JPH0453873B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a 9-phosphabicyclononane derivative and a method for producing the same. The compounds according to the present invention can be used as reactive flame retardants for plastics, monomers, polymer crosslinking agents, or agricultural chemical intermediates. [Prior Art] Although 9-phosphabicyclononane or its alkylated derivative, which is one of the raw materials in the present invention, is a known compound, the 9-phosphabicyclononane derivative according to the present invention is a new compound unknown in literature. be. [Problems to be Solved by the Invention] Conventionally, certain organic phosphorus compounds, especially phosphonic acid esters, have been used as various synthetic resin additives, such as resin stabilizers, flame retardants, etc.

[Formula] The bond is

[Formula] Since the bond is weaker than the bond, its function cannot always be expected to be sufficient. [Means for solving the problem] In view of the above facts, the present inventors

As a result of intensive research into polyfunctional organic phosphorus compounds having a bond of the formula, the present invention was completed. That is, the present invention is based on the general formula (1) [In the formula, R ₁ and R ₂ are H or a C ₁ to C ₄ alkyl group, but R ₁ and R ₂ are never both H, X is O or S, and two ...is P
This refers to a 9-phosphabicyclononane derivative represented by the following formula, which indicates that there are isomers in which the position of the C atom bonded to the atom differs. Furthermore, the present invention provides 9-phosphabicyclononane and general formula (2) R ₁ OOCOH=CHCOOR ₂ [wherein R ₁ and
R ₂ has the same meaning as above] is reacted with an unsaturated aliphatic dicarboxylic acid ester represented by the general formula (3). Obtain a compound represented by [wherein R ₁ and R ₂ have the same meanings as above, and the two ... represent isomers with different positions of the C atom bonded to the P atom], General formula (1), characterized in that the compound is then subjected to an oxidation or sulfurization reaction. [In the formula, R ₁ and R ₂ have the same meanings as above, X is O or S, and the two ... represent isomers with different positions of the C atom bonded to the P atom. ] The present invention relates to a method for producing a 9-phosphabicyclononane derivative shown in the following. [Function] 9-phosphabicyclononane, which is one of the starting materials in the present invention, has structural isomers, and is 9-phosphabicyclo[3,3,1]nonane or 9-phosphabicyclononane.
There are two types: phos-fabicyclo[4,2,1]nonane. The unsaturated aliphatic dicarboxylic acid ester of the general formula (2), which is another starting material, is also an isomer of maleic acid ester or fumaric acid ester. These esterified products may be either monoalkyl esters or dialkyl esters, and the alkyl group thereof is within the range of _C1 to _C4 . Therefore, specific examples of maleic esters include monoester maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, monopropyl maleate, dipropyl maleate, monobutyl maleate, and maleic acid. dibutyl etc. It should be understood that the same applies to fumaric acid esters. In the present invention, when reacting the above-mentioned two types of starting materials, the reaction is carried out in an organic solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, and n-hexane. , n-heptane, n-octane, iso-octane or cyclohexane; oxygenated hydrocarbons such as methanol, ethanol, propanol, ethyl ether or tetrahydrofuran. The first step in this reaction is carried out in a non-oxygen gas atmosphere in which the reaction system is replaced with an inert gas such as nitrogen gas or a reducing gas to prevent oxidation of 9-phosphabicyclononane. The reaction method is generally to gradually add an unsaturated aliphatic dicarboxylic acid ester to 9-phosphabicyclononane and an inert solvent solution under stirring; or by simultaneously adding 9-phosphabicyclononane and an unsaturated aliphatic dicarboxylic acid ester. This reaction proceeds exothermically to produce the target product, but in order to complete the reaction, it is preferable to ripen the product with sufficient stirring at a predetermined temperature. In this case, in order to check the progress of the reaction, the system is followed, for example, by gas chromatography, and the point at which one of the raw materials disappears is determined as the point at which the reaction is completed. The conditions for the above reaction are not particularly limited, but the reaction ratio is 0.5 to 2 mol, preferably 1 to 0.5 mol, of the unsaturated aliphatic dicarboxylic acid ester raw material per 1 mol of 9-phosphabicyclononane.
It may be used in approximately stoichiometric amounts or in a slight excess in the range of 100 to 100°C, and the temperature is preferably in the range of room temperature to 100°C, preferably 70 to 80°C. If the temperature is too low, the reaction rate will be extremely slow, and if the temperature is too high, side reactions may occur due to polymerization of ester raw materials such as maleic esters, which is not preferable. In addition, the reaction time varies depending on the reaction temperature and other conditions, but for example, at 60℃ it is about 15 hours, and at 80℃
That's about 6 to 7 hours. In addition, in the above reaction treatment, it is possible to obtain the desired product to some extent even if the next step, oxidation treatment or sulfidation treatment, is performed in parallel, but as a result, the desired product is not obtained due to side reactions. In the first step, it is first necessary to obtain the intermediate of general formula (3) in a high yield. Next, in the second step, an oxidizing agent or a sulfurizing agent is present in the intermediate of general formula (3) obtained by the above reaction to perform an oxidizing reaction or a sulfurizing reaction.
Unlike the first step, this reaction treatment is carried out extremely quickly. The oxidizing agent is not particularly limited, but oxygen gas, hydrogen peroxide, organic peroxide, etc. are suitable, and air oxidation may also be used. Examples of the sulfiding agent include colloidal sulfur, elemental sulfur such as sulfur powder, and various polysulfides. Since this reaction is accompanied by intense heat generation in either case, it is preferable to carry out the reaction gradually while cooling with stirring. After the reaction is completed, stirring is continued for a while for ripening, and then the solvent and unreacted substances are constantly separated, and if necessary, purification is performed to obtain the target product, a white or yellow 9-phosphabicyclononane derivative. can be obtained as a crystal. [Example] The present invention will be specifically explained with reference to Examples below. Example 1 9-(1,2-dimethoxycarbonyl)ethyl-9-oxo-9-phosphabicyclo[3,
