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Патент USA US3031516

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3,031,506
United States Patent ()??ce
Patented Apr. 24,1962
1
one or two hetero atoms will be‘ present in any single
bridge. If an amino nitrogen ‘atom is present in the
3,031,506
aforementioned bridges, its remaining valence ‘may be
METHBD FGR THE PREPARATION 0F
DIARYL KETQNES
satis?ed by either a hydrogen atom or an alkyl group
Reynold C. Fuson, Urhana, Ill., and Bruno M. Vittim
berga, Philadelphia, Pa, assignors to Rohrn & Haas
Company, Philadelphia, Pa, a corporation of Delaware
of one to twenty-one carbon atoms, such as methyl,
N0 Drawing, Filed July 29, 1958, Ser. No. 751,615
8 Claims. (ill. 260-591)
carbon in nature, such as tetramethylene, hexamethylene,
,
ethyl, butyl, octyl, dodecyl, octadecyl, .and eicosyl.
It
will generally be preferable to have these bridges hydro
octamethylene, dodecamethylene or tridecamethylene,
and when one bridge is tetramethylene, the other may be
_ This invention dealswith a method for the preparation 10
trimethylene, as indicated hereto-fore. The bridges may
also contain alkyl substituents within the number of car
bon atoms mentioned heretofore, such as 1,1,4,4-tetra
of speci?c diaryl ketones.
The present invention deals with a reaction between
a speci?c aromatic compound and a speci?c 2,6-disub
stituted benzoic acid in a manner to be more fully de
scribed hereinafter. The 2,6~disubstituted beuzoic acid 15
reactants of this invention may bewrepresented by the
_ formula
I
'
R3
R5
R1
'
20
coon
Ill-l R2
R1 and R2 indiivdually represent alkyl groups of one to
three carbon atoms in which the three-carbon representa 25
tion is the iso structure and these may be methyl, ethyl,
and isopropyl groups. R1 and R2 preferably represent
the same alkyl group in any one compound but they may
stand for different alkyl representations within the de?ni
tion just given. R3, R4, and R5 may represent the same 30
or di?erent components and these individually include a
hydrogen atom, an alkyl group of one to two carbon
atoms, i.e. methyl or ethyl, an n-alkoxyl group of one
to twenty-one carbon atoms, a phenoxyl group, or a phen
oxyl group substituted with one to ?ve groups preferably
'
4-phenoxy-2,3,5,6-tetramethylbenzoic acid,
4-isopropyl-2,6-dimethylbenzoic acid,
4-tert-butyl-2,G-dimethylbenzoic acid,
4-( a,a-dimethyl) decyl-2,6-dimethylbenzoic acid,
2,6-dimethyl-3,4-rnethylenedioxybenzoic acid,
2,6-dimethyl-3,4-hexamethylenedioxybenzoic acid,
1,2,3,4,5,6,7,8-octahydroantbracene-9—carboxylic acid,
2,3—heXamethylene-5,6hexamethylenebenzoic acid,
carboxylic acid,
-
3 ,4,5,6,7 ,8-hexahydro-2 [ 1H] oxaanthracene-Sl-carboxylic
acid,
and R5 may be methoxyl, propoxyl, butoxyl, octoxyl, dec
phenoxyl, m-nitrophenoxyl, p-methylphenoxyl, and the
acid reactants include
2,6-dimethylbenzoic acid,
2-ethyl-6-methylbenzoic acid,
2,3,5,6-tetramethylbenzoic acid,
3-ethyl-2,5,6-trimethylbenzoic acid,
2,3,4,5,6-pentamethylbenzoic acid,
4-e-thyl-2,3,5,6-tetramethylbenzoic. acid,
4-bro-mo-2,3,5,6~tetramethylbenzoic acid,
4-methoXy-2,3,5,6-tetramethylbenzoic acid,
1,2,3,4,5,6,7,8-octahydro-2~azaanthracene-9-carboxylic
acid,
1,2,3,4,5,6,7,8-octahydro-2-methyl-2—azaanthracene-9
ortho and para directing groups. Typically, in addition
to the alkyl representations previously presented, R3, R4, ,
oxyl, 'dodecoxyl, tetradecoxyl, octadecoxyl, eicosoxyl,
heneicosoxyl, phenoxyl, p-chlorophenoxyl, p-methoxy
methyltetramethylene, l-methyltrimethylene, and the like.
