Note: Descriptions are shown in the official language in which they were submitted.
~o7~ ~79
Field of the Invention
The present invention relates generally to an improved
process for preparing self-condensation products, such as di-
phenoquinones and biphenols, from alkylphenols and alkoxyphenols,
and dinaphthenoquinones and binaphthols from naphthols, and to
a catalyst for use in said process. ~ore particularly, the
invention relates to the preparation of cond~nsation products of
; alkyl- and alko:y- phenols, l-naphthol and substituted l-naphthols
by contacting an aqueous mixture of the phenol or naphthol with
oxygen or an oxygen-containing gas in the presence of a meLal
Icomplex of an aminocarboxylic acid or an amlnosulfonic acid.
I
Description of the Prior Art
¦ It is well known in the art that substituted phenols can
ibe oxidized to yield self-condensation products, including dipheno-
quinones, biphenols and polyphenoxy ethers. The procedure employed
~n the preparation of these derivatives is generally referred to
,as the oxidative coupling of phenols.
¦ The self-condensation products resulting from these
loxidative coupling reactions can be categorized as either the
J~lS:rac esult of carbon-carbon or carbon-oY.ygen coupling of said phenols. !1258-A - 2 -
. . , .
. ' '' ',
.. . '.
I
I
.. i `.
. A
~ ~ l~
1071~79
Dipheno~uinones and biphe3l01s are prepared by carbon-carbon coup-
ling in accordance with the followincJ genercll rcactions depending j
. upon the reactive sites available in the pllenol employed.
R R R R R R R R R K
--OH ~ o= ~ = ~=O + ~10~ OH
R R R R R F~ RR R
Alkylphenol Diphenoquinone Biphenol
OH o O OH OH
~R R~;~ ~ Rn R
R R R R R
wherein R is either hydrogen, alkyl, alkoxy, or another substituent
known in the art.
. Similarly, polyphenoxy ethers are prepared by carbon-
loxygen coupling in accordance with reactions such as the following
.- Igeneral reaction:
OH -> ~ ~ O ~
Alkylphenol Polyphenoxy ether
wherein R is as defined above and n is an integer. -
A variety of materials, including metals and various
salts and complexes thereof, have previously been disclosed as
~seful in promoting the oxidative coupling of alkylphenols. Thus,
J~S:rac ~.S. Patent 2,785,188 issued to Coe, discloses that copper powder
1258-~
_ 3 _
1~
1~ ~071179
may be utilized to prepare diphenocluinones from 2,6-dialkyl-4-
halophenols. Similarly, various copper salt:s and combinations or
complexes prepared from copper salts and a variety of nitrogen-
containing compounds have been disclosed as useful in the prepara-
tion of both diphenoquinones and polyphenoxy ethers. These include,
for example, cupric salts of primary and secondary amines (U.S.
3,306,874 issued to Hay); cupric salts of tertiary amines (U.S.
3,306,875 issued to Hay and U.S. 3,134,753 issued to l~wiatek);
cupric complexes of pyridine (U.S. 3,219,625 and U.S. 3,219,626
both of which were issued to Blanchard et al.) and a mixture of a
cupric halide or a cupric carboxylate and a tertiary amine (U.S.
3,384,619). Additional catalysts prepared from cuprous or cupric
salts and amines have been disclosed as, for example, in U.S.
3,544,516; U.S. 3,639,656; U.S. 3,642,699 and U.S. 3,661,848, all
of which were issued to Bennett and Cooper. Finally, U.S.
3,210,384 issued to Hay discloses the use of complexes of a basic
cupric salt and a nitrile or tertiary amide and U.S. 3,549,670
issued to Spousta et al. describes the use o~ a copper or copper
alloy catalyst and a nitrogen base. The use of cupric salts of
carboxylic acids as the oxidizing agent in an oxidative coupling
reaction is also disclosed in the art. See, in this regard,
U.S. 3,247,262 issued to Xaeding.
The use of manganese and cobalt compounds has also
l been disclosed in U.S. 3,337,501 issued to Bussink et al. and
; U.S. 3,573,257 issued to Nakashu et al.
A variety of basic compounds have also been employed in
oxidative coupling reactions. In many of these syste~s, such as
JMS:rac those disclosed in U.S. 2,905,674 issued to Folbey and in U.S.
1258-~ - 4 -
. I
. 1.
1~71~7'~
~2,785,1~8 issued to Coe, the functioil of the alkaline material was j
to react with an acidic componen~L, such as IICl, liberated duri
¦the course of the reaction and, therefore, a stoichiomctric an-lount
of the base was used.
However, there is no disclosure or suggestion in the
rior art that metal complexes of aminocarboxylic or aminosulfonic
acids would be useful in these oxidative coupling reactions.
It should also be noted that all oE the previous methods
f preparing coupled products of alkyl or alkoxy substituted
henols or naphthols have required the use of either organic
¦solvents or stoichiometric amounts of organic reagents. There has
ot previously been available a catalyst system useful in the
reparation of carbon-carbon coupled phenols and naphthols in an
queous reaction medium. Also, with most of the prior art systems
the resulting product or products were determined by the particular
jcatalyst employed and could not easily bc controlled. Thus, there
~as not been available a system which could be modified to produce l
either the biphenol or diphenoquinone derivative, the stilbene 1,
quinone or bisphenol or the dinaphthenoquinone or binaphthol
irectly from the reaction mixture.
¦ In aeeordance with the present invention, it has been
jfound that certain substituted phenols, l-naphthol and substituted
- ~-naphthol may be oxidatively eoupled in an aqueous medium if there
is employed a eatalytie amount of a metal eomplex of an amino-
carboxylic acid or an aminosulfonic acid. Further improvements
have been discovered when an alkaline material is included with the
metal complex. For example, it has been found that the type of
JMS:rac product which is produced can be eontrolled by the amount of metal j1258-A
. I
. ,
.
' . .
1071179
cornplex or alkaline rnaterial employed in the process. By com-
parison, the prior art processes have a number of d;sadvantages
f~hich have restricted their utility. These include (a) the
requirement that the reaction be conducted in an or~anic solvent,
~(b) the fact that the primary product produced is often the poly-
phenoxy ether, and (c) the inability to form the biphenol, bis-
henol or binaphthol derivative directly WitilOUt requiring that
this material be produced by a subsequent hydrogenation of the
diphenoquinone, stilbene quinone or dinaphthenoquinone respect-
fully, prepared in the oxidative coupling reaction.
SU~ IARY OF TliE INVENTION
In accordance with the present invention it has been
found that the use of a catalytic amount of a metal complex
~of an aminocarboxylic acid or an aminosulfonic acid as is herein-
after defined results in an improved process for the preparation
,of carbon-carbon coupled products of alkylphenols, alkoxyphenols or
l-naphthols via the oxidative coupling of said phenols or naphthols
DESCRIPTION OF T~IE PR~ FERRED EIIBODIMENTS
As mentioned above, in accordance with the present
invention condensation products resulting from the oxidative cou~-
~ing of phenols and naphthols are prepared, in an aqueous medium,
Iby contacting an aqueous solution of the phenol or naphthol with
joxygen or an oxygen-containing gas in the presence of a metal
complex of an amino-carboxylic acid or an aminosulfonic acid.
~he phenols or naphthols and metal complexes which may be utilized
~re critical to the present invention and are described in detail
J~SS:rac below.
1258-~ - 6 -
.. ~1 , . I
,
I
1071~79
Phenols/Naphtl~ols
The phenols which may be employed in carrying out the
present invcntion include both alkylphenols and alkoY.yphenols. Il
The specific phenols which may be utilized are described in detail !
below.
The alkylphenols which may be utilized are defined as
any alkylphenol having at least two alkyl substituents and only
one unsubstituted position ortho or para to the hydroxyl group.
In other words, the phenols must have at least two alkyl sub-
stituents and the substituents must bc in the ortho, ortho (2,6 in
the formula below) or ortho, para (2,4 in the formula below)
ositions. These phenols are frequently referred to by the position
f the alkyl substituent or substituents on the benzene ring as
set forth in the following formula:
I ~
Ho~ever, in the process of the present invention, when an ortho,
para substituted phenol is used, at least one of the alkyl groups
in the ortho (2) or para (4) position must be a tertiary alkyl and
; when an ortho (2), ortho (6) substituted phenol is used only one
of the ortho substituents may be a tertiary alkyl. In addition
~to dialkylphenols, tri- and tetra~ substituted materials may also
be utilized provided that the substituents in the ortho and/or
` J~lS:rac ipara positions satisfy the criteria set forth above.
1258-A - 7 -
..
... . . . I
.
10~
Thus, the alkylphenols will have one of the following
formulas: OH
R6 ~ ~_~, R2
wherein R2 and R6 are alkyl provided that only one of said alkyl
groups may be a tertiary alkyl and R3 and R5 are hydrogen or alkyl.
OH
wherein R2 and R4 are alkyl provided that at least one of said
alkyl groups is a tertiary alkyl and R3 and R5 are hydrogen or
alkyl.
As used herein, the term alkyl refers to any monovalent
radical derived from a saturated aliphatic hydrocarbon by removal
of one hydrogen atom therefrom. The term includes both straight
chain and branched chain materials containing from 1 to about 12
carbon atoms. Preferred results are achieved with alkylphenols
wherein the alkyl substituent contains from 1 to about 5 carbon
atoms.
The alkyl substituents are referred to herein as
primary, secondary or tertiary alkyl depending upon the greatest
number of carbon atoms attached to any single carbon atom in the
chain. Thus, a primary alkyl has up to 1 carbon atom attached to
any single carbon atom as in methyl, ethyl, n-propyl and n-butyl.
- . ~ . .
1071~79
secondary al~yl has two carbon atoms attached to a single carbon
atom as in isopropyl, isobutyl and secondarybutyl. ~ tertiary
alkyl has three carbon atoms attached to a single carbon atom as
.in tertiarybutyl.
Condensation products of any alkylphenol coming within
the above-mentioned de~inition may b~ prepared in accordance with
the present invention. As is apparent from that definition, the
alkylphenols include dialkylphenols, trialkylphenols, and tetra-
alkylphenols. Specifically, the phenols which may be utilized
include the followiny:
ortho, para substituted phenols including 2,4-dialkyl-
phenols, 2,3,4 trialkylphenols, 2,4,5 trialkylphenols, and 2,3,4,5
tetraalkylphenols wherein the alkyl groups are either methyl or a
primary, secondary, or tertiary alkyl provided that at least one ~ -
of the alkyl groups in either the 2 or the 4 position is a tertiary
. .
alkyl, and
ortho, ortho substituted phenols including 2,6-dialkyl-
phenols, 2,3,6 trialkylphenols and 2,3,5,6 tetraalkylphenols
wherein the alkyl groups are either methyl or a primary, secondary,
. or tertiary alkyl provided that a~ least one of the alkyl groups
in either the 2 or the 6 position is either a primary or secondary .
alkyl.
