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WITH COPPER(II)BROMIDE
DECEMBER,
1964
3459
A suspension of copper(I1) bromide in chloroformethyl acetate reacts with ketones to give the corresponding a-bromo ketones. This reaction system is highly
selective when used to brominate hydroxyacetophenones and gives nearly quantitative yields of the wbromohydroxyacetophenones, hydrogen bromide, and
copper(1) bromide according to the following equation.
0
am,
4- ZCuBr,
EtOAc
D h - C H , B r
HO
+ HBrf + 2CuBri
3460
KINGAND OSTRUM
VOL.29
TABLEI
PREPARATION OF
Substituted
acetophenone
2-BROMOHYDROXYACETOPHENONES
Time
required
Acetophenone formed
Yield,a %
2'-Hydroxy-
2-Bromo-2 '-hydroxy-
3-5 hr.
ea. 100
3 '-Hydroxy-
2-Bromo-3 '-hydroxy-
20-40 min.
ea. 100
4'-Hydroxy-
2-Bromo-4'-hydroxy-
15-20 min.
ca. 100
M.p.,* O C .
40"
(45)d
(70-71)e
I
...
(. . )
,
124-126
(130)O
( 128- 129)A
2',4'-Dihydroxy2-Bromo-2 ',4 '-dihydroxy3-5 hr.
ca. 100'
144-145'
(127)k
2',5'-Dihydroxy2-Bromo-2 ',5 '-dihydroxy3-5 hr.
74-87'
112-113"'
(117.5-119)"
a Yield based on weight of crude product isolated and amount of copper(1) bromide recovered.
Literature values in parenthesis.
Not completely crystalline.
N. P. Buu-Hoi and D. Lavit, J . Chem. Soc., 18 (1955). e L. Vargha, J. Ramonczai, and J. Bathory,
J . Am. Chem. SOC.,71, 2652 (1949). Isolated as a liquid which decomposed upon attempted vacuum distillation. 0 X. P. BuuHoi, X. I). Xuong, and I). Lavit, J . Chem. SOC.,1034 (1954).
D. D. Mukerji, Ann., 619, 189 (1958). Isolated ca. 40% as crystalline product.
After several recrystallizations from benzene; crude product m.p. 128-138'.
A. Sonn and S. Falkenheim, Ber., 55,
Isolated crystalline product.
2975 (1922).
Slightly contaminated with unreacted starting material as indicated by C and H analysis
and thin layer chromatography.
M. C. Kloetzel, R. P. Dayton, and B. Y. Abadir, J . Org. Chem., 20, 38 (1955).
'
'
'
'
TABLEI1
PREPARATION
OF SUBSTITUTED
1-BENZOYLMETHYLPYRIDINIUM
SALTS^
Yield,c %
Compd.b
Bromide
rn.p., ' c . ~
2'-Hydroxy-R
85-93
197-200
3 '-Hydroxy-R
68-93
4'-Hydroxy-R
84-99
2 ',4'-Dihydroxy-R
66-72
253-254,5 dec.
2 ',5'-I)ihydroxy-R
75-83
235- 238
(.'.)
222,5-224 dec.
( 2 18-2 19)"
248-250 dec.
(...)
( .. .)
Iodide
m.p., oC.d
Perchlorate
m.p., OC.d
212-217
(211-215)"
236-239 dec.'
(223-228)"
221-223 dec.
(215-219)*
243.5-245.5
(241-242)e
237-239 dec.
201-202
( 193-196)O
222-224
(224-226y
180- 182
( 181-183)e
24C-242'
(253-255y
272-274 dec.
L..)
(...I
( .. .)
Bromide salts were converted to the less soluble iodide and perchlorate salts by the method of King.8
R = benzoylmethylpyridinium salt.
Represent's lowest and highest yields of the bromide salt obtained in a minimum of three preparations.
Literature values
Infrared spectrum was superimposible on that of an authentic sample. 0 T. Goto, J . Pharm. SOC.Japan,
in parenthesis. e Ref. 3b.
74,318 (1954).
a
'
TABLE111
CLEAVAGE
OF SUBSTITUTED
1-BENZOYLMETHYLPYRIDINIUM
SALTS
Salt hydrolyseda
2 '-Hydroxy-R
Substituted
beneoio acid
formedb
2-Hydroxy-
Yield,c %
M.P.,
53
156-158
(156-158)'
3 '-Hydroxy-R
3-Hydroxy67
201-203, 205'
(197-201 )"
4 '-Hydroxy-R
4Hydroxy98
213-215, 218'
(212-213 )"
2',4'-Dihydroxy-R
2,gDihydroxy62
21 1-213'
( 2 18-2 19)"
(208)"
2',5'-Dihydroxy-R
2,blXhydroxy35
201-203'
(201)',h
All had infrared
a R = benzoylmethylpyridinium bromide.
spectra which were superimposible with those of authentic
samples.
Optimum yields were not sought.
Literature
values in parenthesis. e Ref. 3b. f Sublimed sample. 0 R .
Kuhn, F. Zilliken, and H. Trischmann, Ber., 83, 304 (1950).
S. C. Bhattacharyya and D. E. Seymour, J . Chem. SOC.,1139
(1950).
Experimental
All melting points were taken on a Fischer-Johns melting
point apparatus and are uncorrected. Structure assignments
were supported by infrared spectra taken on a Baird Associates
DECEMBER,
1964
DECOMPOSITIONS
OF HYDROPEROXIDES
IN OXIDIZING
OLEFINS
3461
Acknowledgment.-G.
K. 0. acknowledges partial
support of this investigation by the Abbott Foundation
Fund of Northwestern University and the National
Science Foundation (Summer Research Fellowship).
(15) A. K. Bose and P. Yates, J . Am. Chem. SOC.,74, 4703 (1952).