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Патент USA US2265315

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Patented Dec. 9, 1941
Walter Salzer and Hans Andersag, Wuppertal
Elberfeld, Germany, assignors to Winthrop
Chemical Company, Inc., New York, N. Y., a
corporation of New York
No Drawing. Application May 16, 1939, Serial
No. 274,009. In Germany May 17, 1938
20 Claims. (Cl. 260-619)
This invention relates to new condensation
products and to a process of preparing the same.
In accordance with the present invention
2 - keto - 1,2,3,4 - tetrahydronaphthalenes which
contain in the 1-position an alkyl group or a
cyclically substituted alkyl group which group
contains a reactive hydrogen atom at one of the
carbon atoms 3 and 4 numbered from the carbon
atom connected with the naphthalene radical, or
obtainable by reacting upon a 2-keto-l,2,3,4
tetrahydronaphthalene in the presence of a
strongly alkaline condensing agent and of a
solvent which is inert to the starting materials
with a phenyl-alkyl-halide.
The invention is illustrated by the following
examples without being restricted thereto, the
parts being by weight:
1 gram of l-(beta-phenylethyl) -2-keto-l,2,3,4
substitution products of the compounds speci?ed, 10 tetrahydronaphthalene is treated with 5 cos. of
can be converted to tricyclic and if the com
pounds contain the cyclically substituted alkyl
group to tetracyclic condensation products when
subjecting the said starting products to intra
molecular condensation by means of a ringclos
ing-cond‘ensing agent. Such ringclosing-con
concentrated sulfuric acid at 0 to 10° C. After
5 minutes the reaction mixture is poured on to
ice and the precipitated solid substance is dis
solved in ether. Crystals of'the 5,6,11,12-tetra
hydrochrysene (numbering comp. “Annalen der
Chemie” 311, page 257) melting at 105° C. are
densing agents are preferably highly concen-‘
obtained. The reaction proceeds according to
trated sulfuric acid, for instance 98% concen
the following reaction scheme:
trated sulfuric acid or 80% sulfuric acid which
latter may be used together with an indifferent 20
solvent, such as benzene; another suitable con
densing agent is for instance phosphorus oxy
chloride. The condensation temperature is
adapted to the particular condensing agent;
when working with concentrated sulfuric acid 9.5
the condensation is advantageously carried out
at a temperature of 0 to 10° C., when using 80%
sulfuric acid a temperature of 70 to 80° C. has
In an analogous manner the 3-methoxy
proved suitable, when using phosphorus oxychlo
5,6,11,12-tetrahydrochrysene of the formula:
ride short gentle heating is advisable. Thus, for 30
instance, phenanthrene and benzoindene deriva
tives may be obtained; when using 2-keto
1,2,3,4=-tetrahydronaphthalenes containing in the
1-position a phenylmethyl or substituted phenyl
methyl group, benzo?uorene compounds are ob 35
tained; chrysene compounds are formed when
subjecting 2-keto-1,2,3,4-tetrahydronaphthalenes
which contain in the l-position a phenylethyl or
substituted phenylethyl radical to the condensa—
40 is obtained from alcohol in crystals melting at
91° C. from the l-(beta-phenylethyl) -6-meth
The course of the reaction is most surprizing
oxy - 2-keto - 1, 2, 3, 4 - tetrahydronaphthal‘ene ; the
in View of the known fact, that the 2-keto
l,2-benzo-3,4-dihydro-5- (or 7-) -methoxy?uoren
12,3,4-tetrahydronaphthalene has a great ten
the formula:
dency to aromatization; it is for instance con
verted into naphthalene even on heating it to 45
boiling while splitting off water.
The products thus obtainable are intended to
be used for pharmaceutic purposes, if desired
after further transformation of the substituents
present. The condensation products containing 50
alkoxy substituents, such as the methoxy and
ethoxy group show particularly after splitting
off the alkyl groups of the alkoxy substituents
melting at 122° C. (from alcohol) is obtained
from the 1-(3’-methoxybenzyl)-2-keto-1,2,3,4
oestrus activity.
The starting materials above speci?ed are 55 tetrahydronaphthalene. The corresponding Phe
molecular condensation by means of a ringclos
nolic compound, the 1,2-benzo-3,4-dihydro-5
ing-condensing agent.
(or 7-)-hydroxy?uoren, is obtained by demeth
ylating the methoxy compound by treatment
with excess methyl magnesium iodide at 200° C.;
it has a strong oestrus activity on the castrated
female rat; crystals of the 3-methoxy-'5;6,11;12
tetrahydrochrysene melting at 163° C. (from
9. The process which comprises subjecting a
2-keto-1,2,3,4-tetrahydronaphthalene which is
substituted in l-position by a phenylethyl radical
having ‘a reactive hydrogen atom at the phenyl
radical in ‘ortho-posi-ti’on ‘to the ethyl "radical, to
.intramolecular condensation by means of a ring
benzene) containing a further methoxy-group in
7- or 9—position and having in the latter case
closing-condensing agent.
