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Патент USA US3097162

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States
3,097,153
,.
ICC
" 1 atent
Patented July 9, 1963
2
I
organo~metallic complexes, M represents a transition metal
3,097,153
PROCESS FOR Tl-E PREPARATION OF HYDRO
GENATED ORGANIC COMPOUNDS AND PROD
UCTS RESULTING THEREFROM
Karl W. Hubel and Emile Henri Braye, Brussels, Belgium,
assignors to Union Carbide Corporation, a corporation
of New York
No Drawing. Filed Mar. 31, 1960, Ser. No. 18,840
Claims priority, application Great Britain Apr. 7, 1959
10 Claims. (Cl. 204-158)
belonging to the VI, VII or VIII sub :groups of the periodic
table, CO represents a carbonyl group, R’ and/or R" may
be the same or different and represent hydrogen, halo-geno,
carboalkoxy, ‘alkyl, aryl, cycloaliphatic, alkoxy or silyl
groups and the like, including the substituted derivatives
thereof, C2 represent a carbon to carbon bonding, B repre
sents a member selected LfI‘OIl'l the group consisting of hy
drogen, mercury, halogen, alkyl, aryl or acyl, x represents
10 ‘an integer of ‘from '1 to 4, y represents an integer of from
1 to 10, 1 represents an integer of from 1 to 6, and w
represents an integer of from O‘ to 4.
This invention relates to the preparation of organic
compounds and to products resulting therefrom. More
Typical organo~metallic complexes suitable for use in
particularly, it relates to a process for the preparation of
partially or completely hydrogenated linear or cyclic or
the process of this invention include:
Fe2(CO)6(RC2R')2, wherein R represent a phenyl or
15
ganic compounds.
ethyl group or a hydrogen atom and wherein R’ repre~
The present invention greatly ‘facilitates the synthesis
cents a phenyl, methyl, ethyl or \methoxy group or a halo
of substituted or unsubstituted organic compounds in that
gen atom. 'Fe2‘(CO)8(RC2R')2(B)2 wherein R and R'
it provides a new and general one-step method ‘for this
represent hydrogen and 3' represents either hydrogen or a
purpose. The invention is predicated upon the discovery
methyl group. These complexes may be represented by
20
that when certain organo-metallic complexes as herein
the
following structure:
after described, whose organic part contains a preformed
carbon skeleton, are reacted with compounds containing
at least one element or reactant capable of forming stable
00
bonds ‘with the skeleton, the bonding of the element to the
\
OCQFe
/"
00
skeleton is readily achieved. The compounds formed 25
thereby are characterized as containing at least one of the
carbon skeletons and at least one of the elements.
Although the mechanism of the reaction is not yet
fully understood, basic considerations applying to the in
ventive process can be found in the following discussion. 30
It is believed that organo-metallic complexes as \for ex
ample, Fe2'(CO)6(RC2R)2 =or Fez(CO)q(RC2R)2 can be
represented by the structures respectively shown below,
wherein the actual meaning of R has bee-n disregarded for
35
the sake of clarity.
C
00
C
O
Fe2(CO)q(RC2R')2, wherein R and R’ represent phenyl
groups. This complex may be represented by the follow
ing structure:
Fe2(‘CO)6(RC2R'), wherein R and R' represent phenyl
co)FeCT) \co
45 groups.
This complex may be represented by the follow
ing structure:
There are various evidences which indicate that the two
iron atoms contained in these ongano-metallic complexes
have di?erent chemical behavior. In particular it has 50
been found that the iron atom bonded into the ring system
can be more readily removed than the other iron atom.
It can thus be foreseen that the splitting of the iron atoms
which occurs during the reaction isolates a highly reactive
carbon skeleton which can readily react with any element 55
capable of forming stable bonding with that carbon skele
Fe(CO)4(RC2R’)2, wherein R represents a phenyl group
ton. Similar considerations apply to the various or-gano
and wherein R’ represents a phenyl group or a hydrogen
metallic complexes containing only one metal atom or one
atom. This complex ‘may be represented by the following
(R'C2R") group and apply as well to the complexes hav
ing a larger number of metal atoms or (R'C2R") groups 60
in their structure. It is therefore apparent that by proper
ly selecting the reactant containing an element capable of
forming stable bondings with the carbon skeleton, a large
structure:
,
B,
R
variety of organic compounds can be provided.
