WO1994018181A1

WO1994018181A1 - Process for preparing n-substituted-oxazolidine-2,4-diones

Info

Publication number: WO1994018181A1
Application number: PCT/US1994/000168
Authority: WO
Inventors: William Dennis Mcghee
Original assignee: Monsanto Company
Priority date: 1993-02-01
Filing date: 1994-01-05
Publication date: 1994-08-18
Also published as: MX9400808A

Abstract

A process for preparing N-substituted-oxazolidine-2,4-diones comprising (a) contacting carbon dioxide and a primary amine or ammonia in the presence of an aprotic organic solvent and an organic, nitrogenous base to produce the corresponding ammonium carbamate salt, and (b) reacting the ammonium carbamate salt with an α-substituted carboxylic acid ester having the formula X-CHR1CO2R2 to produce the corresponding N-substituted-oxazolidine-2,4-dione. A second embodiment comprises recovering the ammonium carbamate salt of Step (a) prior to reacting the ammonium carbamate salt with the α-substituted carboxylic acid ester in the presence of an aprotic organic solvent and an organic, nitrogenous base. A third embodiment comprises reacting the N-substituted-oxazolidine-2,4-dione with a nucleophile selected from the group consisting of aliphatic or alicyclic primary amines, alcohols and thiols, wherein the reaction is conducted in the presence of a Lewis acid catalyst when the nucleophile is an aliphatic or alicyclic alcohol.

Description

PROCESS FOR PREPARING N-SUBSTITUTED- OXAZOLIDINE-2,4-DIONES

BACKGROUND OF THE INVENTION

This invention relates to a process for preparing N-substituted-oxazolidine-2,4-diones. In one aspect, the invention relates to a new and useful process for preparing N-substituted-oxazolidine-2,4- diones from primary amines or ammonia, carbon dioxide and an α-substituted carboxylic acid ester. In a further aspect, the invention relates to a process for preparing ring-opened N-substituted-oxazolidine-2,4- diones.

N-substituted-oxazolidine-2,4-diones, which are also known as N-substituted 2,4-oxazolidinediones, are chemicals that are useful in applications such as pharmaceuticals, herbicides, fungicides, coatings, and the like.

The most common methods for preparing 2,4- oxazolidinediones involved the reaction of an isocyanate with an α-hydroxy-carboxylic acid amide or an α-hydroxyalkane carboxylic ester. See for example, U.S.

4,187,227, U.S. 4,810,799 and DE 3,115,650. It is a disadvantage of these processes that isocyanates are used as a starting material because of the cost of the isocyanates needed to prepare the 2,4-oxazolidinediones.

Isocyanates are typically produced

commercially by the phosgenation of primary amines. The use of phosgene results in a process having several disadvantages. The phosgenation route is a long, energy-intensive process that requires handling highly corrosive and toxic chemicals, and the use of process equipment that can withstand high temperatures and highly corrosive conditions. These disadvantages result in increased capital and operating costs which effect the overall economics of the process.

A process for preparing N-substituted- oxazolidine-2,4-diones which does not require the use of isocyanates, and is economical and commercially viable would be highly desirable.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a process for preparing N-substituted-oxazolidine-2,4- diones. It is a further object of the invention to provide an efficient and economic process for preparing N-substituted-oxazolidine-2,4-diones that is

commercially viable. It is a still further object of the invention to provide a process for preparing a ring- opened N-substituted-oxazolidine-2,4-dione for use in coating applications as a cross-linking agent.

According to the invention, a process for preparing N-substituted-oxazolidine-2,4-diones is provided which comprises:

(a) contacting CO₂ and a primary amine or ammonia in the presence of an aprotic organic solvent and an organic,

nitrogenous base, under reaction conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, and

(b) reacting the ammonium carbamate salt with an α-substituted carboxylic acid ester represented by the formula X- CHR₁CO₂R₂ under reaction conditions of time and temperature sufficient to produce the corresponding N- substituted-oxazolidine-2,4-dione.

In one embodiment, the ammonium carbamate salt of Step (a) is recovered prior to reacting the ammonium carbamate salt with the α-substituted carboxylic acid ester in the presence of an aprotic organic solvent and an organic nitrogenous base. In another embodiment, the N-substituted-oxazolidine-2,4-dione of Step (b) is further reacted with a nucleophile selected from the group consisting of aliphatic or alicyclic primary amines, alcohols and thiols to ring open the N- substituted-oxazolidine-2,4-dione. In a further

embodiment, the N-substituted-oxazolidine-2,4-dione of Step (b) is recovered prior to reacting the

N-substituted-oxazolidine-2,4-dione with the nucleophile to ring open the N-substituted-oxazolidine-2,4-dione.

Further according to the invention, a process for ring opening the N-substituted-oxazolidine-2,4-dione is provided which comprises reacting an N-substituted- oxazolidine-2,4-dione with a nucleophile selected from the group consisting of aliphatic or alicyclic primary amines, alcohols and thiols, wherein when the

nucleophile is an aliphatic or alicyclic alcohol the reaction is conducted in the presence of a Lewis acid catalyst.

DETAILED DESCRIPTION OF THE INVENTION

A first embodiment of the invention relates to a process for preparing N-substituted-oxazolidine-2,4- dione comprising:

nitrogenous base under reaction

conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, and

(b) reacting the ammonium carbamate salt with an α-substituted carboxylic acid ester represented by the formula X- CHR₁CO₂R₂ under reaction conditions of time and temperature which are sufficient to produce the corresponding N-substituted-oxazolidine-2,4-dione, wherein R₁ is selected from the group consisting of hydrogen and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl, and aralkenyl groups having 1 to about 22 carbon atoms, R₂ is selected from the group consisting of alkyl, cycloalkyl, araryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl and aralkenyl groups having 1 to about 22 carbon atoms, and X is selected from the group consisting of halides, tosylates, triflates, mesylates, brosylates, nosylates, nonaflates and tresylates. A second embodiment of the invention relatesto a process for preparing N-substituted-oxazolidine-2 ,4-dione comprising:

(a) contacting CO₂ and a primary amine or ammonia in the presence of an aprotic organic solvent and an organic

nitrogenous base, under reaction conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt,

(b) recovering the ammonium carbamate salt, and

(c) reacting the ammonium carbamate salt with an α-substituted carboxylic acid ester represented by the formula X- CHR₁CO₂R₂ in tne presence of an aprotic organic solvent and an organic,

nitrogenous base under reaction

conditions of time and temperature sufficient to produce the corresponding N-substituted-oxazolidine-2,4-dione, wherein R₁, R₂ and X are as defined above.

