JPS6150944A - Novel brominated phthalic acid allyl ester - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R1 is H, or CH3; R2 is (meth)acryloyl, or allyloxycarbonyl]. EXAMPLE:3,4,5,6-Tetrabromophthalic acid allyl, 2-acryloyloxyethyl ester. USE:A raw material for producing an optical plastic having high refractive index useful as a material for lens, prism, optical wave guide, and various optical elements. Since the titled compound is colorless liquid or low-melting compounds, it is conveniently cast into a mold or blended with a copolymerizing agent. Since its polymerization can be started from a low temperature, no strain is left in a polymer product. PREPARATION:A compound shown by the formula II is reacted with a compound shown by the formula III to give a compound shown by the formula IV, which is neutralized with an alkali shown by the formula MOH (M is Li, Na, K, or NH4) to give a compound shown by the formula V. Then, a compound shown by the formula VI is reacted with a compound shown by the formula VII in the presence of an amine to give a compound shown by the formula VIII, which is reacted with a compound shown by the formula V to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to novel brominated phthalic acid allyl ester compounds.

[Prior art]

Traditionally, plastic lenses have been made with Y
It is widely used in optical products due to its characteristics.

And, the paulownia wood of such a plastic lens is,
Polymethyl methacrylate, polycarbonate or diethylene glycol bisallyl carbonate (CR-3
91 etc. are commonly used.

However, poly, which is a linear polymer and thermoplastic resin,
Methyl methacrylate and polycarboyte are excellent in terms of mass production, but they have the disadvantage of being inferior to glass in terms of cutting and molding processability.

CR-39, which is a network polymer, also has a refractive index of 1.49.
Since it is relatively low at ~1.50, when used as a lens, there was a problem that the center p) and edge thickness tended to be large.

Therefore, the researchers focused on diallyl phthalate resin, which has excellent dimensional stability, and in order to increase the refractive index of the polymer,
The benzene ring of this monomer, diallyl phthalate, was replaced with bromine, and in order to lower the melting point of the monomer and improve the operability of polymerization, an easily mobile ethylene glycol chain was introduced, and asymmetric mixed esterification was performed to create a new compound. The present invention was completed by synthesizing a certain brominated heptatarate compound.

[Purpose of the invention]

An object of the present invention is to provide novel brominated phthalic acid allyl ester compounds.

[Structure of the invention]

The novel brominated phthalic acid allyl ester compound of the present invention that achieves the above object is represented by the following general formula.

However, in the formula, R3 is a hydrogen atom or a methyl group, and R
2 is an acryloyl group, a methacryloyl group, or an allyloxycarbonyl group.

Examples of the 101-order brominated phthalic acid allyl ester compound of the present invention include those shown by the following compound numbers.

m 3 , 4 , 5 , allyl 6-titrapromophthalate, 2-acryloyloxyethyl ester (2) 3
, 4 , 5 , allyl 6-titrapromophthalate, 2
-methacryloyloxyethyl ester (3) 3,
4,5,6-titrapromophthalic acid allyl, 2-allyluoxine-proponyloxyethyl ester (4) 3,4,5,6-titrapromophthalic acid 2-methyl-2-propenyl, 2-acryloyloxyethyl ester (5-3 r 4 + 5 + 6-titrabromo7tal 2-methyl-2-7'ropenyl, 2-methacryloquine ethyl ester (61 3,4,5,6-titrabromo7
2-methyl-2-7” lobenyl tarrate, 2-7
The novel brominated phthalic acid allyl ester compound of the present invention is prepared from 1- as shown in the following reaction formula.

That is, commercially available 3,4,5,6-titrabromo7tal f('l anhydride (fiJ) was reacted with R1-substituted allyl alcohol (B) to prepare tetrabromophthalic acid R, substituted allyl-7 ester (0 Manufacture.

(A) (B) ■ Here, in (13) and (C), R is a hydrogen atom or methyl! I (is.

Since the reaction in which Hafester (O is further esterified to form a diester) is slow, Hafester (0) can be obtained in high yield.

Next, it is neutralized with Hafestel (C) t-alka IJMOH to convert it into ester salt (■).

However, in MOH and ester salt 0, M is Lr
+ Na l K or NH4, preferably K
It is.

On the other hand, acrylic acid chloride (E-1), methacrylic acid chloride (E-2), or allyl chloride formate (E
-3) and ethylene promohydrin in the presence of an amine as a dehydrochlorination agent to produce the corresponding bromine-terminated esters (F-1, F-2, F-3).

