KR100254048B1 - Process for preparing amide derivatives from haloamines and acid halides - Google Patents

Abstract

PURPOSE: Provided is a preparation method of amide derivatives of acids by a novel reaction which combines the amino group of a haloaminotriazine with the non-halide portion of an acid halide. The reaction also combines the halogen atom of the haloaminotriazine with the halogen atom of the acid halide producing a halogen molecule as a by-product. Also, provided is a novel process of preparing isocyanates and isocyanate adducts from haloaminotriazines and selected acid halides. CONSTITUTION: A process for preparing acid amide from haloamino triazine and acid halides is characterized by contacting a haloaminotriazine with an acid halide at a temperature and for a length of time to produce an acid amide.

Description

PROCESS FOR PREPARING AMIDE DERIVATIVES FROM HALOAMINES AND ACID HALIDES

Amides can be prepared by the reaction of amines with acid halides. The reaction of amines with acid chlorides is very common, but when the amine is inactivated in the presence of at least one electron withdrawing substituent, this reaction is sluggish and often does not occur. In some cases, the preparation of the amide may be possible by first dehydrogenating the amine with a strong base to produce anions and then allowing the amine to react with the acid halide. However, this approach is often impractical, expensive and very limited in some respects, and even if the amine is low in water, it is not feasible with high molecular weight or both.

Triazine tris-carbamate has been prepared by converting aminotriazine to isocyanate groups by reacting aminotriazine with oxalyl chloride followed by alcohol. This two-step approach is described in US Pat. Nos. 4,939,213 and 5,084,541. These patents also describe curable compositions using triazine tris-carbamate. The preparation of other carbamates by the above-mentioned approach is described in a paper by U. Von Gizycki in Angewandte Chemie, International Edition, Vol. 10, page 403 (1971) entitled 'Isocyanato-S-triazine'. It is. The authors here describe up to now that only one isocyanato-S-triazine, ie 2,4-dichloro-6-isocyanate derivative, has been previously separated by a route that cannot be generalized from tetramer cyanogen chloride.

Partially successful attempts to prepare mono- and bis-carbamates from aminotriazines and haloformates have been described by Yuki Gosei Kagaku Kyokai Shi by H. Kitajima, T. Imanaka, and T. Yamomoto 'Melamine Derivatives 18: Melamine and Reaction of Benzoguanamine with Ethyl Chlorocarbonate ', Vol. 32, No. 9, pages 723-726 (1974); Chem. Abstract 82, no. 11: 72946d. However, this article does not mention the preparation of tris-carbamate.

Preparation of halomelamine is described in US Pat. No. 2,184,888; 2,184,886; 2,184,886; And 2,184,883; 3,743,642; And 2,472,361; South African Patent No. 66-03546; And European Patent No. 239,121. The reaction of oxalyl chloride with N, N-dichloroalkylamine or N, N-dichloroamide to form N-chloro-N-alkyloxamyl chloride or isocyanate is described by Zh, Org, Khim. Chemistry Abstract, Vol. 75 (21), item 129306 g, summarized from the Russian paper in Volume 7, p 1541 (1971). The reaction of N-chlorocarboxamide ester with oxalyl chloride is described by Zh, Org. Khim., Vol. 6, No. 1, abstracted from a Russian paper in P 85-88 (1970), Vol. 72 (17), item 90006v.

It is well known that the chemistry of amines and triazines is very different. E.M. entitled "S-triazines and derivatives". A publication by Smolin and L. Rapaport, Interscience Publishers Inc., New York, page 333 (1959), reported that attempts to react amino groups on triazines such as acid halides and melamines have not been successful. Similarly, the reaction of melamine with alkyl halides such as aryl chlorides is known to result in alkyl substitution in nitrogen on the triazine ring resulting in isomeramine derivatives.

Melamine chemistry, in particular halomelamine chemistry, including preparation and application, is described in B. Bann and S.A., entitled 'Melamine and Melamine Derivatives'. The paper by Miller, Chemical Reviews, Vol. 58, pages 131-172 (1958). Here on page 148, it is stated that acyl halides such as benzoyl chloride in the Schotten-Baumann reaction have no effect on melamine. The inactivation of melamine to acid halides is additionally described in Chemical Abstract 30, p 465 (1936) and US Pat. No. 2,557,418.

Given the reported problems faced by practitioners in the field of melamine and aminotriazine chemistry, a novel method of overcoming the above-mentioned problems and providing a general method for preparing acylated aminotriazines from a wide range of useful haloaminotriazine precursors One chemical reaction would be a valuable addition to the very limited methods currently available. When not commercially available, haloaminotriazine is readily prepared by known methods throughout.

It is an object of the present invention to provide a simple process for preparing amides from haloaminotriazines and acid halides.

It is also an object of the present invention to provide a process for preparing isocyanates starting from halo aminotriazines and acid halides.

Another object of the present invention is to provide a process for preparing isocyanate adducts starting from halo aminotriazines and acid halides.

1 diagrammatically illustrates a method for producing triazine tris-methyl carbamate from melamine via trichloromelamine.

2 diagrammatically illustrates a method of producing triazine tris-methyl carbamate via hexachloromelamine from melamine.

The present invention relates to a process for the preparation of amide derivatives of acids by a novel reaction combining the amino groups of haloaminotriazines and the non-halide portions of acid halides. This reaction also combines the halogen atoms of the haloaminotriazine and the halogen atoms of the acid halide to produce halogen molecules as by-products. The present invention also relates to a novel process for preparing isocyanates and isocyanate adducts from haloaminotriazines and selected acid halides.

The present invention involves a novel chemical reaction that combines the amine group of haloaminotriazine and the non-halide portion of an acid halide to produce acid amides and recyclable halogens. The preparation of isocyanates is accomplished by decomposing certain acid amides into isocyanates, and then isocyanate adducts are prepared by reacting the isocyanates with active hydrogen-containing compounds.

The present invention is prepared by the reaction of combining the amino group of haloaminotriazine and the non-halide portion of an acid halide. At the same time, the novel reaction also combines the halogen atoms of the haloaminotriazine with the halogen atoms of the acid halide to produce halogen molecules as recycleable by-products. The invention also provides a process for preparing isocyanates and isocyanate adducts starting from haloaminotriazines and certain acid halides, which degrade the selected acid amide into isocyanates and additionally react the isocyanates with active hydrogen-containing compounds. It consists of forming an isocyanate adduct.

The method of the present invention has many advantages, some of which are described below. For example, these methods produce products characterized by low salt, hazy color, high purity, and high yield. The method is also applicable for use with acid or base sensitive substrates and is carried out in neutral media. Most importantly, the present invention allows easy functionalization and separation of aminotriazine derivatives such as melamine and benzoguanamine without the use of formaldehyde. Another advantage described herein is to allow easy functionalization of insoluble amines such as melamine by simple halogenation, acylation, and dehalogenation cycles. The process of the present invention may also be used with certain acid halides, such as oxalyl chloride or phosgene, to provide a process for the preparation of isocyanates and isocyanate adducts, especially aminotriazines.

The invention also provides novel products made by the process of the invention.

The present invention is a novel process for the preparation of specific acid amides from haloaminotriazines and acid halides, the haloaminotriazines and the acid halides for a temperature and time sufficient to produce the acid amides as products and the halogens as byproducts. Contacting the step.

As used herein, the term 'acid halide' refers to a weak acid or strong hydroxyl acid derivative in which the hydroxy group is converted to halogen. Examples of acid halides usable in the present invention are acetyl chloride, which can be derived from acetic acid by converting the acid hydroxy group to chloride with a suitable reagent. Any acid halide can be used in the present invention. The term 'acid amide' is used in the context of the present invention to denote a product derived from an acid halide by simply replacing the halide atom of the acid halide with the amino group of the halo aminotriazine. Moreover, in the present invention, carbamate can be derived from halo-formates by substituting halides for amino groups, so carbamate can be regarded as 'acid amide' as defined herein.

The term 'haloaminotriazine' is defined herein as an aminotriazine compound in which at least one amino nitrogen-bonded hydrogen is replaced with a halogen atom.

Acid halides and haloaminotriazine reactants and the acid amides resulting from their novel reactions are described in more detail below.

New reactions

The reaction of amines with acid halides is known and can be illustrated by the following formula (1):

Eq. (One)

Amides and amines are known to readily N-acylate with acyl halides, while triazines such as melamine are also known to not N-acylate with acyl halides, as discussed above. Surprisingly, however, new, unreported reactions have occurred between haloaminotriazine and acid halides. The novel reaction is illustrated by the following formula (2):

Eq. (2)

Wherein R ¹ is a triazine nucleus and R ³ is a substituent on the acid halide. The substitution of haloaminotriazines in amino halides instead of amino protons in the novel reactions was totally unexpected based on known amine chemistry. The novel reaction will also occur if the amino hydrogen is replaced by halogen or other substituents.

The reaction according to formula (2) and other similar amide-forming reactions of halo aminotriazines and acid halides are referred to herein as 'new reactions of the present invention'.

Halo aminotriazine

The haloaminotriazine that can be used in the present invention is an aminotriazine compound in which at least one nitrogen-bonded hydrogen is substituted with a halogen atom.

The amine precursors of the haloaminotriazines of the invention may be monomers or polymers. They may be very soluble or slightly soluble in organic solvents. Even halo aminotriazines derived from amine precursors having solubility of up to 10% by weight in organic solvents, especially halogenated organic solvents, are useful.

Haloaminotriazines usable in the process of the invention can be represented by the following formula (1).

[One]

Wherein L is at least 1; When L is at least 2,

Each The groups are the same or different;

X is halogen selected from the group consisting of chloro, bromo, iodo, and fluoro groups and mixtures thereof; B is hydrogen, chloro, bromo, iodo, fluoro, alkyl, alkylenealkoxy, triazino, pyrimidino, pyridino, imidazolo, tetrazolo, silyl, cyano, perfluoroalkyl, perfluoro Roaryl, and a perfluoroaralkyl group, and mixtures thereof;

A is an L-functional anchor selected from the group consisting of triazines represented by the following formulas [2] and [3]:

[2]

[3]

Wherein R is C ₁ -C ₂₀ linear alkyl, C ₃ -C ₂₀ cyclic or branched alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ aralkyl, C _1- C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₂₀ arylthio, C ₁ -C ₂₀ alkylamino, C ₂ -C ₄₀ di Alkylamino, morpholino, piperidino, pyrrolidino, aminotriazino, alkylaminotriazino, aminoalkylaminotriazino, hydrogen, chloro, bromo, iodo, fluoro, perfluoroalkyl, perfluoro Roaryl, and perfluoroaralkyl groups.

Any of the above haloaminotriazine mixtures can be used in the process of the invention.

When A in the general formula [1] is the triazine nucleus represented by the formula [2], the resulting haloaminotriazine is halomelamine represented by the following formula [4]:

[4]

Wherein each X group is the same or different and is selected from the group consisting of hydrogen, chloro, bromo, iodo and fluoro groups, provided that at least one X group is halogen; Wherein each B group is the same or different and is hydrogen, chloro, bromo, iodo, fluoro, triazino, pyrimidino, pyridino, imidazolo, tetrazolo, silyl, cyano, perfluoroalkyl, Perfluoroaryl, and perfluoroaralkyl group.

By way of example, haloaminotriazines include monohalomelamine, dihalomelamine, trihalomelamine, tetrahalomelamine, pentahalomelamine, hexahalomelamine, isomers thereof, and mixtures thereof. Preferred halogen in haloaminotriazine is chloride.

