United States Patent (19) (11) 4,142,060

Kuntz 45 Feb. 27, 1979

(54) TELOMERIZATION PROCESS USING 56 References Cited
SULFONATED TRARYLPHOSPHINE AND U.S. PATENT DOCUMENTS
TRANSTON METAL
3,670,032 6/1972 Romanelli........................ 260/632 R
3,887,627 6/1975 Romanelli........................ 260/632 R
(75) Inventor: Emile Kuntz, Lyons, France 3,992,456 11/1976 Atkins et al. .................... 260/632 R

73 Assignee: Rhone-Poulenc Industries, Paris, Primary Examiner-Joseph E. Evans

France
Attorney, Agent, or Firm-Bacon & Thomas
57 ABSTRACT
(21 Appl. No.: 817,800 A process for the telomerization of dienes with a telom
erizing compound containing a mobile hydrogen atom
22 Filed: Jul. 21, 1977 is disclosed wherein the reaction between the diene and
the telomerizing agent is effected in the presence of a
(30) Foreign Application Priority Data catalytic system comprising a water-soluble sulfonated
triaryl phosphine compound, preferably a water-soluble
Jul. 27, 1976 FR France ................................ 76 22824. salt of a mono-, di-, or trisulfonated triphenyl phosphine
and a transition metal compound, preferably palladium
(51) Int. Cl? .................................r CO7C 29/00 or a palladium-containing compound. Water is added
52 U.S. C. ................................ 568/840; 252/431 P; either before or after the reaction is completed and the
260/505 C; 260/583 H; 560/244; 568/689; reaction products can easily be separated from the aque
568/657; 544/106 ous catalyst solution.
58) Field of Search ................ 260/632 R; 252/431 P;
568/840 41 Claims, No Drawings
 4,142,060
1. 2
ously recycled for economical reasons. Furthermore,
TELOMERZATION PROCESS USING the separation problems outlined above remain.
SULFONATED TRIARYLPHOSPHINE AND SUMMARY OF THE INVENTION
TRANSTION METAL
BACKGROUND OF THE INVENTION
5 It is an object of the present invention to provide an
improved process for reacting a diene with a compound
1. Field of the Invention containing a mobile hydrogen, which avoids these diffi
The invention relates to a process for telomerizing culties attendant the state of the art.
olefins, especially dienes, with a telomerizing com It is a further object of the present invention to pro
pound containing at least one mobile hydrogen atom, 10 vide such a process which permits an easy separation of
particularly to a process wherein the amount of the the catalyst and the reaction products, e.g., by simple
diene is at least equivalent to the amount of mobile decantation or extraction, especially a process which
hydrogen atoms. avoids the contamination of the reaction product with
2. Description of the Prior Art impurities from the catalysts and avoids the loss of ex
The French Pat. No. 2,045,369 discloses a process for 15 pensive catalyst.
preparing diolefinic alcohols containing twice the num It is a special object of the present invention to pro
ber of carbon atoms of the starting 1,3-diolefins. Ac vide such a process wherein the catalyst can easily be
cording to this process, a reaction mixture is formed recovered in a form which can be directly re-used for
containing the diolefin, water, and a solvent wherein the same reaction, e.g., which can be directly recycled
the diolefin, as well as the water are at least partially 20 into the reaction mixture.
soluble in the presence of a catalyst containing palla In order to accomplish the foregoing objects accord
dium or platinum, phosphine and carbon dioxide gas as ing to the present invention there is provided a process
a co-catalyst. The diolefinic alcohol is formed by the for telomerizing dienes, which comprises the step of
reaction of the diolefin with water. For use in this type reacting a diene with a telomerizing compound contain
of process, such solvents are selected which have a 25 ing at least one mobile hydrogen atom in the presence of
certain affinity for the diene and for the water in order a water-soluble catalytic system comprising at least one
to maintain a liquid and homogeneous reaction mixture. water-soluble phosphine having the formula (I)
The solvents which are used are organic solvents such
as, e.g., dioxane, dimethyl acetamide, tert. butanol and (SOM)n
acetOne. 30
Processes for telomerizing diolefins, particularly bu
tadiene, with various compounds containing mobile
hydrogen atoms, such as alcohols, carbocyclic acids,
silanols, ammonia, amines, compounds with reactive
methylene groups, and the like, in the presence of a 35
catalyst usually containing palladium and a co-catalyst,
such as phosphine, are known in the art see Accounts
Chem. Res., 1973, 6(1) 8-15).
The first major problem which arises during carrying
out the prior art processes is the separation of the reac
tion products and the catalyst. It is, in effect, desirable
to recover the catalyst for re-utilization. Yet the prior wherein Arl, Ar2 and Ars each represent an aryl group
art proposes only processes wherein the final separation having from 6 to 10 carbon atoms, which may be alike
step has never been satisfactorily solved by a generally or different from each other; Y1, Y2 and Y3, which may
applicable method. It proves always to be difficult and 45 be alike or different from each other each represent an
incomplete. In effect, in most of the cases, not all of the alkyl group containing 1 to 4 carbon atoms, an alkoxy
reaction products can be separated from the reaction group containing 1 to 4 carbon atoms, a halogen, cyano
medium by simple methods since on the one hand, the , nitro- or hydroxy radical or an
catalyst is soluble in the organic solvents which are used
and on the other hand, certain by-products are too non 50 /
R
volatile to be separated by distillation. If it is possible to amino group -N y
separate the main reaction product by distillation, for
reasons concerning the thermal stability of the catalyst, R2
it is impossible to eliminate the by-products, such as,
oligomers and telomers of the diolefin, by distillation. 55 wherein R1 and R2, which may be alike or different
According to the prior art processes, a loss in catalyst from each other each represent an alkyl group contain
is noted and the latter is present in the reaction product. ing 1 to 4 carbon atoms; M represents a cation which is
In case the compound containing the mobile hydro able to form water-soluble compounds of formula (I)
gen atom is water, the second major problem is how to selected from the group consisting of a proton, a cation
exalt its reactivity. The solutions provided by the prior derived from an alkali metal or an alkaline earth metal,
art exist in, e.g., adding an alcohol to the reaction mix ammonium, a group N(R3R4R5R6)-- wherein R3, R4,
ture (British Pat. No. 1,354,507 and U.S. Pat. No. Rs and R6 each represent hydrogen or an alkyl group
3,670,032). A large amount of carbon dioxide gas has containing 1 to 4 carbon atoms and may be alike or
been used to increase the reaction speed (French Pat. different from each other, and a cation of any other
No. 2,045,369, cited above). In the first case, the major 65 metal, which is able to form water-soluble salts with
inconvenience is the joint formation of undesirable benzosulfonic acids; m1, m2 and m3 each represent a
ether (often even as the major product). In the second whole number from 0 to 5 which may be the same or
case, the amount of carbon dioxide has to be continu different from each other, and n, n2 and in each repre

