JP6310326B2 - Method for producing δ-valerolactone - Google Patents
Method for producing δ-valerolactone Download PDFInfo
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- JP6310326B2 JP6310326B2 JP2014108790A JP2014108790A JP6310326B2 JP 6310326 B2 JP6310326 B2 JP 6310326B2 JP 2014108790 A JP2014108790 A JP 2014108790A JP 2014108790 A JP2014108790 A JP 2014108790A JP 6310326 B2 JP6310326 B2 JP 6310326B2
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- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- TUTVYKJWIWCAEN-UHFFFAOYSA-N 6-ethyl-3,5-dimethyloxan-2-one Chemical compound CCC1OC(=O)C(C)CC1C TUTVYKJWIWCAEN-UHFFFAOYSA-N 0.000 description 12
- 238000007327 hydrogenolysis reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DOSOPEZOHKMQPJ-UHFFFAOYSA-N 6-methyl-3,4-dihydropyran-2-one Chemical compound CC1=CCCC(=O)O1 DOSOPEZOHKMQPJ-UHFFFAOYSA-N 0.000 description 2
- BOQBORSPZGXTCN-UHFFFAOYSA-N CCC1=C(CC(C(=O)O1)C)C Chemical compound CCC1=C(CC(C(=O)O1)C)C BOQBORSPZGXTCN-UHFFFAOYSA-N 0.000 description 2
- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Description
本発明は、γδ不飽和−δ−バレロラクトンから水素化反応によりδ−バレロラクトンを製造する方法に関する。 The present invention relates to a method for producing δ-valerolactone from γδ unsaturated-δ-valerolactone by hydrogenation reaction.
δ−バレロラクトンは、香料、農薬、医薬などの合成中間体や材料として有用である。特にメチル基やエチル基などの置換基を持ったδ−バレロラクトンは利用価値が高い。このようなδ−バレロラクトンの製造方法として、γδ不飽和−δ−バレロラクトンを水素化してδ−バレロラクトンを得る方法が知られている。 δ-valerolactone is useful as a synthetic intermediate or material for fragrances, agricultural chemicals, medicines and the like. In particular, δ-valerolactone having a substituent such as a methyl group or an ethyl group has a high utility value. As a method for producing such δ-valerolactone, a method of obtaining δ-valerolactone by hydrogenating γδ unsaturated-δ-valerolactone is known.
γδ不飽和−δ−バレロラクトンは、例えば、Ｊｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ、１９８９年、５４巻、２３６４−２３６９頁に記載されている方法により、簡便かつ高収率で合成することができ、様々な置換基を持ったγδ不飽和−δ−バレロラクトンを容易に合成することができる。γδ不飽和−δ−バレロラクトンの水素化反応としては、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ、２０１０年、第５１巻、３８２７−３８２９頁に記載のようにパラジウム−カーボンを水素化触媒として用いた方法（製造方法１）が知られている。 The γδ unsaturated-δ-valerolactone can be synthesized easily and in high yield by, for example, the method described in Journal of Organic Chemistry, 1989, 54, 2364-2369, and various substitutions can be made. Γδ unsaturated-δ-valerolactone having a group can be easily synthesized. As a hydrogenation reaction of γδ unsaturated-δ-valerolactone, a method using palladium-carbon as a hydrogenation catalyst as described in Tetrahedron Letters, 2010, Vol. 51, pages 3827-3829 (Production Method 1) It has been known.
