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Patented ‘Nov. 26, 1946 ‘
UNITED STATES PATENT orrica.
2,411,516
ETHERS 0F ENDOETHYLENE-SUBSTITUTED
CYCLOPENTANOLS
'
Herman A. Bruson, Philadelphia, Pa., assignor to I '
The Resinous Products & Chemical Company,
Philadelphia, Pa., a corporation of Delaware
'
No'Drawing. Application May 24, 1944,
Serial No. 537,183
8 Claims. (Cl. 260-611)
This invention relates to addition-rearrange
ment products from organic compounds having
alcoholic hydroxyl groups and adductsof cyclo
pentadiene with mono-ole?nic compounds hav
ing at least three carbon atoms, said products
being ethers of an endoethylene-substituted cy
clopentanol.
.
-
acetate, allyl oleate, vinyl methyl" ketone, vinyl'
acetate, vinyl vbenzoate, and the like. There may
also be used other adducts of cyclopentadiene
with ole?nic compounds, such as coumarone,
sairole, eugenol, and with allyl ethers, such as
,benzyl allyl ‘ether, phenyl allyl ether, octyl allyl
ether, and the like.
In practicing this invention, it has been found
-
In my copending application, Serial No. 476,
640, ?led February 20, 1943, it is shown that non
resinous polycyclopentadienes having two double
bonds per molecule, such as dicyclopentadiene,
tricyclopentadiene, and tetracyclopentadiene add
alcohols in the presence of acidic condensing
agents to- form addition-rearrangement products
which ‘are ethers of a new ring system termed
the “nordicyclopentadiene” ring system.
In accordance with the present invention,
which is a continuation-in-part of copending ap
plication Serial No. 529,195, ?led April 1, 1944,
adducts of cyclopentadiene with mono-ole?nic
compounds having at least three carbon atoms in
the molecule are reacted with alcohols in the
presence of acidic condensing agents to form ad
dition products which are, rearranged ethers
from endo-ethylene-substituted cyclopentanols.
A typical illustration is that, for example, in
volving the action of an alcohol, ROH, upon the
cyclopentadiene-styrene adduct.
The product formed by the molecular addition
that a wide variety of organic compounds con
taining one or more alcoholic hydroxyl groups
may be employed. The hydroxyl group is/pref
erably primary or secondary. Compounds con
taining a tertiary hydroxyl group may also be
used, provided, however, that they are not readily
dehydrated.
.
'
The useful alcoholic hydroxyl-containing com
pounds may be aliphatic, arylaliphatic, cycloali
phatic, hydroaromatic, or heterocyclic and may
be
saturated
or
unsaturated,
straight-
or
branched-chained, or cyclic. It has also been
established that the non-hydroxyl portion of the
reacting hydroxyl-containing compound‘ may
contain a wide variety of groups or substituents,
for example, halogen, cyano, thiocyano', nitro,
keto or acyl, mercapto, ether, acylox'y, alkoxy,
aryloxy. carbalkoxy, or carboxy groups, etc. '
It should be noted at'this point that,~in the
- case of alcoholic hydroxyl-containing compounds
having free carboxyl groups. excess cyclopenta
diene-ole?ne adduct is necessary since esterl?ca
tion of the carboxyl group byaddition and simul
taneous rearrangement occurs in addition 'to
etheri?cation with the alcoholic hydroxyl group.
From the 'above discussion, vit will be evident
that under the in?uence of acidic condensing
,agents' cyclopentadiene-ole?ne adducts of the
rearrangement'is very probably that represented
by formula (A). In any event, the product 'is'not _
a. simple addition of (R,—-O—) to one side of the
type set forth formv rearranged ethers with a wide
variety of alcoholic hydroxyl-containing’ "com
poundsand' that'the reaction is onelof wide ‘ap
plicability. Hydroxyl-containing“ reactants. of
double bond and of H to the other. The reaction 4. > perhaps greatest interest belongv tofthe-g'eneral
involves ‘both addition and ‘rearrangement and‘ . ‘class of iunsubstituted alcohols,‘ whether mono
leads to a new class of substituted cycllclcomhvdric lor-'-polyhydric,..which ‘are‘n'ot dehydrated
pounds which are not available by any previously
pat 60°fC.1by»~sulf_uric acid. J‘There are, however,
proposed method of synthesis.