The N-substituted-oxazolidine-2,4-diones made according to this invention are readily recoverable and well suited for use in pharmaceuticals, herbicides, fungicides, coatings, and as intermediates for use in preparation of ring-opened N-substituted-oxazolidine- 2,4-diones which are useful as cross-linking agents in coating applications.

A third embodiment of the invention relates to a process for preparing a ring-opened N-substituted- oxazolidine-2,4-dione comprising reacting an

N-substituted-oxazolidine-2,4-dione with a nucleophile selected from the group consisting of aliphatic or alicyclic primary amines, alcohols and thiols, wherein when the nucleophile is an aliphatic or alicyclic alcohol, the reaction is conducted in the presence of a Lewis acid catalyst.

The N-substituted-oxazolidine-2,4-diones produced by the process of the invention are represented by the formula:

wherein R1 _is selected from the group consisting of hydrogen and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl and aralkenyl groups, having 1 to about 22 carbon atoms, and R₆ is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, a group represented by the formula:

a group represented by the formula:

and a group represented by the formula:

-(-CH-CB₂-O-)-_x -(-CH₂-CH₂-O -)_y -(-CH-CH₂-O -)- _zCH₂-

CH₃ CH₃

or N-substituted-oxazolidine-2,4-diones are represented by the formula:

wherein R₄

and R₅ are

independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R₃ is hydrogen or methyl, x + z represents an integer from about 2 to about 70, y represents an integer from 0 to about 90, x + y + z represents an integer from about 2 to about 100, a, b, and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol initiator such as glycerine or

trimethylolpropane. In addition, R₆ may contain

nonnucleophilic functional groups which do not react preferentially with the α-substituted carboxylic acid ester. Examples of suitable functional groups include esters, amides, urethanes, carbonates, and the like, and salts thereof.

Examples of N-substituted-oxazolidine-2,4- dione produced by the process of the invention include, but are not limited to, N-cyclohexyl-oxazolidine-2,4- dione, N-phenyl-oxazolidine-2,4-dione, N-(hexamethylene- oxazolidine-2,4-dione)-oxazolidine-2,4-dione, N- (4,4'- methylene diphenyl-oxazolidine-2,4-dione)-oxazolidine- 2,4-dione, the N-substituted-oxazolidine-2,4-dione based on 4-aminomethyl-1,8-octane-diamine, and the like, and mixtures thereof.

The ammonium salt of the carbamate anion is prepared in solution in the presence of an organic, nitrogenous base. The reaction between the primary amine or ammonia and carbon dioxide to form the ammonium carbamate salt may be represented by the equation (1) . The resulting ammonium carbamate salt solutions are normally homogenous.

RNH₂ + CO₂ + Base = RNHCO₂ ^{- +} H Base (1) The result of the reaction of the ammonium carbamate salt with the α-substituted carboxylic acid ester may be represented by the equation (2).

RNHCO₂ ^-+ H Base + x- CHR₁CO₂R ₂

The primary amines for use in the process of the invention for preparing N-substituted-oxazolidine- 2,4-diones are selected from the group consisting of compounds represented by the formula R-NH₂,

polyoxyalkylenediamines represented by the formula:

H₂N-(-CH-CH₂-O -) -_x -( --H₂-CH₂-O -) -_y -(-CH-CH₂-O-)-_z CH₂-CH-NH₂

CH₃ CH₃ CH₃

and polyoxyalkylenetriamines represented by the formula:

(OCH₂CH -)-_c NH₂

wherein R is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, a group represented by the formula:

-(-R₄-)-_n -(-R₅-)-_m NH₂

NH₂ and a group represented by the formula -R₄ -NH₂ , wherein R₃, R₄, R₅, a, b, c, m, n, x, y, z and A are as defined above. Suitable primary amines include diamines and polyamines. In addition, R may contain nonnucleophilic functional groups which do not react preferentially with the α-substituted carboxylic acid ester. Examples of suitable functional groups include esters, amides, urethanes, carbonates and the like, and salts thereof.

Examples of primary amines which can be employed in the process of the invention for preparing N-substituted-oxazolidine-2,4-diones include, but are not limited to, cyclohexylamine, octylamine, 1,4- diaminocyclohexane, aniline, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,

isobutylamine, t-butylamine, n-pentylamine,

isopentylamine, n-hexylamine, n-octylamine, benzylamine, 2,6-methylcyclohexyldiamine,

2,4-methylcyclohexyldiamine, n-hexyldiamine,

4,4'-methylenediphenylamine, hexamethylenediamine, 4- aminomethyl-1,8-octanediamine, polyoxyalkylenediamines such as those available from Texaco Chemical Company under the trademark Jeffamine^® including D-230

(approximate molecular weight = 230), D-400 (approximate molecular weight = 400), D-2000 (approximate molecular weight = 2000), D-4000 (approximate molecular weight = 4000), ED-600 (approximate molecular weight = 600), ED- 900 (approximate molecular weight = 900), ED-2001

(approximate molecular weight = 2000), ED-4000

(approximately molecular weight = 4000), and ED-6000 (approximately molecular weight = 6000),

polyoxyalkylenetriamines such as those available from Texaco Chemical Company under the trademark Jeffamine including T-403 (approximate molecular weight = 440), T-3000 (approximate molecular weight = 3000) and T-5000 (approximate molecular weight = 5000),

tetraethylenepentamine, diethylenetriamine,

triethylenetetramine, pentaethylenehexamine, and the like, and mixtures thereof. Applicable solvents for use in the process of the invention are aprotic organic solvents. While polar and nonpolar aprotic organic solvents, as well as mixtures thereof, may be used, it is currently preferred to use polar aprotic organic solvents due to improved rates of reaction. As utilized herein, the phrase

"polar aprotic organic solvent" means an aprotic organic solvent having a dielectric constant measured at 25°C of greater than about 10e as reported in Reichardt, C., Solvents and Solvent Effects in Organic Chemistry, 2nd Ed., VCH Verlagsgesellschaft, Weinheim, (1988), Table A-1, utilizing toluene (2.38e) and tetrahydrofuran

(7.58e) as standards measured at 25ºC. Other methods for determining dielectric constants are known and suitable polar aprotic organic solvents are those having a dielectric constant greater than that of

tetrahydrofuran utilizing any of such methods.

