Title of Invention

PROCESS FOR ISOLATION OF MONOPHENOLIC- BISARYL TRIAZINES

Abstract A process for isolating a compound of Formula 1 wherein Ar1 and Ar2 are the same or different and are radicals of the compound of Formula 2 And wherein R1 is hydrogen and R2, R3, R4 and R5, are the same or different and are hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR', CONRR', OCOR, CN, SR, SO2R, and optionally with either of R3 and R4 or R4 and R5 taken together being a part of a saturated or unsaturated fused carbocyclic ring and wherein each R, R', R6, R7, R8, R9 and R10 are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, and optionally with either of R6 and R7, R7 and R8, R8 and R9 or R9 and R10, taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally having O, N or S atoms in the ring, and Rs, R7, R7, R9 and R10 may be an alkoxy of 1 to 24 carbons, and Y is a direct bond, O, NR", or wherein R" is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon atoms; wherein said process comprises the step of: contacting a product mixture with a base to form an isolation blend, wherein said product mixture comprises said compound of Formula 1 and a polyphenolic-triazine compound.
Full Text FIELD OF THE INVENTION
This invention relates to a novel, efficient, economic and general-purpose process for
isolating monophenolic-bisaryl triazine compounds from polyphenolic-triazines
compounds and other impurities. More specifically, this invention relates to a process
for isolating the monophenoJic-bisaryf triazine compounds by contacting it with a base,
an alcohol and/or a hydrocarbon solvent.
BACKGROUND OF THE INVENTION
Exposure to sunlight and other sources of ultraviolet (UV) radiation is known
to cause degradation of a wide variety of materials, especially polymeric materials. For
example, polymeric materials such as plastics often discolor and/or become brittle as a
result of prolonged exposure to UV light. Accordingly, a large body of art has been
developed directed towards materials such as UV light absorbers and stabilizers which
are capable of inhibiting such degradation. Other areas of applications for the UV light
absorbers include cosmetics (as sunscreen agents), fibers, spandex, inks, photographic
materials, and dyes.
A class of materials known to be UV light absorbers are compounds which have
aromatic substituents at the 2-, 4-, and 6- positions of the 1,3,5-triazine ring, and in which
at least one of the aromatic rings has a hydroxyl substituent at the ortho position to the
point of attachment to the triazine ring, rn general, this class of compounds is well known
in the art Disclosures of a number of such triazine UV fight absorbers (UVA's) as weU as
processes for preparing can be found in the following references and references cited
therein, all of which are incorporated by reference as fully set forth herein: U.S. Patent No.
6,239,275; U.S. Patent No. 6, 239.276; U.S. Patent No. 6,242,597; U.S. Patent No.
6,225,468 and WO 00/29392.
A preferred class of triazine UVA's are asymmetrical monophenolic-bisaryl triazines
UVA's based on the 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, e.g., compounds
where there are two non-phenolic aromatic groups, and one phenolic aromatic group that
is derived from resorcinol, or substituted resorcinol. The 4-hydroxyl group of the parent
compound. 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-tria2ine, is generally functionalized to
make 2-(2-hydroxy-4-oxyaryl)-4,6-bisaryl-1,3,5-triazine derivatives for end use.
There are several approaches reported in the literature to make the
preferred, 2-(2,4-dihydroxyary1)-4,6-bisaryl-1,3,5-triazine UVA's. (For a review of the
previously known methods for making triazine UVA's, please see the following articles. 1.
H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, vol 55,1972, pages 1566-1595; 2. S.
Tanimoto and M. Yamagata, Senryo to Yakahin, vol. 40(12), 1995, pages 325-339.)
A majority of the approaches consists of three stages. The first stage, which can
involve single or multi-steps from the commercial raw materials, deals with the preparation
of the key intermediate, 2-chloro-4,6-bisaryl-1,3,5-triazine, which is subsequently arylated
in the second stage with 1,3-dihydroxybenzene (resorcinol) or a substituted 1,3-
dihydroxybenzene in the presence of Lewis acid to form the parent compound 2-(2,4-
dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. The parent compound 2-(2,4-dihydroxyaryl)-4,6-
bisaryl-1,3,5-triazine, as mentioned above, is generally functionalized further, e.g.,
alkylated, to make the final product 2-(2-hydroxy-4-oxyaryl)-4.6-bisaryl-1,3,5-triazine.
General Scheme for Making 2-(2-hydroxy-4-oxyaryl)-4,6-bisaryl-triazines
Stage 1: Preparation of 2-chloro-4.6-bisarvl-1.3.S-triazine
It has been recognized that the most versatile and economical method to prepare
asymmetrical monophenolic-bisaryl triazine UVA's is to use a Friedel-Crafts reaction on
cyanuric chloride with non-phenoiic aromatics to first form 2-chloro-4,6-bisaryl-1,3.5-
triazine, followed by another Friedel-Crafts reaction with the phenolic aromatic, in this
case resorcinot, to make the desired monophenolic-bisaryl-triazine. However, it has been
realized in the prior art (see, U.S. Patent No. 3,394,134) that this known process as
disclosed in U.S. Patent No. 3,268,474 gives, only in exceptional cases, rise to the desired
disubstituted derivatives of cyanuric chloride with some selectivity. Even when the
aromatic compound and cyanuric chloride are reacted in molar proportions (1:1), the result
is in general a mixture which contains mono-, di-, and tri-aryl substituted products, and, in
addition, unreacted cyanuric chloride (U.S. Patent No. 3,394,134) (Scheme 1).
Using the above mentioned process, a useful yield of the desired intermediate 2-
chtoro-4,6-bisaryl-1,3,5-triazine is obtained only with m-xylene as the aromatic reactant
(GB 884802). 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. free of
polyresorcinol-triazine impurities, was prepared from the isolated 2-chtoro-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine that was purified by recrystallization, before reacting with
resorcinol in a second step (see U.S. Patent No. 3,244,708). The isolation and
recrystallization of the 2-chloro-4,6-bis(2,4-dimmethylphenyl)-1l3,5-tria2ine results in yield
loss. With other aromatics, a difficult to separate mixture of ail possible products are
formed with no selectivity for the desired 2-chloro-4,6-bisaryl-1,3,5-triazine (For example,
see H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, vol 55,1972, page 1575 and S.
Tanimoto and M. Yamagata, Senryo to Yakahm, vol. 40(12), 1995, pages 325-339).
When the reaction mixture from the first Friedel-Crafts reaction (Scheme 1) without
any purification is treated in a subsequent Friedel-Crafts reaction with resorcinol, the
bisaryl- derivative leads to tfie formation of desired monoresorcinol-bisaryl-triazine, and
the monoaryl-substrtuted product leads to the formation of monoaryl-bisresorcinol
derivative. Whereas, the unreacted cyanuric chloride leads to the formation of bis-and
tris-resorcinol-triazine derivatives, i.e. pofyresorcinol-triazines (see Scheme 2).
SCHEME 2: FORMATION OF POLYRESORCINOL TRIAZINE IMPURITIES IN THE
FRIEDEL-CRAFTS REACTION WITH RESORCINOL
These polyresorcinol-triazine impurities (triazine ring with more than one resorcinol
attached), lead to yellowing in the use of the UV absorbers prepared from the
monoresorcinol-bisaryl-triazine in various polymer substrates, e.g., in polycarbonates, in
lacquers, in automotive top-coatings, etc. Thus it is highly desirable for many such
applications that the monoresorcinol-bisaryl-triazine derivative is free of these impurities.
Unfortunately, there has been no process known in the literature to isolate
monoresorcinol-bisaryl-triazine derivative from the mixture containing polyresorcinol
impurities. The lack of selectivity for the bisaryl substitution in the Friedel-Crafts reaction
of cyanuric chloride, coupled with the problems associated with the isolation of the bisaryl
intermediate and the monoresorcinol-bisaryl-triazine derivative, had severely limited the
usefulness of the most versatile and economic approach to the preferred class of triazine
UVA's.
To overcome this obstacle, and to exclude the formation of polyresorcinol-triazines,
other economically less attractive routes have been developed in which either cyanuric
chloride was not used as starting material, and the triazine ring was synthesized by
different methods, or the formation of polyresorcinol impurities was excluded by means of
the circuitous routes (For example, see: A. Ostrogovich, Chemiker-Zertung No. 78, page
738, 1912; von R. Hirt. H. Nidecker and R. Berchtold, Helvitica Chimica Acta, vol. 33,
page 1365,1950; H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, vol 55, 1972, page
1575; U.S. Patent No. 4,092,466; U.S. Patent No. 5.084,570; U.S. Patent No. 5,106,972;
U.S. Patent No. 5,438.138; U.S. Patent No. 5,726,310; U.S. Patent No. 6,020.490; EP
0941989 and Japanese Patent 09059263)
An alternate direct approach for the preparation of monoresorcinoi-bisaryl-triazine
as described in U.S. Patent No. 6,225,468 B1 from cyanuric chloride also results in the
formation of polyresorcinol products, and no method was disclosed to isolate the
monoresorcinol-bisaryl-triazine product from the mixture.