Hammmamm-au
 3
4,142,060
4.
sent a whole number from 0 to 3, which may be the that obtained at the end of the reaction in the first em
same or different from each other, whereby at least one bodiment is obtained. In this embodiment, of course, it
of these numbers n1, n2 and ng equals at least one and will be necessary to eliminate the water again from the
further comprising a compound selected from the group catalyst in any conventional manner before recycling
consisting of a transition metal, preferably palladium or the latter into the reaction. This can be done, for exam
a transition metal-containing compound, preferably a ple, by adding a heavy solvent which permits to deplete
palladium containing compound. the water.
Either before or after the reaction is completed, In the first embodiment, the phosphines can be intro
water is added to the reaction mixture, whereby an duced into the reaction mixture in the form of an aque
aqueous solution of the catalytic system is formed. 10 ous solution.
When the reaction is finished, the reaction products can Preferred are such phosphine compounds of formula
easily be separated from the reaction mixture and a (I) wherein Ari, Ar2 and Ars each represent phenyl, Y1,
major portion of the aqueous solution of the catalyst can Y2 and Y3, which may be alike or different from each
be recovered for re-use. other, each represent an alkyl group containing 1 to 2
The process is preferably used for telomerizing di 15 carbon atoms, an alkoxy group containing 1 to 2 carbon
enes, especially butadiene and derivatives thereof into atoms or chlorine, M represent a proton, a cation de
diene derivatives containing the double amount of car rived from sodium, potassium, calcium or barium, am
bon atoms than the starting materials. Yet, it can also be monium, tetramethylammonium, tetraethylammonium,
used for tri- or tetramerization of dienes or for addition tetrapropylammonium or tetrabutylammonium; m1, m2
of a mobile hydrogen containing compound to a diene 20 and m3, which may be alike or different from each
molecule. other, each represent a whole number between 0 and 3.
The ratio between the amount of diene and a telomer Among those phosphines of formula (), the most
izing compound is equivalent to at least one molecule of preferred are the sodium, potassium, calcium, barium,
diene per ten atom of mobile hydrogen. ammonium, tetramethylammonium and tetraethylam
Further objects, features and advantages of the pres 25 monium salts of (sulfophenyl)diphenylphosphine, di(-
ent invention will become apparent from the following sulfophenyl)phenylphosphine and tri(sulfophenyl)phos
detailed description of the invention and its preferred phine, wherein the So3-groups preferably are situated
embodiment. in meta-position.
DETAILED DESCRIPTION OF THE Further examples of phosphines of formula (I) which
INVENTION
30 may be used according to the process of the present
invention are alkali metal salts, alkaline earth metal
Amongst the above-defined cations M, cations which salts, ammonium salts or quaternary ammonium salts of
are derived from lead, zinc, or tin, can be cited as exam (m-sulfophenyl)diphenylphosphine, (p-sulfophenyl)di
ples of cations which are able to form water-soluble phenylphosphine, (m-sulfo-p-methylphenyl)di(p-
salts with benzosulfonic acids. 35 methylphenyl)phosphine, (m-sulfo-p-methoxyphenyl)-
The process according to the present invention can di(p-methoxyphenyl)phosphine, (m-sulfo-p-chloro
be effected to either of the following two main embodi phenyl)di(p-chlorophenyl)phosphine, di(m-sulfo
ments. phenyl)phenylphosphine, di(p-sulfophenyl)phenylphos
According to the first embodiment, water is intro phine, di(m-sulfo-p-methylphenyl)(p-methylphenyl)-
duced before the telomerizing reaction is completed. phosphine, di(m-sulfo-p-methoxyphenyl)(p-methoxy
According to the second embodiment, water is intro phenyl)phosphine, di(m-sulfo-p-chlorophenyl)(p-
duced only after the telomerizing reaction is completed. chlorophenyl)phosphine, tri(m-sulfophenyl)phosphine,
Within the first embodiment, two different cases have tri(p-sulfophenyl)phosphine, tri(m-sulfo-p-methyl
to be distinguished. The first is related to the use of a phenyl)phosphine, tri(m-sulfo-p-methoxyphenyl)phos
mobile hydrogen-containing telomerizing compound 45 phine, tri(m-sulfo-p-chlorophenyl)phosphine, (o-sulfo
which is sparingly soluble in water; the other is related p-methylphenyl)(m-sulfo-p-methyl (m,m'-disulfo-p-
to the use of a water-soluble mobile hydrogen-contain methyl)phosphine, (m-sulfophenyl)(m-sulfo-p-
ing telomerizing compound (e.g., the use of methanol). chlorophenyl) (m,m'-disulfo-p-chlorophenyl)phos
If the mobile hydrogen-containing compound is not phine.
water-soluble, two phases will be present at the end of 50 As stated before, a mixture of these phosphines, par
the reaction: an aqueous phase containing the catalyst ticularly a mixture of mono-, di-, or tri-metal-sulfonated
and an organic phase containing the reaction products. phosphines can be used.
In this case, for example, the separation is done simply As a transition metal compound, preferably a palla
by decantation or extraction. If the mobile hydrogen dium, nickel, platinum, cobalt or rhodium compound is
containing compound is at least partially soluble in 55 used. Such compounds are used which are water-solu
water, often only one single phase will be present at the ble or able to be dissolved under the reaction condi
end of the reaction. Then it is necessary to submit this tions. The group which is connected to the transition
reaction mixture to a distillation operation in order to metal is not critical as long as these requirements are
eliminate the remaining unreacted amount of the mobile fulfilled.
hydrogen-containing telomerizing compound, thereby 60 These transition metals can also be used in the form of
obtaining a two-phase system of the kind described metals deposited onto an inert carrier, e.g., carbon
above. black. Among the before-mentioned compounds, palla
The aqueous phase which is recovered after decanta dium compounds are most preferred. The following
tion or extraction can be directly recycled into the reac compounds are cited as non-limiting examples: com
tion. This permits one to carry out the process in a 65 pounds wherein the redox value of the palladium is
continuous operation. other than Zero, e.g., palladium acetate, carbonate, car
Within the second embodiment, water is added only boxylate, borate, bromide, chloride, citrate, hydroxides,
after the reaction is terminated, and a system identical to iodide, nitrate, sulfate, arylsulfonates and alkylsulfon
 4,142,060
5, 6
ates, -acetylacetonate, bis(benzonitrile)palladium chlo clei by means of oleum and then neutralizing the formed
ride, potassium tetrachloro palladate, and, T-allyl com sulfonic groups by means of an appropriate basic deriv
plexes of palladium, especially T-allyl palladium acetate ative of one of the metals, which are represented by M
or -chloride. in the formula (I). The crude sulfonated phosphines
It is not necessary that the palladium compound as which are obtained may contain corresponding oxides
such be soluble in water. For example, the palladium of sulfonated phosphines mixed with them, yet the pres
acetate is not very soluble in water but dissolves very ence thereof does not interfere with performing the
well in an aqueous phosphine solution. hydroxyanation process according to the present inven
Among the compounds wherein the redox value of tion.
