JPH0443063B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Fields] In recent years, guanidine, which is strongly basic and has an unsaturated group, has exhibited its properties as a curing catalyst and performance improver for urethane resins, epoxy resins, and the like. In addition, there is a growing demand for a strongly basic guanidine compound with high reactivity as a performance improver for silicone resins used in various applications such as silicone oil and silicone rubber. The present invention relates to N''-allyl-N,N'-tetra-substituted guanidine, which is a novel compound optimal for the above uses, and also relates to a method for producing the same. Specifically, the present invention relates to the following general formula: [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group or an ethyl group]
Tetramethylurea), phosphorus pentachloride, phosphorus oxybromide, and allylamine are used as raw materials, and once in an organic solvent such as benzene, toluene, etc.
By producing an addition reaction product consisting of an N,N'-tetra-substituted urea such as N,N'-tetramethylurea and the reactant, and then reacting it with allylamine, a strongly basic compound having an unsaturated group is produced. A new compound, the following general formula, [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group or an ethyl group] (May be abbreviated)
It provides: [Prior Art] Conventionally, the following method has been known as a method for producing penta-N-substituted guanidine. The first is “Huain Chemical”, Volume 11 (1982
This is the method described in 2010), p. 15. this is,
The tetraalkylurea is reacted with a toluene solution of phosgene in benzene or ether at 0°C to room temperature to form the Vilsmeyer salt, the solvent is distilled off under reduced pressure, and then the saturated alkylamine, t-butylamine, is reacted. Penta-N- by letting
This is a method for producing substituted guanidine. The second method is a method of reacting a mercuric chloride complex of an isocyanide with a primary amine or a secondary amine, which is described in JP-A-58-128363 (``Method for producing solid guanidines''). It is. However, these two proposals do not consider the use of compounds containing unsaturated groups such as allyl groups, which tend to polymerize and become resinous, when introducing N″-substituents. discloses only chemically relatively inert groups such as saturated alkyl groups. In addition, the latter method requires the use of mercuric chloride, which is relatively expensive, highly toxic, and requires troublesome post-treatment.
The yield of N,N'-diphenyl-N''-t-butylguanidine obtained is low, making it unsuitable for industrial production, and guanidine, which is strongly basic and has an unsaturated group, is not available. [Problems to be Solved by the Invention] The present inventors have solved the problem of strongly basic compounds having unsaturated groups, which have been neglected because they are difficult to produce industrially in a high yield. new N″-allyl-N,
As a result of continuing various studies on production methods for obtaining N'-tetra-substituted guanidine in high yield, it was completely unexpected that not only the so-called Vilsmeyer salt of N,N'-tetra-substituted urea and phosgene, but also the so-called Vilsmeier salt, was found. For other addition reactants, that is, addition reactants of the N,N'-tetra-substituted urea and phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, acid halide of thionyl chloride or aluminum chloride, They discovered that allylamine reacts very easily and completed the present invention. [Means for solving the problem] The present invention has the following general formula: [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group or an ethyl group] The following general formula, [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group or an ethyl group] In an organic solvent, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide,
A method for producing N″-allyl-N,N′-tetra-substituted guanidine, which comprises reacting a reactant selected from the group consisting of thionyl chloride, thionyl bromide, aluminum chloride, and phosgene, and then reacting with allylamine. The N,N'-tetra-substituted urea used in the present invention is
The following general formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a methyl group or an ethyl group, and the compound is liquid at room temperature. Particularly preferred among these compounds is, for example, 1,1,3,3-tetramethylurea, which has a boiling point of about 177°C. The reactants used in the present invention are selected from the group consisting of phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide, aluminum chloride, and phosgene, including industrial chemicals. , reagents, etc. can be used.