10. The'process which comprises subjecting a
which is substituted in l-position by a phenyl
ethyl ‘radical ~having ‘a reactive hydrogen atom at
itheph'enyl .i‘adiéal fin ortho-position to the ethyl
1175 radical, ‘to-intramolecular condensation by means
_ ofja ring-closing-condensing agent.
11. The ‘process which comprises subjecting
1--phenylethyl“-:2-keto-1,2,3,4 - tetrahydro - 6 - al
koxygnaphthalene to intramolecular condensa
tion by means of a ringclosing-condensing agent.
are obtained from 1-(beta-3'-metho>iyphenyl-'
~1l2'.v The ‘process which comprises ‘subjecting
ethyD-fi-met'hoxy- 2 - ketop- 1,2,3,4 '- tetrahydro
naphthalene; the corresponding phenolic 'prod
not, the :3ahydroxy=5;6,1'1,12>tetrahydrochrysene
“létbetaeii'éalkoxyphenyléthyl) ‘~
e ‘km/($12,351
"tetra-hydrm6§alkoxy+naphthalene *t'o --intramole
containing ‘a further hydroxy‘grou‘p in 7- ‘or 9
'c-ular condensation by means of 1a "rin'gclosing
position, is obtained when demethylating the
condensing agent.
'n'iethoXy compound by means :of methylmage
13. The process which comprises subjecting *l
ne’sium iodide; it melts at 215° ,C. and ‘can be
Sublimated under 0.05 mm.ipressur'e ‘at 209° C.;
_it causes full oestrus even in' small doses with
"naphth'alene to intramolecular ‘condensation by
'mean‘siof highly concentrated sulfuric acid.
the castrated rat."
a We claim:
14. The ‘process which comprises subi‘ect‘in‘g
l-phehyl’ethyl - 2 Jkielfo- 1,2514“ téti‘éfhydi‘b ‘ 6 -
'1. Condensation products :of the polycyclic
seriesin which the 1=positionof a 3;4-dihydro
'methoxynaphthalene t'o intramoiecular conden
sation by means of highly concentrated
'naphth?léné fi?g is connected by means of a
bridge ‘selected from the class consisting of .
1-5. The process- which comprises subjecting
'—'CH2- and -'CH2“—‘CH2+ with ‘a benzene ring
and the 2-po'sition ‘of the 3,4-dihydr'onaphthalene
is directly connected with the "benzene ring in
‘tetra-hydro;?ialkoxyfnaphthalene to imp-smote;
ortho-position to said bridge.
trafted sulfuric "acid. __
2. 5,6,11,12¢tetrahydrochrysenes.
'l'-‘(b'eta-3'=a;lkoxyp‘henylethyl) '- 2 ’-' ken)"- “1,72,???
'cu'larjcondensa'tion by means of highly ‘comm
Q16; 3+;hydr‘oXy'- ‘5,6 5111,12 - tetrahydrochrysenes
‘which jaresubstituted
one of. the positions "7
substituted by substituents of the ‘group consist
fand19’ *byja ‘hydl'?kyli’gl’bllp.
ing of hydroxy and methoxyigroups.
< v17. _1,2=bYenzo-3,4=dihydrd?uorenes which are
substituted, 'in'o’ne of the positions 5 ‘and ‘7 by a
4. 5,6,11,lz-tetrahydrochrysenes which are
substituted :in 3-pos'i'tion and in one of “the posi 15
tions 7 and ‘9 "by s'ubstituents of the group- con
sisting of hydroxy and methoxy groups.
5. 1,2~benzo;3.4-dihydro-?uorenes.'
naphthalene " to int'ramolecular condensation ‘by v
means ‘of a 'ringolosingécondensing "agent.
substituted by substituents of the group consist- "
ing of hydroxy and 'methoxy groups.
7. 1,2—benzo-3,4;dihydr0-?u0renes which are
substituted in ‘one-of the positions 5 and 7 by a
19."."I‘he processwhi'ch comprises "subjecting “a
1-‘ ( 3' "-alkoxybenz'y1-‘2j-keto =- f1j2',3_~,'4 - tetrahydro
naphthalene to “intramolecuiar ‘condensation ‘by
substituent of‘thegroup consisting of hydroxy
means ofhighly concentrated ' sulzfuri'c'a‘cid.
v .‘zdf'rne process which comprises subjecting
and methoxy groups.
8. The process which comprises subjecting a
naphthalenefto "intra‘rnolecui’ar condensation 1by
Z-keto-1,2,3,4-tetrahydronaphthalene whichv is
substituted in l-position by a phenylalkyl radical
means ‘or (‘highly-‘concentrated ‘sulfuric acid.
having a hydrogen atom'at'the phenylradical ,
in' ortho-position:to the alkyl radical to .i'ntrae
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