the palladium equals zero, a large number of various 10 The process of the present invention is suited for
complexes can be used. The latter may contain olefins, telomerizing olefins, preferably aliphatic dienes, which
dienes, or cyano groups as a ligand. In particular, there contain 4 to 20, preferably 4 to 8, carbon atoms and may
can be used tetra(biphenyl)phosphine palladium (zero), be substituted by lower alkyl groups. In particular,
bis(cyclo-octadiene-1,5) palladium (zero) or potassium lower aliphatic conjugated dienes, such as, butadiene,
tetracyano palladate. In this latter case, the compound 15 isoprene, piperylene or dimethylbutadiene are treated
may be dissolved in a non-water miscible solvent like according to the process of the present invention.
toluene. An aqeous solution of a sulfonated phosphine A telomerizing compound containing at least one
extracts part of the palladium therefrom, whereby a mobile hydrogen atom is a compound which contains at
yellow coloration develops in the decanted aqueous least one reactive hydrogen atom. The following
solution. 20 groups of compounds may be cited as examples of com
Finally, palladium metal deposited onto an inert sup pounds containing reactive hydrogen atoms: water,
port such as carbon black can also be used. alcohols, phenols, acids, amines, silanols or compounds
The amount of transition metal compounds, espe containing a reactive methylene group.
cially palladium compounds, which are used are chosen Among the alcohols, the following may be cited
in such a range that the reaction solution contains be 25 suitable examples: primary, aliphatic, saturated,
tween about 10 and about 1 gram atoms, preferably branched or straight alcohols containing preferably 1 to
between about 0.005 and 0.5 gram atoms of elementary 8 carbon atoms, such as, methanol, butanol and the like,
metal per liter. unsaturated aliphatic alcohols containing preferably 3
The amount of phosphine compounds of formula (I), to 8 carbon atoms, such as, allyl alcohol, saturated ali
which is used within the reaction medium is chosen in 30 phatic or alicyclic secondary alcohols containing pref
the range that the reaction medium contains between erably 3 to 8 carbon atoms such as isopropanol or cyclo
about 1 to about 2,000, preferably between about 1 and hexanol, aromatic alcohols containing 7 to 12 carbon
3 moles of phosphines per gram atom of elementary atoms, such as, benzyl alcohols, fluorinated aliphatic or
metal. aromatic alcohols, e.g., tertiary alcohols of the formula
Even so, this is not absolutely necessary when palla 35
dium metal or one of the above-mentioned palladium
compounds are used, a palladium reducing agent, pref
erably a palladium reducing agent which reacts with the
palladium under the given reaction conditions, is added
SF,
to the reaction medium. This reducing agent may be an Ar--oh
CF
organic or inorganic agent. The following agents are
cited as non-limiting examples: sodium borohydride, wherein Ar represents an aryl group containing 6 to 10
powdered zinc, magnesium, potassium borohydride and carbon atoms, preferably phenyl or benzyl, or alcohols
other boron hydrides, preferably water-soluble boron of the formula CF3-(CF2)-CH2OH, wherein n is an
hydrides. 45
integer from 1 to 6, or polyols preferably containing 2 to
It is advisable to add an amount of reducing agent
which corresponds to between about 1 and about 10 8 carbon atoms, e.g., glycol.
redox equivalents. Nevertheless, the addition of lower Among the phenols, unsubstituted phenols and phe
amounts or higher amounts which correspond to more nols substituted by lower alkyl, lower alkoxy, or halo
than 10 redox equivalents is not excluded. 50 gen are particularly suited. As examples, there may be
Such a reducing agent may also be added if platinum cited phenol p-chlorophenol, o-methoxyphenol, dime
or rhodium are used. If nickel or cobalt are used, the use thylphenols and cresols.
of a reducing agent is necessary when their redox value Among the acids, lower aliphatic and aromatic
is other than zero, but not imperative if the redox value . mono- or divalent acids, preferably containing less than
equals zero. The same reducing agents which are used 55 12 carbon atoms are particularly suited. As examples,
with palladium can be used. there may be cited aliphatic monocarboxylic acids, such
The sulfonated phosphines which are used within the as acetic acid, aliphatic dicarboxylic acids, such as
process of the present invention can be prepared by adipic acid, aromatic mono- or dicarboxylic acids, such
conventional methods. Thus, according to the teachings as benzoic acid or o-phthalic acid.
of H. Schindlebauer, Monatsch, Chem., 96, pages Among the amines which can be used within the
2051-2057 (1965), the sodium salt of (p-sulfophenyl)- process according to the present invention, primary
diphenylphosphine can be prepared by reacting sodium aliphatic or aromatic amines, e.g., lower alkyl amines,
p-chlorobenzene sulfonate with diphenylchlorophos such as methylamine or aniline, secondary aliphatic or
phine in the presence of sodium or potassium. Accord aromatic amines, e.g., di(lower alkyl) amines, such as
ing to the method which is described in J. Chem. Soc., 65 diethylamine, lower alkyl anilines, such as methyl ani
pp. 276-288 (1958), and in the British Pat. No. line, heterocyclic amines, preferably containing 5 or 6
1,066,261, phenylphosphines of formula (I) can be pre ring members, e.g., piperidine or morpholine. Ammonia
pared by using the method of sulfonating aromatic nu can also be used.
 7
4,142,060
8
Among the compounds containing a reactive methy for example, mineral acids of elements of the Group
lene group acetone derivatives, e.g., lower aliphatic or IIIA, such as, boric acid, acids of elements of the Group
aromatic acyl or carboxyl derivatives of acetone are IVA, such as, carbonic acid, acids of elements of the
particularly suited. The following may be cited as exam
ples: acetylacetone, benzoylacetone, ethyl acetoacetate. 5 Group
five
VA, such as, phosphoric acid and acids of tri- or
valent phosphorous, or arsenic acid, acids of ele
Also suited are nitro compounds e.g., nitro-methane. ments of the Group VIA, such as, sulfuric acid, sulfu
By reacting 2 moles of diene, e.g., butadiene, with one rous acid or alkylsulfonic acid, acids of elements of the
mole of one of the various compounds HX, the follow Group VIIA such as hydrofluoric acid, hydrochloric
ing compounds are obtained: acid, hydrobromic acid, or hydroiodic acid, organic
10 acids such as trifluoromethane sulfonic acid, trifluoro
X
acetic acid, aryl- or alkylsulfonic acids, carboxylic acids
2n-1N1Sat1n
2 X and a-N-N-
2 1. such as, acetic acid and weak acids like phenol.
For each mobile hydrogen containing compound, the
wherein X is: 15 person skilled in the art can choose the appropriate
combination of the above-mentioned additives in order
2 to achieve the best reaction speed and to facilitate the
recycling.
Due to its low reactivity, water will not chemically
=o 20
interfere as a reactant in the case where it is used as a
-oh-or-o-NR-ocor-H. CEO
solvent for the catalyst. It has been found that when
water is used as a mobile hydrogen-containing reactant,
Y the addition of certain water-soluble compounds signifi
-CHNO ot -OSiR cantly increases the reaction speed. Among these com
pounds are alkaline electrolytes, alkali carbonates and
wherein 2 is alkyl or aryl and Y is alkyl, aryl or alkoxy. 25 -bicarbonates, such as, sodium carbonate and -bicarbon
a

