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Патент USA US2130527

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Patented Sept. 20, 1938
2,130,527
UNITED STATES
PATENT OFFlCE
2,130,527
HYDROXY-ALKYL ETHERS OF HYDROXY
DIPHENYL COMPOUNDS
Gerald H. Coleman and John Zemba, Mid
land, Mich., assignors to The Dow Chemical
Company, Midland, Mich., a corporation of
Michigan
No Drawing. Application February 23, 1937,
Serial No. 127,176
11 Claims. (Cl. 260-150)
7 This invention relates to the hydroxy-alkyl
ethers of hydroxy-diphenyl compounds having
the formula:
>
x
Y
oily layer separates. This oily layer may be
fractionally distilled to separate the desired ether
compounds in substantially pure form or it may
be used without further puri?cation as, for ex
ample, in the preparation of fly-spray composi- 5
tions. ‘In certain cases where the hydroxy-di
phenyl compounds employed form alkaline metal
Y
10 in which one Y represents chlorine, bromine, or
an alkyl radical containing from 1 to 8, inclusive,
carbon atoms; the other Y represents chlorine,
bromine, an allgvl radical containing from 1 to 8,
inclusive, carbon atoms, or hydrogen; one X rep
salts which are relatively insoluble in water, it
is convenient to employ su?icient alcohol or other
water miscible organic solvent in the reaction
mixture to dissolve the major portion of the re
actants.
Our new compounds may also be prepared .by
. resents hydrogen; and the other X represents a
reacting the hydroxy-diphenyl compounds with
hydroxy-alkoxy radical having the formula
—O—-CH—-(1JH—-OH
R
wherein each R represents hydrogen or methyl,
2° and the sum of the carbon atoms is not greater
than 3.
alkylene oxides in the presence of suitable cata- '15
lysts, e. g. sulphuric acid.
The following examples describe in detail the
preparation of certain individual members of our
new class of compounds, but are not to be con
strued as limiting the invention:
20
Example 1
We have prepared members of the above new
class of compounds, determined certain of their
429 grams (2 mols) of a mixture of isomeric
physical properties whereby they can readily be . monochloro-2-hydroxy-diphenyls (consisting of
25 identified, and have found them useful as plas
ticizers in cellulose derivative compositions, as in
termediates in the preparation of pharmaceutical
derivatives, and particularly as toxics for inclu
sion in fly-spray compositions.
30' ‘
These compounds are high-boiling, complex de
rivatives obtained as viscous liquids or white,
crystalline solids. They are substantially insolu
ble in water but somewhat soluble in dilute aque
ous alkaline solutions and most organic solvents.
35 These new compounds can be prepared by re
acting an aqueous solution of an alkali metal
salt of a suitable hydroxy-diphenyl compound
with a halo-hydrin, e. g. ethylene chlorohydrin,
propylene bromohydrin, etc.
40 " In preparing the new compounds above-de
scribed, we generally warm an aqueous solution
of an alkali metal salt of the hydroxy-diphenyl
compound to its re?uxing temperature and add
thereto a halo-hydrin, although, if desired, the
45 hydroxy-diphenyl compound and halo-hydrin
may be mixed together and a suitable alkali, e. g.
NaOH or KOH, subsequently added thereto.
While the phenolate and the halo-hydrin can be
reacted together in any desired proportions, high
50 yields of the hydroxy-alkyl others can be ob
tained when equimolecular proportions of the re
actants are used. The reaction mixture is stirred
at the re?uxing temperature until the reaction
is substantially complete, after which the mix
55 ture is cooled and allowed to stand, whereby an
approximately 80 per cent byweight of 2-hydroxy—- 25
3-chloro-diphenyl and 20 per cent of 2-hydroxy
5-chloro-diphenyl), 80 grams (2 mols) of sodium
hydroxide, and 200 milliliters of water were mixed
together and warmed to the re?uxing tempera
ture of the mixture.
192 grams of a 42 per cent 30
aqueous azeotrope of ethylene chlorohydrin was
slowly run into the re?uxing reaction mixture with
constant stirring. Heating was continued for one
hour, after which the mixture was allowed to
stand while an oily layer separated therefrom. 35
The latter was fractionally distilled under re
duced pressure, whereby there was obtained 247
grams of a beta-hydroxy-ethyl ether of 2-hy
droxy-3-chloro-diphenyl
product,
boiling
at
195°-198° C. at 5 to 6 millimeters pressure. This 40
product was recrystallized from 95 per cent
ethanol to obtain substantially pure beta-hydroxy
ethyl ether of 2-hydroxy-3-chloro—diphenyl hav
ing a melting point of l25.5°-126.5° C. This is a
white crystalline compound substantially insolu- 45
ble in water and soluble in most common organic
solvents.