R~presentative ortho, para substituted phenols which
may be used include, for example, 2,4-ditertiarybutylphenol,
2-methyl-4-tertiarybutylphenol, 2-tertiarybutyl-4-methylphenol,
2,4-ditertiaryamylphenol, 2,4-ditertiaryhexylphenol, 2-isopropyl-
4-tertiarybutylphenol, 2-secondarybutyl-4-tertiarybutylphenol,
JMS:rac 2-tertiarybutyl-3-ethyl-4-methylphenol, 2-octyl-3-dodecyl-4-
1258-A ~ _ g _
'l~)71179
tet:riarybutylphenol, 2,5-climethyl-4-tertiarybutylphenol, 2-tertiaryj-
butyl-~,5 dioctylphenol an~ 2-methyl-3-e~llyl-~-tertiarybutyl-5-
nonylphenol.
Representative 2,6-dial~ylphenols ~ortho, ortho
substituted) include, for example, 2,fi-xylenol, 2-methyl-6-butyl-
phenol, 2,6-diisobu~yl phenol, 2-octyl-6-methyl phenol, 2-isobutyl-j
6-dodecyl phenol, 2-ethyl-6-methyl phenol, 2,6-dodecyl phenol,
2-methyl-6-tertiary-butyl phenol, 2,6-diisopropyl phenol, and
2-cyclohexyl-6-methyl phenol. In this regard, it should be I -
mphasized that 2,6-dialkylphenols ~herein both alkyl suhstituents
are tertiary alkyl groups may not be employed in accordance
with the present invention. This is contrary to many of the
eachings in the art which indicate that 2,6-ditertiaryalkyl-
henols such as 2,6-ditertiarybutylphenol are the most easily
xidatively coupled of the phenoJs.
¦ Representative 2,3,6-trialkylphenols which may be
tilized in accordance with the present invention include, for
~xample, 2,3,6-trimethyl phenol, 2,3,6-triethyl phenol, 2,6-di-
ethyl-3-ethyl phenol, 2,3-diethyl-6-tertiary-butyl phenol, 2,3,6-
ridecyl phenol, and 2-octyl-3-decyl-6-dodecyl phenol.
Representative 2,3,5,6-tetraalkylphenols which may be
tilized in accordance with the present invention include, for
example, 2,3,5,6-tetramethyl phenol, 2,3,5-trimethyl-6-tertiary-
butyl phenol, 2,3,6-trimethyl-5-tertiary-butyl phenol, 2,3-dimethyl-
5,6-diethyl phenol, 2,3,5,6-tetradodecvl phenol, and 2-methyl-3-
ethyl-5-isopropyl-6-butylphenol.
When an ortho, para substituted alkylphenol is employed
the coupling reaction proceeds in accordance with the follo~ing
~MS:rac reaction resulting in the o, o' couL~led pro(luct.
1258-A
- 10
ll
1071~79
0~1 Oil 0~1 0 0
n R~RK~ R ~ R ~ R
R R R R R
Phenol Biphenol Diphenoquinone
In this reaction R represents hydrogen or an alkyl group as definec
above depending upon whether a di, tri, or tetra substituted al};yl-,
phenol lS utilized.
Similarly, with the ortho, ortho substituted
alkylphenols, the reaction results in the p, p' coupled product
in accordance with the following reaction wherein R is hydrogen
r alkyl depending upon which of the above-mentioned alkylphenols
s used as the starting material.
R R R R R R R R R R
- OH-~ o= ~ =~ ~ =o +H~
R R R R R R R R R R
Alkylphenol Diphenoquinone Bipnenol
It has also been found that certain alkoxyphenols may be
employed in the process of the present invention. These include
2,6 disubstituted phenols wherein at least one of the substituents
is an alkoxy group containing up to about six carbon atoms such
; as methoxy, ethoxy, propoxy, butoxy and pentoxy. In addition to i
the 2,6 dialkoxyphenols, 2-alkyl-6-alkoxyphenols, wherein the
alkyl groups are as defined above for the alkylphenols, may be
utilized. As used herein the term alkoxyphenols is intended to
include both types of compounds. These compounds may be reprc-
JMS:rac ented by the following general formulas:
125~
' I ~
. I`.
107~179
. . 1,
o~ o~
. ~ R RO _ ~ OR
wherein R is an alkyl group as defined above for the alkylphenols
and OR is an alkoxy group. As above, R may be either methyl or a
primary, secondary or tertiary alkyl and mav contain from 1 to
about 12 carbon atoms and preferably contains from 1 to about 5
carbon atoms. Representative alkoxyphenols which may be utilized
include, for example, 2,6-dimethoxyphenol, 2,6-diethoxyphenol,
2,6-dibutoxyphenol, 2-methoxy,6-pentoxyphenol, 2-metllyl-6 methoxy-
phenol, 2-decyl-6-butoxyphenol and 2-ethyl-6-propoxypllenol.
When these phenols are utilized ~he reaction proceeds i
¦ accordance with the following representative reaction resulting
- in the p, p' coupled material.
OR OR OR OR OR
HO--~ > O =~=~=O+HO~- OH
OR . OR OR OR O
Alkoxyphenol Diphenoquinone Biphenol
~ lixtures of 2 different phenols may also be utilized.
When this is done, there generally results a mixture of three
different materials. Two of these are the products of the oxida-i
ti~e coupling of one mol of one of the phenols with a second mol
of the same phenol. The third product is that resulting from the
oxidative coupling of one mol of the first phenol with one mol of
JMS:rac the second phenol. The products may be separated prior to use.1258-A ~- 12 -
. ' 'I
. I .
! ! : :
'
~ 107~79
Fina]ly, l-naphthol and subc;tituted ]-naphthols having
at least 1 unsubstituted position ortho or par~ to the hydroxyl
roup may be employed. Tlle pre~erred naphtllols which may be
coupled in accordance with the present invention are represented
by the following general formula:
R8 011
. R7 ~ 2
herein
R2, R3 and R4 are hydrogen, alkyl containing from 1 to
5 carbon atoms, or alkoxy containing from 1 to 6 carbon atoms,
provided that either R2 or R4 must be hydrogen and, preferably,
both P~2 and R4 are hydrogen; and
R5, R6, R7 and R8 are hydrogen, alkyl containing from
1 to 5 carbon atoms or alkoxy containing from 1 to 6 carbon atoms
provided that tertiary alkyl or alkoxy groups may not be attached
to adjacent carbon atoms of th~ naphthalene molecul`e.
~ epresentative naphthols which may be utilized include,
for example, l-naphthol, 2-methyl-1-naphthol, 2,3-dimethyl~
¦naphthol, 4-ethyl-1-naphthol, and 2-methoxy-1-naphthol.
When a naphthol is employed, the coupling reaction takes
place in accordance with the following general reactions depending
upon the reactive positions -- i.e., those either ortho or para
to the hydroxy group -- available. Thus, if R2 is hydrogen and
1258-A R4 is alkyl or alkoxy - 13 -
i' ' ' '
. ,.
.
1(~7~179
l l
011 011 ~;
C~ '~+;~ ' J=~ J
P~4 R4 4 R~ R4
2,2-binaphthol 2,2-dinaphthenoquinone
Similarly, if R4 is hydrogen and R2 is alkyl or al~oxy, the
products are the 4,4 binaphthol and the 4,4 dinaphtheno-quinone.
When both R2 and R4 are hydrogen the products may~e a mixture of
the 2,2; 2,4 and 4,4 binaphthols and dinaphthenoquinones.
. 1,
Metal Complex
As mentioned ahove, in accordance with the present
invention, the catalyst system compriscs, as an essential compo-
nent thereof, a metal complex of an amino acid. Representative
acids which may be used in said complexes include both amino
carboxylic acids, i.e., those conventionally referred to simply
as amino aclds, and amino sulfonic acids. Both of these are some-
times referred to hereinafter simply as amino acids.
In accordance with the present invention it has been
found that both primary amino acids, i.e., those containing an
NH2 group, secondary amino acids, i.e., those containing an NHR
group and tertiary amino acids, i.e., those containing an -NRR ¦ -
group may be employed in the catalyst system of the present
invention. Representative amino acids which may be utilized
include those selected from the following group: alpha-amino-
J~lS:rac carbo~ylic acids, alpha-aminosulfonic acids, mono-N-substituted
1258-A
- 14 -
, ~ ~
~0~1179
alpha aminocarboxyl1c acids, N,N-dialkyl ~ninocarhoxylic acids,
mono-N-substitutcd alpha aminosulfoIlic acids, N,N-dialkyl amino-
sulfonic acids, mono-ortho arnino aromatic acids, and beta amino 1
carboxylic acids.
Alpha aminocarboxylic acids, i.e., those in which the
carboxyl and amino groups are attached to the same carbon atorn,
may be represented by the following general formula:
H
R-C-COOII
NH2
Representative alpha aminocarboxylic acids which may be employed
include aliphatic, aromatic, and hydroxy-amino aclds. Specific
compounds which may be utilized include, for example, those given
in the following list wherein R in the above formula is as
identified in said list.
: ?
l N~ME R
1 - !
.¦ Glycine H- ,
'` . I
Alanine CH3- ! :.
..
-Aminobutyric acid CH -CH -
J~13 rac Novaline CH3-CH2-~H2-
. ,'
: !
:. ,.
. .
~71~9
¦N~ME R
Valine 3 ~ C~l
CH3 /
Norleucine CH3-C~l2-cH2-c~2
Isoleucine ,
C2H5
Serine Ho-CH2-
CH H
eucine 3
~ C - CH2- ~
omoserine HO-CH2-C~
lsPartic Acid EIoOC-CH2-
I . ~ l
f lutamic Acid HooC-C~12 -CH 2 ~ .
l I
onylalan~ n ~ ~ C~12
~yrosine 110--~ C~12-
3ihydroxyphenylalanine Ho - ~ CH2-
J~ rac
1258-A ~¦ - 16 -
~ - , I
. :' . .: .' :." ~'
. .
:: . .
~`` 1 ~(~71179
NAMF
3-io~otyrosine ~ 2
~3,5-diiodot} osine HO _ ~ CH2 -
~¦3 5-dibromo rosine Er
3,5,3'triiodothyronir.e HO - ~ -O ~ CH2-
' ~10-~0~ C~
Thyroxine I I 2
¦Ornithine H N-CH2-CH2 C 2
iLysine H2N-CH2-CH2 CH2 2
~ OH
¦Hydroxylysin N2N-C~2-C~-c~2 C 2 , ,~
Cysteine HS-C~12-
30mooysteine llS-C~I -CH -
Methionine 3 2 2
JMS:rac - 17 - .
1258-A . .
7~179 ll
N~ R
_ _ .
' NH2
Cystine 2 2
P~hydroY.y phenyl glycine ~lo~
¦¦AQparagir e H2NOC-CH2-
Glutamine - ~12NOC-CH2-CH2-
P~osphoserine H203PO-CH2-
~histidine N N~l 2
~ypitophar [~ ca
¦ Rrg iIli~l e H~7=C- N - CH - CH 2 -Ca 2 -
itrulline o=C~NH
NH--CH2-C~12-CH2-
~ lp~a aminosulfonic acids -- i.e., those in which both
t~e ~ulfonyl and ami no groups are attac~cd to the s~le car~on
~MS:rac atom -- may be represented by the following general formula: -
12~
- 18 -
~ ~q~ I
c ~ li
_~ 1(~71179
. Il I
R-C~SO31!
