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Патент USA US3440297

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3,440,290
United States Patent 0 "ice
Patented Apr. 22, 1969
1
2
3,440,296
METHOD FOR PREPARING POLYHYDROXY
AROMATI'C COMPOUNDS
IN META
hydro. quinone; N-2 represents. the bis(hydroxypheny1)
ethers having the generic, formula
ORIENTATION
Alexander H. Widiger, Jr., Midland, Mich., assignor to
The Dow Chemical Company, Midland, Mich., a cor- 5
poration of Delaware
No Drawing. Filed Aug. 5 1965 Ser. No. 477 610
Int. Cl. C07c 37/0’0, 39/i28,43/22
US. Cl. 266-613
.
-
’
-
'
*
“.8 Well as the mhydroxy dlphqnyls haw-“g the’ gene“
9 Claims
f‘mm?a
'
The present invention relates to an improved method 10
for preparing resorcinol, ‘catechol, dihydroxy diphenyl
ethers trihydroxydiphenyls and highers in commercially
HO
OH
economical quantities employing milder react-ion condi-
OH
actanténore economical reactants and easier to handle re 15 and N_3 represents the bls (11ydmxyphmoxy )benzene‘s,
tions,
'
.
.
.
-
_
There is much prior art in the ?eld of hydrolyzing chlorobenzenes, dichlorobenzenes and chlorophenols. It is,
I
.1
e'g"
however, believed that none of the prior workers recog-
HO
O
O
OH
nized the signi?cance of the strength of the caustic on 20
the overall yield of valuable products.
The present process comprises reacting about one mole
of a chlorophenol or a mixture of the isomers thereof with
th h d
e
h
y foxy P enoxy
dih d
d- h
1
y roxy 1P any S
from 4 to 8 moles, and preferably 5 to 6 moles, of sodium
hydroxide as a 20 to 50% aqueous solution under the 25
autogenous pressure of the mixture at about 250° to
270° C., and preferably at about 265° C. for from about
1/2. to about 2 hours. The resulting products, rich in meta
HO
O
(0E2
and some tetrahydroxy triphenyls (6%),
orientation, are principally dihydroxy benzenes and d1
droxy diphenyl ethers. The products can conveniently be 30
‘I
separated from the reaction mixture by acidi?cation there~
of to a pH value of about 3 to about 6 and subsequent extraction with an organic extractant, such as sec. butyl alco<
hol, amyl ‘alcohol, and the like, and recovered from the
—-—(OH)4
J
The following examples illustrate the process of the
extractant and from each other by fractional ‘distillation 35 present invention but are not to be construed as limiting.
under vacuum.
The process of the present invention can be carried
out to yield about 60% conversion, :based on the chlorophenol consumed, at 65° C., Within 30 minutes when
_
_
EXAMPLES
_
'
_
A series of experiments were run to Iestabhsh the limits
reactants of the present process. Eac experiment con
using at least some ortho and/ or para isomer in the start- 40 sisted of the reaction at 265° C. of the indicated chloro
in0 chlorophenol. Longer reaction periods do not rna-
phenol isomer with c.p. sodium hydroxide and distilled
teigially increase the yield of desired products, that is, the
water. The reaction was carried out in an iron bomb
dihydroxy benzenes and the dihydroxy diphenyl ethers
placed in a rocker. The reaction time was 30 minutes for
but longer periods are not materially detrimental to the
the ortho and meta isomers and 120 minutes for the para
‘5116523333722?
51003511251322.3335?aldbiinirili?iii ‘*5 ii‘iénivrt?iiiiiénti?ii‘é’iifiif1°?°¥?§liii§ii“£é§i
slightly greater than autogenous pressures the time will
ucts were separated from the aqueous phase :by 4 extrac
vary approximately inversely to the temperature‘.
tions with sec. butyl alcohol. The alcohol _was removed
In the following examples the products are de?ned as
from the extracted organic phase by distillation under
N-l, N—2, and N-3. These symbols represent the number 50 vacuum and the products separated one from the other by
fractional distillation in vacuo. The results of the series
of phenylene nuclei in the compounds. Thus, N-l repre
sents the dihydroxy benzenes, catechol, resorcinol and
NaOH
of runs are set out in the tables below.
