
example tetrabromoethane, chloracetic acid, bromoacetic
acid, acetylbromide, dichlorobutene and dibromobutene,
as well as hydrochlorides, hydrobromides and hydriodides
-- 3 --
"
.. .: . . .. . .
- H.~8239/2~748
.
Z~
of organic bases and quaternary amm~nium bromides and
iodides. It is advantageous also for there -to be
present an alkali metal salt, for example a sodium,
potassium or especially a lithium salt, or an
5 alkaline earth metal salt, for example a beryllium, -
magnesium, calcium or barium salt. Such a salt is
preferably a chloride, bromide or iodide, but may be,
for example, an organic acid salt, especially a salt
with one of the organic acids specified above as
forming suitable copper salts. As examples of such
salts there may be mentioned, lithium chloride, lithium
bromide, lithium iodide, lithium acetate, lithium
propionate, sodium bromide, sodium iodide, sodium acetate,
potassium bromide, potassium iodide, potassillm acetate
and magnesium bromide.
Preferably the halide ion in the catalyst ~ -
consists of a mixture of chloride and/or bromide ion with
iodide ion, since this gives a more active catalyst.
Mixtures of bromide with iodide ion are particularly
suitable. The uptake of oxygen may be assisted by the
presence of oxygen carriers, for example, manganese
compounds, e.g. manganese gluconate.
As solvents for the catalyst there may be used a
wide variety of compounds. The basic reciuirements are
that -the catalys-t components shall dissolve to a greater
or less extent in -the solvent and that the solvent shall
not interfere with the reaction and shall not itself be
. . .
-- 4 --
~.28Z3g/2874~
2~
extensively changed by the reaction. Thus olefinically
unsaturated compounds which react with hydrogen cyanide
under the reaction conditions are unsuitable, as are
solvents, for example mercaptans, which would be
oxidised by -the oxygen-containing gas under the reaction
conditions. The solvent should preferably be liquid at
the reaction temperature and pressure. However, compounds
which are normally solid under the reaction conditions
may be used dissolved in another solvent.
Water is a suitable solvent as are many organic
compounds. Particularly suitable classes of organic
compounds include nitriles, alcohols, phenols, ethers,
acids, ketones and amides. Suitable nitriles include
aliphatic, cycloaliphatic, araliphatic and aromatic
15 nitriles, More especially they include alkyl nitriles
and alkylene dinitriles, particularly those having from
1 to 6 carbon atoms in the alkyl or alkylene residue,
for example acetonitrile, propionitrile, butyronitrile,
hexanonitrile, glutarodinitri~e adiponitrile, dicyano-
2~ butene and succindinitrile, alkenyl nitriles, for exampleacrylonitrile, methacrylonitrile, butenenitriles, methyl
butenenitriles and pentenenitriles, higher polynitriles,
for example tetracyanoethylene, cycloalkyl nitriles,
for example cyclohexyl cyanide, aralkyl nitriles, for
25 example ben%yl cyanide and ~ xylylene dinitrile and
aryl nitriles, for example benzonitriles, tolunitriles,
phthalodinitrile and terephthalodinitrile. Particularly
.', ~; '
- 5 - `
:
~ 2~239/28748
2~
suitable nitriles include acetonitrile, propioni-trile
and adiponitrile.
Suitable alcohols include aliphatic, cycloaliph-
atic and araliphatic alcohols. More especially they
include alkanols, particularly those having from 1
to 6 carbon atoms, for example methanol, ethanol,
n-propanol, isopropanol, butanols, pentanols and
hexanols, alkandiols, particularly those having from
l to 6 carbon atoms, for example ethylene glycol,
propane-1,2-diol, propane-1,3-diol, butane-l,L~-diol,
pen-tane-diols and hexanediols, alkane-polyols, for
example glycerol and trimethylolpropane, aralkanols,
for example benzyl alcohol and 2-phenylethanol, and
cycloalkanols, for example cyclopentanol, methylcycl-
15 opentanols, cyclohexanol and methylcyclohexanols. -
Par-ticularly suitable alcohols include ethanol and
isopropanol.