According to this invention, a process for the prepara 65
tion of partially or completely hydrogenated linear or
073%
O 0 Q
cyclc organic compounds comprises reacting an organo
metallic complex having the formula:
70
with a hydrogenation reagent.
In the above referred to
R
e
Fe(CO)6(RC2R’), wherein R represents a hydrogen
atom or a phenyl group and wherein R’ represents a hy
3,097,153
A
Co2(CO)4(RC2R')3, wherein R represents a carboeth
drogen atom. This complex may be represented by the
following structure:
oxy or methyl group or a hydrogen atom and wherein R’
represents a phenyl group or a trimethylsilyl group. This
00
(|§__C_R
_
complex may be represented by the following structure:
\ /
00-)Fe
007125 \
0
5
R
R
C-C-R
H
»
o O \1 )m
0
00-)0
'Fe3(CO)8(RC2R’)2, wherein R and R’ represent phenyl 10
groups. This complex may be represented by the follow-
0 (37‘ x 7
t
00
ing structure:
O
15
Coz(CO)6(RC2‘I-I)4Hg, wherein R represents a tertiary
butyl or trimethylsilyl group. This complex may be rep
resented by the following structure:
H
‘HO
OH
0
20
___> J,
R
25
OO
H
C
_L(_____
_.K... C
ii R O
0
1
O R FAR
O
Co2(CO)6(RC2H)4, wherein R represents a tertiary
butyl or trimethylsilyl group. This complex may be rep
resented by the following structure:
30
0
H
35
HO lg}
ll
0
H
H
II
Co3(CO)9H(RC2H), wherein R represents a phenyl
0
o '
group. This complex may be represented by the following
Fe2(CO)8(RC2H)3, wherein R represents a phenyl
group. This complex may be represented by the follow- 40 structure:
ing structure:
'
45
00-) Fe
QC)’
QC “5) C0
O
~
(2/?0
50
Fe(CO)4(RC2H)3, wherein R represents a phenyl group
Ni(CO)2(RC2R')4, wherein R and R’ represent phenyl
or a hydrogen atom. This complex may be represented
groups. This complex may be represented by the follow
by the following structure:
ing structure:
60
65
o '0
o
Co2(CO)6(RC2R'), wherein R represents a phenyl
group and R' represents a phenyl group or a carbomethoxy
group. This complex may be represented by the follow
ing structure:
R\ C~—-—G/B 00
00
N
z’ \
t!
0 C.->Oo~ -- —-—- —‘-Co<-C 0
007'
R00
75
'
3,097,153
5
instances. The reaction products are easily removable
and
from the reaction mixture after completion of the reac
tion using any suitable technique. The technique of re
Other useful organo-metallic complexes are those in
which the transition metal is ruthenium, rhodium, palla
moval ‘will of course vary according to the nature of the
reaction product and the occurrence of side reactions.
Suitable process conditions will be further illustrated in
dium, osmium, iridium, platinum, manganese, rhenium,
chromium or tungsten, or are those in which the carbonyl
the speci?c examples hereinafter described relating to the
present invention.
Typical compounds prepared by the process of this
invention ‘may be illustrated by ‘the following general
group bonded to the metal is partially replaced by a ni
etrosyl, a substituted stibine, a substituted arsine, or a
substituted phosphine.
The organo~metallic complexes employed as starting
formulae:
materials in ‘the present invention may be conveniently
prepared by the process described in copending applica
tion 707,111, entitled “Organo-Metallic Compounds and
- Method for Their Preparation,” '?led January 6, 1958, in
the name of Karl Walter Hubel, the description thereof 15
being incorporated herein by reference.