Etrample 2
In a similar manner 2—hydroxy-3,5-dichloro
diphenyl, sodium hydroxide, water, and ethylene
chlorohydrin were reacted together'to obtain the
beta-hydroxy-ethyl ether of 2-hydroxy-3,5-di
chloro-diphenyl as a viscous water white liquid
boiling at 18l°—183° C. at 4 to 5 millimeters pres- 55‘
2,130,527
2
dichloro-diphenyl; hydroxy-propyl ether of 4-hy
sure, and having a speci?c gravity of 1.2873 at
droxy-3-bromo-5-chloro-diphenyl; beta-hydroxy
20°/4° C.
Example 3
0.14 mol. of 2-hydroxy~3,5-di-tertiary-butyl
diphenyl 0.14 mol. of sodium hydroxide, 0.14 mol.
ethyl ether of 2-hydroxy-5-tertiary-butyl-di
phenyl; beta-hydroxy-ethyl ether of Z-hydroxy
of ethylene chlorohydrin as a 42 'per cent aqueous
azeotrope, and 100 milliliters of 95 per cent etha
beta-hydroXy-ethyl ether of 2—hydroxy-¢5-methyl
diphenyl; beta-hydroxy-ethyl ether of Z-hydroxy
3 - tertiary-butyl-diphenyl;
ether
nol were reacted together at the re?uxing tern?
perature of the reaction mixture.
'5 - tertiary - amyl-diphenyl;
The crude re
an oily layer separated therefrom. Fractional
distillation of this oily layer resulted in the isola
tion of the beta-hydroxy-ethyl ether of 2-hy
as
a
5 - tertiary - octyl-diphenyl;
vis
limeters pressure and having a‘speci?c gravity of
‘
'
droxy-3-secondary-butyl-diphenyl; hydroXy-pro
" '
pyl ether of’ 2-hydroxy-5~tertiary-butyl-diphenyl;
Example 4
20
‘ hydroxy-propyl ether of 2-hydroxy-5-methy1-di
In a similar manner 1 mol. of 2-hydroXy-3
phenyl; hydroxy-propyl ether of 2-hydroxy-3
tertiary-butyl-diphenyl; hydroxy-propyl ether of
chloro-diphenyl, 1‘ mol. of propylene chloro
hydrin as a 51 per cent aqueous azeotrope, and 1
2 - hydroxy-ti—normal—butyl-diphenyl;f hydroxy
mol. of sodium hydroxide were reactedv together
in 250 milliliters of 30 per cent by Weight aqueous
25 ethanol. Upon crystallization of the oily layer
from 95 per cent ethanol, 186 grams of the hy
propyl-ether of 2-hydroxy-5-tertiary-octyl-di
phenyl; hydroxy-propyl ether of 4-hydroxy~3
methyl-diphenyl; hydroxy-pro-pyl-ether of 4-hy
droxy-B-normal-propyl-diphenyl; beta-hydroxy
droxy-propyl ether of 2-hydroxy-3-chloro-di
phenyl was obtained as a white crystalline prod
uct melting at 128.5°-l29.5° C.
30
beta-hydroxy-ethyl
ether of 4-hydroxy-3—methyl-diphenyl; beta-hy
droxy-ethyl ether of 4-hydroxy-3-ethyl-diphenyl;
beta-hydroxy-ethyl ether of 4-hydroxy-3-propyl
diphenyl; beta-hydroxy-ethyl ether of 4-hy
cous, yellow liquid boiling at 200°—'205° C. at 6 mil
1.0003 at 65°/4° C.
