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Патент USA US3085128

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United States Patent 0 "ice
1
3,685,118
Patented Apr. 9, 1963
2
glycol and of diethylene glycol. These include ethylene
3,085,118
glycol dimethyl ether, ethylene glycol diethyl ether,
ethylene glycol dibutyl ether, ethylene glycol ethylbutyl
ether, diethylene glycol dimethyl ether, diethylene glycol
diethyl ether, diethylene glycol dibutyl ether, ethylene
glycol ethyl-hexyl ether and diethylene glycol ethyl-hexyl
PREPARATIUN 0F PULYCYCLIC ARYLSODIUM
COMPOUNDS
Donald J. Foster, South Charleston, W. Va., assignor to
gnipin Carbide Corporation, a corporation of New
or
ether.
Also suitable are cyclic ethers such as tetrahydrofuran
and dioxane as well as aromatic ethers such as ethylene
No Drawing. Filed Oct. 6, 1958, Ser. No. 765,300
11 Claims. (Cl. 260-665)
Polycycylic aryl organometallics, in which the metal 10 glycol diphenyl ether and diethylene glycol diphenyl ether.
Yet another class of suitable liquids is the tertiary
amines. These include tri-n-butylamine, trimethylamine,
connected to a carbon atom in an aromatic system, would
atom is substituted for an aromatic hydrogen and directly
triethylamine, N-methylmorpholine, tripropylamine and
be Valuable intermediates for the preparation of a wide
variety of polycyclic derivatives. The extreme reactivity
of organometallic compounds, particularly organosodium
compounds, is such that if polycyclic organometallic com
pounds were available they would greatly facilitate the
preparation of a large number of compounds which can
at present he prepared only by long and involved syn
theses.
‘1 While there have been many methods studied and de
15
the like.
Mixtures of any of the above liquids may be employed
as the suspending liquid for the sodium suspension and
they may be diluted with inert hydrocarbons if desired.
It should be noted however that aliphatic hydrocarbon
solvents alone are not suitable liquids for use in the inven
tion.
The reaction temperature should be no higher than 10°
C. and is preferably maintained below 0° C. At tem
peratures of 0° C. or below, the tendency to form second
ary reaction products which would lower the yield of
arylsodium compounds. Most of this has been done with
phenylsodium with some work on naphthylsodium. The 25 the desired product is reduced. A preferred temperature
dif?culties in making even naphthylsodium has precluded
is about —10° C. Temperatures below about minus 78°
C. are not desirable as they tend to reduce the rate of
extensive studies of its properties or fruitful efforts to
make higher polycyclic organosodium compounds.
reaction to such an extent that the formation of the de
veloped for making alkyl and aralkyl organosodium com
pounds, there has been relatively little work done with
sired product is slowed.
Thus, naphthylsodium has been made by metal-halogen
interchange between butylsodium and oc-bromonaphtha 30 The polycyclic arylhalide may be added to the liquid
lene (H. Gilman and R. G. Jones, Journal of American
Chemical Society, 63, 1441 (1941)). Another method
dispersion of sodium either alone or as a solution of aryl
halide in the same liquid or in a compatible liquid. At
mospheric pressure is ordinarily suitable although some
utilizes the rather general reaction of organomercury of
what higher pressure may be employed if the arylhalide
organozinc compounds with metallic sodium (W. Schlenk
and J. Holtz, Ben, 50, 262 (1917)). A third known 35 or liquid is low-boiling. It is desirable, moreover, that
method utilizes a metal-hydrogen interchange between
the reaction be conducted in an atmosphere that will not
naphthalene and amylsodium. All three methods require
cause side reactions, as would ‘air. Such an atmosphere
may be achieved in any of several ways. One convenient
procedure is to conduct the reaction under an inert gas,
ing polycyclic organometallic compounds having more 40 such as argon or dry nitrogen. Pressure can be atmos
than two rings.
pheric or may be slightly above if the aryl halide or liquid
are low-boiling.
I have now discovered a direct method for the prepara
the making of an organometallic compound as a starting
material and none have been shown to be useful for mak
tion of polycyclic organosodium compounds from metal
is sodium and organohalides.