' ‘
important types of reactantsother than the sim
Various adducts of cyclopentadiene with mono
' ple alcohols. ‘ Other important groups include hy
“ ole?nic compounds having three or more carbon
dr'oxy-acid esters‘. ,hydroxyeacids, hy'droxy-ke
atoms in the molecule may be used for the pur
pose of thisinvention. 'I'hese comprise not only
the so-called “Diels-A'lder” type of adducts of Ul
cyclopentadiene with unsaturated hydrocarbons
tones. hydroxy-lactone's, *hydroxy-aldehydes,
ether alcohols, c'yano alcohols. thiocyano valco-v
as, for‘ example, propylene, cyclopentene, styrene,
indene, allylben'zene, and the like, but also ‘the
vinyl alcohol. polysaccharides, starches,“ sugars, '
adducts of cyclopentadiene with unsaturatedal
cohols,‘ esters, halides, or ketones, as, for-example,
allyl alcohol, allyl chlorlde,;allyl benzoate, allyl 55
hols. halohydrins, nitro: alcohols, andfp'olymeric ‘ .
hydroxylecontaining vcompounds, __includi_ng_' poly- '
cellulose, cellulose e'thers',‘ cellulose esters,;and the p , 9'
like. -
ryglqatg useful ihydroxyl-containingscorn» ,
2,411,516
3
a
4 '
pounds for the purpose of this invention are the
following: methanol, ethanol,
_
.
‘
-
'
toluene sulfonic acid, or aliphatic sulfonic acids,
as butylsulfonic acid and the like.‘
Sulfuric acid is of particular value in promoting reactions involving the lower primary
propanol, , iso- -
propanol, n-butanol, ‘lsobutanol, ‘butanol-Z, the
primary and various isomeric amyl alcohols, n
hexanol, 2-ethylbutanol, n-heptanol, n-octanol,
aliphatic alcohols. It is generally of use in the
case of other alcohols also, which are not readily
polymerized/or dehydrated by the presence of
concentrated sulfuric acid.
The boron tri?uoride group of catalysts is one
capryl ‘alcohol, 2-ethyl hexanol, decanol, 5-'
ethyl-nonanol-2, dodecyl alcohol, tetradecanol, '7
ethyl-2-methyl-undecanol-4, cetyl alcohol, 3,9
diethyl-tridecano1-6, oleyl alcohol, n-octadecanol,
allyl alcohol, crotonyl alcohol, 'cinnamyl alcohol, 10 of considerable value. of these, the complexes
geraniol, phenylethyl alcohol, methoxyethanol,
with ethers are of particular utility since they
ethoxyethanol, butoxyethanol, phenoxyethanol, '
are soluble in the reaction mixtures and pro
ethylene glycol, propylene glycol, butylene' gly
duce no troublesome by-products. Typical of
these complexes are BFB.C:H9—O—C:H5 and
col-1,3, diethylene glycol, triethylene glycol,
polyethylene glycols, di-isopropylene glycol, di 15 BF3.C4H9—O—C4H9, with diethyl ether and di
ethylene glycol monoethyl ether, 'diethylene
n-butyl ether, respectively.
'
.
glycol monobutylether, diethylene glycol mono
The quantity of active catalyst employed may
phenylether, glycerol, glycerol monochlorohy
drin, glycerol dichlorohydrin, glyceryl-a-phenyl
ether,
2 - ethyl - hexandiol - 1,3,
be varied ‘over a wide range. Good results have
been obtained with as little as two per cent of .