Suitable phenols include phenol i-tself, alkyl-
phenols, for example cresols, ethylphenols and
xylenols, and halogenophenols, especially chlorophenols
and di- and tri-chlorophenols. m-Cresol is a particul-
arly suitable phenol.
Suitable e-thers include aliph~tic ethe~ aral-
iphatic ethers, aromatic ethers and cyclic ethers.
More especially they include dialkyl ethers, for
example di-isopropyl ether and methyl butyl ether,
bis-ethers and polyethers for example 1,2-dimethoxy-
ethane, 1,2-dimethyoxypropane and diethyleneglycol
.
~3
H. 28~9/287L~8
~82:Z~4
dimethyl ether (diglyme ), cyclic ethers, for example
tetrahydrofuran, tetrahydropyran, dioxan, diphenylene
oxide and crown e-ther (6, 7, 9, 10, 17, 18, 20, 21 -
octahydrodibenzo (b, k) (1, 4, 7, 10, 13, 16) ~
hexaoxacyclooctadecene), alkyl aryl ethers, for
example anisole and phenetole, diaralkyl ethers, for
example dibenzyl ether, and diaryl ethers for example
diphenyl oxide. Dimethyoxyethane, diglyme and tetra-
hydrofuran are p(srticularly suitable ethers.
Suitable organic acids are especially the
carboxylic acids. Suitable carboxylic acids include
aliphatic, cycloaliphatic, araliphatic and aromatic
carboxylic acids. More especially they include alkane
carboxylic acids, particularly those having from 2 to 6
carbon atoms in the alkane residue, for example acetic
acid, propionic acid, butyric acid, isobutyric acid,
valeric acid or caproic acid, cycloalkane carboxylic
acids, for example cyclohexane carboxylic acid and
cyclohexylacetic acid, aralkyl carboxylic acids, for
example phenylacetic acid, aryl carboxylic acids,
for example benzoic acid, toluic acids and anisic acids,
and napthenic flcids. Acetic acid is particularly
suitable.
Suitable ketones include aliphatic, cycloaliphatic,
araliphatic, aroma-tic and cyclic ketones. More
especially they include dialkyl ketones, particularly ~ -
those having from 1 to 6 carbon atoms in the alkyl
residues, for example acetone, methyl ethyl ketone
- 7 -
H.28239 ~28748
~3222~
and methyl isobutyl ketone, diketones, for exarnple
acetylacetone, cyclic ketones, for example cyclo-
pentanone, methylcyclopen-tanone, cyclohexanone and
methylcyclohexanone, alkyl aryl ketones, for example
acetophenone, and diaryl ketones, for example
benzophenone. Acetone and ace-tylacetone are
particularly suitable ketones. ~-
Suitable amides include in particular aliphatic
carboxylic amides and their N-substituted derivatives.
More especially they include alkane carboxylic amides,
particularly those having from 1 to 4 carbon atoms,
and their N-alkyl and N,N-dialkyl derivatives -
especially those having from 1 to 4 carbon atoms in
the alkyl residues, for example formamide, N-methyl-
formamide, N,N-dimethylformamide, acetamide, N,N-dim-
ethylacetamide and propionamide. They also include
cyclic amides for example N-methyl-2-pyrrolidone.
Dime-thyl~ormamide is a particularly suitable amide. -
Suitable solvents also include compounds which
contain two or more of the functional groups whichcharacterise, respectively, the said nitriles, alcohols,
phenols, ethers, acids, ke-tones and amides, or contain
one or more of the said functional groups in combination
with some other group. Such compounds include, for
example, ether-alcohols, for example ethylene glycol
monomethyl and monoethyl ether, nitrile-acids, for
example cyanoacetic acid and ~-cyanovaleric acid,
- 8 -
.'. , , ' ~ .:
.
- H.282 39! 287L
~ 4
halogeno-acids, for example chloroace-tic acid, dichlor-
oacetic acid and trichloroacetic acid, and nitrile-
esters, for example ethyl cyanoacetate.
