JPS60231644A - Substituted urea compound and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is H or lower alkyl; the group of formula II is ammonia or residue obtained by removing H from a primary or secondary amine). EXAMPLE:1-Methacryloylurea. USE:Useful as an industrial raw material. For example, the homopolymer or copolymer produced by the homopolymerization reaction or copolymerization reaction of the compound by the conjugated double bond in the molecule can be utilized as paint, adhesive, plastic, elastomer, etc. PREPARATION:The compound of formula I can be prepared by reacting the isocyanate compound of formula III with the amino compound of formula IV (e.g. ammonia, alkylamine, alkenylamine, etc.) in an inert solvent at -20-+100 deg.C, preferably 0-30 deg.C.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a substituted urea compound and a method for producing the same, particularly a substituted urea compound having the formula: %formula%(
1) Residues excluding hydrogen atoms are shown. ] It is related with the substituted urea compound represented by these and its manufacturing method.

[Prior Art] Compounds having isocyanic F 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. In pursuit of such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Japanese Patent Application No. 58-22522]
No. 6 1: [wherein R has the same meaning as above. ].

The above-mentioned isocyanate compound (II) is generally a stable liquid at room temperature and is 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 the groups adjacent to them, the activity of the carbon-carbon unsaturated group is increased, and the activity of the isocyanate group is also increased, and it is in a state where it can carry out various addition reactions. . That is, various reactions based on the A part (conjugated double bond) and B part (acylisocyanate group) of the incyanate compound (formerly the following formula), such as radical polymerization, anionic polymerization, trimerization, trimerization, polar addition, It is possible to perform active hydrogen addition, etc. Therefore, incyanate compound (II) is expected to have a wide range of uses as a raw material for industrial production.

[Objective of the Invention 1 The present invention provides an isocyanate compound (II) as described above.
This was done for the purpose of developing one use for the technology.

[Structure of the Invention] The gist of the present invention is a substituted urea compound represented by formula (1), an incyanate compound represented by formula (II), and a residue obtained by removing a hydrogen atom from a secondary amine. . A method for producing a substituted urea compound characterized by reacting ammonia, a primary amine or a secondary amine represented by formula (1) to obtain a substituted urea compound represented by formula (1), and a method for producing a substituted urea compound represented by formula (1).
The invention consists in a polymerizable conjugated double bond-introducing reagent for ammonia, primary or secondary amine, which is composed of an isocyanate compound represented by n).

As mentioned above, since the incyanate compound (II) has the possibility of carrying out various reactions, ammonia, a primary amine or a secondary amine (■) (hereinafter referred to as
It is called Ami-7 compound (I). ), the desired isocyanate compound (former and 7-mino compound (III)
In addition to and/or in place of the addition reaction during ) and isocyanate compounds (n
Although it was predicted that various side reactions would proceed, such as the reaction of (), it was actually confirmed that the desired reactions proceed preferentially in a temperature range that does not exceed at least 100°C. In particular, at relatively low temperatures not exceeding room temperature (0 to 30°C), only the desired reaction proceeds quantitatively, and various predicted side reactions can be virtually completely avoided.

According to the present invention, the substituted urea compound (1) can be produced by reacting the incyanate compound (II) and the 7-mino compound (III).

The amino compound (I) can be selected from a wide range, and specific examples include ammonia, alkyl amines (
(e.g. methylamine, ethylamine, propylamine, isopropylamine, laurylamine, or thearylamine), alkenylamines (e.g. allylamine, pentenylamine), aralkenylamines (e.g. benzylamine, 7enethylamine), aromatic amines (e.g. aniline), Primary amines such as heterocyclic amines (e.g. thiazolylamine), dialkylamines (e.g. dimethylamine, methylethylamine, diethylamine, dipropylamine), dicycloalkylamines (e.g. dicyclopentylamine, dicyclohexylamine), alkyl-aralkylamines (e.g. Methyl-
Examples include secondary amines such as benzylamine, methyl7enethylamine), and cyclic amines (eg, piperidine, morpholine, and aziridine). That is, the groups represented by R' and R11 of the amino compound (I[[) are hydrogen,
Alkyl groups (e.g. methyl, ethyl, propyl, stearyl), alkenyl groups (e.g. allyl, pentenyl), aralkyl groups (e.g. benzyl, 7-enethyl),
Substituted or unsubstituted phenyl groups (e.g. phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, diY
lophenyl), substituted or unsubstituted heterocyclic groups (eg, thiazolyl, oxasilyl, isoxasilyl), and the like. Additionally, R' and R'' may both be substituted together with the nitrogen atom to which they are connected, such as a nitrogen-containing cyclic group (e.g., aziridino, pyrrolidino, piperidino,
Morpholino, thiamorpholino, N-methylpiperazi/)
It may also represent The amino compound (I[[) is often liquid at room temperature and can itself serve as a reaction medium, but whether the amino compound (I[l) is liquid or gaseous or solid, it can be used as an inert solvent. It is common to use . 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, including aliphatic hydrocarbons such as pentane, hexane, and heptane, aromatic solvents such as benzene, toluene, and xylene. Hydrocarbons, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin, hydrocarbon solvents such as petroleum ether and petroleum benzene, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, and 1,2-dichloroethanato, ethyl Ether solvents such as ether, isopubyl ether, anisole, nooxane, and tetrahydro-7rane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ace)phenone, and inphoron, esters such as ethyl acetate, butyl acetate, and acetonitrile. It may be appropriately selected from λ-dimethylformamide, dimethylsulfoxy Y, and the like. These may be used either singly or in mixtures.

