JPS59128358A - Novel allyl carbonate compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula (X is Cl, Br, I or 1-4C alkyl; m is 0 or 1-4; l is 1 or 2; k is 1 or 2). EXAMPLE:2,4,6-Tribromo-1-hydroxyethoxybenzene monoallyl carbonate. USE:It gives a polymer by heat, light, radiation, peroxide, etc., and is useful as an intermediate of resins (thermoplastic resin, thermosetting resin, etc.), and also as a plastic molded article, plastic intermediate, additive for plastic, paint, etc. Although it is a polymerizable compound, it has excellent storage stability. PROCESS:The compound of formula can be prepared by reacting allyl chloroformate with a hydroxyethoxybenzene derivative in the presence of a base such as pyridine, sodium hydroxide, etc. at 20-180 deg.C, preferably <=50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel allyl carbonate compound represented by the following general formula.

General formula (However, chlorine, bromine, iodine, or alkyl M having 1 to 4 carbon atoms, m is 0 or an integer of 1 to 4, 1 is an integer of 1 to 2, and k is an integer of 1 to 2.) The allyl carbonate compound of the general formula disclosed by the present invention is characterized in that it can be polymerized by heat, light, radiation, peroxide, etc., and becomes a useful polymer. Another feature of the compound of the present invention is that it has excellent storage stability despite being a polymerizable compound. Furthermore, the compounds of the present invention have unsaturated bonds, and by epoxidizing all of these bonds, all useful resin intermediates can be provided. Other features will become apparent from the description below.

Specific examples of the novel allyl carbonate compounds represented by the above general formula disclosed in the present invention include ruto, hydroxyethoxybenzene allyl carbonate, and 2,4-dichloro-hydroxyethoxybenzene allyl carbonate) 12
, 4.6 Triglomohytoxyethoxybenzene allyl carbonate, 4-methyl-hydroxyethoxybenzene allyl carbonate, 4-isopropyl-hydroxyethoxybenzene allyl carbonate, 2-t
ert-butyl-4-methyl-hydroxyethoxybenzene allyl carbonate.

2.6-dipromo 4-methyl-hydroxyethoxybenzeneallyl carbonate), 1,4-di(hydroxyethoxyethoxy)benzeneallyl carbonate, 4.6
Allyl carbonate compounds such as -di(tert-butyl)-i, a-di(hydroxyethoxy)benzene allyl carbonate, 1,3-di(hydroxyethoxy) benzene bis allyl carbonate, 6-ethyl-1,
3-di(hydroxyethoxy)benzene bisallyl carbonate, 5-methyl-1,3-di(hydroxy)benzene bisallyl carbonate, 2,5-dibromo-1,
4-Cy(hydroxyethoxy)benzene bisallyl carbonate 14.6-dibromo-1,3-di(hydroxyethoxy)benzene bisallyl carbonate), 1.3
Bisallyl carbonate compounds such as -(dihydroxyethoxyethoxy)benzenebisallyl carbonate and 2,5-dibromo-1,4-di(hydroxyethoxyethoxy)benzenebisallyl carbonate can be mentioned.

The allyl carbonate compound represented by the above general formula of the present invention can be produced by applying a known method. That is, an example of the production method is a method using allyl chloroformate and a hydroxyethoxybenzene derivative as raw materials.

Allyl chloroformate is published in the Journal of Chemi
calSociety, Vol. 125, pp. 26-27 (1
It can be synthesized by the method described in Japanese Patent Publication No. 42-7890, etc.

Further, the hydroxyethoxybenzene derivative 1d can be synthesized, for example, by the following methods (1) to (4).

(1) Method using a phenol derivative and ethylene carbonate (2) Method using a phenol derivative and ethylene carbonate (3) Method using a phenol conductor and a halide Br CH2CH20H Br -CH,CH20CH2CH20H (4) (1
Method for halogenating the hydroxyethoxybenzene substituted product synthesized by the methods (1) to (3) above.
In the synthesis method of 4), for (1), R, B,
Wagner, M.D., Zook, “Ely.
ntheticOrganic Chemlstry
” John Wiley & Bone.

■NG (1953), p. 229 and its cited references, (2) on page 233 of the same book and its cited references, (3) on page 226 of the same book and its cited references, (4) can be applied mutatis mutandis to the methods described in the same book, pages 88 to 110 and the cited documents.

In the method for total synthesis of an allyl carbonate compound from allyl chloroformate and a hydroxyethoxybene visiting conductor, an L1 basic compound such as pyridine,
Dimethylaniline.