beta-hydroxy-ethyl
ether of 2-hydroxy-5-iso-hexyl-diphenyl; beta
hydroxy-ethyl ether of 2-hydroxy-5-iso-heptyl
diphenyl; beta-hydroxy-ethyl ether of 2-hydroxy
10 action product was diluted with water, whereby
droxy-3,5—di-tertiary-butyl“diphenyl
beta-hydroxy-ethyl
of 2 - hydroxy-3-normal-butyl-diphenyl;
,
1
Other compounds prepared in a similar man
ner include the following:
~
Beta-hydroXy-ethyl ether of 2-hydroxy-5
chloro~diphenyl, a water white liquid boiling at
157°~161° C. at 4 millimeters pressure, and having
35 the speci?c gravity 1.2244;
Beta-hydroxy-ethyl ether of 2-hydroxy-5
isopropyl-diphenyl, a white crystalline compound
boiling at 182°-183° C. at 5 millimeters pressure,
ethyl ether of 2-hydroxy-3-chlor0-5-methyl-di
phenyl; beta-hydroxy-ethyl ether of 2-hydroxy
3 - normal - propyl-5-bromoediphenyl;,
beta-hy
droxy-ethyl ether of 2—hydroxy-3-chloro-5rter
tiary-butyl-diphenyl; beta-hydroxy-ethyl ether
of
2 - hydroxy — 3 - iso - amyl-5-chloro-diphenyl; '
beta-hydroxy-ethyl ether of 4—hydroxy¢3-sec0nd~
ary - butyl - 5 - chloro-diphenyl;
hydroxy-propyl
ether of 2-hydroxy-3-methyl-5-chloro-dipheny1;
hydroxy'propyl ether of 2-hydroxy-3-chloro-5
normal-propyl-diphenyl; hydroxy-propyl ether
and having the speci?c gravity 1.0503 at 65° / 4° C.;_ - of Z-hydroxy- 3-tertiary-butyl-5—bromo-diphenyl ; W
40
Beta-hydroxy-ethyl ether of 3-bromo-4-hy
droxy-diphenyl, a white crystalline solid melting
at 74.5°-75.5° C., and boiling at 220°-225° C. at'6
millimeters pressure;
'
‘
‘
Hydroxy-propyl-ether of 2-hydroxy-5-isopro
pyl-diphenyl, a water white liquid boiling at 165°—
168° C. at 4 millimeters pressure and having a
speci?c gravity of 1.0475 at 20°/4° C.;
'
Hydroxy-propyl ether of 2-hydroxy—3,5-di
chloro-diphenyl, a viscous liquid boiling at 173°~
176° C. at 4 millimeters pressure, and having a
speci?c gravity of 1.270 at 20°/4° C. ;
'
Hydroxy-propyl ether of 3-bromo-4éhydroxy
diphenyl, a white crystalline‘ solid boiling at 200°~
205° C. at 4 millimeters pressure, and melting at‘
55
82°—83° C.
'
Among other hydrcxy-alkyl ethers of hyd‘roxy
diphenyl compounds falling within the scope of
our invention which may be prepared according
to the above described procediu'es' are: beta-hy
60 droxy-ethyl ether of Z-hydroxy-3-bromo-diJ
phenyl; beta-hydroxy-ethyl ether of 2-hydroxy~
5-bromo-diphenyl; beta-hydroxy-ethyl ether of
2-hydroxy-3,5-dibromo-diphenyl; beta--hydroxy~
hydroXy-propyl ether of 4-hydroxy-3-iso-butyl 40
5-bromo-diphenyl; beta-hydroxy-ethyl ether of
2 - hydroxy-3-methyl-5-tertiary-butyl - diphenyl;
beta-hydroxy-ethyl ether of 2-hydroxy-3,5-di
secondary - amyl - diphenyl;
beta-hydroxy-ethyl
ether of 4-hydroxy-3,5-di-methyl-diphenyl; beta- j
hydroxy-ethyl ether of 4-hydroxy-3,5-di-tertiary
amyl-diphenyl; hydroXy-propyl ether of 2-hy-,
droxy-3-tertiary-butyl-5-methyl - diphenyl;
hy- .
droxy-propyl ether of 2-_hydroxy-3,5-di-isopro
pyl-diphenyl; hydroxy-propyl ether of 4-hydroxy 501
3-methyl-5-tertiary-octyl-diphenyl, etc.
~
Representative members of the above-described
group of compounds have been, tested by the
Feet-Grady method as described in Soap, 8, No.4,
1932, and found to be particularly valuable as fly
spray toxics. For example, a 5 per cent kerosene.
solution of beta-hydroxy-ethyl 'ether of 2-hy
droxy-3,5—dichloro-diphenyl was found to give
an 83 per cent knock-down and a kill of over 46
per cent in 24 hours. ' 5_per cent kerosene solu 60
tions of beta-hydroxy-ethyl ether of 2-hydroxy
5-isopr'opyl-diphenyl and of hydroxy-propyl ether
of 2-hydroxy-S-isopropyl-diphenyl gave kills of
ethyl ether of 4-hydroxy-3~chJoro-diphenyl ; beta
20 and 25 per cent, respectively, when tested in a
3,5-dibromo-diphenyl; beta-hydroxy-ethyl ether
of 2-hydroxy-3-chloro-5-bromo-diphenyl; beta
hydroxy-ethyl ether of 4-hydroxy-3-bromo-5
February 20, 193"].
65
similar manner.
65 hydroxy-ethyl ether of 4-hydroxy-3,5-dichloro- '
This application is a continuation in part of our
diphenyl; beta-hydroxy-ethyl ether of 4-hydroxy
70 chloro-diphenyl; hydroxy-propyl ether of 2-hy
droxy-3-bromo-diphenyl; hydroxy-propyl ‘ether
of 2-hydroxy-5-bromo-diphenyl; hydroxy-pro
pyl-ether of 2-hydroxy-3,5-dil;>romo-diphenyl;v
hydroxy-propyl ether of 4-hydroxy-3-chloro-di
75 phenyl; hydroxy-propyl ether of 4-hydroxy—3,5
co-pending application'Serial No. 126,809, filed
-
Other modes of applying the principle of our
invention may be employed instead of those ex 70
plained, change being made as regards the mate
rials employed provided the products described in
the following claims be thereby obtained.