N~l 2 '
Representative alpha aminosulfonic acids, wherein R is hydrogen or~
an alkyl group which may be employed are given in the following
list:
N~IE R
amino-methane sulfonic acid H
amino-ethane sulfcnic acid C1~3-
amino-hexane sulfonic acid CH3CH2C~2cH2
Ortho amino aromatic acIds include benzene and naphtha-
lene derivatives wherein the amino and acid substituents are on
adjacent carbon atoms. These materials are represented by the
following general forrnulas:
i ~ R or ~
wherein R is either -COOH or -SO3H. Representative compounds
which may be utilized include the following:
o - amino benzoic acid,
o - amino benzene sulfonic acid,
. . l-amino-2-naphthoic acid,
2-amino-3-naphthioc acid,
l-amino-2-naphthalene sulfonic acid,
. 2-amino-l-naphthalene sulfonic acid, and
JI~S:rac 2-amino-3-naphthalene sulfonic acid.
1258-A . - l9 -
071179
~ .
N-substituted alpha ~uninocarboxylic acids may also be
employed in the present invention. These compounds are represented
by the following general formulas:
(a) ~1
R-C-COOH
NHR'
(b) H
R'' -C-COOH -
¦ NH
! IRepresentative materials having formula (a) above include alkyl,
acyl and aryl substituted compounds -- i.e., those in which R' is
one of said groups. Examples of these compounds are given in the
following list: ~ ¦
N~ R R'
_ _
N-acetylglycine H 3
p-methylglycine H CH3-
- ~-phenylglycine H ~
glycylglycine H H2N-CH2-CO-
lutathione H NH2 H O
HOOC-CH-CH2CH2-C-N-CH-C-
.` . , CH2SH
Examples of compounds coming within formula (b) above
include the following, wherein R" is a hydrocarbon or substituted
ydrocarbon radical containing sufficient carbon atoms to result
in a compound containing a stable ring structure -- i.e~, generally¦
JMS:rac about 3 carbon atoms.
1258~ - 2~ -
., . '
. 1.
., .
:
"' ~ . '
I ~071~79
jN~MR R
proline 2 2 2
hydroxyproline -CH2-C~-C~I2-
. OII
pyrrolidone carboxylic acid O
C 2 C 2
N,N dialkyl alpha aminocarboxylic acids wherein the
lkyl groups contain from 1 to about 12 carbon atoms and pre-
ferably from 1 to about 5 carbon atoms may be utilized. Repre- ¦
entative compou~ds include, for example, N,N dimethylglycine,
N-methyl-N-ethylglycine and N,N didodecylglycine.
N-substituted alpha aminosulfonic acids having one of
the following general formulas wherein R' and R" are as defined
~bove for the N-substituted alpha aminocarboxylic acids and R is
~ydrogen or an alkyl group may also be emploYed. I
(a) ~- : H
R-C-S03H .
. NHR'
. (b) H
C-~03H
NH -
N,N dialkyl alpha aminosulfonic acids wherein the alkyl
roups contain from 1 to about 12 carbon atoms and preferably
rom 1 to about 5 carbon atoms may also be emplo~ed. Repre-
¦ entative compounds include those having the following general
JMS:rac I ormula
1258-~ - 21 -
r
`~ ` ~07~179
~ I
R-C-S03}~ ¦
N
R' R'
wherein R' is an alkyl yroup.
Finally, heta aminocarboxylic acids -- i.e., those in
which the carboxyl and amino ~roups are attac11ed to adjacent
carbon atoms, may also be utilized. These acids are represented
by the following general formula:
.- . I
' R-C-CH2-CH
Representative beta amino acids wherein R is hydroaen,
alkyl or aryl which may be utilized include the following:
N~ ~ R
~Beta ~lanine H
Beta am1no but~ric acid CH3 `
- Beta am1no phenyl propion1c acid ~
Prior to use in the present invention the amino acids
are converted to a metal comrlex thereof. ~s used herein the term
metal complex refers to the product obtained by reacting a source
of the desired metal ion with an aminocarboxylic or an amino-
sulfonic acid. With the divalent metal ions emplo~ed in preparing
~the complexes used in carrying out the present invention, it is
preferred that equivalent amounts of metal ion and acid be
JMS:rac reacted -- i.e., about two mols of acid per mol of metal ion. In
1258-A ~ - 22 -
. . ' 11
',
~071179
accordance with the present invention it has been found to be
critical to the preparation of carbon-carbon coupled products that
either a cupric, cobaltous, manganous or nickelous complex of the
acid be employed.
These complexes may be prepared in any manner and the
preparation thereof has not been found to be critical to the
present invention. The following three methods have generally
been employed but other methods which will be readily apparent
to those skilled in the art from the description of the invention
given herein, may also be utilized.
First, equivalent amounts of the aminocarboxylic or
aminosulfonic acid and a source of cupric, cobaltous, manganous or
nickelous ions may be combined in a suitable medium such as water
and reacted to form the complex. If a copper, cobalt, manganese
or nickel salt is employed, such as cupric acetate, an amount of
a basic compound sufficient to neutralize the acid generated
during the course of the complex forming reaction should be added.
Similarly, if the amino acid used is in the form of an amine salt
such as the hydrochloride, an amount of a basic compound sufficient
to neutralize the acidic portion should be utilized. As used in
this section, a basic compound is any material an aqueous solution
of which has a pH above 7. Although not essential, it is pre-
ferred to employ as said basic compound one of the alkaline
materials described below. The complex is prepared by simply
stirring the solution for a period of time. If desired, heat may
be applied to accelerate formation of the complex.
- 23 -
-
117~
Alternatively, the amino acid and the source of the
metal ion may simply be combined and added to the reaction
mixture wherein the complex of the amino acid is formed. When
this is done any basic compound required to neutralize any acidic
by-products o~ the complex forming reaction is also added di-
rectly to the reaction mixture.
Finally, the amino acid, source of metal ion, and any
required basic compound may be added separately to the reaction
medium and the complex formed in situ. As menti`oned above, the
method by which the metal complex is prepared has not been found
to be critical to the present invention. However, preferred
results have been achieved when the source of metal ion and the
amino acid are combined prior to addition to the reaction medium.
The amount of metal complex employed has not been
found to be narrowly critical to the process of the present inven-
tion. However, it is preferred to employ at least .02 mmols of
the complex per mol of phenol or naphthol. If less than this
amount is used, the reaction is slower and the yields are low.
Similarly, the maximum amount of complex employed is not generally
greater than about 200 mmols of the complex per mol of phenol
or naphthol. At amounts much in excess of this the cost of the
catalyst may result in an uneconomic system.
Although any of the above-mentioned metal complexes
may be used, preferred results have been achieved with the cupric
complexes of alpha-aminocarboxylic acids. Especially preferred
results are achieved when cupric ~lycinate is employed as the
metal complex.
- 24 -
. .
' ;,
- . . .
~07~i79
As mentioned above, an advantage of the catalyst system
and of the process of the present invention is that the reaction
can be carried out in an aqueous medium instead of an organic
solvent as has been used in prior art systems. However, it has
not been found to be critical to the present invention to employ
a water soluble metal complex. Thus, materials which are insoluble
in water as well as those which are soluble may be utilized.
Although not essential to the present invention, an
alkaline material as defined below may also he included in the
]0 reaction mixture. Preferred results have been achieved when such
a material is employed.
Alkaline Material
In accordance with the present invention, there may also
be included in the catalyst system an alkaline material. It has
- been found that the use of an alkaline material in the present
system increases the conversion to carbon-carbon coupled products
and decreases the conversion to carbon-oxygen coupled products.
The use of such a material also increases the rate of the oxida-
tive coupling reaction, increases the total yield of product,
and decreases the amount of the metal complex which must be
utilized.
The alkaline material useful in achieving these improved
results is selected from the group consisting of alkali metal
hydroxides, alkali metal carbonates, and alkali metal bicarbonates.
The alkaline material may be added either as a single compound
or as a mixture of compounds. Representative materials which
- 25 -
1~71179
may be employed include, for example, sodium hydroxide, potas-
sium hydroxide, lithium hydroxide, sodium carbonate, lithium
carbonate, sodium bicarbonate, rubidium carbonate, rubidium
hydroxide, cesium bicarbonate, and cesium hydroxide.
The amount of alkaline material employed has not been
found to be narrowly critical. However, preferred results are
achieved when the amount of said material is equal to at least
about 6 mmols per mol of phenol or naphthol. At this amount it
has been found that the rate of the reaction is acceptable for
most operations. Similarly, except in the case of the 2,4,6 tri-
substituted phenols which are discussed in detail below, the
maximum amount of alkaline mater;al is preferably not greater
than about 100 mmols per mol of phenol or naphthol. In this
regard it should be noted that it is preferred to maintain the
pH of the reaction mixture at from about 6 to about 10 during
the course of the reaction and it is again emphasized that addi-
tional alkaline material may be required to neutralize any acidic
components introduced into the reaction mixture during the for-
mation of the metal complex. The amount of material employed
for this purpose should be sufficient to neutralize said acid
and is in addition to the amount of alkaline mater;al mentioned
above in this section.
Besides the selective production of carbon-carbon
coupled products, an additional advantage of the catalyst system
of the present invention is the ability to control the type of
carbon/carbon coupled product produced. Thus, it is possible to
prepare selectively either diphenoquinone or biphenol or dinaph-
thenoquinone or binaphthol in accordance with the present inven-
tion. This result is achieved by controlling the amount of
- 26 -
~ l~
~71~79
alkaline mater~al and/or metal complex included in the system.
Generally, as the amount of alkalinc material or metal complex
is increased, the pcrcentage of diphelloquinonc or dinaphtheno-
quinone in the resulting product also increases. ~lso, it has
been found that as the reaction temperature or oxyyen pressure
¦is increased the percentage of quinone-type product decreases.
~ s mentioned above, an advantage of tlle p~ocess of tlle
present invention is that it makes it possible for the oxidative
coupling reaction to be carried out i31 an aqueous medium. ~he 1,
amount of water emplGyed has not been found to be critical to
the present invention and any amount of water which will permit
the reaction mixture to be stirred during the course of the
reaction may be employed. It should also be noted again that
it is not essential that the various components be soluble
in water and the term aqueous mixture as used herein is intended
to include solutions, slurries, suspensions and the like.
The components of the reaction mixture may be combined
¦in any suitable manner. Thus, the phenol or naphthol, metal
¦complex, alkaline material, if any, and water may be combined in
¦any order in a suitable reaction vessel. In a preferred method,
¦the phenol or naphthol and metal complex are combined in water in !
a suitable reaction vessel, the mixture is heated to from 50~. to
60C. and an aqueous solution of the alkaline material is added.
In modifications of this procedure the alkaline material may be
added prior to heating or the metal complex and alkaline material
may be combined prior to addition to the reaction mixture.
