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Patented Jan. 14, 1947
2,414,118
Umreo STATES PATENT orrlc
2,414,118
SYNTHESIS OFFLUORENE m rrs
DERIVATIVES
Milton Orchin, Pittsburgh, is, as‘sisnor to the
United States
of America, as represented by the
Secretary of _ the Interior
No Drawing. Application March 27, 1945,
Serial No. 585,177
. 4 Claims.
(01. 260-668)
(Granted under the act of. March 3, 1883, as
amended April 30, 1928; ‘370 0. G. 757)
The invention described herein may be manu
factured and used by or for the Government of
the United States for governmental purposes
without the payment to me of any royalty thereon
in accordance with the provisions of the act of
April 30, 1928 (ch. 460, 45 Stat. L. 467).
This invention relates to ?uorene and its de
rivatives, and to a catalytic process for their prep
aration. More particularly, this invention relates
'
2
be employed tmprepare corresponding ?uorene
compounds in accordance with this invention by
' cyclodehydrogenation include Z-methylbiphenyls
having methyl or other alkyl aliphatic substitu
ent on any of the nuclear carbon atoms excepting
an’ ortho’ position, as previously explained, as
well as the halogenated or nitrated derivatives of
ortho-methylbiphenyls having a nuclear hydro
atom in the ortho' position
to the catalytic cyclodehydrogenation of certain 10- gen
The catalytic c yclodehydrogenation of a suit
alkylated biphenyls to ?uorene and its nuclear " able 2
-methylbiphenyl compound is preferably
substitution products. By the expression “nu
carried out in the vapor- phase in this invention,
clear substitution products” it is intended to in
and generally at a temperature su?icient to main
clude ?uorene compounds having a. ?uorene nu
cleus and having one or more nuclearhydrogen 15 tain the chosen Z-methylbiphenyl compound va
porized but below the temperature at which sub
atoms replaced by other atoms or radicals as
hereinafter to be more fully explained.
'
Accordingly, this invention has for an object ,
the production of ?uorene and its nuclearsubsti
tution products as well as the provision of a cata
~ I stantial thermal cracking takes place. A suitable
temperature range for carrying out the reaction
‘is a temperature between 400 degrees centigrade
- and 500 degrees centigrade such as for example a
lytic process for carrying out the foregoing. An 20 temperature of the order of 450 degrees centi
other object is the preparation of new chemical
grade.
compounds.
-
~
The vaporized reactant may be passed over the
-
catalyst at ordinary atmospheric pressure, super
The foregoing and other related objects are
accomplished in accordance with this invention 25 atmosphericipressure or sub-atmospheric pres
sure, but generally‘ it is preferred to carry out
vwherein ?uorene and its nuclear substitution
the catalytic,cyclodehydrogenation at ordinary
products are prepared by the cyclodehydrogena
atmospheric pressure in the presence of a slow
tion of a compound from the group of ortho
stream of an ‘inert carrier gas. For example, a
methylbiphenyl and its nuclear substitution prod
‘slow stream of hydrogen may concurrently be
ucts having a nuclear hydrogen atom in the or
tho' position. It has been found that the cyclo 30 passed through the reaction apparatus together
dehydrogenation of 2-methylbiphenyl, 2,2’-di
methylbiphenyl and their nuclear, substitution
with the vaporized 2-methylbipheny1 compound.
Other suitable inert carrier gases include nitro- “
gen, helium and argon, but hydrogen is preferred.
products ‘having a nuclear hydrogen atom in the
While a suitable dehydrogenation catalyst may
ortho' position can be carried out in simple fash 35
be employed in massive form, it-is preferred to ion by passing such a compound in the vapor
phase at a temperature of at least 300 degrees - employ it supported upon a suitable carrier ma
terial which permits free passage of‘ gases and
centigrade over a dehydrogenation catalyst, pref
vapors while providing a suitable intimate con
erably palladium-charcoal although other suit
able dehydrogenation catalysts can be employed 40 tact between the vaporized reactant- and the sup
ported catalyst. For example, a‘ preferred pal.
ladium-charcoal catalyst was prepared by mix
such as for. example chromium oxide, platinum
black, Raney nickel and the like either in massive
form or suitably supported on asbestos, kiesel
guhr and the like.