More recently, a major breakthrough discovery in the field has led to the
development of a process for making the desired bisaryl-monochbro-triazine with
exceptionally high selectivity from the Friedel-Crafts reaction of cyanuric halide with
aromatics in general (WO 00/29392). However, the selectivity is not 100%, and that stilt
leads to the formation of small amounts of undesired polyresorcinol impurities, in the
subsequent reaction with resorcinol in a one-pot process, and tris-aryl-triazine impurity.
As is apparent from the above discussion, it would be a very valuable and highly
desirable addition in the field of triazine UV absorbers for a method to isolate
monophenolic-bisaryl triazine that is free from the polyphenolic- or polyresorcinol-triazine
impurities regardless of the synthesis process.
One of the advantages of the present invention is a highly efficient and very
economical method of isolating monophenolic-bisaryl triazine that is substantially free from
polyphenolic or polyresorcinol-triazine impurities, irrespective of the process of its making,
without the need for recrystallization. Thus the present invention also eliminates the need
for purifying and isolating the intermediate 2-chloro-4,6-bisaryl-1,3,5-triazine from the first
Friedel-Crafts reaction of aromatics with cyanuric chloride regardless of its selectivity, and
allows to do the second Friedel-Crafts reaction with phenols, such as resorcinol, in a one-
pot process to make monophenot-bisaryl-triazines.
Another advantage of the present invention is a method to isolate monophenolic-
bisaryl triazine compounds from poryphenotic- or polyresorcinol- triazine, trisaryl-triazine,
resorcinol (or substituted resorcinol), phenols, chlorobenzene or dichlorobenzene
impurities.
SUMMARY OF THE INVENTION
The present invention relates to a process of isolating a compound of Formula 1
where Ar1 and Ar2 are the same or different and are radicals of the compound of
Formula 2
and where R1 is hydrogen and R2. R3, R4 and R5. are the same or different and are
hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to
24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cyctoacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyf of 6 to 24 carbons atoms, substituted or urtsubstituted
biphenylene, substituted or unsubstituted naphthalene, OR, NRR', CONRR', OCOR, CN,
SR, SO2R, and optionally with either of R3 and R4 or R4 and R5 taken together being a
part of a saturated or unsaturated fused carbocydic ring and where each R, R', R6, R7,
R8, R9, and R10 are the same or different and each is hydrogen, alkyl of 1 to 24 carbon
atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24
carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,
cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24
carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted
naphthalene, and optionally with either of R6 and R7, R7 and R8, R8 and R9, or R9 and
R10, taken together being a part of a saturated or unsaturated fused carbocydic ring
optionally containing O, N, or S atoms in the ring, and R6, R7, R8. R9, and R10, may be an
alkoxy of 1 to 24 carbons, and Y is a direct bond, O, NR", or SR", wherein R" is
hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to
24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyf of 6 to 24 carbons atoms. The process involves the step of
contacting a product mixture comprising the compound of Formula 1 with a base, an
alcohol, a hydrocarbon solvent or mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
The present involves a process for isolating a monophenolic-bisary! triazine
compound from polyphenolic- or polyresorcinol-triazine impurities. Typically, these
impurities result from a synthesis reaction to make the monophenolic-bisaryl triazine
compounds from a Friedel-Crafts based reaction as illustrated in General Scheme 1 and
General Scheme 2 above. However, it should be noted that the present isolation
process can be utilized to isolate monophenolic-bisaryl triazine compounds from
polyphenolic- or polyresorcinol-triazine and other impurities in general and should not be
limited to any particular synthesis route. In fact, the present process may be generally
used to isolate monophenolic-bisaryl triazine compounds from polyphenolic- or
polyresorcinol-triazine and other undesired compounds whether or not generated from a
synthesis reaction.
The monophenolic-bisaryl triazine compound has the general Formula 1
where Ar1 and Ar2 are the same or different and are radicals of the compound of
Formula 2
and where R1 is hydrogen and R2, R3, R4 and R5, are the same or different and are
hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to
24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycioalkyt of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyl of 6 to 24 carbons atoms, substituted or unsubstituted
biphenylene, substituted or unsubstituted naphthalene, OR, NRR', CONRR', OCOR, CN,
SR, SO2R. and optionally with either of R3 and R4 or R4 and R5 taken together being a
part of a saturated or unsaturated fused carbocyclic ring and where each R, R', Re. R7.
Rs, R9. and R10 are the same or different and each is hydrogen, alkyl of 1 to 24 carbon
atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24
carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,
cycloacyl of 5 to 24 carbon atoms, araikyi of 7 to 24 carbon atoms, or aracyl of 6 to 24
carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted
naphthalene, and optionally with either of R6 and R7, R7 and R8, R8 and R9, or Rg and
Rio, taken together being a part of a saturated or unsaturated fused carbocyclic ring
optionally containing O, N, or S atoms in the ring, and R6, R7, R8, R9, and R1O, may be an
alkoxy of 1 to 24 carbons, and Y is a direct bond, O, NR", or SR", wherein R" is
hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to
24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyl of 6 to 24 carbons atoms.
A preferred compound of Formula 1 is
where R2. R3 is hydrogen, an alkyl of 1 to 24 carbon atoms or substituted alkyl of 1 to 24
carbon atoms.
A more preferred compound of Formula 1 is:
In one embodiment of the present invention, a "product mixture" which comprises
the compound of Formula 1 as well as polyphenolic- or polyresorcinol-triazine and other
impurities is contacted with a base. These impurities may result from a synthesis
process where reactants, undesired by-products, entrained solvents, and the like, are
agglomerated together with the desired compound of Formula 1. However, it should be
noted that the product mixture does not have to result from a synthesis process and
includes any mixture where the desired compound of Formula 1 is combined with
undesired polyphenolic- or polyresorcinol-triazine compounds and other impurities.
The product mixture can be in solid or liquid form. For example, in the Friedel-
Crafts reaction, the reaction is typically stopped by quenching with water to break the
aluminum complex. The compound of Formula 1 and undesired impurities are
precipitated out to form the product mixture in a solid form. This precipitated solid form
may be directly added to the base, or dissolved with a solvent and added to the base.
Any suitable solvent may be used to dissolve the product mixture. Examples of solvents
that may be used to dissolve the product mixture include methylisobutylketone,
methylethylketone, cyclohexanone, ethyl acetate, butyl acetate, methylene chloride,
chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene,
toluene, xylenes and mixtures thereof.
The bases that are suitable to be used in the present invention include inorganic
bases, organic bases and mixtures thereof. Inorganic bases include LiOH, NaOH, KOH,
Mg(OH)2. Ca(OH)2, Zn(OH)2. AI(OH)3. NH4OH, Li2CO3, Na2CO3. K2CO3, MgCO3,
CaCCb. ZnCCb, (NH4)2CO3. BaCO3. CaMg(CO3)2, NaHC03, KHCO3. (CaO). BaO.
LiNH2, NaNH2l KNH2, Mg(NH2)2, Ca(NH2)2, Zn(NH2)2, AI(NH2)3. NaH, CaH2, KH, LiH,
and mixtures thereof.
Organic bases include hydrocarbon compounds with C1-C9 cyclic or non-cyclic
that contain at least one alkoxide, amine, amide, carboxylate, or thiolate and which may
be substituted in one or more positions with a halide, an hydroxyl, an ether, a polyether,
a thiol, a ftioether, an amine, such as -NHR, -NR'2, -NRR', a carboxylic acid, an ester, or
an amide. Preferably, the organic base is an amine that is primary, secondary, tertiary,
aliphatic, cyclic, acyclic, aromatic, heteroaromatic, or heterocyclic; or salts of primary
amine, secondary amine, alcohol, or acid. Organic bases include CH3O', CH3CH2O',
CH3CH2CH2O-, (CH3)2CHO, ((CH3)2CH)2CHO-, CH3CH2CH2CH2O\ (CH3)3CO\ CH3NH,
CH3CH2NH' CH3CH2CH2NH-, (CH3)2CHNH-. ((CH3)2CH)2CHNH-, CH3CH2CH2CH2NH .
(CH3)3CNH-, (CH3)2N, (CH3CH2)2N-, (CH3CH2CH2)2N-, ((CH3)2CH)2N .
(((CH3)2CH)2CH)2N-, (CH3CH2CH2CH2)2N- ((CH3)3C)2N, formate, acetate, propylate,
butanoate, benzoate; and CH3NHz. CH3CH2NH2, CH3CH2CH2NH2. (CH3)2CHNH2,
((CH3)2CH)2CHNH2, CH3CH2CH2CH2NH2. (CH3)3CNH2, (CH3)2NH, (CH3CH2)2NH,
(CH3CH2CH2)2NH, ((CH3)2CH)2NH. ((CH3)2CH)2EtN, (((CH3)2CH)2CH)2NH.