Other suitable solvents include es-ters, especially
the esters formed from the alcohols and acids already
described as suitable solvents. Particularly suitable
esters are the lower alkylesters (e.g. where lower
alkyl has from 1 to 4 Carbon atoms) of aliphatic mono-
or di-carboxylic acids especially -those having from
1 to 6 carbon atoms, for example methyl acetate, ethyl
~cetate, iso-propyl ~ceta-te, ethyl propionate, methyl
butyra-te, dimethyl succinate, dimethyl glu-tarate and
diethyl adipate.
Other suitable solvents include hyurocarbons
and halogenated hydrocarbons. Such solvents include
both aliphatic, cycloaliphatic and aromatic hydrocarbons,
and their halogenated derivatives, for example hexane,
cyclohexane, benzene, toluene, xylene, chloroform,
carbon tetrachloride, trichloroethylene, tetrachlorethane,
dibromoethane, chlorobenzene, bromobenzene, dichlorobenzene
trichlorobenzene and diphenyl. ;
Other suitable solvents include thioethers, that
is sulphides,including cyclic sulphides, for example
dimethyl sulphide, diethyl sulphide, dipropyl sulphide,
dibu-tyl sulphide, diamyl sulphide, dihexyl sulphide,
methyl ethyl sulphide, thiophen, tetrahydrothiophen,
pentamethylene sulphide, dicyclohexyl sulphide, dibenzyl
sulphide, diphenyl sulphide, ditolyl sulphide and
thiodiglycol.
..
, . , . . . . , ~.
.. . - . . ,- ~ . . .
H.28239/28748
Other suitable solven-ts include sulphoxides and
sulphones, especially dialkyl sulphoxides and
sulphones, particularly where the alkyl group has from
1 to 6 carbon atoms, and cyclic sulphoxides and
sulphones, for example dimethyl sulphoxide, diethyl
sulphoxide, diethyl sulphone, dime-thyl sulphone, tetra-
methylene sulphoxide, tetrame-thylene sulphone
(sulpholane ) and pentamethylene sulphoxide and
pentamethylene sulphone.
The solvents may be used singly or in admixture
with each other in any convenient proportions. More-
over the solvents may be used in admixture with other
organic compounds which are not in themselves solvents
for the catalyst.
The oxygen may be used as such or in admixture
with non-re~ctive gases such as nitrogen. Air is a
particularly sui-table oxygen-containing gas, but
mixtures of oxygen and nitrogen with a higher or lower
proportion of oxygen than that of the air may also be
20 used.
The reaction is conveniently carried out at
temperatures within the range 10 to 150C, preferably
from 35 to 110C. The reaction may be carried ou-t at
atmospheric pressure or at pressures above or below that ; -
25 of the atmosphere. The process may advantageouslybe operated under pressure, and pressures may, for example,
be up to about 50 bar. Pressures in the range 2 to 10 bar~
absolute are very suitable.
- 10 - `
.
,~ . ... . . . . . .. ... . .
lI.2g23g /28748
~8Z~2~
The reaction may conveniently be carried out by
passing butadiene and hydrogen cyanide in vapour form
together with oxygen or an oxygen-containing gas through
a liquid comprising the catalyst and solvent under the
selected tempera-t;ure and pressure conditions.
Alternatively, the butadiene and hydrogen cyanide may
be kept in the liquid phase under pressure with the
catalyst and solvent, and the oxygen or oxygen-containing
gas passed through. It is not essential, however, for ~;
the oxygen or oxygen-containing gas to be con-tacted
simultaneously with the catalyst and solvent. It is
possible, for example, to pass butadiene and hydrogen
cyanide on the one hand and oxygen-containing gas on the ;~
other hand alternately through the liquid comprising the
; 15 catalyst and solvent. Passage of oxygen or oxygen-cont- ;
aining gas in these circumstances leads to a change in
the colour of the liquid to dark brown.
