JPS6159632B2 - - Google Patents
Info
- Publication number
- JPS6159632B2 JPS6159632B2 JP9331381A JP9331381A JPS6159632B2 JP S6159632 B2 JPS6159632 B2 JP S6159632B2 JP 9331381 A JP9331381 A JP 9331381A JP 9331381 A JP9331381 A JP 9331381A JP S6159632 B2 JPS6159632 B2 JP S6159632B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- optically active
- reaction
- acid
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DNRJTBAOUJJKDY-UHFFFAOYSA-N 2-Acetyl-3,5,5,6,8,8-hexamethyl-5,6,7,8- tetrahydronaphthalene Chemical compound CC(=O)C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 DNRJTBAOUJJKDY-UHFFFAOYSA-N 0.000 description 2
- 241000723353 Chrysanthemum Species 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- IEBXZRQOXHLIGF-QMMMGPOBSA-N (4r)-5,5-dimethyl-4-(2-methylprop-1-enyl)oxolan-2-one Chemical compound CC(C)=C[C@H]1CC(=O)OC1(C)C IEBXZRQOXHLIGF-QMMMGPOBSA-N 0.000 description 1
- AZRHCOAXTMKTDJ-CQSZACIVSA-N (4s)-5,5-dimethyl-4-[2-methyl-2-(4-methylphenyl)propyl]oxolan-2-one Chemical compound C1=CC(C)=CC=C1C(C)(C)C[C@@H]1C(C)(C)OC(=O)C1 AZRHCOAXTMKTDJ-CQSZACIVSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LQXGUMYMOOXEIL-GFCCVEGCSA-N 2-[(2s)-1,1,4,4,7-pentamethyl-2,3-dihydronaphthalen-2-yl]acetic acid Chemical compound C([C@@H](CC(O)=O)C1(C)C)C(C)(C)C=2C1=CC(C)=CC=2 LQXGUMYMOOXEIL-GFCCVEGCSA-N 0.000 description 1
- IEBXZRQOXHLIGF-UHFFFAOYSA-N 5,5-dimethyl-4-(2-methylprop-1-enyl)oxolan-2-one Chemical compound CC(C)=CC1CC(=O)OC1(C)C IEBXZRQOXHLIGF-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- -1 malonic acid ester Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
Description
【発明の詳細な説明】
本発明は式（）で示される新規な光学活性ま
たはラセミのラクトン誘導体及びその製造法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel optically active or racemic lactone derivative represented by formula () and a method for producing the same.
（式中、Ｒは水素またはアルキル基を表わす）
式（）で示される化合物は医薬、農薬、香料等
の中間原料として重要な化合物である。例えば式
（）の化合物をフリーデルクラフツ触媒で環化
して式（）の化合物とし、さらに脱炭酸した後
アセチル化した化合物は香料として重要である。 (In the formula, R represents hydrogen or an alkyl group)
The compound represented by the formula () is an important compound as an intermediate raw material for medicines, agricultural chemicals, fragrances, and the like. For example, a compound obtained by cyclizing a compound of formula () with a Friedel-Crafts catalyst to obtain a compound of formula (), which is further decarboxylated and then acetylated, is important as a fragrance.
それらの中で７−アセチル−１，１，３，４，
４，６−ヘキサメチル−１，２，３，４−テトラ
ヒドロナフタレン（商品名トナリツド）は香料の
領域において価値あるじや香様の香りを有し、香
粧品用香料として重要な位置を占めている。式
（）で示される化合物のうち、Ｒがメチル基の
ものを用いればこの化合物へ誘導できる。 Among them 7-acetyl-1,1,3,4,
4,6-Hexamethyl-1,2,3,4-tetrahydronaphthalene (trade name: Tonaritsudo) has a sycamore-like scent that is valuable in the perfume field, and occupies an important position as a perfume for cosmetics. Among the compounds represented by the formula (), if R is a methyl group, this compound can be derived.
本発明の式（）で示される化合物の重要性に
ついては前述の通りであるが式（）で示される
化合物の製法について次に詳しく説明する。 The importance of the compound represented by formula () in the present invention has been described above, but the method for producing the compound represented by formula () will be explained in detail below.
本発明者らは４−（２−メチルプロペニル）−
５，５−ジメチルテトラヒドロ−２−フラノン、
通称パイロシンを酸触媒の存在下芳香族炭化水素
と反応させると緩和な条件下に式（）で示され
る新規化合物が好収率で合成できることを新たに
見い出した。芳香族炭化水素としてはベンゼン、
トルエン、エチルベンゼン、プロピルベンゼン、
ブチルベンゼン等の無置換もしくはアルキル置換
ベンゼンを用いる。 We have 4-(2-methylpropenyl)-
5,5-dimethyltetrahydro-2-furanone,
We have newly discovered that a new compound represented by the formula () can be synthesized in good yield under mild conditions by reacting so-called pyrosin with aromatic hydrocarbons in the presence of an acid catalyst. Aromatic hydrocarbons include benzene,
toluene, ethylbenzene, propylbenzene,
Unsubstituted or alkyl-substituted benzene such as butylbenzene is used.