Typical representations of the 2,6-disubstituted benzoic
1,2,3,4,5,6,7,8-octahydro-2,7-diazaanthracene-9
40
like.
In addition, when R3 and R4 represent hydrogen atoms,
then R5 can also represent alkyl groups of three to
twelve carbon atoms in any of the known structural con
?gurations but preferably branch chained, such as iso
carboxylic acid,
.
1,2,3,4,5,6,7,8-octahydro-2,7-dimethyl-2,7-diaza
anthracene-Q-carboxylic acid,
1,2,3,4,5,6,7,8-octahydro-l-azaanthracene-IO
carboxylic acid,
2,3,4,5,6,7,8-heptahydro-l-oxaanthracene-IO
carboxylic acid,
propyl, tert-butyl, hexyl, octyl, nonyl, tert-decyl, undecyl,
1,3,4,5,7,8,9,10-octahydro-naphth[2,3-c] [2,S]oxa
and tert-dodecyl. Furthermore, it is possible for R3 and
azepine-ll-carboxylic acid,
'
R5 collectively or R4 and R5 collectively to represent a
2,3,4,5,6,7,8-heptahydro-l-thiaanthracene-IO
bridge having the formula
carboxylic acid,
50
in which n is an integer of one to ten, preferably one
to two. In ‘addition, R1 and R3 collectively or R2 and
R4 collectively, or both, may represent bridges contain
ing from three to thirteen carbon atoms. When R1 and 55
R3, as well as R2 and R4, both represent bridges, then
there is the requirement that the total number of carbon
atoms in the two bridges must be at least seven.
The
term, bridges, in the above sense, is used to include both
the carbon atoms in a direct chain and also these chains 60
with alkyl substituents vas will be apparent to one skilled
1,3,4,5,6,7,8-heptahydro-2-oxa-7-azaanthracene-9=
carboxylic acid,
2,3,4,5,6,7,8-heptahydro-1-oxa-6-azaanthracene~l0
carboxylic acid,
5,6,7,8~tetrahydrobenz[f]isoindoline-9-carboxylic acid,
1,3,5,6,7,8-hexahydrobenz[f]isothianaphthene-9.
carboxylic acid,
1
-
2,7r-dimethylal,2,3,4,5,6,7,8-octahydroanthracene-9
carboxylic acid, and
Z-methyl-1,2,3,4,5,6,7,8-octahydroanthracene-9
carboxylic acid.
in ‘the art. While is is preferable and usual that these
The other reactant employed in the present process, the '
bridges be entirely hydrocarbon in nature, it is quite per
speci?c aromatic compound, may be represented by the
missible that they contain hetero atoms, such as oxygen,
sulfur, and nitrogen. These hetero atoms will be present 65
in ether, thioether, amino, or substituted amino groups
with the restriction that these hetero atoms must not be
in the ortho position with respect to the carboxyl group
and also that there be at least two carbon atoms between
each of the hetero atoms present. There may be present 70
as many hetero atoms in these bridges as is possible with
formula
‘in the above de?nition and restriction, but generally only
II
The symbols W, X, Y, and Z may represent hydrogen
3,031,506
3
4
atoms or alkyl groups of one to three carbon atoms, in
It is important to note here that aluminum chloride
should be employed at the milder temperatures within
which the three-carbon atom member is iso in structure,
in any possible combination of hydrogen atoms and de
?ned alkyl groups. If only two, or three of these sym
the de?ned range or otherwise it sometimes causes un
desired isomerizations. The preferred catalyst is phos
bols represent hydrogen atoms,'then the remaining two UK phorous pentoxide, phosphoric acid and combinations
or one may represent alkyl groups of up to twelve car
thereof particularly those known as polyphosphoric acid
bon atoms including all of the known con?gurations,
in that higher yields and shorter reaction times are con
sistently observed with this catalyst. The above agents
such as normal, iso, and tertiary. It is also possible
to have one or two chlorine or bromine atoms present
may be de?ned in the present circumstances as carboxyl
provided they are the only substituents. It is further 10 removing catalysts.
