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Патент USA US2137236

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Patented Nov. 22, 1938
' 2,137,236
“ UNITED‘ “ STATES PATENT-l OFFICE
2,137,236
’ 1 MERCURI ALnYnPnENoL nnmvnrlvns
».Walter G. Ghristiansen, Glen Ridge, N. J., and “
7 Eugene Moness, Long Island City, N. Y.;'as
. signorst'o E. It; Squibb & Sons, New York,'N. Y.,
a corporation of New York
_
No Drawing. Application September 13, 1934,. ‘
Serial No. 743,840
‘
1
.
I
(Cl. 260-622)
4 Claims.
This invention relates to, and has for its object
‘20 cc. methyl‘alcohol, and while the solution is
the provision of, certain ‘mercuri alkyl phenol
Ire?uxed‘ on a steam-bath, 8 g. mercuric acetate
derivatives and an advantageous method of pre
dissolved in'20 ccfwaterslightly aciclulated with
paring them.
acetic acid’ is. added rapid-dropwise with me
chanical stirring. After one and one-half hours
of re?uxing, a' test for divalent mercury ‘being
-
The compounds of this invention are mercuri
alkyl phenol derivatives of the group consisting“
of;
--
.
.
~
negative and heavy white crystals having ,formed,
.
en
7
j *0
the residue is ?lteredout and washed as in the
_‘
?rst
example.
,
l
>
.
v
-
>
'
Anhydro-mercuri' 2-or-4-chloro, ‘3,5-dimethyl
10
» anion-Hg
'
and
g—
10
'
-~
1.
Tphenol
.
15 I wherein Z represents .a member of the group
»
_
or
consisting of halogen ‘and nitr0,and R, repre
sents a branched-chain alkyl.
l
O
Hg
HaC
They maybe
CH3
prepared by interacting thecorresponding un
mercurated 'alkyl phenol derivatives with mer
20 curic acetate, and replacing the acetoxy with the >_'Ifl1'is_ compound is prepared precisely in accord- " 20
ance: with the preceding example except that
desired anion by means of the compound, of that
25
anion with an alkali metal (of. Whitmore’s Or
chloro 3,5-dimethyl phenol is substituted for
ganic Compoundsof Mercury, 1921, pp. 257, 258) .'
These mercuri alkyl phenol derivatives have been
chloro 3,6-dimethyl: phenol. '
found to be active germicides.
}
~ Anhydro-mercuri
2-chloro 4-tertiary-amyl
phenol
‘
25
EXAMPLES '
Anhydro-mercu'rz' Z-chloro 4-tertiary-butyl
'
'
.
v
phenol
'
30
30
C1
4.02 g. 2-chloro fl-tertiary-amyl phenol is dis
solved in 40 cc. methyl alcohol, and while the 35
solution is re?uxed on a steam-bath, 6.40 g.
CO U!
(CHa)s
mercuric acetate - dissolved in 30 cc. slightly
Wise with mechanical stirring. ,After two hours
‘acidulatedwater is added rapid-dropwise with
mechanical stirring. After seven hours of re
?uxing, a‘test for divalent mercury being nega
;tive,.the desired compound is obtained in the form
ofwhit'e crystals by ?ltering, washing, and drying
as in the foregoing examples‘
of re?uxing, a test for divalentmercury being
Hydroxymercnri 3-methyl p4-chloro phenol
5.25 g. 2-chloro 4-tertiary-butyl phenol is dis-7
solved in 36 cc. methyl alcohol, and while the
40 solution is re?uxed on a steam-bath, 9 g. mer
curic acetate dissolved, in 26 cc. water slightly
acidulated With acetic acid is added rapid-drop- .
negativeand white crystals having formed, the
45
mixture is' ?ltered; the residue, upon being
washed successively with methylralcohol, ‘water,
and methyl alcohol, and dried, is found to be
soluble in dilute alkali.
.
.
'
I .
.
50
Anhydro-mercuri 2-or-4-chloro 3,6-dz'methyl
phenol
‘
s
.
,
Cl
7.25‘ g. 3-methyl 4§chloro phenol is. dissolved.’
in 50 cc. methyl alcohol, and while the solution
, is refluxed on a steam-bath, 16 g. mercuric ace-v
tate dissolvedinl50 ccrwater is added dropwise
withmechanical stirring; v,After ?ve hours of
V re?uxing, a test 'for divalent mercury being nega
tive, the desired compound is obtained in the
so 4 g. chloro, ,3?-dimethyl-phenol ‘is dissolved in ‘_ formhof grayish-white crystals by ?ltering, Wash
55
2
2,137,236
ing, and drying as in the foregoing examples.