Examples of nonpolar aprotic organic solvents which can be employed in the process of the invention include dichloromethane, toluene, tetrahydrofuran, o-dichlorobenzene, triethylamine and the like, and mixtures thereof. Currently preferred nonpolar aprotic organic solvents include dichloromethane and toluene.

Examples of polar aprotic organic solvents which can be employed in the process of the invention include dimethylformamide, N-methyl-2-pyrrolidone,

N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, sulfolane, pyridine and the like, and mixtures thereof. Currently preferred polar organic solvents include acetonitrile and N,N-dimethylacetamide.

Although not specifically required, it is preferred to utilize the same solvent to carry out both reaction steps of the present invention for preparing N- substituted-oxazolidine-2,4-dione in order to avoid additional process equipment for recovering additional solvents. The amount of solvent utilized in the process of the invention for preparing N-substituted- oxazolidine-2,4-dione is at least the amount necessary to solubilize the ammonium carbamate salt present.

To obtain high selectivities and yields for the desired N-substituted-oxazolidine-2,4-diones, an organic nitrogenous base is employed in the process of the invention. The phrase "organic, nitrogenous base" as used herein refers to a base utilized in addition to the reactant primary amine. Applicable organic,

nitrogenous bases for use in the process of the

invention include guanidine compounds, amidine

compounds, phosphazene compounds and mixtures of any 2 or more thereof. The organic, nitrogenous base

preferably has one of the general structures shown below:

1₅

wherein R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals; or one of R₉ or R₁₀ together with one of R₁₁ or R₁₂, one of R₁₃ or R₁₄ together with one of R₁₁ or R₁₂, and R₈ together with one of R₉, or R₁₀ or one of R₁₃ or R₁₄ independently form a nitrogen-containing heterocycle; or R₉ together with R₁₀, R₁₁ together with R₁₂, and R₁₃ together with R₁₄ independently represent a radical represented by the formula:

R ₁₁

1₂

wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are as defined above; R₁₅, R₁₆, R₁₇ and R₁₈ are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals; or R₁₅ together with R₁₆ or R₁₇ and R₁₈ together with R₁₆ or R₁₇ independently form a nitrogen- containing heterocycle;

R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals; or R₁₉ together with one of R₂₀, R₂₁, R₂₂ or R₂₃, R₂₂ and R₂₃, and R₂₀ and R₂₁ independently form a nitrogen-containing heterocycle.

Examples of organic, nitrogenous bases which can be employed in the process of the invention include tetramethylguanadine (TMG),

cyclohexyltetramethylguanadine (CyTMG),

butyltetraethylguanadine (n-BTEG),

cyclohexyltetraethylguanadine (CyTEG),

tetraethylguanadine (TEG), t-butyltetraethylguanadine (t-BTEG), 7-methyl-1,5,7-triazabicylo[4.4.0]dec-5-ene

(MTBD), t-butyldimethylformamidine (t-BDMF),

t-butyldimethylacetamidine (t-BDMA),

1,5-azabicyclo[4.3.0]non-5-ene (DBN),

1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),

[t-butyliminotris(dimethylamino)phosphorane], [t- butyliminotris (diethylamino) -phosphorane], {1-t-butyl-

4,4,4-tris (dimethylamino)-2,2-bis-

[tris(dimethylamino) phosphoranylideneamino]-2λ,4λ-catena di (phosphazene)}, and the like, and mixtures of any two or more thereof.

The amount of organic, nitrogenous base utilized in the process of the invention will depend upon the particular embodiment of the process.

In the first embodiment wherein the ammonium carbamate salt is not recovered prior to reaction with the α-substituted carboxylic acid ester, the amount of organic, nitrogenous base can be conveniently expressed in terms of a ratio based on the number of equivalents of amine in the primary amine charged or the number of moles of ammonia charged. Broadly, the ratio of the number of moles of organic, nitrogenous base to the number of equivalents of amine in the primary amine or the number of moles of ammonia will be about 1:1 to about 20:1, preferably about 2:1 to about 10:1, and most preferably about 2:1 to about 4:1. The organic, nitrogenous base can be completely charged at the the beginning of the process and the remainder charged at any time prior to the reaction of the ammonium carbamate salt with the α-substituted carboxylic acid ester.

In the second embodiment wherein the ammonium carbamate salt is recovered prior to reaction with the α-substituted carboxylic acid ester, the amount of organic, nitrogenous base can be conveniently expressed in terms of a ratio based on a number of equivalents of amine in the primary amine charged or the number of moles of ammonia charged for reaction with carbon dioxide, and the amount of organic, nitrogenous base can be conveniently expressed in terms of a ratio based on a number of equivalents of carbamate in the ammonium carbamate salt charged for the reaction of the ammonium carbamate salt with the α-substituted carboxylic acid ester. For the reaction of the primary amine or ammonia with carbon dioxide, the ratio of the number of moles of organic, nitrogenous base to the number of equivalents of amine in the primary amine or the number of moles of ammonia will broadly be about 0.5:1 to about 10:1, preferably about 1:1 to about 5:1, and most preferably about 1:1 to about 2:1. For the reaction of the

ammonium carbamate salt with the α-substituted

carboxylic acid ester, the ratio of the number of moles of organic, nitrogenous base to the number of

equivalents of carbamate in the ammonium carbamate salt will broadly be about 0.5:1 to about 10:1, preferably about 1:1 to about 5:1, and most preferably about 1:1 to about 2:1.

Applicable α-substituted carboxylic acid esters for use in the process of the invention can be represented by the formula X-CHR₁CO₂R₂ wherein R₁ is selected from the group consisting of hydrogen and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl, and aralkenyl groups having 1 to about 22 carbon atoms, R₂ is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl and aralkenyl groups having 1 to about 22 carbon atoms, and X is selected from the group consisting of halides, tosylates,

triflates, mesylates, brosylates, nosylates, nonaflates and tresylates. Preferably, X is selected from the group consisting of halides, tosylates, triflates and mesylates wherein said halides are selected from the group consisting of chlorine, bromine and iodine, preferably chlorine.

Examples of suitable α-substituted carboxylic acid esters include, but are not limited to,

α-chloromethylacetate, α-tosylmethylacetate, α- chloroethylacetate, α-chloromethylpropionate, and the like, and mixtures thereof.