しかしながら、γδ不飽和−δ−バレロラクトンの水素化反応は、加水素分解が起こりやすいため、δ−バレロラクトンの実用的な製造方法はほとんどない。例えば、Ｏｒｇａｎｉｃ Ｌｅｔｔｅｒｓ、２００９年、第１１巻、１６２３−１６２５頁に記載のように、γδ不飽和−δ−バレロラクトンにパラジウム−カーボン触媒を用いた水素化反応ではδ−バレロラクトンは得られず、加水素分解されたカルボン酸が高収率で得られている。上記の製造方法１においても加水素分解が起きているため、δ−バレロラクトンの収率が低く、実用的でない。 However, since the hydrogenation reaction of γδ unsaturated-δ-valerolactone is likely to undergo hydrogenolysis, there are few practical methods for producing δ-valerolactone. For example, as described in Organic Letters, 2009, Vol. 11, pages 1623-1625, δ-valerolactone cannot be obtained by hydrogenation reaction using a palladium-carbon catalyst for γδ unsaturated-δ-valerolactone. The hydrogenolysis carboxylic acid is obtained in high yield. In the production method 1 described above, since hydrogenolysis occurs, the yield of δ-valerolactone is low and not practical.
本発明は、γδ不飽和−δ−バレロラクトンの水素化反応における副反応である加水素分解を抑え、γδ不飽和−δ−バレロラクトンからδ−バレロラクトンを高収率で製造することを目的とする。 The present invention aims to produce δ-valerolactone in high yield from γδ unsaturated-δ-valerolactone by suppressing hydrogenolysis, which is a side reaction in the hydrogenation reaction of γδ unsaturated-δ-valerolactone. And
本発明者らは、上記課題を解決するために鋭意検討を行った結果、γδ不飽和−δ−バレロラクトンをパラジウム−アルミナ触媒存在下で水素化反応させるとδ−バレロラクトンを収率よく得られることを見出した。 As a result of intensive studies to solve the above problems, the present inventors obtained δ-valerolactone in a high yield when hydrogenation reaction of γδ unsaturated-δ-valerolactone is carried out in the presence of a palladium-alumina catalyst. I found out that
さらに、本発明者らは、γδ不飽和−δ−バレロラクトンをパラジウム−アルミナ触媒存在下、エステル系溶媒中で水素化反応させるとδ−バレロラクトンを非常に収率よく得られることを見出し、本発明を完成するに至った。 Furthermore, the present inventors have found that when γδ unsaturated-δ-valerolactone is hydrogenated in an ester solvent in the presence of a palladium-alumina catalyst, δ-valerolactone can be obtained in a very high yield. The present invention has been completed.
すなわち、本発明は第一に、式（１）
第二に、前記水素化反応で使用される溶媒が、Ｒ1ＣＯＯＲ2（式中Ｒ1は炭素数１〜３の分岐していてもよいアルキル基、Ｒ2は炭素数１〜２のアルキル基を表す。）で表されるエステルであることを特徴とする、上記第一に記載のδ−バレロラクトンの製造方法である。
That is, the present invention firstly has the formula (1)
Second, the solvent used in the hydrogenation reaction is R 1 COOR 2 (wherein R 1 is an alkyl group having 1 to 3 carbon atoms which may be branched, and R 2 is alkyl having 1 to 2 carbon atoms). The method for producing δ-valerolactone according to the first aspect, wherein the ester is represented by the following formula:
以下、本発明に係るδ−バレロラクトンの製造方法についてさらに詳細に説明する。 Hereinafter, the method for producing δ-valerolactone according to the present invention will be described in more detail.
γδ不飽和−δ−バレロラクトンである上記式（１）におけるＲ1〜Ｒ3は水素原子、メチル基、エチル基を表し、その組み合わせは自在に選択できる。 R 1 to R 3 in the above formula (1) which is γδ unsaturated-δ-valerolactone represents a hydrogen atom, a methyl group or an ethyl group, and the combination thereof can be freely selected.
水素化触媒は、市販のパラジウム−アルミナ触媒を使用することができる。パラジウム−アルミナ触媒の使用量は、上記式（１）で表されるγδ不飽和−δ−バレロラクトンの重量に対して、０．０１〜０．３倍量の範囲で使用でき、好ましくは０．０２〜０．１５倍量である。 A commercially available palladium-alumina catalyst can be used as the hydrogenation catalyst. The amount of the palladium-alumina catalyst used can be 0.01 to 0.3 times the weight of the γδ unsaturated-δ-valerolactone represented by the above formula (1), preferably 0. 0.02 to 0.15 times the amount.