20 catalyst, based on the weight of the cyclopenta
glyceryl - a?
dimethyl ether, trimethylene glycol, tetramethyl
ene glycol, decamethylene glycol-1,10, pentaery
thritol, ethylene/chlorohydrin, propylene chloro
hydrin, ethylene bromohydrin, propargyl alcohol,
ethylene - cyanohydrin,
diene adduct, up to and exceeding a molar equiv
alent of the catalyst per mol of adduct used. The
catalysts need not be used under anhydrous con
ditions. In fact, the presence of water in small
25 amounts often increases the rate of reaction.
p - thiocyanophenoxye
ethanol, 2-nitro-2-methyl-1-propanol, p - thio
cyanoethoxyethanol, p - tertiary-butylphenoxy
The addition-rearrangement reaction involv- '
ing an alcoholic hydroxyl-containing compound
ethanol, 0 -' cyclohexylphenoxyethanol, 2,4-di
and the adduct of cyclopentadiene and a mono‘
chlorophenoxyethanol, p - ter - octylphenoxy—
ole?nic- compound is readily carried out in the.
ethanol, plphenylphenoxyethanol, p-naphthox'yg
30 presence of one or more acidic condensing agents.
ethanol, 2 - nitrophenoxyethanol, p ,- acetyl
phenoxyethanol, p-benzoylphenoxyethanol, cyclo
The reaction may be initiated bymixing the
components and catalyst at room temperature,
hexanol, 0-, m-, or p-methylcyclohexanol, cyclo
pentanol, 0- or p-cyclohexyl-cyclohexanol, p-tert
at temperatures even around 0° C. in some cases,
or at elevated temperatures. While it is gener
amylcyclohexanol, hydroxydihydronordicyclo
~entadiene, borneol, fenchol, cholesterol, ‘ethyl
glycolate, ethyl lactate, dimethyl tartrate, ethyl
citrate, benzyl alcohol, 2enitro'—2-methyl-l,3
propanediol, ethyl-IO-hydroxy-stearate, tetrahy
drofurfuryl alcohol, phenyl thioethanol, ceryl
alcohol, 2-nitro-2-ethyl-1,3-propanediol, castor
oil, hydrogenated castor oil, ethyl ricinoleate,
ethyl maleate, sorbitol, dibutyl tartrate, glyceryl
apy-diphenyl ether, mannitol, ethylene glycol
35 ally desirable to control the temperature at the
start, the reaction may be carried to completion
either by continuing the reaction for a long time
or by raising the temperature to accelerate the
reactions involved. ‘Temperatures as high as 100°
The re
40 C. to about 200° C; may thus be used.
action range of about 50° to 125°C. is, however,
generally the most useful and is to be preferred.
In some cases the reactions are su?lciently
‘exothermic that it is desirable to cool the react
ing mixture in order to control the reaction.
This may also be ‘controlled by the rate of mix
monobenzylether, and many others. The hy
droxyl-containing compound need not be pure.
There may be used, for instance, technical al
ing the. reactants and by the use of a solvent or
diluent such as ethylene dichloride or dioxane.
After the'reaction' has been carried to a de-'
cohol mixturessuch as are obtained as by-prod
ucts from the synthetic production of methanol
by the reaction of hydrogen and carbon monoxide 50 sired point,~ the acidic condensing agent is re
and known
as
“higher
alcohols
moved, as by washing with water or by neutral
ization. The reaction product may then be dis
tilled in many cases, or otherwise puri?ed, as by
treatment with decolorizing clay or carbon, strip
from the
methanol synthesis.” These comprise branched
chained primary and‘ secondary-alcohols having
from about 7 to about 18 carbon atoms and in ’
.some cases even more.
_ ping, extraction, etc.
Mixtures of higher ali
phatic alcohols obtained by the catalytic hy
The following examples illustrate this inven
drogenolysis of fatty glycerides or of higher fatty
tion, it being understood that the proportions,
acid esters may likewise be used.
temperatures and time can be varied to a con
'
siderable extent without departing from the
Among the acidic condensing agents or cat
alysts which serve to promote the addition-rear 60 spirit of the invention.