Sodium hydroxide, potassium hydroxide, sodium/lium carbonate, potassium carbonate or, if necessary, calcium hydroxide,
The presence of magnesium hydroxide, barium hydroxide and other compounds capable of reacting with hydrochloric acid is desirable. dissolution of reactants,
Acetone, xylene for removal of reaction heat and other purposes.

Toluene, chloroform, tetrahydrone.

Mediums such as diethyl ether and water can be used alone or in combination of two or more yuzu.

The reaction can be carried out at a temperature in the range of 20°C to 180°C, but in order to prevent rapid reaction progress at the initial stage of the reaction, it is preferable to keep the temperature relatively low, that is, 50°C or less.

To show the specific procedure of the synthesis reaction, first, the hydroxyethoxyben fatty conductor is placed in a reaction vessel equipped with a jacket in which a heat medium circulates, and then, if necessary, the medium is added.

Further, the basic compound is added and stirred, and the heating medium outside the reaction container is adjusted so that the raw materials in the reaction container maintain a predetermined reaction temperature. Next, the aforementioned allyl chloroformate or the allyl chloroformate solution diluted with the aforementioned medium is gradually added into the reaction vessel. At this time, it is preferable to monitor the temperature inside the reaction vessel in order to avoid the occurrence of undesirable side reactions due to rapid progress of the reaction.

The above-mentioned allyl chloroformate and the basic compound have 1
, O-2,, o It is desirable to use the proof. If it is less than 1.0 equivalent, the reaction rate will be reduced and unreacted substances will remain, and if it exceeds 20 equivalents, undesirable side reaction products will be produced, so both are preferable. do not have.

By this method, J! ! ! The produced allyl carbonate compound of the present invention can be purified by a conventional method. That is, recrystallization, distillation, or an adsorption method using activated carbon, activated alumina, silica gel, etc. can be employed.

The allyl carbonate compound disclosed in the present invention usually has
It is a colorless or light-colored liquid or solid and can be mixed with many organic compounds. In addition, since it has at least 91 allyl groups per molecule, it can be combined into a single unit under appropriate conditions, such as irradiation with heat and/or light, radiation, and/or addition of a radical generator.

The polymer can take various forms depending on the degree of polymerization and the molecular structure of the allyl carbonate compound. That is, monoallyl carbonate compounds generally become viscous liquids or thermoplastic resins through polymerization. On the other hand, a bisallyl carbonate compound generally becomes a thermoplastic resin or an insoluble and infusible thermosetting resin. Furthermore, the allyl group can also be epoxidized with a suitable epoxidizing agent, such as peracetic acid. Such properties enable the allyl carbonate compound of the present invention to be used as a plastic molded article, a plastic intermediate, and an additive to plastics or paints.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, some parts in the examples indicate parts by weight.

Example 1 2,4.6-) 500 parts of ripromophenol, 150 parts of ethylene carbonate, 100 parts of toluene, and 25 parts of anhydrous potassium carbonate were mixed and kept at a temperature of 70°C for 8 hours, then the temperature ( The reaction was maintained at 5110°C for 12 hours with stirring, and after the reaction was completed, the reaction solution was allowed to cool to the room @, and the reaction solution was washed with water and distilled to produce 506 parts of (i-)ribromo l-hydroxyethoxybenzene. I got it.

400 parts of 2,4,6-dolipromo-1-hydroxyethoxybenzene was dissolved in 2,000 parts of tetrahydrofuric acid, 150 parts of pyridine was then added, and the temperature was cooled to 5° C. while stirring the entire solution.

In this state, a 30% toluene solution containing 200 parts of allyl chloroformate was added dropwise over 6 hours. After the dropwise addition was completed, the temperature of the reaction solution was returned to room temperature, and after stirring for 2 hours,
The humidity was raised to 60° C. over time and maintained at that temperature for 3 hours. After distilling off tetrahydrofuran and toluene from the reaction solution under reduced pressure, 500 parts of toluene was added to the residue again.
Insoluble matter was removed by 1' filtration, and the solution f was thoroughly washed with water and dried by adding anhydrous sodium sulfate. Finally, after all toluene was distilled off under reduced pressure, the entire residue was vacuum distilled at 0.05 mm HV to obtain 412 parts of a white solid product.

The melting point of the product is 50.1 °C, and the results of elemental analysis are 0%:==31.2, p%=Z7, Br%=51.9
Met. In addition, the 13C-IJMR spectrum showed the following resonance convergence position (ppm): 0 154.5 i17・5 134.8 70.5131.4
6 & 3 11 & 7 66.2 Furthermore, the mass spectrum showed a quality of parent ion peak values of number 456. From these facts, 2,4.6-tIJ
It was confirmed that the product was bromo-1-hydroxyethoxybenzene monoallyl carbonate, and the yield was 84 mol.