Preferred haloaminotriazine is chloromelamine. Most preferred chloromelamines are hexachloromelamine and the N, N ', N'-trichloromelamine isomers represented by the following formulas;

N, N ', N'-trichloromelamine (also known as N, N', N'-trichloro-2,4,6-triamino-1,3,5-triazine) is an off-white powder as Wisconsin Available from Aldrich Chemical Company, Milwaukee, Ltd. Preparation of mono-, di-, tri-, and hexa-chloromelamines, and bromo- and iodo-melamines are described in B. Bann and S.A. Miller's papers can be found on pages 159-162 and additionally described in detail in US Pat. No. 2,472,361. When A of Formula [I] is a triazine nucleus represented by Formula [3], the resulting haloaminotriazine is haloguanamine represented by Formula [5]:

[5]

X and B are the same as described above for the general formula [4]; Wherein R is C ₁ -C ₂₀ linear alkyl, C ₃ -C ₂₀ cyclic or branched alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ aralkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₂₀ arylthio, C ₁ -C ₂₀ alkylamino, C ₂ -C ₄₀ dialkyl Amino, morpholino, piperidino, pyrrolidino, aminotriazino, alkylaminotriazino, aminoalkylaminotriazino, hydrogen, chloro, bromo, iodo, fluoro, perfluoroalkyl, perfluoro And aryl and perfluoroaralkyl groups.

Haloguanamine is also among the preferred haloaminotriazines of the present invention and includes N-substituted mono-, di-, tri- and tetra-halo acetoguanamine, cyclohexyl-carboguanamine and benzoguanamine. . Especially preferred are haloguanamines in which the halogen is chloride.

Acid halide

By way of example, acid halides usable in the practice of the present invention can generally be represented by the formula:

Wherein M is at least 1; When M is at least 2 each The groups are the same or different;

X is halogen selected from the group consisting of chloro, bromo, iodo, and fluoro groups, and mixtures thereof;

Each Y in a group is the same or different and each is independently selected from the group consisting of functional groups represented by the following formulas:

Wherein each R is independently an alkyl, aryl, or alkoxy group; And

Z is hydrogen, chloro, bromo, iodo, fluoro, vinyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkylene, C ₆ -C ₂₀ arylene, C ₁ -C ₂₀ of the halo Alkyl, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₇ -C ₂₀ aralkyl, C ₇ -C ₂₀ haloaralkyl, C ₂ -C ₂₀ acyl, C ₂ -C ₂₀ haloacyl, halocarbonyl, C ₂ -C ₂₀ alkoxycarbonyl, C ₂ -C ₂₀ alkylthiocarbonyl, C ₂ -C ₂₀ haloalkoxy, aminocarbonyl, C ₂ -C ₂₀ alkyl Amino carbonyl, C ₃ -C ₂₀ dialkylaminocarbonyl, C ₄ -C ₂₀ alkenylaminocarbonyl, C ₇ -C ₄₀ dialkenyl aminocarbonyl, C ₅ -C ₂₀ alkylalkenylamino Carbonyl, triazino, pyrimidino, pyridino, imidazolo, tetrazole, C ₁ -C ₂₀ perfluoroalkyl, C ₆ -C ₂₀ perfluoroaryl, C ₇ -C ₂₀ perfluoro To aralkyl, C ₃ -C ₂₀ alkoxycarbonylalkyl, C ₂ -C ₂₀ cyanoalkyl, C ₂ -C ₂₀ Formylalkyl, C ₃ -C ₂₀ ketoalkyl, C ₄ -C ₂₀ trialkoxy silylalkyl, C ₃ -C ₂₀ dialkylaminoalkyl, C ₂ -C ₂₀ alkoxyalkyl, C ₁ -C ₂₀ Alkoxy, C ₆ -C ₂₀ aryloxy, C ₃ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkylenedioxy, C ₆ -C ₂₀ arylenedioxy, C ₂ -C ₄₀ N, N-dialkylamino, N, N-dialkenylamino of C ₆ -C ₄₀ , N, N-diarylamino of C ₁₂ -C ₄₀ , N, N-alkylalkenylamino of C ₄ -C ₂₀ , C _7- C ₂₀ N, N-alkylarylamino, C ₉ -C ₂₀ N, N-alkenylarylamino, aziridino, azetidino, pyrrolidino, piperidino, morpholino, C _1- M-functional anchor selected from the group consisting of C ₂₀ alkyl mercapto, C ₃ -C ₂₀ alkenyl mercapto, C ₆ -C ₂₀ aryl mercapto.

Preferred halogen groups are chloro, preferred Y groups are carbonyl groups, and preferred anchor Z groups are selected from alkyl, haloalkyl, and alkoxy groups.

Among the preferred acid halides suitable for use in the practice of the present invention are the following classes:

Alkyl chloroformates, aryl chloroformates, acyl chlorides, haloalkylcarbonyl chlorides, acryloyl chlorides, carbamoyl chlorides, alkylene bis acid chlorides, arylene bis acid chlorides, alkylene bis chloroformates, and phosgene.

Specific examples of acid halides usable in the present invention are the following compounds represented by the formula:

Most preferred acid halides are methyl chloro formate, n-butyl chloroformate, phenyl chloroformate, 2-chloroethyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, isobutyl chloroformate Mate, 2-ethylhexyl chloroformate, chloroacetyl chloride, 4-chlorobutyryl chloride, acryloyl chloride, methacryloyl chloride, oxalyl chloride, ethyl oxalyl chloride, benzoyl chloride, para-nitrobenzoyl chloride, Acetyl chloride, stearoyl chloride, and phosgene.

Acid amide products

The acid amide product resulting from the reaction of the above-mentioned haloamino triazine and acid halide is represented by the following formula when M = 1.

Wherein A, B, Y, Z and L are as defined above.

When M is greater than 1 but L is equal to 1, the acid amide product of the invention can be represented by the formula:

Wherein A, B, Y, Z and M are as defined above.

If both L and M are equal to 2, linear amide oligomers or polymers may be formed.

Finally, if either L or M is at least 2 and the other is greater than 2, a crosslinked polyamide network can be formed.

An example of the acid amide product of the invention resulting from the reaction of N, N ', N'-trichloromelamine with methyl chloro formate is triazine tris-carbamate represented by the formula:

Another example resulting from the reaction of N, N ', N'-trichloromelamine and 4-chlorobutyryl chloride is N, N', N'-tris (4-chlorobutyryl) melamine represented by the following formula: to be :

Another example of the acid amide product resulting from hexachloromelamine and methyl chloroformate is triazine trichloro tris-carbamate represented by the following formula.

Trichloro tris-carbamate products can be readily reduced to commercially available N-H compounds using well-known reducing agents such as alcohol / triethylamine, hydrogen halides, or sulfur compounds. The reduction product is triazine tris-carbamate and is identical to the sample prepared previously by a more direct reaction of N, N ', N'-trichloromelamine with methyl chloroformate described above. The amine-methanol reduction step is shown below:

New way

The novel process of the present invention consists in contacting haloaminotriazine with an acid halide at a temperature and for a time sufficient to produce acid amide as product and halogen as by-product.

Although higher or lower temperatures may be used, suitable reaction temperatures range from about 20 ° C to about 120 ° C. The reaction is typically carried out at about 70 ° C., but any temperature at which significant decomposition of the starting material does not occur is generally suitable.

Suitable reaction times range from about 10 minutes to about 24 hours. The reaction is typically completed within 2 to 8 hours at about 70 ° C.

The method can be performed as a continuous or batch method. It is typically performed by simply mixing the haloaminotriazine and acid halide reactants in any order. Alternatively, one of the excess reactants may be used as the liquid medium to carry out the amide formation reaction. However, liquid media are typically solvents for haloaminotriazines and acid halides. The solvent is typically an aprotic solvent that is inert to chlorine or to the reactants. The reaction can also be carried out as a biphasic reaction, illustrated as a liquid / solid biphasic reaction.

Suitable solvents in the process of the invention are halogenated solvents. Most preferably, the halogenated solvent is methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, chlorobenzene, ortho-dichlorobenzene, 1,2-dichloroethane, and any at least two of the foregoing solvents. Selected from the group consisting of mixtures.

The reactants may generally be mixed in various amounts, but at least one equivalent of acid halide per equivalent of haloaminotriazine is generally required. In particular, when the acid halide used is volatile and can be easily removed by distillation, or when the acid halide is used as the solvent in which the amide formation reaction of the present invention is carried out, the use of an excess of acid halide is appropriate.

The reactants may be conveniently mixed at room temperature in the presence or absence of a solvent, or especially below ambient temperature when the reaction is exothermic. In the endothermic reaction, after the reaction is mixed at room temperature, the reaction mixture is typically heated to promote product formation.

The reaction is usually carried out in an inert gas atmosphere under moisture free conditions. This minimizes the decomposition of reactants by moisture in the atmosphere and also minimizes the formation of undesirable hydrogen halides that can be formed from the reaction of reactants with moisture.

Under the conditions of the process of the invention, the halogen by-products produced during the reaction are substantially free of hydrogen halides.

Kinetic catalysts such as trialkyl and triaryl phosphines, quaternary ammonium halides, or monomeric or polymer 4-dialkylaminopyridine derivatives may be added to the reactants, but the method is typically performed without addition of catalyst.

Suitable dialkylaminopyridine catalysts include 4-dimethylaminopyridine, 4-pyrrolidinopyridine, 4-piperidinopyridine, and poly-2-vinyl-4-dimethylaminopyridine (polydimethylaminopyridine). Suitable quaternary ammonium halides are available from ALIQUAT® available from Kodak Laboratory Chemicals (Rochester, NY) ^. 336 tricapryl methyl ammonium chloride.

When the acid amide reaction product is obtained as a solution, a method may be used that additionally includes reaction product separation by removing volatiles under reduced pressure. Volatiles can be removed by distillation. Alternatively, or after removing the volatiles and re-dissolving the residue in the solvent, the amide is probably precipitated by adding a solvent in which the amide is substantially insoluble.

The product can be further purified by recrystallization, distillation or chromatography.

Process for producing acidamide from melamine by recycling halogen byproducts

It is the finding of the present invention that melamine can be converted to acidamide by two different methods, each involving recycling of halogen byproducts. No additional halogen input is necessary except to compensate for incidental halogen losses.

The conversion in the first new method is via trihalomelamine, and in the second new method, the conversion is via hexahalomelamine.

Both the first and second methods are characterized by the following: Halogen by-products are recycled for use in converting additional melamine to hexahalomelamine. The two methods differ in that the second method involves contacting hexahalomelamine with an acid halide, while the first method involves contacting trihalomelamine with an acid halide.

New first and second methods involving halogen recycle are described in detail below:

From trihalomelamine

The first method is a process for producing acid amides, more specifically triazine tris-acid amides, from triamines from melamine, consisting of the following steps (a)-(d):

(a) contacting the melamine with a halogen to produce hexahalomelamine;

(b) contacting melamine with hexahalomelamine to produce trihalomelamine; And

(c) contacting said trihalomelamine with an acid halide at a temperature and for a time effective to produce triazine tris-acid amide as a product and halogen as a byproduct; And

(d) Halogen by-products are recycled to step (a) to halogenate the melamine with hexahalomelamin.

Steps (a) and (b) of this method are performed by the methods disclosed in US Pat. Nos. 2,472,361, 2,184,888, 2,184,886 and 2,184,883 and in European Patent 239,121.

Step (c) is carried out under the conditions described above in the section entitled 'New Method'.