For the purpose of this invention it is desir
rangement of alcoholic hydroxyl-containing’
able, although not necessary, to employ not more
compounds with cyclopentadiene mono-ole?nes
than one mol equivalent of the alcohol per mol
of the type set forth are boron tri?uoride and
its coordination complexes with oxygenated
of the adduct. ,-
)BF'mCaH'iOC3H'1; carboxylic acids, as
-
-
Example -1
compounds, such as ethers, as, ‘for example,
A mixture of 4 g. of BF:.O(C4I-Ia)a 108 g. of
“ ethylene chlorohydrinand 134 g. of the cyclo
‘
aatzcmooon
pentadiene-ally1 phenyl ether adduct
carboxylic esters, as BFaCH'sCOOCzHs; ketones, 70
such
as
BF3.CH3COCH3;
alcohols,
such
as
BF_5.2C4H9OH; and water, such as BFs.(H2O)=
where :c is one or two. There may also be used
as a catalyst sulfuric acid, its esters, such as ethyl
acid sulfate, aromatic 'sulfonic acids, such as 75
1
on
I ll\CHa
H: J)
2,411,510
6
'
.
at 95_°-9'l° C. for seven hours. The product was
was stirred at 95° C. for six hours. The product
washed with sodium hydroxide solution and with
water, then dried, and "distilled in vacuo. The
was washed with dilute sodium hydroxide solu
tion, then ,with water, ‘dried, and distilled in
p-hydroxyethyl ether of phenyl endoethylene
5 cyclopentanol having the probable formula
vacuo to yield 138 g. of the p-chloroethoxy endo- '
ethylene phenoxymethyl cyclopentane as a color
less oil boiling at‘ 166°-169° C./1 mm. having the
CHIw
CgL\CH1
probable formula
4.
1H1
'
Ho-cmcm-o- 11;? <:>
10
@ distilled over at 160°-163° C./2 mm. as a color
"Z less oil in a yield 01' '17 gr Upon redistillation;
The cyclopentadiene-allyl phenyl ether adduct 15 the pure compound boiled at 153E163” C./1 mm.
v
,H'
C
i
.
.
.
_ used is a colorless oil boiling at 134° C./6 mm.
I
i
_
obtainable by heating cyclopentadiene or dicy
clopentadiene with allyl phenyl ether at
Example 5
A mixture of 11.6 g. of allyl alcohol, 1 g. of
BFa.O(C2I-I5_)z, and 17 g. of 2,5-endomethylene
1,2,5',6-tetrahydro-diphenyl wasv heated at 90° C.
1'70°-180° C. as described in copending applica
tion Serial No. 529,196, filed April 1, 1944.
20 for four hours.
Example 2
The product was worked up as
in Example 3. The allyloxy phenyl endothylene"
cyclopentane having the*probable formula
A mixture of 9.6 g. of methanol, 2 g. 01.95% sulfuric acid, and 1'7 g. of the cyclopentadiene- v
styrene adduct
'
on
>
l]: H:
\l{
* H
distilled over at 155°—1'l0° C./10 mm. as a'color
H<:>
less oil. Upon redistillation the pure compound
boiled at 164°-168°- C./10 mm.
known as 2,5-endoniethylene-1,2,5,6-tetrahydro
diphenyl was boiled under re?ux for seven hours
at 72°-81° C. The product was washed with
'
Example 6 -
A mixture of 3g. of nraowlmn, 64 g. of
dilute sodium hydroxide solution, then with 35'' ethyleneochlorohydrin
and 90 g. of cyclopentawater,.dried, and distilled in vacuo.‘
diene-allylbenzoate adductwas stirred at 97° C.