The reaction mixture comprising phenol or naphthol,
water, metal complex, and alkaline material, if any, is contacted
ith a suitablc oxidizing agent to convcrt the phenol or napllthol
JMS:rac to the desired product. Oxidizing agents which ma~ be emplo~ed ini
1258-~ ~ - 27 - I -
1 1~71179
Icarrying out the present invention inclucle oxygen either alone or
as an oxygen-containing gas, such as air. The oxygen may be intro
duced into the reaction mix~ure ei~her directly as oxygen gas or
as an oxygen-generating material such as ozone, hydrogen peroxide,
or an organic peroxide. l~he amount of oxygen utilized should be
sufficient to convert all of the phcnol or naphthol to the dcsircd
product and~to assure that sufficient oxygen is prescnt, oY.~gen
should be introduced into the reaction mixture continuously during
the course of the reaction.
Although not essential to the process of the present
invention, especially preferred results are achieved when there
is also included in the reaction mixture a surfactant. A variety I
of surfactants are well known in the art and, as used herein, the I -
term surfactant is intended to refer to organic compounds that con
tain in the molecule two dissimilar structural groups, such as
a water-soluble and water-insoluble moiety.
Surfactants are often classified, based on the hydro-
philic (water liking) group which they contain, as either anionic,
cationic, nonionic, or amphoteric. ~ny of these types of sur-
factants may be utilized. In selecting a surfactant, the only
criteria are (a) that it be inert -- i.e., one which will not
oxidize or othen~ise interfere with the oxidative coupling reaction
and (b) that it be capable of keeping the heterogeneous phases of
the reaction mixture suspended. Although it does not affect the
total yièld or quality of the product, the surfactant facilitates
stirring and removal of the product from the reaction vessel when
¦the process has been completed. A variety of surfactants which
J~SS:rac ¦may be employed are described, for cxample, in Xirk-Othmer,
1258-~ ~ - 28 -
`- 1~71179
Encyc1opedia of _ emical echnolo~y, 2nd J~dition, Volume 19,
Interscience Publishers, i~ew York, 1969 at pages 507-593. Repre-
sentative surfactants which may be emp]oyed include~ for example~
sodiu~ lauryl sulfate, sodium dodecyl benzene sulfonate, sodium
di(2-ethylhexyl)phosphate, polyoxyethylene nonylphenol, polyoxy-
ethylene octylphenol, polyoxyethylene oleyl alcohol, polyoxyethyle7e
tridecy] alcohol, glycerol monooleate, glycerol dioleate, glycerol'
monostearate, sorbitan monolaurate, sorbitan tristearate, poly-
oxyethylene sorbitan monooleate, ethylene glycol stearate,
diethylene glycol oleate, polyethyleneglycol monolaurate, polyoxy-
ethylene stearylamine, polyoxyethylene tallowamine, 2-heptadecyl-
l-(hydroxyethyl)-2-imidazoline, distearyldimethylammonium chloride,
cetylbenzyldimethylammonium chloride, lauryltrimethylammonium
bromide, cetylpyridinium chloride, N-coco-3 amino-propionic acid,
(l-carboxyheptadecyl) trimethylamminium hydroxide and l,l-bis(car-¦
I boxymethyl)-2-undecyl-2-imidazolinium hydroxide, disodium salt.
The reaction conditions -- i.e., tine and temperature --I
employed have not been found to be narrowly critical to the process
of the present invention. Preferred results have been achieved
when the reaction mixture is maintained at from about 80C. to
90C. during the course of the reaction. ~lowever, temperaturcs
above and below this preferred range may be utilized. ~t lower
temperatures the reaction rate is reduced and at tem~eratures
below about 40C. is so slow as to result in an uneconomic system.'
Similarly, when operating at atmospheric pressure, as is desirable
in some commercial operations, the practical upper limit on the
JMS:rac temperature is 100C., the boiling point of the water.
1258-A :, - 29 -
~ I .
. I
.. I
.
1~71179
The amount of time required for completion of the
reaction depends on the temperature employed and the other
variables such as the concentration of phenol or naphthol and
the amount of metal complex and alkaline material employed.
However, it has been found that, ;n general, the reaction is
completed in 6 hours or less. If the reaction is conducted at
elevated oxygen pressure, the time required will be less.
Although, as mentioned above, the process of the
present invention results primarily in the production of carbon-
carbon coupled products, there are also sometimes included inthe solids removed from the reaction mixture the following:
(a) unreacted phenol or naphthol, and (b) low molecular weight
polyphenoxy ether. The polyphenoxy ether and phenol or naphthol
may be removed by washing the solids with a solvent in which these
materials are soluble, such as an aromatic hydrocarbon -- e.g~,
benzene or a halogenated solvent -- e.g~, methylene chloride~ If
! it is desired to separate the materials from each other and from
the solvent, this may be done by distillation.
If the reaction results in the mixture of biphenol and
diphenoquinone or binaphthol and dinaphthenoquinone, these mate-
rials may be separated by any method known in the art. An espe-
cially convenient way of separating the materials is to stir the
solid product with a dilute aqueous solution of sodium hydroxide,
which has the ef~ect of converting the biphenol or binaphthol to
to the sodium salt which is soluble in water. The insoluble di-
phenoquinone or dinaphthenoquinone may then be filtered off and
the biphenol or binaphthol recovered by adding the aqueous
- 30 -
107~
solution of the sodium salt thereof ~to a dilute solution of ~n
acid sucll as hydrochloric or acetic from whic}l ~,he biphenol or
binaphthol precipitates. ~lternatively, the entire product may be
hydrogenated or chemically reduced and converted to the biphenol
or binaphthol.
When the metal-amino acid complex is insoluble in water,
it has been found that during ~-le course of the reaction the
material is in some way changed so that it dissolves in the reaction
medium. Thus, it has not been found to be necessary to employ
any special techniques to remove this material from the reaction
medium at the termination of the process. However, it is desir-
able to remove any residual metal remaining in the products. This
may be accomplished by filtering off the desired product, washing
the solids with a dilute aqueous solution of a strong acid such as
hydrochloric acid to remove the metal, followed by a water wash to
ei,lo~e ~1~ hydrocilioric a~id.
¦ The diphenoquinones and/or biphenols as well as the
binaphthols and dinaphthenoquinones produced in accordance with the
¦present invention are suitable for any of the uses of these types
¦of materials which uses have heretofore been described in the art.
¦Thus, the diphenoquinones and dinaphthenoquinones may be used as
¦inhibitors of oxidation, peroxidation, polymerization and gum
formation in gasolines, aldehydes, fatty oils, lubricating oils,
ethers and similar compounds. ~s mentioned in U.S. 2,905,674
issued to Filbey, the diphenoquinones may also be hydrogenated,
JMS:rac employing conventional techniques, to yield the corresponding
1258-A
- 31 -
:~ 1,
'
. . I
-~ l
~71179
biphenols. Tl-e biphenols may be employed as stabilizers in
gasoline and other petroleum products as described in U.S.
,479,948 issued to Luten et al. ~ ¦
The catalyst system of this invention may also be
employed to prepare coupled products o~ al~ylphenols wherein all
of the positions ortho and para to the hydroxy group are sub-
stituted and the substituent para to the hydroxy group is either
a primary or secondary alkyl group containing 1-5 carbon atoms.
~hese alkylphenols may be represented by the follo~ing general
formula: 6 ~ 2
wherein 4
R3 is hydroge~, a primary, secondary or tcrtiary alkyl
or an alkoxy group;
R4 is a primary or secondary alkyl group containing
from 1-5 carbon atoms, and
R2 and R6 are a primary, secondary or tertiary alk~l or 1
an alkoxy group provided that only one of said substituents may be !
a tertiary alkyl-
Representative compounds which may be employed include,for example, 2,4,6-trimethyl phenol; 2,6-di-secondary butyl-4-
methyl phenol; 2-methyl-6-t-butyl-4-methyl phenol; and 2,3,4,6-
JMS:rac tetramethyl phenol.
1258-A ~ - 32 -
'
. .
, .
~ ~071~79
When one of these alkylphenols is employed the reaction
proceeds in accordance with the following general xeaction to
produce the stilbcnequinone or bisphenol derivative. These
materials are useful in the s~:e applications set forth above for 1
the diphenoquinones, dinaphthenoquinones, biphenols and binaphthols'.
R R R R R R
~ ~ R~ o = ~ = R - R = ~ ~ +
alkylphenolstilbene quinone
HO ~ R - R ~ OH
bisphenol
In carrying out this reaction, the same procedures and
conditions are employed as those given above for the other alkyl-
phenols, alkoxyphenols and naphthols. However, with these
¦ particular phenols it has been found that the preferred amount
of alkaline material employed is equal to at least about l mol
per mol of phenol. When less than this amount is utilized the
total conversion as well as the yield of carbon-carbon coupled
product are reduced.
In order to describe the present invention so that it
may be more clearly understood, the following examples are set
forth. These examples are set forth primarily for the purpose of
illustration and any enumeration of detail contained therein
should not be interpreted as a limitation on the concept of the
JMS:rac present invention.
1258-~
. , ' .
. .
: , :
`. . ' ~ ~
~ ' ~07~179 ''
As uscd hcrein, thc tcrm mol pcrcent refers to: !~ .
mols of product (actual) X 100
¦ mols of produc~ (~heorctica])
Ultrawet~ soft r~fers to sodium ~odecyll~enzene ?
sulfonate.
~ EXAMPLE 1
Into a first flask there were added:
0.40 grams t2 mmols) of cupric acetate monohydrate,
0.30 grams (4 mmols) of glycine, and
50 ml of ion exchanged water.
Into a 500 ml creased Morton flask, fitted with a
gas addition tube, a condenser, a thermometer, and a sLirrer
capable of operating at speeds iIl the range of from about 8,000
to about 10,000 rpm, there were added: I -
48.8 grams (400 m~lols) of 2,6-xylenol, and
150 ml of ion exchanged water.
To the resulting slurry there was added the copper/
. qlycine composition prepared above. The resulting mixture was
stirred under o~ygen and heated to a temperature of 50C. There
~as then added 8.0 ml of a 1.0 Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,
he reaction was flushed with nitrogen and cooled to a temperature
JMS:rac f 20C.
1258-A
` ~ 34 -
- * Registered Trade Mark
''` '' ' '~~ ~ ~
The reaction mixture was filtered and the solids washed
with water. A sample of the solid was removed, dissolved in
acetone and analyzed by gas-liquid chromatography. The analysis
indicated that 1 mol percent of the 2,6-xylenol was unreacted.
The dried solid weighing 43.8 grams was washed twice
with 100 ml of benzene to remove 2,6-xylenol and polyphenoxy ether.
The resulting solid was dried at 60C. Analysis of the product
indicat~d a yield of tetramethyl diphenoquinone equal to 44.2 mol
percent. The yield of tetramethylbiphenol was calculated as
34.7 mol percent.
EXAMPLE 2
Into a first flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.41 grams (4 mmols) of 2-aminobutyric acid, and
25 ml of ion exchanged water.