Recycling step (d) is performed by removing halogen by-products by means such as a carrier inert gas stream and foaming through an aqueous caustic solution to collect the halogen vapor to form a hypohalide solution to be used as the halogenating agent. Suitable halogens most suitable for recycling are chlorine and bromine. Chlorine is the most suitable halogen.

Alternatively, the halogen can be collected in an organic solvent and used as such to halogenate additional melamine.

From hexahalomelamine

The second method is a process for producing acid amides, more particularly triazine tris-acidamides, via hexahalomemelamine from melamine, consisting of the following steps (I)-(IV).

(I) contacting the melamine with halogen to produce hexahalomelamine and to produce hydrogen halide as a byproduct;

(II) contacting said hexahalomemelamine with an acid halide at a temperature and for a time sufficient to produce halogen as triazine N, N ', N'-trihalo tris-acidamide as an intermediate product and as a byproduct; And

(III) The triazine N, N ', N'-trihalo tris-acid amide intermediate of step (II) is contacted with hydrogen halide to produce additional halogen as triazine tris-acidamide as a final product and by-product and; And

(IV) The halogen by-products of steps (II) and (III) are recycled to step (I) to halogenate the melamine with hexahalomelamine.

Step (I) of this method is carried out by the methods disclosed in US Pat. Nos. 2,472,361, 2,184,888, 2,184,886 and 2,184,883.

Step (II) is carried out under the conditions described above in the section entitled 'New Method'.

Step (III) is carried out by slowly introducing hydrogen halide into the reaction mixture for several minutes to several hours at a temperature in the range of -20 to 120 ° C.

Suitable hydrogen halides are hydrogen chloride and hydrogen bromide. Gas hydrogen chloride is the most suitable hydrogen halide.

Recycling step (IV) is carried out by removing the halogen by-products from both steps (II) and (III) with a carrier inert gas stream and foaming through an aqueous caustic solution to collect the halogen vapor and use it as a halogenating agent. Suitable halogens most suitable for recycling are chlorine and bromine. Chlorine is the most suitable halogen.

Alternatively, the halogen is collected in an organic solvent and can be used by itself to halogenate additional melamine.

The method of the present invention can be better understood with reference to FIGS. 1 and 2 as follows:

Tris-carbamate (FIG. 1) from trichloromelamine:

Thus, in FIG. 1 showing a process for producing triazine tris-methyl carbamate from melamine via trichloromelamine, melamine is introduced via line (1) into reaction zone A (3) of the process and chlorine Is introduced via line (2) to form hexachloromelamine.

Hexachloromelamine is then sent to reaction zone B (6) of the process via line (4) and additional melamine is sent via line (5) to give trichloromelamine by chlorine exchange reaction between melamine and hexachloromelamine. Form.

Trichloromelamine is then sent to reaction zone C (9) of the process via line (7) and methyl chloroformate is sent via line (8) to form

1. triazine tris-methyl carbamate as the product to be removed via line 10, and

2. Chlorine gas as by-product recycled to zone A (3) via line (11).

Tris-carbamate from hexachloromelamine (Figure 2):

In Figure 2 showing a process for producing triazine tris-methyl carbamate from melamine via hexachloromelamine, the chlorine introduced via line 21 into the reaction zone I (23) of the process is Input via (22) to form hexachloromelamine.

Hexachloromelamine is then sent to reaction zone II (26) of the process via line 24 and methylchloroformate is sent via line 25 to form:

1. N, N ', N'-trichloro triazine tris-methyl carbamate, as intermediate products to be further reacted, and

2. Chlorine gas as by-product recycled to zone I (23) via line (27) via line (27).

The intermediates N, N ', N'-trichloro triazine tris-methyl carbamate are then sent by line 28 to reaction zone III (29) of the process and the hydrogen chloride gas is sent by line (3) Forms the following:

1. Triazine tris-methyl carbamate as the final product removed via line 31, and

2. Additional chlorine gas as a byproduct recycled to line 22 via line 32 to zone I 23.

Process for preparing isocyanate and isocyanate adducts

The process of the present invention is also directed to contacting haloaminotriazine with an acid halide selected from the group consisting of oxalyl chloride, phosgene and phosgene analogues to form acidamide intermediates and break down the intermediates to isocyanates to produce isocyanates. Can be applied.

Acidamide intermediates are preferentially prepared in the same manner as discussed above with regard to the acidamides of the present invention. When the acid halide used is oxalyl chloride or phosphogen, the resulting acidamide intermediate is expected to be carbamoyl carbonyl chloride or carbamyl chloride, respectively. Representative examples of phosgene analogues include, without limitation, diphosgene and triphosgen. Triphosgen (trichloromethyl carbonate) is understood to be a source of phosgene to those skilled in the art. See, yes, M. Jay, Koglan and B. a. Cali, 'Trichloromethyl carbonate as a practical source of phosgene' Tetrahedron Letters, Vol. 30, no. 16, pp. 2033-2036 (1989).

Isocyanates are prepared by decomposing intermediates. This decomposition can be accomplished by heating the intermediate or adding a base that acts as a catalyst or acid scavenger. Representative base is triethylamine.

Preferentially, the intermediate is broken down into isocyanates by heating. Higher or lower temperatures may be used if decomposition occurs, but suitable degradation degrees for forming isocyanates from acidamide intermediates range from about 40 ° C to about 140 ° C. The reaction is typically carried out at about 100 ° C. to 110 ° C., but any temperature is sufficient to allow the acidamide intermediate to degrade into isocyanates.

The time can vary greatly depending on the temperature at which the reaction takes place, but suitable reaction times for decomposing the acidamide intermediate into isocyanates range from about 1 hour to about 24 hours.

It is not necessary to separate the acidamide intermediate before decomposition to isocyanates. However, if desired, the intermediate can be separated from the reaction mixture prior to decomposition. Preferably, the acidamide intermediate is decomposed without separating the intermediate from the reaction mixture, which typically also contains a halogenated solvent such as ortho-dichlorobenzene.

The process of the present invention may additionally be applied to the preparation of isocyanate adducts by reacting isocyanates prepared by the process described above with active hydrogen containing compounds. The active hydrogen containing compound used in this process has at least one active hydrogen component selected from the group consisting of carboxyl, hydroxyl, thiol, sulfonamide, amido, primary amine, secondary amine, salts thereof and mixtures thereof. It includes those known to those skilled in the art.

The active hydrogen containing compounds used in the present invention include known blocking agents. For example, active hydrogen-containing compounds include polyols such as ethylene glycol, propylene glycol, diethylene glycol, and the like, as well as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, 2-ethylhexyl, octyl, nonyl, 3,3, Aliphatic alcohols having 1 to 12 carbons, such as 5-trimethylhexyl, decyl and lauryl alcohol, cycloaliphatic alcohols such as cyclopentanol and cyclohexanol, aromatic alkyls such as phenyl carbinol, and phenol, o-, m-, and phenols such as p-cresol, p-chlorophenyl, beta naphthol and the like.

Active hydrogen containing compounds may also include oximes of aldehydes or ketones (eg, methylethyl-ketoxime, acetone oxime and cyclohexanone oxime), lactams (eg, caprolactam), which are blocked at relatively low temperatures, such as below about 125 ° C., Other known blocking groups, such as hydroxyacid esters, imidazoles, pyrazoles, N-hydroxyimides (eg, N-hydroxyphthalimide), dimethylamine, or other blocking groups as cited in US Pat. No. 4,444,954. can do.

In addition to the blocking agent, other active hydrogen containing compounds can also be used in the process of the invention to obtain isocyanate adducts having various functional groups attached to the acid amide. For example, 4-amino-2,2,6,6-tetramethyl piperidine can react with isocyanates to produce isocyanate adducts having urea bonds, the product of which can be a hindered amine light stabilizer. Additionally, an active hydrogen containing compound having two or more active hydrogen components can be used to produce an isocyanate adduct having an unreacted active hydrogen component.

Most preferably, the active hydrogen-containing compounds used in the process of the present invention are methanol, ethanol, isopropanol, propanol, isobutanol, butanol, tert-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol And aliphatic alcohols having 1 to 18 carbons, such as lauryl alcohol, 2-ethyl hexanol, alkylalcohol, glycidol and stearyl alcohol.

Since the reaction of the active hydrogen containing compound with the isocyanate is generally exothermic, the reaction temperature is preferably in the range of about -20 ° C to about 100 ° C. Most preferably, the reaction mixture is cooled to about 0 ° C. before adding the active hydrogen containing compound to the isocyanate.

Typically, the reaction mixture is stirred and cooled for a time ranging from about 5 minutes to about 2 hours after addition of the active hydrogen containing compound into the isocyanate. Generally, the mixture is then allowed to come to room temperature and stirred for a time ranging from about 10 minutes to about 10 hours. The isocyanate adduct can be separated by any desired method, such as by distillation of the solvent and purification by distillation of the residue under vacuum and recrystallization.

The process for preparing the isocyanates and isocyanate adducts of the present invention is particularly suitable when the starting haloaminotriazine is halomelamine or haloguanamine. Specifically, the process may be used to prepare triazine tris-isocyanates or triazine tris carbamate, such as triazine tris butyl carbamate.

Usefulness

The products produced by the process of the invention have utility in a variety of areas. In general, the usefulness of a particular product depends on its class.

A. Triazine Tris-Carbamate

In curable compositions, members of the triazine tris-carbamate class are described for polyfunctional active hydrogen compounds comprising hydroxy and amino functional materials, as detailed above in U.S. Patent No. 4,939,213, cited above. It has utility as a crosslinking agent. The curing compositions disclosed therein can be used as solvent based, water based, or powder coatings, or they can be used as aqueous dispersions which are particularly suitable for application by electrodeposition. They are therefore useful in single component thermoset systems, catalyzed or uncatalyzed, for applications such as coating, in particular powder coating, coil coating and can coating. They can also be used in non-coating applications such as conventional molding, reactive injection molding, composites, adhesives and binders.

The triazine tris-carbamate of the present invention has utility as an intermediate to be another crosslinker. For example, they can be pyrroled to provide triazine triisocyanates, which are excellent crosslinkers as disclosed in US Pat. No. 4,939,213.

The triazine tris-carbamate of the present invention has utility as an intermediate to be a polymer additive. They can additionally be converted to ultraviolet (UV) light stabilizers by substitution of at least one alkoxy or aryloxy group in the triazine tris-carbamate prepared by the process of the invention. The product may be a hindered amine light tablet (HALS).

For example, the reaction of triazine tris-phenyl carbamate with 4-amino-2,2,6,6-tetramethyl piperidine in the temperature range of 25 ° C. to 160 ° C.

constitutional formula

A tris-urea derivative of melamine having the chemical name of tris- (2,2,6,6-tetramethyl-piperidin-4-yl-aminocarbonyl) melamine represented by is produced in excellent yield.

B. Triacyl Melamine

An example of the triacyl melamine class is N, N ', N'-tristearylmelamine, which has utility in abrasive waxes and in waterproof nonwoven finishing as disclosed in US Pat. No. 2,507,700.

C. Tris- (Omegahaloacyl) melamine

Another class of compounds that may be prepared by the process of the invention are

General formula

Tris represented by formula wherein n is an integer from 1 to 5 and X is a leaving group selected from the group consisting of chloride, bromide, iodide, fluoride, alkyl sulfonate, arylsulfonate and mixtures thereof -(Omegahaloacyl)-and the related melamine class. Suitable compounds are those wherein X is chloride and n is 3 or 4.