(E-3) (F-3) As the dehydrochlorination agent, triethylamine, pyridine, or the like is used.

Bromine-terminated esters (F-1,
When F-2, F-3) is reacted with the Hafester salt (1), the novel asymmetric brominated phthalic acid allyl ester compound (G) of the present invention is produced.

In addition, in (G), R1 is as described above, and R2
Is it an acryloyl group, a methacryloyl group, or an ali? It is a leoxycarbonyl group.

Hafester salt ■ and bromine-terminated esters (F-1, F
-2, F-3) A polar aprotic solvent such as dimethyl sulfoxide is preferably used as the reaction solvent.

Although the novel brominated phthalic allyl ester of the present invention has four bromine atoms, it is a colorless liquid at a rich temperature and a low melting point. It is convenient to inject into a mold or mix with a copolymerizing agent, and since the polymerization can be carried out at a low temperature from 1.ri to 11 filtration, there is no distortion in the polymer product. There are no advantages.

Moreover, such polymers are colorless and transparent, and 1.59~],
It has a high refractive index of , 61 and a pencil hardness of about 4H.

Accordingly, the novel brominated allyl phthalate compound's proboscis of the present invention can be used for lenses, prisms, optical waveguides, fr
Optical high refractive index 1noi' useful as material for lΦ optical elements
4< Suitable as a raw material for the production of plastics 4ruru 1, In addition, ・l,: Qing's brominated phthalic acid allyl ester f 71'13 of the proboscis! I! Polymerization or copolymerization with a copolymerization agent is carried out using a radical polymerization initiator, such as benzene-metallic acid, etc. esters,
Acrylic esters such as acrylic acid and allyl esters such as diallyl phthalate are used.

〔Effect of the invention〕

As described above, the bromine f-hyphthalate allyl ester compounds according to the present invention are all new compounds, and as described below, elemental analysis, custom-made infrared absorption, and NMR fl
(It can be identified from the constant value of
Easily produces colorless and transparent homopolymers or copolymers with acrylic esters, methacrylic esters, etc.

Such polymers have a high refractive index and are useful as optical plastic materials.

Examples of the present invention will be described below.

[Example 1] Example I Production of compound (1) A compound of compound number (1) was produced according to the method shown in the reaction formula below.

3r prisoner (B) (D, R12H) CH2=CI-I COCl+Br CH2-CI(!
0I-I-(E-1,) CI-I2=CH-CO-CH, -CH2-Br(['
-1) (D I R-2H) + (F-1) That is, 30 g (64,7811 mol) of 3,4,5.6-titrabromophthalic anhydride was added to allyl alcohol (B, R1= H) Add in 130m1 ;j′j,
The mixture was heated to 80°C without stirring to gradually dissolve the mixture. After dissolution.

After another 2 hours at 80°C, cool to 60°C and add KOH4,5? (68.8 mmol) was added to neutralize and cooled.

After that, stirring was continued for 2 hours at 60°C, excess allyl alcohol was distilled off under reduced pressure, and the residue was washed with a small amount of ethanol and dried to produce 3,4°5.6-titrabromophthalate. Potassium acid, 2-propenyl (D, R, =H
) 33.47 (59.6 mmol) was obtained. Yield 87
It was Chi.

This item has I/L, 1 point above 250°C, and IR
at 1710 Cm-' (Ester W: i Calpol)
+ It showed the characteristic absorption of 1605Crn' (salt type carbonyl).

Next, this (L, compound (F-1) to be reacted with compound 0)
Manufactured.

The acrylic acid chloride (E-1) used in this production was obtained by distilling a commercially available product according to 1) II, and the ethylene bromohydrin and triethylamine (dehydrochlorination agent) were
Commercially available products were each used after drying and distillation.

30 units equipped with a temperature variable meter, 1 drip condenser, and a stirrer.
In a 0me four-hole flask, add 715 ml of the above ethylene bromohydride (120 mmol) and 715 ml of triethylamine.
! / (149 mmol) total dry benzene 100 mJ
Dissolve 1'l'r in water and set aside.

While keeping the temperature below 8° C., a ζ solution of 13.4 r of acrylic L1 chloride dissolved in 50 ml of dry benzene was added dropwise from the dropping funnel over a period of about 1 hour.

