JPH0557978B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to substituted urea compounds and methods for producing the same, particularly those of the formula: [In the formula, R represents a lower alkyl group,

[Formula] represents a residue obtained by removing a hydrogen atom from ammonia, a primary amine, or a secondary amine. ] It is related with the substituted urea compound represented by these and its manufacturing method. [Prior Art] Compounds having isocyanate groups are widely used in the field of polymer chemistry because of their excellent reactivity. In particular, compounds that have both a polymerizable carbon-carbon unsaturated group and an isocyanate group in the same molecule are used in a wide range of industrial technology fields because both of these functional groups participate in various reactions with different reaction mechanisms. I can do it. Focusing on such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Patent Application No. 58-225226]
issue]: [In the formula, R has the same meaning as above. ]. The above-mentioned isocyanate compound () is generally a stable liquid at room temperature and easy to handle. However, it not only has a polymerizable carbon-carbon unsaturated group and an isocyanate group in its molecule, but also has both of these functional groups. Since a carbonyl group exists between and adjacent to them, the activity of the carbon-carbon unsaturated group is enhanced, and the activity of the isocyanate group is also enhanced, and it is in a state where it can carry out various addition reactions. That is, the isocyanate compound () can be used for various reactions based on the A part (conjugated double bond) and B part (acylisocyanate group) of the following formula, such as radical polymerization, anionic polymerization, dimerization, trimerization, polar addition, and activation. Hydrogen addition, etc. can be carried out: Therefore, isocyanate compounds () are expected to have a wide range of uses as raw materials for industrial production. [Object of the Invention] The present invention was carried out for the purpose of developing one use of the above-mentioned isocyanate compound (). [Structure of the Invention] The gist of the present invention is to provide a substituted urea compound represented by the formula () and an isocyanate compound represented by the formula () and the formula: [In the formula,