The rearranged methyl ether of phenyl endo
for eight hours. The product was washedwith
ethylene cyclopentanol- having the probable
dilute soda solution, then with water, dried, and
distilled in vacuo to yield 96 g. of the ,B-chloro
“40 ethoxy
c
derivative as a viscous oil boiling at
195°-200° C./1-2 mm. having the probable
formula
_
-
_
formula
-
'
'
distilled over at 135°-148° C./10 mm. as a color-'
less oil. Upon redistillation the pure compound
boiled at 14;0f’,,-145° (IL/10 mm. _
Example 3
50
A mixture of 16 g. of ethylene-chlorohydrin,
1
Example 7
A mixture of 11.9 g. of 2-nitro-2-methyl-1
propanol, 0.5 g. of BR.O(C2H5) 2, and 1'1 g. of
1 g. of BF3.0'(C4H9)2, and 17 g. of 2,5-endo-v
methylene - 1,2,5,6 - tetrahydrodlphenyl
0
"
was i
2,5-endomethylene - 1,2L5,6' - tetrahydrodiphenyl
stirred at 959-970 C. for four hours.‘ The prod-I
was stirred at 90° C. for three hours. The prod
duct was washed with sodium carbonate solu- .
uct was washed with water, dried, and'distilled
tion and water, dried, and distilled in vacuo.
in vacuo.
The p-chloroethyl ether of phenyl endo
ethylene cyclopentanol having‘ the probable
formula
60
‘
'
Cami... .
0
65
Q
Cgl\CH|
\\,
i H,
CHa-J)—CH2—0—
H-l-(a O
lilo:
-
‘
i
A mixture of 31 g. of ethylene glycol (0.5 mol)‘.
_2 8. 0f BF3.0(C4H9) 2,‘ and 31 3., 0f 2,5-endo
methylene-1,%5,6-tetrahydrodiphenyl was‘stirred
It was a paleE
yellow oil.
less oil. Upon redistillation the pure compound
70
boiled at 148°-152° C./0.5-1 mm.
VF.
on,
boiled at 180°-183° C./11 mm.
distilled over at 1604-170“ (1/1 mm. ‘a. a col 1}
Example 4
CH
Y
l. l I
cicmc'm-o- 11-, g
The nitro-isobutyloxy-phenyl endoethylene
cyclopentane having the probable formula
I Example 8
A mixture of 17' g." of 2,5-endomethylene
1,2,5,6-tetrahydrodiphenyl, 14.7 ‘g. of p-thiocy
anoethoxyethanol, and 3 g. of BF3.O(C4H9)2 was .
stirred at 95° C. for seven hours. The product
75 was washed with dilute soda solution and water,
autism
then
“f1
in vacuo. The thiocyanoethoiw
and 2 a. or Brim
' was stirred at 95° C.
ethoxy-phenyl endoethylene' cyclopentane hav- “ for
six hours. The product was washed with wa
insthe probable formula
'ter and with
A dilute soda solution and then dis~
'
tilled in vacuo.
‘on _
C(sl \OHs
“its;
Hr
.
GE
_
?lled over at 225°=2$5°CJ3 mm. as a viscous
pale yellow oil. Uh reation the
compound hoiled at 222%227" (IL/1.5 mm.
'
‘
The ether ester having the probable formula
_
€£\cm
-
so
om-on-o-miz
Hal .‘
e‘
OOCaHs ‘
4 distilled over at l60°=~l70° Q/LM min‘: as acol
orless oil.
Example‘ 9
A mixture of 3 e. o? BFeACMh, 100 s. of E5
ethylene ehlorohymt and 160 g. of the cycle
ethylene chlorohy,v and 158 g.
pentadiene-allyiowethanol adduct
peritadlene=p=tertumhutylphenyl allyl ether ad
duct
Essa/awe 22
A mixture or s so of ammcimur ass a. dc
‘
of the cycles -
on
cg \on
0H2:
Ha
CEir-é
o-om-ln. l ' H -
23H};
~
\ {
.
was stirred at 95° e. for six hours. The product
was washed with dilute sodium hydroxide solu
was stirred at 95° c. ior eight hours. The prod-.
tion, then with water, dried, and distilled in
lution, then with water, dried,’ and distilled 'in
uct was washed with dilutesodium hydroxide so
vacuo to yield 180 e.- oi the p-chloroethoxy de
vacuo to yield 89 g. of the pj-chloroethoxy deriv- _
rivative as a colorless oil boiling at 185°-195° 80 ative as a colorless oil boiling at 162°-'185°
(‘L/0.54 mm. having‘the probablev formula
C./0.5-1 mm. having the probable folfmula
CH
on
O| l\§OH|
_
s.
m
t
.r \
H’
-
The cyclopentaidienekp-tertiary butylphenyl
Example 13
A mixture oi’ 24.9 s. ot'p-chloroethoxyethanol,
17 g; of 2.5-endomethylene-1,2,5.6-tetrahydro~
in: cyclopezitadiene or dicyclopent'adiene with p
tertiary buylphenyl allyl ether at 170°-_175° 0.