水素の反応圧力は、常圧から高圧まで使用可能であり、具体的には常圧から５ＭＰａの範囲であり、好ましくは常圧から３ＭＰａの範囲である。 The reaction pressure of hydrogen can be used from normal pressure to high pressure. Specifically, the reaction pressure is from normal pressure to 5 MPa, preferably from normal pressure to 3 MPa.
反応温度は、１０℃〜６０℃が好ましく、より好ましくは２０℃〜４５℃である。 The reaction temperature is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 45 ° C.
水素化反応における溶媒としては、エステル系やアルコール系など特に制限はないが、パラジウム−アルミナ触媒とエステル系の溶媒との組み合わせが加水素分解を顕著に抑えることができるため、δ−バレロラクトンの収率が格段に向上するので、エステル系の溶媒が特に好適である。エステル系の溶媒としては、具体的には酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、イソ酪酸メチル、イソ酪酸エチルの中から１種類または複数種類の組み合わせで使用することができる。溶媒の使用量は、上記式（１）で表されるγδ不飽和−δ−バレロラクトンの重量に対して、１〜２０倍量であり、好ましくは３〜１０倍量である。 The solvent in the hydrogenation reaction is not particularly limited, such as ester-based or alcohol-based solvents. However, since the combination of a palladium-alumina catalyst and an ester-based solvent can remarkably suppress hydrogenolysis, δ-valerolactone Since the yield is remarkably improved, an ester solvent is particularly suitable. Specific examples of ester solvents include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl isobutyrate, and ethyl isobutyrate. can do. The usage-amount of a solvent is 1-20 times amount with respect to the weight of (gamma) delta unsaturated-delta-valerolactone represented by the said Formula (1), Preferably it is 3-10 times amount.
反応終了後は、触媒を濾過し、濾液を減圧濃縮することにより、上記式（２）で表されるδ−バレロラクトンを高収率で得ることができる。 After completion of the reaction, the catalyst is filtered, and the filtrate is concentrated under reduced pressure, whereby δ-valerolactone represented by the above formula (2) can be obtained in high yield.
本発明によれば、γδ不飽和−δ−バレロラクトンの水素化反応における副反応である加水素分解を抑え、γδ不飽和−δ−バレロラクトンからδ−バレロラクトンを高収率で製造することができる。 According to the present invention, production of δ-valerolactone in high yield from γδ unsaturated-δ-valerolactone is suppressed by suppressing hydrogenolysis, which is a side reaction in the hydrogenation reaction of γδ unsaturated-δ-valerolactone. Can do.
以下に実施例を挙げて本発明を詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
５０ｍｌのナスフラスコに６−エチル−３，５−ジメチル−３，４−ジヒドロ−２Ｈ−ピラン−２−オン（１．０ｇ）、５％パラジウム−アルミナ触媒（１００ｍｇ）、酢酸エチル（１０ｍｌ）を加え、水素で置換し、水素圧力は常圧とした。室温で５時間撹拌後、反応容器を窒素で置換した。反応溶液を濾過し、濾液を減圧濃縮し、粗生成物（１．０ｇ）を得た。ガスクロマトグラフィー分析によると、６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンが９６％、加水素分解物であるカルボン酸が４％であった。 In a 50 ml eggplant flask, 6-ethyl-3,5-dimethyl-3,4-dihydro-2H-pyran-2-one (1.0 g), 5% palladium-alumina catalyst (100 mg), ethyl acetate (10 ml) were added. In addition, the hydrogen pressure was replaced with normal pressure. After stirring at room temperature for 5 hours, the reaction vessel was replaced with nitrogen. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to obtain a crude product (1.0 g). According to gas chromatography analysis, 96% of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one and 4% of carboxylic acid as a hydrogenolysis product were found.
酢酸エチルの代わりにイソ酪酸メチルを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は９６％であった。 The same operation as in Example 1 was performed except that methyl isobutyrate was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 96%.