Product grams
Percent
Chloro-
Grams
Strength,
phenol, g.
Percent Dist. dihydroxy
compounds in N-l
_
Cl¢OH
N-l’
N-2"
N-3‘
Conv.
Yield
percent
74. 5
20
on'rno
1 87.0
107
121
30
35
1 125
l 143
148
197
256
40
50
65
l 174
113
150. 5
74. 5
88
107
128
148
197
20
25
30
35
40
50
4
4
l
1
l
74. 5
26. 5
20
30
4 126
1 125
60
11
3. 9
.......... __
31
64
61. 5
48
49
8
13. 5
31. 5
53
53. 4
42
50. 8
10
10
22. 9
23
21. 3
2. 8
6. 5
2
9. 5
18
52
66
72
93
91
81
82
83
73
79
69
71
28
22. 7
21
8
27. 5
36
33. 2
44. 5
49. 2
32
13.0
19. 2
24
29. 5
25
21
53
6. 5
17
20
38
25
47
54
77
85
88
93
88
89
92
89
92
88
6. 3
9
__________ __
.......... .1
17
36
79
69
10. 2
9. 0
48
13. 5
15. 2
52
14. 8
12. 8
70
2 Balance if any para.
9 Balance if any ortho.
| Three replicates.
68
73
72
META
130. 5
153. 6
125
150
168
115
PAR
128
148
197
35
40
50
1 91. 2
l 87. 8
115
104. 5
79
84
83.8
34
10
17
20
24. 5
20. 5
*These symbols have the signi?cance aforesaid.
1 Two replicates of this experiment were run and the data is that ob
tained by combining the two products recovered on removal of the sec.
butyl alcohol.
0
M
P
3,440,290
3
I claim:
4
.
6. The method of claim 5 wherein the reaction period
‘
‘ 1. A method for preparing a polyhydroxy aromatic
is about'l/z hour. '
product which comprises reacting a mixture consisting
7. The method of claim 4 wherein said reaction tem
essentially of a chlorophenol with from 4 to 8 moles of
perature is 265° C. and the reaction period is 120 minutes.
20 to 50% aqueous solution of sodium hydroxide under 5
8. The method of claim 3 wherein said reaction tem
the mixtures autogenous pressure at a temperature of
perature is 265° C. and the reaction time is 16 hour.
from about 250° to 270? C. for between about 1/2 to 2
9. The method of claim 1 which consists essentially
hours, and separating from the reaction mixture a prod
of reacting a chlorophenol with 5 to 6 moles of 20 to 50%
uct rich in meta oriented dihydroxybenzene, dihydroxy
aqueous solution of sodium hydroxide at about 265°
diphenyl ethers and trihydroxy diphenyl, and low in
C. for 1/2 to 2 hours.
hydroxy phenoxy phenoxyphenols, and highers.
2. The method of claim 1 wherein the chlorophenol
is meta chlorophenol.
3. The method of claim 1 wherein the chlorophenol
is ortho chlorophenol.
15
4. The method of claim 1 wherein the chlorophenol
is para chlorophenol.
5. The method of claim 2 wherein the reaction tem
perature of'265" C.
References Cited
UNITED STATES PATENTS
'
-
2,041,592
5/1936
Burroughs ________ __ 260-629
BERNARD HELFIN, Primary Examiner.
U.s.' c1. X.R.
260-620, 629
U.S. DEPARTMENT OF COMMERCE
PATENT OFFICE
Washington, 0.6. 20231
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3 ,440 ,290
April 22 , 1969
Alexander H. Widiger, Jr.
It is certified that error appears in the above identified
patent and that said Letters Patent are hereby corrected as
shown below:
Column 1, line 38, "65° C." should read —- 265° C. ——.
Columns 1 and 2, in the table, second column, line 14 thereof,
"26.5" should read
-—
62.5
——.
Signed and sealed this 14th day of April 1970.
(SEAL)
Attest:
Edward M. Fletcher, J r.
Attesting Officer
WILLIAM E. SCHUYLER, JR.
Commissioner of Patents
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