The currently preferred α-substituted carboxylic acid esters are the α-halocarboxylic acid esters because of availability and good results achieved therewith. Especially preferred are the

α-chlorocarboxylic acid esters.

In the first embodiment wherein the ammonium carbamate salt is not recovered prior to reaction with the α-substituted carboxylic acid ester, the amount of α-substituted carboxylic acid ester can be conveniently expressed in terms of a ratio based on the number of equivalents of amine in said primary amine starting material or the number of moles of ammonia starting material. Broadly, the ratio of the number of moles of α-substituted carboxylic acid ester to the number of equivalents of amine in the primary amine or the number of moles of ammonia will be about 1:1 to about 4:1, preferably about 2 : 1 to about 3:1.

In the second embodiment wherein the ammonium carbamate salt is recovered prior to reaction with the α-substituted carboxylic acid ester, the amount of α-substituted carboxylic acid ester can be conveniently expressed in terms of a ratio based on the number of equivalents of carbamate in the ammonium carbamate salt charged for the reaction of the ammonium carbamate salt with the α-substituted carboxylic acid ester. Broadly, the ratio of the number of moles of α-substituted carboxylic acid ester to the number of equivalents of carbamate in the ammonium carbamate salt will be about 1:1 to about 4:1, preferably about 2 : 1 to about 3:1.

The reaction between the primary amine or ammonia and carbon dioxide is conducted under a CO₂ atmosphere. The pressure of CO₂ during this reaction is 0 psig (atmospheric pressure) to about 150 psig, preferably 0 psig to about 100 psig, and most preferably 0 psig to about 80 psig. It is preferred to charge the CO₂ to the reaction vessel containing the primary amine or ammonia below the liquid level in the reaction vessel. Although not specifically required, it is preferred to conduct the reaction of the ammonium carbamate salt with α-substituted carboxylic acid ester under a CO₂ atmosphere. However, the reaction of ammonium carbamate salt with α-substituted carboxylic acid ester can be conducted under any inert atmosphere, e.g., nitrogen, argon or air, provided the atmosphere is substantially dry. The pressure during this reaction is 0 psig to about 150 psig, preferably 0 psig to about 100 psig, and most preferably 0 psig to about 80 psig.

The temperature and time used in the process of the invention for preparing N-substituted- oxazolidine-2,4-dione will depend on the particular reaction involved. For the reaction of primary amine or ammonia with CO₂, the temperature is about 20°C to about 100ºC, preferably about 25°C to about 60°C, and most preferably about 30ºC to about 50°C. The time will broadly be the time required to achieve complete mixing of reactants to about 4 hours , preferably about 5 minutes to about 1 hour, and most preferably about 10 minutes to about 30 minutes. For the reaction of ammonium carbamate salt with α-substituted carboxylic acid ester, the temperature is about 20°C to about

100°C, preferably about 25ºC to about 60ºC, and most preferably about 30°C to about 50°C. The time will broadly be the time required to achieve complete mixing of the reactants to about 24 hours, preferably about 30 minutes to about 15 hours, and most preferably about 1 hour to about 10 hours.

For the embodiment where the ammonium carbamate salt is recovered prior to reaction with α-substituted carboxylic acid ester, the ammonium carbamate salt can be recovered by any conventional means known in the art. The desired N-substituted- oxazolidine-2,4-diones produced by the process of the invention can be recovered by any conventional means known in the art such as that disclosed in the examples herein.

The reaction of N-substituted-oxazolidine- 2,4-dione with a nucleophile to produce the ring-opened N-substituted-oxazolidine-2,4-dione occurs via attack of the nucleophile at the N-C = O bonds of the N- substituted-oxazolidine-2,4-dione.

The nucleophiles for use in the process of the invention are selected from the group consisting of aliphatic or alicyclic primary amines, alcohols and thiols wherein when the nucleophile is an aliphatic or alicyclic alcohol the reaction is conducted in the presence of a Lewis acid catalyst. The nucleophiles are preferably selected from the group consisting of R₇-NH₂, R₇-OH and R₇-SH wherein R₇ is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups having 1 to about 22 carbon atoms. In addition, R₇ may contain nonnucleophilic functional groups which do not react preferentially with the N-substituted-oxazolidine-2,4-dione. Examples of suitable functional groups include esters, amides, urethanes, carbonates, and the like .and salts thereof.

Examples of nucleophiles which can be employed in the process of the invention for preparing ring- opened N-substituted-oxazolidine-2,4-diones include, but are not limited to, cyclohexylamine, methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, n-hexylamine, n-octylamine, cyclooctylamine, cyclopentylamine,

2-(1-cyclohexenyl) ethylamine, 2-propynylamine,

hexamethylene diamine, n-hexyldiamine, 1,4-diamino- cyclohexane, 4-aminomethyl-1, 8-octanediamine, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-hexanol, n-octanol, cyclohexanol,

cyclopentanol, cyclooctanol, 2-buten-1-ol, 3-buten-1-ol, 2-penten-1-ol, 1-penten-3-ol, 2-cyclohexene-1-ol,

2-hexen-1-ol, 2-propyn-1-ol, 2-butyn-1-ol, 3-butyn-1-ol, 2-pentyn-1-ol, 1-pentyn-3-ol, 5-hexyn-1-ol,

ethyleneglycol, 1,3-propanediol, hexamethyleneglycol, 1,4-cyclohexanediol, 1,2,6-trihydroxyhexane,

1-methanethiol, 1-ethanethiol, 1-propanethiol,

1-butanethiol, 2-methyl-1-propanethiol,

cyclohexanethiol, cyclopentanethiol, and the like, and mixtures thereof.

When the nucleophile is an aliphatic or alicyclic primary amine, the reaction between the primary amine and the N-substituted-oxazolidine-2,4- dione may be represented by equation (3).