The butadiene used in the process of our invention
may contain other constituents. For example the
bu-tadiene may be admixed with other C4 hydrocarbons
for example butenes and butane. Instead of using
bu-tadiene itself, a crude CL~ stream from a cracker
containing possibly less than 50% of butadiene may be
used as the feed in our process to produce dicyanobutene.
Water is formed in the process of our invention,
and it may be desirable, for example when using organic
solvents, to remove the water from the reaction system.
The water is usually taken up into the reactant gas
- 11 - .
~8239 /28748
Z~9~
stream and is preferably condensed ou-t from the
effluent gas stream at least in par-t, prior to any
recycle.
In carrying out the process of our invention
the molar ratio of hydrogen cyanide -to butadiene may
vary widely, for example over the range 1:10 to 10:1,
but preferably over the range 1:2 to 4:1. The oxygen
is preferably used in molar excess in relation to
whichever of the hydrogen cyanide and butadiene is
10 used in the smaller molar amount.
The catalyst is used in catalytic amount.
The amoun-t of copper ion may vary, for example, from
0.001 mole to 0.2 mole per mole of butadiene, although
higher proportions are not excluded. The amount of ;
15 halide ion in total may vary, for example, wi-thin the
same molar range, although we prefer that there is at
least one mole of halide ion per mole of copper ion.
Where, as we prefer, the halide ions consists of a
mixture of chloride and/or bromide ion with iodide
20 ion the relative proportions of iodide to chloride
and/or bromide may vary within wide limits, for
example -the iodide may vary from 0.1% to 90% of the
combined chloride, bromide and iodide on a molar
basis, but we prefer the iodide proportion to be
25 between 1% and 10%. The amount of solvent used may
vary widely. There should preferably be at least one
mole of solvent per mole of copper ion, and amounts
between 5 moles and 100 moles are convenient. When
- 12 -
'
.
~,: . . , . : .
H ~8239 '/28748
an alkali metal or alk;~line earth metal compound is
present it may be used in amounts up to several times
the molar amount of copper, for example in amounts of
from 0.5 to 15 moles per mole of copper.
The dicyanobutene obtained as the product of
our process is normally present in the liquid reaction
mixture and may be separated therefrom by conventional
methods, for example by fractional distillation under
:,
reduced pressure, by extraction with solvents, or by
a combination of such methods.
The process of our invention is particularly -
adapted to continuous operation. I-t may be convenient
to take the reaction to only partial completion, to
separate at least some of the product and to recycle
unchanged material. For this reason times of contact
with the catalyst may vary widely. Such times may
vary from a few minutes, for example 5 minutes, up to
many hours, for example 50 hours.
The dicyanobutene product of our process is
principally 1,4-dicyanobutene. This is a valuable
intermediate, since it may, by hydrogenation of the double
bond, be converted to adiponitrile which itself, on ;~
hydrogenation of the nitrile groups, give hexamethylene
diamine, an intermediate useful in the manufac-ture of
polymers, for example polyurethanes and especially
polyamides, in particular polyamides made by polycond-
ensation with dicarboxylic acids, for example with adipic
acid to give polyhexamethylene adipamide (nylon 6.6) ~
- 13 - ~:
, . . . . .
... . , . . . ~ . . , . . . -: . - , :
H~ 2823~/287L~8
useful for the manufacture of mouldings and for melt-
spinning into synthetic fibres.
The invention is illustrated but not limited by
the following Examples.
ExamE~
Into a solution of 3g cupric bromide and 0.75g
li-thium bromide in 30g propionitrile maintained at 50C
there was passed butadiene at a rate of 2.5 l/hour into
which had been evaporated liquid hydrogen cyanide at a
10 rate of 4 ml/hour. After 1 hour the passage of the
butadiene/hydrogen cyanide mixture was stopped and
oxygen was passed through the solution at a rate of
3.5 l/hour for 1 hour when the mixture had become dark
brown. The cycle was then repeated. After a total
15 reaction time of 46 hours the reaction mixture was found
to contain 2.22g of 1,4-dicyanobutene with no significant
amounts of other unsaturated nitriles. The product was
isolated by evaporation of the solvent and extraction
of the residue with hot toluene.