(CH3CH2CH2CH2)2NH. ((CH3)3C)2NH. (CH3)3N, (CH3CH2)3N. (CH3CH2CH2)3N1
((CH3)2CH)3N, (((CH3)2CH)2CH)3N. (CH3CH2CH2CH2)3N, ((CH3)3C)3N. pyrrotidine,
piperidine, N-alkylpiperidine, piperazine, N-aikylpiperazine. N,N-dialkylpiperazine,
morpholine, N-alkylmorpholine, imidazole, pyrrole, pyridine, lutidine, 4-N.N-
dimethytaminopyridine, aniline, N.N-dialkylaniline, tetramethyienediamine and mixtures
thereof. Organic bases also includes salts of deprotonated carboxylic acids such as
salts of formate, acetate, propylate, butanoate, benzoate, with Li, Na, K, Mg, Ca, Al, Zn,
or any other suitable cation.
The suitable bases may be dissolved, if desired, in water, an organic solvent, or a
mixture of solvents before or after contacting with the product mixture. Examples of
suitable solvents include, but are not limited to water, alcohols, acetonitrile,
tetrahydrofuran, toluene, heptane and mixtures thereof.
The amount of base to be added to the isolation blend should be enough to adjust
the pH of the blend to between about 7.0 to about 14, preferably between about 9 to
about 12.
The temperature of the base isolation step may be carried out at temperatures
between about 10°C and about the reflux temperature of the isolation blend. Preferably,
the temperature is at about 40°C to about the reflux temperature, or about 60° to about
the reflux temperature.
Preferably, the isolation blend is mixed or stirred by any suitable method such as
flow or tine mixers, or in agitated vessels using mechanical or gas agitation.
The amount of time needed for the isolation step is between about 10 minutes
and about 10 hours, more typically between about 1 to about 4 hours and about 1 to
about 2 hours. If heat is used in the isolation step, the isolation blend may be allowed to
cool.
If the product mixture is contacted with the base in solid form, the isolation blend
after the isolation step is typically filtered to isolate the compound of Formula 1.
Although not wishing to be bound by any theory, it is believed that the base solubilizes
many of the polyphenolic- or polyresorcinol-triazine compounds and halogen-containing
impurities used in the typical Friedel-Crafts reaction such that the solid mass after the
isolation step contains mainly the compound of Formula 1 and trisaryl-triazines. The
filtrate will be rich in the polyphenolic- or polyresorcinol-triazines and halogen-containing
impurities. Impurities in the typically Friedel-Crafts reaction that is believed to be
solubilized by the base include, but are not limited to compounds with the following
formulas:
where X, X1, X2 is a halogen or hydroxy and the other substituents are defined above.
Preferred impurities which are solubilized by the base are:
If a solvent is used to dissolve the product mixture, it is preferred that the solvent
used to dissolve the base is substantially immiscible with the solvent used to dissolve
the product mixture such that at least two distinct layers are formed. Preferably, the
solvent used to dissolve the base is aqueous-based and the solvent used to dissolve the
product mixture is organic-based. After the isolation step, it is believed that the
aqueous-based layer will contain most of the halogen and polyresorcinol impurities,
while the organic-based layer will contain mainly the compound of Formula 1 and trisaryl
triazine compounds that are not soluble in the aqueous-based layer. The aqueous-
based layer may be removed by any suitable process to leave the organic layer rich in
the compound of Formula 1.
Typically, the base isolation step involves treating the reaction mixture such that
is "substantially free" of polyphenolic- or polyresorcinol-triazines and halogen-containing
impurities. "Substantially free" in the present application means that at least about 80%
of the undesired impurities are removed from the reaction mixture during the isolation
step. Preferably the amount of impurities removed are at least about 90%, more
preferably at least about 95% and even more preferably at least about 98%.
It should be noted that the base isolation step of the present invention may also
be used to isolate the polyphenolic- or polyresorcinol-triazine compounds. As mentioned
above, the filtrate or the aqueous-based layer is rich in polyphenolic-triazine compounds.
If an acid is added to the filtrate or aqueous-based layer, the polyphenolic-triazine
compounds precipitate out to a solid form and may be filtered. Any suitable organic or
inorganic acid may be used to precipitate the polyphenolic- or polyresorcinol-triazine
compounds. Preferably, an inorganic acid is used. Examples of such inorganic acids
include, but are not limited to: HCI, HBr. HI. HNO3. HNO2. H2S, H2SO4, and H3PO4
Alternatively, after the acidification of the filtrate, the polyphenolic- or
polyresorcinol-triazine compounds may be isolated from the aqueous layer by solvent
extraction. Any suitable solvent may be used for the solvent extraction. Examples of
such suitable solvents include, out are not United to: ethyl acetate, butyl acetate,
dichloromethane and dicnJoroetnane.
In another embodiment of the present invention, the product mixture containing
the compound of Formula 1 in solid form is contacted with a hydrocarbon solvent to
remove trisaryl-triazine impurities. Suitable hydrocarbon solvents include C1-C20
hydrocarbon compounds, saturated or unsaturated, cyclic or non-cyclic, and aromatic or
non-aromatic. Examples of hydrocarbon solvent that may be used include, but are not
limited to: benzene, toluene, ethylbenzene, diethylbenzene, xylene, mesitylene, tetralin,
hexane, heptane, octane, cyclohexane, and mixtures thereof.
The amount of said hydrocarbon solvent present in the isolation step is about 1 to
about 20 parts per part compound of Formula 1, preferably about 3 to about 10 parts
hydrocarbon solvent per part compound of Formula 1.
The temperature of the hydrocarbon solvent isolation step is not critical and may
be carried out at temperatures between about 10°C to about the reflux temperature of
the isolation blend. Preferably, the temperature is about 40°C to about the reflux
temperature, or about 60°C to about the reflux temperature of the isolation blend.
The amount of time needed for the isolation step is typically between about 10
minutes to about 10 hours, more typically between about 1 to about 4 hours or about 1
to about 2 hours. If heat is used in the isolation step, the isolation blend is preferably
allowed to cool.
Preferably, the isolation blend is mixed or stirred by any suitable method such as
flow or line mixers, or in agitated vessels using mechanical or gas agitation.
After the isolation step, the isolation blend is typically filtered to isolate the
compound of Formula 1.
Although not wishing to be bound by any theory, it is believed that the
hydrocarbon solvent solubilizes the trisaryl triazine compounds from the solid form
leaving it richer in the compound of Formula 1 after the isolation step. Typically, the
hydrocarbon solvent isolation step involves treating the reaction mixture such that is
substantially free of trisaryl-triazine impurities. The filtrate can be concentrated to isolate
trisaryl-triazine.
Preferably, the base isolation step and the hydrocarbon isolation step are both
used together either in a one-step or in a step-wise fashion, in any order, to isolate the
compound of Formula 1. In the present application, the term "step-wise" means a series
of isolations steps are conducted. The term "one-step" means when only one isolation
step is conducted.
In another embodiment of the present invention, the product mixture containing
the compound of Formula 1 is contacted with an alcohol. The product mixture preferably
is in solid form. The eolation blend is heated to a temperature of about 40°C to about
200°C, preferably about 60°C to about 200oC, and more preferably to the reflux
temperature of the blend. This isolation step is conducted for a period of about 10
minutes to 10 hours, preferably about 1 to about 4 hours or about 1 to about 2 hours.
Preferably, the blend is allowed to cool to below about 40°C. If the product mixture is in
solid form during this alcohol isolation step, the blend would be typically filtered to isolate
the compound of Formula 1.
Any suitable alcohol may be used in this embodiment. Suitable alcohol
compounds include carbon compounds of C1-C20. straight chain or branched, saturated
or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, which has at least one
hydroxyl group. Examples of suitable alcohol compounds include, but are not limited to:
methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, 1,2-ethanediol,
3-chloro-1-propanol, 2-hydroxyl-acetic acid, 1-hydroxyl-3-pentanone, cyclohexanol,
cyclohexenol, glycerol, benzyl alcohol and mixtures thereof.
The amount of alcohol added in the isolation step is about 1 to about 20 parts per
part compound of Formula 1, preferably about 3 to about 10 parts alcohol to per part
compound of Formula 1.
Preferably, the isolation blend is mixed or stirred by any suitable method such as
flow or line mixers, or in agitated vessels using mechanical or gas agitation.
Although not wishing to be bound by any theory, it is believed that the alcohol
solubilizes many of the polyresorcinol and halogen containing impurities used in the
typical Friedel-Crafts reaction such that the solid mass after the isolation step contains
mainly the compound of Formula 1 and reduced levels of trisaryl-triazines. Typically, the
alcohol isolation step involves treating the reaction mixture such that it is substantially
free of polyresorcinol and halogen-containing impurities. The alcohol soluble filtrate can
be concentrated to recover polyresorcinol-triazines.