D. Lactam Substituted Triazine Crosslinkers

The tris- (omegahaloacyl) melamines of the present invention are intermediates that lead to the preparation of lactam substituted triazine crosslinkers represented by the following general formula:

Where n is an integer from 1-5

Preferred lactam substituted triazine crosslinkers of the invention are those in which n is 3 or 4.

Preparation of lactam crosslinking agent

The tris-lactam substituted triazine crosslinkers of the present invention described in the preceding paragraphs above have a high dielectric constant for dissolving the various ionic intermediates, typically from room temperature, from the corresponding tris- (omegahaloacyl) -melamines. Eggplants are readily prepared in an aprotic solvent via intermediate cyclization reactions by the action of strong bases.

Intermediate cyclization may be performed at about 0 ° C. to about 120 ° C. in a time period in the range of 10 minutes to 24 hours.

However, it is generally sufficient to carry out the intermediate cyclization reaction at room temperature for a period of only 1 to 6 hours.

The water-ice mixture is added to the reaction mixture to precipitate the lactam crosslinker of the present invention to separate the product. Instead, the product can be extracted.

Examples of the tris- (omegahaloacyl) -melamine class are N, N ', N'-tris- (4-chlorobutyryl) -melamine represented by the following structural formula:

It has the utility of being an N-substituted pyrrolidine crosslinker 2,4,6-tris (pyrrolidin-2-on-1-yl) -1,3,5-triazine, a thermosetting resin material and Its usefulness as a curing agent is disclosed in JP 58 146582. Tris- (N-pyrrolidoneyl) -triazine is represented by the following structural formula:

It can be readily prepared by the basic catalyst intermediate cyclization reaction of each of the 4-chlorobutyryl amino groups of the N, N ', N'-tris- (4-chlorobutyryl) melamine precursor.

E. N-halo acid amide

Other classes of compounds that can be prepared by the methods of the present invention are described in US Pat. No. 3,920,832; No. 4,732,899; And the N-haloacid amide intermediate products of the invention which are potentially useful as herbicides and pesticides as suggested by 4,824,845.

Typical N-halo acid amide products of the present invention are compositions of matter represented by the following general formula:

Where Q is Or; or

Q is C ₁ -C ₂₀ linear alkyl, C ₃ -C ₂₀ cyclic or branched alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ aralkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₂₀ arylthio, C ₁ -C ₂₀ alkylamino, C ₂ -C ₄₀ dialkyl Amino, morpholino, piperidino, pyrrolidino, aminotriazino, alkylaminotriazino, aminoalkylaminotriazino, hydrogen, chloro, bromo, iodo, fluoro, perfluoroalkyl, perfluoroaryl Is selected from the group consisting of perfluoroaralkyl groups;

bracket X in the group is hydrogen or halogen and at least one halogen is each selected from the group consisting of chloride, bromide, iodide and fluoride.

bracket Wherein Y is the same or different and each is selected from the group consisting of the following functional groups represented by the formula:

Wherein each R is each an alkyl, aryl or alkoxy group; And

Z is hydrogen, chloro, bromo, iodo, fluoro, vinyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ alkylene, C ₁ -C ₂₀ in the aryl alkylene of C ₆ -C ₂₀ aryl, C ₆ acyl, C ₂ -C ₂₀ -C ₂₀ in the haloaryl, C ₇ -C ₂₀ aralkyl, C ₇ -C ₂₀ aralkyl, halo, C ₂ -C ₂₀ of the Haloacyl, halocarbonyl, C ₂ -C ₂₀ alkoxycarbonyl, C ₂ -C ₂₀ alkylthiocarbonyl, C ₂ -C ₂₀ haloalkoxy, aminocarbonyl, C ₂ -C ₂₀ alkyl amino Carbonyl, C ₃ -C ₂₀ dialkylaminocarbonyl, C ₄ -C ₂₀ alkenylaminocarbonyl, C ₇ -C ₄₀ dialkenylaminocarbonyl, C ₅ -C ₂₀ alkylalkenylaminocarbon Carbonyl, triazino, pyrimidino, pyridino, imidazole, tetrazole, C ₁ -C ₂₀ perfluoroalkyl, C ₆ -C ₂₀ perfluoroaryl, C ₇ -C ₂₀ perfluoro ar alkyl, when the C ₁ -C ₂₀ haloalkyl, C ₃ -C ₂₀ alkoxycarbonylalkyl, C ₂ -C ₂₀ of the Of the furnace alkyl, C ₂ -C ₂₀ grains of Fort keel, C ₃ -C _{20-keto-alkyl,} C ₄ -C ₂₀ alkyl trialkoxy silyl, C ₃ -C ₂₀ dialkyl amino alkyl, C ₂ -C ₂₀ of the Alkoxyalkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₃ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkylenedioxy, C ₆ -C ₂₀ arylenedioxy, C ₂ -C ₄₀ N, N-dialkylamino, C ₆ -C ₄₀ N, N-dialkenylamino, C ₁₂ -C ₄₀ N, N-diarylamino, C ₄ -C ₂₀ N, N-alkylalkenylamino, C ₇ -C ₂₀ N, N-alkylarylamino, C ₉ -C ₂₀ N, N-alkenylarylamino, aziridino, azetidino, pyrrolidino, piperidino , Morpholino, C ₁ -C ₂₀ alkyl mercapto, C ₃ -C ₂₀ alkenylmercapto, and C ₆ -C ₂₀ aryl mercapto.

The product produced by the process of the invention is obtained by contacting haloaminotriazine and acid chloride reactants under the process conditions described above. They may consist of carboxylic acid amides, carbamates, sulfonamides, phosphoramides, ureas, thioureas, thiophosphoramides, amidines, amidate esters and mixtures thereof. In addition, isocyanate products can be obtained by decomposing acid amide intermediates such as carbamoyl carbonyl chloride and carbamoyl chloride produced by contacting haloaminotriazine with certain acid chlorides such as phosgene or oxalyl chloride. In addition, isocyanate adducts such as carbamate and urea are obtained by contacting the isocyanate produced according to the invention with an active hydrogen containing compound.

The following examples illustrate various embodiments of the present invention.

Example 1

Triazine trismethylcarbamate from hexachloromelamine

A mixture of 3.33 g hexachloromelamine, 23.6 g methyl chloroformate and 200 mg polydimethylamino pyridine was heated at 70 ° C. for 6 hours under argon. Excess methyl chloroformate was removed under reduced pressure. The residue was cooled and dissolved in 50 ml methanol and 25 ml CH ₂ Cl ₂ mixture. Then, it was treated dropwise with 5 ml triethylamine while cooling it. The mixture was concentrated and the residue was treated with methanol. Triazine trismethylcarbamate was crystallized, filtered and identified by ¹ H NMR, ¹³ C NMR, IR and Fast Atom Bombardment (FAB) mass spectra. (2.4 g; 80%);

Melting point is at least 300 ° C; Decomposition starts at about 220 ° C. and peaks at about 250 ° C .;

¹ H NMR (CDCl 3, Delta): 3.8 (s, 9H, 3X OCH ₃ ) 8.8 (s, 3X NH);

¹³ C NMR (DMSO-d ₆ , Delta): 52.3, 151.9, 164.9 IR (CHCl ₃ ): 1760 cm ^-1 (C = 0):

Mass (FAB, M + H ⁺ ): 301.

Example 2

Triazine trismethylcarbamate from trichloromelamine

(Solvent-free method)

A mixture of 2.3 g trichloromelamine, 20 ml methylchloroformate and 200 mg poly-dimethylaminopyridine was heated under argon at 75 ° C. for 3 hours. Excess methyl chloroformate was removed under reduced pressure. The residue was dissolved in a mixture of 100 ml methanol and 50 ml CH ₂ Cl ₂ . 1 ml Et ₃ N was added dropwise to it. It was filtered and the solvent was removed from the filtrate under reduced pressure. The residue upon treatment with 20 ml methanol yielded the same crystalline product as triazine trismethylcarbamate (2.27 g; 76%) as the product according to Example 1.

Example 3

Triazine trisbutylcarbamate from trichloromelamine

(Dichlorobenzene solvent)

A mixture of 11.5 g trichloromelamine, 57.2 ml n-butylchloroformate and 50 ml o-dichlorobenzene was heated under argon with stirring at 58-62 ° C. for 5 hours. It was cooled to rt and diluted with 30 ml o-dichlorobenzene. The 40 ml liquid was then collected by heating the reaction mixture at 55 ° C. under reduced pressure. The residue was cooled and diluted with 300 ml hexanes. The precipitated material was then filtered off and washed with 200 ml hexanes. The residue was purified by silica gel column chromatography using CH ₂ Cl ₂ / MeOH (97: 3) as eluent. The triazine trisbutalcarbamate thus obtained was confirmed by ¹ H NMR, ¹³ C NMR and mass spectra. (17.2 g; 81% yield);

Melting point 149-51 ° C .;

¹ H NMR (CDCl ₃ , Delta): 0.9 (t, 9H, 3X CH ₃ CH ₂ CH ₂ O-), 1.3 (m, 6H, 3X CH ₃ CH ₂ CH ₂ CH ₂ O-), 1.6 (m, 6H, 3X CH ₃ CH ₂ CH ₂ CH ₂ O-), 4.1 (t, 6H, 3X CH ₃ CH ₂ CH ₂ CH ₂ O-), 8.7 (s, 3H, 3XNH);

¹³ C NMR (CDCl ₃ , Delta): 8, 20 66, 150, 164;

Mass (FAB, M + H ⁺ ): 427.

Example 4

Triazine Trisphenylcarbamate from Trichloromelamine

(Carbon tetrachloride solvent)

A mixture of 2.3 g trichloromelamine, 10.0 ml phenyl chloroformate and 40 ml CCl ₄ was heated under argon at 50 ° C. for 3 hours. It was cooled to rt and filtered. The residue was dissolved in a mixture of CH ₂ Cl ₂ / MeOH and the solvent was evaporated under reduced pressure. The residue was treated with anhydrous methanol and the resulting precipitate was filtered and dried (4.2 g; 86% yield). The product thus obtained was identified as triazine trisphenylcarbamate by ¹ H NMR, ¹³ C NMR, IR and mass spectra;

Desorption (decomposition) starts at about 100 ° C. and peaks at about 160 ° C .;

¹ H NMR (DMSO-d ₆ , Delta): 7.2-7.5 (m, 15H, 3X ArH ₅ ), 112. (s, 3H, 3XNH);

¹³ C NMR (DMSO-d ₆ , Delta): 122, 126, 129, 149, 151, 165;

Mass (FAB, M + H ⁺ ): 487.

Example 5

N, N ', N'-tris (4-chlorobutyryl) melamine

A mixture of 2.3 g trichloromelamine, 20 ml carbon tetrachloride, 8.46 g 4-chlorobutyryl chloride and 30 ml N, N-dimethylaminopyridine was placed in a 100 ml flask equipped with a magnetic stir bar, reflux condenser and argon inlet. The reaction mixture was slowly heated to 60 ° C. in an oil bath and stirred at 60 ° C. for 5 hours. Then it was cooled to room temperature and diluted with 50 ml hexanes. The contents were stirred for 30 minutes at room temperature and then filtered. The residue was washed with hexanes and dried under reduced pressure. It was identified as N, N ', N'-tris (4-chlorobutyryl) melamine based on NMR and mass spectra. (4.2 g; 95% yield);

¹ H NMR (DMSO-d ₆ , Delta): 2.0 (m, 6H, 3X CH ₂ CH ₂ CH ₂ Cl), 2.8 (t, 6H, 3X NHCOCH ₂ CH ₂ CH ₂ Cl), 3.6 (t, 6H, 3 × CH ₂ CH ₂ Cl), 11.8 (broad s, 3H, 3 × NHCO);

¹³ C NMR (DMSO-d ₆ , Delta): 27, 34, 44, 161, 174;

Mass (FAB, M + H ⁺ ): 439.