To the resulting clear, dark blue mixture there was
added 4.0 ml of a 1.0 Normal solution of sodium bicarbonate.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultra~7et*K soft (sodium
dodecyl benzene sulfonate), and
200 ml of ion exchanged water.
- 35 -
* Registered Trade Mark
0~1179
To the resul~ing solution t1-ere ~as added lO0 ml of the
composition prcpared above. The resu]ting mix~ure was stirrcd
under oxygen and heated to a temperaturc of 50C. and there was
then added 4.0 ml of a l.0 Normal sodium bicarbonate solution.
The reaction mixture was heated to a te~perature of ~0C.
and a slow stream of oxygen was introduced. ~t the end of 6 hrs.,
the reaction was flushed wlth nitrogen and cooled to a temperature
of 250C I,
The reaction mixture was filtered, the solid was washed !
with water, and a sample of the solid was re~loved, dissolved in
acetone and analyzed by gas-liquid chromatography. The analysis
indicated that 4 mol percent of the 2,6-xylenol ~as unreacted.
The solid was air dried and washed twice with 200 ml of i
¦benzene to remove 2,6-xylenol and polyphenoxy ether. The resulting
¦black solid was dried at 60C. Analysis of the product indicated
la yield of tetramethylbiphenol equal to 24.4 mol percent and a
¦yield of diphenoquinone equal to 35.0 mol percent.
.,, . I .
! ~ EX~MPLE 3
Into a first flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate, ¦
0.47 grams t4 mmols) of DL-valine, and
50 ml of ion exchanged water.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
JMS:rac lO,000 rpm, there were added:
1258-~ - 36 -
. . . I
.
:
1,
1 ~71~L79
48.8 grams (400 mmols) of 2,6-~ylenol,
0.2 grams of Ultrawet*K soft, sodiuln
dodecyl benzene snlfonatc, and
150 ml of ion eY.changed water.
To the resulting solution there was added 100 ml of the
catalyst composition prepared above. The resultin~ mixture was
stirred under oxygen and heated to a temperature of 52C. There
was then added 8.0 ml of a 1.0 Normal sodium bicarbonate solution.,
The reaction mixture was heated to a temperature o~ 80~C.'
and a slow stream o~ oxygen was introduced. At the end of 6 hrs.,¦
the reaction was ~lushed with nitrogen and cooled to a temperature,
f 20C. -
- The reaction mixture was filtered, and the solids washed
ith water. A sample of the solid was removed, dissolved in
acetone and analyzed by gas-liquid chromatography. The analysis
indicated that ail of the 2,6-xylenol had reacted.
The solid was air dried and washed twice with 100 ml of I
benzene to remove 2,6-xylenol and polyphenoxy ether. Tlle resulting
dar~ green solid was dried at 60C. Analysis of the product
indicated a yield of tetramethylbiphenol equal to 39.3 mol percent
and a yield of diphenoquinone equal to ~5.2 mol percent.
E ~PLE 4
Preparation of Catalyst Composition
Into a reaction flas~ there were added: ¦
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.525 grams t4 mmols) of L-Leucine, and
JMS:rac 100 ml of ion exchanged water.
1258-~ ~ 37 -
l * Regis ed ~rade Mark ¦
. ~.
! I
...
I 1071179
To the xesulting slurry there was added 4.0 ml o a
l.0 l~ormal solu~ion of sodium bicarbonate resul~ g in the for1na- 1
ion of a hlue solid. The resulting ~ix~ure ~JaS diluied to ~00 ml !
with water, shaken, and heated to GO~C. ~hen this tempcrature
as reachcd, the solid still had not dissolved. The mi~ture was
cooled and bottled.
. l
Oxidative Cou~ling
Into a 500 ml creased, Morton flask fitted with a gas
addition tube, condenser, thermometer, and a stirrer capable of
perating at speeds in the range of from a~out 8,000 to about
0,000 rpm there were added:
¦ 48.8 grams (400 mmols) o~ 2,6-xylenol, and
¦ 200 ml of the catalyst composition prepared above.
The catalyst composition was rinsed in with 50 ml of
water. There was then added 0.2 grams of Ultrawet*K, soft.
¦The resulting reaction mixture was stirred under oxygen and
heated to a temperature of 50C. ~lhen this temperature was
xeached, there was added 4.0 ml of a l.0 Normal sodium bicarbonate ;
¦solution. The reaction mixture was then heated to a temperature
f 80C. and a slow stream of oxygen was introduced. At the end ,
of 6 hrs., the reaction was flushed with nitrogen and cooled to
a temperature of 20C.
The reaction mixture was filtered, a sample of the solid'
was removed, dissolved in acetone and analyzed by gas-liquid
chromatography. The analysis indicated that l mol percent of the
JMS:rac 2,6-xylenol was unreacted. }
1258-~ - 38 -
ll ~ Re ~tered Trade ~ark
,,,,,.~,,"
.. . . , .. . .. ~ . .
~ ~o7~179 '~
The solid was ai~ d~ied and washed t~;ce ~/ith 100 rn] of ~
benzene to remove 2,6-xyleno] and po]yphenoxy ether. The resulting
black solid was dried at 60C. The dlphenoquinone and biphenol
were separated by the following procedure.
37.5 grams of the solid were stirred with 1 liter of
acetone, filtered, and the solid washed with 100 ml of acetone.
The insoluble red diphenoquinone was dried and weighed 16.5 grams.
The material melted at 198C. The acetone filtrate was treated
with 1 gram of hydroxylamine hydrochloride and 2 ml of pyridine
after which it was poured into 2 volumes of water. The pre-
cipitated tetramethylbiphenol was filtered, washed with 200 ml
f water and dried at 60C. The resulting cream-colored solid
¦weighed 21.2 grams and melted at 221C. The results indicated a
¦yield of tetramethylbiphenol equal to 45.5 mol percent and a yield
¦of diphenoquinone equal to 35.6 mol percent.
EX~lPLE 5
Into a reaction flask there were added: i
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.66 grams (4 mmols) of phenylalanine, and
40 ml of ion exchanged water. '1
To the resulting slurry there was added 4.0 ml of a
1.0 Normal solution of sodium bicarbonate.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
JMS:rac 10,000 rpm, there were added:
1258-A
. I,
~ ~ 1 ~71~79
lO0 ml o~ ion cxchancJed ~:ater,
4~.8 grams (400 mmols) of 2,6-xylenol, and
0.2 yr~ms of Ultrawet ~;, soft. To the resulting mixture
there was added lO0 ml of the catalyst composition preparcd above. I
The catalyst composition was rinsed in with an additional~
5 ml of water. ~The resulting reaction mixture was stirred under
¦oxygen and heated to a temperature of S2C. ~hen this temperature
jwas reached, there was added 4.0 ml of a 1. 0 Normal sodium
bicarbonate solution. The reaction mixture was then heated to a
¦temperature of 80C. and a slow stream of oY.ygen was introduced.
At the end of 6 hrs., the reaction was flushed with nitrogen and
~cooled to a temperature of 20C.
The reaction mixture was filtered, a sample of the solid
!was removed, dissolved in acetone and analyzed by gas-liquid
¦chromatography. The analysis indicated that 25 mol percent of
the 2,6-xylenol was unreacted.
The solid was air dried and washed t~ice with lO0 ml
of benzene to remove 2,6-xylenol and polyphenoxy ether. The
resulting solid was dried at 60C. Analysis of the product
ndicated a yield of tetramethylbiphenol equal to 62.5 mol percent.
l ..
EX~IPLE 6
Into a 500 ml creased Morton flas~, fitted with a gas
addition tube, a condenser, thermometer, and a stirrer capable of
loperating at speeds in the range of from about 8,Q00 to about
J~lS:rac lO,000 rpm, there were added: 1
1258-A
- 40 -
* Registered Trade Mark
. . . I
. 1.
1071~79
48.8 grams (400 mmols) of 2,6-xylenol,
250 ml of ion exchanged water,
4.0 ml of a 1.0 Normal solution of sodium
bicarbonate, and
0.2 grams of Ultrawet*K, soft.
The resulting mixture was heated to 50C. and there
was then added 0.25 grams of cupric glutamate.
The reaction mixture was then heated to a temperature of
80C. and a slow stream of oxygen was introduced. At the end of
6 hrs., the reaction was flushed with nitrogen and cooled to a
temperature of 20C.
The reaction mixture was filtered. A sample of the
solid was removed, dissolved in acetone and analyzed by gas-
liquid chromatography. The analysis indicated that 12 mol percent
of the 2,6-xylenol was unreacted.
The solid was washed with water, dried and washed twice
with 50 ml of benzene to remove 2,6-xylenol and polyphenoxy ether.
The resulting solid was dried at 60C. Analysis of the product
indicated a yield of tetramethylbiphenol equal to 56.5 mol
percent.
The cupric glutamate was prepared in accordance with
the following procedure:
Into a suitable reaction flask there were added:
7.36 grams (.05 mol) of glutamic acid, and
200 ml of water.
There was then added approximately 50 ml of dilute
sodium hydroxide solution until the pH of the mixture was equal
to 7.5 and all of the glutamic acid had dissolved. At this time
- 41 -
* Registered Trade Mark
ll 1071 179
~~ ~there ~Jas added 4.99 grams (.025 mols) of cupric ace~ate. The
PiI decreased to 4.6 and the solutiol- turned a deep blue color.
The p~l was adjusted to 8.0 with dilutc sodi~-m hydro~.;ide. Thc
reaction mixture was stripped under vacuum and thc residue treated !
¦with a mixture of ethanol and water. The insoluble fraction was
filtexQd and dried at 80C. There resulted 5.0 grams of cupric
glutamate.
.- . '~',
EX~IPLE 7
Into a first reaction flas~ there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.34 grams (4 mmols) of L(+)ornithine hydrochloride, and~
50 ml of ion exchanged water.
To the xesulting clear, dar}; blue solution there was
~i added 8.0 ml of a 1.0 Normal solution of sodium bicarbonate.
¦ Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added: i
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet X soft, and
200 ml of ion exchanged water.
To the resulting solution there was added the catalyst
composition prepared above. The resulting mixture was stirred
; under oxygen and heated to a temperature of 50C. There was
hen added 4.0 ml of a 1.0 Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80C.
nd a slow stream o~ ox~cJen was introduced. ~t thc elld o~ 6 hrs.,
the reaction was flushed with nitrogcn and cooled to a teml~craturc
~;IS: rac of 20 C. I
1''58-~ - ~2 -
l ~ Regis ed Trade Mark
r C
''
1071179
The reaction mixture was stirred .7ith acetone, ~iltered ¦
and the solids were washed with 200 m] of ben~ene to remove
2,6-xylenol and polyphenoxy e~her. The reulting solid was dried
t 60C. Analysis of the product indicated a yield of tetrametllyl
biphenol equal to 50 mol percent.
EX~MYLE 8
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric aceta~e monohydrate,
0.72 grams (4 mmols) of lysine hydrochloride, and
50~ml of ion exchanged water.
To the resulting clear, dark blue solution there was
added 8.0 ml of a 1.0 Normal solution of sodium bicarbonate.