By reacting one mole of butadiene with one mole of ate, sodium silicates and alkaline salts of phosphorous
a compound HX, wherein X, is -Od-OCOCH3 or phosphoric and arsenic acids.
NR2, the following compounds are obtained: It may be advisable to add to the reaction mixture an
30 organic solvent which is inert towards the various com
ponents of the reaction mixture. There can be used a
solvent which is immiscible with water or a solvent
which is miscible with water. In the latter case, the
solubility of, e.g., the butadiene in water increases and
In the case that the mobile hydrogen-containing com- 35 the reaction speed can be increased. Solvents which are
pounds include more than one mobile hydrogen atom immiscible with water provide for a better decantation.
per molecule, a replacement of all the mobile hydrogen The following are cited as examples for water misci
atoms can be obtained. Thus, starting from butadiene ble solvents: acetone, acetonitrile, dimethylether or
and an amine RNH2 dioctadienyl alkyl- or aryl amines diethylene glycol, dimethoxyethane, dioxane, tert. buta
of the nol, dimethyl acetamide, n-methyl pyrolidone and eth
ylene carbonate, dimethoxyethane, and as examples of
formula ( 1N1-1s-1-NR immiscible solvents, benzene, benzonitrile, acetophe
none, isopropyl ether, octane, methylethylacetone and
are obtained. propionitrile can be mentioned.
According to the present invention, the following 45 The temperature at which the reaction is performed
compounds are prepared: may vary within wide ranges. Moderate temperatures
1-methoxy-2,6-dimethyloctadiene-2,7 starting from between -20 to 200° C., preferably temperatures be
1-isoprene and methanol tween about 20 and about 125 C., are particularly
octadiene-2,7-ol-1 starting from butadiene and water suitable.
1-acetocyoctadiene-2,7 starting from butadiene and 50 According to an embodiment of the process of this
acetic acid invention, an appropriate reaction vessel, which has
1-phenoxyoctadiene-2,7 starting from butadiene and been purged by means of an inert gas (nitrogen or ar
phenol gon) is charged either with an aqueous catalytic solu
N,N-diethylamino-1-octadiene-2,7 and N,N-die tion which was prepared before or with the various
thylamino-1-butene-2 starting from butadiene and 55 components: a phosphine, water, the transition metal
diethylamine compound optionally together with a reducing agent,
N-octadienyl-2,7-morpholine starting from butadiene an additive, and an organic solvent. The reaction vessel
and morpholine. is brought to the reaction temperature before or after
The compounds which are obtained according to the the mobile hydrogen-containing compound is intro
present invention are useful as intermediates for the 60 duced, which itself may be introduced before, after or
synthesis of plasticizers, plastic materials, perfumes, simultaneously with the diene.
pharmaceuticals and galvano plastics. After stopping the reaction, the mixture is cooled to
The process according to the present invention may room temperature. The content of the reaction vessel is
be effected in the presence of further additives. Suitable drawn from the vessel, and afterwards, the reaction
additives are bases, such as hydroxides of alkali metals, 65 product has only to be recovered by subsequent decan
alkaline earth metals, tertiary aliphatic or aromatic tation or eventually by extraction by means of appropri
amines, phenolates, or solutions corresponding to mix ate solvents such as, e.g., the water immiscible solvents
tures of the beforementioned bases and acids, such as, which were cited above.
 4,142,060
10
The remaining aqueous solution may be recycled into 78.6 g of methanol
the reaction vessel for catalyzing a new reaction. The This was purged for 30 minutes with argon, then 70 g
aqueous solution may also stay in the reaction vessel of butadiene was introduced. The autoclave was then
when the organic compounds are drawn from it. agitated at 95 C. for 18 hours and then cooled to 50° C.
Another embodiment of the process according to the in order to eliminate the unreacted butadiene (less than
present invention comprises carrying out the above 2 g). Then at 35° C. and under argon, the content of the
operation but introducing the water only after the reac autoclave was transfered into a conical distillation appa
tion as such has stopped. In this case, before recycling ratus through which argon was passed. The reaction
the catalyst, the water has to be eliminated again by any mixture comprised two phases. Methanol was removed
convenient means. 10 by distillation. The distillation was carried out at atmo
It was found that the process according to the present spheric pressure by heating the boiler to 101" C.,
invention allows to obtain yields which depending on whereby the temperature at the top of the column was
the respective reaction can be as high as 95%. 90.5' C. During the distillation, 10 ml of water were
The following examples are intended only to further added in order to obtain an aqueous phase the volume of
illustrate the invention without limiting it. 15 which was between about 15 and 30 ml. This aqueous
phase, which contained the catalyst, was recycled into
EXAMPLE 1 the autoclave under argon. The supernatant organic
Into a 500 ml stainless steel autoclave which was phase, the weight of which was 75.6 g., comprised
equipped with a knock-type agitation system, the fol mainly methoxyoctadienes.
lowing were introduced: 20 According to chromatographical analysis, the fol
40 g of a solution containing: lowing results were obtained by the above procedure:
0.0178 g (0.1 m mole) of palladium chloride and percentage of conversion of the butadiene: d95%
0.124 g (0.3 m mole) of the mono sodium salt of yields per amount of used up butadiene:
(m-sulfophenyl)diphenylphosphine dihydrate -MOD: 78%