When the nucleophile is an aliphatic or alicyclic alcohol, the reaction between the alcohol and the N-substituted-oxazolidine-2,4-dione in the presence of a Lewis acid catalyst may be represented by equation (4). Levis O O

R₇ 7-OH + R₆,

Acid ----→

R₆-N-C- O-CHR -C - OR₇

Catalyst

+ (4)

O O

R₆ -N-C-CHR₁ -O-C - OR₇

H

O O

R₇- SH- R₆-

I

E 6 -K-C-O-CHR, 1 -C- SR₇

H⁺ (5)

O O

I

R₆ -N-C-CHR₁ -O-C - SR₇

H

Lewis acid catalysts are well-known to those skilled in the art. Examples of Lewis acid catalysts include, but are not limited to, BF₃,AlCl₃, SnCl₄, FeCl₃, ZnCl₂ and H₃C-CH₂-CH₂-CH₂-Sn(O₂CCH ( CH₂CH₃ )CH₂CH₂CH₂CH₃)₃. The preferred Lewis acid catalysts for use in the reaction of an alcohol with the N-substituted-oxazolidine-2,4- dione are the tin compounds, particularly

H₃C-CH₂-CH₂-CH₂-Sn(O₂CCH(CH₂CH₃)CH₂CH₂CH₂CH₃)₃. The amount of Lewis acid catalyst utilized in the reaction of an aliphatic or alicyclic alcohol with N-substituted- oxazolidine-2,4-dione will depend upon the particular catalyst and reactants used. Typically, the amount of Lewis acid catalyst is about 5 wt.% based on the N- substituted-oxazolidine-2,4-dione.

When the nucleophile is an aliphatic or alicyclic thiol, the reaction between the thiol and the N-substituted-oxazolidine-2,4-dione may be represented by equation (5).

The amount of nucleophile can be conveniently expressed in terms of a ratio of the number of moles of nucleophile to the number of equivalents of

oxazolidine-2,4-dione in the N-substituted-oxazolidine- 2,4-dione. Broadly, the ratio of the number of moles of nucleophile to the number of equivalents of oxazolidine- 2,4-dione in the N-substituted-oxazolidine-2,4-dione will be 1:1 to about 20:1, preferably 1:1 to about 10:1, and most preferably 1:1 to about 5:1.

The reaction between the nucleophile and the N-substituted-oxazolidine-2,4-dione can be conducted under any inert atmosphere, e.g., nitrogen, argon or air. The pressure during this reaction is not critical.

The temperature and time used in the reaction of the nucleophile with the N-substituted-oxazolidine- 2,4-dione will depend on the particular reaction

involved, e.g., on the nucleophile and R groups of the N-substituted-oxazolidine-2,4-dione. For example, if R₆ of the N-substituted-oxazolidine-2,4-dione is an

aromatic group, the ring-opening reaction has a higher rate of reaction. Broadly, the temperature of the reaction is about 20°C to about 200ºC, preferably about 25°C to about 150°C, and most preferably about 30°C to about 130°C. The time will depend on the temperature of the reaction and will vary from about 10 minutes to about 2 days.

The use of an added solvent for the reaction of the nucleophile with the N-substituted-oxazolidine- 2,4-dione is optional because the nucleophile can serve as a solvent when used in excess of the stoichiometric amount. When an added solvent is used, an aprotic organic solvent as defined herein is preferred. In the embodiment wherein the N-substituted-oxazolidine-2,4- dione is not recovered prior to reaction with the nucleophile, the solvent used is preferably the solvent used during the production of the N-εubstituted- oxazolidine-2,4-dione. In the embodiment wherein the N- substituted-oxazolidine-2,4-dione is recovered prior to reaction with the nucleophile, the solvent used is preferably excess nucleophile.

For the embodiment where the N-substituted- oxazolidine-2,4-dione is recovered prior to reaction with the nucleophile, the N-substituted-oxazolidine- 2,4-dione can be recovered by any conventional means known in the art.

The desired ring-opened compounds produced by the process of the invention can be recovered by any conventional means known in the art, such as that disclosed in the examples herein.

Contemplated equivalents of the general formulas set forth above for the primary amines, N- substituted-oxazolidine-2,4-diones, alcohols and thiols are compounds otherwise corresponding thereto and having the same general properties wherein one or more of the various R groups are simple variations of the

substituents as defined herein.

In addition, where a substituent is designated as, or can be, a hydrogen, the exact chemical nature of a substituent which is other than hydrogen at that position is not critical so long as it does not

adversely affect the overall process.

The chemical reactions described above are generally disclosed in terms of their broadest

application to the preparation of the compounds of this invention. Occasionally, the reactions may not be applicable as described to each compound included within the disclosed scope. The compounds for which this occurs will be readily recognized by those skilled in the art. In all such cases, either the reactions can be successfully performed by conventional modifications known to those skilled in the art, e.g., by appropriate protection of interfering groups, by changing to

alternative conventional reagents, by routine

modification of reaction conditions, and the like, or other reactions disclosed herein or otherwise

conventional, will be applicable to the preparation of the corresponding compounds of this invention. In all preparative methods, all starting materials are known or readily preparable from known starting materials.

The invention will now be further disclosed in the following illustrative examples wherein parts and percentages are given on a molar basis unless otherwise specified.

EXAMPLES

N-cyclohexyl-N',N',N",N"-tetraethyl guanidine (CyTEG) was synthesized according to the general

proceure set forth in Bredereck, H. and Bredereck, K., Chem . Ber. , 94, 2278-95 (1961).

Gas chromatographic analysis was performed on a Varian model 3400 gas chromatograph with a model 8000 auto sampler using a 30 meter Megabore DB-1 (3μm) J & W Scientific column. Products were purified and

identified by ¹H NMR and IR spectroscopy. Nuclear

Magnetic Resonance spectra were obtained on Varian VXR- 300 or VXR-400 spectrometers. Infrared spectra were obtained on a Nicolet FT-IR.

The following examples, namely Examples 1-4, illustrate preparation of a variety of N-substituted- oxazolidine-2,4-diones according to the teaching of the present invention.

Example 1

Into a Fischer-Porter bottle was charged 0.93 g (0.01 mol) aniline, 6.3 g (0.025 mol) CyTEG, 154 mg (0.001 mol) biphenyl (as internal G.C. standard) and 20 mL CH₃CN. This was attached to a pressure head and 80 psig CO₂ was added above the reaction mixture with stirring. Addition of carbon dioxide caused an

exothermic reaction to occur.

Into a second Fischer-Porter bottle was added 2 g (0.02 mol) α-chloromethyl acetate and 10 mL CH₃CN. This was attached to a pressure head and 80 psig CO₂ added above the solution. After one hour this solution was added all at once to the carbamate solution

generated in the first Fischer-Porter bottle. The reaction was run at room temperature under 80 psig CO₂ for 14 h during which time a dark red color developed. An aliquot was taken, diluted with diethyl ether and extracted with aq. 0.5 M HCl and by G.C. a 91% yield of N-phenyl-2,4-oxazolidinedione (1) was calculated.