A solvent of the volatile, but relatively high boiling,
possible to have one or two n-alkoxyl substituents in
which the alkyl portion contains from one to twenty-one
inert organic type, may be desirable in some instances,
particularly if the catalyst and reactants are solids. How
carbon atoms or one to two phenoxyl or phenoxyl groups
ever, if the catalyst, such as polyphosphoric acid, is liquid
ortho- and para-directing groups”
15 or at least one of the reactants is liquid, then the reac
Typical representations of W, X, Y, and Z, according
tion proceeds favorably without a solvent. It is fre
quently possible, when the aromatic hydrocarbon react
to the above de?nition, in addition to the methyl, ethyl
and isopropyl vgroups referred to heretofore include butyl,
ant of Formula II, referred to hereinbefore, is a liquid,
pentyl, hexyl, nonyl, decyl, and dodecylin any of the
to employ an extra amount of said reactant to function
substituted with from one to ?ve groups, preferably
known spatial con?gurations, methoxyl, ethoxyl, pro
poxyl, heptoxyl, octoxyl, dodecoxyl, octadecoxyl, eicos
as a solvent as well.
When a solvent is deemed neces- ,
sary or desirable, there may be employed'saturated ali
oxyl, phenoxyl, p-chlorophenoxyl, p-methoxyphenoxyl,
phatic hydrocarbons, such as hexane, decahydronaphtha
lene, and the like, or high molecular weight aliphatic
others, such as dipentyl ether, dihexyl ether, and the
m-nitrophenoxyl, p-methylphenoxyl, and the like.
Typical representations of the aromatic reactant just
de?ned include benzene, 1,2,3,4-tetramethylbenzene, m 25 like. These may be removed at the conclusion of the
xylene, o-xylene, 1,2,3-trimethylbenzene, 1,3,4-trimethyl
benzene, toluene, anisole, 1,2-dimethoxybenzene, octa~
decyl phenyl ether, 2,4-di-tert-butylbenzene, l-methyl-3
tert-dodecylbenzene, 1,2-dichlorobenzene, 1,3-dichloro
benzene, 1-bromo-3-chlorobenzene, chlorobenzene, bro
mobenzene, and diphenyl ether.
reaction as desired by known methods such as by distilla
tion under reduced pressure.
At the conclusion of the reaction, the diaryl ketone
product, which may be represented by the formula
30
W
.
The present reaction is conducted in the temperature
range of about 25° to 235° C., preferably 50" to 200°
C., with the restriction that a temperature must be em
ployed in this range at which the carboxyl-bearing react
W
X
V
35
'
X
if
Y
O
Z
Y
Z
ant is freed of its carboxyl group. This temperature
may be determined by the fact that the carboxyl-bearing
may be isolated by known methods. The present proc
reactant, once freed of its carboxyl group, is generally
ess provides a direct method for the preparation of the
isolable or removable from the reaction medium by
de?ned ketones in an ef?cient, controllable, and con
known methods and frequently may be recognized by its 40 venient way free from the use of corrosive, poisonous,
volatility or sublimity. The reaction is conducted until
and troublesome reactants and intermediates. The pres
the carboxyl group is substantially completely removed
ent invention also provides an essentially one-step proc
from the carboxyl-bearing reactant at which time the
ess for making compounds whose preparation by known
reaction is consummated and highest yields are obtained.
methods would require three or more steps. The ketone
One skilled in the art will be able to determine readily
, products have known utilities as insecticides and fungi
the necessary temperature within the de?ned range from
cides.
the teachings of this invention.
