JPH0524142B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Fields] The present invention relates to carbamate esters and their production methods, which have a wide range of uses as raw materials in the fields of organic synthesis and polymer production, particularly due to their excellent reactivity. [wherein R is a lower alkyl group (e.g. methyl,
A represents an organic group having a tertiary amino group (e.g., di(lower)alkylamino(lower)alkyl, di(lower)alkylaminophenyl, lower alkyl-phenylamino(lower)alkyl, lower Alkyl-phenyl (lower)
Alkylamino (lower) alkyl, pyrrolidino,
piperidino, morpholino, pyrrolidino(lower)alkyl, piperidino(lower)alkyl, morpholino(lower)alkyl, di(lower)alkylamino(lower)alkoxy(lower)alkyl, etc.). ] The present invention relates to a novel carbamate ester represented by the following and a method for producing the same. [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 isocyanate symbol () 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 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, the isocyanate compound () can be used for various reactions based on the A part (conjugated double bond structure) and B part (acyl isocyanate structure) of the following formula, such as radical polymerization, anionic polymerization, dimerization, trimerization, polar addition, Active 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. For example, the isocyanate compound () has the formula: R′OH (′) [wherein R′ represents a residue obtained by excluding the hydroxyl group from a hydroxyl compound. ] When reacted with a hydroxyl compound represented by the formula, the addition reaction proceeds preferentially between the isocyanate group of the former and the hydroxyl group of the latter, and the formula: [In the formula, R and R' have the same meanings as above. ] A carbamate ester represented by the following is obtained.
Therefore, isocyanate compounds () are generally useful as reagents for introducing polymerizable conjugated double bonds into hydroxyl compounds [Patent Application No.
No. 87606 (hereinafter referred to as "Application A")]. As mentioned above, isocyanate compounds ()
has the potential to carry out various reactions, so when the hydroxyl compound (') is reacted with it, in addition to and/or in place of the addition reaction between the isocyanate compound () and the hydroxyl compound ('), Isocyanate compounds ()
Dimerization, trimerization, multimerization (polymerization), etc.
Polymerization of the produced carbamate ester ('), amide form of the produced carbamate ester (')
It was predicted that various side reactions would proceed, such as the reaction between the NH group and the isocyanate compound (), but in reality, it was confirmed that essentially only the above addition reactions proceed preferentially at temperatures not exceeding 100°C. It was done. [Purpose of the Invention] By the way, the introduction of a polymerizable conjugated double bond using the isocyanate compound () according to the invention of Application A above is generally applicable to compounds having a hydroxyl group. When some kind of functional group is further present in the compound having the above, the possibility that some kind of side reaction originating from this functional group will proceed cannot be denied. Therefore, based on the invention of Application A, we will further develop this to determine whether side reactions will proceed with hydroxyl compounds in which such functional groups exist, and even if they do, whether it is possible to select conditions to avoid this. We conducted research on this topic. That is, a hydroxyl compound having a tertiary amino group was selected as a hydroxyl compound having a functional group, and research was conducted to clarify how the reaction with an isocyanate compound () proceeds. As a result, under the same conditions as the invention of Application A (100℃