[Formula] represents a residue obtained by removing a hydrogen atom from ammonia, a primary amine, or a secondary amine. ] A process for producing a substituted urea compound, which comprises reacting ammonia, a primary amine, or a secondary amine represented by the formula (2) to obtain a substituted urea compound represented by the formula (). As mentioned above, isocyanate compounds ()
has the potential to carry out various reactions, so ammonia, primary amines, or secondary amines () (hereinafter referred to as amino compounds ()) are added to them.
In addition to and/or instead of the addition reaction between the desired isocyanate compound () and the amino compound (), the isocyanate compound () itself undergoes dimerization, trimerization, multimerization (polymerization), etc. It was predicted that various side reactions would proceed, such as the polymerization of the substituted urea compound () produced, and the reaction between the produced substituted urea compound () and the isocyanate compound (), but in reality, the polymerization of the substituted urea compound () and the reaction between the produced substituted urea compound () and the isocyanate compound () were predicted to occur. It was confirmed that the desired reaction proceeded preferentially. Especially at room temperature (0~
At a relatively low temperature (not exceeding 30°C), only the desired reaction or quantitatively proceeds, and various predicted side reactions can be virtually completely avoided. According to the present invention, a substituted urea compound () can be produced by reacting an isocyanate compound () with an amino compound (). Amino compounds () can be selected from a wide range, specific examples being ammonia, alkylamines (e.g. methylamine, ethylamine, propylamine, isopropylamine, laurylamine, stearylamine), alkenylamines (e.g. allylamine, primary amines such as pentenylamine), aralkenylamines (e.g. benzylamine, phenethylamine), aromatic amines (e.g. aniline), heterocyclic amines (e.g. thiazolylamine), dialkylamines (e.g. dimethylamine, methylethylamine, diethylamine, dipropyl amines), dicycloalkylamines (e.g. dicyclopentylamine, dicyclohexylamine), alkyl-aralkylamines (e.g. methyl-benzylamine, methylphenethylamine), cyclic amines (e.g. piperidine, morpholine, aziridine)
Secondary amines such as That is, the groups represented by R′ and R″ of the amino compound () are
Hydrogen, alkyl groups (e.g. methyl, ethyl, propyl, stearyl), alkenyl groups (e.g. allyl, pentenyl), aralkyl groups (e.g. benzyl, phenethyl), substituted or unsubstituted phenyl groups (e.g. phenyl, tolyl, xylyl,
chlorophenyl, bromophenyl, nitrophenyl), substituted or unsubstituted heterocyclic groups (eg, thiazolyl, oxazolyl, isoxazolyl), and the like. Furthermore, R' and R'' together represent a nitrogen-containing cyclic group (e.g., aziridino, pyrrolidino, piperidino, morpholino, thiamorpholino, N-methylpiperidino) that may be substituted with the nitrogen atom to which they are connected. Amino compounds () are often liquid at room temperature and can themselves serve as reaction media;
When the amino compound () is in liquid form, it is common to use an inert solvent, regardless of whether it is gaseous or solid. There are no particular restrictions on the inert solvent as long as it does not adversely affect the reaction, and various solvents can be used.For example, aliphatic hydrocarbons such as pentane, hexane, and heptane, benzene,
Aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylclohexane, and decalin, hydrocarbon solvents such as petroleum ether and petroleum benzyl, carbon tetrachloride, chloroform, 1,2-dichloroethane, etc. Halogenated hydrocarbon solvents, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and isophorone, ethyl acetate, butyl acetate, etc. It may be appropriately selected from esters, acetonitrile, dimethylformamide, dimethyl sulfoxide, and the like. These may be used alone or in mixtures. The reaction is generally preferably carried out at -20 to 100°C, but it is particularly advantageous to carry out the reaction near room temperature (0 to 30°C) or under ice cooling. At high temperatures of 100°C or higher, side reactions may occur, while at too low temperatures the reaction rate decreases, which is disadvantageous. During the reaction,
Although the use of tin-based catalysts may be considered, the need for catalyst use is usually not found. [Function and Effect] As is clear from the above explanation, the isocyanate compound () very easily reacts with the amino compound () to form a group having a polymerizable conjugated double bond in the amino nitrogen atom of the latter, i.e. , an alkyl acryloylcarbamoyl group is introduced. As a result, the amino compound () is imparted with polymerizability derived from the conjugated double bond. For example, polymerization can be easily carried out in the presence of a radical polymerization catalyst such as azobisisobutyronitrile. On the other hand, the substituted urea compounds () obtained by the present invention have the advantage of being easy to handle because they are generally in solid form, easy to purify, and stable at room temperature. Moreover, since it shows solubility in most organic solvents, it can also be used in the form of a solution. As mentioned above, substituted urea compounds () can undergo homopolymerization reactions and copolymerization reactions due to the conjugated double bonds present in their molecules, and the resulting homopolymers and copolymers can be used in paints, adhesives, and plastics. , used for elastomers, etc. Furthermore, the presence of acylurea bonds has a high intermolecular cohesive force and intermolecular hydrogen bond forming ability, and as a result, the produced polymer has excellent physical properties (such as toughness, adhesiveness, and dispersibility). As described above, the substituted urea compound () itself is useful as a raw material for industrial production. In addition, when the amino compound () has a plurality of primary and/or secondary amino groups, the isocyanate compound () usually reacts with each of the primary and/or secondary amino groups. Therefore, if the number of moles of the isocyanate compound () corresponding to or more than the number of primary and/or secondary amino groups is used per mole of the amino compound (), all the primary Or/and a substituted urea compound () in which the isocyanate compound () reacts with the secondary amino group is obtained. At least 1 including such grades
As long as each of the primary or secondary amino groups reacts with the isocyanate compound (), the resulting product can be used as a substituted urea compound (), which is the object compound of the present invention.
must be understood as falling within the scope of Furthermore, when ammonia or a primary amine is used as the amino compound (), it is possible that 2 to 3 moles of the isocyanate compound () will react with 1 mole of the amino compound (), but at least the reaction described above may occur. As long as the reaction is carried out under these conditions, the production of such products is virtually not observed. The isocyanate compound (), which is the raw material, is
It can be produced by the reaction of α-alkylacrylamide and oxalyl halide. The reaction can usually be carried out at a temperature of 0 to 80°C in the presence of an inert solvent such as a halogenated hydrocarbon. In addition,
In order to avoid unnecessary polymerization of terminal double bonds, a polymerization inhibitor may be present in the reaction system. Specific examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-
Methylphenol, 4-t-butylcatechol,
Bisdihydroxybenzylbenzene, 2,2'-methylenebis(6-t-butyl-3-methylphenol), 4,4'-butylidenebis(6-t-butyl-3-methylphenol), 4,4'-thiobis( 6-t-butyl-3-methylphenol), p-
Nitrosophenol, diisopropylxanthogen sulfide, N-nitrosophenylhydroxylamine ammonium salt, 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferudazil, 2,6- Di-t-butyl-α-(3,5-di-t-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-trioxy, 2,2,6,6-tetramethyl- 4-piperidone-1-oxyl, dithiobenzoyl sulfide, p,p'-ditolyltrisulfide, p,p'-ditolyltetrasulfide,
Examples include dibenzyltetrasulfide and tetraethylthiuram disulfide. [Example] Examples are given below to specifically explain the method for producing the substituted urea compound (). Example 1 1-methacryloyl urea Ammonia gas was blown into 50 g of dry chloroform to prepare a chloroform solution containing 0.18 g (10.5 mmol) of ammonia. Add 1.11 g (10 mmol) of methacryloyl isocyanate to this solution under ice cooling.
A 2 ml solution of 1,2-dichloroethane was added dropwise in a stream of dry nitrogen. After dropping, chloroform and 1,2-dichloroethane were distilled off under reduced pressure, and 1-
1.28 g of methacryloyl urea was obtained. Recrystallization from benzene-hexane gave colorless needle crystals. m.
p.137-138℃. Example 2 1-Methacryloyl-3-methylurea A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 2 ml of 1,2-dichloroethane was added dropwise to a solution of 0.35 g (11.29 mmol) of methylamine in 30 ml of chloroform under ice cooling in a nitrogen stream. After the dropwise addition, chloroform, 1,2-dichloroethane and excess methylamine were distilled off under reduced pressure to obtain 1.42 g of 1-methacryloyl-3-methylurea. Recrystallization from benzene-hexane gave colorless plate crystals.
mp112~113.5℃. Example 3 1-Methacryloyl-3-allylurea A solution of 1.35 g (12.2 mmol) of methacryloyl isocyanate in 2 ml of 1,2-dichloroethane was added dropwise to a 30 ml solution of chloroform containing 0.695 g (12.2 mmol) of allylamine under ice cooling in a nitrogen stream. did. After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 2.04 g of 1-methacryloyl-3-allylurea. Recrystallization from petroleum ether gave colorless needles. mp42~43℃. Example 4 1-methacryloyl-3-(2-thiazolyl)
A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 2 ml of 1,2-dichloroethane was added dropwise to a solution of 1.0 g (10 mmol) of urea 2-aminothiazole in 20 ml of chloroform under ice cooling in a nitrogen stream. After dropping, chloroform and 1,2-dichloroethane were distilled off under reduced pressure, and 1-methacryloyl-3-
2.11 g of (2-thiazolyl)urea was obtained. Recrystallization from benzene-hexane gave colorless needle crystals.
mp166~167℃. Example 5 1-Methacryloyl-3,3-dicyclohexylurea A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 2 ml of 1,2-dichloroethane was added dropwise to a 20 ml solution of chloroform containing 1.81 g (10 mmol) of dicyclohexylamine under ice cooling in a nitrogen stream. . After dropping, chloroform and 1,2-dichloroethane were distilled off under reduced pressure, and 1-methacryloyl-3,
2.92 g of 3-dicyclohexylurea was obtained. Recrystallization from benzene gave colorless prism crystals. m.
p.165.5~166.5℃. Example 6 1-Methacryloyl-3-stearylurea A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 1,2-dichloroethane was added dropwise to a solution of 2.69 g (10 mmol) of stearylamine in 50 ml of chloroform at room temperature in a nitrogen stream. After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 3.80 g of 1-methacryloyl-3-stearylurea. Colorless solid. mp37.5~40.5℃. Example 7 1-methacryloyl-3-phenylurea 0.93 g (10 mmol) of aniline in chloroform 30
methacryloyl isocyanate under ice cooling in ml solution.
1.11 g (10 mmol) of 1,2-dichloroethane 2
ml solution was added dropwise in a nitrogen stream. After dropping, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 1-methacryloyl-3-phenylurea.
2.04g was obtained. Recrystallization from benzene-hexane gave colorless needle crystals. mp129.5~131℃. Example 8 1-Methacryloyl-3-benzylurea A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 2 ml of 1,2-dichloroethane was added dropwise to a solution of 1.07 g (10 mmol) of benzylamine in 30 ml of chloroform under ice cooling in a nitrogen stream. After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 2.18 g of 1-methacryloyl-3-benzylurea. Recrystallization from benzene-hexane gave colorless needle crystals. mp69.5~9.8℃. Example 9 1-methacryloyl-3,3-dimethylurea A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 20 ml of 1,2-dichloroethane was added dropwise to a 20 ml solution of chloroform containing 0.45 g (10 mmol) of dimethylamine under ice cooling in a nitrogen stream. . After dropping, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 1.56 g of 1-methacryloyl-3,3-dimethylurea as a colorless needle-like substance. IR spectrum has νNH at 3280 cm ^-1 and 1700 cm ^-1
νC=O of the methacryloyl group, ν at 1670cm ^-1