Example 6

N, N ', N'-trischloroacetyl melamine

460 mg trichloromelamine was placed in a three-neck (100 ml) flask equipped with a reflux condenser, argon inlet, magnetic stir bar and rubber diaphragm inlet. 10 ml of carbon tetrachloride and then 1.4 ml chloroacetylchloride were added to the flask with a syringe under stirring. The reaction mixture was heated to 60 ° C. in an oil bath for 4.5 h. Then, it was cooled to room temperature and excess reagent and carbon tetrachloride were removed under reduced pressure. The residue is diluted with hexanes, the precipitated material is filtered off, washed with hexanes and dried under reduced pressure, based on ¹ H NMR, ¹³ C NMR and mass spectral data N, N ', N'-tris The product identified by chloroacetyl melamine was obtained. (689 mg; 97% yield);

¹ H NMR (DMSO-d ₆ , Delta): 4.8 (s, 6H, 3X CH ₂ Cl), 11.1 (s, 3H, 3X NHCO);

¹³ C NMR (DMSO-d ₆ , Delta): 45.8, 163.8, 167.1;

Mass (FAB, M + H ⁺ ): 355.

Example 7

Triazine Tricetyl Carbamate

The procedure of Example 2 was repeated at 80 ° C. using methyl chloroformate (20.0 ml) instead of methyl chloroformate. The product has a melting point of at least 300 ° C; The degradation was triazine tris-ethyl carbamate (2.2 g, 76% yield), starting at about 200 ° C. and peaking at about 260 ° C.

Example 8

Triazine Trispropyl Carbamate

The procedure of Example 4 was basically repeated using propyl chloroformate (10.0 ml) instead of phenyl chloroformate. The product was triazine tris-propyl carbamate. 2.3 g of trichloromelamine were placed in a 250 ml flask equipped with a magnetic stir bar, reflux condenser and argon inlet. To it was added 50 ml CCl ₄ followed by 10.0 ml propyl chloroformate. The reaction mixture was gradually heated to 75 ° C. in an oil bath and maintained at 75 ° C. for 6 hours. Removal of excess propyl chloroformate, followed by general operation, yielded the product identified as triazine tris-propyl carbamate by ¹ H NMR, ¹³ C NMR IR and mass spectra; Melting point 178-182 ℃

Example 9

Triazine Tris- (2-chloroethylcarbamate)

The procedure of Example 4 was repeated using 2-chloroethyl chloroformate (3.5 ml) instead of phenyl chloroformate. The product was triazine tris- (2-chloroethylcarbamate). The procedure was as follows:

To a stirred suspension of 1.15 g trichloromelamine in 30 ml CCl _{4 in} a 100 ml flask with reflux condenser, magnet stir bar and argon inlet, 3.5 ml (4.8 g) of 2-chloroethyl chloroethyl chloroformate was added. did. The reaction mixture was stirred for 0.5 h at room temperature and then slowly heated to 75 ° C. in an oil bath. Heating was continued for 6 hours and then the reaction was cooled to room temperature. Excess 2-chloroethyl chloroformate and CCl ₄ were removed under reduced pressure and the residue was purified by column chromatography (silica gel) using a mixture of CH ₂ Cl ₂ and MeOH (95: 5) as diluent, to give ¹ H. Triazine tris (2-chloroethyl) carbamate, identified by NMR, ¹³ C NMR, mass and IR spectra; Melting Point 130 ° C (Decomposition)

Example 10

Triazine tris- (2-ethylhexylcarbamate)

The procedure of Example 4 was repeated using 2-ethylhexyl chloroformate (86.7 g) instead of phenyl chloroformate. The product was triazine tris- (2-ethylhexylcarbamate). The procedure was as follows: A mixture of 11.5 g trichloromelamine, 150 ml o-dichlorobenzene and 86.7 g 2-ethylhexyl chloroformate was heated in a flask equipped with a magnetic stir bar, argon inlet and reflux condenser. The temperature of the oil bath was gradually increased to 67 ° C. After 6 hours at 67 ° C., heating was stopped and the reaction mixture was concentrated under reduced pressure. In general work of the reaction mixture, a product identified as triazine tris- (2-ethylhexyl carbamate) based on spectral data was obtained.

Example 11

Triazine tris- (iso-butylcarbamate)

The procedure of Example 3 was slightly modified to use isobutyl chloroformate (16.4 ml) instead of n-butyl chloroformate. The product was triazine tris- (iso-butylcarbamate). The slightly modified procedure was as follows:

To the flask with a magnetic stir bar, reflux condenser and argon inlet, 4.6 gm of trichloromelamine, 40 ml o-dichlorobenzene and 16.4 gm isobutyl chloroformate were added. The reaction mixture was heated at 65-70 ° C. for 6 hours in an oil bath. Then it was cooled and excess isobutyl chloroformate and o-dichlorobenzene were removed under reduced pressure. The residue was treated with 100 ml hexanes and the precipitated material was filtered off, washed with 50 ml hexanes and dried. The product was identified by triazine tris-isobutyl carbamate by ¹ H NMR, ¹³ C NMR, IR and mass spectra. It decomposed starting at about 230 ° C. and peaked at about 245 ° C.

Example 12

Triazine Mixed Alkyl Carbamate

The procedure of Example 3 was repeated intact using a mixture of haloformates consisting of 2-ethylhexyl chloroformate (4 ml) and methyl chloroformate (6.2 ml) instead of n-butyl chloroformate.

The product was triazine tris- (mixed alkyl carbamate) in which the mixed alkyl group consisted of 2-ethylhexyl and methyl groups in a ratio ranging from about 1: 1.8-about 1: 0.77. Detailed experimental procedures are as follows:

A mixture of 4.6 g of trichloromelamine, 4 ml 2-ethylhexyl chloroformate and 30 ml o-dichlorobenzene was heated under argon with stirring at 60 ° C. for 4 hours. It was cooled at room temperature. Then, 6.2 ml of methyl chloroformate was added. The reaction mixture was then heated under argon with stirring to 65 ° C. for 2 hours. It was cooled to rt and diluted with 15 ml of dichlorobenzene; Then 10.5 ml liquid was collected by heating the reaction mixture to 40 ° C. under reduced pressure. The residue was cooled down and diluted with 200 ml hexanes. The precipitated material was filtered off and washed with 300 ml hexanes. 5 g of solid was stirred with 250 ml methylene chloride, 2.6 g of insolubles were filtered off and 'N- (2-ethylhexoxycarbonylamino) -N' with an ethylhexyl / methyl ratio of 1: 1.8 by H NMR. , N'-di (methoxycarbonylamino) triazine (52% yield). The methylene chloride solution was washed twice with 5% sodium bisulfite and twice with deionized water, dried over magnesium sulfate and the solvent stripped to give 1.3: 1 (or 1: 0.77) ethylhexyl / as identified by H NMR. Methyl ratio afforded 1.86 g of N- (ethylhexoxycarbonylamino) -N '-(methoxycarbonylamino) triazine. (37% yield).

Example 13

N, N ', N'-tris- (3-chloropropionyl) melamine

To a stirred suspension of 2.3 g trichloromelamine in 40 ml CCl ₄ was added 7.62 g 3-chloropropionyl chloride under argon. The reaction mixture was heated at 65-70 ° C. for 6 hours in an oil bath. The reaction mixture was cooled down and diluted with 50 ml hexanes. The precipitate was filtered off, washed with hexanes and dried under reduced pressure. (3.9 g; 98% yield). The product thus obtained was identified as N, N ', N'-tris (3-chloropropionyl) melamine by' H NMR, ¹³ C NMR, IR and mass spectra.

Example 14

N, N ', N'-triacetyl melamine

The procedure of Example 6 was repeated for 20 hours at room temperature using acetyl chloride (15 ml) instead of chloroacetyl glolide. The product was triacetyl melamine.

Example 15

N, N ', N'-trihexanoyl melamine

The procedure of Example 6 was repeated intact using hexanoyl chloride (8.07 g) instead of chloroacetyl chloride. The product was trihexanoyl melamine. The experimental procedure was as follows:

A mixture of 2.3 g trichloromelamine, 8.07 g hexanoyl chloride, and 25 ml carbon tetrachloride were heated with stirring under argon at 70-78 ° C. for 6 hours. The reaction mixture was cooled to rt and 100 ml hexane was added to precipitate the product. The precipitate was filtered off, washed with 50 ml hexanes and dried. The spectral data were consistent with the N, N 'and N'-trihexanoyl melamine structures.

Example 16

N, N ', N'-tributyl melamine

The procedure of Example 6 was repeated intact using butyryl chloride (6.4 g) instead of chloro acetyl chloride. The product was tri-butyryl melamine. The procedure was as follows:

2.3 g of trichloromelamine was treated with 6.4 g butyryl chloride in 40 ml CCl ₄ at 65 ° C. for nearly 6 hours. The reaction mixture was cooled down and diluted with 100 ml hexanes. The precipitate material was filtered off, washed with hexanes and dried. Mass spectral analysis revealed that the product was N, N ', N'-tributyryl melamine.

Example 17

N, N ', N'-tribenzoyl melamine

The procedure of Example 6 was repeated intact using benzoyl chloride (6.7 ml) instead of chloroacetyl chloride. The product was tribenzoyl melamine. The procedure was as follows:

6.7 ml benzoyl chloride was added to a stirred suspension of 2.3 g of trichloromelamine in 40 ml CCl _{4 in} a flask equipped with a magnetic stir bar, argon inlet and reflux condenser. The reaction mixture was heated at 68-70 ° C. for 7 hours in an oil bath. The reaction mixture was then cooled and diluted with 30 ml hexanes. The precipitated material was filtered off and the residue was washed with 150 ml hexanes and then dried under reduced pressure. (4.3 g; 98% yield) The product was identified as N, N ', N'-tribenzoyl melamine by' H NMR, ¹³ C NMR, IR and mass spectra.

Example 18

N, N ', N'-tri-paranitrobenzoyl melamine

The procedure of Example 6 was repeated intact, using para-nitro benzoyl chloride (5.55 g) instead of chloroacetyl chloride. The product was tri-paranitro benzoyl melamine. The procedure was as follows:

To a stirred suspension of trichloromelamine (1.15 g) in CCl ₄ (20 ml) was added 5.55 g of p-nitrobenzoyl chloride solution in 30 ml CCl ₄ . The reaction mixture was heated in an oil bath under argon atmosphere at 70 ° C. for 6 hours, cooled and diluted with 25 ml CCl ₄ . The precipitate was filtered off, washed with 100 ml CCl ₄ and dried under reduced pressure. The product was identified as N, N ', N'-tri-paranitrobenzoyl melamine by' H NMR, ¹³ C NMR spectrum.

Example 19

Tris- (2,2,6,6-tetramethylpiperidin-4-yl-amino carbonyl) melamine

A mixture of the triazine tris-phenylcarbamate (4.86 g) product of Example 4 and 4-amino-2,2,6,6-tetramethylpiperidine (15.4 ml) in toluene solvent (80 ml) was added to 8 Heat at 115 ° C. for hours. After cooling and addition of hexane (100 ml), a tris-urea derivative identified as tris- (2,2,6,6-tetramethylpiperidin-4-yl-aminocarbonyl) melamine was obtained (5.95 g, 89% yield). It decomposes starting at about 220 ° C. and peaks at about 270 ° C.