The present process may be more fully understood
It is preferred to use an excess of the aromatic hydro
from the following examples which are offered by way
carbon reactant. It is necessary for the successful con
of illustration and not by way of limitation. Parts by
summation of the reaction to react two equivalents of the
Weight are used throughout.
aromatic hydrocarbon reactant with one of the carboxyl 50
containing reactants, and it is preferred to employ an
EXAMPLE 1
excess of the aromatic hydrocarbon reactant beyond that
Preparation
of Di-p-Anz'syl Ketone
necessary to combine with the carboxyl-containing react
ant in order to induce maximum yields of the desired
Into a 200 ml. three-necked, ground-glass ?ask, ?tted
product.
with a condenser, stirrer, and stopper, is poured 35 parts
It is ‘possible to employ an equivalent of two different
of warm polyphosphoric acid. To this is added 2 parts of
aromatic hydrocarbon reactants with an equivalent of the
coarsely ground duroic acid and 35 parts of anisole. The
carboxyl-bearing reactant to form a mixture of three
products, two symmetrical. and one unsymmetrical, as
will be apparent to one skilled in the art. It is pre
ferred to employ two equivalents of a single aromatic
hydrocarbon reactant in order to minimize problems of
separation of product. The reaction is generally con
mixture is stirred rapidly while the temperature is raised,
by means of a sand bath, to 80° C. over a period of one
hour. The temperature is held at 80° C. for four hours.
The system is opened, and the temperature raised to 160°
C. Where it is maintained for seven hours. The hot reac
tion mixture is then poured into 100 parts of distilled
water, and the ?ask is rinsed with water. The water
ducted at atmospheric pressures but reduced pressures
may be employed, if desired, as would be apparent to 65 organic mixture is extracted four times with ether. This
one skilled in the art in applying the teachings of this
ether solution is washed three times with aqueous 5%
invention.
sodium bicarbonate, and twice with distilled water; it is
The present reaction requires a narrowly de?ned cata
then dried over anhydrous sodium sulfate.
7
lyst, including phosphorous pentoxide, at least essentially
The ?ltered ether solution is concentrated under water
85% phosphoric acid, combinations of phosphorous pent 70 aspirator vacuum and dried under high vacuum for ?ve
oxide and the de?ned phosphoric acid, particularly those
combinations known as polyphosphoric acid, and Lewis
acids such as zinc chloride, ferric chloride, mercuric chlo
ride, stannic chloride, aluminum chloride, boron tri
?uoride,.and boron tri?uoride etherates and complexes. 75
minutes, giving orange crystals. One crystallization from
ethanol yields 1.35 parts of organe-tinted plates, M.P.
140°—143° C. (Literature value for di-p-anisyl ketone,
143°-144° C.). The yield is 50% of the theoretical
amount. By concentration of the mother liquor it is pos
3,031,506
.
.
.
5
yield is 55-60%.
employed in Example 1.
In a similar manner, employing m-xylene and duroic
’
In like manner, there is prepared a ketone product of
acid there is produced 2,4,2',4’-tetramethylbenzophenone,
this invention by reacting octadecyl phenyl ether with 2
ethyl-6-methylbenzoic acid, using stannic chloride as the
catalyst.
-
6
butylbenzophenone, is isolated in a manner similar to that
sible to obtain an additional quantity of crystals; the total
an orange-red oil having a value 111,26 1.5853. '
EXAMPLE 5
‘
EXAMPLE 2
Preparation of 2,3,4,5,2',3',4’,5’-0ctamethylbenzophenone
Preparation of 4,4'-Di-(p-Phenoxybenzoyl)Diphenyl
Into a 200 ml. three-necked ?ask ?tted with a condene '
Ether
ser, mechanical stirrer, and glass stopper is placed 35 parts
of warm polyphosphoric acid. Then 3 parts of 2,6-di
Into ‘a 200 ml. three-necked ?ask ?tted with a re?ux
condenser, stirrer, and glass stopper is placed 35 parts of
methyl-3,4-methylenedioxybenzoic acid is added, with 35
parts of 1,2,3,4-tetramethylbenzene. The mixture is
warm polyphosphoric acid. To this is added 2 parts of
coarsely ground 4-phenoxy-2,3,5,6-tetramethylbenzoic
stirred and the temperature is raised to 80° C. over a pe
acid and 10 parts of diphenyl ether. The mixture is 15 riod of one hour, by means of a sand bath, and held at
stirred while the temperature is raised to 80° C. (by
this level for four hours. The temperature is then raised
means of a Sand bath) over a period of one hour. The
to 160° C. where it is maintained for four hours longer.