It should be noted that it is possible to dissolve the solid product mixture in an
organic solvent in this alcohol isolation process. Preferably, the solvent used to dissolve
the product mixture is immiscible with the alcohol such that at least two distinct layers
are formed. It may be necessary to add some water to the alcohol to form the separate
layers. It is believed that the alcohol-based layer will contain most of the halogen and
polyresorcinol impurities, and the organic-based layer will contain mainly the compound
of Formula 1 and trisaryl triazine compounds that are not soluble in the alcohol-based
layer. The alcohol-based layer may be removed by any suitable process to leave the
organic layer rich in the compound of Formula 1.
Preferably, the alcohol isolation step and the hydrocarbon isolation step are both
used together either in a one-step or in a step-wise fashion, in any order, to isolate the
compound of Formula 1.
In another embodiment of the present invention, the product mixture comprising
the compound of formula 1 is contacted with at least two components selected from the
group consisting of a base, an alcohol and a hydrocarbon solvent. The same
processing conditions and amounts as described above may be used in this
embodiment. The contacting may be performed in a step-wise or one-step fashion.
Preferably, either the base and hydrocarbon solvent components, or the alcohol and
hydrocarbon solvent components are processed together.
EXAMPLES
Certain embodiments and features of the invention are illustrated, and not limited,
by the following working examples.
Example 1: Isolation of 2-(2.4-dihydroxvphenyl)-4.6-bis(2,4-ditnethvtohenyl)-
1.3.5-triazine by Treating with 5 % Aqueous Sodium Carbonate
a. Preparation of 2-(2.4-dihvdroxvphenvn-4,6-bis(2.4-dimethvlphenyl)-1.3.5-
triazine (following a procedure in WO 00/29392):
To a reaction flask equipped with a reflux condenser, a nitrogen inlet, and a
mechanical stirrer was added 50 g of cyanuric chloride, 191 mL of ortho-
dichlorobenzene (ODCB), and 108.5 gm of aluminum chloride. The mixture was
cooled in an ice-bath to 5°C and 6.5 gm of concentrated HCI was added over a
period of 20 minutes. The mixture was allowed to warm room to temperature, and
stirred for 2 hours. It was cooled back to 5°C and then 51.8 gm of m-xylene was
slowly added over a period of 4 hours, while allowing the temperature to go up to
21°C. The mixture was stirred at room temperature for additional 16 hours. The
reaction mixture was heated to about 69°C and 32.8 gm of resorcinol was added over
a period of 30 minutes. The mixture was held at about 65°C for 4 hours. It was then
added to 500 mL water and ODCB distilled off azeotropically. The precipitated solid
was filtered off to give 120 gm of water wet 2-(2.4-dihydroxyphenyl)-4,6-bis(2.4-
dimethylpheny!)-1,3,5-triazine. The HPLC analysis showed it to contain about 7% of
polyresorcinols consisting mainly of trisresorcinol-triazine and bisresorcinol-
monochloro-triazine.
b. Isolation of 2-(2.4-dihvdroxyphenvn-4.6-bis(2.4-dimethvlphenyl)-1.3.5-
triazine:
To a reaction flask equipped with a reflux condenser, a Dean-Stark apparatus,
a nitrogen inlet, and a mechanical stirrer was added 225 mL water and 11.25 gm of
sodium carbonate. To the resulting solution was then added 100 gm crude 2-(2.4-
dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, (about 50% wet) bisaryl-
monoresorcinol-triazine prepared by procedure of Example 1a containing
polyresorcinol-triazines as impurities. The pH of the mixture was about 10. The
resulting mixture was heated to reflux, and it was held at reflux for 2 hours while
residual OOCB was collected as azeotropic mixture in the Dean-Stark apparatus.
The heating was discontinued, and the mixture filtered around 50 to 60°C. The filter
cake was twice washed with 112.5 mL of 5% aqueous sodium carbonate solution
followed by 600 mL of 50°C water, and filtered to give 97.5 gm of 2-(2,4-
dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3.5-triazine (about 50% wet). The
HPLC analysis showed no detectable amounts of polyresorcinol-triazines remaining
in 2-(2,4-dihydroxyphenyi)-4,6-bis(2,4-dimethylphenyl)-1,3.5-triazine. It was also free
of ODCB.
The filtrate was analyzed by HPLC to contain no 2-(2,4-dihydroxyphenyl)-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 2: Isolation of 2-(2.4-dihydroxyphenyl)-4,6-bls(2.4-dimethvlphenyl)-
1.3.5-triazine by Treating with 3 % Aqueous Sodium Carbonate
To a reaction flask equipped with a reflux condenser, a Dean-Stark apparatus,
a nitrogen inlet, and a mechanical stirrer was added 112.5 mL of 3% aqueous sodium
carbonate and 50 gm crude 2-(2,4-dihydroxyphenyl)-416-bis(2,4-cfimethylphenyl)-
1,3,5-triazine from Example 1a containing polyresorcinol-triazines as impurities. The
resulting mixture was heated to reflux, and it was held at reflux for 2 hours while
residual ODCB was collected as azeotropic mixture in the Dean-Stark apparatus.
The heating was discontinued, and the mixture filtered around 80°C. The filter cake
was washed with 112.5 mL of 3% aqueous sodium carbonate solution followed by
300 mL of 50°C water. The 47 gm of residue thus obtained was analyzed by HPLC
to be 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine containing no
polyresorcinol impurities.
a. Isolation of Polvresorcinol-triazine:
The filtrate was acidified with aqueous HCI, and extracted with ethyl acetate.
The organic layer was analyzed by HPLC which showed it to contain mainly
polyresorcinol-triazines, with almost no 2-(2.4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine.
Example 3: isolation of 2-(2,4-dihvdroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1.3.5-triazine by Treating with Aqueous Sodium Hydroxide
To a reaction flask equipped with a reflux condenser, a Dean-Stark apparatus,
a nitrogen inlet, and a mechanical stirrer was added 50 gm of crude 2-(2,4-
dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine prepared by procedure of
Example 1a containing polyresorcinol-triazines as impurities, followed by 175 mL of
0.25% aqueous sodium hydroxide solution. The reaction mixture was heated to
reflux while residual ODCB was collected as azeotropic mixture in the Dean-Stark
apparatus. An additional 175 mL of 0.25% aqueous sodium hydroxide was added to
maintain the pH at about 10, and the reftuxing continued for another hour. The
heating was discontinued. The mixture was filtered, the filter cake washed first with
300 mL of 0.25% aqueous sodium hydroxide solution, followed by 500 mL water. The
HPLC analysis of the product (47 gm) thus obtained showed no detectable amounts
of polyresorcinol-triazines remaining in 2-(2,4-dihydroxyphenyi)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine.
Example 4: Removal of Resorcinol and Polyresorcinol Impurities from 2-(2,4-
dihvdroxvphenvn-4.6-bi3(2.4-dimethylphenyl)-1,3,5-triazine
A mixture of 5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 250 mg of resorcinol and 200 mg of polyresorcinol-triazines
(polyresorcinol-triazines were prepared by reacting cyanuric chloride with resorcinol
using AICI3) was heated with 50 mL of 5% aqueous sodium carbonate solution. The
mixture was heated to reflux for 3 hours. The heating was discontinued, and the
mixture was filtered, the filter cake washed first with 5% aqueous sodium carbonate
solution followed by with water. The 4.6 gm of the solid product thus obtained was
analyzed by HPLC to be 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazine and contained no resorcinol or polyresorcinol-triazines.
Example 5: Removal of Cyanuric Chloride from 2-(2.4-dihydroxyphenyl)-4.6-
bis(2.4-dimethvlphenvl)-1,3,5-triazine using 2% Aqueous Sodium Hydroxide
To a mixture of 9 gm 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethytphenyl)-
1,3,5-triazine and 1 gm cyanuric chloride in a flask equipped with magnetic stirrer, a
nitrogen inlet and a reflux condenser was added 60 mL of 5% aqueous sodium
carbonate. The mixture was heated to reflux for 2 hours. The heating was
discontinued, the mixture was filtered, and the filter cake was washed first with 5%
aqueous sodium carbonate, then with water, and dried to give 8.8 gm of 2-(2,4-
dihydroxyphenyl)-4.6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The product was
analyzed by HPLC to be free of cyanuric chloride.
Example 6: Removal of Resorcinol. Cyanuric Chloride and Polyresorctaol-
triazine from 2-(2.4-dihvdroxvphenyl)-4,6-bis(2.4-dimethvlphenvn-1,3,5-triazine
Using 2% Aqueous Sodium Hydroxide
To a mixture of 10 gm crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines, 1 gm resorcinol and
1 gm cyanuric chloride in a flask equipped with magnetic stirrer, a nitrogen inlet and a
reflux condenser was added 75 mL of 2% aqueous sodium hydroxide. The mixture
was heated to reflux for 1 hour. The pH of the mixture was about 11. The heating
was discontinued, the mixture cooled to room temperature and filtered. The filter
cake was washed first with 50 mL of 2% aqueous sodium hydroxide, then three times
with 50 mL water, and then dried to give 9.4 gm of 2-(2,4-dihydroxyphenyl)-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine that was free of cyanuric chloride, resorcinol
and polyresorcinol-triazine impurities by HPLC analysis.