content in trivalent phosphorus 95% of the theo 25 3-MOD: 7%
retical amount) in methanol. C8: 11 %
40 g of additional methanol The remainder to 100% was comprised of mainly
0.100 g (1.8 m mole) of potash oligomers and telomers.
0.030 g (1 m mole) of sodium borohydride 30 EXAMPLE 3
The autoclave was purged for 30 minutes with argon, Into a 125 ml stainless steel autoclave, which was
then 25 g of butadiene were introduced. The autoclave equipped with a knock-type agitation system, the fol
was than agitated for 21 hours at 30°C. Then also at 30 lowing were introduced:
C., 4 g of butadiene were degassed. The reaction mix 0.039 g of palladium acetate
ture was transferred into a distillation apparatus. It was 0.958g of the tetramethylammonium salt of tri(m-sul
composed of one yellow limpid phase. Butadiene and 35 fophenyl) phosphine (purity 60%)
methanol were removed by distillation at a pressure of 8.5g of methanol.
100 mm mercury by heating the flask up to 33 C. and The autoclave was purged for 30 minutes with argon
adding water. The concentrated reaction mixture con then 10.5 g of butadiene were introduced. The auto
tained two phases: clave was then agitated for 16 hours at 95 C. The auto
7.9 g of an aqueous phase of yellow color containing 40
the catalytic system clave was cooled, then the reaction products were dis
a colorless organic phase comprising mainly the me tilled at a pressure of 0.1 mm mercury by heating the
thoxy octadienes. autoclave to 80 C.
According to chromatographical analysis, the fol 45 With the catalytic system which remained in the
lowing results were obtained by the above proce autoclave the same operation was repeated three times
dure: using the following reactants:
percentage of conversion of the butadiene: 56% 2nd operation - 25 g ofbutadiene, 23 g of methanol;
yields per amount of used up butadiene: 3rd operation - 21 g of butadiene, 24 g of methanol;
4th operation - 24 g of butadiene, 25g of methanol.
50 According to the analytical data, the percentage of
1-MOD: 95% MOD = methoxyoctadiene conversion of the butadiene was 100% and it was trans
3-MOD: 4% formed into:
C8: traces of C = other hydrocarbon compounds
less than 1% containing 8 carbon atoms dimer hydrocarbons 20%, mainly octatriene-1,3,7.
per molecule 1-MOD: 59%-3-MOD: 10% - heavy products: 11%
55 The catalytic system was separated from the heavy
The catalytic system was in the aqueous phase. products by adding water and decanting.
EXAMPLE 2 EXAMPLES 4, 5 and 6
Into a 500 ml stainless steel autoclave which was Into a 125 ml stainless steel autoclave which was
equipped with a knock-type agitation system, the fol 60 equipped with a knock-type agitation system, tests with
lowing were introduced: different phosphines were carried out. After introduc
0.224 g (1 m mole) of palladium acetate ing the reactants and the catalytic system and allowing
0.464 g (4 m mole) of sodium phenolate the reaction to take place for 18 hours at 95 C., the
2 g (3.9 m mole) of the mono sodium salt of (m-sul separation of the catalytic system was effected by add
fophenyl) diphenylphosphine dihydrate (content in 65 ing water. The results are shown in the Table below:
trivalent phosphorus 80% of the theoretical Example 4: tetraethylammonium salt of tri(m-sul
amount). fophenyl) phosphine (purity: 60% determined as triva
15 ml of water lent phosphorus)
 4,142,060
11 12
Example 5: monosodium salt of (m-sulfophenyl)- 10% of C8-hydrocarbons mainly octatriene-1,3,7
diphenyl phosphine dehydrate (purity 85%). 63% of octadiene-2,7-ol-1 (=ol-1).
Example 6: disodium salt of di(m-sulfophenyl)phenyl 21% of octadiene-1,7-ol-3 (=ol-3)
phosphine (purity 100%, determined as trivalent phos The remainder to 100% comprises mainly butadiene
phorus). Amound of methanol: 20 ml, amount of butadi 5 and heavier products than octadienols. The aqueous
ene: 20 ml. layer is used for carrying out further new operations.
Con
EXAMPLES 8-16
Weight of version According to the method described in Example 7, a
the Pd(oAc), of Selectivity 2% O certain number of tests were carried out adding differ
Ex. ligand(g) mg butadiene 1-MOD 3-MOD C8 ent co-catalysts to the water. The results demonstrate
4.
5
0.96
0.32
39
34
100
90
70
83
14
7 9
well the necessity of finding out the appropriate combi
6 0.35 38 83 78 8 11 nations of acids and bases for each telomerization reac
tion in order to obtain the best results. For example,
1 5 palladium in an aqueous solution of sulfonated phos
With the mono sodium salt of (p-sulfophenyl)diphenyl phine is not very active in catalyzing the addition of
phosphine prepared according to Schindlbauer, essen water; on the contrary, adding carbonate, bicarbonate,
tially the same results were obtained. phosphate, phosphites, silicates or arsenates, permits to
EXAMPLE 7 markedly accelerate the reaction.
TABLE
Results per amount of butadiene
Charges .. . . Percentages Level of
Palladium of Yields . Yields catalysis
Examples Butadiene acetate Phosphine Additives conversion Cs 1-o 3-ol (1)
8 22g 0.135 g 1.6 g. 1.3% 66% 28% 6% 4.5
0.6 m mole 2.4 m mole
9 18 g FF K2CO3 71% 10% 63% 21% 202
1.38 g
1 mol/
10 19 g 1.22g f 76% 2% 64% 20% 229
.8 m mole
11 16.2g AA p KH CO. 35% 9% 78% 13% 90
lg
1 molal .
12 20 g 0.0337 g 0.4g K2CO 13% 6.5% 71%. 22% 162.5
0.15 m mole 0.6 m mole fo/
13 23g FF pp. H PO4 9% 25% 62% 12.3% 129
1 mol/1
NaOH
2.5 mol/
14 28g Fy t H PO 14.5% 16.9% 58% 21% 254
1 mol
NaOH
2.5 mol/l c
5 13 g 0.0337 g 0.4g Na2H AsO4 8% 24% 56% - 5% 65
0.15 m mole 0.6 m mole mol/ .
NaOH
0.5 mol/
16 18g Sodium 24% 16% 68% 15% 270
Silicate (2)
(1) The level of catalysis was determined as the ratio between the weight ofbutadiene which had reacted and the weight of the palladium which was
applied.
(2) 5 ml of an aqueous solution having a density of 1.3 (sold by Societe PROLABO)