Example 2
Example 1 was repeated except that a solution of
3g of cupric bromide in 30g of propionitrile was used as
the catalyst solution. After 46 hours the reaction
mixture was found to contain 1.26g of 1,4-dicyanobutene, -
5 and after 160 hours 2.56g of 1,4-dicyanobutene.
Example 3
Butadiene at a rate of 6000 parts by volume per
hour and oxygen at a rate of 6000 parts by volume per
_ 14 _
H 28239/28748
hour were passed together through liquid hydrogen
cyanide, which was thereby evaporated into the gas
stream, and the resulting gas stream was passed through
a mixture of 20 parts of cupric acetate and 42 parts
of lithium bromide in 200 parts by volume of glacial
acetic acid held at 90 -to 100C for a period of 9
hours, during which 44 parts by volume of liquid -
hydrogen cyanide were evaporated into the gas ~tream.
The reaction mixture was diluted with water, extracted
10 with toluene, and the toluene evaporated from the
extract. The residue consisted of 9.8 parts, 5% of ;~ ~;
which was 1,4-dicyanobutene-2 and 91% partly converted i
ma-terial capable of further conversion to dicyanobutene. :
Example.s 4 - 7
For operation at atmospheric pressure the ;
reactor consisted of a heated, efficiently stirred
vessel with a reflux condenser cooled to -6C. The
initial charge contained:
propionitrile 77 parts by weight
cupric bromide 8 parts by weight
lithium bromide 2 parts by weight
and iodine compounds as shown in Table 1 and was
maintained at 50C.
The reactants
butadiene 7 parts by wt. per hr.
hydrogen cyanide 6 parts by wt. per hr.
oxygen 8 parts by wt. per hr.
were fed -to the re~ctor. The excess gas can be
recovered for recycle.
.
- 15 -
;":''''
- . ~ . . -
H.28239/28748
2Z4
When steady reactlon conditions had been achieved
trans-l,L~dicyanobutene-2 was formed at the rates :
indicated in Table 1~ which rates were higher when
iodine compounds were present than when they were
absent. Moreover, the rates of formation of by-product
cyanogen, also indicated in Table 1, were less when :
iodine compounds were present.
:
;!
- 16 -
H. 28239/28748
o ~ ~ ~ ':
1 ~ ~ c~ .,
o~ ~O o ~ o ~ o :~ .
a~ ~S~ ~ . '
~, . ','''-
_ . . .
a) .
s ~ l , ~ .
,~ o C~ ~ ~ ~ . ':
s~ ~ ~ o ~ o . .
a~ ~ o o o o Q)
~1) h O O O O O S
~5: . . . . . i~ `,, .
h ~o ~ .
. _ .. ~o '~':
S~ ~ ;,. .
+~ .
~ Q)
S-
~h) ~ ~ cO
" h O ~) H ~ H
~d O O O O O S~
~1 ~ ~3 . .. .
~! ~ . s .i ':`
~ h ` :
+' X~
S~ ~ ~ ~ ~ O ~ .
3: O O O ~ ~ ~;' , .
. U~ ' '
a) ~ . .
.S: ~ ~ P~ '....... .
orcl ~i ~o
H ~ ~ ~ S~ H ..
~ o ~ 1 tn
~> ~ ~; $ ~0 ~ O ':
~ O H H ~1 S~
~ V ~0 ::~ :'` .`
~ .~ . . . ~. `: . . .
O .,. ,~ .
~o s~l q
~ Z o ~
_ . V ~ '' ,
_ . . " ' :
-- 17 --
28239~/28748
Example 8
To a solution of 4 parts by weight of cupric bromide,
2 parts of cuprous iodide and l part o~ thium bromide
in 40 parts of propibnitrile held a-t 50C in a hot
5 water jacketed tubular reac-tor at atmospheric pressure
was added a vapour phase mixture of hydrogen cyanide
(1.15 parts by weight per hour), bu-tadiene (5.8 parts/
hour) and oxygen (3.4 parts/hour) via a gas bubbler.