Example 20

Of 2,4,6-tris (pyrrolidin-2-one-1-yl) -1,3,5-triazine from N, N ', N'-tris (4-chlorobutyryl) melamine Produce.

Sodium hydrate (200 ml, 60% in mineral oil) was placed in a three-necked flask with argon inlet, stopper, rubber bulkhead and magnetic stir bar. 5 ml n-hexane was added to it and the mixture was stirred for several minutes. Agitation was stopped and n-hexane was removed using a syringe. To this washed NaH was added 5 ml dimethylformamide (DMF). The flask was cooled to 0 ° C. in an ice bath and 440 mg of the product of Example 5, N, N ′, N′-tris (4-chlorobutyryl) melamine, dissolved in 5 ml DMF containing NaH while stirring. Was added to the flask. The reaction mixture was stirred for 5 h at 0 ° C. The cooling bath was then removed and the reaction mixture was warmed to room temperature. The reaction mixture was then slowly added to 100 ml ice cold water. The reaction mixture was extracted with CH ₂ Cl ₂ (3 × 30 ml), washed with water (20 ml) and the combined organic extracts dried over MgSO ₄ filtered and the filtrate was concentrated under reduced pressure. Then the solvent was removed and the residue was dried under reduced pressure. The product was essentially pure compound (270 mg, 82% yield), 2,4,6-tris- (pyrrolidin-2-one-1-yl) -1,3,5- by NMR and mass spectra Triazine was identified as:

¹ H NMR, (CDCl ₃ , Delta: 2.0 (m, 6H, 3XCH ₂ CH ₂ -CH ₂ CO), 2.6 (t, 6H, 3X CH ₂ CH ₂ CO), 4.0 (t, 6H, 3X NCH ₂ CH ₂ ); mass (FAB, m + H ⁺ ): 331.

Example 21

1.15 g trichloromelamine, 30 ml CCl ₄ , 4.2 g benzoyl chloride and 50 mg ALIQUAT in 0.5 ml CCl ₄ ^?? A mixture of 336 (tricaprylylmethyl ammonium chloride) was stirred at room temperature. The formation of chlorine, indicated by yellow formation, was recognized within 20 minutes. Thin layer chromatography analysis of the reaction mixture after 30 minutes resulted in the formation of N, N ', N'-tribenzoylmelamine.

In a second experiment, 1.15 g trichloromelamine was stirred in 30 ml CCl ₄ with 4.2 g benzoyl chloride at room temperature without added catalyst. In this case, no color was observed after 20 minutes. Moreover, thin layer chromatography analysis after 30 minutes and even 4 hours showed no product corresponding to N, N ', N'-tribenzoyl melamine.

From this comparative experiment, it was concluded that the reaction of the present invention is catalyzed by quaternary amine halides.

Example 22

U.S. The procedure of Example 4 was basically repeated using hexabromomelamine (5.2 g) prepared by the procedure described in patent 2,472,361.

The experimental details are as follows:

Part A: Preparation of hexabromomelamine.

W. in US 2,472,361. Shii. Consistent with the process outlined by W. Cl Arsem:

4.1 g of melamine was suspended in 100 g of deionized water and 24.1 g of glacial acetic acid was added. The mixture was cooled to about 5 ° C. and to this was added an aqueous solution containing 25 g of sodium hypobromite at approximately 5% concentration over a period of 2 hours with stirring. Additional acetic acid was added during the reaction to maintain the pH at 7 or below. After 30 minutes of completion of NaOBr addition, the solid product was filtered off, washed with 700 ml of water and dried under reduced pressure at room temperature. The product was a dark yellow powder (14.85 g; 88% yield) identified by ¹³ C NMR and IR. Titration for active bromine content yielded a value of 8.97 mmol of bromine per gram of product, which is 89.6% of theory.

Part B: Preparation of N, N ', N'-tribromo-2,4,6-trismethoxycarbonylaminotriazine from hexabromomelamine in carbon tetrachloride

A mixture of 5.2 g of hexabromomelamine, 9.45 g of methyl chloroformate, and 50 ml of carbon tetrachloride was heated with stirring at 55-75 ° C. for 5 hours under a nitrogen atmosphere. The generation of BrCl vapor was observed during the reaction. After cooling, the solid product was filtered off, washed with 200 ml of CCl ₄ and dried at room temperature under reduced pressure.

The product was a yellow powder (2.30 g: 43% yield) analyzed by ¹ H NMR, ¹³ C NMR, and IR. Titration for active bromine content yielded a value of 5.85 mmol bromine per gram of product, corresponding to 104.6% of theory. From spectroscopic analysis and from titration results, it was determined that the product was N, N ', N'-tribromo-N, N', N'-tris (methoxycarbonylamino-1,3,5-triazine) It became.

Example 23

Part A: N, N ', N'-trichlorobenzoguanamine from benzoguanamine.

A mixture of 18.72 g benzoguanamine, 24.25 ml glacial acetic acid, and 350 ml deionized water was cooled at 9 ° C. in an argon ice bath. To this was added 641 ml of 5% aqueous sodium hypochlorite with stirring over a period of 70 minutes at 9 ° C. The mixture was stirred for half an hour, filtered and the residue was washed with 700 ml of deionized water. The solid was dried at room temperature under reduced pressure to yield N, N, N'-trichlorobenzoguanamine. The product was subjected to N, N, N'-trichlorobenzoguanamine (93% of theoretical value of active chlorine) by ¹ H NMR and IR spectroscopy and by chlorine titration; (27.93 g, 91.7% yield).

Part B: Preparation of 2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine from trichloro benzoguanamine.

A mixture of 2.5 g N, N, N'-trichlorobenzoguanamine, 5.5 ml butyl chloroformate and 20 ml o-dichlorobenzene was heated under argon with stirring at 70 ° C. for 8 1/2 hours. It was cooled to rt and 125 ml of hexanes were added. The mixture was filtered and the solid was dried at room temperature under reduced pressure. The product is 2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine by ¹ H NMR, ¹³ C NMR, active chlorine titration and TLC; (2.5 g, 90.5%).

Example 24

Part A: preparation of N, N, N ', N'-tetrachloroacetoguanamine,

As fine powder, acetoguanamine (12.5 g) was mixed with 200 g of deionized water and 27 g of glacial acetic acid. The mixture was then cooled to about 13 [deg.] C. and an aqueous solution containing 33.5 g of sodium hypochlorite was added with stirring at approximately 5% concentration over a period of 1 hour. Additional acetic acid was added occasionally during the reaction to maintain the pH of the solution below 7. 30 minutes after completion of NaOCl addition, the solid product was filtered, washed with 700 ml of water and dried at room temperature under reduced pressure, N, N, N ', N'-tetra by ¹ H NMR, ¹³ C NMR, and IR. A light yellow powder (22.65 g; 86% yield) identified as chloroacetoguanamine was yielded. Titration regarding active chlorine content yielded a value of 14.64 mmol of chlorine per gram of product, corresponding to 96.2% of theory.

Part B: N-chlorinated 2,4-di (butoxycarbonylamino) -6-methyl-1,3,5- from N, N, N ', N'-tetrachloroacetoguanamine and butyl cloformate Preparation of Triazines.

A mixture of N, N, N ', N'-tetrachloroacetoguanamine 2.5 g, 6 ml of n-butyl chloroformate, 20 ml of o-dichlorobenzene, and 30 mg of N, N-dimethylaminopyridine at 68 ° C Heated under argon with stirring for 24 h. The reaction solution was then cooled to room temperature and excess reagent and o-dichlorobenzene were removed under reduced pressure.

The resulting sulfur-orange solid (2.15 g) was unreacted by ¹ H and ¹³ C NMR, and by TLC analysis, mono-butoxycarbonylamino (22%), and di-butoxycarbonylamino (16 %) Was found to be a mixture of chloroacetoguanamine.

Part C: of 2,4-di (butoxycarbonylamino) -6-methyl-1,3,5-triazine from N, N, N ', N'-tetrachloroacetoguanamine and butyl chloroformate Produce.

2.5 g of N, N, N ', N'-tetrachloroacetoguamine, 6 ml of n-butyl chloroformate, 20 ml of o-dichlorobenzene, and Aliquat ^?? 0.12 g of 336 was heated under argon with stirring at 68 ° C. for 24 h. At the same time as cooling, 100 ml of hexane was added. The resulting precipitate was isolated, dried under reduced pressure (1.65 g, 56.3% yield), 2,4-di (butoxycarbonylamino by ¹ H NMR, ¹³ C NMR, IR, TLC, and active chlorine analysis ) -6-methyl-1,3,5-triazine.

Example 25

Preparation of N, N ', N' Triacetylmelamine from N, N ', N'-trichloromelamine and acetyl bromide.

A mixture of N, N ', N'-trichloromelamine 1.38 g, 5.90 g of acetyl bromide, and 40 ml of carbon tetrachloride was heated with stirring at 61 ° C. under argon for 2 hours. The development of reddish brown steam (Br Cl) was observed during the reaction. After cooling, the orange solid was filtered off, washed several times with CCl ₄ and dried at room temperature under reduced pressure to yield a white powder (0.76 g, 50% yield).

The recovered product was identified as N, N ', N'-triacetylmelamine as the product of Example 14 by ¹ H MMR, ¹³ C NMR and TLC analysis.

Example 26

Debromination of N, N ', N'-tribromo-2,4,6-tri (methoxycarbonylamino) -1,3,5-triazine with hydrogen chloride:

Preparation of 2,4,6-tri (methoxycarbonylamino-1,3,5-triazine hydrochloric acid

In 50 ml of carbon tetrachloride, a slurry of 0.98 g of material from Example 22, Part B was cooled to 17 ° C. with an external water bath. The mixture was then saturated with anhydrous hydrogen chloride and stirred for 1 hour. The solution color darkened from yellow to red orange during the reaction. After 1 hour, the solid product was filtered off, washed several times with CCl ₄ and air dried overnight.

The product was a pale yellow powder (0.66 g, 98% yield) identified as HCl salt of 2,4,6-trimethoxycarbonylamino-1,3,5-triazine by ¹ H and ¹³ C NMR. It was.

Example 27

Part A: Preparation of N, N'-Dichloroacetoguanamine

Slurry of N, N, N ', N'-tetrachloroacetoguanamine (5.3 g), acetoguanamine (2.5 g), deionized water (90 ml) and glacial acetic acid (0.2 ml) at 50 ° C under nitrogen for 1 hour Heated with stirring. At the same time as cooling, the solid product was filtered off, washed with 140 ml of water and dried at room temperature under reduced pressure, white powder identified as N, N'-dichloroacetoguanamine by ¹ H NMR, ¹³ C NMR and IR (7.4). g, 95% yield). Titration regarding active chlorine content yielded a value of 10.19 mmol of chlorine per gram of product, corresponding to 98.8% of theoretical value. mp 186-187 ° (dec).

Part B: Preparation of 2,4-di (butoxycarbonylamino) -6-methyl-1,3,5-triazine from N, N'-dichloroacetoguanamine and butyl chloroformate

A mixture of 2.5 g of N, N'-dichloroacetoguanamine, 8.3 ml of n-butyl chloroformate and 20 ml of o-dichlorobenzene was heated with stirring at 70 ° C. under argon for 5 hours. At the same time as cooling, the insoluble solid was filtered and washed with nucleic acid. The combined hexanes / o-dichlorobenzene filtrate was concentrated under reduced pressure. The resulting colorless residue (2.3 g, 55% yield) was obtained using the same 2,4-di (butoxycarb as in Example 24, part C, by IR, TLC, ¹ H NMR, ¹³ C NMR and active Cl analysis. Carbonylamino) -6-methyl-1,3,5-triazine.