Example 7: Isolation of 2-(2.4-dihvdroxvphenyn-4.6-bis(2.4-dimethylphenyl)-
1.3.5-triazine and Polvresorcinol-triazines
a. Preparation of 2-(2.4-dlhvdroxvphenyl)-4,6-bis(2.4-dimethylphenyl)-1.3.5-
triazihe with High Levels of Polvresorcinol-triazines:
To a reaction flask equipped with a reflux condenser, a nitrogen inlet, and a
magnetic stirrer was added 2 gm of cyanuric chloride, 25 mL chlorobenzene, 4.4 gm
of aluminum chloride and 2.34 gm of m-xylene. The reaction mixture was stirred at
room temperature for about 40 hours. To it was then added 3.6 gm of resorcinol and
heated to 90°C for 2 hours. The reaction mixture was quenched with water, and
chlorobenzene removed azeotropically. The precipitated material was filtered, the
filter cake washed with water and dried to give 4.5 gm of a crude product. The HPLC
analysis showed that the product mixture contained a total of 62% of polyresorcinote
(consisting of about 53% of trisresorcinol-triazine, 9% of bisresorcinol-monoxylyl-
triazine), and only 34% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazine.
b. Isolation of 2-(2.4-dihvdroxvphenyl)-4,6-bis(2.4-dimethvlphenvn-1.3.5-
triazine:
To a reaction flask, 1 gm of the above mixture in Example 7a was heated with
30 mL of 5% aqueous sodium carbonate solution for 2 hours. The pH of the mixture
was about 10. The heating was discontinued and the mixture was filtered, the filter
cake was first washed with 5% aqueous sodium carbonate solution, and then with
water. The solid product (300 mg) isolated was identified by HPLC to be 2-(2,4-
dihydroxyphenyl)-4l6-bis(2,4-dimethylphenyl)-1,3.5-triazine, which was free of
polyresorcinol-triazine impurities.
c. Isolation of Polvresorcinol-triazines:
The filtrate from the part (b) above was cooled in an ice-bath and was acidified
with aqueous hydrochloric acid. It was extracted with ethyl acetate. The organic
layer was separated and was analyzed by HPLC to contain only polyresorcinol-
triazines and no 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 8: Process to Isolate 2-(2.4-dihvdroxvphenyl)-4.6-bi8(2.4-
dimethv1phenvl)-1,3.5-triazine by Removing Both Polvresorcinol-triazines and
Trisxvlvl-triazine: Procedure 1
A: Removal of Polvresorcinol-triazines:
To 10 gm crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dirnethylphenyl)-1,3,5-
triazine (50% water wet) prepared by the procedure of WO 00/29392 containing
polyresorcinol-triazines and trisxylyl-triazine as impurities was added 50 mL of 5%
aqueous sodium carbonate in a flask equipped with magnetic stirrer, a nitrogen inlet
and a reflux condenser. The mixture was heated to reflux for 2 hours. The pH of the
mixture was about 10. The heating was discontinued, and the mixture was filtered,
the filter cake washed with water, and dried to give 2-(2,4-dihydroxyphenyl)-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine which was analyzed by HPLC to be free of
polyresorcinol-triazines, but had 11 % trisxylyl-triazine impurity.
B: Removal of Trisxvlvl-triazine:
9.5 gm of the water wet 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3.5-triazine obtained in Example 8a above was heated to reflux with 60 mL of
heptane for 1 hour. The mixture was cooled, filtered and the filter cake washed with
additional heptane. The HPLC of the 4 gm dry-solid product thus obtained showed it
to be 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine that was free
of polyresorcinol-triazine impurities, and the trisxylyl-triazine was reduced to 0.3%.
Example 9: Process to Isolate 2-(2.4-dihvdroxvphenvl)-4.6-bis(2.4-
dtmethvlphenvl)-1.3.5-triazine by Removing Both Trisresorcinol-triazine and
Trisxylyt-triazine: Procedure 2
A: Removal of Trisxylyl-triazine:
A mixture of 10 gm of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine (50% wet) prepared by the procedure of WO 00/29392
containing 10% of trisxylyl-triazine and 4% polyresorcinol-triazines as impurities, and
70 mL heptane was heated to reflux for 1 hour. The mixture was cooled, filtered and
the filter cake washed with additional heptane and dried to give 4.5 gm of 2-(2,4-
dihydroxyphenyl)-4,6-bis(2,4-dirnethylphenyl)-1,3,5-triazine which by HPLC analysis
has only 0.9% trisxylyl-triazine remaining, but there was no change in the level of
polyresorcinol-triazine impurity.
B: Removal of Polyresorcinol-triazines;
To 4.5 gm of dry 2-(2.4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazine (containing polyresorcinol-triazines as impurities) obtained in Example 9A
was added 25 mL of 5% aqueous sodium carbonate in a flask equipped with
magnetic stirrer, a nitrogen inlet and a reflux condenser. The mixture was heated to
reflux for 1 hour. The pH of the mixture was about 10. The heating was
discontinued, and the mixture was filtered, the filter cake washed with water, and
dried to give 4 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazine which was analyzed by HPLC to be free of polyresorcinol-triazines.
Example 10: Process to Isolate 2-(2.4-dihvdroxyphenyl)-4.6-bis(2,4-
dimethvlphenyl)-1.3.5-triazine by Removing Trtsxvlvl-triaztne:
A mixture of 20 gm of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine prepared by the procedure of WO 00/29392 (about
40% wet; which had been treated with 3% aqueous sodium carbonate to remove
polyresorcinol-triazines), 20 mL toluene and 80 mL heptane was heated to reflux for 1
hour. The heating was discontinued and the mixture cooled to 30°C. The mixture
was filtered, the filter cake washed with a mixture of 20 mL toluene and 80 mL
heptane and dried to give 11.7 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine which was analyzed by HPLC to be free of trisxylyl-
triazine impurity.
Example 11: Removal of p-Chlorophenol Impurity from 2-(2.4-dihydroxvphenvD-
4.6-bis(2.4-dimethvlDhenvl)-1.3.S-triazine
To a mixture of 5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dirnethylphenyl)-
1,3,5-triazine and 1 gm of p-chtorophenol was added 50 mL of 5% aqueous sodium
carbonate solution. The mixture was heated to reflux for 3 hours. The heating was
discontinued and the mixture was filtered, the filter cake washed first with 5%
aqueous sodium carbonate solution and then with water. The HPLC of the solid
product (4.9 gm) showed it to be 2-(2.4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine with no detectable amount of p-chlorophenol remaining.
Example 12: Preparation of 2-(2.4-dihvdroxvphenyl)-4.6-bis(3.4-
dimethvlphenyl)-1,3.5-triazirte:
To a flask equipped with a reflux condenser, a nitrogen inlet, and a mechanical
stirrer is added 50 gm of cyanuric chloride, 191 mL of ODCB and 108.4 gm of
aluminum chloride. The mixture is cooled in an ice-bath to 5°C and 6.5 gm of
concentrated HCI was added over a period of 20 minutes. The mixture was allowed
to warm to room temperature, and stirred for 2 hours. It was cooled back to 5°C and
then 54.7 gm of o-xylene was slowly added over a period of 3 hours, while allowing
the temperature to go up to 21°C. The mixture was stirred at room temperature for
additional 16 hours. The reaction mixture was heated to about 63°C and 34 gm of
resorcinol was added over a period of about 30 minutes. The mixture was held at
about 75°C for 3 hours. It was then added to 500 mL water and ODCB distilled off
azeotropically. The precipitated solid was filtered off and washed with water. The
material was dried in a vacuum oven to give 96 gm of crude 2-(2,4-dihydroxyphenyl)-
4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine. The HPLC analysis showed it to contain
about 5% of polyresorcinol-triazines and 10.7% tris-o-xylyl-triazine.
Example 13: Isolation of 2-(2.4-dihydroxvphenvl)-4.6-bis(3.4-dtmethvlphenyl)-
1,3.5-triazine: Procedure 1
A: Removal of Polyresorcinol-triazines:
In a flask equipped with magnetic stirrer, a nitrogen inlet and a reflux
condenser was added 5 gm crude 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-
dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines as impurities and 30
mL of 3% aqueous sodium carbonate. The mixture was heated to reflux for 2 hours.
The pH of the mixture was about 10. The heating was discontinued, and the mixture
was filtered, the filter cake washed with water to give 2-(2,4-dihydroxyphenyl)-4,6-
bis(3,4-dimethylphenyl)-1,3,5-triazine which was analyzed by HPLC to be free of
polyresorcinol-triazines, but had 11% trisxylyl-triazine impurity.