It has been found that the addition reaction between the hydroxyl group and the isocyanate group proceeds preferentially at a temperature not exceeding 100% (temperature not exceeding 100%) without being affected by any effects derived from the tertiary amino group. [Structure of the Invention] The gist of the present invention is to provide a carbamate represented by the formula () and an isocyanate compound represented by the formula (), and the formula: A-OH () [wherein A has the same meaning as above]. ] A process for producing a carbamate ester, characterized by reacting a hydroxyl compound represented by the following to obtain a carbamate ester represented by the formula (). Both isocyanate compounds () and hydroxyl compounds () have various functional groups and have the potential to carry out many reactions. Therefore, when the isocyanate compound () is reacted with the hydroxyl compound (), not only is there an addition reaction between the isocyanate compound () and the hydroxyl compound (), but also an addition reaction between the isocyanate compound () and the isocyanate compound (). Progress of various side reactions such as quantification, trimerization, multimerization (polymerization), polymerization of the produced carbamate ester (), and reaction between the amide NH group of the produced carbamate ester () and the isocyanate compound (). However, in reality, the addition reaction between the isocyanate group of the isocyanate compound () and the hydroxyl group of the hydroxyl compound () actually proceeds preferentially in a temperature range that does not exceed at least 100°C. confirmed. That is,
At a relatively low temperature not exceeding 100°C, only the desired reaction proceeds, and various predicted side reactions can be substantially avoided. According to the invention, carbamate ester ()
can be produced by reacting an isocyanate compound () with a hydroxyl compound (). Typical examples of hydroxyl compounds () include di(lower) alkylamino(lower) alkanols (e.g. dimethylamino methanol,
dimethylaminoethanol, dimethylaminopropanol, diethylaminoethanol, diethylaminopropanol, N-methyl-N-ethylaminopropanol), di(lower) alkylaminophenols (e.g. o-dimethylaminophenol, m-dimethylaminophenol, p-dimethylamino Phenol, m-diethylaminophenol), lower alkyl-phenylamino (lower)
Alkanols (e.g. N-methyl-N-phenylaminoethanol, N-methyl-N-phenylaminopropanol), lower alkyl-phenyl (lower) alkylamino (lower) alkanols (e.g. N-methyl-N-benzylaminoethanol) , N-ethyl-N-benzylaminoethanol, N-ethyl-N-phenethylaminopropanol), N-hydroxypyrrolidine, N-hydroxypiperidine, N-hydroxymorpholine,
pyrrolidino (lower) alkanols (e.g. pyrrolidinoethanol, pyrrolidinopropanol),
piperidino (lower) alkanols (e.g. piperidinoethanol, piperidinopropanol),
morpholino (lower) alkanols (e.g. morpholinoethanol, morpholinopropanol),
Examples include di(lower)alkylamino(lower)alkoxy(lower)alkanols (eg, dimethylaminoethoxyethanol, dimethylaminoethoxypropanol, diethylaminoethoxypropanol), atropine, and the like. If the hydroxyl compound () is liquid at room temperature, it can itself serve as a reaction medium;
Whether the hydroxyl compound () is a liquid or a solid, it is common to use an inert solvent. 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 benzine, carbon tetrachloride, chloroform,
Halogenated hydrocarbon solvents such as 1,2-dichloroethane, 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, acetic acid It may be appropriately selected from esters such as ethyl and butyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide, and the like. These may be used alone or in mixtures. The reaction may generally be carried out at temperatures not exceeding 100°C, but it is particularly advantageous to carry out the reaction near room temperature (0-30°C) or under ice-cooling. If the temperature exceeds 100°C, side reactions may occur, while if the temperature is too low, the reaction rate will decrease, which is disadvantageous. Although the use of a tin-based catalyst may be considered during the reaction, the necessity of using a catalyst is usually not recognized. In addition, when carrying out the reaction, the hydroxyl compound () may be added to the isocyanate compound (), or the isocyanate compound () may be added to the hydroxyl compound ().