Example 28

Reaction of Trichloromelamine with Benzoyl Chloride Using 4-Dimethylamino Pyridine (DMAP) as Catalyst

To a stirred suspension of 1.15 g of trichloromelamine in 30 ml CCl ₄ was added 4.2 g of benzoyl chloride followed by 40 mg of 4-dimethylamino pyridine. The reaction mixture was stirred at room temperature under argon. After 0.5 hour the reaction mixture turned yellowish. Thin layer chromatography analysis revealed the formation of tribenzoyl melamine as one of the products compared to the tribenzoyl melamine sample on which it was based.

In the control experiment without catalyst but under the same reaction conditions, the formation of tribenzoyl melamine was not observed after 0.5 hours. From this comparative experiment it is determined that 4-dimethylaminopyridine is an effective catalyst for the novel inventive reactions.

Example 29

Triazine trisbutyl carbamate from hexachloromelamine and phosgene

About 5 ml of phosgene is condensed by passing into 20 ml of o-dichlorobenzene at -10 ° C in a two-necked flask equipped with a reflux condenser with rubber septum, magnetic stir bar and CaCl ₂ drying tube. A solution of 1.67 gm of hexachloromelamine in 10 ml of o-dichlorobenzene was slowly added to the flask using an argon injector. After 15 minutes of stirring at −10 ° C., the cooling bath was removed and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then heated to 110 ° C. in an oil bath and maintained at this temperature for 3 hours. The heating was stopped and the reaction mixture was cooled to room temperature and then cooled to about 0 ° C. in an ice bath. 10 ml of n-butanol were added and then concentrated by removing volatiles under reduced pressure and the residue was treated with 50 ml of n-hexane. The white precipitated product was filtered and dried under reduced pressure to yield 1.95 gm of product. TLC analysis of this product showed that as the main product, the same triazine trisbutylcarbamate was formed as the product obtained in Example 3.

Example 30

Triazine tris butylcarbamate from hexachloromelamine and oxalyl chloride

1.66 gm of hexachloromelamine was placed in a 2-neck 100 ml flask equipped with a magnetic stir bar, reflux condenser, argon inlet and rubber septum. To this 10 ml of o-dichlorobenzene were added and the mixture was cooled in an ice bath. 2 ml of oxalyl chloride was added with an injector and the reaction mixture was stirred at about 0 ° C. for 1 hour. It was then heated to about 100 ° C. for nearly 16 hours in an oil bath. Heating was stopped and the reaction flask was cooled to about 0 ° C. 10 ml of n-butanol was added to the reaction flask and the reaction mixture was stirred at room temperature for 2 hours. The formation of triazine trisbutylcarbamate as the main product was confirmed by direct comparison with the underlying sample on the TLC plate. The reaction mixture was concentrated under reduced pressure and the residue was treated with 50 ml of n-hexane. The precipitate was filtered off and dried under reduced pressure (1.8 gm). Triazine trisbutylcarbamate, the product formed in the reaction, was the same as the product obtained in Example 3.

Example 31

Triazine tris butylcarbamate from trichloromelamine and oxalyl chloride

Following the above procedure for the reaction of hexachloromelamine with oxalyl chloride, 2.29 gm of trichloromelamine was reacted with 4 ml of oxalyl chloride in 20 ml of ortho-dichlorobenzene. TLC analysis of the crude product obtained after treatment of the reaction mixture with n-butanol recognized the formation of triazine trisbutylcarbamate.

Example 32

2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine from N, N, N'-trichlorobenzoguanamine and oxalyl chloride

2.9 gm of N, N, N'-trichlorobenzoguanamine prepared in Example 23, Part A was placed in a 3-necked 100 ml flask with reflux condenser, magnetic stir bar, argon inlet, glass stopper and rubber bulkhead. . To the flask was added 25 ml of o-dichlorobenzene followed by dropwise addition of 6.35 gm of oxalyl chloride. The reaction mixture was stirred at rt for 0.5 h and then heated at 50-55 ° C. for 20 h in an oil bath. The heating was stopped and the reaction mixture was cooled to about -10 ° C. n-butanol (20 ml) was added to the reaction flask. After 10 minutes the cooling bath was removed and the reaction mixture was stirred at room temperature for 2 hours. TLC analysis of the reaction mixture showed large spots with the same R _f as in 2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine prepared in Example 23, Part B. Presented. The formation of 2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine was better confirmed by mass spectroscopy.

Example 33

Triazine trisbutylcarbamate and triazine tris methyl carbamate from hexachloromelamine and trichloromethyl chloroformate (diphosgene)

To a stirred solution of 1.65 gm of hexachloromelamine in 20 ml of ortho-dichlorobenzene, in a 2-necked flask with reflux condenser, rubber bulkhead, magnetic stir bar and argon inlet, 4.0 gm of trichloromethyl chloroformate was added dropwise by injector. It was. The rubber bulkhead was replaced with a glass stopper and the reaction mixture was heated to 60-65 ° C. for 6 hours in an oil bath. The temperature was then increased to 110 ° C. for about 20 hours. The reaction mixture was cooled to room temperature and divided into two equivalents 'A' and 'B'.

Part 'A' was added to the two-necked flask containing 20 ml of n-butanol at 0 ° C. under argon with stirring. The reaction mixture was then stirred at rt for 2 h. TLC analysis of the reaction mixture confirmed the formation of triazine trisbutylcarbamate when compared directly to the grounded sample prepared in Example 3. The volatiles were removed under reduced pressure leaving behind 1.0 gm of crude product.

700 g of crude product containing predominantly triazine tris methylcarbamate, identified by direct comparison on TLC with the base sample prepared in Example 2 by treating 'B' part with 20 ml of methanol at about 0 ° C Calculated.

Example 34

Triazine trisbutylcarbamate from hexachloromelanin and bis (trichloromethyl) carbonate (triphosgen)

A mixture of 1.66 gm of hexachloromelamine, 1.78 gm of triphosgen and 10 ml of ortho-dichlorobenzene was heated at 60 ° C. in an oil bath with stirring under argon in a two-neck flask with reflux condenser and glass stopper. After 24 hours at 60 ° C., the temperature of the oil bath was raised to 100 ° C. for 24 hours and then the reaction mixture was slowly cooled to about 0 ° C. n-butanol (10 ml) was added to the cooled reaction mixture which was then brought to room temperature and stirred for 4 hours. The reaction mixture was then diluted with 20 ml of CH ₂ Cl ₂ and filtered. The filtrate showed a large spot corresponding to triazine trisbutylcarbamate on TLC, which was identified in direct comparison with the underlying sample.

Example 35

Reaction of N, N ', N'-trichloromelamine and trichloromethyl chloroformate (diphosgene)

In a stirred suspension of 2.3 gm of N, N ', N'-trichloromelamine in 25 ml of ortho-dichlorobenzene in a 2-necked flask with reflux condenser, argon inlet, magnetic stir bar and rubber septum, trichloromethyl as injector 7.9 gm of chloroformate was added dropwise. The reaction flask was heated at 60-65 ° C. for 20 hours in an oil bath. It was then cooled to rt and diluted with 50 ml of n-hexane. The contents were stirred at rt for 2 h. The precipitate was filtered off, washed with n-hexane and dried under reduced pressure to yield 2.32 gm of product as indicated by TLC.

Example 36

Reaction of N, N ', N'-trichloromelamine and bis (trichloromethyl) carbonate (triphosgene)

A mixture of N, N ', N'-trichloromelamine 2.29 gm, bis (trichloromethyl) carbonate (triphosgene) and 30 ml of ortho-dichlorobenzene was added to a magnetic stir bar, reflux condenser, argon inlet and Heated at 60-65 ° C. (oil bath) under stirring in a 2-neck flask with glass stopper. The formation of chlorine gas was observed. The reaction mixture was heated at 60-65 ° C. for 24 hours. It was then cooled to rt and diluted with 50 ml of n-hexane. The reaction mixture was then stirred at rt for 2 h. The precipitate was filtered off, the residue was washed with 50 ml of n-hexane and dried under reduced pressure to yield 2.3 gm of product as indicated by TLC.

Example 37

2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine from N, N, N'-trichlorobenzoguanamine and trichloromethyl chloroformate (diphosgene)

1.45 gm of N, N, N'-trichlorobenzoguanamine (prepared in Part 23 A) was placed in a 2-neck 100 ml plesk with magnetic stirring rod, reflux condenser, argon inlet and rubber septum. 15.0 ml of ortho-dichlorobenzene was added to the reaction flask, and trichloromethyl chloroformate was added dropwise at about 0 ° C. The cooling bath was removed and heated at 50 ° C. for 4 hours in an oil bath. The temperature of the oil bath was increased to 100 ° C. and the reaction mixture was heated at this temperature for 24 hours. The heating was stopped and the reaction mixture was cooled to room temperature. It was then cooled to about 0 ° C. in an ice bath and 10 ml of n-butanol were added above. The contents were stirred at about 0 ° C. for 10 minutes and then stirring was continued at room temperature for 2 hours. Product analysis by TLC confirmed the formation of 2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine.

Example 38

2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-tri from N, N, N'-trichlorobenzoguanamine bis (trichloromethyl) carbonate (triphosgene) Ajin

1.45 gm of N, N, N'-trichlorobenzoguanamine (prepared in Part 23A) and 1.78 gm of triphosgen, two-necked flask with magnetic stirring rod, reflux condenser, argon inlet and rubber bulkhead Put on. 10 ml of ortho-dichlorobenzene was added to the reaction mixture and the contents were heated at 60 ° C. for 24 h in an oil bath. The temperature of the oil bath was increased to 100 ° C. and the reaction mixture was heated at this temperature for an additional 24 hours. The heating was stopped and the oil bath was replaced with an ice bath. n-butanol (10 ml) was added dropwise to the reaction mixture at about 0 ° C. and the reaction mixture was first stirred at about 0 ° C. for 10 minutes and then at room temperature for 4 hours. TLC analysis of the reaction mixture confirmed the formation of 2,4-di (butoxy carbonylamino) -6-phenyl-1,3,5-triazine.

Example 39

2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine from N, N, N'-trichlorobenzoguanamine and phosgene

1.45 gm of N, N, N'-trichlorobenzoguanamine (prepared in Part 23A) was placed in a 2-neck 100 ml flask with magnetic stirring rod, reflux condenser, argon inlet and rubber septum. To the reaction flask was added 15.0 ml of ortho-dichlorobenzene at about 0 ° C., followed by dropwise addition of 20 ml of a 20% phosgene solution in toluene. The reaction mixture was stirred at about 0 ° C. for 1 hour and at room temperature for 4 hours. The reaction mixture was then heated for 24 h at approximately 110 ° C. in an oil bath. The reaction mixture was then cooled to about 0 ° C. and 10 ml of n-butanol were added. The contents were stirred at about 0 ° C. for 1 hour and at room temperature for 2 hours. TLC of the reaction mixture confirmed the formation of 2,4-di (butoxycarbonylamino) -6-phenyl-1,3,5-triazine.

