ALPHA, BETA-UNSATURATED ALDEHYDE PRODUCTION METHOD

Abstract

A method for producing an α,β-unsaturated aldehyde, including reacting a compound represented by formula (I) with a compound represented by formula (II) in the presence or absence of a solvent to provide a compound represented by formula (III), wherein titanium oxide is used as a catalyst, and an amount of the solvent is 50 parts by mass or less relative to 100 parts by mass in total of the compound of formula (I) and the compound of formula (II),

##STR00001##

Claims

1. A method for producing an α,β-unsaturated aldehyde, comprising reacting a compound represented by formula (I) with a compound represented by formula (II) in the presence or absence of a solvent to provide a compound represented by formula (III), wherein titanium oxide is used as a catalyst, and an amount of the solvent is 50 parts by mass or less relative to 100 parts by mass in total of the compound of formula (I) and the compound of formula (II), ##STR00010## where R.sup.1 represents a hydrogen atom or an alkyl group having 1 or more and 10 or less of carbon atoms, R.sup.2 represents a hydrogen atom, an alkyl group having 1 or more and 6 or less of carbon atoms, or an alkoxy group having 1 or more and 6 or less of carbon atoms, and R.sup.3 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less of carbon atoms, or R.sup.2 and R.sup.3 form 1,3-dioxolane together with carbon atoms to which R.sup.2 and R.sup.3 are attached, and R.sup.4, R.sup.5, and R.sup.6 each independently represent a hydrogen atom or an alkyl group having 1 or more and 3 or less of carbon atoms.

2. The method according to claim 1, wherein the amount of the solvent is 0 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass in total of the compound of formula (I) and the compound of formula (II).

3. The method according to claim 1, wherein the amount of the solvent is 0 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass in total of the compound of formula (I) and the compound of formula (II).

4. The method according to claim 1, wherein an amount of the compound represented by formula (II) is 0.8 molar equivalents or more and 15 molar equivalents or less relative to the compound represented by formula (I).

5. The method according to claim 1, wherein R.sup.1 is an alkyl group having 3 or more and 8 or less of carbon atoms.

6. The method according to claim 1, wherein R.sup.2 represents a hydrogen atom or an alkyl group having 1 or more and 6 or less of carbon atoms, and R.sup.3 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less of carbon atoms.

7. The method according to claim 1, wherein the compound represented by formula (II) is a compound represented by any of the following formulae ##STR00011##

8. The method according to claim 1, wherein the titanium oxide comprises an anatase-type titanium oxide.

9. The method according to claim 1, wherein the titanium oxide has a crystallite diameter of 80 Å or more and 500 Å or less.

10. The method according to claim 1, wherein the titanium oxide has a crystallite diameter of 100 Å or more and 400 Å or less.

11. The method according to claim 1, wherein the titanium oxide is present in an amount of 1 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound of formula (I).

12. The method according to claim 1, wherein the titanium oxide present in an amount of 2 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the compound of formula (I).

13. The method according to claim 1, wherein the reacting is performed at 20° C. or higher and 200° C. or lower.

14. The method according to claim 1, wherein the compound represented by formula (I) is octanal, the compound represented by formula (II) is benzaldehyde, and the compound represented by formula (III) is hexyl cinnamic aldehyde.

15. The method according to claim 1, wherein an amount of the compound represented by formula (II) is 1.2 molar equivalents or more and 7 molar equivalents or less relative to the compound represented by formula (I).

16. The method according to claim 1, wherein R.sup.2 represents a hydrogen atom or an alkyl group having 1 or more and 6 or less of carbon atoms, and R.sup.3 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less of carbon atoms.

17. The method according to claim 1, wherein the titanium oxide has a crystallite diameter of 120 Å or more and 300 Å or less.

18. The method according to claim 1, wherein the solvent contains a hydrocarbon solvent.

19. The method according to claim 1, wherein the solvent contains an aromatic hydrocarbon solvent.

20. The method according to claim 1, wherein the reacting is performed at 50° C. or higher and 160° C. or lower.

Description

EXAMPLES

[0094] In the following examples and comparative examples, the term “%” means “% by mass” unless otherwise specified.

[0095] The materials used in the reaction were as follows:

[0096] benzaldehyde: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade;

[0097] octanal: manufactured by Kao Corporation;

[0098] toluene: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade;

[0099] tetradecane: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade; and

[0100] diethyl ether: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade.

