Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
1993-10-15
2001-03-06
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C544S194000, C544S200000, C544S205000, C544S207000, C544S212000
Reexamination Certificate
active
06197957
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the preparation of isocyanate and carbamate functional derivatives of optionally halogenated amino-1,3,5-triazines via carbonylation using carbon monoxide and a metal promoter for promoting carbonylation.
2. Description of Related Art
Various derivatives of (halo)amino-1,3,5-triazines are described in the literature as being utilized in a wide variety of fields. An important use of certain of these derivatives, such as methoxymethyl derivatives of melamine and guanamines, is as crosslinkers and/or reactive modifiers in curable compositions which contain resins having active hydrogen groups. While these methoxymethyl derivatives provide excellent results in a number of aspects, they also have the disadvantage of releasing formaldehyde as a volatile by-product under curing conditions. It has long been a desire of industry to find acceptable alternatives which do not emit formaldehyde upon cure.
One such alternative that has shown great promise is carbamate functional 1,3,5-triazines which are disclosed in commonly owned U.S. Pat. No. 4,939,213, U.S. Pat. No. 5,084,541, U.S. application Ser. No. 07/968,871, now U.S. Pat. No. 5,288,865 (filed Oct. 30, 1992, which is a continuation-in-part of U.S. application Ser. No. 07/793,077, filed Nov. 15, 1991 and now abandoned), U.S. application Ser. No. 07/998,313, now U.S. Pat. No. 5,571,103 (filed Dec. 29, 1992) and U.S. application Ser. No. 08/061,905, now abandoned (filed May 14, 1993), all of which are hereby incorporated by reference herein as if fully set forth. Specifically, the carbamate functional 1,3,5-triazines disclosed in these references have been found to be particularly useful as crosslinkers in coating compositions based upon hydroxy functional resins, with the cured coatings possessing a wide range of desirable properties.
One hinderance to the commercial use of these carbamate functional 1,3,5-triazines has been that the known preparation methods can be somewhat cumbersome, difficult and expensive. For example, in previously incorporated U.S. Pat. No. 4,939,213 and U.S. Pat. No. 5,084,541, the 1,3,5-triazine carbamates are produced in a two-step process by first reacting an amino-1,3,5-triazine with oxalyl chloride to produce an isocyanate functional intermediate, then reacting this intermediate with an alcohol. Further, in previously incorporated U.S. application Ser. No. 07/968,871, now U.S. Pat. No. 5,288,865, carbamate functional 1,3,5-triazines are produced in a one-step process by reacting a haloamino-1,3,5-triazine with an acid halide. The primary disadvantages to these process include the use of certain costly halogenated starting materials, production of substantial amounts of halogenated by-products, and low ultimate yield of the desired products.
Many of the problems with these processes have been solved by the process disclosed in previously incorporated U.S. application Ser. No. 08/061,905, wherein carbamate functional 1,3,5-triazines are produced by reacting an at least bis-amino 1,3,5-triazine with an acyclic organic carbonate in the presence of a strong base. Disadvantages to this process include, for example, that the strong base must be neutralized to remove it from the end product, and that certain aspects of the reaction must be carefully controlled in order to avoid color in the end product.
It has now been surprisingly discovered after extensive research that isocyanate functional 1,3,5-triazines can be produced without many of the disadvantages of the prior art processes by the carbonylation of (halo)amino-1,3,5-triazines with carbon monoxide in the presence of a metal promoter for promoting carbonylation. These isocyanate functional 1,3,5-triazines may be readily converted to the carbamate counterparts either by carrying out the carbonylation in the presence of a hydroxy compound or by adding the hydroxy compound to the isocyanate functional 1,3,5-triazine without isolating it.