図示すれば以下の如くである。 The diagram is as follows.
本発明反応で用いる酸としては硫酸、燐酸、Ｐ
−トルエンスルホン酸、ナフタレンスルホン酸等
の触媒として使用できる。 Acids used in the reaction of the present invention include sulfuric acid, phosphoric acid, P
- Can be used as a catalyst for toluenesulfonic acid, naphthalenesulfonic acid, etc.
本反応を実施するに際して本反応を本質的に阻
害しない溶媒を用いることもできるし、また芳香
族炭化水素をあらかじめ多く用いて溶媒を兼ねる
ことも可能である。反応温度は通常−30℃から芳
香族炭化水素の沸点下で充分である。反応時間は
反応条件によつて変りうるが、通常５分から10時
間で目的を達することができる。緩和な条件下で
有利に反応が進行する。通常の単離操作でも高純
度のものが得られるが、必要あらばさらに再結晶
あるいはクロマトグラフイー等の手段で精製でき
る。 When carrying out this reaction, it is possible to use a solvent that does not essentially inhibit this reaction, or it is also possible to use a large amount of aromatic hydrocarbon in advance to also serve as a solvent. The reaction temperature is usually from -30°C to below the boiling point of the aromatic hydrocarbon. Although the reaction time may vary depending on the reaction conditions, the desired reaction time can usually be achieved in 5 minutes to 10 hours. The reaction proceeds advantageously under mild conditions. High purity can be obtained by ordinary isolation procedures, but if necessary, it can be further purified by means such as recrystallization or chromatography.
本反応において光学活性パイロシンを用いれば
生成する式（）で示されるラクトン誘導体も光
学活性体として得られる。一般に生物活性化合物
はそのキラリテイにより活性に差が現われる。こ
のため、光学活性化合物を製造する技術を開発す
ることは重要な意義を有する。従つて本発明の化
合物から誘導される例えば前述のトナリツドは所
望により光学活性体として得られることになる。
かゝる点からも本発明は格別の特徴を有するもの
である。 If optically active pyrosine is used in this reaction, the lactone derivative represented by the formula () produced can also be obtained as an optically active substance. Generally, biologically active compounds exhibit differences in activity depending on their chirality. Therefore, it is of great significance to develop a technology for producing optically active compounds. Therefore, for example, the above-mentioned tonalide derived from the compound of the present invention can be obtained as an optically active form, if desired.
From this point of view as well, the present invention has special features.
本発明の方法で用いる原料のパイロシンは菊酸
の加熱開裂反応（Botyu Kagaku，15，１
（1950））によつてあるいは２，５−ジメチル−
２，４−ヘキサジエンを酸化してモノエポキサイ
ドとし、ナトリウム化マロン酸エステルと反応さ
せた後加水分解する方法（テトラヘドロン・レタ
ーズ Tetrahedron Letters，1845−1846
（1978））等によつて得られる。 Pyrosine, the raw material used in the method of the present invention, is produced by a thermal cleavage reaction of chrysanthemum acid (Botyu Kagaku, 15 , 1).
(1950)) or 2,5-dimethyl-
A method in which 2,4-hexadiene is oxidized to form a monoepoxide, reacted with sodified malonic acid ester, and then hydrolyzed (Tetrahedron Letters, 1845-1846
(1978)).
また光学活性なパイロシンは光学活性菊酸を加
熱することによつて合成することができる（アグ
リカルチユラル・バイオロジカル・ケミストリー
Agr・Bial・Chem，34，1115（1970））。 In addition, optically active pyrosine can be synthesized by heating optically active chrysanthemum acid (Agricultural Biological Chemistry).
Agr. Bial. Chem, 34 , 1115 (1970)).
次に実施例によつて本発明の化合物及び製造法
を説明する。 Next, the compounds and production methods of the present invention will be explained with reference to Examples.