'
diphenyl, and 1,. g. 01.315.0(04Hs): was stirred at
' 95° C. .for four hours and
propionitrile adduct
worked upby washing
45 with soda solution and with water, followed by
To a, mixture of 80.5 g. of ethylene chlorohy
drin and 88.5 s. or
“
clcmom-o- 11-1? “capo-(nudismHv
i
allyl ether_ ad uct used above is a low melting»
' solid boiling a 140° C‘./i mm. obtained by heat
‘Example 10
'
'o€i\iom ‘
a
H-O-CHsCHsCl
r
t'
vacuum distillation.-
cyclopentadiene-p-allyloxy
_
’
'
The product having the probable formula.
0
1nil-Z
dO1
olomom-o-omom-odistilled- over at mot-1st’ c./1.|s mm. as a 0010!‘
, there was added 4' s. of momma: and the 55 lessviscous oil.
mixture stirred at 95°-97° C. for seven hours.
Example 14.
’
The product was washed with dilute sodium hy- ~
A
mixture
or
22
g.
of
glyceryl-—¢-monochloro
droxide solution, then with water, dried, and '
hydrin, 17 4g. of 2,5-endomethylene-i,2,5,6-tetra
‘distilled in vacuo.
hydro-diphenyl. and 1 g. of B1'5.O(C4Ha)= was
The p-chloroethoxy derivative obtained boiled
stirred at 90°~95°
y one-half hoursl
C. for tour and
then cooled,‘ washed with dilute sodium hydrox
ide solution and‘ water, and distilled in vacuo.
'at 184°-169".’C./1 mm. It was a colorless thick
oil, having the probable formula
OH
The product having the probable formula
calm.
H: i
.
.
-OHr-O—CH:OH|ON'
l
'
The yield “amounted to '14
-
Example 11
y
70
~
A mixture of as g. of ethyl lactateyi'z g. of
3.5-endomiethylene-1,2,5,8 - tetralwdro - diphenyi 75
olonscrjron~onrofln+ O
‘
cg
boiled at ism-195° 0./: mm. It is a thick oil.
’ E's-ample 15
_
.
'
‘A mixture of 35.4 g. of nebutoxyethanol cm.
2,411,516
tyl Ceilosolve”), 1'! g. or 2,5-endomethylenel,2,5,6-tetrahydro-diphenyl, and 3 g. of
.7
"
B175 (Noah):
'
a colorless oil boiling at 130°-135° C./1Vmm. ob
tained by heating cyclopentadiene or dicyclopen
'
tadiene with sairole at PUP-180° C.
g -
was stirred at 95°-‘9'l° C. for seven hours. -i The 5
Example 18
product was washed with dilute sodium hydroxA mixture of 6 g. o! BF'a.O(C4H9)2,‘160 g. or
ide solution, then with water, and distilled in
ethylene chlorohydrin, and 148 g. of cyclopen
vacuo. The n-but'oxyethoxy endoethylene phenyl
tadiene-vinyl acetate adduct
.
cyclopentane having the probable formula
’
0
1°
.
.
'
o
I
r .
1
The product was cooled washed with dilute soda
4
.
.
’
SOIlltIOIL'thGII
with
water,
dried, and distilled in
'
vacuo to yield 85 g. of the rearranged ether as a
'
20' colorless oil boiling at 108°-115° C./1 mm. having
A mixture of 10.6 g. of diethylene glycol, 34 g.