3,1]nonane and 9-(1,2-dimethoxycarbonyl)ethyl-9-oxo-9-phosphabicyclo[4,2,1]nonane Stirrer, thermometer, cooler, dropping funnel, and nitrogen gas inlet tube Nitrogen gas was introduced into the four-necked flask provided, and the inside of the system was replaced with nitrogen gas. Then a mixture of 9-phosphabicyclo[3,3,1]nonane and 9-phosphabicyclo[4,2,1]nonane
377 g (1 mol) of a 37.7% toluene solution was charged into the four-necked flask. While maintaining a nitrogen atmosphere, 159 g (purity equivalent: 1.05 mol) of dimethyl maleate (a reagent with a purity of 95%) was added dropwise over 30 minutes to cause a reaction. With fever, the temperature rose to 57°C. Further, the reaction mixture was heated to 80°C and aged for 5 hours. The completion of the reaction was confirmed by gas chromatography analysis, where the peaks of 9-phosphabicyclo[3,3,1]nonane and 9-phosphabicyclo[4,2,1]nonane and dimethyl maleate disappeared, and the product 9
-(1,2-dialkoxycarbonyl)ethyl-
9-Phosphabicyclo[3,3,1]nonane and 9-(1,2-dimethoxycarbonyl)ethyl-
This was confirmed by the growth of the peak of 9-phosphabicyclo[4,2,1]nonane. Next, 93.5 g of 35% by weight hydrogen peroxide was added to this solution.
(equimol) was added dropwise over 1 hour for oxidation.
Since this oxidation treatment is a violently exothermic reaction, the temperature was kept below 70°C by water cooling. Completion of the reaction was confirmed by dropping a drop of the reaction solution onto carbon disulfide and seeing no red coloration due to trivalent phosphine. Although the reaction solution became suspended, it was separated into an aqueous layer and a toluene layer by stopping stirring. Transfer to a separating funnel and
-(1,2-dimethoxycarbonyl)ethyl-9
-oxo-9-phosphabicyclo[3,3,1]
Nonane and 9-(1,2-dimethoxycarbonyl)
The aqueous layer containing ethyl-9-oxo-9-phosphabicyclo[4,2,1]nonane was separated. On the other hand, since the toluene layer also contained a small amount of the product, it was extracted with water and combined with the aqueous layer. By distilling off water from this aqueous layer, 9-(1,2-dimethoxycarbonyl)ethyl-9-oxo-9-phosphabicyclo[3,3,1]nonane and 9-(1,
279 g of a yellow viscous liquid consisting of a mixture of 2-dimethoxycarbonyl)ethyl-9-oxo-9-phosphabicyclononane was obtained. This corresponds to a yield of 92.4% by weight based on the starting materials 9-phosphabicyclo[3,3,1]nonane and 9-phosphabicyclo[4,2,1]nonane. This viscous liquid was once dissolved in methanol, and then the methanol was distilled off, resulting in crystallization to obtain white crystals, the melting point of which was 60-75°C. However, it has strong deliquescent properties and could maintain its crystalline form only in dry air or nitrogen gas. GC-MAS
As a result of the analysis, it was confirmed that the molecular weight was 302, which matched the theoretical value. In addition, the results of elemental analysis are described below. Moreover, the infrared absorption spectrum is shown in FIG. Actual value (wt%) Calculated value (wt%) C 56.09 55.62 H 7.12 7.67 P 9.80 10.25 (Note) The calculated value is 9-(1,2-dimethoxycarbonyl)ethyl-9-oxo-9-phosphabicyclo[3,3 , 1] nonane and 9-(1,2
-dimethoxycarbonyl)ethyl-9-oxo-9-phosphabicyclo[4,2,1]nonane. Example 2 9-(1,2-dimethoxycarbonyl)ethyl-9-thioso-9-phosphabicyclo[3,
3,1]nonane and 9-(1,2-dimethoxycarbonyl)ethyl-9-thio-9-phosphabicyclo[4,2,1]nonane 9-(1,2-dimethoxycarbonyl) in the same manner as in Example 1 275 g (0.962 mol) of a mixture of ethyl-9-phosphabicyclo[3,3,1]nonane and 9-(1,2-dimethoxycarbonyl)ethyl-9-phosphabicyclo[4,2,1]nonane
A toluene solution containing . Next, 30.8 g (equivalent mole) of sulfur powder was added to this solution over 1 hour to cause a reaction. Since this reaction was also accompanied by heat generation like the oxidation reaction described above, the reaction temperature was kept below 70°C by water cooling. Thereafter, the reaction was aged by heating at 70°C for 1 hour. Completion of the reaction was confirmed by dropping a drop of the reaction solution onto carbon disulfide and seeing no red coloration due to trivalent phosphine. Toluene and low-boiling substances in the resulting reaction mixture were distilled off under reduced pressure to obtain 9-(1,2-dimethoxycarbonyl)ethyl-9-thio-9-phosphabicyclo[3,3,
1] 30.3 g of a yellow viscous liquid consisting of a mixture of nonane and 9-(1,2-dimethoxycarbonyl)ethyl-9-thio-9-phosphabicyclo[4,2,1]nonane was obtained. This is 95.3 for the starting materials 9-phosphabicyclo[3,3,1]nonane and 9-phosphabicyclo[4,2,1]nonane.
Corresponds to % by weight. As a result of GC-MAS analysis, it was confirmed that the molecular weight was 318, which matched the theoretical value. Further, the results of elemental analysis were as follows. The infrared absorption spectrum is shown in Figure 2. Actual value (weight%) Calculated value (weight%) C 53.40 52.83 H 7.01 7.28 P 9.33 9.73 S 9.72 10.07 (Note) Calculated value is 9-(1,2-dimethoxycarbonyl)ethyl-9-thio-9-phosphabicyclo[ 3,3,1]nonane and 9-(1,2-
dimethoxycarbonyl)ethyl-9-thio-9
-phosphabicyclo[4,2,1]nonane. [Effects of the Invention] The 9-phosphabicyclononane derivative according to the present invention is a new compound, and since it is difunctional, it is useful as a polymer monomer, a polymer crosslinking agent, or an agricultural chemical intermediate. . For example, as a reactive flame retardant for polymer compounds, this compound and polyhydric alcohol are polycondensed,
It can be used as a polyester compound to make fibers and resins with flame retardancy, and as a polymer crosslinking agent, it can be used as a crosslinking agent for polyvinyl alcohol, etc., and it can also be used by polycondensing this compound with polyvalent amines. Polyamide fibers and resins can be obtained by this process.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the infrared absorption spectrum of the 9-phosphabicyclononane derivative in Example 1, and FIG. 2 is a graph showing the infrared absorption spectrum of the 9-phosphabicyclononane derivative in Example 2. It is a diagram.