temperature is held there for four hours. Then the tem
The excess 1,2,3,4-tetramethylbenzene is removed at this
perature is raised to 160° C. and maintained at this point
temperature under vacuum. The reaction mixture is treat
for seven hours while the excess diphenyl ether is re 20 ed in the manner described in Example 1. The product,
moved under vacuum. The hot reaction mixture is then
2,3,4,5,2’,3',4',5'-octarnethylbenzophenone, is puri?ed by
poured into 100 parts of distilled water and the ?ask is
recrystallization from ethanol.
rinsed with water. The water-organic mixture is extracted
There is similarly produced a ketone of this invention
with ether. The ether solution is washed several times
by reacting benzene with 2,6-dimethyl-3,4-hexamethyl
with aqueous 5% sodium bicarbonate, twice with distilled 25 enedioxy-benzoic acid, using ferric chloride as the catalyst.
water and then is dried over anhydrous sodium sulfate.
EXAMPLE 6
The drying agent is removed by ?ltration and the sol
vent by evaporation at reduced pressure at a temperature
Preparation of 2,2'-Dimethyl-4,4'-Di-Tertd I
of 35° C. The product, 4,4’-di-(p-phenoxybenzoyl)di
phenyl ether, is puri?ed by chromatography on alumina.
Dodecylbenzophenone
In a similar way, there is produced a ketone product
of this invention by reacting 4—methoxy-2,3,5,6-tetrameth
ylbenzoic acid with diphenyl ether, using zinc chloride
as the catalyst.
EXAMPLE 3
‘In a 200 m1. three-necked ?ask ?tted with a condenser,
stirrer, and glass stopper is placed 40 parts of polyphos
phoric acid, 2 parts of 1-methyl-3-tert-dodecylbenzene
and 10 parts of 1,2,3,4,5,6,7,8-octahydro-2-azaanthra
cene-9-carboxylic acid. The mixture is stirred rapidly
35 while the temperature is raised to 80° C. over the period
Preparation of 4,4’-Dichlorobenz0phenone
Polyphosphoric acid (35 parts) is placed in a three
necked ?ask ?tted with a condenser, mechanical stirrer
of one hour and held there for four hours. The tem
perature is then raised to 160° C. where it is maintained
for four hours. The hot reaction mixture is then treated
as described in Example 1. The product, 2,2'-dimethyl
and glass stopper. To this is added, with vigorous stirring, 40 4,4'-di-tert-dodecylbenzophenone, is puri?ed by recrystal
35 parts of chlorobenzene and 3 parts of 1,2,3,4,5,6,7,8
lization from chloroform-ethanol.
octahydroanthracene-9-carboxylic acid. The temperature
is increased to 160° C. within a period of two hours, using
a sand bath to e?ect heating, and held at this temperature
In an analogous way, there is produced a ketone of
this invention by reacting 2,7-dimethyl-1,2,3,4,5,6,7,8
octahydroanthracene-9-carboxylic acid with 1,2,3-trimeth
for one-half hour longer. The system is then opened and 45 ylbenzene, using boron tri?uoride etherate as the catalyst. '
the temperature raised to 170° C. within a period of one
half hour and maintained at this temperature for four
hours longer. The work-up of the reaction mixture is
carried out in the same manner as in Example 1. The
We claim:
_1. A method for the preparation of a diaryl ketone
having the formula
W
product, 4,4'-dichlorobenzophenone, is puri?ed by recrys~ 50
tallization from ethanol.