I
the Probable formula:
of 2,5-endomethylene-1,2,5,6-tetrahydro-diphen-
yL-and 3 g. of B .O(C4H9)2 was stirred for seven
hours at 85°—90° C. and worked up as in Example 15.
H:
15 was stirred at 95° C. for ?ve and one-half hours.
a
Example 16' ' '
‘
>
'
\_> ,
M
~
.
-
l
c ,
Example 19
A mixture er 5 gjer'BFrowrHm, 36 g. of
Cg \CH2
.
3o ethylene cyanohydrin, and 55 g. or cyclopenta
,
-diene-indene adduct
H’
. I
OH
HO-cmom-o-cmcmo- n-l? O
The other
. - product
A
was a thick
' oil{a
boiling at
‘ 285°- 35'
on
'
I
c'gjjcm
.
’
'
n
.
1
.-
l
H:
on
C{L\_CH__C/ \CH
‘ 290° C./1.5 mm. having the probable formula -
CH,
GICHICHr-O—CH—‘—- —- —-q9,—.cm
a colorlessoil boiling at 200°-210° C. at 12 mm.
having the probable formula
'
-
01!\
HI
-.
CH
-
of,
Two products were obtained. One product was 25
'
I
c{l\cm
'
_ 1,
giilstlll'lllidy?sldlli ._1
208grags
5 mm _ as a c o l0?1 ess '
_
on
H;
_ \
on
'
n
n
v \cé, \c?m
.
v
.
l\on,
'
‘
-
.
‘
H2
2
.
.
This example illustrates the factthat in the 45 was stirred at 95° C. for four hours. The product
case of polyhydric alcohols one or more of the
was washed with water, dried, and distilled in
alcoholic, hydroxyl groups may be reacted to
vacuo to yield 50 g. of ‘the rearranged cyanoethyl
give one or more ether linkages to an endoethylene cyclopentane ring system.
‘
Example 1,?
ether as a colorless oil boiling at l'74°-1'l6° C./2
>
mm. having the probable formula
~
r0
Y
.
"Y
Y
A mixture of 5 g. of BFa.O(C4H9)2,» 101 g. of
011
.
‘
C ’
‘
.
v
{~on\ _.
'
1pm
H
H1‘ L
'
r -
_0
c1! . \
'
'
o\
13-43}!
H
"
w
,
-
l'
_
7°11’ '
CH
I
Nc_--cH,cH,_0_ H___
r,-
-
I
H,
'
'
_
/. \
‘Hi-c
ethylene chlorohydrin, and 158 g. of the cyclo- ‘
pentadiene-safrole adduct
CH
\ .Y
v
'
v
',
’
v
/
,
80h, \c?
Example 20 .
'
.
A mixture of 10 g. or BFa.O(C4H9)2, 92 g. o
-—0
' glycerol, and 55 g. of cyclopentadiene-indene ad-v
\C{
(so duct was stirred at 90°-95° C. for eight hours.
A The product was washed with dilute sodium hy
droxide solution, then with water, dried, and‘ dis
tilledv in vacuo to yield 42 g. ofthe rearranged
The product was washed with dilute potassium
glyceryl mono-ether as a colorless oil boiling at
hydroxide solution, then with water, dried, and
distilled in vacuo to yield 110 g. of the p-chloro 6;] 200° C./0.5 mm. having the probable formula
ethoxy derivative as a pale yellow oil boiling at
was stirred’ at 95° C. for eight and one-half hours.
180°—190° c./1-2 mm. having the probable for-
mula
'
Ca
_
cg]: OH: I‘
i
112 L
ClCHaCHr-0-—CH—--Z —CH
C ’
'
'
/°\
'
/CHI -
0 _
v
‘
-
'
CH '
GE
cg \CH-—C/ \cn
L
H-
I
70 HOCHr-CHOH-CHr-O- n-‘‘
v
/ H
of, 0Q, \c?
Example 21
'
A mixture of 60 g. of ethylene chlorohydrin, 5
The cyelopentadiene-satrole adduct used above is 75 g. or BF:.O(C4H0)2, and 91 g. of cyclopentadiene
.
