Preparation method of acrylic ester compound

Abstract

The present disclosure relates to a preparation method of an acrylic ester compound. The preparation method of an acrylic ester compound according to the present disclosure enables the use of acrylic anhydride as a reactant instead of acryloyl chloride, which is difficult to handle, by using an alkane diamine as a catalyst. Therefore, not only can the reaction be carried out at a low temperature, but also conversion to an acrylic ester compound and a yield of the acrylic ester compound can be improved.

Claims

1. A preparation method of an acrylic ester compound represented by the following Chemical Formula 4, comprising a step of reacting a compound represented by the following Chemical Formula 1 with a compound represented by the following Chemical Formula 2 in the presence of a catalyst represented by the following Chemical Formula 3: ##STR00013## wherein, in Chemical Formula 1, R.sub.1 is a substituted or unsubstituted C.sub.1-30 alkylene, a substituted or unsubstituted C.sub.2-30 alkenylene, or a substituted or unsubstituted C.sub.2-30 alkynylene, and R.sub.2 and R.sub.3 are each independently hydrogen or a C.sub.1-20 alkyl, ##STR00014## wherein, in Chemical Formula 2, R.sub.4 and R.sub.5 are each independently hydrogen or a methyl, ##STR00015## wherein, in Chemical Formula 3, R.sub.6 to R.sub.9 are each independently hydrogen or a substituted or unsubstituted C.sub.1-10 alkyl, and R.sub.10 is a substituted or unsubstituted C.sub.1-10 alkylene, ##STR00016## wherein, in Chemical Formula 4, R.sub.1 to R.sub.5 are as defined above.

2. The preparation method of claim 1, wherein the R.sub.1 is a substituted or unsubstituted C.sub.1-10 alkylene, a substituted or unsubstituted C.sub.2-10 alkenylene, or a substituted or unsubstituted C.sub.2-10 alkynylene.

3. The preparation method of claim 1, wherein the R.sub.2 and R.sub.3 are each independently a C.sub.1-5 alkyl.

4. The preparation method of claim 3, wherein the R.sub.2 and R.sub.3 are methyl.

5. The preparation method of claim 1, wherein the R.sub.4 and R.sub.5 are hydrogen.

6. The preparation method of claim 1, wherein the R.sub.6 to R.sub.9 are each independently a substituted or unsubstituted C.sub.1-10 alkyl.

7. The preparation method of claim 1, wherein the R.sub.6 and R.sub.7 are methyl, and R.sub.8 and R.sub.9 are hydrogen or methyl.

8. The preparation method of claim 1, wherein the R.sub.10 is a substituted or unsubstituted C.sub.1-5 alkylene.

9. The preparation method of claim 8, wherein the R.sub.10 is ethylene.

10. The preparation method of claim 1, wherein Chemical Formula 1 is any one of the following Chemical Formulae 1-1 to 1-4: ##STR00017##

11. The preparation method of claim 1, wherein the compound represented by Chemical Formula 2 is acrylic anhydride.

12. The preparation method of claim 1, wherein the catalyst represented by Chemical Formula 3 is N,N,N′,N′-tetramethylethylenediamine or N,N-dimethylethane-1,2-diamine.

13. The preparation method of claim 1, wherein the reaction is carried out at a temperature of 30° C. to 80° C.

14. The preparation method of claim 1, wherein conversion of the reaction is 90 to 99.9% and a yield of the reaction is 70 to 95% a.

15. The preparation method of claim 1, wherein the R.sub.1 is any one selected from the group consisting of 2-methyl-1-pentenylene, 3,3-dimethyl-1-propynylene, propylene, and methyl ethylene.

16. The preparation method of claim 1, wherein 2.1 to 3.5 equivalents of the compound represented by Chemical Formula 2 and 0.05 to 0.5 equivalents of the compound represented by Chemical Formula 3 are reacted based on 1 equivalent of the compound represented by Chemical Formula 1.

17. The preparation method of claim 1, wherein the step of reacting the compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 2 is carried out from 4 hours to 24 hours.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Hereinafter, the present invention will be explained in detail with reference to the following examples. However, these examples are only to illustrate the invention, and the scope of the invention is not limited thereto.