Claims (1)

[Claims] 1 General formula (1) [In the formula, R ₁ and R ₂ are H or a C ₁ to C ₄ alkyl group, but R ₁ and R ₂ are not both H, X is O or S, and two ... indicates that there are isomers having different positions of the C atom bonded to the P atom] 9-phosphabicyclononane derivative. 2 The compound represented by general formula (1) is 9-(1,2-
dialkoxycarbonyl)ethyl-9-oxo-
9-phosphabicyclo[3,3,1]nonane or 9-(1,2-dialkoxycarbonyl)ethyl-9-thio-9-phosphabicyclo[3,3,
1] 9 of Claim 1 which is nonane
- Phosphabicyclononane derivative. 3 The compound represented by general formula (1) is 9-(1,2-
dialkoxycarbonyl)ethyl-9-oxo-
9-phosphabicyclo[4,2,1]nonane or 9-(1,2-dialkoxycarbonyl)ethyl-9-thio-9-phosphabicyclo[4,2,
1] 9 of Claim 1 which is nonane
- Phosphabicyclononane derivative. 4 9-Phosphabicyclononane and general formula (2)
Unsaturated fat represented by R ₁ OOCCH=CHCOOR ₂ [wherein R ₁ and R ₂ are H or a C ₁ to _{C 4} alkyl group, but R ₁ and R ₂ are not both H] By reacting with group dicarboxylic acid ester, the general formula
(3) Obtain a compound represented by [wherein R ₁ and R ₂ have the same meanings as above, and the two ... represent isomers with different positions of the C atom bonded to the P atom], General formula (1), characterized in that the compound is then subjected to an oxidation or sulfurization reaction. [In the formula, R ₁ and R ₂ have the same meanings as above, X is O or S, and the two ... represent isomers with different positions of the C atom bonded to the P atom. ] A method for producing a 9-phosphabicyclononane derivative. 5. The method for producing a 9-phosphabicyclononane derivative according to claim 4, wherein the 9-phosphabicyclononane is 9-phosphabicyclo[3,3,1]nonane. 6. The method for producing a 9-phosphabicyclononane derivative according to claim 4, wherein the 9-phosphabicyclononane is 9-phosphabicyclo[4,2,1]nonane.