実施例
（Ｒ）−４−（２−メチルプロペニル）−５，５
−ジメチルテトラヒドロ−２−フラノン（〔α〕D
＋62.0゜（C0.54，エタノール））0.35ｇ
（2.08mmol）をトルエン10mlに溶解し0.3mlの濃
硫酸を加え、室温で１時間撹拌した。トルエン層
を水酸化ナトリウム水溶液で洗浄し、芒硝で乾燥
後減圧下溶媒を留去し0.27ｇ（1.05mmol，50
％）の（Ｓ）−５，５−ジメチル−４−（２−メチ
ル−２−Ｐ−トリルプロピル）−テトラヒドロ−
２−フラノンを得た。その物性測定値は次の通り
である。〔α〕546＋32.5゜（C1，ベンゼン）NMR
（CDCl3）δ（ppm）＝1.16（3H，ｓ）、1.29
（3H，ｓ）、1.30（6H，ｓ）、1.60〜1.85（5H，
ｍ）、2.28（3H，ｓ）、7.04（4H，ｓ）、IR（cm
-1）1760
参考例
（Ｓ）−５，５−ジメチル−４−（２−メチル−
２−Ｐ−トリルプロピル）−テトラヒドロ２−フ
ラノン100mgを10mlのトルエンに溶解し、130mgの
無水塩化アルミニウムを加え、70℃で30分間撹拌
した。Example (R)-4-(2-methylpropenyl)-5,5
-dimethyltetrahydro-2-furanone ([α] D
+62.0゜(C0.54, ethanol)) 0.35g
(2.08 mmol) was dissolved in 10 ml of toluene, 0.3 ml of concentrated sulfuric acid was added, and the mixture was stirred at room temperature for 1 hour. The toluene layer was washed with an aqueous sodium hydroxide solution, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to give 0.27 g (1.05 mmol, 50
%) of (S)-5,5-dimethyl-4-(2-methyl-2-P-tolylpropyl)-tetrahydro-
2-furanone was obtained. The measured values of its physical properties are as follows. [α] 546 +32.5゜(C1, benzene) NMR
(CDCl 3 ) δ (ppm) = 1.16 (3H, s), 1.29
(3H, s), 1.30 (6H, s), 1.60~1.85 (5H,
m), 2.28 (3H, s), 7.04 (4H, s), IR (cm
-1 ) 1760 Reference example (S)-5,5-dimethyl-4-(2-methyl-
100 mg of 2-P-tolylpropyl)-tetrahydro-2-furanone was dissolved in 10 ml of toluene, 130 mg of anhydrous aluminum chloride was added, and the mixture was stirred at 70°C for 30 minutes.
反応液を希塩酸で洗浄後、乾燥、濃縮して単離
すると95mgの（Ｓ）−３−（カルボキシメチル）−
１，１，４，４，６−ペンタメチル−１，２，
３，４−テトラヒドロナフタレンを得た。その物
性値は次の通りである。 The reaction solution was washed with dilute hydrochloric acid, dried, concentrated, and isolated to yield 95 mg of (S)-3-(carboxymethyl)-
1,1,4,4,6-pentamethyl-1,2,
3,4-tetrahydronaphthalene was obtained. Its physical property values are as follows.
NMR（CCl4）δ（ppm）＝1.08（3H，ｓ）、1.25
（6H，ｓ）、1.34（3H，ｓ）、2.26（3H，ｓ）、
1.52〜2.79（5H，ｍ）、6.75〜7.15（3H，ｍ）、
12.17（1H，ｓ）、IR（cm-1）1705
〔α〕546＋26.3゜（C1，ベンゼン）。 NMR (CCl 4 ) δ (ppm) = 1.08 (3H, s), 1.25
(6H, s), 1.34 (3H, s), 2.26 (3H, s),
1.52-2.79 (5H, m), 6.75-7.15 (3H, m),
12.17 (1H, s), IR (cm -1 ) 1705 [α] 546 +26.3° (C1, benzene).
Claims (1)
ラクトン誘導体。 （式中、Ｒは水素またはアルキル基を表わす） ２ 光学活性またはラセミの４−（２−メチルプ
ロペニル）−５，５−ジメチルテトラヒドロ−２
−フラノンとベンゼン又はアルキルベンゼンを酸
を触媒として反応させることを特徴とする式
（）で示される光学活性またはラセミのラクト
ン誘導体の製造法。 （式中、Ｒは水素またはアルキル基を表わす）[Scope of Claims] 1. An optically active or racemic lactone derivative represented by formula (). (In the formula, R represents hydrogen or an alkyl group) 2 Optically active or racemic 4-(2-methylpropenyl)-5,5-dimethyltetrahydro-2
- A method for producing an optically active or racemic lactone derivative represented by formula (), which comprises reacting furanone with benzene or alkylbenzene using an acid as a catalyst. (In the formula, R represents hydrogen or an alkyl group)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9331381A JPS57209282A (en) | 1981-06-16 | 1981-06-16 | Lactone derivative and its preparation |
| EP82105071A EP0071006B1 (en) | 1981-06-11 | 1982-06-09 | Tetrahydronaphthalene derivatives and their production |
| DE8282105071T DE3266350D1 (en) | 1981-06-11 | 1982-06-09 | Tetrahydronaphthalene derivatives and their production |
| US06/902,063 US4767882A (en) | 1981-06-11 | 1986-08-26 | Tetrahydronaphthalene derivatives and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9331381A JPS57209282A (en) | 1981-06-16 | 1981-06-16 | Lactone derivative and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57209282A JPS57209282A (en) | 1982-12-22 |
| JPS6159632B2 true JPS6159632B2 (en) | 1986-12-17 |
Family
ID=14078820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9331381A Granted JPS57209282A (en) | 1981-06-11 | 1981-06-16 | Lactone derivative and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57209282A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04131621U (en) * | 1991-05-24 | 1992-12-03 | 隆之 井田 | helmet |
-
1981
- 1981-06-16 JP JP9331381A patent/JPS57209282A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04131621U (en) * | 1991-05-24 | 1992-12-03 | 隆之 井田 | helmet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57209282A (en) | 1982-12-22 |
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