Cyclic urea derivative

Abstract: Disclosed is cyclic urea derivatives represented by the following formula (A): wherein n is an integer of 0 or 1; m is an integer of 1 to 15; X is oxygen, sulfur or -NR₁- (R₁ is hydrogen or an alkyl group having 1 to 5 carbon atoms); R is an alkyl-, cycloalkyl -, aryl-, aralkyl-, alkaryl- and glycidyl group having 1 to 27 carbon atoms, or an alkyl-, cycloalkyl-, aryl-, aralkyl- and alkaryl group containing at least one - -, O, S and N and having 1 to 27 carbon atoms with a molecular weight of 15 to 500, said groups substituted by glycidyl-, hydroxylic-, nitro groups, halogens, cyano-, formyl- or amino groups, or polyester-, polyether-, polyurethane and polyamide groups having a molecular weight of 500 to 100,000.

Description: FIELD OF THE INVENTION The present invention relates to cyclic urea derivatives and to methods of producing them. BACKGROUND OF THE INVENTION JP-A-56151720 discloses thermosetting resin compositions containing a cyclic urea of formula (P) wherein n is 2 or more, i.e. the heterocyclic ring is at least a seven-member ring. Chilly et al, J. Org. Chem. 29(11):3347-501 (1964), disclose the compound of formula (P) wherein n is 1 and R is ethyl. This compound is obtained by a complicated method. Compounds containing a 5 to 7-member ring, as shown by formula (P) but which have no oxygen connected directly to a carbonyl group, are disclosed by Ulrich et al, J. Org. Chem. 43 (8) (1978). It is reported that the compounds containing a five-member or six-member ring do not undergo ring-opening on thermal decomposition, which is a specific feature of a cyclic urea structure. EP-A-0240370 discloses cyclic ureas analogous to those of formula (P), but without an O atom between CO and R. These cyclic ureas are proposed as blocked isocyanates in one-component polyurethane systems. It is suggested that they may be ring-opened, by thermal dissociation, to give an isocyanate and an amide. SUMMARY OF THE INVENTION The cyclic urea derivatives according to the present invention are of formula (A) wherein m is an integer of 1 to 15; X is -O-, -S- or -NR₁- (R₁ is hydrogen or an alkyl group having 1 to 5 carbon atoms); and R is glycidyl, an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group having up to 27 carbon atoms, or such a group also containing at least one -CO-, -O-, -S- or -N- link and having a molecular weight of 15 to 500, and either group optionally being substituted by halogen atoms, by glycidyl, hydroxyl, nitro, cyano, formyl or amino groups, or by polyester, polyether, polyurethane or polyamide groups having a molecular weight of 500 to 100,000; with the provisos that when m is 1 and X is -O-, R is not C₁₋₂ alkyl, and that, when R is glycidyl, m is 1. DESCRIPTION OF THE INVENTION One method of synthesising the cyclic urea derivatives according to the present invention, when X is -O-, comprises reacting propylene urea with a compound of the formula Y-COOR (formula C) wherein Y is a halogen atom or OR (the R's being the same or different). The compounds represented by formula (C) are in general compounds obtained by reaction of phosgene with ROH. Compounds (C) include methyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, ethoxyethyl chloroformate, sec-butyl chloroformate, benzyl chloroformate, 2-ethylhexyl chloroformate, methoxyethyl chloroformate, tetradadecyl chloroformate, hexadecyl chloroformate and phenyl chloroformate. This reaction is conducted at temperatures of 0 to 200 °C, preferably 50 to 150 °C, in the presence of a suitable solvent. In the reaction, basic catalysts, such as triethyl amine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene-7, pyridine, sodium methoxide, sodium ethoxide, t-butoxy potassium and hexamethyl phosphoric triamide, may be used if necessary, or may not be used. The suitable solvent is a solvent having no active hydrogen. It may be selected from the group consisting of for example hydrocarbons, halogenated hydrocarbons, ethers and esters. Preferred are aliphatic hydrocarbons (such as, pentane, hexane and heptane), aromatic hydrocarbons (such as, benzene, toluene and xylene), alicyclic hydrocarbons (such as cyclohexane, methylcyclohexane and decaline), petroleum hydrocarbons (such as, petroleum ether and petroleum benzine), halogenated