Into a 500 ml creased Morton flas~ ~itted with a gas
ddition tube, a condenser, a thermometer, and a stirrer capable
f operating at speeds in the range of ~rom about 8,000 to about
0,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet R soft, ana
200 ml of ion exchanged water.
To the resulting solution there was added 50 ml of the
catalyst composition prepared above. The resulting mixture was
stirred under o~ygen and heated to a temperature of 508C There
as then added 4.0~ml of a 1.0 Normal sodium bicarbonate solution.¦
The reaction mixture was heated to a temperature of 80C.j
and a slow stream of oxygen was introduced. ~t the end of 6 hrs.,j
J~lS:rac the reaction was flushed with nitroyen and cooled.
1258-~
_ 43 -
* Registered Trade Mark
. I
t
10~11~9
The solids were separated from the reaction mixture,
dried, and washed twice with 50 ml of benzene to remove 2,6-xylenol
and polyphenoxy ether. The resulting solid was dried, slurried
in water and treated with solid sodium hydroxide until a red
slurry resulted. The solid diphenoquinone was filtered and dried
at 60C. The yield was equal to 31 mol percent. The filtrate
was poured into dilute hydrochloric acid from which the biphenol
precipitated. The solid biphenol was filtered, washed with water
and dried at 60C. The yield of biphenol was equal to 18.7 mol
percent.
EXAMPLE 9
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.60 grams (4 mmols) of methionine, and
25 ml of ion exchanged water.
To the resulting clear, slurry there was added 4.0 ml
- of a 1.0 Normal solution of sodium bicarbonate.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, and
150 ml of ion exchanged water.
To the resulting solution there was added 50 ml of the
catalyst composition prepared above. The resulting mixture was
stirred under oxygen and heated to a temperature of 50C. There
was then added 4.0 ml of a 1.0 Normal sodium bicarbonate solution.
- 44 -
i
* Registered Trade Mark
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
of 20C.
The reaction mixture was filtered. The solid was air
dried and washed twice with 100 ml of benzene to remove 2,6-xylenol
and polyphenoxy ether. The resulting solid was dried at 60C.
Analysis of the product indicated a yield of tetramethylbiphenol
equal to 73 mol percent.
EXAMPLE 10
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.84 grams (4 mmols) of L(~)histidine hydrochloride, and
100 ml of ion exchanged water.
To the resulting clear, dark blue solution there was
added 8.0 ml of a 1.0 Normal solution of sodium bicarbonate.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, sodium
dodecyl benzene sulfonate, and
150 ml of ion exchanged water.
To the resulting solution there was added 100 ml of the
catalyst composition prepared above. The resulting mixture was
- 45 -
* Registered Trade Mark
~07~179
stirred under oxygen and heated to a temperature of 60C. When
the temperature reached 60C. there was added 4.0 ml of a 1.0
Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80 C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
of 25C.
The reaction mixture was filtered, a sample of the
solid was air dried and washed twice with 100 ml of benzene to
remove 2,6-xylenol and polyphenoxy ether. The resulting brown
solid was dried at 60C. Analysis of the product indicated a
yield of tetramethylbiphenol equal to 54 mol percent.
EXAMPLE 11
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.55 grams (4 mmols) of anthranilic acid, and
50 ml of ion exchanged water.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rmp, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, sodium dodecyl
benzene sulfonate, and
200 ml of ion exchanged water.
- 46 -
* Registered Trade Mark
11)71~79
To the r~sulting solutiorl there was added the catalyst
composition prepared above. The resulting mixture was stirred
under oxygen and heated to a temperature of 55C. at which time
there was added 8.0 ml of a l.0 Normal sodium bicarbonate solu-tion;
The reaction mixture was heated to a te~perature of 80C
and a slow stream of oxygen was introduced. ~t the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
of 25C.
~The reaction mixture was filtered, the solid was washed
with water and air dried. The dry solid was washed twice with
200 ml of benzene to remove 2,6-xylenol and polyphenoxy ether
and air dried at 60C. Analysis of the product indicated a yield !
of tetramethylbiphenol equal to 54.8 percent. ¦
. , ' ~ ' I
EX~PLE 12
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.44 grams (4 mmols) of amino methane sulfonic acld, and
40 ml of ion exchanged water.
To the resulting solution there was added 4.0 ml of a
1.0 Normal solution of sodium bicarbonate.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
190 ml of ion exchanged water,
48.8 gr~ms (400 mmols) of 2,6-xylenol, and
~IS:rac 0.2 grams of Ultrawet K soft.
1258-~ _ ~7 _ !
.` . . ,~
* Registered Trade Mark
.
,1
~ ~ . I
' ' . ' ~ ~ ` '
.
. ~ ~ ~
1~71179
To the resulting mi~ture there was added 60 ml of the
catalyst composition prepared above. I
The xesulting reaction mixture was stirred under oxygen j
and heated to a temperature of 55C. When this temperature was
reached, there was added 4.0 ml of a 1.0 r~ormal sodium bicarbonate
solution. The reaction mixture ~7as then heated to a temperature
of 80C. and a slow stream of oxygen was introduced. At the end
of 6 hrs., the reaction was flushed with nitrogen and cooled to a !
temperature of 20C.
The reaction mixture was filtered, a sample of the solid
was removed, dissolved in acetone and analyzed by gas-liquid
chromatography. The analysis indicated that 20 mol percent of
¦the 2,6-xylenol was unreacted.
The water-washed solid was air dried and washed twicc I -
¦with 100 ml of benzene to remove 2,6-xylenol and polyphenoxy
ether. The resulting solid was dried at 60C. Analysis of the
product indicated a yield of tetramethylbiphenol equal to 31.4
mol percent.
EXAMPLE 13
¦ Into a reaction flask there were added:
¦ 0.40 grams (2 mmols) of cupric acetate monohydrate,
¦ 0.73 grams (4 mmols) of aniline-2-sulfonic acid, and
¦ 50 ml of ion exchanged water.
To the resulting solution there was added 4.0 ml of
a 1 0 Normal solution of sodium bicarbonate
~ Into a 500 ml creased Morton flask fitted with a gas
JMS:rac addition tube, a condenser, a thermometer, and a stirrer capablc
1258-A ~ - 48 -
. I
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, and
200 ml of ion exchanged water.
To the resulting solution there was added 50 ml of the
catalyst composition prepared above. The resulting mixture was
stirred under oxygen and heated to a temperature of 53C. When
the temperature reached 53C. there was added 4.0 ml of a 1.0
Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.
the reaction was flushed with nitrogen and cooled to a temperature
of 20C.
The reaction mixture was evaporated. The solids were
stirred into 200 ml of benzene to remove 2,6-xylenol and poly-
phenoxy ether. The resulting solids were filtered, washed with
benzene, washed with water, and dried at 60C. Analysis of the
product indicated a yield of tetramethylbiphenol equal to 41 mol
percent.
EXAMPLE 14
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.36 grams (4 mmols) of N-methyl glycine, and
50 ml of ion exchanged water.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
- 49 -
* Registered Trade Mark
'-' `
~ 7~L~79
¦of operating at speeds in the range of from about 8,000 to about
10,0~0 xpm, there ~ere added: i
; 48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet ~ soft, sodium
dodecyl benzene sulfonate, and
150 ml of ion exchanged water.
To the resulting solution there was added the catalyst
composition prepared above. The resulting mixture was stirred
under oxygen and heated to a temperature of 55C. There was
then added 8.0 ml of a 1.0 Normal sodium ~icarbonate solution.
The reaction mixture was heated to a tem?erature bf 80~C.
and a slow stream of oxygen was introduced. At the er.d of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a tempcrature
of 25C.
The reaction mixture was filtered and was}Ied with water.
A sample of the solid was removed, dissolved in acetone and
analyzed by gas-liquid chromatography. The analysis indicated
that 23 mol percent of the 2,6-xylenol was unreacted.
~ he solid was air dried and ~7ashed twice with 200 ml of ,
benzene to remove 2,6-xylenol and polyphenoxy ether. The resulting
¦yellow solid was dried at 60C. Analysis of the product indicated
a yield of tetramethylbiphenol equal to 58.2 mol percent.
I
~ EXAMPLE 15
: i
lnto a reaction flas~ there were added:
0.40 grams ~2 mmols~ of cupric acetate monohydrate,
0~47 grams (4 mmols) of N-acetyl glycine, and
J~IS:rac 50 ml of ion exchangcd watcr.
1~58-A
: - 50- :
* Registered Trade Mark
, .. .... .. _ .. ... . . ..... .... ~ . . _ _ .... _._. _ ... ..
`: '107'1~'79
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, sodium
dodecyl benzene sulfonate, and
200 ml of ion exchanged water.
To the resulting solution there was added 100 ml of the
catalyst composition prepared above. The resulting mixture was
stirred under oxygen and heated to a temperature of 57C. at which
time there was added 8.0 ml of a 1.0 Normal sodium bicarbonate
solution.
The reaction mixture was heated to a temperature of 80 C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
of 20C.
The reaction mixture was filtered, and the solid was
washed with water, dilute HCl and again with water. A sample of
the solid was removed, dissolved in acetone and analyzed by gas-
liquid chromatography. A sample of an oil removed in the first -
water wash was extracted with methylene chloride and analyzed by
gas-liquid chromatography. The analysis indicated that 23.3 mol
percent of the 2,6-xylenol was unreacted.
The solid was air dried and washed twice with 100 ml of
benzene to remove 2,6-xylenol and polyphenoxy ether. The resulting
yellow solid was dried at 60C. Analysis of the product indicated
a yield of tetramethylbiphenol equal to 3 mol percent.
* Registered Trade Mark
.
1~71~79
Example 16
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.55 grams (4 mmols) of N-phenylglycine, and
25 ml of ion exchanged water~
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condensor, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet* K soft, and
200 ml of ion exchanged water.
To the resulting solution there was added the catalyst
composition prepared above. The resulting mixture was stirred
under oxygen and heated to a temperature of 50C. At that time
there was added 8.0 ml of a 1.0 Normal sodium b;carbonate solu-
, tion
The reaction mixture was heated to a temperature of
80C and a slow stream of oxygen was introduced~ At the end of
6 hrs., the reaction was flushed with nitrogen and cooled to a
temperature of 20C.
The reaction mixture was filtered, the solids air
dried, a sample of the solid was removed, dissolved in acetone
and analyzed by gas-liquid chromatography. The analysis indî-
cated that 5 mol percent of the 2,6-xylenol was unreacted.
The dry solid was washed twice with 200 ml of benzene
to remove 2,6-xylenol and polyphenoxy ether. The resulting light
yellow solid was dried at 60C. Analysis of the product indi-
cated a yield of tetramethylbiphenol equal to 61 mol percent.
*~egistered Trade Mark
- 52 -
' ~ t79
~ E~MPL~ 17
Into a reaction flas~ there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.53 yrams (~ mrnols) o~ glycylglycine, and
50 ml of ion exchanged water.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-~.ylenol,
0.2 grams of Ultrawet K soft, and
200 ml of ion exchanged water.