,
ing 12 grams of charcoal with 8 grams of palla
dium chloride and 24 cubic centimeters of 40%
It has been found for example that 4-methyl‘ 45 formaldehyde, cooling the mixture with stirring,
and then stirring 48 cubic centimeters of 50% po
?uorene can be prepared from 12,2'dimethylbi
-. phenyl in accordan cc with this invention, and ' tassium hydroxide solution into the thus prepared
mixture by drop-wise addition. The thus pre
similarly, ?uorene from 2 -methylb'iphe_nyl or 2
pared mixture was ?ltered away from the super
methyl-1', 2', 3', 4'-tetrahydrobiphenyl. Other
nuclear substituted 2 -methylbiphenyls which may 5 0 natalunt liquid, washed with water unti1__free 01'
GS and dried. Thereupon, 30 parts by weight
2,414,118
of the dried "palladium-charcoal mixture thus
prepared was mixed with 70 parts by weight of
asbestos and the resulting supported palladium
charcoal catalyst was employed for the dehydro
' genation in accordance
with this invention.
The following illustrative examples show how
4
A similar yield was obtained when the cat
alyst employed was prepared by shaking 5 grams
of 30% palladium-charcoal with 9 grams of ig
nited asbestos and adding glass helices to this
mixture.
Example 2
Employing the method, apparatus and catalyst
of Example, 1, 9.8 grams of 2-methylbiphenyl
the invention may be carried out, but it is not
limited thereto. Parts and percentage composi
was passed once over the supported palladium
tions are by weight unless otherwise designated,
and the indicated temperatures are on the centi 10 charcoal catalyst at 450 degrees centigrade. The
mixture of oil‘ and solid-collecting in the receiver .
grade scale.
‘
.
was taken up in alcohol, cooled and the precipi
tated solid ?ltered from the liquid. 2.8 grams of
solid material having a melting point of 104-110
An iron pipe about 70 centimeters in length
and 15 millimeters inside diameter was wrapped 15 degrees centigrade was obtained. Upon ‘recrys
tallization from alcohol, pure ?uorene was ob
with asbestos and then with 24 feet 01' No. 22 ni
tained having a melting point of 1150-1158 de
chrome electrical resistance wire to serve as a
grees centigrade. By passing the original mother
heating element. The wire windings were cov
> Example 1
ered with a second layer of asbestos and the
liquor through a bed of Activated Alumina to
wrapped pipe placed inside a cylindrical length 20 selectively adsorb the colored material, and
of heat-resisting glass tubing.‘ A suitable source
of electrical current was then connected to the
nichrome winding and controlled through a
thereafter extracting the bed with an excess of
alcohol, 0.54 gram of additional ?uorene was ob
tained by evaporation of the alcoholic extract.
In a further test, 9.0 grams of 1’,2’,3',4'-tetra
switch and rheostat. An inner tube having an
outside diameter of 14 millimeters and made of 25 hydro-Z-methlylbiphenyl were passed in a sin
gle pass over the supported palladium-charcoal
“Pyrex” glass was then inserted to form aninner
lining for the iron pipe and the entire apparatus
catalyst described in Example 1, and 2.06 grams
was mounted on a suitable support so that its
of pure fiuorene were obtained.
There was no
diminution in'catalyst activity with successive
long dimension was about 20 degrees from the a
horizontal. The lower portion of the inner glass 30 batches of raw, material, and therefore it is ap
parent that the catalyst has an extremely long
tube was connected to a suitable receiver pro
life. Byproducts are very small in quantity and
vided with means for excluding atmospheric air
and the upper end of the tube was connected to
by successively- recycling unconverted Z-methyl
grade, and then 12 grams of 2,2'-dimethylbi
; the mixture with a quantity of petroleum ether or
biphenyl, yields approaching quantitative propor
a suitable device for feeding liquid reactant and
hydrogen gas to the catalyst tube. Thereupon, 35 tions can be obtained.