B: Removal of Tris-o-xylyl-triazine:
In a flask equipped with a Dean-Stark apparatus, a nitrogen inlet and a
magnetic stirring bar was added 11.4 gm of the wet filter cake in Example 13A
containing 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine was
heated to reflux with 40 mL of toluene. Water was removed azeotropically. The
heating was discontinued after 2 hours. The mixture was cooled, filtered and the filter
cake washed with additional toluene to give 3.9 gm of the product. The HPLC of the
solid product thus obtained showed it to be 2-(2.4-dihydroxyphenyl)-4,6-bis(3.4-
dimethylphenyl)-1,3,5-triazine that was free of polyresorcinol impurities, and the tris-
o-xylyl-triazine was reduced to 0.3%.
Example 14: Isolation of 2-(2,4-dihydroxyphenyl)-4.6-bis(3.4-dimethYlphenyl)-
1.3.5-triazine: Procodure 2
A: Removal of Tris-o-xylyl-triazine:
A mixture of 5 gm of the crude 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-
dimethylphenyl)-1,3,5-triazine prepared from the procedure in Example 13A was
heated to reflux with 30 mL of toluene in a flask equipped with a nitrogen inlet and a
magnetic stirring bar. The heating was discontinued after 2 hours. The mixture was
cooled, filtered and the filter cake washed with additional toluene to give 4.1 gm of
the product. The HPLC of the solid product thus obtained showed it to be 2-(2,4-
dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1.3,5-triazine that contained 3.9%
polyresorcinol impurities, and the tris-o-xytyl-triazine was reduced to 1.6%.
B: Removal of Polvresorcinol-triazines:
In a flask equipped with magnetic stirrer, a nitrogen inlet and a reflux
condenser was added 4.1 gm of the above 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-
dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines as impurities and 30
mL of 3% aqueous sodium carbonate. The mixture was heated to reflux for 2 hours.
The pH of the mixture was about 10. The heating was discontinued, and the mixture
was filtered, the filter cake washed with 3% aqueous sodium carbonate followed by
water to give 3.8 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-
triazine which was analyzed by HPLC to be free of polyresorcinol-triazines, and had
1.7% tris-o-xylyl-triazine impurity.
Example 15: Isolation of 2-(2.4-dihydroxvphenyl)-4.6-bis(2.4-dimethylphenyl)-
1.3.5-triazine by Treatment of Its Solution with
Aqueous Potassium Carbonate
To a flask equipped with a reflux condenser, a nitrogen inlet, and a magnetic
stirrer was added 50 mL of ethyl acetate and 5 gm of crude 2-(2,4-dihydroxyphenyl)-
4,6-bJs(2,4-dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines as
impurities and stirred at room temperature to form a solution. To it was then added
25 mL 5% aqueous potassium carbonate solution, and the contents stirred for 10
minutes at room temperature. The organic layer was then separated, washed with
water twice and dried over anhydrous sodium sulfate. The solvent was then removed
under reduced pressure to give 4.7 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine which was analyzed by HPLC to contain no
polyresorcinol-triazine impurities.
Example 16: Isolation of 2-(2.4-dihvdroxyphenyn-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine by Treatment of Its Solution with Aqueous Triethvlamine
To a flask. 5 gm of 2-(2,4-dihydroxyphenyl)-4.6-bis(2,4-dimethylphenyl)-1,3,5-
triazine containing polyresorcinol-triazine impurities was dissolved in 50 mL of ethyl
acetate. To it was added 15 mL of 5% aqueous triethylamine solution. The mixture
was stirred at room temperature for 10 minutes. The organic layer was separated,
washed twice with water, dried over anhydrous Na2SO4 and solvent removed under
reduced pressure to give 4.6 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine, which was analyzed by HPLC to be free of
polyresorcinol-triazine impurities.
Example 17: Isolation of 2-(2.4-dihydroxvphenyl)-4,6-bis(2.4-dimethylphenvn-
1.3.5-triazine by Treating It in Solid Form with Aqueous Triethylamine
To a flask was added 5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines as impurities and 25
mL of 5% aqueous triethylamine solution. The mixture was heated to 80°C for 1
hour. The pH of the mixture was about 10. The heating was discontinued, and the
mixture cooled to room temperature. It was then filtered, the filter cake washed first
with 5% aqueous triethylamine solution and then with water, and dried to give 4.7 gm
of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, which was
analyzed by HPLC to be free of polyresorcinol-triazine impurities.
Example 18: Isolation of 2-(2.4-dihvdroxvphenyl)-4,6-bis(3.4-dimethylPhenyl)-
1,3,5-triazine bv Treatment of the Solid Mixture with Aqueous Triethvlamine
A mixture of 5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-
1,3,5-triazine containing polyresorcinol-triazines as impurities and 25 mL of 5%
aqueous triethylamine solution. The mixture was heated to 80°C for 1 hour. It was
cooled to room temperature, filtered, the filter cake washed first with 15 mL 5%
aqueous triethylamine solution, followed by three 15 mL water washes. The filtered
product (4.7 gm) was analyzed by HPLC to contain 2-(2,4-dihydroxyphenyl)-4,6-
bis(3,4-dimethylphenyl)-1.3,5-triazine with no polyresorcinol-triazine detected.
Example 19: Isolation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3.5-triazine bv Treatment of the Solid Mixture with
Aqueous Methanolic Triethvlamine
To a flask was added 5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines as impurities and 25
mL of 5% triethylamine solution prepared in aqueous methanol (1:1). The mixture
was heated to 60°C for 1 hour. It was cooled to room temperature, filtered, the filter
cake washed first with 15 mL 5% aqueous methanolic triethylamine solution, followed
by three 15 mL water washes. The filtered product (4.6 gm) was analyzed by HPLC
to contain 2-(2,4-dihydroxyphenyl)-4,6-bis(2l4-dimethylphenyl)-1,3,5-triazine with no
polyresorcinol-triazine detected.
Example 20: Isolation of 2-(2.4-dihvdroxvphenyl)-4.6-bis(2,4-dimethvlphenvD-
1.3,5-triazine bv Treatment of the Solid Mixture with Methanolic Triethvlamine
To a flask was added 5 gm of 2-(2,4-dihydroxyphenyi)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine containing polyresorcinol-triazines as impurities and 25
mL of 5% triethylamine in methanol. The mixture was heated to 60°C for 1 hour. It
was cooled to room temperature, filtered, the filter cake washed first with 15 mL 5%
methanolic triethylamine solution, followed by two 15 mL methanol washes. The
filtered product (4.2 gm) was analyzed by HPLC to contain 2-(2,4-dihydroxyphenyl)-
4,6-bis(2,4-dimethylphenyl)-1l3,5-triaztne with no polyresorcinol-triazine detected.
Example 21: Isolation of 2-(2,4-dihydroxyphenyl)-4,6-bis(ethylphenyI)-1,3,5-
triaztne by Treatment of Its Solution with Aqueous Sodium Carbonate
To a flask equipped with a reflux condenser, a nitrogen inlet, and a magnetic
stirrer was added 50 mL of ethyl acetate and 5 gm of crude 2-(2,4-dihydroxyphenyl)-
4,6-bis(ethylphenyl)-1,3,5-triazine prepared by the procedure in WO 00/29392
containing polyresorcinol-triazines as impurities and stirred at room temperature to
form a solution. To it was then added 25 mL 5% aqueous sodium carbonate solution,
and the contents stirred for 10 minutes at room temperature. The organic layer was
then separated, washed with water twice and dried over anhydrous sodium sulfate.
The solvent was then removed under reduced pressure to give 4.6 gm of 2-(2,4-
dihydroxyphenyl)-4,6-bis(ethylphenyl)-1,3,5-triazine which was analyzed by HPLC to
contain no polyresorcinol-triazine impurities.
Example 22: Isolation of 2-(2,4-dihydroxyphenvl)-4,6-bis(methylphenynyl)-1,3,5-
triazine by Treatment with Aqueous Sodium Carbonate
To a flask equipped with a reflux condenser, a nitrogen inlet, and a mechanical
stirrer was added 30 mL of 5% aqueous sodium carbonate, and 5 gm of crude 2-
(2,4-dihydroxyphenyl)-4,6-bis(methylphenyl)-1,3,5-triazine containing polyresorcinol-
triazines as impurities prepared by the procedure in WO 00/29392. The resulting
mixture was heated to reflux, and it was held at reflux for 1 hour. The pH of the
mixture was about 10. The heating was discontinued, and the mixture was allowed to
cool to room temperature. It was then filtered, the filter cake washed with 15 mL 5%
aqueous sodium carbonate solution followed by three 20 mL water washes. The
fittered product (4.7 gm) thus obtained was analyzed by HPLC to be 2-(2,4-
dihydroxyphenyl)-4,6-bis(methylphenyl)-1,3,5-triazine free of polyresorcinol-triazine
impurities.