After 78 hours, passage of gas was stopped and
lOthe liquid reaction mix-ture was evaporated to dryness
and the residue extracted with toluene from which 15.8
parts of trans-1,4-dicyanobutene-2 crystallised out on
cooling to 0C, a yield of 5.25 moles per mole of
copper present in the reaction mixture.
Example_9
The mixture
prbpionitrile16 parts by weight
cupric bromide 4 parts by weight
lithium bromide l parts by weigh-t
sodium iodide0.5 parts by weight
butadiene6.2 parts by weight
hydrogen cyanide 6.9 parts by weight
was charged to a suitable pressure vessel and the
pressure adjusted to L~. 5 bar absolute with air. After
heating and maintaining the temperature at ~0C for l
hour the reactor was cooled and the excess gas vented.
From the product 0.74 parts by weight of trans-1,4-
dicyanobutene-2 was obtained equivalent to a rate of
0.174 mol/litre/hour based on the volume of reaction
mixture.
H28239`/28748
2fl~
Example 10
Example 9 was repeated except that pure oxygen -~
was used instead of air. 2.04 parts by weight of
trans-1,4-dicyanobutene-2 were obtained equivalent to
a production rate of 0.480 mol/litre/hour based on the
volume of reaction mixture.
Example 11
A mixture consisting of:
propionitrile 20 ml
cuprous bromide 2 g
cuprous iodide 1 g
lithium bromide 1.5 g
butadiene 10 ml
hydrogen cyanide 15 ml
cyanoacetic acid 1 g
acetone 1 ml
triphenylphosphine 0.1 g
was stirred in a pressure vessel and charged with oxygen
at 4.5 bar absolute then heated at 60C for 5.5 hr.
After releasing pressure the contents were analysed by
G.L.C.(gas/liquid chromatography) and found to contain
11.84 g trans-l J 4-dicyanobutene-2.
Exampl~s12 - 16
Reaction mixtures containing in each case
propioni-trile 20 ml.
cupric bromide 2 g.
cuprous iodide 1 g.
lithium bromide 0.5 g.
oxygen 4.5 bar absolute
and the constituents shown in Table 2 were reacted at
the temperatures for the times shown in Table 2. The -
production of dicyanobutene shown in the Table is up to
: - :
- 19 -
H.2g23g/28748
Z~
6 mols/mol copper for Examples 12 to 14 and approxim-
a-tely 9 mols!mol copper for Examples 15 and 16.
~ '
.
;~
_ 20 -
" H, 2823~/28748
._ .,_. _.................. . ~ - .
N
~D N N r~ 0 2 N ~ .
` ___ ,. _
oo ~ a~
L~ O ~ - O N
r I N N ~Ir--l O L~ N
~ ....... ... ...... ,.............. ~'
O rl N ~ ~
~ o ~ ,~ 0 2 ~ ~
. . . _
o :.
~ O N . ~ o ~1~ O .
~ r-l r-l~1 0 Li~ ~ .~ "
_ _.. _~_, _
N 1~ 0 O 1~ 0 . ~ .
~1 ~ ;. .
__ . ~: ' ~" " '
N ¦ ~ "
m . .
CC .
l ~ "
: ~ 0 ~; ~ OV ~ ~ ,-',
. ~ ::
~ ~0
~d ~d ~ ~ . :
. S~ o ~.
O ~r~ :
~>~ 5-1 rd a) ~
oo ~ ~ S ~ I
a~ ~ ~ .,
~1 ~ ., -, .
a~ I) ~1 , '
~3 ,1 bO ~QU O h I .. ..
~a d O O ~a o ~1 (L) u~
X ~ S~
~d a) ~ ~d
m x ~
. - . . -
-- 21 -- ~
. -- .