The pressure was released and the crude reaction mixture was poured into H₂O. This was extracted with EtOAc. The ethyl acetate layer was extracted with aq. 0.5 M HCl and brine. The organic layer was dried over Na₂CO₃, filtered and concentrated. The crude material (brown oil) was dissolved in CH₂Cl₂ and passed through silica gel using CH₂Cl₂, giving a clear filtrate. This was concentrated and the residue crystallized from ethyl acetate/hexane giving 1.03 g (58%) of 1. ¹H NMR (CDCl₃) δ 7.6 - 7.4 (m, 5 H), 4.87 (s, 2 H). ¹³C{¹H} δ 169.8, 155.0, 131.2, 129.9, 129.5, 126.1, 68.2. IR (CHCl₃) 1825, 1746.

Example 2

Into a Fischer-Porter bottle was charged 1.98 g (0.01 mol) 4,4'-methylenedianiline, 10.5 g (0.04 mol) CyTEG and 20 mL CH₃CN. This was attached to a pressure head and 80 psig CO₂ was added above the reaction mixture with stirring. Addition of carbon dioxide caused an exothermic reaction to occur.

Into a second Fischer-Porter bottle was added

6.51 g (0.06 mol) α-chloromethyl acetate and 10 mL CH₃CN. This was attached to a pressure head and 80 psig CO₂ added above the solution. After one hour this solution was added all at once to the carbamate solution

generated in the first Fischer-Porter bottle. The reaction was run at 40ºC for 14 h under 80 psig CO₂ during which time a dark red color developed.

The pressure was released and the crude reaction mixture was poured into H₂O. This was extracted with EtOAc. The ethyl acetate layer was extracted with aq. 0.5 M HCl and brine. The organic layer was dried over Na₂CO₃, filtered and concentrated. The crude material (brown oil) was dissolved in CH₂Cl₂ and passed through silica gel using CH₂Cl₂/EtOAc (50:50), giving a light pink filtrate. This was concentrated and the residue crystallized from ethyl acetate/hexane giving 2.0 g (55%) of the bis-2, 4-oxazolidinedione. ¹H NMR (CDCl₃) δ 7.4-7.3 (m, 8 H), 4.86 (s, 4H), 4.08 (s, 2H).

Example 3

Into a Fischer-Porter bottle was charged 8.65 g (0.05 mol) 4-aminomethyl-1,8-octanediamine (TAN), 75.9 g (0.3 mol) CyTEG and 80 mL CH₃CN. This was attached to a pressure head and 60 psig CO₂ was added above the reaction mixture with stirring. Addition of carbon dioxide caused an exothermic reaction to occur . Into a second Fischer-Porter bottle was added 38 g (0.35 mol) α-chloromethyl acetate. This was attached to a pressure head and 60 psig CO₂ added above the solution. After two hours this solution was added all at once to the carbamate solution generated in the first Fischer-Porter bottle. The reaction was run at 40°C for 14 h under 60 psig CO₂ during which time a dark red color developed.

The pressure was released and the crude reaction mixture was poured into H₂O. This was extracted with EtOAc. The ethyl acetate layer was extracted with aq. 0.5 M HCl and brine. The organic layer was dried over Na₂CO₃, filtered and concentrated. The crude material (red-brown oil) was dissolved in CH₂Cl₂ and passed through silica gel using CH₂Cl₂/EtOAc (50:50), giving a light yellow filtrate. This was concentrated giving 11.2 g (58.5%) of a light yellow glassy material identified as the tris-2,4-oxazolidinedione. IR (CHCl₃) 1817, 1738.

Example 4

A 1 gallon autoclave was charged with 100 g (0.862 mol) 1,6-hexamethylenediamine, 871 g (3.44 mol) CyTEG and 1.2 l CH₃CN. This was pressurized to ca. 100 psig with carbon dioxide giving rise to an exothermic reaction. After 1 h 375 g (3.46 mol) α-chloromethyl acetate was added to the reaction mixture. The reaction was then heated to 40°C for 16 h after which time the reaction was allowed to cool and the pressure released. The crude reaction mixture (dark red) was concentrated and extracted with EtOAc/ aq. 0.5 M HCl. The organic layer was extracted with brine and then dried over

Na₂CO₃, filtered and concentrated giving a heavy red oil. This was dissolved in CH₂Cl₂ and filtered through silica gel to remove the red color. Concentration of the filtrate gave a white solid which was crystallized from EtOAc/hexane giving 136.1 g (56%) of the bis-2,4- oxazolidinedione. ¹H NMR (DMSO-d₆) δ 4.83 (s, 4 H), 3.39 (t, J = 7.2 Hz, 4 H), 1.54 (m, 4 H), 1.29 (m, 4 H).

1³C{¹H} NMR (DMSO-d₆) δ 171.4, 156.3, 68.1, 39.2, 26.7, 25.4. IR (CHCl₃) 1815, 1746.

The following examples, namely Examples 5-6, illustrate the preparation of ring-opened N- substituted-oxazolidine-2,4-diones according to the present invention.

Example 5

Into a NMR tube was added 35 mg (0.20 mmol) N-phenyl-2,4-oxazolidinedione, 76 mg (0.59 mmol)

n-octylamine and 1 mL CD₃CN. The reaction mixture was heated to 40ºC for 2.5 h. By ¹H NMR analysis the

N-phenyl-2,4-oxazolidinedione was completely converted to a mixture of PhNHCO₂CH₂CONHC₈H₁₇ and PhNHCOCH₂OCONHC₈H₁₇.

Example 6

Into a NMR tube was added 0.177 g (1 mmol) N- phenyl-2,4-oxazolidinedione, 0.099 g (1 mmol)

cyclohexylamine, 0.084 g (0.5 mmol) 1,3,5- trimethoxybenzene (as internal NMR standard) and 1 mL DMSO-d₆. The reaction was monitored periodically at room temperature by ¹H NMR spectroscopy. (30 min at R.T., 4% conversion; 17 h at R.T., 56% conversion; 114 h at R.T., 91% conversion). Products identified as PhNHCO₂CH₂CONHCy and PhNHCH₂OCONHCy in a ratio of ca. 85:15.