The preferred form for the metallic sodium is sub-divi
sion into particles of about 50 micron size or below, 21
cyclic arylhalide, wherein a halogen is substituted for
tion.
hydrogen on a ring, is added to a suspension of ?nely di
action, however, probably because the aryl halide reacts
In a preferred embodiment of my invention a poly 45 though much larger particles are operable in the inven
The smaller particle size increases the rate of re
vided sodium dispersed in a suitable liquid. ‘Preferably,
on the surface of the metallic sodium and the small par
ticle size presents greater surface area. The necessity
the reaction is carried out in an atmosphere which will
not promote side reactions and at a temperature below 50 for extremely ?ne sub-division of the sodium decreases
0° C.
when vigorous agitation of the reaction mixture is pro
‘Polycyclic arylsodium compounds which can be made
vided. This is because such agitation aids in the removal
by the process of the invention include naphthylsodium,
of arylsodium and sodium chloride from the surface of
pyrenylsodium, anthrylsodium, phenanthrylsodium, benz
the metal and thereby exposes fresh metallic surfaces.
anthrylsodium, benzphenanthrylsodium, dibenzanthryl
sodium, naphthoanthrylsodium, dibenzphenanthrylso
dium, naphthophenanthrylsodium, ?uoranthrylsodium,
The aryl halide is preferably added in less than the
of the foregoing. Also preferred are ethers of ethylene
ture begins to darken noticeably. The reaction mixture
stoichiometric amount or slightly less than the stoichio
metric amount necessary to react with all the sodium
perylenylsodium and the like.
present, so as to assure reaction of all’ the aryl halide.
The polycyclic arylhalides may be a chloride, a bro~
From 0.40 to 0.50 mols of aryl halide per gram atom of
mide or an iodide. The chlorides are preferred because 60 sodium is ordinarily employed. The rate of addition of
they do not undergo the side reaction of Wiirtz-type cou
aryl halide can be varied from immediate mixing of the
plings as readily as do the other halides. The liquid in
entire amount to a very slow addition. Rapid addition re
which the sodium is suspended must be a liquid which, at
quires the removal of the considerable heat of reaction,
temperatures of about 0° C. or less, does not react with
but is generally preferred because with slower addition
sodium or with the polycyclic arylhalides and which is it 65 the probability of undesirable side reactions is greatly in
self a stable liquid under the reaction conditions. A pre
creased, decreasing the yield of arylsodium.
ferred class of liquids for use in the invention are the
A preferred method of operation is to ?rst add a small
aliphatic ethers containing from 2 to 12 carbon atoms.
quantity of aryl halide to a suspension of ?nely divided
Such ethers include methyl ether, methyl ethyl ether,
sodium in an aliphatic ether, in an inert atmosphere such
ethyl ether, n~propyl ether, isopropyl ether, n-butyl ether, 70 as dry nitrogen and at room temperature. An exothermic
reaction ensues almost immediately and the reaction mix
isobutyl ether, amyl ethers, hexyl ethers and mixed ethers
3,085,118
4
3
is then cooledyprefera'bly to ‘about 0° C., ‘and the re
mainder of the aryl halide'is added portion-Wise, either
directly or dissolved in more of the aliphatic ether, Pref
erably, agitation of the reaction mixture is continued after
addition of the aryl halide is complete, in order to insure
completion of the reaction.
Because of its high reactivity, thearylsodiurn product
is preferably stored in an inert liquid, which may be the
liquid'in which it was made, and under an inert atmos
phere such as dry nitrogen.
Example I
There was prepared a suspension of 28 grams (1.2 gram
Example III
There was prepared a suspension of 28 grams (1.2 gram
atoms) of ?nely divided sodium dispersed in 700 milli
liters of ethyl ether. A total of 118 grams (0.5 mol) of
3-chloropyrene were dissolved in 200 milliliters of a mix
ture of ethyl ether and benzene. The sodium suspension
was placed in an inert atmosphere of dry nitrogen at at
mospheric pressure and was cooled to a temperature of
0° C. The 3~chloropyrene solution was added with stir—
10 ring to the sodium suspension over a period of one hour,
with the temperature ‘maintained at 0° C. The reaction
commenced immediately with the formation of a black,
substantially insoluble compound identi?ed as 3-pyrenyl
sodium. After the‘addition was complete the mixture
atoms) of ?nely divided sodium dispersed in 700 milli
liters of ethyl ether. A total of 82 grams (0.5 mol) of 15 was stirred for an additional thirty minutes to insure com
alpha-chloronaphthalene was dissolved in 100 milliliters
pletion of the reaction.