Example 1

Production of Hexyl Cinnamic Aldehyde (formula (III-1))

[0101] ##STR00009##

[0102] In a reaction tube 34 mm in inner diameter equipped with a condenser, the following were placed: titanium oxide as a catalyst (SSP-M, an anatase-type titanium oxide manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., in accordance with a sulfuric acid method (liquid phase method), 0.19 g, 10% by mass relative to octanal, 10 parts by weight relative to 100 parts by mass of the compound of formula (I)); octanal (formula (I-1), 1.9 g, 15.0 mmol); benzaldehyde (formula (II-1), 8.0 g, 75.0 mmol, 5 molar equivalents relative to octanal); and tetradecane (GC internal standard, 0.2 g). The inside of the reaction tube was replaced with nitrogen, and the liquid mixture in the reaction tube was stirred for 4 hours at 150° C. Then, the reaction tube was cooled to 30° C. to finish the reaction.

[0103] Using gas chromatography (GC), a quantitative analysis of the filtered reaction product was performed by an internal standard method to determine the composition for each component of the reaction product. The results of the reaction were calculated by the following formulae based on the composition of the reaction product thus obtained. The internal standard substance was tetradecane, and the solvent was diethyl ether. Table 2 below shows the calculated yield of hexyl cinnamic aldehyde (relative to octanal), selectivity of hexyl cinnamic aldehyde (relative to benzaldehyde), and HCA-to-dimer formation ratio.

[0104] Specifically, 0.2 mL of the reaction solution was sampled, put in a screw bottle, and precisely weighed. To dilute the reaction solution, 4 mL of diethyl ether was added thereto. The solution was filtered with a membrane filter (polytetrafluoroethylene (PTFE), 0.2 μm) to remove the catalyst, and the filtrate thus obtained was analyzed by GC.

[0105] The GC analysis used both DB-1 column (GC column, 100% dimethylpolysiloxane manufactured by Agilent Technologies Japan, Ltd.) and DB-WAX column (GC column, polyethylene glycol manufactured by Agilent Technologies Japan, Ltd.).

Yield of Hexyl Cinnamic Aldehyde (Relative to Octanal)

[0106] The yield of the target hexyl cinnamic aldehyde (relative to octanal) was calculated by the following formula. A larger value indicates better yield.

[00001]$\begin{array}{cc}\mathrm{Yield}\mathrm{of}\mathrm{hexyl}\mathrm{cinnamic}\mathrm{aldehyde}\left(\mathrm{relative}\mathrm{to}\mathrm{octanal}\right)\left[\%\right]=& \left[\mathrm{Formula}1\right]\end{array}$$\frac{\left[\frac{\begin{array}{c}[\mathrm{Mass}\mathrm{of}\mathrm{hexyl}\\ \mathrm{cinnamic}\mathrm{aldehyde}\mathrm{in}\mathrm{product}]\end{array}}{\begin{array}{c}[\mathrm{Molecular}\mathrm{weight}\\ \mathrm{of}\mathrm{hexyl}\mathrm{cinnamic}\mathrm{aldehyde}]\end{array}}\right]}{\left[\frac{\left[\mathrm{Mass}\mathrm{of}\mathrm{charged}\mathrm{octanal}\right]}{\left[\mathrm{Molecular}\mathrm{weight}\mathrm{of}\mathrm{octanal}\right]}\right]}\times 100$

Selectivity of Hexyl Cinnamic Aldehyde (Relative to Benzaldehyde)

[0107] The selectivity of the hexyl cinnamic aldehyde (relative to benzaldehyde), which is a measure of the disproportionation of aldehydes, was calculated by the following formula. A larger value indicates better selectivity.

[00002]$\begin{array}{cc}\mathrm{Selectivity}\mathrm{of}\mathrm{hexyl}\mathrm{cinnamic}\mathrm{aldehyde}\left(\mathrm{relative}\mathrm{to}\mathrm{benzaldehyde}\right)\left[\%\right]=\frac{\left[\frac{\begin{array}{c}[\mathrm{Mass}\mathrm{of}\mathrm{hexyl}\\ \mathrm{cinnamic}\mathrm{aldehyde}\\ \mathrm{in}\mathrm{product}]\end{array}}{\begin{array}{c}[\mathrm{Molecular}\mathrm{weight}\\ \mathrm{of}\mathrm{hexyl}\\ \mathrm{cinnamic}\mathrm{aldehyde}]\end{array}}\right]}{\left[\frac{\begin{array}{c}[\mathrm{Mass}\mathrm{of}\mathrm{charged}\\ \mathrm{benzaldehyde}]-[\mathrm{Mass}\mathrm{of}\\ \mathrm{benzaldehyde}\mathrm{in}\mathrm{product}]\end{array}}{\begin{array}{c}[\mathrm{Molecular}\mathrm{weight}\\ \mathrm{of}\mathrm{benzaldehyde}]\end{array}}\right]}\times 100& \left[\mathrm{Formula}2\right]\end{array}$