W
X
X
'In an analogous manner, there is prepared a ketone of
this invention by reacting 1,3,4,5,7,8,9,10-octahydro
naph-[2,3-c][2,5]oxaazepine-1l-carboxylic acid with 1
t?
Y
.0
Y
N
Z
Z
‘ —X
bromo-3-chlorobenzene, using 85% phosphoric acid as 55
which comprises reacting substantially two equivalents
the catalyst.
of a compound having the formula
EXAMPLE 4
Preparation of 2,4,2',4’-Tetra~Tert-Butylbenz0phenone
Polyphosphoric acid (40 parts) is placed in a three 60
necked ?ask ?tted with re?ux condenser, mechanical
I.
stirrer, and glass stopper. To this is added 2 parts of
Y
2,3,4,5,6,7,8 - heptahydro-l-thiaanthracene-10-carboxylic
with one equivalent of a compound having the formula
acid and 10 parts of 2,4-di-tert-butylbenzene. The stirrer
R3 R1
is started and the temperature of the mixture is raised to 65
80° C. over a period of one hour and held there for four
hours. The system is opened and the temperature raised
to 160° C. where it is maintained for four hours longer.
The hot reaction mixture is then poured into 100 parts
of distilled water and the ?ask rinsed with water. The 70
water-organic mixture is extracted twice with ether and
twice with chloroform. The extracts are combined,
washed with aqueous 5% sodium bicarbonate and twice
R5-
COOH
l
R4
'
l
R1
in the temperature range of about 25° to 2359 C. until
the carboxylrbearing reactant is substantially free of its
.carboxyl group in the presence of a carboxyl-removing
asidis:v type catalyst from the group ‘consisting of phos
hydrous sodium sulfate. The product, 2,4,2',4'-tetra-tert 75 phorous pentoxide, at least essentially 85 % phosphoric
with distilled water. The solution is then dried over an
3,031,506
8
acid, polyphosphoric acid, zinc chloride, ferric chloride,v
mercuric chloride, stannic chloride, aluminum chloride,
4. A method for the preparation'of a diaryl ketone
having the formula
boron tri?uoride, and boron tri?uoride etherates, in which
W, X, Y, and Z are members from the class consisting
'
W
of hydrogen, methyl, ethyl, isopropyl, tert-alkyl groups
x
of four to twelve carbon atoms, chlorine, bromine, n‘
alkoxyl groups of one to twenty-one carbon atoms,
Y
phenoxyl, chlorophenoxyl, methoxyphenoxyl, nitrophen
‘W
X
it0
Y
z
z
'
oxyl, and methylphenoxyl, such that said n-alkoxyl, phen
which comprises reacting substantially two equivalents of
oxyl, substituted phenoxyl, chlorine, and bromine repre 10 a compound having the formula
sentations are possible only when two to three of said W,
X, Y, and Z represent hydrogen, R1 and R2 individually
represent members from the class consisting of methyl,
ethyl, and isopropyl groups, R3, R4, and R5 individually
represent members from the class consisting of a hydro 15
gen atom, an alkyl. group of one to two carbon atoms,
an n-alkoxyl group of one to twenty-one carbon atoms,
with one equivalent of a compound having the formula
phenoxyl, chlorophenoxyl, methoxyphenoxyl, nitrophen
R1
oxyl, and methylphenoxyl, When R3 and R4 represent hy
drogen atoms R5 additionally represents an alkyl group 20
m©ooon
of three to twelve carbon atoms, R3 and R5 when con
sidered collectively represent an oxygenated bridge hav
ing the formula
in the temperature range of about 25° to 235° C. in the
—O—-(CI-I2)n—O
presence of polyphosphoric acid in which R1 and R2 are
in which n is an integer of 1 to 10 and R4 and R5 when 25 alkyl groups of one to three carbon atoms, R5 is a tert
considered collectively represent an oxygenated bridge
having the ‘formula
alkyl group of four to twelve carbon atoms, and W, X,
Y, and Z represent alkyl groups of one to three carbon
'
atoms.