Example 40

Reaction of 4-amino-2,2,6,6-tetramethyl piperidine after the reaction of hexachloromelamine with oxalyl chloride

1.66 gm of hexachloromelamine was treated with 2 ml of oxalyl chloride in 10 ml of ortho-dichlorobenzene following the procedure described in Example 30. After heating at 100 ° C. for 16 hours, the reaction mixture was cooled to 0 ° C. Then 4 ml of 4-amino-2,2,6,6-tetramethyl piperidine were added dropwise with stirring. The contents were stirred at about 0 ° C. for 1 hour and then at room temperature for 2 hours. The reaction mixture was diluted with 50 ml of n-hexane. The precipitate material was filtered off, washed with 100 ml of n-hexane and dried. The TLC of the obtained product was then large, having the same R _f as the product obtained from the reaction of 4-amino-2,2,6,6-tetramethyl piperidine and triazine trisphenylcarbamate described in Example 19. The spot was presented.

While the present invention has been described in terms of certain preferred embodiments, it is apparent that one skilled in the art can make improvements and variations of the present invention without departing from the scope of the invention as defined in the appended claims.

Claims (9)

A process for preparing acid amides from haloamino triazines and acid halides comprising contacting the halo aminotriazines with an acid halide for a time and at a temperature sufficient to produce the acid amide, wherein the haloaminotriazine is )-(iii) selected from the group consisting of: (i) halogenated melamine represented by the following general formula (I): Wherein each X group is the same or different and is selected from the group consisting of hydrogen, chloro, bromo, iodo and fluoro groups, provided that at least one X group is halogen; Each B group is the same or different and is hydrogen, chloro, bromo, iodo, fluoro, alkyl, alkylenealkoxy, triazino, pyrimidino, pyridino, imidazole, tetrazole, silyl, cyano, perfluoro Selected from the group consisting of alkyl, perfluoroaryl, and perfluoroaralkyl groups; (ii) halogenated guanamine represented by the following general formula (II): Wherein X and B are as described above; R is linear alkyl of 1 to 20 carbon atoms, cyclic or branched alkyl of 3 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, 1 to Alkoxy of 20 carbon atoms, aryloxy of 6 to 20 carbon atoms, alkylthio of 1 to 20 carbon atoms, arylthio of 6 to 20 carbon atoms, alkylamino of 1 to 20 carbon atoms, dialkyl of 2 to 40 carbon atoms Amino, morpholino, piperidino, pyrrolidino, aminotriazino, alkylaminotriazino, aminoalkylaminotriazino, hydrogen, chloro, bromo, iodo, fluoro, perfluoroalkyl, perfluoro Aryl, and perfluoroaralkyl group; And (iii) a mixture of any of (I) and (II). The haloaminotriazine according to claim 1, wherein the haloaminotriazine is monohalomelamine, dihalomelamine, trihalomelamine, tetrahalomelamine, pentahalomelamine, hexahalomelamine, haloacetoguanamine, halobenzoguanamine, halo. Cyclohexylcarboguanamine, isomers thereof and mixtures thereof, and acid halides are selected from the following general formulas; M is at least 1; When M is 2 or more, each The groups are the same or different; X is halogen selected from the group consisting of chloro, bromo, iodo, fluoro, and mixtures thereof; bracket Y in a group is the same or different and each is independently selected from the group consisting of functional groups represented by the formula: Wherein each R is independently an alkyl, aryl or alkoxy group; And Z is hydrogen, chloro, bromo, iodo, fluoro, vinyl, alkyl of 1-20 carbon atoms, alkylene of 1-20 carbon atoms, arylene of 6-20 carbon atoms, haloalkyl of 1-20 carbon atoms, 6- Aryl of 20 carbon atoms, haloaryl of 6-20 carbon atoms, aralkyl of 7-20 carbon atoms, halo aralkyl of 7-20 carbon atoms, acyl of 2-20 carbon atoms, haloacyl of 2-20 carbon atoms, halocarbonyl, 2 Alkoxycarbonyl of 20 carbon atoms, alkylthiocarbonyl of 2-20 carbon atoms, haloalkoxy of 2-20 carbon atoms, aminocarbonyl, alkylaminocarbonyl of 2-20 carbon atoms, dialkylaminocarbonyl of 3-20 carbon atoms , Alkenylaminocarbonyl of 4-20 carbon atoms, dialkylaminocarbonyl of 7-40 carbon atoms, alkylalkenylaminocarbonyl of 5-20 carbon atoms, perfluoroalkyl of 1-20 carbon atoms, of 6-20 carbon atoms Perfluoroaryl, perfluoroaralkyl of 7-20 carbon atoms, 1-20 carbon source Of haloalkyl, alkoxycarbonylalkyl of 3-20 carbon atoms, cyanoalkyl of 2-20 carbon atoms, formylalkyl of 2-20 carbon atoms, ketoalkyl of 3-20 carbon atoms, trialkoxysilylalkyl of 4-20 carbon atoms, Dialkylaminoalkyl of 3-20 carbon atoms, alkoxyalkyl of 2-20 carbon atoms, alkoxy of 1-20 carbon atoms, aryloxy of 6-20 carbon atoms, alkenyloxy of 3-20 carbon atoms, alkylenedioxy of 2-20 carbon atoms , Arylenedioxy of 6-20 carbon atoms, N, N-dialkylamino of 2-40 carbon atoms, N, N-dialkenylamino of 6-40 carbon atoms, N, N-diarylamino of 12-40 carbon atoms, 4 -40 carbon atoms of N, N-alkylalkenylamino, 7-20 carbon atoms of N, N-alkenylarylamino, 9-20 carbon atoms of N, N-alkenylarylamino, aziridino, azetidino, pyrroli Dino, piperidino, morpholino, alkyl mercapto of 1-20 carbon atoms, alkenylmercapto of 3-20 carbon atoms, and aryl of 6-20 carbon atoms A process for preparing acid amides from haloaminotriazines and acid halides, which is an M-functional anchor selected from the group consisting of mercapto. Compound represented by the following general formula Wherein n is an integer of 3-5; And X is a leaving group selected from the group consisting of chloride, bromide, iodide, fluoride, alkylsulfonate, arylsulfonate, and mixtures thereof. Compound represented by the following formula Compound represented by the following general formula Where Q is Or; or Q is linear alkyl of 1-20 carbon atoms, cyclic or branched alkyl of 3-20 carbon atoms, alkenyl of 2-20 carbon atoms, aryl of 6-20 carbon atoms, aralkyl of 7-20 carbon atoms, alkoxy of 1-20 carbon atoms, Aryloxy of 6-20 carbon atoms, alkylthio of 1-20 carbon atoms, arylthio of 6-20 carbon atoms, alkylamino of 1-20 carbon atoms, dialkylamino of 2-40 carbon atoms, morpholino, piperidino, pipe From the group consisting of lololidino, aminotriazino, alkylaminotriazino, aminoalkylaminotriazino, hydrogen, chloro, bromo, iodo, fluoro, fifluoroalkyl, fifluoroaryl, and fifluoroaralkyl groups Is selected; bracket X in the group is hydrogen or halogen, provided that at least one X is halogen each selected from the group consisting of chloride, bromide, iodide and fluoride; bracket Wherein Y is the same or different and each is selected from the group consisting of functional groups represented by the formula: Wherein each R is each an alkyl, aryl or alkoxy group; And Z is hydrogen, chloro, bromo, iodo, fluoro, vinyl, alkyl of 1-20 carbon atoms, alkylene of 1-20 carbon atoms, arylene of 6-20 carbon atoms, haloalkyl of 1-20 carbon atoms, 6- Aryl of 20 carbon atoms, haloaryl of 6-20 carbon atoms, aryl of 7-20 carbon atoms, haloaryl of 6-20 carbon atoms, aralkyl of 7-20 carbon atoms, haloaralkyl of 7-20 carbon atoms, of 2-20 carbon atoms Acyl, haloacyl of 2-20 carbon atoms, halocarbonyl, alkoxycarbonyl of 2-20 carbon atoms, alkylthiocarbonyl of 2-20 carbon atoms, haloalkoxy of 2-20 carbon atoms, aminocarbonyl, of 2-20 carbon atoms Alkylamino carbonyl, dialkyl aminocarbonyl of 3-20 carbon atoms, alkenylaminocarbonyl of 4-20 carbon atoms, dialkylaminocarbonyl of 7-40 carbon atoms, alkylalkenyl amino carbonyl of 5-20 carbon atoms, Perfluoroalkyl of 1-20 carbon atoms, perfluoroaryl of 6-20 carbon atoms, Perfluoro aralkyl of 7-20 carbon atoms, haloalkyl of 1-20 carbon atoms, alkoxycarbonylalkyl of 3-20 carbon atoms, cyanoalkyl of 2-20 carbon atoms, formylalkyl of 2-20 carbon atoms, 3-20 Keto alkyl of carbon atoms, trialkoxysilylalkyl of 4-20 carbon atoms, dialkylaminoalkyl of 3-20 carbon atoms, alkoxyalkyl of 2-20 carbon atoms, alkenyloxy of 3-20 carbon atoms, alkylenedioxy of 2-20 carbon atoms , Arylenedioxy of 6-20 carbon atoms, N, N-dialkylamino of 2-40 carbon atoms, N, N-dialkenylamino of 6-40 carbon atoms, N, N-diarylamino of 12-40 carbon atoms, 4 -20 carbon atoms of N, N-alkylalkenylamino, 7-20 carbon atoms of N, N-alkylarylamino, 9-20 carbon atoms of N, N-alkenylarylamino, aziridino, azetidino, pyrrolidino , Piperidino, morpholino, alkyl mercapto of 1-20 carbon atoms, alkenyl mercapto of 3-20 carbon atoms, and aryl of 6-20 carbon atoms M-functional anchor selected from the group consisting of mercapto. Compound represented by the following general formula Where Q is Or; or Q is linear alkyl of 1-20 carbon atoms, cyclic or branched alkyl of 3-20 carbon atoms, alkenyl of 2-20 carbon atoms, aryl of 6-20 carbon atoms, aralkyl of 7-20 carbon atoms, alkoxy of 1-20 carbon atoms, Aryloxy of 6-20 carbon atoms, alkylthio of 1-20 carbon atoms, arylthio of 6-20 carbon atoms, alkylamino of 1-20 carbon atoms, dialkylamino of 2-40 carbon atoms, morpholino, piperidino, pipe It is selected from the group consisting of a lollidino, hydrogen, chloro, bromo, iodo, fluoro, perfluoroalkyl, perfluoroaryl, perfluoro aralkyl group; Each X is hydrogen or halogen, Each Z is selected from the group consisting of alkoxy of 1-20 carbon atoms and aryloxy of 6-20 carbon atoms, respectively, provided all Z groups are not identical. Compound represented by the following general formula Where Q is Or; or Q is linear alkyl of 1-20 carbon atoms, cyclic or branched alkyl of 3-20 carbon atoms, alkenyl of 2-20 carbon atoms, aryl of 6-20 carbon atoms, aralkyl of 7-20 carbon atoms, alkoxy of 1-20 carbon atoms, Aryloxy of 6-20 carbon atoms, alkylthio of 1-20 carbon atoms, arylthio of 6-20 carbon atoms, alkylamino of 1-20 carbon atoms, dialkylamino of 2-40 carbon atoms, morpholino, piperidino, pipe It is selected from the group consisting of a lollidino, hydrogen, chloro, bromo, iodo, fluoro, perfluoroalkyl, perfluoroaryl, perfluoro aralkyl group; Each X is hydrogen or halogen, Each Z is a butoxy group. 8. The method of claim 7, wherein Q is Phosphorus compounds. 9. A compound according to claim 7 or 8 wherein X is hydrogen.