HCA-to-Dimer Formation Ratio

[0108] A formation ratio of dimers, which are products of the dimerization of aldehydes, to HCA, which is a target product, was calculated by the following formula.

[0109] A larger value indicates less by-products.

[00003]$\begin{array}{cc}\mathrm{HCA}-\mathrm{to}-\mathrm{dimer}\mathrm{formation}\mathrm{ratio}[-]=\frac{\left[\frac{\begin{array}{c}[\mathrm{Mass}\mathrm{of}\mathrm{hexyl}\\ \mathrm{cinnamic}\mathrm{aldehyde}\\ \mathrm{in}\mathrm{product}]\end{array}}{\begin{array}{c}[\mathrm{Molecular}\mathrm{weight}\\ \mathrm{of}\mathrm{hexyl}\mathrm{cinnamic}\\ \mathrm{aldehyde}]\end{array}}\right]}{\left[\frac{\begin{array}{c}[\mathrm{Mass}\mathrm{of}\mathrm{dimer}\\ \mathrm{in}\mathrm{product}]\end{array}}{\begin{array}{c}[\mathrm{Molecular}\mathrm{weight}\\ \mathrm{of}\mathrm{dimer}]\end{array}}\right]}& \left[\mathrm{Formula}3\right]\end{array}$

Example 2

[0110] Example 2 was performed in the same manner as Example 1 except for the use of titanium oxide (AMT-600, an anatase-type titanium oxide manufactured by TAYCA CORPORATION in accordance with a sulfuric acid method (liquid phase method)) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.) as a catalyst. Table 2 shows the evaluation results of the product thus obtained.

Example 3

[0111] Example 3 was performed in the same manner as Example 1 except for the use of titanium oxide (MC-150, an anatase-type titanium oxide manufactured by ISHIHARA SANGYO KAISHA, LTD., in accordance with a sulfuric acid method (liquid phase method)) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.) as a catalyst. Table 2 shows the evaluation results of the product thus obtained.

Example 4

[0112] Example 4 was performed in the same manner as Example 1 except for the use of titanium oxide (MC-50, an anatase-type titanium oxide manufactured by ISHIHARA SANGYO KAISHA, LTD., in accordance with a sulfuric acid method (liquid phase method)) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.) as a catalyst. Table 2 shows the evaluation results of the product thus obtained.

Example 5

[0113] Example 5 was performed in the same manner as Example 1 except for the use of titanium oxide (MC-90L, an anatase-type titanium oxide manufactured by ISHIHARA SANGYO KAISHA, LTD., in accordance with a sulfuric acid method (liquid phase method)) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.) as a catalyst. Table 2 shows the evaluation results of the product thus obtained.

Example 6

[0114] Example 6 was performed in the same manner as Example 1 except that the amount of benzaldehyde relative to octanal was changed to 1.5 molar equivalents instead of 5 molar equivalents. Table 2 shows the evaluation results of the product thus obtained.

Example 7

[0115] Example 7 was performed in the same manner as Example 1 except that toluene as a solvent (3.0 g, 30% by mass relative to the total amount of the compound of formula (I) and the compound of formula (ID) was placed in the reaction tube together with the catalyst, octanal, benzaldehyde, etc. Table 2 shows the evaluation results of the product thus obtained.