hydrocarbons (such as, carbon tetrachloride, chloroform and 1,2-dichloroethane), ethers (such as, ethyl ether, isopropyl ether, anisole, dioxane and tetrahydrofurane), ketones (such as, acetone, metylethyl ketone, methylisobutyl ketone, cyclohexanone, acetophenone and isophorone), esters (such as, ethyl acetate and butyl acetate, acetonitrile, dimethylformamide, dimethylsulfoxide and the like. These compounds may be used singly or in combination. In the reaction, a polymerization inhibitor may be added in case of need but it is not essential. A cyclic urea derivative, in which X is -NH-, according to the present invention is obtained by a reaction of propylene urea with isocyanate compounds represented by the following formula (E): R-(N=C=O) m wherein R and m are same as in the formula (A). The isocyanate compounds used here include aliphatic compounds, such as trimethylene monoisocyanate, tetramethylene diisocyanate, pentamethylene monoisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene monoisocyanate, 2,3-butylene diisocyanate, 1,3-butylene monoisocyanate, ethylidine diisocyanate and butylidine monoisocyanate; cycloalkylene compounds, such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane monoisocyanate and 1,2-cyclohexane diisocyanate; aromatic compounds, such as m-phenylene diisocyanate, 1,5-naphthalene monoisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene monoisocyanate and 1,4-naphthalene diisocyanate; aliphaticaromatic compounds, such as 4,4'-diphenylenemethane diisocyanate, 2,4- or 2,6-toluene monoisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate and 1,4-xylylene diisocyanate; nucleus-replaced aromatic compounds, such as dianisidine diisocyanate, 4,4'-diphenyl ether monoisocyanate and chlorodiphenylene diisocyanate; triisocyanates, such as triphenylmethan-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; tetraisocyanates, such as 4,4'-diphenyldimethylmethane-2,2',5,5'-tetraisocyanate; polymerized polyisocyanates, such as toluidene diisocyanate dimer and trimer. This reaction is in general conducted at temperatures of 25 to 200 °C, preferably 50 to 100 °C, in a suitable solvent. The suitable solvent includes the solvent mentioned above. In this reaction, catalysts, for example tin compounds (dibutyltin laurate, dibutyltin oxide, FASCAT 4102® (M&T CHEMICALS INC.), TK-l, lL (TAKEDA)), mixture catalysts (dimethyltin diiodide/tetraphenyl antimony iodide, dimethyltin diiodide/hexamethyl phosphoric triamide), acidic compounds (p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, trifluoroboron ethelate), basic compounds (triethyl amine, 1,4-diazabicyclo-[2,2,2]-octane, 1,8-diazabicyclo-[5,4,0]-undecene-7, pyridine, sodium methoxide, sodium ethoxide, t-butoxy potassium hexamethylphosphoric triamide), metal oxides or salts of metals (manganese acetate, cobalt acetate, calcium acetate, lithium acetate, zinc acetate, magnesium acetate, antimony trioxide, lead dioxide, ferric chloride, aluminium triisopropoxide, tetraisopropoxide) may be used. The most general method of producing the cyclic urea compounds according to the present invention consists in a reaction of compounds represented by the following formula (F): wherein Z is halogen, an alkoxy-, aryloxylic- or aralkyloxylic group having 1 to 15 carbon atoms; with compounds represented by the following (G): R-(X-H) m wherein R, m and X are same in the formula (A), to replace Z by R-X. The compounds represented by the formula (F) can be easily obtained by a reaction of said cyclic urea compounds (B) with phosgene itself or compounds obtained by a reaction of phosgene with ZOH. In addition, the compounds (G) used in the present invention are in general used in the form of active hydrogen-containing compounds having a carbon atom directly connected to oxygen, sulfur and nitrogen. Such the active hydrogen-containing compounds include alcohols [X=O], for example m=1 R: methanol, ethanol, stearyl alcohol, benzyl alcohol, phenanthyl alcohol, phenol, methylphenol bromophenol, glycidyl alcohol; m=2 :ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butane diol, 1,10-decane diol, pentaethylene glycol, 2,5-furan dimethanol, 1,2-cyclohexane diol, dicyclohexyl-4,4'-diol, 1,2-benzene dimethanol, 2,2-bisphenol; m>3 : glycerol, trimethylol