[Formula] (urea carbonyl group), an amide absorption band at 1500 cm ^-1 and an amide absorption band at 1200 cm ^-1 were observed. The NMR spectrum includes methyl protons (methacryloyl group) at 2.03ppm, methyl protons (N-methyl group) at 3.07ppm, vinyl protons of methacryloyl groups at 5.68ppm and 6.06ppm, respectively.
A signal of urea NH proton was observed at 9.42 ppm. Example 10 N-methacryloylmorpholine carboxamide Morpholine 0.87 g (10 mmol) in chloroform
Methacryloyl isocyanate under ice cooling in 20ml solution
1.11 g (10 mmol) of 1,2-dichloroethane20
ml solution was added dropwise under a nitrogen stream. After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure, and hexane was added for crystallization to obtain 1.98 g of N-methacryloylmorpholine carboxamide. Recrystallize from ethyl acetate to form colorless prismatic crystals with a mp of 104-105°C.

Claims (1)

[Claims] 1 Formula: [In the formula, R represents a lower alkyl group,
[Formula] represents a residue obtained by removing a hydrogen atom from ammonia, a primary amine, or a secondary amine. ] A substituted urea compound represented by. 2 formula: [In the formula, R represents a lower alkyl group. ] An isocyanate compound represented by the formula: [In the formula, [Formula] represents a residue obtained by removing a hydrogen atom from ammonia, a primary amine, or a secondary amine. ] By reacting ammonia, primary amine or secondary amine represented by the formula: [In the formula, R and [Formula] have the same meanings as above. ] A method for producing a substituted urea compound, characterized by obtaining a substituted urea compound represented by the following. 3. The production method according to claim 2, wherein the reaction is carried out in an inert solvent.