JPH0257553B2 - - Google Patents
Info
- Publication number
- JPH0257553B2 JPH0257553B2 JP62085833A JP8583387A JPH0257553B2 JP H0257553 B2 JPH0257553 B2 JP H0257553B2 JP 62085833 A JP62085833 A JP 62085833A JP 8583387 A JP8583387 A JP 8583387A JP H0257553 B2 JPH0257553 B2 JP H0257553B2
- Authority
- JP
- Japan
- Prior art keywords
- cineole
- reaction
- mentene
- hexane
- observed
- 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
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 5
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000003921 oil Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 vinyl methyl Chemical group 0.000 description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HTGSXANWVMWFEM-UDNWOFFPSA-N [(2s)-2,4-dimethyl-3-oxabicyclo[2.2.2]octan-2-yl]methanol Chemical compound C1CC2[C@@](C)(CO)OC1(C)CC2 HTGSXANWVMWFEM-UDNWOFFPSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 3
- FAMJUFMHYAFYNU-UHFFFAOYSA-N 1-methyl-4-(propan-2-yl)cyclohex-1-ene Chemical compound CC(C)C1CCC(C)=CC1 FAMJUFMHYAFYNU-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical class CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000000193 1,8-cineol derivatives Chemical class 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001271990 Tomicus piniperda Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
（産業上の利用分野）
本発明は、新規化合物である９―アセトキシ―
１，８―シネオール等の１，８―シネオール―９
―置換体及びこれらの製造方法に関するものであ
る。
（従来の技術とその問題点）
天然製油、例えばテレビジヨン油中に含まれる
２―ピネンは、主成分として多く含まれているの
で低廉な価額で入手することができる。
一方、低毒性の農薬の開発が近年進められ、特
にメンタン誘導体からの研究が盛んになつてきて
いる。
しかし、経済的な合成法の開発は未だ成功して
いない。
本発明者は、メンタン誘導体からの農薬等の合
成法開発合戦の先端を切るべく、１，８―シネオ
ール―９―置換体の新規な合成法をデザインし、
その合成デザインにしたがつて、これらを完成し
た。
（問題点を解決するための手段）
即ち、本発明は新規な１，８―シネオール―９
―置換体およびその製造方法である。
１，８―シネオール―９―置換体は次に示す構
造式を有する。
（式中Ａは水素原子もしくは炭素数１〜４のアシ
ル基を示す。）
本発明の１，８―シネオール―９―置換体は、
１，８―ｐ―メンタジエンを四酢酸鉛で酸化して
１―ｐ―メンテングリコールモノアセテートと
し、次いで酸性硫酸水素塩による分子内環化反応
を行うことにより得られる。
１―ｐ―メンテングリコールモノアセテートの
合成は、四酢酸鉛で酸化して行うことができる。
四酢酸鉛は、例えば氷酢酸、無水酢酸および四酸
化三鉛から得られるほか、市販品を用いることが
できる。
酸性硫酸水素塩としては、酸性硫酸水素カリウ
ム、酸性硫酸水素ナトリウム等を用いることがで
きる。
分子内環化反応は酸性硫酸水素塩を反応物に加
え、好ましくは２〜８時間撹拌しながら加熱還流
することにより行うことができる。反応溶媒とし
てはヘキサン、ベンゼン、トルエン等を用いる。
本発明の製造法における反応式は次の式により
示される。
()：１，８―ｐ―メンタジエン
()：１―ｐ―メンテングリコールモノアセテー
ト
()：９―アセトキシ―１，８―シネオール
()：９―ヒドロキシ―１，８―シネオール
以下、実施例により本発明を説明する。
（実施例）
原料の１，８―ｐ―メンタジエン（）は市販
品（安原油脂工業(株)製）を、さらに希炭酸ナトリ
ウム水溶液で洗浄してから精留して得た。
ガスクマトグラフイー純度100％
bp55〜58℃／10mmHg，
d25 4＝0.8406、n25 0＝1.4716、
α30 0＝＋96.7゜
反応で得られた化合物の機器分析については、
ガスクロマトグラフイーはポリエチレングリコー
ル20Mキヤピラリーカラム（φ0.28×20m）を装
備した柳本商事(株)G2800型液体ガスロクマトグラ
フイー（高感度検出器）を用いて60〜180℃（昇
温速度２℃／分）の温度範囲で分析した。質量ス
ペクトルは日本電子HX―100質量分析計を使用
し、加熱電圧3500V、イオン化電圧70eV、イオ
ン源温度270℃、トラツプ電流60μAを用いて測定
した。また核磁気共鳴スペクトルは日本電子FX
―200型核磁気共鳴吸収装置、そして旋光度は日
本分光DIP―140型旋光計を用いて測定した。
◇１―ｐ―メンテングリコールモノアセテート
（）の合成
１，８―ｐ―メンタジエン（）1.0mol（136.0g）
を氷酢酸1920g、無水酢酸685gの混合溶液に溶解
し、内温60±２℃に保ちながら油浴で加熱撹拌
し、四酸化三鉛1.0mol（685g）を２時間を要して
少量ずつ投入したのち、さらに同温度で0.5時間
かきまぜた。反応終了後、水1000mlを加え、炭酸
ナトリウムでアルカリ性にし、ヘキサン100mlで
５回抽出し、水200mlで３回洗浄後、無水硫酸ナ
トリウムで乾燥、ヘキサンを留出し、反応油
165.0gを得た。
反応油165.0gを採り、マクマホン式精留塔を用
いて110〜170℃／mmHgの減圧下に精留し、第１
表に示す生成物を得た。
(Industrial Application Field) The present invention is directed to a novel compound, 9-acetoxy-
1,8-cineole-9 such as 1,8-cineole
- Concerning substituents and their production methods. (Prior art and its problems) Natural oils, such as television oil, contain a large amount of 2-pinene as a main component and can be obtained at a low price. On the other hand, the development of low-toxicity pesticides has been progressing in recent years, and research on menthane derivatives in particular has become active. However, the development of an economical synthesis method has not yet been successful. The present inventor designed a new method for synthesizing 9-substituted 1,8-cineole in order to take the lead in the race to develop methods for synthesizing agricultural chemicals from menthane derivatives.