酢酸エチルの代わりにプロピオン酸メチルを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は９５％であった。 The same operation as in Example 1 was performed except that methyl propionate was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 95%.
水素圧力を常圧の代わりに０．４ＭＰａとした以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は９７％であった。 The same operation as in Example 1 was performed except that the hydrogen pressure was changed to 0.4 MPa instead of normal pressure. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 97%.
水素圧力を常圧の代わりに１．０ＭＰａとした以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は９７％であった。 The same operation as in Example 1 was performed except that the hydrogen pressure was changed to 1.0 MPa instead of normal pressure. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 97%.
水素圧力を常圧の代わりに３．０ＭＰａとした以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は９１％であった。 The same operation as in Example 1 was performed except that the hydrogen pressure was changed to 3.0 MPa instead of the normal pressure. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 91%.
［比較例１］
５％パラジウム−アルミナの代わりに５％パラジウム−カーボンを触媒として用い、酢酸エチルの代わりに２−プロパノールを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は６９％であった。
[Comparative Example 1]
The same operation as in Example 1 was performed except that 5% palladium-carbon was used as a catalyst instead of 5% palladium-alumina and 2-propanol was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 69%.
［比較例２］
５％パラジウム−アルミナの代わりに５％パラジウム−炭酸カルシウムを触媒として用い、酢酸エチルの代わりに２−プロパノールを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は５９％であった。
[Comparative Example 2]
The same operation as in Example 1 was performed except that 5% palladium-calcium carbonate was used as a catalyst instead of 5% palladium-alumina, and 2-propanol was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 59%.
［比較例３］
５％パラジウム−アルミナの代わりに５％パラジウム−硫酸バリウムを触媒として用い、酢酸エチルの代わりに２−プロパノールを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は６９％であった。
[Comparative Example 3]
The same operation as in Example 1 was performed except that 5% palladium-barium sulfate was used as a catalyst instead of 5% palladium-alumina, and 2-propanol was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 69%.
［比較例４］
５％パラジウム−アルミナの代わりに５％パラジウム−カーボンを触媒として用い、酢酸エチルの代わりにメタノールを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は６２％であった。
[Comparative Example 4]
The same operation as in Example 1 was performed except that 5% palladium-carbon was used as a catalyst instead of 5% palladium-alumina and methanol was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 62%.
［比較例５］
５％パラジウム−アルミナの代わりに５％パラジウム−カーボンを触媒として用い、酢酸エチルの代わりにエタノールを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は６４％であった。
[Comparative Example 5]
The same operation as in Example 1 was performed except that 5% palladium-carbon was used as a catalyst instead of 5% palladium-alumina and ethanol was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 64%.
実施例１〜６より、γδ不飽和−δ−バレロラクトンをパラジウム−アルミナ触媒存在下、エステル系溶媒中で水素化反応させると、δ−バレロラクトンが９１％以上という非常に高い収率で得られた。一方、パラジウム−アルミナ触媒以外の触媒存在下、アルコール系溶媒中で水素化反応させた比較例１〜５では、δ−バレロラクトンが最大６９％という低い収率であった。 From Examples 1 to 6, when γδ unsaturated-δ-valerolactone was hydrogenated in an ester solvent in the presence of a palladium-alumina catalyst, δ-valerolactone was obtained in a very high yield of 91% or more. It was. On the other hand, in Comparative Examples 1 to 5 in which hydrogenation reaction was performed in an alcohol solvent in the presence of a catalyst other than the palladium-alumina catalyst, the yield of δ-valerolactone was as low as 69% at the maximum.
６−エチル−３，５−ジメチル−３，４−ジヒドロ−２Ｈ−ピラン−２−オンの代わりに６−メチル−３，４−ジヒドロ−２Ｈ−ピラン−２−オンを原料として用いた以外は実施例１と同様の操作を行い、粗生成物（１．０ｇ）を得た。ガスクロマトグラフィー分析によると、６−メチルテトラヒドロ−２Ｈ−ピラン−２−オンが９２％、加水素分解物であるカルボン酸が８％であった。 Except that 6-methyl-3,4-dihydro-2H-pyran-2-one was used as a raw material instead of 6-ethyl-3,5-dimethyl-3,4-dihydro-2H-pyran-2-one The same operation as in Example 1 was performed to obtain a crude product (1.0 g). According to gas chromatography analysis, it was found that 92% of 6-methyltetrahydro-2H-pyran-2-one and 8% of carboxylic acid as a hydrogenolysis product.