Example 8

[0116] In a 200 mL separable flask, the following were placed: titanium oxide as a catalyst (MC-90L, an anatase-type titanium oxide manufactured by ISHIHARA SANGYO KAISHA, LTD., in accordance with a sulfuric acid method (liquid phase method), 19.2 g, 30% by mass relative to octanal, 30 parts by weight relative to 100 parts by mass of the compound of formula (I)); and benzaldehyde (formula (II-1), 80.0 g, 0.75 mol, 1.5 molar equivalents relative to octanal). A mechanical stirrer, a thermometer, a Dean-Stark trap, a condenser, a nitrogen line, and an aldehyde supply line were attached to the separable flask. An octanal supply line was connected with a dropping pump to supply octanal at a constant speed. The inside of the reaction tube was replaced with nitrogen and then heated to 150° C., and the mixture in the separable flask was stirred. When the temperature reached 150° C., octanal (formula (I-1)) was supplied to the reaction mixture in the separable flask using the dropping pump. A total of 64 g (0.5 mol) of octanal was supplied to the reaction mixture in 6 hours, at a supply rate of 12.8 g/h in the former 3 hours and at a supply rate of 8.5 g/h in the latter 3 hours. Thereafter, the reaction mixture was continuously stirred at 150° C. for 0.5 hours. The separable flask was then cooled to 30° C. to finish the reaction. Table 2 shows the evaluation results of the product thus obtained.

Example 9

[0117] Example 9 was performed in the same manner as Example 1 except for the use of titanium oxide (TK-1460, an anatase-type titanium oxide manufactured by TAYCA CORPORATION in accordance with a sulfuric acid method (liquid phase method)) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.) as a catalyst. Table 2 shows the evaluation results of the product thus obtained.

Comparative Example 1

[0118] Comparative Example 1 was performed in the same manner as Example 1 except for the use of magnesium oxide (Kyowamag 30 manufactured by Kyowa Chemical Industry Co., Ltd., 0.19 g, 10% by mass relative to octanal) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., 0.19 g, 10% by mass relative to octanal) as a catalyst. Table 3 shows the evaluation results of the product thus obtained.

Comparative Example 2

[0119] Comparative Example 2 was performed in the same manner as Example 1 except for the use of hydrotalcite (hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd., 0.19 g, 10% by mass relative to octanal) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., 0.19 g, 10% by mass relative to octanal) as a catalyst. Table 3 shows the evaluation results of the product thus obtained.

Comparative Example 3

[0120] Comparative Example 3 was performed in the same manner as Example 1 except for the use of aluminophosphate (aluminophosphate manufactured by KANTO CHEMICAL CO., INC., 0.19 g, 10% by mass relative to octanal) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., 0.19 g, 10% by mass relative to octanal) as a catalyst. Table 3 shows the evaluation results of the product thus obtained.

Comparative Example 4

[0121] Comparative Example 4 was performed in the same manner as Example 1 except for the use of silicoaluminophosphate zeolite (SAPO-34 manufactured by JGC Catalysts and Chemicals Ltd., 0.19 g, 10% by mass relative to octanal) in place of titanium oxide (SSP-M manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., 0.19 g, 10% by mass relative to octanal) as a catalyst. Table 3 shows the evaluation results of the product thus obtained.

Comparative Example 5

[0122] Comparative Example 5 was performed in the same manner as Example 1 except that toluene as a solvent (7.4 g, 75% by mass relative to the total amount of the compound of formula (I) and the compound of formula (II)) was placed in the reaction tube together with the catalyst, octanal, benzaldehyde, etc. Table 3 shows the evaluation results of the product thus obtained.

[0123] Tables 2 and 3 below summarize the reaction conditions and results in Examples 1 to 9 and Comparative Examples 1 to 5. Table 2 also shows the primary particle diameter of the titanium oxide used as a catalyst, the sulfur content, the BET specific surface area, and the crystallite diameter.

Primary Particle Diameter

[0124] Using an X-ray diffraction instrument (model “MiniFlex600” manufactured by Rigaku Corporation), the primary particle diameter was determined by an X-ray diffraction method from a peak of 2θ=25° to 26°.

BET Specific Surface Area

[0125] Using a specific surface area measuring instrument (model “FlowSorbIII” manufactured by Micromeritics Instrument Corporation), the BET specific surface area was measured.

Method for Measuring the Crystallite Diameter of Titanium Oxide in Powder X-Ray Diffraction Measurement

[0126] Using a powder X-ray diffraction instrument (model “MiniFlex600” manufactured by Rigaku Corporation), a half-width of a peak at 2θ of 25° to 26° is measured by a powder X-ray diffraction measurement to determine the crystallite diameter of titanium oxide by the Scherrer equation represented by the following general formula (S) (where K=0.9, λ=1.5418 [Å]).