propane, 1,2,3-pentane triol, pentaerythritol, dipentaerythritol, neopentyl glycol, lactose, xylose, mannitol, polyester polyol, polyether polyol, epoxy resins; Amines [X=N], for example methylamine, ethylamine, propylamine, stearylamine, benzylamine, aniline, dimethylamine, methylethylamine, diethylamine, methylbenzylamine, ethylenediamine, 1,2-diaminopropane, 1,8-diaminooctane, 1,2-phenylenediamine, 2,4-diaminotoluene, N-(2-aminoethyl)-1,3-propanediamine, N,N-bis(2-aminoethyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1, 3-propanediamine; aminoalcohols, for example dimethylaminoethyl alcohol, dimethylaminoethyl alcohol, dimethylaminopropyl alcohol, m-dimetylamino phenol, N-methyl-N-phenylaminoethyl alcohol, N-ethyl-N-benzylaminoethyl alcohol, pyrolidinoethyl alcohol, pyrolidinopropyl alcohol, morpholinoethyl alcohol, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-1-hexanol, ethanol amine; oximes, for example acetoaldehyde oxime, acetone oxime, methylethyl ketone oxime, phenylmethyl ketone oxime, acetylacetone oxime; thiols, for example ethyl thiol, propyl thiol, cyclohexyl thiol, phenyl thiol, naphthyl thiol, 1,2-ethane dithiol, 2,3-butane dithiol, 1,2-benzene dithiol; polyester polyol compounds, for example polyether polyols obtained by adding polyalkylene glycols (for example polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol) or alkylene oxides (for example ethylene oxide, propylene oxide, tetrahydrofuran) to polyols (for example ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylol propane, 1,3- butane diol, 1,4-butane diol, 1,5-hexane diol, 1,2,6-hexane triol, pentaerythritol, sorbitol, sorbitan, sucrose); epoxy compounds, for example bisphenol A type epoxy resins, bisphenol F type epoxy resins, polyvalent carboxylic ester type epoxy resins, epoxidized type resins of aliphatic unsaturated compounds; star polymer compounds, for example star polymers having an active hydrogen at an end thereof obtained by a cation polymerization of pentol and ethylene oxide; polyester polyol compounds, for example polyester polyols obtained by a condensation reaction of polybasic acids (for example phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorphthalic acid, tetrabromphtalic acid, hexahydrophthalic acid, hymic acid, headic acid, succinic acid, maleic acid, fumalic acid, adipic acid, sebacic acid, dodecenylsuccinic acid, pyromellitic acid) or anhydrides thereof and polyvalent alcohols (for example ethylene glycol diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylol propane, 1,3-butane diol, 1,6-hexane diol, neopentyl glycol, 1,2,6-hexane triol, polyester polyols obtained by a reaction of the above described polyvalent alcohols, epoxy compounds (for example Cardula E, n-butyl glycidyl ether, allyl glycidyl ether) and said polybasic acids, polyester polyols obtained by a reaction of the above described epoxy compounds and the above described polybasic acids, alkyd type polyols obtained by a reaction of higher fatty acids (soybean oil, linseed oil, saffron oil, coconut oil, dehydrated castor oil, paulownia oil, rosin), the above described polybasic acids and the above described polyvalent alcohols, polymerized type polyester polyols obtained by a ring-opening polymerization of ε-caprolactam, ε- caprolactone, γ- valerolactone, δ-valerolactone and β-methylvalerolactone, and the above described polyvalent alcohols; polyurethane polyol compounds, for example polyurethane polyols obtained by an addition reaction of for example isocyanate compounds (for example ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1-methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-diisocyanate cyclohexane, ω,ω'-diisocyanate diethylbenzen, ω,ω' - diisocyanate dimethylaminotoluene, ω,ω' -diisocyanate dimethyl xylene, ω,ω' -diisocyanate diethyl xylene, lysin diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 4,4'-ethylenebis(cyclohexylisocyanate), ω,ω'-diisocyanate-1,3-dimethyl benzene, ω,ω'-diisocyanate-1,4-dimethyl benzene, isophorone diisocyanate, 2,4-toluidene diisocyanate, 2,6-toluidene diisocyanate, 1,5-naphthylene diisocyanate, 4,4-methylenebis(phenylisocyanate), triphenylmethane triisocyanate or polymers thereof to an excessive amount of low molecular polyols (for example ethylene glycol, propylene