[/7
indene adduct heated at 95° G. ?or- ?ve hours
was stirred ‘for six‘ hours at 95°
yielded 102 g. of the c-chloroethyl ether of endo~ - l
was washed'with dilute sodium
with water, dried, and distilled in vacuo to yiel
ethylene hydroxycyclopentanoindsne as acolor
less oil boiling at 155°-157° 0.11 mm. having the
88g. of a colorless oil boiling at 210°-213° c./0.
I mm.
10
having the, probable formula
OlQHaCHr-O-e
I Ezemi?le 22
1 a.
ski-toast
l
1
"are g. of memoirs»; s4 3. or‘ ' I The products obtained according to this in
hol, and 55 g. oi’ cyclcpentadiene-in-=. 15 vention are of potential value as intermediates
l
dene adduct was
for the preparation of resins, plasticizers, insecti
cides, and
at 95° C. Eor seven and
one-quarter hours wd worked up as above.
\
pharmaceuticals.
-
' The benwl ether of endmthylene-hydroxycy»
clopentanoindane distilled over at 1909-2100" 011
mm. as a colorless oil, in a'yield amounting to
as a... having the probable formula
‘
'
-
-
I claim:
1. As a new compound, an acid-catalyzed ad
20 lditiomrear‘rangement
product of an aliphatic
alcohol and an adduct' oi’ cyclopentadiene with
styrene, said‘ product being
an ether of endo
ethylene-substituted phenyl cyclopentanoi.
2. As a new compound, an acid-catalyzed ad
dition-rearrangernent
product of an aliphatic
25 chloro alcohol and an adduct of cyclopentadiene
'_ with styrene, said pro duct being a chloro alkyl
ether of
pentanol endoethylene-substituted phenyl cyclo
Eeanwle 23
' A mixture of 51 a‘. of tetrahydro-iuri’uryl alco
30
hol, 6 g. of BFa.O(CrHs)a, and 55 g. of cyclopens
tadiene-indene adduct was heated sixand one
, quarter hours at 90°-95°_C. and yielded thetetra
‘lwdro-i'uriuryl ether of endoethylene-hydroiw
cyclopentanoindane as a colorless oil boiling at
Mir-173° C./0.5 mm. having the probable tor
mula:
'
era-om "
on
o{l'\on-_o/
\cn‘
H‘ '
l
rr-c
‘on
n-—
>
.
product ‘being a p-chloroethoxyethyl ether of.
_ endoethylene-substituted phenyl cyclopentanol.
A method for. preparing a chloroalkyl ether
40 '01’ 5.endoethylene
phenyl cyclopentanol, which
l
0-
4. ‘As, a new comp‘ound, an acid-catalyzed ad
dition-rearrangement product of p-chloroeth'oxy
ethanol and cyclopentadiene-styrene
adduct, said
comprises reacting in the presence of an acidic '
H
an aliphatic chloro alcohol with
the adduct of cyclopentadiene and styrene‘.
6. A method for preparing ethers which com
“
‘Example 24'
'
'
45 prises reacting in the presence oi'an' acidic con
A mixture of 50 g. of cyclohexahol, 7 g. of
densinz agent an aliphatic ‘ alcohol- with the
‘showman. and 55 s. of cyclopentadiene-. adduct of cyclopentadi
ene vand styrene.
indene adduct heated seven hours at 95° 0. yielded
the cyclohexyl ether or endoethylene-hydroxy 60
cyclopentanoindane as a colorless oil boiling at
51/
H"
or \cr. \cg
169-166’ was mm.
.
' Emmple 25
'
’
_
'
48.6 of
ethylene chlorohy 8. . ofandBF:.O(C:H53I,
92 s. or cyclopenta
diene adduct oi.’- 2,4,5-trichlcrophe'nyl allyl» ether
or:
"'
‘
. {k If?“
.
said product being a 'y-choro-p-hydroxy
endoethylene-substltuted phenyl
mum A. mason,
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