Moreover, if desired, two or more of these reactants can be used in combination. Among these, it is preferable to use phosphorus pentachloride, phosphorus oxychloride, or thionyl chloride, which are easy to handle, have low toxicity, and can obtain ATAG in high yield. Furthermore, the organic solvents used in the present invention include:
N,N'-tetra-substituted urea, reactant, intermediate so-called Vilsmeyer salt, etc., alisamine and
Any organic solvent that does not substantially react with any compound of ATAG can be used without restriction depending on the purpose. These organic solvents can be used alone or in combination of two or more. Such organic solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, or their halides; for example, n-hexane,
Cyclohexane, isooctane, petroleum ether,
Examples include aliphatic hydrocarbons such as ligroin, and halides of aliphatic hydrocarbons such as methyl chloride, chloroform, carbon tetrachloride, and ethylene chloride. These organic solvents preferably have a water content of 1% by weight or less. The ATAG according to the present invention can generally be made as follows. A suitable amount of an organic solvent and a reactant are placed in a reactor equipped with a reflux condenser, a stirrer, a raw material inlet and a dropper, and stirred under constant conditions at a temperature of about 0°C to about 50°C. If the reactant is solid at room temperature, such as phosphorus pentachloride, use the amount of organic solvent required to dissolve most of the reactant, or use a slightly excess amount of the organic solvent to dissolve the reactant solution or Make a suspension. The number of moles of the reactant used is slightly in excess of the number of moles of the N,N'-tetra-substituted urea, and a previously prepared solution of N,N'-tetra-substituted urea in an organic solvent (e.g., toluene) is stirred. from the dropper to the solution or suspension of the reactant. Addition reactants are formed upon addition, and the reactant solution in the reactor generally begins to become cloudy. After the dropwise addition of the solution of N,N'-tetra-substituted urea is completed (the total time required for the dropwise addition is approximately 1 hour), stirring is continued for a predetermined period of time to complete the formation of the addition reaction product. In particular, the Vilsmeyer salt produced from phosgene is relatively unstable and decarboxylated and changes to dichloroamidine, so when using phosgene, the next reaction with allylamine will be a Vilsmeyer salt. The reaction may be carried out directly, or the reaction may be carried out using a compound that is converted into a dichloroamidine form. The addition reaction product produced is
It seems to have the following structure. Next, while stirring and maintaining the temperature at a constant temperature as described above, allylamine in an amount several times the number of moles of N,N'-tetra-substituted urea used is added to the organic solvent solution suspended by the addition reaction product. is dropped very slowly from the dropper, followed by stirring for a predetermined period of time, and then cooled to a temperature of about 10°C to about 20°C to neutralize and make the aqueous layer alkaline. At this time, a large amount of precipitated crystals are removed by filtration, an organic solvent layer and an aqueous solution layer are separated and collected, and the aqueous solution layer is extracted with an organic solvent to extract ATAG dissolved in the aqueous solution layer. and the organic solvent layer liquid are combined and dried using a drying agent such as anhydrous sodium sulfate. The allylamine and organic solvent contained in the organic solvent solution are removed by distillation from the dry organic solvent solution thus obtained, and the remaining liquid is rectified under reduced pressure to obtain the desired ATAG. In the production method of the present invention, the reaction temperature for the allylamine addition reaction in an organic solvent is 20°C to 50°C.
Preferably it is .degree. If the reaction temperature is less than 20℃, the reaction tends to become viscous and difficult to proceed.
If the temperature exceeds this temperature range, the loss of allylamine tends to increase, so it is preferable to carry out the reaction within this temperature range. The amount of the reactant used is preferably 0.95 to 1 mole of N,N'-tetra-substituted urea.
1.4 mol, more preferably 1.05 to 1.2 mol,
The amount of allylamine used is not particularly limited, and can be determined as appropriate depending on the type of addition reaction product between the N,N'-tetra-substituted urea and the reactant. For example, 2-allyl-1,1,3,3-tetramethylguanidine obtained by the present invention exhibits the following physical properties. Boiling point: 88-89℃/23mmHg Properties: Colorless and transparent liquid, easily soluble in water and most organic solvents, and gradually turns yellow when left standing. The results of purity analysis, elemental analysis, etc. of the substance having the above boiling point and properties are as follows. Purity analysis (a) Neutralization titration using methyl red indicator with 0.1N-HCl Purity: 99% (b) Gas chromatography analysis: 98% or more Conditions Liquid phase: Ucon-Cil (50HB5100) 20% + NaOH6
% Support: Celite545, 40-60 mesh Column: 3mmφ
Raise the temperature to 200℃. Carrier gas: Helium 40ml/min (The retention time of 2-allyl-1,1,3,3-tetramethylguanidine was 5 minutes.) Elemental analysis, etc. (a) Elemental analysis C ₈ H as follows. The theoretical value obtained from ₁₇ N ₃ and the measured value were in good agreement.