Claims

THAT WHICH IS CLAIMED IS:

1. A process for preparing an N-substituted- oxazolidine-2,4-dione comprising:

(a) contacting CO₂ and a primary amine or ammonia in the presence of an aprotic organic solvent and an organic, nitrogenous base, under reaction conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, and (b) reacting said ammonium carbamate salt with an α-substituted carboxylic acid ester represented by the formula X-CHR₁CO₂R₂ under reaction conditions of time and temperature sufficient to produce the corresponding N-substituted oxazolidine-2,4-dione, wherein

R₁ is selected from the group consisting of hydrogen and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl, and aralkenyl groups having 1 to about 22 carbon atoms, R₂ is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl and aralkenyl groups having 1 to about 22 carbon atoms, and X is selected from the group consisting of halides, tosylates, triflates, mesylates, brosylates, nosylates, nonaflates and tresylates.

2. The process of Claim 1 wherein said aprotic organic solvent is selected from the group consisting of acetonitrile, N-methyl-2-pyrrolidone, dimethylsulfoxide, N,N-dimethylacetamide, toluene, dichloromethane and tetrahydrofuran.

3. The process of Claim 2 wherein said aprotic organic solvent is present in at least an amount sufficient to solubilize said ammonium carbamate salt.

4. The process of Claim 1 wherein said organic, nitrogenous base is selected from the group consisting of guanidine compounds, amidine compounds, phosphazene compounds and mixtures thereof.

5. The process of Claim 4 wherein the ratio of the number of moles of said organic, nitrogenous base to the number of equivalents of amine in said primary amine starting material or the number of moles of said ammonia starting material is about 1:1 to about 20:1.

6. The process of Claim 1 wherein X is selected from the group consisting of halides,

tosylates, triflates and mesylates wherein said halides are selected from the group consisting of chlorine, bromine and iodine.

7. The process of Claim 6 wherein X is chloride, R₁ is hydrogen and R₂ is a methyl group.

8. The process of Claim 1 wherein the ratio of the number of moles of said α-substituted carboxylic acid ester to the number of equivalents of amine in said primary amine starting material or the number of moles of said ammonia starting material is about 1:1 to about 4:1.

9. The process of Claim 1 wherein said primary amine is selected from the group consisting of compounds represented by the formula R-NH₂,

polyoxyalkylene diamines represented by the formula

H₂N-(-CH-CH₂-O -)-_x-(- CH₂-CH₂-O -)-_y -(- CH-CH₂-O-)-_z CH₂-CH-NH₂

CH₃ CH₃ CH₃

and polyoxyalkylene triamines represented by the

formula: (OCH₂CH-)-_a FH₂

R₃

(OCH₂CH-)-_b NH₂

R ₃

(OCH₂CH-)-_c NH₂

R₃

wherein R is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, a group represented by the formula

-(R₄-)-_n -(-R₅-)-_m NH₂

NH₂

and a group represented by the formula -R₄-NH₂, or R as defined above containing nonnucleophilic functional groups; wherein R₄ and R₅ are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, m represents a integer from 0 to about 100, n represents an integer from 0 to about 8, R₃ is hydrogen or methyl, x + z represents an integer from about 2 to about 70, y represents an integer from 0 to about 90, x + y + z represents an integer from about 2 to about 100, a, b and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol

initiator.

10. The process of Claim 9 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes,

carbonates and salts thereof.

11. The process of Claim 1 wherein said

N-substituted-oxazolidine-2,4-dione is represented by the formula

wherein R₁ is as defined above and R₆ is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, a group represented by the formula

a group represented by the formula

and a group represented by the formula

-(-CH-CH₂-O-)-_x -(-CH₂-CH₂-O -)-_y -(-CH-CH₂-O _z-) -CH₂ CH-N

CH₃ CH₃ CH₃

or R₆ as defined above containing nonnucleophilic functional groups; or said N-substituted-oxazolidine- 2,4-dione is represented by the formula (OCH₂CH-)-_a

R₃

(OCH₂CH-)-_b

R₃

(OCH₂CH-)-_c

wherein R₄ and R₅ are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl,

cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R₃ is hydrogen or methyl, x + z represents an integer from about 2 to about 70, y represents an integer from 0 to about 90, x + y + z represents an integer from about 2 to about 100, a, b, and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol

initiator.

12. The process of Claim 11 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes,

carbonates and salts thereof.

13. The process of Claim 1 further comprising: (c) reacting said N-substituted-oxazolidine-

2,4-dione with a nucleophile selected from the group consisting of aliphatic or

alicyclic primary amines, alcohols and thiols, wherein when said nucleophile is an aliphatic or alicyclic alcohol, said

reaction is conducted in the presence of a Lewis acid catalyst.

14. The process of Claim 13 wherein the ratio of the number of moles of said nucleophile to the number of equivalents of oxazolidine-2,4-dione in said

N-substituted-oxazolidine-2,4-dione is 1:1 to about 20:1.

15. The process of Claim 13 wherein said nucleophile is selected from the group consisting of R₇-NH₂, R₇-OH and R₇-SH wherein R₇ is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups having 1 to about 22 carbon atoms.

16. The process of Claim 1 further comprising

(c) recovering said N-substituted-oxazolidine- 2,4-dione and,

(d) reacting said N-substituted-oxazolidine- 2,4-dione with a nucleophile selected from the group consisting of aliphatic or

reaction is conducted in the presence of a

Lewis acid catalyst.

17. The process of Claim 16 wherein the ratio of the number of moles of said nucleophile to the number of equivalents of oxazolidine-2,4-dione in said

N-substituted-oxazolidine-2,4-dione is 1:1 to about 20:1.

18. The process of Claim 16 wherein said nucleophile is selected from the group consisting of R₇-NH₂, R₇-OH and R₇-SH wherein R₇ is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups having 1 to about 22 carbon atoms.

19. A process for preparing N-substituted- oxazolidine-2,4-dione comprising:

(a) contacting CO₂ and a primary amine or ammonia in the presence of an aprotic organic solvent and an organic, nitrogenous base, under reaction conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt,

(b) recovering said ammonium carbamate salt, and

(c) reacting said ammonium carbamate salt with an α-substituted carboxylic acid ester represented by the formula X-CHR₁CO₂R₂ in the presence of an aprotic organic solvent and an organic, nitrogenous base under reaction conditions of time and temperature sufficient to produce the corresponding N-substituted-oxazolidine-2,4-dione, wherein R₁ is selected from the group consisting of hydrogen and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl, and aralkenyl groups having 1 to about 22 carbon atoms, R₂ is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl and aralkenyl groups having 1 to about 22 carbon atoms, and X is selected from the group consisting of halides, tosylates, triflates, mesylates, brosylates, nosylates, nonaflates and tresylates.