glycol, 1,3-butyl glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentane diol, hexamethylene glycol, cyclohexane dimethanol, trimethylol propane, hexane triol, glycerine, sorbitol sorbitan, sucrose, pentaerythritol), polyurethane polyols obtained by an addition reaction of polyol compounds having relatively low molecular weights of said polyether polyols, polyester polyols, polymerized type polyester polyols and acrylic polyols to isocyanate compounds such as monoisocyanate, diisocyanate and triisocyanate; polyamide amine compounds, for example polyamide amine compounds obtained by an addition reaction of the above described isocyanate compounds to compounds such as ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-phenylene diamine and N-(2-aminoethyl)-1,3-propane diamine. This reaction is in general conducted at temperatures of 0 to 200 °C, preferably 50 to 70 °C, by the use of the above described solvents having no active hydrogen. In the synthesis, catalysts may be used in case of need. In the case where X is oxygen, tin-containing catalysts are suitable while in the case where X is -NR₁, the reaction makes progress without using catalysts. According to the present invention, various kinds of cyclic urea derivative can be formed by variously changing R. The cyclic urea derivatives according to the present invention form compounds having one or two isocyanate groups upon heating, i.e. either O=C=N-(CH₂)₃-NH-CO-XR or O=C=N-(CH₂)₃-N=C=O + HX-R Accordingly, since the compounds having isocyanate groups are in general used as the curing agents, the cyclic urea derivatives according to the present invention are useful as compounds latently containing isocyanate curing agents. In addition, the derivatives according to the present invention can be used also as intermediated products for a synthesis of various kinds of other compound. EXAMPLE The present invention is below in more detail described with reference to the preferred embodiments. Example 1 Phenoxycarbonylpropyleneurea Propyleneurea (730 g, 7.3 mol), triethylamine (404 g, 4 mol) and dichloroethane (1.5 liters) were charged in a reaction vessel and heated to 82 to 85 °C. Then, a solution of benzyl chloroformate (604 g, 4.0 mol) in dichloroethane (0.5 liters) was added drop by drop to the heated mixture in about one hour followed by continuing to heat with stirring for further one hour. The resulting solution was condensated. Crude crystals were washed with water and then dried. Phenoxycarbonylpropyleneurea (438 g; 49.3 %) was obtained by column chromatography. NMR (1H): 7.40 to 7.17 (m), 3.89 (t), 3.35(dt), 2.27 (tt) IR (cm⁻¹):3240, 1780, 1675 Melting point: 149 to 151 °C Example 2 N-(2-hydroxyethyl)aminocarbonylpropyleneurea Phenoxycarbonylpropyleneurea (1.0 g; 4.5 mmol) and ethanolamine (0.5 g; 8.2 mmol) were dissolved in dioxane by heating at 50 °C. The resulting solution was stirred for 30 minutes. The resulting white precipitation was filtrated and rinsed with ether to obtain the title substance (790 mg; 96 %). NMR (1 H): 7.27, 4.70 (t), 3.84 (t), 3.43 (t) 3.30 (t), 3.20 (t), 3.12 (dt), 1.78 IR (cm⁻¹): 3350, 1710, 1630 Melting point: 151 to 153 °C Example 3 Ethylene glycol-di-(ethyloxycarbonylpropyleneurea)ether Phenoxycarbonylpropyleneurea (10 g; 45.5 mmol) and triethylene glycol (3.4 g; 22.7 mmol) were dissolved in dioxane (50 ml) by heating. The resulting mixture was stirred for 10 hours and the resulting solution was concentrated. A crude product was refined by column chromatography to obtain the title substance (1.8 g; 15 %). NMR (1 H): 5.99, 4.36 (t), 3.7 to 3.6 (m), 3.30 (dt), 1.96 (tt) IR (cm⁻¹): 3300, 1760, 1700 C p : 62976 (EH type 25 °C) Melting point 225 to 230 °C Example 4 N-benzylaminocarbonylpropyleneurea Phenoxycarbonylpropyleneurea (1 g; 4.5 mmol) and benzylamine (1 g; 9.3 mmol) were dissolved in dioxane (40 ml) by heating to 50 °C. The resulting solution was heated with stirring for 30 minutes. After confirming the completion of the reaction by thin layer chromatograpy, the reaction product was obtained by condensation. The obtained crude crystals were washed with ether to obtain the title substance (975 mg; 93 %). NMR (1 H): 9.54, 7.29 (m), 4.49 (d), 3.87 (t), 3.37 (dt), 1.94 (tt). IR (cm⁻¹): 3225, 1715, 1680 Melting point: 159 