Into a 125 ml stainless steel autoclave which is

equipped with a knock-type agitation system, the fol EXAMPLES 17 AND 18
lowing were introduced: 50
Into a 125 ml stainless steel autoclave purged with
. 0.135 g of palladium acetate (0.6 m mole) argon and equipped with a knock-type agitation system,
1.61 g of trisodium salt of tri(m-sulfophenyl)phos the following were introduced:
phine (purity 90%) (2.4 m mole) (TPPS)
10.8 ml of water
1.38 g of potassium carbonate (10 m moles), that is a 55 Wa-
Sodium
Pheno- Buta
concentration of one mole/l water. ter TPPS Salt late Phenol diene
The autoclave was purged for 30 minutes with argon, Ex.17 10.8 2.4 Pd(oAc) 1.25 g 18.8g 23g
then 18 g ofbutadiene were added. Then the autoclave cm3 in mole 0.6 m mole mole/1
was agitated for 3 hours at 80° C., then cooled to 60° C. 60 Ex.8 10.8 1.36 PtCl2
cm3 m note 0.45 m mole
1.25g
1 moleA1
18.8g 23 g
for eliminating the major portion of unreacted butadi
ene by degassing. After cooling to 20 C., and opening
the autoclave, a reaction mixture comprising two layers The autoclave was then agitated for 3 hours at 80° C.
were removed into a decantor. The two layers were: then cooled to 60° C. in order to eliminate the major
an aqueous layer (10.6 g) containing the catalytic portion of the unreacted butadiene. After cooling to 20
system 65 C. and opening of the autoclave, the reaction mixture
an organic layer (11.8 g) containing the following comprising two layers were recovered into a decantor.
components according to chromatographical anal The upper phase contained the organic products, the
ysis: below aqueous phase contained the catalyst and sodium
 4,142,060 14
13
phenolate. According to the analysis, the percentage of supernatant organic colorless phase weighed 21 g and
conversion and the yields were as follows: contained 70% of methoxy-1-dimethyl-2,6-octadiene
2,7, the remainder to 100% consisting of dimer hydro
Ex. 17 Ex. 18 carbons, as isomer and heavier products. The aqueous
Percentage conversion of butadiene 90% 40% phase contained the catalytic system.
Yield in hydrocarbons C8 18% 5.5% EXAMPLE 22
Yield in 1-phenoxybutene-2 1% 18.5%
Yield in 3-phenoxybutene-1 0.8% 18.5%
Yield in 3-phenoxyoctadiene-1,7
Yield in 1-phenoxyoctadiene-2,7
21%
56%
4.46%
46.2%
Into a 125 ml stainless steel autoclave purged with
O
argon and equipped with a knock-type agitation system,
the following were introduced:
20 ml of methanol
EXAMPLE 19 0.45 g of sodium salt of (m-sulfophenyl)bis(phenyl)-
Into a 125 ml stainless steel autoclave purged with phosphine, (purity 97%)
argon and equipped with a knock-type agitation system, 15 0.5g of palladium on carbon black 10%
the following were charged: 19 g of butadiene
10.8 g water The mixture was then agitated during 3 hours at 85
1.83 g trisodium salt of tri(m-sulfophenyl)phosphine C., then cooled to 60° C. in order to eliminate a portion
(purity 90%) of the unreacted butadiene. The reaction mixture was
0.135 g of palladium acetate 20 filtered in order to eliminate the carbon black therein.
14.6 g of diethylamine The organic phase contained unreacted methanol and:
19 g of butadiene. 15 g of methoxy-1-octadiene-2,7
The autoclave was then agitated during 3 hours at 85 0.75 g of methoxy-3-octadiene-1,7
C., then cooled to 60° C. in order to eliminate a portion 0.75 g of a dimer of butadiene
of the unreacted butadiene. The reaction mixture The catalyst can be separated from the reaction mix
formed two distinct immiscible layers which were de 25 ture as described in Example 2.
canted. The aqueous layer containing the catalyst
weighed 12.5 g. The colorless organic layer weighed 26 EXAMPLE 23
g, it contained: Into a 10 ml glass tube, the following were intro
13.5% of butadiene
46.5% of 1-(N,N-diethylamino)butene-2 30 duced under argon atmosphere:
40% of 1-(N,N-diethylamino)octadiene-2,7 0.679 g of mono sodium salt of (m-sulfophenyl)di
0.6% of 3-(N,N-diethylamino)octadiene-1,7 phenylphosphine, (purity 97%)
5 ml of ethanol.
EXAMPLE 20 The tube was cooled to -78 C. and then were intro
Into a 125 ml stainless steel autoclave purged with 35 duced:
argon and equipped with a knock-type agitation system, 0.107 g of anhydrous nickel chloride
the following were introduced: 0.27g of butadiene
12 g of acetic acid 0.123 g of sodium borohydride
17.8g of dimethylamino-2-ethanol The glass tube was then isolated and closed by means
0.33 g of tetraethylammonium salt of tri(m-sulfophe of a Bakelite screw closure which comprised a rubber
nyl) phosphine (purity 90%) insert which allowed the injection of liquids by means
0.050 g of palladium acetylacetonate of a syringe.
10.5g of butadiene The mixture was allowed to warm up to -40°C. 1.36
The autoclave was then agitated for two hours at 90 g of butadiene and 0.8 ml of morpholine were added.
C., then cooled to 60° C. in order to eliminate a porton 45 The reaction mixture was reheated to 20 C. and main
of the unreacted butadiene. The reaction mixture was tained at 20° C. for 1 hour and 30 minutes. According to
distilled. The catalytic system was separated from the chromatographical analysis, the percentage of conver
heavy products by adding water and decanting. Ac sion of morpholine was above 95% with a yield of 90%
cording to the analysis of the distillates, the percentage of N-octadienylmorpholine. The ethanol was removed
of conversion of the butadiene was 94%, namely 56% 50 by distillation. The catalyst was separated from the
of 1-acetoxyoctadiene-2,7 and 36% of dimer hydrocar reaction products by adding water.
bons that is octatriene-1,3,7.
PREPARATION OF THE PHOSPHINES WHICH
EXAMPLE 21 WERE USED IN THE EXAMPLES
Into a conical 250 ml flask purged with argon, the 55 (1) Preparation of the sodium salt of (metasulfophenyl)-
following were introduced: diphenylphosphine
80.8g of methanol This phosphine was prepared according to the prepa
0.330 g of mono sodium salt of (m-sulfophenyl)di ration method, which is described by S. Ahrland, J.
phenylphosphine, (purity 97%)
0.045 g of palladium acetate Chatt, N. R. Davies, A. A. Williams, Journal of Chemi
0.6 g of potash cal Society, 276-288 (1958).
0.035 g of sodium borohydride (2) Preparation of the sodium salt of (p-sulfophenyl)di
phenylphosphine -
28 g of isoprene.
The homogeneous mixture was agitated for 68 hours This phosphine was prepared according to the prepa
at 45° C. The mixture was cooled and 60 ml of water 65 ration method described by H. Schindlbauer, Monatsch.
and 0.33 g of phosphine were added, then methanol and Chem., 96, pp. 2051-2057 (1965) by reacting sodium
isoprene were removed from the boiler by heating them p-chlorobenzene sulfonate with diphenylchlorophos
to 36 C. under a pressure of 100 mm of mercury. The phine in the presence of sodium.
 15
4,142,060
16
(3) Preparation of the sodium salt of tri-(metasulfo By carrying out the reaction at 18-20 C. during 48
phenyl)phosphine hours a product having a purity of above 95% is ob
Into a 2 liter balloon flask which was equipped with tained.
a central stirring system, a thermometer and an ascen (4) Preparation of an ammonium salt of tri(metasulfo
dent cooler and which was cooled from the outside by phenyl)phosphine
an ice water bath, there was introduced a liter of oleum A suitable amount of the sodium salt of tri(m-sulfo
containing 20% by weight of sulfuric anhydride, then phenyl)phosphine which was prepared as described
the flask was purged with argon. The stirring was above, was dissolved in water and the solution was
started, subsequently 100 g of triphenylphosphine were passed through a column which contained an excess
introduced within 2 hours thereby keeping the tempera 10 (about 4 times the theoretical amount) of a strongly acid
ture between 20' and 40 C. When the addition was ion exchange resin (sulfonic acid) which is known under
finished, stirring of the mixture was continued at the the tradename Amberlite IR 120H, finally was eluated
above temperature during 15 to 25 hours. The reaction with water. The resulting acid solution was neutralized
was then cooled to 10° C. and was carefully poured into with tetraethylammonium hydroxide and then was
a 10 liter balloon flask which contains 2 liters of water 15 evaporated to dryness under reduced pressure.
which was cooled to 0 C. 1,500 g of sodium hydroxide All triphenylphosphine salts can be prepared accord
pastils were added to the reaction mixture, whereby the ing to the same procedure.
temperature of the reaction medium was maintained at (5) Preparation of the sodium salt of di(metasulfo
