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Патент USA US2406645

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Apg. 27, 1946.
>
c. L. THOMAS, y
2,406,645
ySYNTHESIS OF AROMATIC COMPOUNDS
Filed sept. 2s,v 1944
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Patented Aug. 27, 1946
2,406,645
UNITE-D STATES .PATENT -oFFi-CE
SYNTHESIS OFAROMATIC COMPOUNDS
Gharles‘L.;Th'omas, Riverside,` Ill.„-assìgnor,tn1lni’ Y versal1Qil5I’roducts Company, Chicago, Ill., a
'_corporationrof- Delaware
Application ~September 28, 19.44, SerialìNo. 556,263
Y
(01.;260-67-1)
l»1li-.Claims
l
This invention relates‘to the> treatment of-= poly
nuclear ‘aromatic compounds `'containing «a con
-jugated dienefstructure -in 'a Diels-Alder--type re
action.
More particularly the present 'invention'is‘ di
rected to the reaction fof Ipolynuclear »aromatic
compounds comprising anthracene #and substi
tution Àproducts thereof lwith an - unsaturated» hy
drocarbon.
_
Theftypical Diels-Alder reaction or dienesyn
thesis, `_as it is also knoWnfinvolves-‘the 11,4‘addi
'tion of asys'tem of conjugateddoublebonds'to a
compound known as -a -dienophile Aandcontaining
an l“activated” ygroup ofthe type: -C=C`»--C'=O
vor C~=-ïC-`C=O, -Although the--dienophile-isespe 15
cially, active ' When> 4the »- carbonyl ' group is present,
'-the reaction -will halso occur Yif -o'ther substituent
_groups replace »or Yaugment 'the `carbonyl »group
>in the dienophilic compound. 'I‘hesesubs'tituent
groups include acetoxyl, nitro, sulfonyl, cyano,
amino, etc. The-present invention ‘dea‘ls'vwith the
reactionlbetween polynuclear-«aromatics and sub- '
stitution products thereof, with unsaturated ïhy
drocarbons in the absence of 'suchfï‘activatin
groups.
~
«
Broadly,'the present inventionßrelatesetoa proc
ess which ’comprises thermally, -~ non-catalytically
reacting an unsaturated hydrocarbon‘andfapoly
nuclear Y'aromatic -‘compound Àcontaining a con
jugated diene structure and'capable of-forming a 30
‘bridge »between the carbon -atoms 'in v`the'L‘l lposi
tions of the diene part of the molecule.
In'one embodiment this îinvention Jrelates to a
4process which comprises thermally, `non-cat
~ alytically reacting ananthracene compound tcon
taining a conjugated dienestructure `>with an vali
phatic oleiin at a temperaturewithinlthe‘range
of »about 100 to about-300i’ C.
In another embodiment'my‘invention relates
to 'a process Awhich comprises thermally, non-‘cat
alytically reacting an'ant‘hra'cene compound con- '
The polycyclic aromatic hydrocarbons 'which
are 'suitable for ‘the ¿present process include, in
addition to -anthracen-e, V4benzanîtl'iracenes, tetra
35
cene, 'pentacene, hexacene, dibenzan'thracenes,
Vchrysene, Ycholanthrene, 1naphthacene and Vtheir
substitution products including alkyl, alkoxyl,'=hydroXyl, amino,íha-logenand~nitro derivatives. (All
of these »contain .one Yor «more conjugated dienic
40 structures.) Anthraquinone and 9,10-dihydro
anthracene derivatives are not substituted an
taining a conjugated diene'structurewith’a cyclic
thracenes land .are :not jincluded ini/this ¿group
o1e1’1`.n«at'a> temperatureNwithin theerange of about
.which ¿comprises onlyipolynuclear aromaticsf con
~100ito about 300°' C.
taining .a „conj ugated l,diene structure.
The reactions of my invention may-jbe "illustrat 45 The unsaturated -compounds vwhich fare. reacted
>ed "by the 'following »equations which show the
'with .the ¿anthracene :hydrocarbons »comprise
compositions formed when anthracene i«is 1reacted
mono-,oleñnsfsuchfas;ethy1ene,3propylene, ,1- and
-with ‘an aliphatic olefin and va Ecyclo-olefin, re
spectively.
,fZ-butylenes, «isobutylenean-d the likefueither alone,
ïadmixed :or `mixed Y@in non-,reactive substances.
50 Dioleñn .hydrocarbons which maybe used lin
cludesallene, butadiene, piperylene, isoprene, v.di
allyl, ¿eta -Cyclo-.oleñns l«such ¿as cyclopentene,
cyclohexene, cycloheptene, .-etc„ .and the Lcorre
sponding -fcyclodienes 'are falso «suitable for the
process. :Acetylenics'compoundsromprisingeither
aliphatic ,hydrocarbons oriaromatichydrocarbons
2,406,645
3
having acetylenic side chains may also be used.
No catalyst is employed in this reaction which
takes place at temperatures from about 100° to
ing a bridge between the carbon atoms in the 1,4 v
positions of the diene part of the molecule.
2. A process which comprises thermally, non
catalytically reacting an oleñnic hydrocarbon with
about 300° C.` The reaction can be effected in
the presence or absence of a solvent and can take
place in a batch type operation, as for example
a polynuclear aromatic compound containing a
conjugated diene structure and capable of form
in an autoclave, or in a continuous manner by
ing a bridge between the carbon atoms in the
conducting the reactants through the reaction
zone.
1,4 positions of the diene part of the molecule
Pressures below 2000 pounds per square
inch are generally satisfactory.
at a temperature within the range of about 100
to about 300° C.