To the resulting solution there was added the catalyst
composition prepared above. The resulting mixture was stirred
under oxygen and heated to a temperature of 52~C. ~t this
emperature there was added 8.0 ml Oc a 1.0 Normal sodium
¦ bicarbonate solution.
The reaction mixture was heated to a temperature of 80C~
and a slow stream of oxygen was introduced. At the end of 6 hrs. "
the reaction was flushed with nitrogen and cooled to a temperature
of 20C.
The reaction mixture was filtered and the solids were
washed with water. Analysis of the oil phase remaining in the
filtrate indicated that 27 mol percent of the 2,6-xylenol was
unreacted.
The solid was air dried and washed twice with 100 ml of I
benzene to remove 2,6-xylenol and polyphenoxy ether. The resulting
yellow solid was dried at 60C. ~nalysis of the product indicated
J;;S:rac a yield of tetramethylbiphenol equal to 35.2 mol percent.
1258-A - 53 - ¦
~ t Regis red Trade MQrk
~ !
. . . .. ...
: .:
" I - 107~79
EX~MPL~ 18
Into a reaction flas~ there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
1.28 grams (4 mmols) of glutathione, and
25 ml of ion exchanged water.
To the resu]ting mixture there was added 4.0 ml of a
1.0 ~ormal solution of sodium bicarbonate.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of sodium dodecyl benzene sulfonate, and
200 ml of ion exchanged water.
To the resulting solution there was added the catalyst
composition prepared above. The resulting mixture was stirred
under oxygen and heated to a temperature of 57C. at which time
there was added 4.0 ml of a 1.0 ~ormal sodlum bicarbonate solutionl
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxyyen was introduced. At the end of 6 hrs.,!
the reaction was flushed with nitrogen and cooled to a temperature¦
o~ 20C.
The reaction mixture was filtered and the filtrate was
treated with hydrochloric acid and refiltered. The solid fraction
was washed with water. A sample of the solid was removed,
dissolved in acetone and analyzed by gas-liquid chromatography.
The analysis indicated that 59.6 mol percent of the 2,6-xylenol
JMS:rac was unreacted.
1258-~ - 54 -
. ' . I
iO'711~ -
The solid was air dried and washed twice with 200 ml
of benzene to remove 2,6-xylenol and polyphenoxy ether. The
resulting yellow solid was dried at 60C. Analysis of the product
indicated a yield of tetramethylbiphenol equal to 20.7 percent.
EXAMPLE 19
.
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.36 grams (4 mmols) of ~-alanine, and
50 ml of ion exchanged water.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, sodium dodecyl
benzene sulfonate, and
200 ml of ion exchanged water.
To the resulting solution there was added 100 ml of the
catalyst composition prepared above. The resulting mixture was
stirred under oxygen and heated to a temperature of 50C. There
was added 8.0 ml of a 1.0 Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80 C.
`and a slow stream of oxygen was introduced. At the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
of 20C.
The reaction mixture was filtered and the solids washed
with water. A sample of the solid was removed, dissolved in
acetone and analyzed by gas-liquid chromatography. The analysis
indicated that 11 mol percent of the 2,6-xylenol was unreacted.
- 55 -
* Registered Trade Mark
:
The solid was air dried and washed twice with lO0 ml of
benzene to remove 2,6-xylenol and polyphenoxy ether. The resulting
light yellow solid was dried at 60C. Analysis of the product
indicated a yield of tetramethylbiphenol equal to 62 mol percent.
EXAMPLE 20
Into a reaction flask there were added:
0.40 grams (2 mmols) of cupric acetate monohydrate,
0.41 grams (4 mmols) of 3-amino butyric acid, and
25 ml of ion exchanged water.
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of Ultrawet*K soft, sodium dodecyl
benzene sulfonate, and
200 ml of ion exchanged water.
To the resulting solution there was added 100 ml of the
catalyst composition prepared above. The resulting mixture was
stirred under oxygen and heated to a temperature of 50C. at
which time there was added 8.0 ml of a 1.0 Normal sodium
bicarbonate solution.
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
of 20C.
- 56 -
* Registered Trade Mark
1071179
The reaction mixture was filtered, the solid wa-; waslled
with water, and rernoved, dissolvcd in acetone and analyzed by
yas-liquid chromatography. The analysis indicated that all of
the 2,6-xylenol had reacted.
The solid was air dried and washed twice with 200 ml of
benzene to remove 2,6-xy]enol and polyphenoxy ether. The resultincl
yellow solid was dried at 60C. Analysis of the product indicatcd,
a yield of tetramethylbiphenol equal to 66.3 mol percent.
EXA~LE 21
¦ Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
iof operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added: j
65.7 grams (400 mmols) of 2-methyl-6-t-butyl phenol,
û.2 grarns of sodium lauryl sulfate, and
150 ml of ion exchanged water. The resulting mixture
was stirred and there was added:
¦ 0.25 grams of cupric glycinate in
50 ml of ion exchanged water. After stirring for
munutes there was added:
10 ml of a 1.0 ~ormal solution of sodium bicarbsnate 11
d the resulting mixture was stirred for an additional 5 minutes, ¦
~he reaction mixture was then heated to a temperature of 9QC.
~nd a slow stream of oxygen was introduced. At the end sf 6 hrs ,
~he reaction was flushed with nitrogen and cooled to a tempera~ure
JMS:rac of 20C.
1258-A
- . .
1 1071179
.,
l'he reaction mixture was filtered, a sample of the
solid was removed, dissolved in acetone and analy~ed by gas-
liquid chromatography. The analysis indicated that all of the
methyl-t-butyl phenol had reacted.
The solid was air dried and hydrogenated in methanol in
the presence of palladium or carbon to yield the biphenol having a
melting point of from 184C.-185C.
EX~MPL~ 22
Into a 500 ml creased Morton flask fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
c 71.3 grams (400 mmols) of 2,6-diisopropylphenol, 1 1
0.2 grams of sodium lauryl sulfate, and ¦ ¦
'50 ml of ion exchanged water. There was then added:
0.25 grams of cupric glycinàte in
25 ml of ion exchanged water. The reaction mixture was ¦
stirred for 5 minutes and there was then added:
10 ml of a 1.0 Normal solution of sodium bicarbonate.
The reaction mixture was then heated to a temperature of 90C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,,
the reaction was flushed with nit~ogen and cooled to a temperature'
of 200C
The reaction mixture was filtered, a sample of the solid
was removed, dissolved in acetone and analyzed by gas-liquid
chromatography. The analysis indicated that all of the 2,6-
3MLS~rac diisopropylphenol had reacted.
'
;
1~ ,
1 1071179
The solid was washed with wa~er and the resulting red
solid was air dried yieldiny 68 grams of product having a melting ¦
point of 197-199C. This corresponded to a 97 mol percent con- j
version to the tetra isopropyl diphenoquinone.
EX~L~ 23
Into a first flask there were added:
0.20 grams (1 mmol) of cupric acetate monohydrate,
0.15 grams (2 mmols) of glycine, and
30 ml of ion exchanged water. I
Into a 500 ml creased Morton flask, fitted with a
gas addition tube, a condenser, a thermometer, and a stirrer
capable of operating at speeds in the range OL from about 8,000
to about 10,000 rpm, there were added:
82.3 grams (400 mmols) of 2,4-ditertiarybutylphenol,
0.20 grams of sodium lauryl sulfate, and
120 ml of ion exchanged water.
To the resulting mixture there was added the copper/
lycine composition prepared above. The resulting mixture was
stirred under oxygen for 15 minutes and there was then added
12.0 ml of a 1.0 Normal sodium bicarbonate solution.
The reaction mixture was heated to a tem~eraturc of 80C.
and a slow stream of oxygen was introduced. I~fter 2-1/3 hours a
¦sample was removed and analyzed by gas-liquid chromatography the
results of which indicated that all of the phenol had reacted.
!After an additional 10 minutes, the reaction was flushed with
JMS:rac litrogen and cooled to a temperature of 20C.
1~58-~ - S9 -
.
_
~071179
The reaction mixture was filtered and the solids were
blended with cold water, filtered, washed with 400 ml of dilute
~ICl and washed with water until neutral. The resulting solids
were dried at 60C. and purified as follows.
76 grams of the solids were stirred with 400 ml of
acetone and heated to reflux resulting in a clear solution.
Acetone was distilled off to the cloud point and the mixture was
cooled to room temperature, filtered and the solids were washed
with methanol. The solids were dried at 60C. resulting in 39.2
grams of white crystals having a melting point of 196.5C. and
identified as the 2,2',4,4'tetratertiarybutyl-6,6'biphenol.
EX~?LE 24
Into a fir~t flask there were added: ¦
0.20 grams (l mmol) of cupric acetate monohydrate,
G.i; gr~i,s ~2 m~,olsj of glycine, and
30 ml of ion exchanged water.
Into a 500 ml creased Morton flask, fitted with a
gas addition tube, a condenser, a thermometer, and a stirrer
capable of operating at speeds in the range of from about 8,000
to about lO,000 rpm, there were added: ¦
65.2 grams (400 mmols) of 2-methyl-4-tertiarybutylphenol,
0.2-grams of sodium lauryl sulfate, and
150 ml of ion exchanged water.
To the resulting mixture there was added the copper/
glycine composition prepared above. The resulting mixture was
stirred for 15 min. and there was then added 12.0 ml of a l.0 ¦
JMS:rac Normal sodium bicarbonate solution.
1258-A - 60 -
1071179
. ~
The xeaction mixture was heated to a tempcrature of 80C
and a slow stream of oxygen was in~roduced. At the end of 6 hrs.~l~
the reaction was flushed with nit`rogen and cooled to a temperature;
of 20C.
The reaction mixture was filtered and the solids treatedl
with 200 ml of methanol. The remaining bright yellow solid weighed
14.1 grams, had a melting point of 215-218C. and was identified ¦
as a mixture of the 0,O'biphenol and the 0,O'diphenoquinone.
EXAMPL~ 25
Into a first flask there were added: !
0.49 grams (2 mmols) of manganous acetate tetrahydrate,
0.30 grams (4-mmols) of glycine, dnd
30 ml of ion exchanged water.
Into a 500-ml creased Morton flask, fitted with a
gas addition tube, a condenser, a tnermometer, and a stirrer
capable of operating at speeds in the range of from about 8,000
to about 10~000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of sodium lauryl sulfate, and
130 ml of ion exchanged water.
To the resulting mixture there was added the manganese/ '
glycine composition prepared above. The resulting mixture was
stirred for 15 minutes and there was then added 16.0 ml of a 1.0
Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,~
the reaction was flushed with nitrogen and cooled to a temperature
~MS:rac of 20C.
~258~ - 61 -
. , ,~.
.,
. I~
' ' - .
1 1071179
The reaction mixture was filtered and the solids washed
with water and dried.
The dried solid weighing 33.1 grc~ls was washed twice
with 150 ml of benzene to remove any 2,6-xylenol and polyphenoxy
ether. The resulting solid was dried at 60C. Ana]ysis of the
product indicated a yield of tctramethyl}~ipllenol equal to 22.8
mol percent.