below 20 C. The resulting solution was allowed to phenyl)phosphine
stand for several hours at room temperature, at about 20 This phosphine is obtained by the following reaction.
20° C. Into an 0.5 liter balloon flask which was equipped with
At the end of this period, the precipitated sodium a central stirring system, a thermometer and an ascen
salts were recovered by filtration and washed twice dent cooler and which was cooled from the outside by
with 1,500 ml of ice water each. The combined filtrates an ice water bath, there were introduced 100 ml of
and washing waters were concentrated to a total vol 25 oleum containing 20% by weight of sulfuric anhydride,
ume of 1,500 ml by heating at reduced pressure. then the flask was purged with argon. The stirring was
The precipitate which was obtained at the end of the started, subsequently 10 g of triphenylphosphine were
concentrating operation was filtered and washed three introduced thereby keeping the temperature at 25 C.
time with 300 ml ice water each. The combined filtrate Stirring of the mixture was continued at this tempera
and washing waters were concentrated to a volume of
30 ture during 17 hours. The reaction mixture was poured
500 ml by heating under reduced pressure. into a flask which contained 1,000 g of ice then the
To the mixture remaining from the above concentra mixture was neutralized by means of 400 ml of an aque
ous 10 N sodium hydroxide solution.
tion step, 500 ml of methanol were added, then the The precipitated salts were filtered and then dried to
forming precipitate was filtered and washed with 500 35 constant weight. 18 g of a solid was obtained and was
ml of a mixture of methanol/water 50/50. The com introduced into 65 ml of water, which was heated to
bined filtrate and washing solutions were then concen boiling. The insoluble particles were separated by hot
trated to a volume of 200 ml, then 1,000 ml of methanol filtration and the filtrate was left to cool to 20' C. The
were added. The precipitate which was formed was precipitated solid was separated by filtration, washed
filtered, then washed six times with 1,000 ml of metha with 10 ml of cold water, then dried at 25 C. under a
nol heated to 60° C. The molten liquors and washing pressure of 0.1 mm mercury during 30 hours. Thus, 8g
solution were combined and evaporated to dryness. The of the disodium salt of pure di(m-sulfophenyl)phosphine
evaporation residue was introduced into 500 ml of abso were recovered.
lute ethanol. The resulting solution was filtered and the
solids on the filter were washed with 20 ml of ethanol 45 EXAMPLE 24
and then dried at 25°C. under reduced pressure (0.1 mm A test was carried out analogous to Example 12, but
mercury) during 30 hours. 172g of a white solid remain. replacing the potassium carbonate by 1.64 g of sodium
The results of analyzing the solid product by elemen phenyl sulphinate (i.e., a concentration of 1 mole per
tary analysis (determination of the content in C, H, S, P) liter). The degree of conversion of the butadiene was
by infra red spectroscopy by nuclear magnetic reso 50 55%. The supernatant organic phase contained hydro
nance of hydrogen and phosphorus and by chemical carbon dimers of butadiene (yield 9.7%), of 2-trans,7-
determination of the trivalent phosphorus (iodometric octadiene-1-ol (yield 62%) and of 1,7-octadiene-3-ol
determination), and the sulfonated groups by ion ex (yield 16%).
change indicated that the product was a mixture of tri EXAMPLE 25
sodium salts of tri(metasulfophenyl)phosphine and of 55
tri(metasulfophenyl)phosphine oxide. In a 125 cm stainless steel autoclave equipped with a
The composition of the mixture of salts may vary shaker were introduced:
according to the temperature and the reaction time of 0.040 g of platinum chloride (PtCl2)
the sulfonation. When the addition of the triphenyl 0.38g of the trisodium salt of tri(meta-sulphophenyl)-
phosphine is effected at a temperature of about 30° C., 60 phosphine (purity 95%)
and agitating of the mixture is continued at this temper 10.8 cm of water
ature for about 20 hours, a mixture is recovered wherein 13.8g of diethylamine.
80% by weight of the salts in the solution are sodium The autoclave was purged for 30 minutes with argon
salts of tri(metasulfophenyl)phosphine and 20% by and then 18 g of butadiene were introduced. The auto
weight are sodium salts of tri(metasulfophenyl)phos 65 clave was then agitated for 3 hours at 80 C. and then
phine oxide. When working at 40° C. for 24 hours, the cooled to 60° C. in order to remove the bulk of the
obtained mixture of salts contains 60% by weight of the butadiene which had not reacted, by degassing. After
sodium salt of the tri(metasulfophenyl)phosphine. cooling to 20 C. and opening the autoclave, a reaction
 4,142,060 18
17
mixture, which consisted of the following two layers, about 20 carbon atoms, aryl having 6 to about 20 carbon
was collected in a decanter: atoms, Or an
an aqueous layer (9.1 g) containing the catalytic sys
ten
an organic layer (15.6 g) containing part of the reac 5
tants which had not reacted and 3.99 g of 1-die
thylamino-2-trans-butene as the sole reaction prod
lict.
wherein R6 and R7 are the same or different and each
EXAMPLE 26 10 are hydrogen, alkyl having 1 to 20 carbon atoms or
Following the procedure of Example 25, an experi alkenyl having 3 to 20 carbon atoms or R6 and R7 to
ment was carried out with the following materials: gether with the nitrogen atom form a 5- or 6-membered
0.036 g of RhCl(cycloocta-1,5-diene)2 heterocyclus to form a reaction product containing a
0.114 g of trisodium salt of tri(m-sulfophenyl)phos 15 major portion of dimer derivatives of the compound of
phine (purity 95%) formula (II).
10.8 cm of water While the invention has now been described in terms
14.8g of diethylamine, and of various preferred embodiments, and exemplified with
19 g of butadiene. respect thereto, the skilled artisan will appreciate that
The degree of conversion of the butadiene was about 20 various substitutions, changes, omissions, and modifica
10%. It had been converted into 1-diethylamino-2- tions may be made without departing from the spirit
trans-butene (23%) and 1-N-diethylamino-2-trans,7- thereof. Accordingly, it is intended that the scope of the
octadiene. i
invention be limited solely by that of the following
claims.
EXAMPLE 27 What is claimed is:
When a taxogen, such as diethylamine is used, the 25 1. A process for telomerizing dienes which comprises
addition of acid can effect the selectivity. For example, the step of reacting a diene with a telomerizing com
by following the procedure of Example 19, but adding pound containing at least one mobile hydrogen atom,
0.024 mole of sulphuric acid a reaction mixture was said telomerizing compound being water, in the pres
obtained containing, by mole: ence of a water-soluble catalytic system comprising at
13.9% of C3 hydrocarbon 30 least one water-soluble phosphine having the following
64.4% of 1-N-diethylamino-2,7-octadiene formula (I):
13.9% of octadienol.
The absence of 1-diethylamino-2-trans-butene is
noted. 35
EXAMPLE 28
The following constituents were introduced into a
125 cm stainless steel autoclave fitted with a shaker:
0.107 g of platinum chloride (PtCl2) 40
0.815 g of trisodium salt of tri(m-sulfophenyl)phos
phine (purity 95%)
10.8g of water
14.6 g of diethylamine
20 g of isoprene. 45
The autoclave was then agitated for 20 hours at 80 wherein Arl, Ar2 and Ars each represent an aryl group
C. After cooling, 32.2 g of an organic phase were de having from 6 to 10 carbon atoms, which may be alike
canted. The degree of conversion of the amine was or different from each other; Y1, Y2 and Y, which may
about 93%, it had been converted into: be alike or different from each other each represent an
1-N-diethylamino-2-methyl-2-trans-butene (24%). 50 alkyl group containing 1 to 4 carbon atoms, an alkoxy
1-N-diethylamino-3-methyl-2-trans-butene (72%). group containing 1 to 4 carbon atoms, a halogen, cyano
The process according to the present invention is , nitro-, or hydroxy radical or an
preferably suited for reacting a sufficient amount of a
compound of formula (II)
55 amino group -N y
N
N R
C-C-CHC
/ N
R Rs wherein R1 and R2, which may be alike or different
60 from each other each represent an alkyl group contain
containing 4 to about 20 carbon atoms, ing 1 to 4 carbon atoms; M represents a cation which is
wherein at least one of the substituents R1, R2, R3, R4 able to form water-soluble compounds of formula (I)