of ethyl ether. The sodium suspension was placed in an
The ethyl ether slurry of S-pyrenylsodium thus obtained
inert atmosphere ofldry nitrogen at atmospheric. pressure
was poured over solid carbon dioxide to yield sodium
and was cooled to a temperature of 0° C. The alpha
pyrene-S-carboxylate. About 250 milliliters of water
chloronaphthalene solution was added with stirring to the
sodium'suspension over a period of one hour, with the
temperature maintained at 0° C. The reaction com
menced immediately with the formation of a black, sub
were then added to react with the excess sodium and to
dissolve the sodium salts. The aqueous solution of sodi
urn pyrene-B-carboxylate was then acidified with hydro
chloric acid to liberate pyrene-3-carboxylic acid. This
pyrene-B-carboxylic acid was extracted with ethyl ether
sodium. After the addition was complete the mixture 25 and puri?ed by recrystallization from ethanol. There
was stirred for an additional thirty minutes to insure com
were ‘obtained 98 grams of pyrene-3-carboxylic acid for
pletion of the reaction.
a yield of 80 percent. The physical and spectroscopic prop
The ethyl ether slurry of alpha-naphthylsodium thus
erties of the pyrene-3-carboxylic acid thus obtained were
obtained ‘was poured over solid carbon dioxide to yield
compared with those of a known sample of pyrene-3
sodium alpha-naphthoate. About 25 0 milliliters of water 30 carboxylic acid and found to be identical.
were then added to react with the excess sodium and to
Example IV
dissolve the sodium salts. The aqueous solution of sodi
um alpha-naphthoate was then acidi?ed with hydrochloric
:There was prepared a suspension of 28 grams (1.2 gram
acid to liberate alpha-naphthoic acid. This alpha-naph
atoms) of ?nely divided sodium dispersed in 700 milli
thoi-c acid was extracted with ethyl ether and puri?ed by 35 liters of ethyl ether. A total of 106 grams (0.5 mol) of
recrystallization from ethanol. There were obtained 77
9-chloroanthracenewere dissolved in 200 milliliters of
grams of alpha~naphthoic acid for a yield of 90 percent.
ethyl ether. The sodium suspension was placed in an
The physical and spectroscopic properties of the alpha
inert atmosphere of dry nitrogen at atmospheric pressure
naphthoic acid thus obtained were compared with those
and was cooled to a temperature of 0° C. The 9-chloro
of a known sample of alpha-naphthoic acid and found to 40 anthracene solution was added with stirring to the sodium
stantially insoluble compound identi?ed as alpha-naphthyl
be‘identical.
Example II
suspension over a period of one hour, with the tempera
ture maintained at 0° C. The reaction commenced im
mediately with the formation of a black, substantially in
There was prepared a suspension of 28 grams ( 1.2
soluble compound identified as 9-anthrylsodium. After
gram atoms) of ‘?nely divided sodium dispersed in 700
milliliters of ethyl ether. A total of 104 grams (0.5 mol) 45 the addition was complete the mixture was stirred for an
vadditional thirty minutes to insure completion of the re
of alpha~bromonaphthalene were dissolved in 100 milli
action.
liters of ethyl‘ether. The sodium suspension was placed
The ethyl ether slurry of 9-anthrylsodium thus obtained
in an inert atmosphere of dry nitrogen at atmospheric
pressure and were cooled‘to a temperature of 0° C. The
was poured over solid carbon dioxide to yield sodium 9
About 250 milliliters of water were then
added to react with the excess sodium and to dissolve the
sodium salts. The aqueous solution of sodium 9-anthro
ate was then acidi?ed with hydrochloric acid to liberate
9-anthroic acid. This 9 anthroic acid was extracted with
alpha-bromonaphthalene solution was added with stirring 50 anthroate.
to the sodium suspension over a period of one hour, with
the temperature maintained at 0° C. The reaction com~
menced immediately with the formation of a black, sub
stantially insoluble compound identi?ed as alpha-naphthyl
sodium. After the addition was complete the mixture 55 ethyl ether and puri?ed by recrystallization from ethanol.
was stirred for an additional thirty minutes to insure com
pletion of the reaction.