Brie?y stated, the organo-metallic complexes can be
prepared by reacting an acetylenic compound with a metal
carbonyl in a non-aqueous neutral medium at a tempera
ture of between room and 300° C.
As a consequence, a
20
stable orga-no-metallic carbonyl reaction product is formed.
The acetylenic vreactant has the formula:
R’CECR"
wherein R represents hydrogen or hydroxyl, halogeno,
wherein R’ and R" represent a substituent selected from 25 carboalkoxy, alkyl, aryl, cycloaliphatic, alkoxy or silyl
the group consisting of hydrogen, an organic group, and
groups, including the substituted derivatives thereof.
substituted derivatives thereof, a functional group and sub
These substituted alkan'e, alkene, butadiene and cyclo
stituted derivatives thereof and an organo-substituted hy
pentenone compounds are ‘by way of illustration only.
dride group, the substituent being substantially inert to
The hydrogenated compounds produced by this invention
and inactive with the carbonyl group. The metals of the 30 will also include many other representative cis or trans,
metal carbonyl group are selected from the group consist
linear or cyclic types of compounds. Generally speak
ing of iron, nickel, ruthenium, rhodium, palladium, os
ing, the hydrogenated compounds formed by the process
mium, iridium, platinum, manganese, rhenium,'chromium,
of this invention will contain at least one (R’C2R") unit
molybdenum, cobalt and tungsten.
wherein R’ and R" have the meanings previously de?ned.
35
Any hydrogenation reagent may be employed in the
The invention may be vfurther illustrated by the fol
practice of this invention. Exemplary of the hydrogena
lowing examples:
tion reagents that may be employed in the process of this
Example I
invention are: lithium aluminum hydride, sodium boron
hydride, sodium amide, sodium in liquid ammonia,
Na-Hg, Li/diethylamine, nascent hydrogen, hydrogen
with conventional hydrogenation catalysts and strong
acids such as hydrochloric acid and sulfuric acid, particu
larly in alcohol solutions. However, for the purpose of
this invention it is preferable to employ lithium alumi
num hydride, sodium in liquid ammonia, sodium amal
gam in ‘various organic solvents, hydrochloric acid and
sulfuric acid.
The process of this invention can be carried out ‘using
stoichiometric amounts of the starting materials. How
To 1 ‘gram of LiAlH4 in 150 ml. tetrahydrofuran
(THF) a solution of 0.5 gram Fe(CO)3(C6H5C2C6-H5)2
in THF was added under stirring. After 1 hour, the
reaction mixture was treated with ethanol, and then with
dilute hydrochloric acid. The mixture was then extracted
with benzene and the organicphase was dried over CaClz
and the excess of solvent evaporated.
The residue was
thereupon crystallized from ethanol yielding 0.3 ‘gram
(92%) of 1,2,3,4~tetraphenylbutadiene (M.P. 182—184°
C.).
When the reduction was carried out with Na in liquid
ever, it has been found that an excess of the aforesaid
NH3 at ~60° C., the complex being initially dissolved
hydrogenation reagents is generally preferable. The re
in a mixture of THF and absolute ethanol (10 ml), the
action is usually carried out in a polar or non-polar
stereoisomer, M.P. ‘185° C. (3% yield) is also obtained.
Example II
To 1 gram of Fe2(CO)6(C6H5C2C6I-l5)2 dissolved in
organic solvent such as benzene, petroleum ether, ether,
tetrahydrofuran, beta-ethoxy ethanol and the like. When‘
side reactions are to be avoided, the selected solvent
should preferably be of an inert kind. However, no
addition of solvent is necessary when one of the starting
materials is liquid at the reaction temperature.
The reaction is usually achieved by heating the reac
tion‘mixture, or by activating the reaction mixture with
ultraviolet radiations, or by combining both ‘heating and
ultraviolet radiations. However, when employing react
ants normally used at relatively low temperatures such
as sodium in liquid ammonia, it is advisable to cool the
200 ml. ether, a solution of 0.9 gram LiAlH4 in ether is
added under stirring. After one hour at room tempera
ture, the reaction mixture was re?uxed for one hour.