[Formula 4]

D=λK/(βcosθ)   (S)

[0127] In general formula (S),

[0128] D represents a crystallite diameter [Å],

[0129] λ represents a wavelength of X-ray [ÅA],

[0130] K represents a Scherrer constant, and

[0131] β represents a half-width of a peak at 2θ of 25° to 26°.

[0132] The unit of β and θ is radian.

TABLE-US-00002 TABLE 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Catalyst Catalyst Titanium Titanium Titanium Titanium Titanium Titanium Titanium Titanium Titanium oxide oxide oxide oxide oxide oxide oxide oxide oxide Maker SAKAI TAYCA ISHIHARA ISHIHARA ISHIHARA SAKAI SAKAI ISHIHARA TAYCA CHEMICAL COR- SANGYO SANGYO SANGYO CHEMICAL CHEMICAL SANGYO CORPOR- INDUSTRY POR- KAISHA, KAISHA, KAISHA, INDUSTRY INDUSTRY KAISHA, ATION CO., LTD. ATION LTD. LTD. LTD. CO., LTD. CO., LTD. LTD. Product SSP-M AMT-600 MC-150 MC-50 MC-90L SSP-M SSP-M MC-90L TK-1460 name Primary 13 28 6 25 19 13 13 19 22 particle diameter (nm) Cry- 162 207 124 187 184 162 162 184 98 stallite diameter (Å) BET 103 55 273 54 90 103 103 90 108 specific surface area (m.sup.2/g) Ben- [Molar 5 5 5 5 5 1.5 5 1.5 5 zaldehyde equiv- equivalent alent] Octanal Added at Added at Added at Added at Added at Added at Added at Dropping Added at supply a time in a time in a time in a time in a time in a time in a time in a time in method initial initial initial initial initial initial initial initial stage stage stage stage stage stage stage stage Solvent Solvent None None None None None None Toluene None None Amount — — — — — — 30 — — of solvent [% by mass] Reaction [hours] 4 4 4 4 4 4 4 4 4 time Yield [%] 87.0 87.3 86.5 80.1 87.0 66.0 74.3 90.8 60.4 of hexyl cinnamic aldehyde (relative to octanal) Selectivity [%] 92.7 92.3 90.4 95.6 94.2 77.6 93.3 90.8 87.0 of hexyl cinnamic aldehyde (relative to ben- zaldehyde) HCA- [−] 15.7 15.3 14.7 11.4 14.7 5.5 11.1 37.9 8.7 to-dimer formation ratio

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Catalyst Catalyst Magnesium oxide Hydrotalcite Aluminophosphate Silicoalumino- Titanium oxide phosphate zeolite Maker Kyowa Chemical Kyowa Chemical KANTO CHEMICAL JGC Catalysts and SAKAI CHEMICAL Industry Co., Ltd. Industry Co., Ltd. CO., INC. Chemicals Ltd. INDUSTRY CO., LTD. Product Kyowamag 30 Hydrotalcite Aluminophosphate SAPO-34 SSP-M name Benzaldehyde equivalent [Molar 5 5 5 5 5 equivalent] Octanal supply method Added at a time Added at a time Added at a time Added at a time Added at a time in initial stage in initial stage in initial stage in initial stage in initial stage Solvent Solvent None None None None Toluene [% by mass] — — — — 75 Reaction time [hours] 4 4 4 4 4 Yield of hexyl cinnamic [%] 49.2 55.4 49.2 47.4 24.3 aldehyde (relative to octanal) Selectivity of hexyl cinnamic [%] 78.8 85.5 78.8 82.1 69.3 aldehyde (relative to benzaldehyde) HCA-to-dimer formation 2.9 3.0 2.9 4.5 5.4 ratio

[0133] Tables 2 and 3 confirmed that the use of titanium oxide as a catalyst in the step of reacting the compound of formula (I) with the compound of formula (II) to provide the α,β-unsaturated aldehyde of formula (III) improves the selectivity of the α,β-unsaturated aldehyde (relative to the compound of formula (II)) and the yield of the α,β-unsaturated aldehyde (relative to the compound of formula (I)) while reducing the formation of by-products.

[0134] The production method of the present invention enables production of a target aldehyde at a high yield with satisfactory selectivity while reducing the formation of by-products, thereby producing an α,β-unsaturated aldehyde with high efficiency and high purity. Such a production method can be used suitably as a production method of an aldehyde that is useful as a fragrance material.