The ethyl ether slurry of alpha-naphthylsodium thus
obtained was poured over solid carbon dioxide to yield
sodium-alpha-naphthoate. About 250 milliliters of water
were then added to react with the excess sodium and to
dissolve the sodium salts. The aqueous solution of sodi
um alpha~naphthoate wasthen acidi?ed with hydrochloric
There were obtained 61 grams of 9-anthroic acid for a
yield of 55 percent. The physical and spectroscopic prop
erties of the 9-anthroic acid thus obtained were compared
with those of a known sample of 9-anthroic acid and
found to be identical.
Example V
There was prepared a suspension of 28 grams (1.2 gram
atoms) of ?nely divided sodium dispersed in 700 milli~
acid to liberate alpha-naphthoic acid. This alpha
naphthoic acid was extracted with ethyl ether and puri?ed 65 liters of ethyl ether. A total of 106 grams (0.5 mols)
of 9~chlorophenanthrene was dissolved in 100 milliliters
by recrystallization from ethanol.‘ There were obtained
of ethyl ether. The sodium suspension was placed in an
56 grams of alpha-naphthoic acid for a yield of 65 per
inert atmosphere of dry nitrogen at atmospheric pressure
cent. The physical and spectroscopic'properties of the
and was cooled to a temperature of 0° C. The 9-cliloro
alphanaphthoic acid thus obtained were compared with
those of a known ‘sample of alpha-naphthoic acid and 70 phenanthrene solution was added with stirring to the
found to be identical.
There were also obtained 16 grams of binaphthyls, pri
sodium suspension over a period of one hour, with the
temperature maintained at 0° C. The reaction com
marily the alpha, alpha prime isomer. This represented
menced immediately with the formation of a black, sub
a 25 percent yield of binaphthyls, based on alpha~bromo
stantially insoluble compound identi?ed as 9-pl1enanthryl
sodium. After the addition was complete the mixture
naphthalene.
3,085,118
5
6
prises reacting 9-chloroanthracene with ?nely divided me
tallic sodium dispersed in an inert liquid, selected from
the group consisting of aliphatic ethers containing from
was stirred for an additional thirty minutes to insure com
pletion of the reaction.
The ethyl ether slurry of 9-phenanthylsodium thus
obtained was poured over solid carbon dioxide to yield
sodium phenanthrene-9-carboxylate.
2 to 12 carbon atoms, cyclic ethers, aromatic ethers,
tertiary amines, and mixtures thereof said reaction being
About 250 milli~
liters of water were then added to react with the excess
carried out under an inert atmosphere and at a tempera
ture below 0° C.
sodium and to dissolve the sodium salts. The aqueous
solution of sodium phenanthrene-9-carboxylate was then
acidi?ed with hydrochloric acid to liberate phenanthrene
7. Process for making 9-phenanthrylsodium which com
prises reacting 9-ehlorophenanthrene with ?nely divided
9-carboxylic acid. This phenanthrene-9-carboxylic acid 10 metallic sodium dispersed in an inert liquid, selected from
was extracted with ethyl ether and puri?ed by recrystalli
the group consisting of aliphatic ethers containing from
zation from ethanol. There were obtained 39 grams of
2 to 12 carbon atoms, cyclic ethers, aromatic ethers, ter
phenanthrene-9-carboxylic acid for a yield of 35 percent.
tiary amines, and mixtures thereof said reaction being
The physical and spectroscopic properties of the alpha
carried out under an inert atmosphere and at a tempera
phenanthrene-9-carboxylic acid thus obtained were com
pared with those of a known sample of phenanthrene-9~
carboxylic acid and found to be identical.
15 ture below 0° C.