We, therefore, particularly point out and dis
tinctly'claim as our invention:
-
»
75
3
2,130,527
1. A compound having the formula:
Y
I
and the sum of the carbon atoms in the hydroxy
alkoxy radical is not greater than 3.
5. A compound having the formula:
X
t
in which one Y represents a substituent selected
from the group consisting of chlorine, bromine,
and an alkyl radical containing from 1 to 8 car
10 bon atoms, inclusive; the other Y represents a
substituent selected from the group consisting of
hydrogen, chlorine, bromine and an alkyl radical
containing from 1 to 8 carbon atoms, inclusive;
one X represents hydrogen; and the other X rep
15 resents a hydroxy-alkoxy radical having the for
mula:
——O—CH—CH—OH
in which each Y represents an alkyl group con 10
taining from 1 to 8 carbon atoms, inclusive; one X
represents hydrogen; and the other X represents
a hydroxy-alkoxy radical having the formula:
15
wherein each R represents a substituent selected
from the group consisting of hydrogen and methyl
and the sum of the carbon atoms in the hydroxy
20 wherein each R represents a substituent selected
from the group consisting of methyl and hydro
alkoxy radical is not greater than 3.
6. A compound having the formula:
gen, and the sum of the carbon atoms in the
hydroxy-alkoxy radical is not greater than 3.
2. A compound having the formula:
26
X
01
25
XY
@G’‘
I
Y
30 in which one Y represents a substituent selected
from the group consisting of chlorine, bromine,
20
in which one X represents hydrogen; and the
other X represents a hydroxy-alkoxy radical hav
30
ing the formula:
and an alkyl radical containing from 1 to 8 car
bon atoms, inclusive; the other Y represents a
substituent selected from the group consisting of
hydrogen, chlorine, bromine, and an alkyl radi
cal containing from 1 to 8 carbon atoms, inclu
sive; one X represents hydrogen; and the other X
40
represents the beta-hydroxy-ethoxy radical.
3. ~A compound having the formula:
Xi’
OOX
wherein each R represents a substituent selected
from the group consisting of hydrogen and methyl 35
and the sum of the carbon atoms in the hydroxy
alkoxy radical is not greater than 3.
'7. A compound having the formula:
X
QOX
|
01
l
'
45
Y
in Which one Y represents a substituent selected
from the group consisting of chlorine, bromine,
and an alkyl radical containing from 1 to 8 car
bon atoms, inclusive; the other Y represents a
50 substituent selected from the group consisting of
hydrogen, chlorine, bromine, and an alkyl radical
containing from 1 to 8 carbon atoms, inclusive;
one X represents hydrogen; and the other X rep
resents a hydroxy-propyloxy radical having the
55 formula:
cln
in which one X represents hydrogen, and the 45
other X represents the beta-hydroxy-ethoxy radi
cal.
8. Beta-hydroxy-ethyl ether of 2-hydroxy-3,5—
dichloro-diphenyl.
9. A compound having the formula:
50
55
—O—CH-—-CH—OH
t It
wherein one R represents methyl and the other R
60
represents hydrogen.
4. A compound having the formula:
in which Y represents an alkyl group containing
from 1 to 8 carbon atoms, inclusive; one X repre
sents hydrogen; and the other X represents a hy
droxy-alkoxy radical having the formula:
60
-o—cH-cI;H—oH'
R
R
wherein each R represents a substituent selected
65
in which each Y represents halogen; one X repre
sents hydrogen; and the other X represents a
70
from the group consisting of hydrogen and methyl 65
and the sum of the carbon atoms in the hydroxy
alkoxy radical is not greater than 3.
10. A compound having the formula:
hydroxy-alkoxy radical having the formula:
—O—OH—-CH—OH
R
R
wherein each R represents a substituent selected
from the group consisting of hydrogen and methyl
wherein Y represents an alkyl group containing 75
4
, 2,130,627
from 1 to 8 carbon atoms, inclusive; one X repre
from 1 to 8 carbon atoms, inclusive; one X repre
sents the beta-hydroxy-ethoxy radical; and the
other X represents hydrogen.
11. A compound having the formula:
sents hydrogen; and the other X represents a
hydroxy-propyloxy radical having the formula:
wherein one R represents methyl and the other R
represents hydrogen.
GERALD H. COLEMAN.
in which Y represents an alkyl radical containing
JOHN ZEMBA.
10
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