3. A process which comprises thermally, non
-
The following examples illustrate the reaction
comprising my invention but should not be con
catalytically 'reacting an oleñnic hydrocarbon
strued as unduly limiting the invention in accord-ance therewith.
with a substituted polynuclear aromatic com
15 pound containing a conjugated diene structure
Eœample I
and capable of forming a bridge between the
carbon atoms in the 1,4 positions of the diene part
of the molecule at a temperature within the range
of about 100 to about 300° C.
4. A process which comprises thermally, non
catalytically reacting an olefinic hydrocarbon with
a polynuclear aromatic compound containing
three benzene rings and having a conjugated diene
structure and capable of forming a bridge be
tween the carbon atoms inthe 1,4-positions of
the diene part of the molecule.
5. A process which comprises thermally, non
catalytically reacting anthracene with an oleñnic
hydrocarbon at a temperature within the range
100 grams of anthracene was placed in an auto
clave and the vessel closed. Ethylene was added
to a pressure of 50 atmospheres and the tern
perature raised to 200° C. Ethylene was slowly
absorbed. AUpon cooling and opening the auto
clave, a somewhat impure product was removed
which melted at 140° to 141° C. Unreacted an
thracene was also found to be present. 130 grams
of toluene was added as a solvent and the auto
clave again closed, pressured to 50 atmospheres
with ethylene and heated to 200° C. Again eth
ylene was absorbed. The reaction product was
removed from the bomb and crystallized from the
of about 100 to about 300° C.
toluene followed by recrystallization from alco 30
hol. The product which comprised 9,10-ethano
,
«
.
6. A process which comprises thermally, non
-catalyticallyrreacting an oleñnic hydrocarbon with
a polynuclear aromatic compound containing
9,10-dihydroanthracene was in the form of white
needle-like crystals which melted at 142° to 153°
C. and which boiled at atmospheric pressure with
out noticeable decomposition. An analysis of the
three benzene rings and having a Vconjugated
diene structure and capable of forming a bridge
.between the carbon atoms in the 1,4 positions i
of the diene part~of the molecule at a tempera-‘
ture within the range of about 100 to about
anthracene-ethylene reaction product showed
that it comprised 93.12% carbon and 6.71% hy
drogen, while the calculated percentages of carbon
and hydrogen for 9,10-ethano-9,l0-dihydroanthracene were 93.20 and 6.8 respectively.
4
conjugated diene structure and capable of form-,
300°
The 40 Í
C.-
»
-
_
Y
7. A process which comprises thermally, non
catalytically reacting anthracene with an aliphatic
reaction product did not form a picrate, indicat
ing that it no longer contained the normal an
vole?ìn at a temperature within the range of about
thracene structure.
-100 to about 300° C.
catalytically reacting anthracene with a mono
oleñn at a temperature within the range of about
„100 to about 300° C.
9. A process which comprises thermally, non
100 grams of anthracene was placed in a re-V
action vessel to which was added 1000 cc. of
cycloheXene.
'
8. A process which comprises thermally, non
Example II
The mixture was heated to 250°
C. for eight hours. A solid product was formed' " lcatalytically reacting anthracene with a cyclic ole
which was recrystallized to remove unreacted an 50 ñn at a temperature within »the range of about
100 to about 300° C.
thracene. Two isomers of 9,10-cyclohexano-v
10. A process which comprises thermally, non
v,catalytically‘ reacting anthracene with an unsat
9,10-dihydroanthracene, one melting at 145-149“
C. and the other at,159-160° C. were found on
analysis to comprise carbon and hydrogen as fol-`Y
lows: (l) 92.51% carbon and 7.42% hydrogen
and (2) 92.39% carbon and ’7.59% hydrogen.
The calculated values for the reaction product
were 92.31 % carbon and ’7.6% hydrogen.
Example III
Íurated hydrocarbon in the presence of an unre
active solvent at a temperature within the range
y of about 100 to about 300° C.
11. A process which comprises thermally, non
Acatalytically'reacting anthracene with a mono
_olefinic hydrocarbon in the presence of a non
60 polar hydrocarbon solvent> at a temperature with
in the range of about 100 to about 300° C.
12. A process which comprises thermally, non
Ultraviolet absorption spectra for the ethylene
adduct and for the cycloheXene-anthracenere
catalytically reacting anthracene with ethylene
action products, the latter prepared according to p
at a temperature within the range of about 100
the procedure of Example II, are shown on the'
to about 300° C. in the presence of a solvent com
65
accompanying figure. The spectra were obtained
prising toluene.
*by means of a Beckman Quartz spectrophotom
13. A process which com-prises thermally, non
eter, following the standard procedure for this
catalytically reacting anthracene with cyclohex
instrument. As shown on the graph the absorp
tion spectra of the ethylene-anthracene and>`
cyclohexene-anthracene reaction products are
very similar to that of 9,10-dihydroanthracene.
I claim as my invention:
l; A process which comprises thermally, non
' catalytically reacting an oleñnic hydrocarbon with
-a polynuclear aromatic compound containing a
ene at a temperature within the range of about
100 to about 300° C. in the presence of a solvent
comprising toluene.
'
.
’
14. The :compound `~9,10-cyclohexano-9,10¿di
hydroanthracene.
„
,
,
.
CHARLES L. THOMAS.
7.5
Certificate of Correction
Patent No. 2,406,645
'
"
August 27, 1946
CHARLES L. THOMAS
It is hereby certified that error appears inthe printed specification of
the above numbered patent requiring correction as follows:
Column 3, lines 33 and 34, for “142° to 153°;` C.” read 142° to 143° 0.;
and that the said Letters Patent should be read afs corrected above, so that
the same may conform to the record of the case in the‘ï-,Patent Oíîìce.~
~ Signed and sealed this 24th day of April, A. D. 195.1.
[SEAL]
THOMAS F. MURPHY,
Assistant ó'ofmm'ssz'oner of Patents.
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