It is generally preferred to carry out the reaction at -20 to 100°C, but it is particularly advantageous to carry out the reaction near room temperature (0 to 30°C) or under water cooling. A high temperature of 100° C. or higher may cause a side reaction, while a too low temperature is disadvantageous because the reaction rate decreases. Although the use of a tin-based catalyst may be considered during the reaction, the necessity of using a catalyst is usually not recognized.

[Action and Effect] As is clear from the above explanation, isocyanate-F compound (II) reacts with amino compound (I) very easily, forming a polymerizable conjugated double bond in the amino nitrogen atom of the latter. ie, an alkyl acryloylcarbamoyl group is introduced. As a result, the amino compound (I) 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. Therefore, the isocyanate compound (It) is useful as a polymerizable conjugated double bond-introducing agent or a polymerizable agent for amino compounds.

On the other hand, the substituted urea compound (I) obtained by the present invention has the advantage of being easy to handle because it is generally in a 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 compound (1)
It is possible to perform homopolymerization reactions and copolymerization reactions due to the conjugated double bonds present in its molecules, and the resulting homopolymers and copolymers are used in paints, adhesives, plastics, elastomers, etc. Furthermore, because of the presence of acylurea bonds, the intermolecular cohesive force and ability to form intermolecular hydrogen bonds are high, and the resulting polymers have excellent physical properties (toughness, adhesion, dispersibility, etc.). As described above, the substituted urea compound (1) itself is useful as a raw material for industrial production.

In addition, the amino compound (I[l) has primary or/and secondary
When multiple primary amino groups are present, each one usually
Isocyanate compound (Il) 7! for 7 primary or/and secondary ami groups! l' react. Therefore, per mole of the amino compound (■), the number of moles of the isocyanate compound corresponding to the number of its primary and/or secondary amino groups or more (if the former is used, all 1 of the amino compound (1) A substituted urea compound (I) is obtained by reacting the isocyanate compound (II) with the primary or/and secondary amino group.
As long as the primary or secondary amine 7 group reacts with the isocyanate compound (1), the resulting product must be understood to belong to the category of the substituted urea compound (1), which is the target compound of the present invention. .

Furthermore, 1. When ammonia or a primary amine is used as the amino compound (III), the amino compound (III)
■) Isocyanate compound (II) or 2 to 1 mole
Although it is possible that a 3 molar reaction may occur, as long as the reaction is carried out at least under the above-mentioned reaction conditions, the production of such a product is not substantially observed.

Incyanate compound (II), which is a raw material, can be produced by reacting a-alkylacrylamide and oxalyl halide. The reaction is usually carried out in the presence of an inert solvent such as a halogenated hydrocarbon at a temperature of 0 to 80°C. In addition, in order to avoid unnecessary polymerization of the terminal double bond, 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, diisopropylxanthodensulfide, N-nitrosophenyl Hydroxylamine ammonium salt, 1,1-diphenyl-2-picrylhydrazyl, 1,3.5-triphenyl-7-eldazyl, 2,6-di-t-butyl-Q-(3
,5-di-butyl-4-oxo2,5-cyclohexadien-1-ylidene)-p-)lioxy,2,2
, 6゜6-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, I)+l)'-ditolyl trisulfide, +1+ll'-ditolyl tetrasulfide, dibenzyl tetrasulfide, tetraethylthiuram disulfide, etc. Can be mentioned.

[Example 1] Examples are given below to specifically explain the method for producing the substituted urea compound (1).

Example 1 Ammonia gas was blown into 50 g of dry chloroform to prepare a chloroform solution containing 0.18++ (10.5 mmol) of ammonia. Add 1.11 g of methacryloyl isocyanate (10 mmoffi) to this solution under water cooling.
) in 1,2-dichloroethane was added dropwise in a stream of dry nitrogen. After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 1.21 h of 1-methacryloyl urea. Recrystallized from benzene-hexane,
Colorless needle crystals were obtained.

m, p, 137-138°C0 Example 2 1,2 of methacryloyl isocyanate 1,119 (10 mmol) was added to a chloroform 30i solution of 0.3'5 g (11,29 mmol) of yonimethacryloyl-3-methylurea methylamine under water cooling. - A dichloroethane solution from 2 companies was added dropwise in a nitrogen stream. After dropping, the chloroform, 1,2-dichloroethane solution 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.

m, p, 112-113.5°C.