The infrared spectrum of this compound is shown in FIG.

9 [2.4.6-1-IJbromophe/-lumi in Example I The reaction was carried out in the same manner as in Example 1 except that the phenol derivatives listed in Table 1 were used to obtain product No. 1E. All results are shown in Table 1.

/ / Example 300 parts of resorcin and 880 parts of 2-bromoethanol were dissolved in 3000 parts of xylene, 1100 parts of 1ON-sodium hydroxide aqueous solution was gradually added dropwise at room temperature, and after one painting was completed, the mixture was heated to 90°C. The reaction was carried out for 8 hours to obtain 270 parts of 1,3-di(hydroxyethoxy)-benzene.

A complete reaction was carried out in the same manner as in Example 1 using 200 parts of 1,3-hydroxyethoxy)-benzene, 200 parts of pyridine and 260 parts of allyl chloroformate to obtain 187 parts of a solid product.

The elemental analysis value of the product is 0%-59,2, H%-5,96
The parent ion peak according to the mass spectrum had a quality cap number of 366.

In addition, the resonance absorption position (p
pm) was as follows, and it was found to be 1,3-di(hydroxyethoxy)benzene bisallyl carbonate. Yield: 51 mol.

159, 3 106.9 154.5 10.1.5 131.3 6 & 1 129, 6 65.8 118.4 65.3 Example Example 6 The resorcinol gold was used as the phenol derivative listed in Table 2. The reaction was carried out in the same manner as MiN6,
The product gold shown in Table 2 was obtained. The results are shown in Table 2.

Examples 10 to 11 The reaction was carried out in the same manner as in Example 6, except that 1,3-bis(hydroxyethoxy)benzene in Example 6 was replaced with the bishydroxyethoxy derivative in Table 3. The product obtained was gold. The results are shown in Table 3.

Example 12 22.5 parts of 4,6-di-t-butylresorcin and 33 parts of 2-chloroethyl-2-hydroxyethyl ether were dissolved in 100 parts of dimethylformamide, and while heating to 80°C, a 40% caustic soda solution was added. 30 parts were added dropwise and reacted for 2 hours with stirring. After the reaction was complete, the reaction solution was cooled to room temperature, the solid content was separated, and the p solution was heated to 130°C, and light boiling components such as the solvent were removed under reduced pressure. Distilled away. To the viscous substance thus obtained, 33 parts of 2-chloroethyl-2-hydroxyethyl ether and 100 parts of dimethylformamide were added, heated to 80°C, and 30 parts of a 40% caustic soda solution was added.
of the mixture was added dropwise, stirred, and reacted for 2 hours. After the reaction is completed, the reaction solution is cooled to room temperature, and the solid content 'kP' is divided into 1 part.
The mixture was heated to 30°C and light boiling components were distilled off again under reduced pressure. 100 parts of the obtained viscous material ttetrahydrofuran and 50 parts of toluene
36 parts of allyl chloroformate were added thereto, and 30 parts of a 40% caustic soda solution was added dropwise while maintaining the temperature at 5 to 10°C, followed by reaction for 3 hours. After the reaction is complete,
After washing with water, the obtained +5A layer was further treated with 1% caustic soda,
The sample was washed with water, 1% hydrochloric acid, and water, dehydrated with magnesium sulfate, and purified by adsorption with 10 parts of activated carbon. This solution was further heated to 130°C and after removing light boiling components under reduced pressure, n
- Dissolved in heptane 502, cooled to -78°C, collected the precipitated solid, and after repeating this deep cooling precipitation with n-heptane, the collected solid was completely dried to 14.8 parts. A product consisting of a viscous solid was obtained.

The parent ion peak of the product was determined to be 566, and the C-NMR spectrum showed the following resonance absorption (I)1)i
n) held a meeting.

155.7 98.6 34.1
154.5 69.6 29.8
131.4 68.5 128.7 67.8 124.3 67.0 118.1 66.6 From the above results, the product was found to be a compound of the following formula0

[Brief explanation of the drawing]

FIG. 1 is an infrared spectrum of the uninvented allyl carbonate produced according to Example 1. Substitute press l, inside 1 [1 light

Claims (2)

[Claims] (1) General formula (wherein, An allyl carbonate compound represented by (2) The allyl carbonate compound according to claim 1, wherein in the general formula, 1 is 1.