Then, following the procedure ‘described in Example I,
a yield of 0.36 gram (66%) of l,2,3,4-tetraphenyl
butene-l, M.P. 151-152" C. was obtained.
Example III
A solution of 4 grams Fe3(CO)8(C6H5C2‘C6'H5)2 in
Generally
100 ml. THF was added to 4 grams of LiA'll-I4 in 300
speaking, the reaction temperature at which the process
ml. THF. After re?uxing the mixture for 11/2. hours, 1
of this invention may be carried out ranges from about
gram (51%-yield) of 1,2,3,4-tetraphenyl-butene, M.P.
reaction mixture down to 0° C. or lower.
185° C. was obtained plus a small amount of 1,2,15,4
—60° C. to about 250° C. The speci?c temperatures
employed will, of course, depend upon the nature of the
tetraphenyl-butene- 1 .
reactants employed. It is preferable to perform the re 70
Example 'IV
action in a closed system whenever one of the react-ants,
To 2 ‘grams of FEz(CO)q(C6H5C2C6H5)2, dissolved
or the reaction products formed thereby or the solvent
in‘ a mixture of 50 ml. THF and 100 ml. acetic acid,
employed, are too volatile at the reaction temperatures.
there was added 15 ml. of concentration HCl. The mix
The reaction is usually completed within a few hours,
although longer reaction ‘times may be necessary in some 75 ture was re?uxed for 11/2 hours. The reaction yielded
3,097,153
7
8
,2,3,4,S-tetraphenyl-cyclopenten-Z-one-1, having a MP. of
substituted butadiene compounds can be used in .the
163° C.
production of synthetic rubber, as for example, polyiso~
Example V
prene.
' Of course, the substituted ethylenic compounds have a
wide range of uses but are particularly useful as mono
mers in the preparation of useful polymers. The com
A solution of 1 gram Fe2(CO)7(C6H5C2C6H5)2 in
tetrahydrofurane was added to a suspension of sodium
amide, prepared from 10 grams Na in 100 ml. liquid
NH3. After 1 hour the ammonia was allowed to evapo
pounds produced by the process of this invention can
also serve as intermediates for the production of com
rate, H20 and CGHS were added, and after drying, the
pounds which Will have utility as plasticizers and sta
organic layer was treated chromatographically. The ben
zene-ether fraction contained 0.03 gram 1,2,4,5-tetraphen 10 bilizers. Moreover, the cyclic ketonic structures can be
employed in the production of lactones.
yl-pentanone-3 as colorless needles having the M.P.
119-121" C.
The cyclic ketones produced by the process of this
‘invention are also useful as intermediates for the synthesis
Example VI
‘of fulvenes. They may also be employed as starting mate
A solution of 2.32 ‘grams (5 mM.)
rials for the production of organo-metallic complexes and
in particular vr-complexes.
CO2 ( CO) 6 (csHsczcsHs)
What is claimed is:
l. A process for the preparation of hydrogenated linear
and cyclic organic compounds free of carbon to metal
bonds, which comprises reacting an organo-mctallic com
in 30 ml. CHHOH containing 3.5 ml. H2504 (10 M.) was
re?uxed for 3 hours. The extraction with petroleum
ether of the water diluted mixture yielded 0.135 gram
(15%) trans-stilbene, M.P. 120° C.
Example VII
wherein M is a transition metal selected from the group
Following the same procedure as described in Example
VI, but employing as the organo-metallic complex 2.23
consisting of subgroups VI B, VII B and VIII of the
periodic table, CO represents a carbonyl group, R’ and
plex having the formula: MX(CO)y(R’C2R")z(B)W
R" represent a member selected from the group con
grams (5 mM.) Co2(CO)6(C6H5C2COOCH3), a yield of
sisting of hydrogen, halogeno, carboalkoxy, alkyl, aryl,
20.5% methyl cinnamate was obtained.
cycloaliphatic, alkoxy and silyl groups, C2 represents a
Example VIII
carbon~to~carbon bonding, B represents a member se
A solution of 0.15 gram Co4(CO)m(C6H5C2C6I-I5) in _
15 ml. CH3OH containing 2 ml. 30% H2504 was re?uxed
for 1/2 hour. The blue color disappeared and 0.03 gram
trans-stilbene was extracted with petroleum ether.