Example 3 1-methacrylate-3-allylurea allylamine 0
．． 695 g (12,2 mmoN) of chloroform 30'
Add methacryloyl isocyanate 1 to the R1 solution under water cooling.
．． A solution of 35 g (12.2 mmoN) of 1,2-dichloroethane from Company 2 was added dropwise in a nitrogen stream.

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. m, p, 42-43°C9 Example 4 1-methacryloyl-3-(2-thiazolyl) radical 2-aminothiazole 1.0y (10 river moβ) was added to a chloroform 20 solution under water cooling (methacryloyl isocyanate) 1 .111? A solution of 1,2-dichloroethane 2a1 (10 mmol) was added dropwise in a nitrogen stream. After dripping,
Chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 1-methacryloyl-3-(2-thiazolyl).
2.11 g of urea was obtained. Recrystallization from benzene-hexane gave colorless needle crystals. m, p.

166-167°C0 Example 5 1-Methacryloyl-3,3-dicyclohexyl λ dicyclohexylamine 1,81 ir (10 mmo
1.11 g (10 mmon) of methacryloyl isocyanate was added to a 20×N solution of methacryloyl isocyanate in chloroform 20×N solution under water cooling.
-Dichloroethane 2zN solution was added dropwise in a nitrogen stream.

After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure, and 2.929% of 1-methacryloyl-3°3-dicyclohexylurea was dissolved. Recrystallization from benzene gave colorless prism crystals. m, p.

165.5-166.5°C.

Example 6 1-methacryloyl-3-stearylurea stearylamine 2.69y (10mmoβ) in chloroform 50z
/methacryloyl isocyanate 1. to the solution at room temperature. l1
A solution of g (10 mmoβ) in 1,2-dichloroethane was added dropwise in a nitrogen stream. After dropping, chloroform and 1,
2-dichloroethane was distilled off under reduced pressure to obtain 3.8 og of 1-methacryloyl-3-stearylurea. Colorless solid. m, p, 37.5-40.5°C.

Example 7 1-799170yl-3-phenylurea aniline 0.
Add 1.11 g (10
A solution of 211 g of 1,2-dichloro-1 (20%) was added dropwise in a nitrogen stream. After dropping, chloroform and 1,2
-dichloroethane was distilled off under reduced pressure to obtain 2.04 g of 1-methacryloyl-3-phenyl it. Recrystallized colorless needle crystals were obtained from benzene-hexane. m, p, 12
9.5-131°C0 Example 8 1.11 g of methacryloyl isocyanate was added to a solution of 1-methacryloyl-3-benzylurea benzylamine 1.0'B (10 mmoβ) in chloroform 30 under cooling with water.
(10nunoN) of 1,2-dichloroethane 2i+N
The solution was added dropwise under a stream of nitrogen. After the dropwise addition, chloroform and 1.2-7 chloroethane were distilled off under reduced pressure to obtain 2.18 g of 1-methacryloyl-3-benzylurea. Recrystallization from benzene-hexane gave colorless needle crystals. m
, p, 96.5-98°C0 Example 9 1-methacryloyl-3,3-dimethylurine l dimethylamine 0.45y (10 mmo included) glue o roform 20I
1.1 of methacryloyl isocyanate under water cooling to ll solution.
1y(10++unol) of 1,2-dichloroethane 2
The Oy+ffi solution was added dropwise 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-dimethyl urine i as a colorless oil.

The IR spectrum shows I/NH at 3280 cm-', ↑5
Amide ■ absorption band at 00cz', 12 ('l Ocm-
An amide ■ absorption band was observed in '.

The NMR spectrum shows methyl protons (methacryloyl groups) at 2 and 03 HHrtn, and 3. Methyl proton (N-methyl group) in O7ppm, 5.68ppm, '6
．． A vinyl proton signal of a methacryloyl group was observed at 0.06 ppm, and a signal of a urea NH proton was observed at 9.42 ppm.

Example 1O N-methacryloylmorpholine carboxamide morpholine 0.87 g (10 mmol) Nocro'aform 20r
Add 1.1 methacryloyl isocyanate to the pl solution under water cooling.
．． 1 g (10 mmo included) of 1,2-dichloroethane 20
11. The I2 solution was added dropwise under a nitrogen stream. After dropping, 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 obtain a colorless prism product with m, p, and 104-105°C.

Claims (1)

[Claims] 1. Formula; [In the formula, R represents a lower alkyl group, and -N-R'H... 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: %Formula% [In the formula, R represents a lower alkyl group. The isocyanate compound represented by 1 and the formula: %Formula % [In the formula, -N-R" represents ammonia, a primary amine, R'", or a residue obtained by removing a hydrogen atom from a secondary amine. A method for producing a substituted urea compound, which comprises reacting ammonia, a primary amine, or a secondary amine represented by the following formula to obtain a substituted urea compound represented by the formula: 3. Claim 2 in which the reaction is carried out in an inert solvent
Manufacturing method described in section. 4, Formula: R/CH2=C\C-N=C=○ 1 [In the formula, R represents a lower alkyl group. Ammonia, primary or secondary, consisting of an isocyanate compound represented by 1
Polymerizable conjugated double bond introduction reagent for class amines.