From the viewpoint of preventing the progress of side reactions, it is preferable to dissolve the hydroxyl compound () in an inert solvent, and then add a solution of the isocyanate compound () in an inert solvent little by little dropwise to the solution under ice cooling. [Operation and Effect] As is clear from the above explanation, the isocyanate group of the isocyanate compound () easily and selectively reacts with the hydroxyl group of the hydroxyl compound () to give the carbamate ester (). Carbamate ester obtained here ()
generally has high solubility and is soluble in most common organic solvents. In addition, when A is a dimethylaminoethyl group, for example, this product has various active structures or groups as shown in the formula below, so it is highly reactive, and therefore, it cannot be stored without polymerization. It is preferable to add inhibitors or store in a cool and dark place: In the above formula, the conjugated double bond structure A' has polymerization reactivity, and therefore the carbamate ester () can be used for producing homopolymers and copolymers. For example, it can be used to modify synthetic fibers, synthetic resins, natural polymers, etc. by graft polymerization, or it can be used by itself or with other polymerizable monomers (such as styrene, alkyl acrylates,
varnish by polymerizing with alkyl methacrylate),
Used in the production of paints, adhesives, plastics, elastomers, etc. In the polymerization, it is advantageous to use a radical polymerization catalyst such as azobisisobutyronitrile. Since the acyl urethane structure B' has high intermolecular cohesive force and intermolecular hydrogen bond forming ability, polymers obtained using carbamate ester () have excellent properties in terms of toughness, adhesion, and dispersibility. contribute to waste disposal. The tertiary amino group-containing structure C' is basic and highly reactive, or exhibits strong cationic properties when quaternized. Therefore, the reaction product obtained using carbamate ester (2) is highly water-soluble or hydrophilic, has good dyeability with acid dyes, and has reactivity or adsorption to anions. In addition, it exhibits cohesive properties against negative colloids such as sewage sludge and cellulose, has excellent electrical properties such as chargeability and conductivity, and has good adhesion and dispersibility. In this way, carbamate ester () is
It has a wide range of uses as a raw material for industrial production. In addition, the isocyanate compound () which is a raw material can be manufactured by the reaction of α-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 terminal double bonds, a polymerization inhibitor may be present in the reaction system. Specific examples of polymerization inhibitors used here or during storage of the carbamate ester () are hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4-t -butylcatechol, bisdihydroxybenzylbenzene, 2,2'-methylenebis(6-t-butyl-3-methylphenol), 4,
4'-Butyldenbis(6-t-butyl-3-methylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), p-nitrosophenol, diisopropylxanthogen sulfide, N-nitro Sophenylhydroxylamine・
Ammonium salt, 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl, 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, dithiobenzoylsulfur phide, p, p'-ditolyltrisulfide, p, p'-
Examples include ditolyltetrasulfide, dibenzyltetrasulfide, and tetraethylthiuram disulfide. [Example] Examples are given below to specifically explain the method for producing carbamate ester (2). Example 1 N-methacryloylcarbamic acid dimethylaminoethyl ester dimethylaminoethylethanol 0.89g
(10 mmol) was dissolved in 20 ml of dry chloroform,
Ice cold. A solution of 1.11 g (10 mmol) of methacryloyl isocyanate in 5 ml of 1,2-dichloroethane was added dropwise to this solution in a nitrogen stream. After the dropwise addition, chloroform and 1,2-dichloroethane were distilled off under reduced pressure to obtain 2.00 g of N-methacryloylcarbamic acid dimethylaminoethyl ester. Recrystallization from benzene-hexane gives colorless needles with a melting point of 71-73°C. Examples 2-7 The compounds shown in Table 1 were obtained in essentially the same manner as in Example 1. The viscosity is a value measured at 25°C using an E-type viscometer EHD (for high viscosity) manufactured by Tokyo Keiki Co., Ltd.

【table】

[Table] As understood from the above explanation, the present invention utilizes the technical idea of the invention of Application A described above in that a specific isocyanate compound () is used to introduce a polymerizable conjugated double bond into a hydroxyl compound. However, in that the target hydroxyl compound has an active group, that is, a tertiary amino group, in addition to a hydroxyl group, it can be said that the technical idea of the invention of Application A is further expanded.

Claims (1)

[Claims] 1 Formula: [In the formula, R represents a lower alkyl group, and A represents an organic group having a tertiary amino group. ] Carbamate ester represented by. 2 formula: [In the formula, R represents a lower alkyl group. ] An isocyanate compound represented by the formula: A-OH [wherein A represents an organic group having a tertiary amino group. ] By reacting a hydroxyl compound represented by the formula: [In the formula, R and A have the same meanings as above. ] A method for producing a carbamate ester, characterized by obtaining a carbamate ester represented by the following. 3. The production method according to claim 2, wherein the reaction is carried out in an inert solvent.