in which n is an integer of one to ten, and at least one of 30
R1 and R3 when considered collectively and R2 and R4
when considered collectively represent alkylene bridges
5. A method for the preparation of a diaryl ketone
having the formula
containing from three to thirteen carbon atoms provided
that when R1 and R3, considered collectively, and R2 and
R4, considered collectively, both represent said alkylene 35
0
bridges, the total number of carbon atoms in the two
said alkylene bridges must be at least 7 and in which these
bridges contain from zero to two atoms from the class
which comprises reacting substantially two equivalents of
consisting of ether oxygen, thioether sulfur, and amino
nitrogen provided that there be at least two carbon atoms
a compound having the formula
between any two atoms of said oxygen, sulfur and
nitrogen.
2. A process according to claim 1 in which the reaction
temperature range is about 50° to 200° C. and in which
the reaction is conducted in the presence of an inert 45
Y
volatile organic solvent, and the catalyst is polyphos
phoric acid.
-
with one equivalent of a compound having the formula
~
3. A method for the preparation of a diaryl ketone
having the formula
W
50
W
X
0
x
‘i
Y
COOH
R:
O
Y
z
z
55 in the temperature range of about 25° to 235° C. in the
presence of polyphosphoric acid in which R1 and R2 are
which comprises reacting substantially two equivalents of
alkyl groups of one to three carbon atoms, n is an integer
a compound having the formula
of one to ten, and W, X, Y, and Z represent alkyl groups
of one to three carbon atoms.
60
z
6. A method for the preparation of a diaryl ketone
having the formula
x
Y
with one equivalent of a compound having the formula
/
65
R1
R:
which comprises reacting substantially two equivalents of
70
-
a compound having the formula
W
in the temperature range of about 25° to 235° C. in the
presence of polyphosphoric acid in which R1 and R2 are
alkyl groups of one to three carbon atoms and W, X, Y,
and Z represent alkyl groups of one to three carbon
atoms.
i
0
00011
Y
X
75
3,031,506
R1‘
@0001;
10
8. A‘ method for the preparation of a diaryl ketone
having the formula
with one equivalent of a compound having the formula
w
w
X
X
‘
‘t
Y
O
Y
in ‘the temperature range of about 25° to 235° C. in the
z
z
presence of polyphosphoric acid in which R1 and R2 are
10
which
comprises
reacting
substantially
two equivalents of
alkyl groups of one to three carbon atoms and W and X
a compound having the formula
represent alkyl groups of one to three carbon atoms.
7. A method for the preparation of a diaryl ketone
_ W
having the formula
W
W
X
15
z
X
X
Y
‘If
Y
0.
Z
with one equivalent of a compound having the formula
Y
Z
R3
which comprises reacting substantially two equivalents of 20
R1
'
OOOH
a compound having the formula
W
|
Y
with one equivalent of a compound having the formula
R4
R2
in the temperature range of about 50° to 200° C. in the
25 presence of polyphosphoric acid in which R1 and R2 are
alkyl groups of one to three carbon atoms, R3 and R4
are alkyl groups of one to two carbon atoms, and W, X,
Y, and Z represent alkyl groups of one to three carbon
30 atoms.
References Cited in the ?le of this patent
UNITED STATES PATENTS
(CHnn
COOH
1,866,717
(C Hahn
in the temperature range of about 50° to 200° C. in the
presence of polyphosphoric acid in which n and m- are
integers of tour to thirteen and W, X, Y, and Z repre
sent alkyl groups of one to three carbon atoms.
35
Meyer et a1 ___________ __ July 12, 1932
OTHER REFERENCES
Thomas: Anhyd. Aluminum Chloride in Org. Chem.
pp. 683—4 (1941).
Snyder et al.: I. Am. Chem. Soc, vol. 77, pp. 364-5
(1955).
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