Puri?cation may be effected by dissolving in
dilute alkali, ?ltering, and precipitating either by
treating the ?ltrate with dilute acetic acid or by
saturating the ?ltrate with carbon dioxide.
Acetoxymercuri s-methyl 4-chloro ?-isopropyl
phenol
0H1’
(CHQQCH
CHaC O OHg
~CH:
o1
15
.
dissolved in 10 cc. ethyl alcohol, and while the
solution is re?uxed, 1.5 g. mercuric acetate dis
solved in‘lO cc. water is added. After two hours
of re?uxing, a test for divalent mercury being
negative, and the reaction mixture being brown
ish and turbid, the alcohol is evaporated off and
the mass dissolved in dilute alkali. Finely di
vided reduced mercury is ?ltered out. Precipi
tation is effected by means of acetic acid. For
puri?cation, the precipitate is dissolved in boiling 10
alcohol, and a slight residue ?ltered out. Dilut
ing the alcoholic solution with water yields the
desired compound as a pinkish precipitate.
Acetoxymercuri Z-nitro 4-tertiary-butyl phenol
9.25 g. 3-methyl 4-chloro 6-isopropy1 phenol is
dissolved in 50 cc..methyl alcohol, and while the
OH
N09
solution is re?uxed on a steam-bath, 14.7 g.
CHaC 0 011g
mercuric acetate dissolved in 50 cc. water slightly
'20 acidulated with acetic acid is added. After ?ve
hours of re?uxing, a test for divalent mercury
(013103
being negative, the reaction mixture is ?ltered,
5.14 g. 2-nitro 4-tertiary-butyl phenol is dis
Washed, and dried as in the foregoing examples,
yielding the desired compound in the form of
solved in 50 cc. methyl alcohol, and while the
White crystals.
.
Acetoxymercuri 2-chloro 4-pr0pyl ‘phenol
OH
15
20
solution is re?uxed on a steam-bath, 8 .g. mer
curic acetate dissolved in 3000. water slightly
acidulated with acetic acid is added. After ?ve
hours of re?uxing, a test for divalent mercury
being negative, the precipitate, which is the de
sired compound, is ?ltered off, washed succes
sively with a little methyl alcohol, water, and:
methyl alcohol, and dried to yellow-orange crys
tals, ' which give an orange solution in dilute
4.71 g. 2-chloro 4-propyl phenol is dissolved in
25 cc. methyl alcohol, and while the solution is
35 re?uxed on a steam-bath, 8.7 g. mercuric acetate
dissolved in 25 cc. water slightly acidulated with
acetic acid is added rapid-dropwise with me
chanical stirring. After three hours of re?uxing,
a test for divalent mercury being negative, the
reaction mixture is ?ltered, washed, and dried
as in the foregoing examples, yielding the desired
compound in the form of white: crystals.
45
Hydromy mew-curt‘ 3-z'sopropyl 4-chloro 6-methyl
phenol
0H,
'
Acetoxymercuri 2-nit1'o-3,6-dimethyl phenol
oH
H36
N02
onloo OHg
C H3
2.19 g. 2-nitro 3,6-dimethyl phenol is dissolved 40
in 13 cc. methyl alcohol, and while the solution is
re?uxed on a steam-bath, 3.93 g. mercuric ace
tate dissolved in 13 cc. water slightly acidulated
with acetic acid is added. After seven hours of
re?uxing, a test for divalent mercury being nega 1.. (A
tive, the reddish-brown crystal precipitate, the
desired compound, is ?ltered, washed, and dried
113C
HOHg
CH(CH3)2
50
A solution of 8 g. 3-isopropyl 4-chloro G-methyl
phenol in 150 cc. ethyl alcohol is treated in the
manner of the foregoing examples with 12.5 g.
mercuric acetate in 45 cc. water. After twelve
hours of refluxing, a test for divalent mercury
as in the preceding example, and is found to give
a light-red solution with dilute alkali.