[Table] (b) Mass spectrometry As a result of measurement at room temperature and 25 eV, M ⁺ =155 was obtained, which is consistent with the molecular weight. (c) Nuclear magnetic resonance analysis CDCl ₃ , using trimethylsilane as an internal standard.
Measure at 60MHz.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 In a 4-necked flask with a capacity of 2, 281.6 phosphorus pentachloride was added.
Add g (1.05 mol) and 500 ml of toluene and stir.
Make a suspension in which approximately phosphorus pentachloride is dissolved. The reaction temperature was maintained at 35° C., and a previously prepared solution consisting of 116.2 g (1 mol) of tetramethylurea and 100 ml of toluene was gradually dropped into this suspension from the dropping funnel over 1 hour. When this solution is added dropwise, an addition reaction product is immediately generated and the solution becomes cloudy. After the completion of the dropwise addition, stirring was continued at 35°C for another 30 minutes, and allylamine 428 was added while maintaining the reaction conditions.
g (7.5 mol) was added dropwise over 2 hours and maintained for an additional 30 minutes. After that, the temperature of the reaction system was increased to 35℃.
50℃ for 10 minutes while maintaining the temperature.
650 g (8.1 mol) of a wt % aqueous solution of caustic soda is added dropwise. At this time, a large amount of crystals precipitates. The precipitated crystals are separated by filtration, the obtained toluene layer and aqueous layer are separated, and the aqueous layer is subjected to shaking extraction twice using 200 ml of toluene, and the toluene layer is collected after separation. Both toluene layers thus obtained were combined, dried over anhydrous sodium sulfate, and then first distilled at normal pressure to recover allylamine and toluene, and the residual liquid was distilled under reduced pressure of 26 mmHg. 88~91℃
The yield of the fraction was 130 g, and the yield from tetramethylurea was 83%. The above fraction was analyzed using the method described above, and it was confirmed to be 2-allyl-1,1,3,3-tetramethylguanidine, with a purity of 98.3%.
It was hot. Example 2 Toluene solution containing 10% by weight of phosgene
Put 1087.9 g (1.1 mol as phosgene) into a four-necked flask, and while stirring the solution at 5°C, gradually drop 116.2 g (1 mol) of tetramethylurea into the solution from the dropping funnel over 1 hour. . As a result of this dropwise addition, an addition reaction product is immediately produced and the mixture becomes cloudy, while carbon dioxide gas begins to be generated. After completing the dropwise addition of tetramethylurea, the temperature was gradually raised and maintained at 35°C for 3 hours with stirring. Then, while maintaining the temperature, allylamine 143
g (2.5 mol) was gradually added dropwise over 1 hour, and the state was maintained for another 1 hour after the addition was completed. Thereafter, the temperature of the reaction system was cooled from 35°C to 10°C, and while maintaining this temperature, 200 g (2.5 mol) of a 50% by weight aqueous solution of caustic soda was added dropwise over 10 minutes, and the precipitated sodium chloride was filtered out. The same procedure as in Example 1 was carried out to obtain 125 g of a fraction having a temperature of 88 to 91° C. under a reduced pressure of 26 mmHg (80% yield from tetramethylurea). The analysis results of the above fraction are 2-allyl-1,1,
3,3-tetramethylguanidine, purity
It was 99.1%. Note that instead of using phosphorus pentachloride in Example 1,
26mmHg, 88% obtained by carrying out the reaction according to Example 1 except for using phosphorus oxychloride or thionyl chloride
The fractions at ~91°C are all 2-allyl-1,1,
The product was 3,3-tetramethylguanidine, and the same results as in Example 1 were obtained in terms of purity and yield.

Claims (1)

[Claims] 1. The following general formula, [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group or an ethyl group] N″-allyl-N,N′-tetra-substituted guanidine represented by the following general formula. , [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group or an ethyl group] In an organic solvent, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide,
A method for producing N″-allyl-N,N′-tetra-substituted guanidine, which comprises reacting a reactant selected from the group consisting of thionyl chloride, thionyl bromide, aluminum chloride, and phosgene, and then reacting with allylamine. .