Example 1

(2) ##STR00006##

(3) 3,7-dimethyl-2-octene-1,7-diol (30.0 g, 174 mmol), N,N,N′,N′-tetramethylethylenediamine (6.07 g, 52.2 mmol, 0.30 eq.), and acrylic anhydride (65.89 g, 522.4 mmol, 3.0 eq.) were placed in a 250 mL round-bottom flask, and reacted at 60° C. for 12 hours or more. Thereafter, it was filtered using a celite pad with 300 mL of n-hexane, and concentrated to obtain a product DA 1 (39.1 g, yield 80%).

(4) .sup.1H NMR (500 MHz, CDCl.sub.3): δ 6.39-6.02 (m, 2H), 6.01-5.80 (m, 2H), 5.75-5.72 (m, 2H), 5.44-5.37 (m, 2H), 4.69-4.65 (m, 2H), 2.15-2.03 (m, 2H), 1.77-1.23 (m, 13H).

Example 2

(5) ##STR00007##

(6) 2,5-dimethyl-3-hexyne-2,5-diol (30.0 g, 210.9 mmol), N,N,N′,N′-tetramethylethylenediamine (7.36 g, 63.3 mmol, 0.30 eq.), and acrylic anhydride (79.82 g, 632.9 mmol, 3.0 eq.) were placed in a 250 mL round-bottom flask, and reacted at 60° C. for 12 hours or more. Thereafter, it was filtered using a celite pad with 300 mL of n-hexane, and concentrated to obtain a product DA 2 (43.8 g, yield 83%).

(7) .sup.1H NMR (500 MHz, CDCl.sub.3): δ 6.34 (dd, 2H), 6.06 (dd, 2H), 5.76 (dd, 2H), 1.68 (s, 12H).

Example 3

(8) ##STR00008##

(9) 4-methylpentane-1,4-diol (20.0 g, 169 mmol), N,N,N′,N′-tetramethylethylenediamine (5.9 g, 50.8 mmol, 0.30 eq.), and acrylic anhydride (64.03 g, 508 mmol, 3.0 eq.) were placed in a 250 mL round-bottom flask, and reacted at 60° C. for 12 hours or more. Thereafter, it was filtered using a celite pad with 200 mL of n-hexane, and concentrated to obtain a product DA 3 (32.9 g, yield 86%).

(10) .sup.1H NMR (500 MHz, CDCl.sub.3): δ 6.43 (1H, dd), 6.32 (2H, dd), 6.13 (1H, dd), 6.04 (1H, dd), 5.84 (1H, dd), 5.77 (1H, dd), 4.17 (2H, t), 1.88 (2H, m), 1.75 (2H, m), 1.50 (6H, s).

Example 4

(11) ##STR00009##

(12) 2-methylpentane-2,4-diol (20.0 g, 169 mmol), N,N,N′,N′-tetramethylethylenediamine (5.9 g, 50.8 mmol, 0.30 eq.), and acrylic anhydride (64.03 g, 508 mmol, 3.0 eq.) were placed in a 250 mL round-bottom flask, and reacted at 60° C. for 12 hours or more. Thereafter, it was filtered using a celite pad with 200 mL of n-hexane, and concentrated to obtain a product DA 4 (31.8 g, yield 83%).

(13) .sup.1H NMR (500 MHz, CDCl.sub.3): δ 6.38 (1H, dd), 6.31 (1H, dd), 6.08 (1H, dd), 6.01 (1H, dd), 5.25 (1H, m), 1.57 (3H, s), 1.51 (6H, s), 1.28 (2H, d).

Example 5

(14) ##STR00010##

(15) 2-methylpentane-2,4-diol (20.0 g, 169 mmol), N,N-dimethylethane-1,2-diamine (4.5 g, 50.8 mmol, 0.30 eq.), and acrylic anhydride (64.03 g, 508 mmol, 3.0 eq.) were placed in a 250 mL round-bottom flask, and reacted at 60° C. for 12 hours or more. Thereafter, it was filtered using a celite pad with 200 mL of n-hexane, and concentrated to obtain a product DA 4 (31.8 g, yield 79%).