'lected from the group consisting of hydrogen, mercury,
halogen, alkyl, 'aryl and acyl, x represents an integer of
from 1 to 4, y represents an integer of from 1 to 10, z
represents an integer of from 1 to 6, and w represents an
‘integer of from'0 to 4, with at least a stoichiometric
amount of a hydrogenation reagent, whereby the carbon
to metal bond in said organo-metallic complex is broken
and hydrogen is added to the C2 group present in said
Example IX
To a suspension of 1.5 grams LiAlI-I4 in 150 ml. THF,
ml.
8. solution
THF was
Of 1added dropwise
MO2(cO)4(C6H5C2C6H5)5
at room temperature
in in a
complex to form said organic compounds.
2. A process as claimed in claim 1, in which the metal
period of 30 minutes. Afterwards, the mixture was stirred
for about 3 hours. Excess of LiAlH4 was destroyed by
addition of water; after acidi?cation with HCl, a part of
of the organo-metal-lic complex is iron.
3. A process as claimed in claim 1, in which the metal
of the organo-metallic complex is cobalt.
THF was removed under vacuum and the mixture was
4. A process as claimed in claim 1, in which the metal
extracted with benzene. Chromatography of the benzenic
solution yielded:
(a) 0.12 gram of dibenzyl and small amounts of stilbene,
(b) 0.12 grams of 122:3:4-tetraphenyl-butadiene,
of the organo-metallic complex is molybdenum.
(d) 2:3 :4 : 5-tetraphenyl-cyclopentene-2-one-1.
6. A process [as claimed in claim 1, in which the hy
drogenation reagent is a member selected from the group
of the organo-metallic complex is nickel.
5. A process as claimed in claim 1, in which the metal
(c) Tetracyclone and
Example X
To a suspension of 1.5 gram LiAlI-L, in 150 m1. of 50
‘acid.
7. A process as claimed in claim '1, in which a stoichio
metric excess of the hydrogenation reagent is employed.
8. A process as claimed in claim 7, in which an organic
THF, one added to a solution of 1 gram
MO(CO)2(C6H5C2C6H5)4
this mixture was heated for 2'hours at 60° C. By Working
up as in Example IX, the following product was obtained:
0.37 gram of a colorless compound (M.P.: 253—254° C.),
solvent selected from the group consisting of benzene,
petroleum ether, ether, tetrahydrofuran and beta-ethoxy
‘ethanol is employed.
the analysis of which corresponded to (C6H5C2H5)3H2:
9. A process as claimed in claim 8, in which the re
action is carried out at a temperature of between --60° C.
vand 250 C.
10. A process as claimed in claim 1, in which the
ANALYSIS
Found
C _______________________________________ __
H
_
M.W ____________________________________ _.
94. 19
6. 08
539
Theoretical
cal. for 0411132
93. 99
6. 01
536. 72
reaction mixture is initially activated by ultraviolet radi
ation.
65
The compounds produced by the process of this inven
tion have art-recognized utility or will serve as intermedi
ates in the production of compounds having a wide range
of artn'ecognized ‘utility. ,
For example, the cyclopentenones have utility as polar
solvents particularly for organo-metallic reactions. The
consisting of lithium aluminum hydride, sodium boron
‘hydride, sodium amide, sodium in liquid ammonia, lithi
‘um diethylamine, hydrogen, hydrochloric and sulfuric
70
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,810,737
2,818,416
2,849,470
Haven ______________ .. Oct. 22, 1957
Brown et al. ________ __ Dec. 31, 1957
Benson ______________ __ Aug. 26, 1958
2,852,542
2,898,359
Sweeney ____________ __ Sept. 16, 19:58
Leedham et al __________ __ Aug. 4, 1959
2,916,503 I
Kozikowski __________ __ Dec. 18, 1959
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