It should be noted that it is generically known to obtain isocyanates via the carbonylation of (halo)amines, and carbamates by the further reaction of those isocyanates with hydroxy compounds. As representative disclosures, reference can be made to the following, which are incorporated by reference herein as if fully set forth:
Saegusa, T. et al., “Carbonate Formation by the Reaction of Cupric Methoxide and Carbon Monoxide,”
Tetrahedron Letters
, 7, pp. 831-833 (1968);
Saegusa, T. et al., “Carbamoyl Chloride Formation from Chloroamine and Carbon Monoxide,”
J. Org. Chem
., 36(6), pp. 858-860 (1971);
Fukuoka, S. et al., “A Novel Catalytic Synthesis of Carbamates by Oxidative Alkoxycarbonylation of Amines in the Presence of Palladium and Iodide,”
J. Chem. Soc., Chem. Commun
., pp. 399-400 (1984);
Chow, Y. L. et al., “A Novel Catalytic Synthesis of Carbamates by the Oxidative Alkoxycarbonylation of Amines in the Presence of Platinum Group Metal and Alkali Metal Halide or Onium Halide,”
J. Org. Chem
., 49, pp. 1458-1460 (1984);
P. Giannoccarro, “Palladium Catalysed N,N′-Disubstituted Urea Synthesis by Oxidative Carbonylation of Amines under CO and O
2
at Atmospheric Pressure,”
Journal of Organometallic Chemistry
, 336, pp. 271-278 (1987);
Davies, C. and M. Kilner, “A Study of Palladium-Catalysed Carbonylation of N-Chloroamines,”
Journal of Catalysis
, 136, pp. 403-414 (1992);
U.S. Pat. No. 3,405,156; U.S. Pat. No. 3,641,092; EP-A-0083096; U.S. Pat. No. 5,008,435; U.S. Pat. No. 5,068,424 and U.S. Pat. No. 5,194,660.
This chemistry, however, has apparently not been applied to (halo)amino-1,3,5-triazines. Indeed, one of ordinary skill in the art could not reasonably expect success in doing so, since it is well-known to the skilled person that the amine functionality of amino-1,3,5-triazines (such as the amine functionality of melamines and guanamines) is not equivalent to the other types of typical amine functionality. Melamines and guanamines are among the least reactive of the “amines” and the most difficult to functionalize, and their behavior cannot normally be correlated to that of other known amines, even structurally similar amines such as pyrimidines.
For example, most “typical” amines are highly reactive with acid halides. In a publication by E. M. Smolin and L. Rappaport entitled “S-Triazines and Derivatives,” Interscience Publishers Inc., New York, page 333 (1959), it is reported that attempts to react an acid halide with the amino group on a 1,3,5-triazine such as melamine were not successful. Further, attempts to functionalize amino-1,3,5-triazines often results in substitution at the nitrogen on the triazine ring. For example, it is known that the reaction of melamine with alkyl halides, such as allyl chloride, results in alkyl substitution at the nitrogen on the triazine ring resulting in isomelamine derivatives.
In light of the known literature, therefore, it is in fact quite surprising that amino- and haloamine-1,3,5-triazines can be carbonylated under the conditions as described below.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a process for preparing carbonylated derivatives of (halo)amino-1,3,5-triazines, comprising the step of contacting
(a) a (halo)amino group-containing 1,3,5-triazine represented by the formula:
wherein each Q is independently selected from the group consisting of hydrogen and halogen,
Z is selected from the group consisting of a group represented by the formula —N(Q
1
)
2
, and a group represented by the formula:
Z
1
is selected from the group consisting of hydrogen, hydrocarbyl, a group represented by the formula —N(Q
1
)
2
, and a group represented by the formula:
A is an n-functional anchor,
n is at least 2,
each Q
1
is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl and a hydrocarbyloxy hydrocarbyl, and
each Z
2
is independently selected from the group consisting of hydrogen, hydrocarbyl and a group represented by the formula —N(Q
1
)
2
;
(b) carbon monoxide; and
(c) a metal catalyst system con
Flood Lawrence A.
Forgione Peter S.
Gupta Ram B.
Valentine Donald H.
Cytec Technology Corp.
Didamo Valerie T.
Negron Liza
Raymond Richard L.
Schultz Claire M.
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