to 162 °C (colorless needle-like crystal) Example 5 Hexamethylene diaminocarbonylpropyleneurea Phenoxycarbonylpropyleneurea (0.89 g; 4 mmol) and hexamethylenediamine (0.24 g; 2 mmol) were dissolved in dioxane of 20 ml by heating. After one hour, completion of the reaction was confirmed by thin layer chromatography, and then the reaction product was obtained by condensation. The obtained crude product was washed with ether to obtain the title substance (705 mg; 94 %). NMR (1 H): 9.23, 3.26 (m), 5.42, 1.92 (tt) 3.83 (t), 1.54 (m), 3.33 (dt), 1.35 (m) IR (cm⁻¹): 3300, 1700, 1630 Melting point: 196 to 198 °C (colorless prismatic crystal) Example 6 Benzyloxycarbonylpropyleneurea A mixture of phenoxycarbonylpropyleneurea (1.0 g; (4.5 mmol), benzyl alcohol (2.4 g; 22.2 mmol), dibutyltin dilaurate (20 mg; 0.6 wt %) and dimethylaminopyridine (20 mg; 0.6 wt %) was heated for 3 hours at 100 °C with stirring. After confirming the completion of the reaction by thin layer chromatograpy, the reaction product was concentrated and the resulting crude substance was separated by chromatography to obtain the title substance (600 mg; 56.4 %). NMR (1 H): 7.34 (m), 5.52 (br), 5.28 (s), 3.78 (t) 3.32 (td), 1.96 (tt) IR (cm⁻¹): 3225, 3120, 1780, 1725, 1700 Melting point: 108 to 110 °C (colorless prismatic crystal) Example 7 4-hydroxyphenyloxycarbonylpropyleneurea Phenoxycarbonylpropylenenurea (1.1 g; 5 mmol), hydroquinone (1.1 g; 10 mmol) and dibutyltin dilaurate (20 mg; 2 wt %) were dissolved in dioxane (30 ml) by heating. The resulting solution was refluxed for 4 hours at 100 °C to form a white precipitate. This precipitate was filtered and washed with methanol to obtain the title substance (840 mg; 67 %). NMR (1 H): 6.97 (d), 6 79 (d), 3.71 (t), 3.15 (brt), 1.88 (t), 9.40 IR(cm⁻¹): 3340, 1780, 1660 Melting point: 225 to 230 °C. Example 8 Hexamethylenedioxycarbonylpropyleneurea Hexamethylene diol (10.7 g; 0.091mol) and phenoxycarbonylpropyleneurea (40 g) were dissolved in dioxane (300 g) at an elevated temperature, to which dibutyltin dilaurate (1 g) was added. The resulting solution was mixed with heating at 85 °C for 8 hours. The reaction product was concentrated and the crude product was washed with ether. The washed product was purified with benzene by column chromatography, to obtain hexamethylenedioxycarbonylpropyleneurea (18.3 g; 50 % yield). NMR: 6.71 (b,s), 4.21 (t), 3.75 (m), 3.32 (d,t), 1.88-1.47 (m) Melting point:74 - 77 °C

Claims: A cyclic urea derivative represented by formula (A): wherein m is an integer of 1 to 15; X is -O-, -S- or -NR₁- (R₁ is hydrogen or an alkyl group having 1 to 5 carbon atoms); and R is glycidyl, an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group having up to 27 carbon atoms, or such a group also containing at least one -CO-, -O-, -S- or -N- link and having a molecular weight of 15 to 500, and either group optionally being substituted by halogen atoms, by glycidyl, hydroxyl, nitro, cyano, formyl or amino groups, or by polyester, polyether, polyurethane or polyamide groups having a molecular weight of 500 to 100,000; with the provisos that when m is 1 and X is -O-, R is not C₁₋₂ alkyl, and that, when R is glycidyl, m is 1. A derivative as claimed in claim 1, wherein m is from 2 to 15. A method of producing a derivative as claimed in claim 1 or claim 2, when X is -O-, which comprises reacting propylene urea with a compound of the formula Y-COOR wherein Y is a halogen atom or OR (the R's being the same or different). A method of producing a derivative as claimed in claim 1 or claim 2, when X is -NH-, which comprises reacting propylene urea with an isocyanate of the formula R-(N=C=O) m . A method of producing a derivative as claimed in claim 1 or claim 2, which comprises reacting a compound of formula (F): wherein Z is a halogen atom or an alkoxy, aryloxy or aralkyloxy group having 1 to 15 carbon atoms with a compound of the formula R-(X-H) m .

Inventors: SAKAMOTO HIROYUKI, TOBINAGA KENSHIRO, TSUBONIWA NORIYUKI, TSUCHIYA YASUYUKI, UMEMOTO HIROTOSHI, URANO SATOSHI, TOBINAGA, KENSHIRO, TSUBONIWA, NORIYUKI, TSUCHIYA, YASUYUKI, UMEMOTO, HIROTOSHI, URANO, SATOSHI
Applicants: NIPPON PAINT CO LTD, NIPPON PAINT CO., LTD.
Application year: 1989
Main classification: C07D233
IPC codes: C08G18, C07D233, C07D239