JPH0247460B2 - TANRYOTAIKAGOBUTSUNOGOSEIHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to organic materials particularly useful in the photographic field, particularly to copolymerizable monomers for forming polymer couplers, and more particularly to a novel method for synthesizing an acrylamide-type hardening functional monomer having an active methylene group. Particularly preferred is a novel method for synthesizing N-(2-acetoacetoxyethyl)acrylamide, which has excellent crosslinking ability when formed into a homopolymer or copolymer. Conventionally, methods for deriving amide compounds from halides have been known, for example, as described in the Journal of Organic Chemistry (Journal of Organic Chemistry).
Organic Chemistry) 32, 824 (1967), Organic Synthesis, Wiley, Collective, No. 3
It is derived from ammonia and an amine by the method described in Vol. 490 (1955). In addition, an example of reacting only the amino group with the acid chloride in the reaction of a bifunctional amine having a hydroxyl group in the side chain with the acid chloride is also reported in the Journal of Organic Chemistry.
32, 3069 (1967), etc. Furthermore, in the reaction between a polymerizable acid chloride and a bifunctional amine having a hydroxyl group at the terminal, an example in which only the amine is selectively reacted while suppressing polymerization is also described in JP-A-54-74430. There is. However, it is extremely difficult to stably extract a product that has undergone further chemical modification (e.g., acetylation, reaction with diketene) from a polymerizable amide compound that has a hydroxyl group at the end because of the high polymerizability of the compound. . In the synthesis of N-(2-acetoacetoxyethyl)acrylamide, which is particularly preferred among the polymerizable compounds disclosed in U.S. Pat. No. 4,215,195, the polymerizable amide compound 2-hydroxyethyl The vinyl group of acrylamide is taken out as a protected compound as a norbornene derivative, reacted with diketene, and then subjected to a reverse Diels-Alder reaction by high temperature treatment (cracking at 650°C) to regenerate the vinyl group and lead to the desired amide type active methylene monomer. ing. The norbornene method for protecting this unsaturated bond is described in the Journal of Polymer Science; Polymer Chemistry Edition.
Chemistry Edition) 12, 985 (1974), Journal of Organic Chemistry 44, 4003
(1979), Journal of Polymer Science;
Chemistry Edition) 17, 3499 (1979), 17,
3509 (1979), Ibid. 18, 2293 (1980) {Ignatius S. Ponticello}, α-alkyl acrylic acid ester, α-
This method is attracting attention as a new method for synthesizing alkyl acrylonitriles. However, according to the method described in the above-mentioned literature, the desired monomer cannot be obtained unless operations are performed under significantly lower temperatures (preparation of a dichloromethane solution of cyclopentadiene) and at significantly higher temperatures (cracking treatment) than under normal organic reaction conditions. I can't do that. Therefore, it is difficult to say that it is necessarily a simple method. An object of the present invention is to provide a method for synthesizing an acrylamide type active methylene monomer (particularly N-(2-acetoacetoxyethyl)acrylamide) using milder and simpler reaction conditions and reaction operations. A feature of the present invention is that by using inorganic sulfur during the synthesis of the monomer compound represented by the general formula [], a predetermined property can be obtained while suppressing the deterioration (polymerization) of the compound during the reaction and during the purification operation after the reaction. A method for synthesizing a target compound. More specifically, in the method of synthesizing the compound represented by the general formula It lies in the method of synthesizing the target compound. If a method other than this method is used, for example, when generally well-known hydroquinones are used as a polymerization inhibitor, it is extremely difficult to obtain the desired product stably and in a pure state. The reason for this is that when the target product is purified by distillation under reduced pressure, due to the high sublimation properties of hydroquinones, even if an extra amount of hydroquinones is added before distillation, the polymerization inhibiting ability of the hydroquinones is not sufficient for the purpose of the present invention. This is thought to be because it is not sufficient to suppress the high polymerizability of the compound, and the residue during distillation quickly turns into a resin due to a slight increase in heating conditions, making it impossible to obtain the desired product. Column purification can be considered as a purification method other than distillation, but since it is essential to separate the target compound and polymerization inhibitor during the polymerization reaction, a strict separation operation is required and the yield is extremely low. The polymerization inhibitor or retarder used in the method of the invention is inorganic sulfur. Therefore, the purpose of the present invention is to overcome the unsatisfactoriness of the conventional state of the art by using inorganic sulfur as a polymerization inhibiting or polymerization retarding substance, and to significantly improve problems such as yield, reaction operation, and safety. The object of the present invention is to provide a method for synthesizing a monomeric compound represented by the general formula []. The general formula [] and its synthesis process are described below. General formula [] (R ₁ in the formula is a hydrogen atom or a methyl group, and R ₂
teeth