［比較例６］
５０ｍｌのナスフラスコに実施例７と同様の原料である６−メチル−３，４−ジヒドロ−２Ｈ−ピラン−２−オン（１．０ｇ）、５％パラジウム−カーボン触媒（１００ｍｇ）、２−プロパノール（１０ｍｌ）を加え、水素で置換し、水素圧力は常圧とした。室温で５時間撹拌後、反応容器を窒素で置換した。反応溶液を濾過し、濾液を減圧濃縮し、粗生成物（１．０ｇ）を得た。ガスクロマトグラフィー分析によると、６−メチルテトラヒドロ−２Ｈ−ピラン−２−オンが６８％、加水素分解物であるカルボン酸が３２％であった。
[Comparative Example 6]
6-Methyl-3,4-dihydro-2H-pyran-2-one (1.0 g), 5% palladium-carbon catalyst (100 mg), 2-propanol, which are the same raw materials as in Example 7, in a 50 ml eggplant flask (10 ml) was added and replaced with hydrogen, and the hydrogen pressure was adjusted to normal pressure. After stirring at room temperature for 5 hours, the reaction vessel was replaced with nitrogen. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to obtain a crude product (1.0 g). According to gas chromatographic analysis, 6-methyltetrahydro-2H-pyran-2-one was 68%, and carboxylic acid as a hydrogenolysis product was 32%.
実施例７と比較例６より、実施例１とは置換基が異なるγδ不飽和−δ−バレロラクトンを原料としてパラジウム−アルミナ触媒存在下、エステル系溶媒中で水素化反応させてもδ−バレロラクトンが非常に高い収率で得られた。 From Example 7 and Comparative Example 6, γ-valero can be obtained by subjecting a hydrogenation reaction in an ester solvent in the presence of a palladium-alumina catalyst using γδ unsaturated-δ-valerolactone having a different substituent as in Example 1 as a raw material. The lactone was obtained in very high yield.
酢酸エチルの代わりに２−プロパノールを溶媒として用いた以外は実施例１と同様の操作を行った。６−エチル−３，５−ジメチルテトラヒドロ−２Ｈ−ピラン−２−オンの収率は８６％であった。 The same operation as in Example 1 was performed except that 2-propanol was used as a solvent instead of ethyl acetate. The yield of 6-ethyl-3,5-dimethyltetrahydro-2H-pyran-2-one was 86%.
実施例８より、γδ不飽和−δ−バレロラクトンをパラジウム−アルミナ触媒存在下、アルコール系溶媒中で水素化反応させると、δ−バレロラクトンが高い収率で得られた。 From Example 8, when γδ unsaturated-δ-valerolactone was hydrogenated in an alcohol solvent in the presence of a palladium-alumina catalyst, δ-valerolactone was obtained in high yield.
以上より、γδ不飽和−δ−バレロラクトンをパラジウム−アルミナ触媒存在下で水素化反応させるとδ−バレロラクトンが高い収率で得られ、さらに、γδ不飽和−δ−バレロラクトンをパラジウム−アルミナ触媒存在下、エステル系溶媒中で水素化反応させるとδ−バレロラクトンが非常に高い収率で得られることが分かった。 As described above, when γδ unsaturated-δ-valerolactone is hydrogenated in the presence of a palladium-alumina catalyst, δ-valerolactone is obtained in a high yield. Further, γδ unsaturated-δ-valerolactone is converted to palladium-alumina. It was found that δ-valerolactone was obtained in a very high yield when hydrogenated in an ester solvent in the presence of a catalyst.
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