Example 23: Isolation of 2-(2.4-dihvdroxvphenvl)-4.6-bi3phenvl-1.3.5-triazine by
Treatment with Aqueous Sodium Carbonate
To a flask equipped with a reflux condenser, a nitrogen inlet, and a mechanical
stirrer was added 10 mL of 5% aqueous sodium carbonate, and 2 gm of crude 2-(2,4-
dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine containing polyresorcinol-triazines as
impurities prepared by the procedure in WO 00/29392. The resulting mixture was
heated to reflux, and it was held at reflux for 1 hour. The heating was discontinued,
and the mixture was allowed to cool to room temperature. It was then filtered, the
fitter cake washed with 5 mL 5% aqueous sodium carbonate solution followed by
three 10 mL water washes. The filtered product (1.8 gm) thus obtained was analyzed
by HPLC to be 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine free of
polyresorcinol-triazine impurities.
Example 24: Isolation of 242.4-dthvdroxvPhenvn-4.6-bis(chlorophenvl)-1,3,5-
triazine by Treatment with Aqueous Sodium Carbonate
To a flask equipped with a reflux condenser, a nitrogen inlet, and a mechanical
stirrer was added 30 mL of 5% aqueous sodium carbonate, and 5 gm of crude 2-(2,4-
dihydroxyphenyl)-4,6-bis(chlorophenyl)-1,3,5-triazine containing polyresorcinol-
triazines as impurities prepared by the procedure in WO 0029392. The resulting
mixture was heated to reflux, and it was held at reflux for 1 hour. The heating was
discontinued, and the mixture was allowed to cool to room temperature. It was then
filtered, washed the filter cake with 15 mL 5% aqueous sodium carbonate solution
followed by three 20 mL water washes. The filtered product (4.6 gm) thus obtained
was analyzed by HPLC to be 2-(2,4-dihydroxyphenyl)-4,6-bis(chlorophenyl)-1,3,5-
triazine-free of polyresorcinol-triazine impurities.
Example 25: Isolation of 2-(2.4-dihvdroxyphenvl)-4.6-bis(2.4-dimethvlphenvn-
1.3.5-triazine by Treating with Methanol to Remove Polyresorcinol-triazines
To a flask equipped with a reflux condenser, a nitrogen inlet, and a mechanical
or magnetic stirrer was added 6 gm of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine prepared by procedure in WO 00/29392 containing
polyresorcinol-triazines as impurities and 60 mL of methanol. The mixture was
heated to reflux for 1 hour. The heating was discontinued and the mixture allowed to
cool to room temperature. It was then filtered, and the filter cake washed with 25 mL
methanol. The filtered material (5.3 gm) was identified by HPLC to be 2-(2,4-
dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine containing no
polyresorcinol-triazines.
WE CLAIM:
1. A process for isolating a compound of Formula 1
wherein Ar1 and Ar2 are the same or different and are radicals of the
compound of Formula 2
And wherein R1 is hydrogen and R2, R3, R4 and R5, are the same or different
and are hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon
atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of
1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24
carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons
atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted
naphthalene, OR, NRR', CONRR', OCOR, CN, SR, SO2R, and optionally with
either of R3 and R4 or R4 and R5 taken together being a part of a saturated or
unsaturated fused carbocyclic ring and wherein each R, R', R6, R7, R8, R9 and
R10 are the same or different and each is hydrogen, alkyl of 1 to 24 carbon
atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1
to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyl of 6 to 24 carbon atoms, substituted or unsubstituted
biphenylene, substituted or unsubstituted naphthalene, and optionally with
either of R6 and R7, R7 and R8, R8 and R9 or R9 and R10, taken together being
a part of a saturated or unsaturated fused carbocyclic ring optionally having
0, N or S atoms in the ring, and R6, R7, R8, R9 and R10 may be an alkoxy of 1
to 24 carbons, and Y is a direct bond, 0, NR", or wherein R" is hydrogen,
alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to
24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon
atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon atoms;
wherein said process comprises the step of:
contacting a product mixture with a base to form an isolation blend,
wherein said product mixture comprises said compound of Formula 1 and
a poiyphenoiic-triazine compound.
2. The process as claimed in claim 1 wherein said base is an inorganic
base such as herein described.
3. The process as claimed in claim 2 wherein said inorganic base is
selected from the group consisting of :LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2,
Zn(OH)2AI(OH)3, NH4OH, Li2CO3,Na2CO3, K2CO3, MgCO3, CaCO3, ZnCO3,
(NH4)2CO3/BaCO3/ CaMg(CO3)2, NaHCO3, KHCO3, (CaO), BaO, LiNH2, NaNH2,
KNH2, Mg(NH2)2, Ca(NH2)2, Zn(NH2)2, AI(NH2)3, NaH, CaH2, KH, LiH, and
mixtures thereof.
4. The process as claimed in claim 1 wherein said base is an organic base
is an organic base such as herein described.
5. The process as claimed in claim 4 wherein the organic base is an amine
that is primary, secondary, tertiary, aliphatic, cyclic, acyclic, aromatic,
heteroaromatic, or heterocyclic; or salts of primary amine, secondary amine,
alcohol, or organic acid.
5. The process as claimed in claim 5 wherein said organic base is selected
from the group consisting of the salts of CH3O",CH3CH2O', CH3CH2CH2O,
(CH3)2CHO\ ((CH3)2CH)2CHCr, CH3CH2CH2CH2O-, (CH3)3CO', CH3NH",
CH3CH2NH', CH3CH2CH2NH-, (CH3)2CHNH'f ((CH3)2CH)2CHNrf,
CH3CH2CH2CH2NH-/ (CH3)3CNH-/(CH3)2N,(CH3CH2)2N-, (CH3CH2CH2)2N'
,((CH3)2CH)2N,(((CH3)2CH)2CH)2N-, (CH3CH2CH2CH2)2N,((CH3)3C)2N-/
formate, acetate, propylate, butanoate, benzoate, and CH3NH2,
CH3CH2NH2, CH3CH2CH2NH2, (CH3)2 CHNH2((CH3)2CH)2CHNH2/
CH3CH2CH2CH2NH2, (CH3)3CNH2,(CH3)2NH, (CH3CH2)2INIH, (CH3CH2CH2)2NH/
((CH3)2CH)2NH, ((CH3)2CH)2EtN, (((CH3)2CH)2CH)2NHXCH3CH2CH2CH2)2NH/
((CH3)3C)2NH, (CH3)3N/(CH3CH2)3N, (CH3CH2CH2)3N,(((CH3)2CH)2CH)3N/
(CH3CH2CH2CH2)3N/ ((CH3)3C)3N, pyrrolidine, piperidine, N-alkylpiperidine,
piperazine, N-alkylpiperazine, N,N-dialkyliperazine, morpholine, N-
alkylmorphoiine, imidazole, pyrrole, pyridine, Iutidine,4-N,N-
dimethylaminopyridine, aniline, N,N-dialkylaniline tetramethylenedlamine and
mixtures thereof.
7. The process as claimed in claim 1 wherein said product mixture is in a
solid form.
8. The process as claimed in claim 1 wherein said base is dissolved in at
least one first solvent such as herein described.
9. The process as claimed in claim 8 where said first solvent is selected from
the group consisting of: water, an alcohol, acetonitrile, tetrahydrofuran,
toluene, heptane and mixtures thereof.
lO.The process as claimed in claim 7 further comprising the step of filtering
said isolation blend.
ll.The process as claimed in claim 8 wherein said contacting step is at a
temperature of between about 10°C to about the reflux temperature.
12. The process as claimed in claim 1 wherein said contacting step is at a
pH between about 7 to about 14.
13.The process as claimed in claim 10 further comprising the step of
contacting a filtrate from said filtering step with an acid to isolate a
polyphenolic triazine compound.
14. The process as claimed in claim 1 wherein said product mixture is
dissolved in at least one second solvent such as herein described.
15. The process as claimed in claim 14 wherein said second solvent is
selected from the group consisting of: methylisobutylketone,
methylethylketone, cyclohexanone, ethyl acetate, butyl acetate, methylene
chloride, chloroform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene,
dichlorobenzene, toluene, xylenes and mixtures thereof.
16. The process as claimed in claim 1 wherein said base is dissolved in at
least one first solvent and said product mixture is dissolved in at least one
second solvent, wherein said second solvent is substantially immiscible in said
first solvent, and wherein at least two distinct layers are formed.
17. The process as claimed in claim 16 wherein at least one of said layers
is aqueous-based and at least one of said layers is organic-based, wherein
said process further comprises the step of separating said aqueous-based
layer from said organic-based layer.