~X~1PLr. 26
Into a first flask there were added:
0.50 grams (2 mmols) of nickel acetate
tetrahydrate (Ni(OAC)24EI2O)
3.30 grams (4 mmols) of glycine, and
30 ml of ion exchanged water.
Into a 500 ml creased Morton flask, fitted ~ith a
gas addition tube, a condenser, a ihermo~Qeter, and a stirrer
capable of operating at speeds in the range of from about 8,000
to about 10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
0.2 grams of sodium lauryl sulfate, and
130 ml of ion exchanged water.
To the resulting slurry there was added the nickel/
glycine composition prepared above. The resulting mixture was
stirred for .5-min. and there was then added 8.0 ml of a 1.0
Normal sodium bicarbonate solution.
The reaction mixture was heated to a temperature of 80C.
and a slow stream of oxygen was introduced. At the end of 6 hrs.,
the reaction was flushed with nitrogen and cooled to a temperature
JMS:rac of 20C.
125S-A - 62 -
1071179
.
The ~-eaction mixture was filtered and the solids washccl ¦
with water and dried.
The dried solid, weighing 22.8 grams was washed twice
with 100 ml of benzene to remove 2,6-xylenol and polyphenoxy ether.
The resulting solid was dried at 60C. A}lalysis of the product
indicated a yield of tetramethylbiphenol cqual to 3l.5 mol percent~
EX~LE 27
Into a 500 ml creased r1orton flas~, fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol, and
300 ml of ion exchanged water.
The resulting mixture was stirred and heated to 50C.
at which time there was added 5 grams of cupric glycinate.
The reaction mixture was heated to 80C. and a slow stream of
¦ oxygen was introduced. At the end of 6 hrs;, the reaction was
¦flushed with nitrogen and cooled to a temperature of 20C. The
¦reaction mixture was filtered and the solids washed Wit]l watcr.
¦The solids were then air dried and washed twice with 100 ml of
¦benzene to remove 2,6-xylenol and polyphenoxy ether. The result-
¦ing solid was dried at 60C. Analysis of the product indicated
JMS:rac ¦a yield of tetramethylbiphenol equal to 33.5 mol percent.
1258-A
- 63 -
' . ' I ~.
. I
107 ~179
EX~L~, 2
Into a first flask there were added:
O.S0 grams (2 mmols) of cobalt acetatc tetxahydrate,
0.30 grams (~ mmols) of glycine, and
40 ml of ion exchanged water.
To the resulting mixtu~e there was added 39.2 mI of
a 0.1028 Normal solution of potassium hydroxide. The potassium
hydroxide solution was added drop-wise and the total amount added
~was equal to 4.03 ml equivalents o~ potassium hydroxide. The
¦resulting mixture, which had a pH of 8.3, was bottled and stored.
¦ Into a 500 ml creased Morton flask fitted with a gas
addition tube, condenser, thermometer, and a stirrer capable of
¦operating at speeds in the range of from about 8,000 to about
¦10,000 rpm, there were added:
¦ 48.8 grams (400 mmols) of 2,6-xylenol,
185 ml of ion exchanged water, ' ¦
0.2 grams of Ultrawet K soft, and
¦ 65 ml of the metal complex prepared above.
¦ The resulting reaction mixture was heated to 53C. at
!which time there was added 4.0 ml of a 1.0 Normal sodium bicarbo- ,
¦nate solution. The reaction mixture was then heated to a tempera-
ture of 80C. and a slow stream of oxygen was introduced. At
the end of 6 hrs., the reaction was flushed with nitrogen and
cooled to a temperature of 20C.
The reaction mixture was filtered and a sample of the
solid removed, dissolved in acetone and analyzed by gas-liquid
chromatography. The analysis indicated that 72 percent of the
JMS:rac 12,6-xylenol had reacted. The solid was air dried and washed
1258-A
- 64 -
l l
il
Il .
~ 71179
twice witll 50 ml of bcnzene to remove 2,6-xylenol and polyphenoxy-l,
ether. -The resul-ting solid was dried at 60C. res~lting in 15
grams of a light yellow solid having a melting point of 222C.
The results indicated a yield of tetramethylbiphenol equal to
31 mol percent.
I EXAMPLE 29
Into a reaction flask there were added:
0.50--grams (2 mmols) of cobalt acetate tetrahydrate,
0.30 grams (4 mmols) of glycine, and
40 ml of ion exchanged water.
¦ To the resulting slurry there was added 4.0 ml of a 1.0
¦Normal solution of sodium bicarbonate.
¦ Into a 500 ml creased Morton flask fitted with a gas
lladdition tube, a condenser, a thermometer, and a stirrer capable
llof operating at speeds in the range o~ ~rom about 8,U00 to about
¦10,000 rpm, there were added:
48.8 grams (400 mmols) of 2,6-xylenol,
200 ml of ion exchanged water, and
- 0.2-grams of Ultrawet 1~ soft.
To the resulting mixture there was added the metal complex
prepared above and the reaction mixture was then heated to 80C.
When this temperature was reached there was added 4.0 ml of a 1.0
¦¦Normal sodium bicarbonate solution. The reaction mixture was main-
jtained at 80C. and a slow stream of oxygen introduced for 6 hrs.
j¦At the end o this time, the reaction was flushed with nitrogen
JMS:rac land cooled to a temperature of 20C.
1258~ - 65 -
. ll l
. ,1 ',
~ J
ll
1071179
Tlle reaction mixture ~as Li ltered and a sample of the
solid was removed, dissolved in acetone, and analy~ed by gas-
liquid chromatography. The analysis indicated that 53 percent
of the 2,6-xylenol had reacted.
The solid was air dried and washed twice with 100 ml
of benzene to remove 2,6-xylenol and polyphenoxy ether. The
resulting solid was dried at 60C. to yield 12 grams of product
having a melting point of 224C. These results indicated a
yield of tetramethylbiphenol equal to 25 mol percent.
.
EXAMPLE 30
Into a 500 ml creased Morton flask, fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
¦10,000 rpm there were added:
¦ 31.2 grams (200 mmols) of 2,6-dimethoxyphenol,
¦ 0.10 gram (0.3 mmol) of sodium lauryl sulfate, and
170 ml of ion exchanged water.
The resulting reaction mixture was stirred and there
was added a mixture comprising:
0.20 grams (1 mmol) of cupric acetate monohydrate,
0.15 grams (2 mmols) of glycine, and
30 ml of ion exchanged water.
The resulting reaction mixture was stirred under oxygen
~and heated to a temperature of 80C. and maintained at that
temperature for 2 hrs. At the end of this time the heat and
oxygen were discontinued and the reaction mixture allowed to
JMS:rac cool to room temperature. I
1258-A - 66 -
:
107~179
i
The reactlon mixture was filtered and the purp]e solids
were washed with water. A sample of the solids analyzed by ~as- !
liquid chromatography incidated that 93 percent of the dimethoxy-
phenol had reacted. The solid was washed with xylene to remove
any unreacted dimethoxyphenol and dried at 60C. The dried
product weighed 16.9 grams and infrared analysis indicated that
the material was the tetramethoxy diphenoquinone~ The yield of
product was equal to 55 mol percent.
.
~ EXAMPL~ 31
Into a 500 ml creased Morton flask, fitted with a gas
! addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm there were added:
43.3 grams (300 mmols) of l-naphthol,
0.20 gram (0.6 mmol) of sodium lauryl sulfate, and
190 ml of ion exchanged water.
The resulting reaction mixture was stirred and there
was added a mixture comprising:
¦ 0.10-gram (0.5 mmol) of cupric acetate monohydrate,
¦ 0.08 gram (1 mmol) of glycine, and
30 ml of ion exchanged water.
Il The mixture was stirred for 15 minutes and there was
¦¦then added 16 ml of a 1.0 Normal solution of sodium bicarbonate.
The resulting reaction mixture was stirred under oxygen I
and heated to a temperature of 90C. and maintained at a temperature
of from 90-95C. for 5 hrs., during which time oxygen was con-
tinuously introduced. ~At the end of this time the heat and
J~SS:rac . oxygen were discontinued and the reaction mixture cooled to 25C. i1258-A ¦~ - 67 -
I
1 .
1.
,
, 1~71179
The reaction mixture was filtered resulting in a clear, i
red filtrate which had a pII of 8.7. The filtrate was acidified
with ~Cl to a pll of 2 and again fil~ered to reMove so]ids. The
filtrate was discarded and the solids were washed ~ith 200 ml of
water and air dried. A sample of the solid was removed and
analyzed by gas-liquid chromatography. The analysis indicated
¦that all of the l-naphthol had reacted.
¦ The solid was air dried and washed twice with 150 ml
of xylene. The resulting solid was dried at 60C. to yeild 39.2
¦grams of a dark brown solid Infrared analysis indicated a yield
1f carbon-carbon coupled products equal to 90.7 mol percent
consisting of 1 part of the naphthenoquinone and 2-3 parts of
¦the binaphthol.
Il l
EXA~LE 32
Into a 500 ml creased Morton flask, fitted with a gas
addition tube, a condenser, a thermometer, and a stirrer capable
of operating at speeds in the range of from about 8,000 to about
10,000 rpm there were added:
55.4 grams (400 mmols) of 2,4,6-trimethylpnenol (98.3
0.20 gram (0.6 mmol) of sodium lauryl sulfate, and
1 150 ml of ion exchanged water.
The resulting reaction mixture was stirred and there
was added a mixture comprising:
0.40 gram (2 mmols) of cupric acetate monohydrate,
0.30 gram (4 mmols) or glycine, and
JMS:rac 25~ml of ion exchanged water.
;258-A
- 68 -
1071179
The mixture was stirred for 5 minutcs and there was then
added 20 ml of a 1.0 Normal solutioll of sodium bicarbollate.
The resulting reaction mixtur~ was s~irred under oxy(jen
and heated to a tempcrature of 80C. and maintained at t}-at
temperature for 6 hrs. During this time the pll of the reaction
mixture was checked and malntained at ~etween 9.0 and 9.4 by the
addition of solid sodium hydroxide pellets. The total a~ount of
NaOH added during the course of the reaction was equal to 16.2
grams. At the end of this time the heat and o~ygen were dis-
Icontinued and the reaction mixture cooled to 25C.
¦~ The reaction mixture was filtered to separate a solid
product and a dar~ red filtrate which was acidified with 37 ml of
concentrated HCl to precipitate a brown-red solid. This solid
I fraction was washed with 100 ml of xylene and dried at 60C. to
¦Iyield 8.33 grams of a brown solid. The first solid fraction
¦Iremoved by the original filtration was washed with water, air
¦¦dried and washed with 150 ml of xylene. ~fter this it was dried
at 60C. to yield 12.73 grams of a brown solid. Total yield of
¦¦product was equal to 38 mol percent. Infrared analysis of the
¦¦product indicated a mixture of the following two materials:
¦I CH3 3
¦~ }IO ~ C - C ~ OEI
CH3 3
CEl3 3
~1 o = ~) = c i~ = ~ = o
CH3 3
I '~
JMS:rac I - 69 -
1258-~
!l