Acetoazymercnri Z-nitro 4-tertiary-amyl phenol
OH
NO;
CHaCO OHg
being slightly positive and some crystals having
formed, the mixture is ?ltered. The ?ltrate is
made strongly alkaline with dilute alkali, and the
grayish muddy precipitate is ?ltered out. The
4.4 g. 2-nitro 4-tertiary-amyl phenol is dissolved
in 45 cc. methyl alcohol, and while the solution
dark-red alkaline ?ltrate is acidi?ed with dilute
is re?uxed on a steam-bath, 6.7 g. mercuric ace
acetic acid, and the reddish-brown precipitate,
the desired compound, is ?ltered 01f, washed with
tate dissolved in 25 cc. water slightly acidulated
with acid is added. After eight hours of re?ux
ing, a test for divalent mercury being negative,
water and then with alcohol, and dried to a red
dish powder, which gives a dark-red solution with
dilute alkali.
Acetoxymercuri 1,3-dihydroccy, 4-butyl 6-chloro
benzene
on
70
alkali.
>
HzC(CHa)a
60
the crystalline yellow precipitate, the desired
compound, is isolated as in the preceding ex
amples.
Hydrorymercnrz' Z-nitro 4-p1‘opyl phenol
'
on
NO;
01
70
HOHg
011300011’ —
0H
4H9
" 75 0.9 g; 1,3-dihydroxy 4-butyl 6~chloro benzene is
3H1
2.3 g. 2-nitro 4-propyl phenol is dissolved in 25 cc. 75
*3
2,137,236
methyl alcohol, and while the solution is re?uxed
on a steam-bath, a solution of 4 g. mercuric ace
tate in 12 cc. water slightly acidulated with acetic
acid is added. After four hours of re?uxing, a
test for divalent mercury being negative, the
crystalline orange precipitate, the desired com
pound, is isolated as in the preceding examples.
Puri?cation may be e?'ected by dissolving (to an
orange solution) in dilute alkali, ?ltering out the
slight
residue, _ and precipitating with dilute
acetic acid.
Acetoxymercw'i 3-methiyl 4-m‘tro 6-z'sopropyl.
phenol
'
"
nol.
.
Acetoxymercuri 1,3-dihydroxy 4-amyl 6-chloro.
benzene.
Acetoxymercuri 1,3-dihydroxy 4-hexyl 6-chloro
benzene.
Chloromercuri 2-chloro 4-propyl phenol.
Acetoxymercuri 2-bromo 4-propyl phenol.
Nitratomercuri 2-nitro 4-_normal-buty1 phenol.
Thiooyanomercuri 2-nitro 4-normal-amyl phenol.
1O
Chloromercuri 2-nitro 4-propyl phenol.‘
It is to be‘ understood that the foregoing ex?
amples are merely illustrative and by no means
limitative of the invention, which may be vari
ously otherwise embodied within the scope of the 20
CH3
N02
2.5 g. B-methyl 4-nitro ?-isopropyl phenol is dis
solved in 13 cc. methyl alcohol, and while the
solution is re?uxed on a steam-bath, 4 g. mer-‘
curic acetate dissolved in 12 cc. water slightly
acidulated with acetic acid is added. After seven
hours of re?uxing, a test for divalent mercury
being negative, the crystalline yellowish precipi
tate, the desired compound,'is isolated as in the
preceding examples, and found to give an orange
30 solution with dilute alkali.
-
Hydroxymercuri 2-propyl 4-nitro phenol.
(CHahCH
cmooong
7
nol.
Anhydro-mercuri 2-chloro 4-normal-amyl phe
_ Acetoxymercuri 2-propyl 4-chloro phenol.
OH
15
Anhydro-mercuri 2-chloro 4~normal-butyl phe
»
appended claims.
We claim:
.
Y1. Anhydro-mercuri 2-chloro 4-tertiary-buty
phenol.
"
~
'
2. Acetoxymercuri
phenol.
-
.
2 - nitro
4 - tertiary-butyl
.
3. Mercuri' alkyl phenol derivatives of the
group consisting of
>
OH
7
Among the numerous other compounds that
'may be prepared in accordance with the inven
tion are the following (the chloro, the cyano, the
thiocyano, the nitrato, and the hydroxy com
pounds being formed by treating solutions of the
35 acetoxy compound with. respectively, the chlo
ride, the cyanide, the, thiocyanide, the nitrate,
and the hydroxide, of an alkali metal).
Cyanomercuri 2-chloro 4-tertiary-butyl phenol.
Anhydro-mercuri 2-bromo 4-tertiary-butyl phe
nol.
consisting of halogen and nitro; and R repre
sents a branched-chain alkyl.
Chloromercuri 2-chlor0 4-tertiary-butyl phenol.
40
35
wherein Z represents a member of ‘the group
'
4. Acetoxymercuri
2 - nitro
4 - tertiary-amyl
phenol.
WALTER G. CHRISTIANSEN.
EUGENE MONESS.
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