18. The process as claimed in claim 1 wherein said compound of Formula
lis
19. The process as claimed in claim 17 further comprising the steps of
isolating a polyphenolic-triaziner compound from said aqueous-based layer by
contacting said aqueous-based layer with an acid;
and extracting said polyphenolic-triazine compound by solvent extraction.
20. A process for isolating a compound of Formula 1
Wherein Ar1 and Ar2 are the same or different and are radicals of the
compound of Formula 2
And wherein R1 is hydrogen and R2, R3, R4 and R5, are the same or different
and are hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon
atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of
1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24
carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon
atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted
naphthalene, OR, NRR', CONRR', OCOR, CN, SR, SO2R, and optionally with
either of R3 and R4 or R4 and R5 taken together being a part of a saturated or
unsaturated fused carbocyclic ring and wherein each R, R', R6, R7, R8, R9 and
R10 are the same or different and each is hydrogen, alkyl of 1 to 24 carbon
atoms, haloalkyl of 1 to 24 carbon atos, aryl of 6 to 24 carbon atoms, alkenyl
of 2 to 24 carbon atoms, acryl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24
carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon
atoms, or aracyl of 6 to 24 carbon atoms, substituted or unsubstituted
biphenylene, substituted or unsubstituted naphthalene, and optionally with
either of R6 and R7 , R7 and R8, R8 and R9 or R9 and R10, taken together
being a part of saturated or unsaturated fused carbocyclic ring optionally
having O, N, or S atoms in the ring, and R6, R7, R8, R9 and R10 may be an
alkoxy of 1 to 24 carbons, and Y is direct bond, 0, NR", or SRI/wherein R" is
hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms,
aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24
carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon
atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms;
wherein said process comprises the steps of:
contacting a product mixture with an alcohol such as herein described to form
an isolation blend;
heating said isolation blend at a temperature of about 40°C to about 200°C
for a period of 10 minutes to 10 hours,
wherein said product mixture comprises said compound of Formula 1 and a
polyphenolic-triazine compound.
21.The process as claimed in claim 20 wherein said product mixture is in a
solid form.
22.The process as claimed in claim 21 further comprising the step of filtering
said isolation blend.
23.The process as claimed in claim 20 wherein said alcohol is selected from
the group consisting of: methanol, ethanol, propanol, isopropanol, butanol,
isobutanol, 1-butanol, 1,2-ethanediol, 3-chloro-l-propanol, 2-hydroxyl-acetic
acid, l-hydroxy-3-pentanone, cyclohexanol, cyclohexanol, glycerol , benzyl
alcohol and mixtures thereof.
24. The process as claimed in claim 20 wherein the amount of said alcohol is
about 1 to about 20 parts per part compound of formula 1.
25. The process as claimed in claim 20 wherein said compound of
Formula 1 is
26. A process for isolating a compound of Formula 1
wherein Ar1 and Ar2 are the same or different and are radicals of the
compound of Formula 2
And wherein R1 is hydrogen and R2, R3, R4 and R5 are the same or different
and are hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon
atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of
1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24
carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons
atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted
naphthalene, OR, NRR', CONRR', OCOR, CN SR, SO2R, and optionally with
either of R3 and R4, or R4 and R5 taken together being a part of a saturated or
unsaturated fused carbocyclic ring and wherein each R, R', R6, R7, R8, R9, and
Rio are the same or different and each is hydrogen, alkyl of 1 to 24 carbon
atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1
to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyl of 6 to 24 carbon atoms, substituted or unsubstituted
biphenylene, substituted or unsubstituted naphthalene, and optionally with
either of R6 and R7, R7 and R8, R8 and R9 or R9 and R10, taken together being a
part of a saturated or unsaturated fused carbocylic ring optionally having 0,
N, or S atoms in the ring and R6, R7, R8, R9 and R10 may be an alkoxy of 1 to
24 carbons, and Y is a direct bond, 0, NR", or wherein R" is hydrogen, alkyl
of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24
carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl
of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms;
wherein said process comprises the step of:
contacting a product mixture with a hydrocarbon solvent such as herein
described to form an isolation blend, wherein said product mixture is in solid
form and comprises said compound of Formula I and a trisaryl-triazine
compound.
27. The process as claimed in claim 26 wherein said hydrocarbon solvent
is selected from the group consisting of benzene, toluene, ethylbenzene,
diethylbenzene, xylene, mesitylene, tetralin, hexane, heptane, octane,
cyclohexane, and mixtures thereof.
28. The process as claimed in claim 26 wherein said contacting step is at a
temperature of between about 10°C. to about the reflux temperature of said
isolation blend.
29. The process as claimed in claim 26 further comprising filtering said
isolation blend.
30. The process as claimed in claim 26 wherein the amount of said
hydrocarbon solvent is about 1 to about 20 parts per part compound of
Formula 1.
31. The process as claimed in claim 26 wherein said compound of Formula
1is
32. A process for isolating a compound of Formula 1
wherein Ar1 Ar2 are the same or different and are radicals of the compound of
Formula 2
and wherein R1 is hydrogen and R2, R3, R4 and R5 are the same or different
and are hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon
atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of
1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24
carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons
atoms, substituted or unsubstituted biphenylene,, substituted or
unsubstituted naphthalene, OR, NRR', CONRR', OCOR, CN, SR, SO2R, and
optionally with either of R3 and R4 or R4 and R5 taken together being a part of
a saturated or unsaturated fused carbocyclic ring and wherein each R, R', R6,
R7, R8, R9 and R10 are the same or different and each is hydrogen, alkyl of 1
to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon
atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cyloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl
of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, substituted or
unsubstituted biphenylene, substituted or unsubstituted naphthalene, and
optionally with either of R6 and R7, R7 and R8, R8 and R9 or R9 and R10 taken
together being a part of a saturated or unsaturated fused carbocyclic ring
optionally having O, N, or S atoms in the ring, and R6 R7, R8, R9. R10 may be
an alkoxy of 1 to 24 carbons, and Y is a direct bond, 0, NR", or wherein R" is
hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms,
aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24
carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon
atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms;
wherein said process comprises the step of:
contacting a product mixture with at least two components selected from the
group consisting of a base, an alcohol and a hydrocarbon solvent, wherein
said product mixture comprises said compound of Formula 1 and a
polyphenolic-triazine compound.
33. The process as claimed in claim 32 wherein said components are a
base and a hydrocarbon solvent.
34. The process as claimed in claim 32 wherein said components are an
alcohol and a hydrocarbon solvent.
35.The process as claimed in claim 32 wherein said contacting is performed
in a step-wise manner.
36. The process as claimed in claim 32 wherein said contacting is performed
in one-step manner.
37. The process as claimed in claim 32 wherein said compound of Formula 1
is
A process for isolating a compound of Formula 1
wherein Ar1 and Ar2 are the same or different and are radicals of the
compound of Formula 2
And wherein R1 is hydrogen and R2, R3, R4 and R5, are the same or different
and are hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon
atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of
1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24
carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons
atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted
naphthalene, OR, NRR', CONRR', OCOR, CN, SR, SO2R, and optionally with
either of R3 and R4 or R4 and R5 taken together being a part of a saturated or
unsaturated fused carbocyclic ring and wherein each R, R', R6, R7, R8, R9 and
R10 are the same or different and each is hydrogen, alkyl of 1 to 24 carbon
atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1
to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24
carbon atoms, or aracyl of 6 to 24 carbon atoms, substituted or unsubstituted
biphenylene, substituted or unsubstituted naphthalene, and optionally with
either of R6 and R7, R7 and R8, R8 and R9 or R9 and R10, taken together being
a part of a saturated or unsaturated fused carbocyclic ring optionally having
O, N or S atoms in the ring, and Rs, R7, R7, R9 and R10 may be an alkoxy of 1
to 24 carbons, and Y is a direct bond, O, NR", or wherein R" is hydrogen,
alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to
24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon
atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon atoms;
wherein said process comprises the step of:
contacting a product mixture with a base to form an isolation blend,
wherein said product mixture comprises said compound of Formula 1 and
a polyphenolic-triazine compound.

Documents:


Patent Number 224698
Indian Patent Application Number 00042/KOLNP/2004
PG Journal Number 43/2008
Publication Date 24-Oct-2008
Grant Date 22-Oct-2008
Date of Filing 13-Jan-2004
Name of Patentee CYTEC TECHNOLOGY CORP.
Applicant Address 300 DELAWARE AVENUE, WILMINGTON, DE
Inventors:
# Inventor's Name Inventor's Address
1 GUPTA, RAM BABOO 511 WEST MAIN STREET, UNIT 19 STAMFORD, CA 06902
2 SINGH, HARGURPREET 2 BEHRLE DRIVE, ANSONIA, CT 06401
3 CAPPADONA, RUSSELL C. 63VALLEY VIEW COURT NORWAK, CT 06851
PCT International Classification Number C07D 251/00
PCT International Application Number PCT/US02/16055
PCT International Filing date 2002-05-21
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/887,128 2001-06-22 U.S.A.