(16) .sup.1H NMR (500 MHz, CDCl.sub.3): δ 6.38 (1H, dd), 6.31 (1H, dd), 6.08 (1H, dd), 6.01 (1H, dd), 5.25 (1H, m), 1.57 (3H, s), 1.51 (6H, s), 1.28 (2H, d).

Comparative Example 1

(17) ##STR00011##

(18) 2-methylpentane-2,4-diol (20.0 g, 169 mmol), methylene chloride (120 mL), triethylamine (51.38 g, 508 mmol, 3.0 eq.), and and 4-dimethylaminopyridine (2.07 g, 16.92 mmol, 0.1 eq.) were placed in a 250 mL round-bottom flask, and a solution of acryloyl chloride (45.95 g, 507.7 mmol, 3.0 eq.) and methylene chloride (50 mL) was slowly added thereto at 0° C. for 2 hours. Thereafter, they reacted at 0° C. for 1 hour, and the temperature was gradually raised to room temperature, followed by reacting for 12 hours. Then, methylene chloride, which is a solvent, was removed under reduced pressure, diluted with 200 mL of n-hexane and washed twice with 200 mL of water. Magnesium sulfate was added to the n-hexane solution to remove water, and the mixture was filtered using a celite pad and then concentrated to obtain a mixture of DA 4 and A 1.

Comparative Example 2

(19) ##STR00012##

(20) 2-methylpentane-2,4-diol (20.0 g, 169 mmol), toluene (170 mL), triethylamine (51.38 g, 508 mmol, 3.0 eq.), and 4-dimethylaminopyridine (2.07 g, 16.92 mmol, 0.1 eq.) were placed in a 250 mL round-bottom flask, and acrylic anhydride (64.03 g, 507.7 mmol, 3.0 eq.) was slowly added thereto at 110° C. for 2 hours. Thereafter, they reacted at 110° C. for 12 hours. Then, toluene, which is a solvent, was removed under reduced pressure, diluted with 200 mL of n-hexane, and washed twice with 200 mL of water. Magnesium sulfate was added to the n-hexane solution to remove water, and the mixture was filtered using a celite pad and then concentrated to obtain a mixture of DA 4 and A 1.

(21) Experimental Example

(22) The conversion and yield were calculated according to the following Formulae 1 and 2 for the above examples and comparative examples, respectively, and the results are shown in Table 1 below.
Conversion (%)=[(the number of moles of acrylic ester prepared before extraction)/(the number of moles of Chemical Formula 1 provided)]*100  [Formula 1]
Yield (%)=[(the number of moles of acrylic ester prepared after extraction)/(the number of moles of Chemical Formula 1 provided)]*100  [Formula 2]

(23) TABLE-US-00001 TABLE 1 Con- Yield version Ratio of to DA of DA Reactant Catalyst (%) DA:A (%) Ex.1 Acrylic N,N,N′,N′- 98 98:2  80 anhydride tetramethylethyl- enediamine Ex.2 Acrylic N,N,N′,N′- 99 99:1  83 anhydride tetramethylethyl- enediamine Ex.3 Acrylic N,N,N′,N′- 99 99:1  86 anhydride tetramethylethyl- enediamine Ex.4 Acrylic N,N,N′,N′- 98 98:2  83 anhydride tetramethylethyl- enediamine Ex.5 Acrylic N,N- 95 98:2  79 anhydride dimethylethane- 1,2-diamine Comp.Ex.1 Acryloyl NEt.sub.3, DMAP 85 86:14 62 chloride Comp.Ex.2 Acrylic NEt.sub.3, DMAP 80 80:20 52 anhydride

(24) Referring to Table 1, Examples 1 to 5 using N,N,N′,N′-tetramethylethylenediamine or N,N-dimethylethane-1,2-diamine as a catalyst had a conversion to acrylic ester of 95% or more and a yield of acrylic ester of 79% or more, which are superior to the comparative examples using NEt.sub.3 and DMAP as a catalyst.

(25) Further, it was confirmed that all of Examples 1 to 5 had excellent conversion and yield as shown in Table 1 even though the reaction proceeded at a temperature of 60° C., which is significantly lower than the esterification temperature of acrylic anhydride (110° C.) of Comparative Example 2.