After the addition was completed, the mixture was left as it was for 1 hour, and then stirring was continued with α7 product for 4 to 5 hours.

After separating the resulting precipitate of triethylamine hydrochloride with F, the precipitate was washed with 100 ml of benzene, the mother liquor and the washing liquid were combined, and this was washed three times with 100 ml of 0.5 N aqueous hydrochloric acid solution, followed by 0.
5N potassium hydroxide aqueous solution 100+nl.

Plus 100mI of pure water! After washing twice with K and drying with anhydrous magnesium sulfate.

This benzene solution was concentrated, the concentrated liquid was distilled under reduced pressure, and 2
14. of 2-bromoethyl acrylate (F-1) at mmHg, 25°C. El (yield 69%) was obtained.

Next, 11 of the previously synthesized potassium 3,4,5.6-titrabromo heptatarate, 2-propenyl (D, R, = H).
29 (20 mmol) and 2-bromoethyl acrylate (F-1) 3.7 y (21 mmol) were added to a flask containing 100 mi of DMSO dried with molecular sieves at 40-50°C for 12 hours.

When heated and stirred, Compound 0 dissolved to become a bright yellow transparent liquid.

This clear liquid was added to 500 ml of 0.5N hydrochloric acid solution overnight, and then 150 ml of 0.5N hydrochloric acid solution was added overnight. The mixture was extracted with ether three times.

Combine the ether extracts and add 0.5N caustic potassium water/8
After extracting once with 1Q Cuti powder to remove components soluble in alkaline solution, the ether solution was further washed with water, then dried over anhydrous magnesium sulfate, and the ether was distilled off.

The remaining oily substance was purified by silica gel column chromatography for minute #1 to obtain compound (1) in a yield of 40%.

This compound (1) was a colorless and transparent liquid.

Elemental analysis and spectral data are shown in Table 1.

(Margins below this page) C Example 2 Production of Compound (2) and Compound (3) Compound (D, R, =) obtained in Example 1.

Compound (2) was produced by reacting H) with 2-bromoethyl methacrylate (F-2).

(D. 2) 21.57 (238 mmol) was added to triethylamine 25?(2
It was produced by reacting in the same manner as in Example 1 in the presence of 48F (17 mol).

CH2= C-COCl + BrCH2CH20H-
→g) 1° (E-2) The yield of compound (F-2) was 29.3f, and the yield was 76%.

Next, 14.5 P (25
, 8 mmol) and 2-bromoethyl methacrylate (
Example 1 6.29 (32.1 mmol) of F-2)
Compound (2) was obtained in a yield of 68% by reacting in the same manner as above.

The properties of this compound (2) are shown in Table 1.

Similarly, ethylene bromohydrin 19.3F (15
4#remol) and allyl chloride formate (E-3) 21.4
P (178 mmol) and hylysine 15.2 f (
Allyl 2-bromoethyloxyformate (F-3) was obtained. Yield 23.
2F, yield was 72%.

CH2=CHCH20-CCl + Br-CH2=H
t OH→(E-31 CH2=CH-CH, -0-C-OCH2-CH2-B
r(F-3) 10 F (47,8S9 mol) of this compound (F-3) and 21 ? of compound 0? (37,5811 mol) was reacted to obtain compound (3) in a yield of 7.7 f and a yield of 32 g.

The physical properties are shown in Table 1.

(F-3) Compound (3) Example 3 Production of compounds (4), (5) and (6) 3.4, 5.
6-titrapromo7talic anhydride (4) 40 t (8
6 mmol), methallyl alcohol (B) 200 ml
, and KOH69 (107 mmol).
= CH3) of 44.29. (77 mmol) was obtained. The yield was 89%.

Br Br (A) (B) This compound (D, R, diCH3) was added with the compound (F-1) obtained in Example 1, the compound (F-2) obtained in Example 2, or (F-3) was reacted in the same manner as in Example 1 in the amounts shown in Table 2 below to form compound (4).
, (5) and (6) were produced. These compounds (・I
), 1! ”)) and (6) are shown in Table 1.

(D, R, 2CH31 (F'-3)' Compound (6)

Claims (1)

[Claims] A novel brominated phthalic acid allyl ester compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, in the formula, R_1 is a hydrogen atom or a methyl group,
R_2 is an acryloyl group, a methacryloyl group, or an allyloxycarbonyl group.