8. Process for making benzanthryl sodium which com
prises reacting chlorobenzanthrene with ?nely divided
There were also obtained 35 grams of 9,9’-biphenan
thryl, representing a 40 percent yield based on 9-chloro
phenanthrene.
metallic sodium dispersed in an inert lique, selected from
the group consisting of aliphatic ethers containing from
20 2 to 12 carbon atoms, cyclic ethers, aromatic ethers,
What is claimed is:
1. Process for making a polycyclic arylsodium com
pound of more than two rings wherein the sodium is
tertiary amines, and mixtures thereof said reaction being
carried out under an inert vatmosphere and at a tempera
ture below 0'‘ C.
directly attached to a carbon atom in an aromatic
9. Process for making dibenzanthryl sodium which
ring which comprises reacting a polycyclic aryl halide 25 comprises reacting chlorodibenzanthrene with ?nely di
with ?nely divided metallic sodium suspended in an
vided metallic sodium dispersed in an inert liquid, selected
inert liquid, selected from the group consisting of ali
from the group consisting of aliphatic ethers containing
phatic ethers containing from 2 to 12 carbon atoms,
from 2 to 12 carbon atoms, cyclic ethers, aromatic ethers,
tertiary amines, and mixtures thereof said reaction being
cyclic ethers, aromatic ethers, tertiary amines, and
mixtures thereof said reaction being carried out at a tem 30 carried out under an inert atmosphere and at a tempera~
perature below 0° C. and under an inert atmosphere.
ture below 0° C.
2. ‘Process for making a polycyclic arylsodium com
10. Process for making ?uoranthryl sodium which com
pound of more than two rings of more than two rings
prises reacting chlorofluoranthrene with ?nely divided
wherein the sodium is directly attached to a carbon atom
metallic sodium dispersed in an inert liquid, selected
in an aromatic ring which comprises reacting a poly 35 from the group consisting of aliphatic ethers containing
cyclic aryl halide with ?nely divided metallic sodium sus
pended in an inert liquid, selected from the group con
sisting of aliphatic ethers containing from 2 to 12 carbon
atoms, cyclic ethers, aromatic ethers, tertiary amines, and
mixtures thereof said reaction being carried out at a tem 40
perature below 10° C. and under an inert atmosphere.
3. Process for making a polycyclic arylsodium com
pound of more than two rings wherein the sodium
is directly attached to a carbon atom in an aromatic
from 2 to 12 carbon atoms, cyclic ethers, aromatic ethers,
tertiary amines, and mixtures thereof said reaction being
carried out under an inert atmosphere and at a tempera
ture below 0° C.
11. Process for making a polycyclic arylsodium com
pound of more than two rings wherein the sodium is
directly attached to a carbon atoms in an aromatic ring
which comprises reacting a polycyclic aryl halide with
?nely-divided metallic sodium suspended in an ether se
ring which comprises reacting a polycyclic aryl halide 45 lected from the group consisting of ethyl ether, propyl
with ?nely divided metallic sodium suspended in an
ether containing between two and twelve carbon atoms,
said reaction being carried out at a temperature below
0° C. and under an inert atmosphere.
4. Process for making a polycyclic arylsodium com 50
pound of more than two rings wherein the sodium is di
rectly attached to a carbon atom in an aromatic ring
which comprises reacting a polycyclic aryl chloride with
?nely divided metallic sodium dispersed in an inert liquid
selected from the group consisting of aliphatic ethers con 55
taining from 2 to 12 carbon atoms, cyclic ethers, aromatic
ethers, tertiary amines, and mixtures thereof, said reac
tion being carried out under ‘an inert atmosphere and at
a temperature below 0° C.
5. Process for making 3-pyrenylsodium which com 60
prises reacting 3-chloropyrene with ?nely divided metallic
sodium dispersed in an inert liquid, selected from the
group consisting of aliphatic ethers containing ‘from 2
to 12 carbon atoms, cyclic ethers, aromatic ethers, tertiary
amines, and mixtures thereof said reaction being carried 65
out under an inert atmosphere and at a temperature be
low 0° C.
6. Process for making 9-anthrylsodium which com
ethers, butyl ethers, hexyl ethers, diethylene glycol ether
and ethylene glycol dibutyl ether, said reaction being car
ried out under an inert atmosphere and at a temperature
below 0° C.
References Cited in the ?le of this patent
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2,019,832
2,023,793
2,027,000
2,108,277
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Scott _______________ _.. Aug. 2,
1935
1935
1936
1938
1938
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Scott ________________ _.. Sept.
Nobis et a1. _________ __ June
Nobis et a1. __________ __ June
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1939
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1957
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26,
11,
11,
25,
OTHER REFERENCES
'Coates: “Organo-Metallic Compounds” (1956), pp. 16
and ‘17, John Wiley & Sons, N.Y.
Jeanes et al.: “J. Am. Chem. Soc. 59,” 2609-2615.
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