[Formula] where R ₄ is an alkyl group having 1 to 6 carbon atoms, and R ₃ is 1 to 12
an arylene group having 6 to 12 carbon atoms, an arylene alkylene group having 7 to 24 carbon atoms, an arylenebisalkylene group having 8 to 32 carbon atoms, or an arylene group having 13 to 32 carbon atoms; Represents an alkylenebisarylene group having 34 carbon atoms. ) The compound of general formula [] is synthesized by a synthetic method using inorganic sulfur under reaction conditions. An outline of the synthesis method is described below. Synthesis method General formula obtained by reacting an amine having a hydroxyl group at the terminal or side chain with a polymerizable acid halide in the presence of an acid absorbent amine [] (R ₁ represents a hydrogen atom or a methyl group. R ₃ represents 1
alkylene group with ~12 carbon atoms, 6-12
arylene group with 7 to 24 carbon atoms, arylene alkylene group with 7 to 24 carbon atoms, 8 to 24 carbon atoms
It represents an arylenebisalkylene group having 32 carbon atoms or an alkylenebisarylene group having 13 to 34 carbon atoms. ) in the presence of a compound represented by the general formula [ ] and inorganic sulfur. (R ₅ is a hydrogen atom or an alkyl group, preferably 1
~5 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, chloromethyl. ) A method for synthesizing a compound represented by the general formula [] by reaction of a compound represented by the formula [ ]. A particularly preferred compound synthesized by this method is N-(2-acetoacetoxyethyl)
Examples include acrylamide and N-(2-acetoacetoxyethylmethacrylamide.The reaction operations for synthesis method A of the present invention are shown in more detail below. A compound represented by the general formula [] synthesized according to a similar method is dissolved in tetrahydrofuran, dimethyl ether, dichloromethane, benzene, etc. together with inorganic sulfur in the presence of triethylamine, tripropylamine, pyridine, etc., and the internal temperature is 20 React with the compound represented by the general formula [] at ~60°C for 1 to 72 hours. After the reaction, the solvent is distilled off and the resulting crude product is purified by distillation under reduced pressure, and then further column purification is performed. Conventional crosslinking Monomers that provide polymers with this ability include U.S. Patent Nos. 3459790 and 3488708
Compounds derived from acrylic esters and methacrylic esters are known, which are disclosed in Japanese Patent No. 3,554,987, and No. 3,658,878. Particularly useful polymers are said to be those synthesized in part or in whole from 2-acetoacetoxyethyl methacrylate or 2-acetoacetoxyethyl acrylate. This time, N-(2
- acetoacetoxyethyl acrylamide) and a compound obtained by polymerizing 2-acetoacetoxyethyl methacrylate, it is found that the latter, which is a compound outside the present invention, does not undergo purification treatment such as dialysis or ultrafiltration after polymer synthesis. It was observed that the crosslinking ability was significantly reduced, and when copolymers were formed with other vinylamide type monomers, extremely non-homogeneous polymers were obtained. However, the polymer synthesized according to the present invention maintained a high crosslinking ability regardless of the presence or absence of post-synthesis purification operations, and the copolymer with vinylamide type monomer was a homogeneous polymer. It has thus been found that the polymer synthesized from the compound of the present invention exhibits extremely good functionality when used as a photographic material. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Example Synthesis step 1 of N-(2-acetoacetoxyethyl)acrylamide Synthesis of N-(2-hydroxyethyl)acrylamide The above compound is disclosed in U.S. Pat.
It was synthesized according to the method described in No. 2593888. Purification was performed by vacuum distillation to obtain a bp 135-140°C/1.5 mm fraction. Step 2 Synthesis of N-(2-acetoacetoxyethyl)acrylamide 58 g (0.5 mole) of the product obtained in Step 1 was dissolved in 200 ml of benzene along with 2.5 g of powdered sulfur and 1 ml of triethylamine. 46 g (0.55 mole) of diketene was added dropwise while stirring at an internal temperature of 60°C. After dripping,
The mixture was stirred for 6 hours while maintaining the reaction temperature at 60°C. After the reaction, distill off the benzene and then perform vacuum distillation b.
After collecting the p.108-132°C/2 mm fraction, 40 g of a transparent liquid was obtained by column purification. The structure is <NMR><
Confirmed with FD-Mass>. N-(2) synthesized by the method described in the present invention
-acetoacetoxyethyl acrylamide) is
Ignatius S. Ponticello (IS)
The physical properties matched those of the monomer obtained by the Ponti-cello norbornene method, and the above structure was also supported mechanically. For comparison, an example will be given in which a polymerization inhibitor other than the one according to the invention was used in the reaction step of the example. Comparative Example 1 N-(2-hydroxyethyl)acrylamide
58 g (0.5 mole) was dissolved in 200 ml of benzene along with 1 g of hydroquinone and 1 ml of triethylamine. 46g of diketene while stirring at an internal temperature of 60℃
(0.55 mole) was added dropwise. After dropping, reduce the reaction temperature to 60°C.
The mixture was stirred for 6 hours while maintaining the temperature at °C. After the reaction, an attempt was made to purify the product by distillation under reduced pressure, but the residue during the distillation turned into a polymer and the desired product could not be obtained.

Claims (1)

[Claims] 1. By reacting a compound represented by the following general formula [] with a compound represented by the following general formula [] in the presence of inorganic sulfur as a polymerization inhibiting or polymerization retarding substance, the following general formula [] A method for synthesizing a monomeric compound represented by General formula [] (R ₁ represents a hydrogen atom or a methyl group. _{R 3} represents an alkylene group having 1 to 12 carbon atoms, 6 to
Arylene group with 12 carbon atoms, arylene alkylene group with 7 to 24 carbon atoms, 8
represents an arylenebisalkylene group having ~32 carbon atoms or an alkylenebisarylene group having 13 to 34 carbon atoms. ) General formula [] (R ₅ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. General formula [] [In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a [formula] group (here, R ₄ represents an alkyl group having 1 to 6 carbon atoms), and R ₃ is 1
Alkylene groups with 12 carbon atoms from , arylene groups with 6 to 12 carbon atoms, 7 to
It represents an arylenealkylene group having 24 carbon atoms, an arylenebisalkylene group having 8 to 32 carbon atoms, or an alkylenebisarylene group having 13 to 34 carbon atoms. ]