the tube was charged with palladium-charcoal
While the produced fluorene and its derivatives
in the foregoing examples and description can
' catalyst supported on asbestos prepared asabove
described, a slow stream of hydrogen was ad
be chromatographically separated from uncon
mitted and suitable means for measuring the in
verted raw material by passing the crude prod
ternal temperature of the catalyst tube was con 40 uct directly over a suitable absorbent material,
nected. By rhea.N of the electrical heating ele~
for example, Activated Alumina or a mixture of
ment and rheostat the temperature inside the
Activated Alumina with “Supercell" or other ad
catalyst tube was adjusted to 450 degrees centi
sorbent earth, it has been found that diluting
phenyl was passed over the catalyst bed in the
vapor phase together with an excess of hydro
gen gas to act as a diluent carrier. The 2,2’-di
methylbiphenyl is admitted to the catalyst tube
at the rate of about 5 to 8 cubic centimeters per ’
hour. After all the reacted material was con- ,
densed and collected in the receiver, it was again
passed over the catalyst for a total of 5 succes
sive cycles, thus giving the effect of a catalyst
tube having 5 times the length of the tube em
ployed. 10.5 grams of liquid product (1125:),
1.5968) was separated by‘dilution with petroleum
other light hydrocarbon distillate before adsorp
tion provides a more rapid through-put of prod
uct. After selective adsorption, the adsorbed
.highly colored product may be removed by any
desired means, preferably by extraction with hot
alcohol or other volatile solvent for fluorene com
pounds.
Various changes can be made in the invention
as illustrated and described without departing
from the spirit and scope thereof, since many
varying and widely differing embodiments of the
invention will occur to one skilled in the art.
ether in excess and selective adsorption of the
What I claim is:
converted constituent thereof on Activated Alu
1. A process for the production of fluorene and
mina. The absorbed product exhibited fluores
its nuclear substitution products which comprises
cence under ultra-violet light. 6.5 grams of ma
passing a compound from the group of ortho
terial was unconverted. The fluorescent frac
methylbiphenyl and its nuclear substitution prod
tion, upon extraction with excess in benzene and
vucts having a nuclearhydrogen atom in the
evaporation to dryness, gave 100 mg. of a col
ortho’ position, in the vapor phase at a temper
ored high molecular weight material which was
ature of at least 300 degrees centigrade over a
not further investigated and 2.75 grams of crys 65 dehydrogenation catalyst.
talline 4-methyl-?uorene which had a melting
_ 2. A process for the production of ?uorene and
point of 70.4-71.2 degrees centigrade after re
its nuclear substitution products which comprises
peated crystallization from methanol. This 4
passing a compound from the group of 2-meth
methyl ?uorene has properties substantially dif
ylbiphenyl and its nuclear substitution products
fering from those reported in the literature, as 70 having a nuclearhydrogen atom in the 2’ posi
indicated by the above-indicated melting point.
_ Also, the ultra-violet absorption of this 4-methyl
tion in the vapor phase at a temperature be
tween 400 degrees and 500 degrees centigrade
?uorene showed maxima at 2660 A., log E 4.31
over a dehydrogenation catalyst comprising pal
,and 2960 A., log E 3.60 and minima at 2340 A.,
iadium-charcoal.
75
108 E 3.40 and 2940 A.,10g E 3.53.
2,414,118
a
-
5
3. A process which comprises passing vapor
ized 2,2'-dimethy1biphenyl at a temperature of
about 450 degrees centigrade over an’ asbestos
supported palladium-charcoal catalyst, adsorbing
the formed 4-methyl?uorene on Activated Alu
mina, extracting the absorbate with a suitable
solvent, and recovering 4-methyl?uorene by
‘6
4. ‘As a new compound, 4-methyl?uorene hav
ing a melting point of 71.5-72.5 degrees centi
grade, and an ultra-violet absorption spectra
' showing maxima at 2660 A. log E 4.31 and 2960
A. 102: E 3.60 and minima at 2340“ A. 10g E 3.40
. and 2940 A. 108 E 3.53.
evaporative crystallization.
MILTON oRcmN.
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