. .:
- H.28239/28748
2Z;~4
Example 17
A mixture consisting of:
propionitrile 18 ml ~
crown ether 6 ml : -
cuprous bromide 2 g
cuprous iodide 1 g
lithium bromide 0.5 g
butadiene 6 ml
hydrogen cyanide10 ml
was stirred in a pressure vessel and charged with
oxygen at 4.5 bar absolute, then heated at 50C for ~;
4 hours, The product contained 6.8 g. of trans-1,4-
dicyanobutene-2.
Example 18
15This example shows the use of a crude C4 s-tream
from a cracker (containing 41.7% of butadiene) ` :
A mixture consisting of:
propionitrile 20 ml
cuprous bromide 2 g
cuprous iodide 1 g
lithium bromide 0.5 g
A C4 stream containing
41.7% of butadiene10 ml
hydrogen cyanide10 ml
was stirred in a pressure vessel and charged with
oxygen at 4.5 bar absolute then heated at 50C for
15 hours. The product contained 3~44 g of trans-1,4-
dicyanobutene 2.
Example 19
The effect of various solvents was examined by
charging the following mixture to a pressure vessel
- 22 -
,.' , ' .. ' .
~-28239/28748
, :
Z~L
equipped wi-th a stirrer.
Solvent 20 parts by vol.
Cupric bromide 4 par-ts by weight
Lithium bromicle 0.5 parts by weight
sodium iodide 0.5 parts by weight
Butadiene 10 parts by volume
Hydrogen cyanide 10 parts by volume :
Oxygen (4.5 bar absolute
equivalent to) .045 parts by weight
10 The reactor and contents were heated to 50C and
this temperature maintained for 2 hours before cooling
and venting excess gas. The residue was dissolved
in solven-t and the amount of trans-1,4-dicyanobutene-2
in parts by weight was de-termined by G.~.C. The
15 results are summarised in the Table. _ _
``,- .
'. " '
'.
, .
- 23 - ;
' ~'" .
.. ~
', ;, ' ,
H.28239/28748
r Solven-t Trans-1,4-dicyano-
, _ _ butene-2
Water 0.68
Methanol 0.73
Ethanol 2.17
isopropanol 3.20
t-butanol .95
2 Phenylethanol .22
Ethylene glycol .23
Propane-1,2-diol .23
m-cresol 6.52
Tetrahydrofuran 2.42
Tetrahydropyran 1.16
Dioxan .56
1,2-Dimethoxyethane 3.91
Diglyme 2.54
Anisole .45
Acetic acid 1.55
Naphthenic acid .07
Methyl acetate .97
Diethyl adipate .41
Acetone 3.89
Cyclohexanone .17
Acetophenone 1.61
Acetylacetone 3.39
Ethyl cyanoacetate 1.17
N-Methylformamide 1.79
Dimethyl fprmamide 2.21
N-Methyl-2-pyrrolidone .43
n-hexane .17
Toluene .93
Brombenzene .52
Dichloromethane 1.03
Tetrachlorethane .90
._
_ 24 -
H,28239/28748
h~Z~
E,xample 20 :.
Example 19 was repeated, except that the
reaction mixture was heated for 5 hours 9 using .
the following compounds as solvent and the
quantity of trans-1,4 dicyanobu-tene-2 indicated
(in parts by weight) was obtained. ~ .
.
. _ _.
Solvent Trans-1,4-dicyano-
butene-2 ..
_ _ _ _
Benzonitrile 4.11 :
10 Adiponi-trile 6.24 ~:
Sulpholane - 5.02 :~
.
~ ç~_2
A gas stream consisting of butadiene at a -~
rate of 3 l/hr and oxygen at a rate of 6 l/hr and :;.
15 into which liquid hydrogen cyanide at a rate of --
:: 8 ml/hr was fed was passed through a mix-ture of;
Benzonitrile 100 ml .
Cupric bromide 7.9 g -
Lithium bromide 2 g
20 at 50C stirred at atmospheric pressure for 11
hours. Trans-1,4-dicyanobutene-2 was formed at a
rate of 10.7 millimoles per li-tre of reaction
mixture per hour. :~
, ,
- ' ," '
: - 25 ~
'
-~