and R5 is hydrogen and the remaining substituents R1, selected from the group consisting of a proton, a cation
R2, R3, R4 and R5 are the same or different and each derived from an alkali metal or an alkaline earth metal,
represent hydrogen, alkyl having 1 to 5 carbon atoms or 65 ammonium, a group N(R3R4R5R6)+, wherein R3, R4,
alkenyl having 3 to 5 carbon atoms, with a telomerizing R5 and R6 each represent hydrogen or an alkyl group
compound HOR, wherein R represents hydrogen, alkyl containing 1 to 4 carbon atoms and may be alike or
having 1 to about 20 carbon atoms, alkenyl having 3 to different from each other, and a cation of any other
 4,142,060
19 20
metal, which is able to form water-soluble salts with 14. The process as defined in claim 13, wherein the
benzosulfonic acids; m1, m2 and m3 each represent a transition compound is palladium.
whole number from 0 to 5 which may be the same or 15. The process as defined in claim 14, wherein the
different from each other and n1, n2 and n each repre palladium is deposited onto an inert carrier material.
sent a whole number from 0 to 3, which may be the 16. The process as defined in claim 13, wherein at
same or different from each other, whereby at least one least part of the transition metal is zero valent.
of these numbers n, n2 and ns equals at least one and 17. The process as defined in claim 1, wherein the
further comprising a compound selected from the group transition metal-containing compound is a compound
consisting of a transition metal or a transition metal-con containing palladium, nickel, platinum, cobalt or rho
taining compound. 10 dium.
2. The process as defined in claim 1, wherein the 18. The process as defined in claim 17, wherein the
diene is a diene having 4 to about 20 carbon atoms. transition metal-containing compound is a palladium
3. The process as defined in claim 1, wherein the ratio compound.
between the amount of diene and of telomerizing com 19. The process as defined in claim 18, wherein the
pound is equivalent to at least one molecule of diene per 15 palladium compound is a compound from the group of
ten atom of mobile hydrogen. palladium-acetate, -carboxylate, -carbonate, -borate,
4. The process as defined in claim 1, wherein Art, -bromide, -chloride, -iodide, -citrate, -hydroxide, -ni
Ar2 and Ars each represent phenyl. trate, -sulfate, -arylsulfonates, -alkylsulfonates, -acetyl
5. The process as defined in claim 1, wherein Y1, Y2 acetonate, bis(benzonitrile)palladium chloride, and po
and Y, which may be alike or different from each 20 tassium tetrachloro palladate.
other, each represent an alkyl group containing 1 to 2 20. The process as defined in claim 18, wherein the
carbon atoms, an alkoxy group containing 1 to 2 carbon palladium compound is a compound from the group of
atoms or chlorine. bis(cyclooctadiene-1,5) (palladium (zero), tetra (tri
6. The process as defined in claim 1, wherein M rep phenylphosphine) palladium (zero), and potassium tet
resents a proton, a cation derived from sodium, potas 25 racyano palladate.
sium, calcium or barium, ammonium, tetramethyl am 21. The process as defined in claim 1, wherein the
monium, tetraethyl ammonium, tetrapropyl ammonium reaction is effected in the presence of a reducing agent
or tetrabutyl ammonium. capable of reducing the transition metal.
7. The process as defined in claim 1, wherein m1, m2 22. The process as defined in claim 21, wherein the
and m3, which may be alike or different from each other 30 reducing agent is an agent from the group of sodium
each represent a whole number between 0 and 3. borohydride BH4Na), potassium borohydride, zinc
8. The process as defined in claim 1, wherein Arl, powder, and magnesium.
Ar2 and Ars each represent phenyl, Y1, Y2 and Y3, 23. The process as defined in claim 1, wherein the
which may be alike or different from each other, each amount of transition metal is from about 10 to about
represent an alkyl group containing 1 to 2 carbon atoms, 35 1 gram atom per liter.
an alkoxy group containing 1 to 2 carbon atoms or 24. The process as defined in claim 23, wherein the
chlorine, M represents a cation of the group consisting amount of transition metal is from about 0.005 to about
of a proton, a cation derived from sodium, potassium, 0.5 gram atom per liter.
calcium or barium, ammonium, tetramethyl ammonium, 25. The process as defined in claim 1, wherein the
tetraethyl ammonium, tetrapropyl ammonium or tet amount of a phosphine of the formula (I) is from about
rabutyl ammonium and m1, m2 and m3, which may be 0.5 to 2,000 moles per gram atom of transition metal.
alike or different from each other each represent a 26. The process as defined in claim 25, wherein the
whole number between 0 and 3. amount of a phosphine of formula (I) is from about 1 to
9. The process as defined in claim 1, wherein Ar1, about 30 moles per gram atom of transition metal.
Ar2 and Ars each represent phenyl, n1 represents 1, n2, 45 27. The process as defined in claim 1, wherein the
n3, m1, m2 and m3 each represent zero, and M represents reaction is effected in the presence of an additive se
a proton, a cation derived from sodium, potassium, lected from the group consisting of a basic compound
calcium or barium, ammonium, tetramethyl ammonium and a mixture of a basic compound and an acid.
or tetraethyl ammonium, 28. The process as defined in claim 27, wherein the
10. The process as defined in claim 1, wherein Arl, 50 additive is selected from the group consisting of alkaline
Ar2 and Areach represent phenyl, n1 and n2 each repre metal hydroxide, alkaline earth metal hydroxides, ter
sent 1, m1, m2, m3 and ng each represent Zero, and M tiary aliphatic amines, tertiary aromatic amines and
represents a proton, a cation derived from sodium, po phenolates.
tassium, calcium or barium, ammonium, tetramethyl 29. The process as defined in claim 27, wherein the
ammonium or tetraethyl ammonium. 55 acid is a mineral acid of an element of the Groups IIIA,
11. The process as defined in claim 1, wherein Ari, IVA, VA, VIA and VIIA of the periodic system.
Ar2 and Ars each represent phenyl, n1, n2 and ng each 30. The process as defined in claim 27, wherein the
represent 1, m1, m2 and m3 each represent Zero, and M acid is a carbocyclic arylsulfonic or alkylsulfonic acid.
represents a proton, a cation derived from sodium, po 31. The process as defined in claim 27, wherein the
tassium, calcium or barium, ammonium, tetramethyl 60 telomerizing agent is water and the additive is selected
ammonium or tetraethyl ammonium. from the group consisting of alkaline carbonates, alka
12. The process as defined in claim 7, wherein at least line bicarbonates, sodium silicates and alkaline salts of
one of the sulfo groups which are present therein in phosphorus acid, phosphoric acid and arsenic acid.
each of the phenyl groups Ar1, Ar? or Ars is situated in 32. The process as defined in claim 31, wherein the
m-position. 65 additive is sodium carbonate.
13. The process as defined in claim 1, wherein the 33. The process as defined in claim 1, wherein the
transition metal is a metal from the group of palladium, reaction mixture comprises an organic water immiscible
nickel, platinum, cobalt, and rhodium. solvent.
 4,142,060
21 22
34. The process as defined in claim 33, wherein the 37. The process as defined in claim 1, wherein the
solvent is a solvent of the group of benzene,al benzoni- reaction is performed at a temperature between about
-20 C. and about 200 C.
trile, acetophenone, ethyl ether, propyl ether, isopropyl 38. The process as defined in claim 1, which com
ether, methylethylketone and propionitrile. 5 prises reacting butadiene with water whereby octadi
35. The process as defined in claim 1, wherein the ene-2,7-ol-1 is formed.
reaction mixture further comprises on organic water 39. The process as defined in claim 2, wherein the
miscible solvent. diene is a diene having 4 to about 8 carbon atoms.
36. The process as defined in claim 35, wherein the 40. aThe
s process as defined in claim 3, wherein the
solvent is a solvent of the group
group
of acetone,
s
acetonitrile s
10 diene is selected from the group consisting ofbutadiene,
isoprene, piperylene and dimethylbutadiene.
dimethylether of diethylene glycol and dimethoxyeth- 41. The process as defined in claim 1, the said cata
ane, dioxane, tert, butanol, dimethyl acetamide, n- lytic system being present in aqueous solution.
methyl pyrolidone and ethylene carbonate.
15

25

30

35

45

50

55

65