20. The process of Claim 19 wherein said aprotic organic solvent is selected from the group consisting of acetonitrile, N-methyl-2-pyrrolidone, dimethylsulfoxide, N,N-dimethylacetamide, toluene, dichloromethane and tetrahydrofuran.

21. The process of Claim 20 wherein said aprotic organic solvent is present in at least an amount

sufficient to solubilize said ammonium carbamate salt.

22. The process of Claim 19 wherein said organic, nitrogenous base is selected from a group consisting of guanidine compounds, amidine compounds, phosphazene compounds and mixtures thereof.

23. The process of Claim 22 wherein the ratio of the number of moles of said organic, nitrogenous base to the number of equivalents of amine in said primary amine starting material or the number of moles of said ammonia starting material in Step (a) is about 0.5:1 to about 10:1, and the ratio of the number of moles of said organic, nitrogenous base to the number of equivalents of carbamate in said ammonium carbamate salt starting material in Step (c) is about 0.5:1 to about 10:1.

24. The process of Claim 19 wherein X is selected from the group consisting of halides,

25. The process of Claim 24 wherein X is chloride, R., is hydrogen and R₂ is a methyl group.

26. The process of Claim 19 wherein the ratio of the number of moles of said α-substituted carboxylic acid ester to the number of equivalents of carbamate in said ammonium carbamate salt is about 1:1 to about 4:1.

27. The process of Claim 19 wherein said primary amine is selected from the group consisting of compounds represented by the formula R-NH₂, polyoxyalkylene diamines represented by the formula

and polyoxyalkylene triamines represented by the

formula: H₂N-(-CH-CH₂-O -) -_x-(-CH-CH₂-O -) -_y -(-CH-CH₂-O -) -_z CH₂-CH-NH₂

CH₃ CH₃ CH₃

(OCH₂CH-)-_a NH₂

R₃

(OCH₂CH-)-_b NH₂

R₃

(OCH₂CH-)-_c NH₂

R₃

-(R₄-)-

_n -(-R₅-)-_m NH₂

NH₂

initiator.

28. The process of Claim 27 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes,

carbonates and salts thereof.

29. The process of Claim 19 wherein said N-substituted-oxazolidine-2,4-dione is represented by the formula

a group represented by the formula

and a group represented by the formula -(-CH-CH₂-O -) -_x-(-CH-CH₂-O -) -_y -(-CH-CH₂-O -) -_z CH₂-CH-N

CH₃ CH₃ CH₃

or R₆ as defined above containing nonnucleophilic functional groups; or said N-substituted-oxazolidine- 2,4-dione is represented by the formula

(OCH₂CH-) _a

R₃

(OCH₂CH-)-_b

R₃

(OCH₂CH-)-_c

R₃

cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R₃ is hydrogen or methyl, x + z represents an integer from about 2 to about 70, y represents an integer from about 0 to about 90, x + y + z represents an integer from about 2 to about 100, a, b, and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol

initiator.

30. The process of Claim 29 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes,

carbonates and salts thereof.

31. The process of Claim 19 further comprising: (d) reacting said N-substituted-oxazolidine-

2,4-dione with a nucleophile selected from the group consisting of aliphatic or

reaction is conducted in the presence of a Lewis acid catalyst.

32. The process of Claim 31 wherein the ratio of the number of moles of said nucleophile to the number of equivalents of oxazolidine-2,4-dione in said

N-substituted-oxazolidine-2,4-dione is about 1:1 to about 20:1.

33. The process of Claim 31 wherein said nucleophile is selected from the group consisting of R₇-NH₂, R₇-OH and R₇-SH wherein R₇ is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups having 1 to about 22 carbon atoms.

34. The process of Claim 19 further comprising: (d) recovering said N-substituted-oxazolidine-

2,4-dione and,

(e) reacting said N-substituted oxazolidine-

2,4-dione with a nucleophile selected from the group consisting of aliphatic or

alicyclic primary amines, alcohols and thiols, wherein when said nucleophile is an aliphatic or alicyclic alcohol, said reaction is conducted in the presence of a Lewis acid catalyst.

35. The process of Claim 34 wherein the ratio of the number of moles of said nucleophile to the number of equivalents of oxazolidine-2,4-dione in said

N-substituted-oxazolidine-2,4-dione is about 1:1 to about 20:1.

36. The process of Claim 34 wherein said nucleophile is selected from the group consisting of R₇-NH₂, R₇-OH and R₇-SH wherein R₇ is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups having 1 to about 22 carbon atoms.

37. A process comprising reacting an

N-substituted-oxazolidine-2,4-dione with a nucleophile selected from the group consisting of aliphatic or alicyclic primary amines, alcohols and thiols, wherein when said nucleophile is an aliphatic or alicyclic alcohol, said reaction is conducted in the presence of a Lewis acid catalyst.

38. The process of Claim 37 wherein the ratio of the number of moles of said nucleophile to the number of equivalents of oxazolidine-2,4-dione in said

N-substituted-oxazolidine-2,4-dione is 1:1 to about 20:1.

39. The process of Claim 37 wherein said nucleophile is selected from the group consisting of R₇-NH₂, R₇-OH and R₇-SH wherein R₇ is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups having 1 to about 22 carbon atoms.

40. The process of Claim 37 wherein said N-substituted-oxazolidine-2,4-dione is represented by the formula

wherein R₁ is selected from the group consisting of hydrogen and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkenyl, alkenaryl and aralkenyl groups having 1 to about 22 carbon atoms and R₆ is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, a group represented by the formula

a group represented by the formula

CH₃ CH₃ CH ₃

or R₆ as defined above containing nonnucleophilic functional groups;, or said N-substituted-oxazolidine- 2,4-dione is represented by the formula

(OCH₂CH-)-_a

(OCH₂CH-)-_b

(OCH₂CH-)-_c

wherein R₄ and R₅ are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl groups having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R₃ is hydrogen or methyl, x + z represents an integer from about 2 to about 70, y represents an integer from about 0 to about 90, x + y + z represents an integer from about 2 to about 100, a, b, and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol

initiator.