These were completed according to the composite design. (Means for solving the problems) That is, the present invention provides novel 1,8-cineole-9
- Substituted products and their production methods. The 1,8-cineole-9-substituted product has the structural formula shown below. (In the formula, A represents a hydrogen atom or an acyl group having 1 to 4 carbon atoms.) The 1,8-cineole-9-substituted product of the present invention is
It is obtained by oxidizing 1,8-p-mentadiene with lead tetraacetate to produce 1-p-mentene glycol monoacetate, and then performing an intramolecular cyclization reaction with acidic hydrogen sulfate. 1-p-Menthene glycol monoacetate can be synthesized by oxidation with lead tetraacetate.
Lead tetraacetate can be obtained from, for example, glacial acetic acid, acetic anhydride, and trilead tetroxide, or commercially available products can be used. As the acidic hydrogen sulfate, acidic potassium hydrogen sulfate, acidic sodium hydrogen sulfate, etc. can be used. The intramolecular cyclization reaction can be carried out by adding acidic hydrogen sulfate to the reaction mixture and heating to reflux with stirring for preferably 2 to 8 hours. Hexane, benzene, toluene, etc. are used as the reaction solvent. The reaction formula in the production method of the present invention is shown by the following formula. (): 1,8-p-mentadiene (): 1-p-mentene glycol monoacetate (): 9-acetoxy-1,8-cineole (): 9-hydroxy-1,8-cineole The present invention will be explained below with reference to Examples. (Example) The raw material 1,8-p-mentadiene () was obtained by rectifying a commercially available product (manufactured by Yasushi Oil Industries Co., Ltd.) after further washing with a dilute aqueous sodium carbonate solution. Gas chromatography purity 100% bp55-58℃/10mmHg, d 25 4 = 0.8406, n 25 0 = 1.4716, α 30 0 = +96.7゜ For instrumental analysis of the compound obtained in the reaction,
Gas chromatography was performed using a Yanagimoto Shoji Co., Ltd. G2800 liquid gas chromatography (high sensitivity detector) equipped with a polyethylene glycol 20M capillary column (φ0.28 x 20 m) at 60 to 180°C (heating rate 2). The analysis was carried out over a temperature range of 10°C/min). Mass spectra were measured using a JEOL HX-100 mass spectrometer with a heating voltage of 3500 V, an ionization voltage of 70 eV, an ion source temperature of 270°C, and a trap current of 60 μA. In addition, the nuclear magnetic resonance spectrum is JEOL FX
-200 model nuclear magnetic resonance absorption device, and the optical rotation was measured using a JASCO DIP-140 model polarimeter. ◇Synthesis of 1-p-mentene glycol monoacetate () 1,8-p-mentadiene () 1.0 mol (136.0 g)
was dissolved in a mixed solution of 1920 g of glacial acetic acid and 685 g of acetic anhydride, heated and stirred in an oil bath while keeping the internal temperature at 60±2℃, and 1.0 mol (685 g) of trilead tetroxide was added little by little over 2 hours. After that, the mixture was further stirred at the same temperature for 0.5 hour. After the reaction is complete, add 1000 ml of water, make alkaline with sodium carbonate, extract 5 times with 100 ml of hexane, wash 3 times with 200 ml of water, dry over anhydrous sodium sulfate, distill off the hexane, and remove the reaction oil.
Obtained 165.0g. 165.0g of reaction oil was taken and rectified under reduced pressure of 110-170℃/mmHg using a McMahon type rectifier.
The products shown in the table were obtained.
【表】
分析結果
（ａ）：
マススペクトル
ｍ／z194（M+，１％），152(2)，134（Ｍ―Ac，
73），119（Ｍ―AcOH―CH3，91），106（100），91
（58），84（39），79（50），77（24），68（52），55
(2)，
43（79），41（27），39（17）
1H―NMR
δ1.64ppm（3H，ｓ，C7H3），2.08（3H，ｓ，
C9H2―０―CO―CH3），4.56（2H，ｓ，C9H2―
０―CO―CH3），4.92，5.02（2H，２×ｓ，＝
C9H2），5.36（1H，brs，＝C2H）（ａ）のマスス
ペクトルにはｍ／z194に分子イオンピーク、134
に脱酢酸、119に酢酸とメチル基の両者の脱離に
基づくフラグメントイオンが認められ、 1H―
NMRスペクトルにはδ1.64ppmに7位ビニルメチ
ル、2.08にアセトキシル基のメチル、4.56にアセ
トキシル基付け根のメチレン、4.92、5.02にC10位
の末端メチレン、5.36にC2位のオレフインプロト
ンが認められたことから１，８―ｐ―メンタジエ
ン―９―アセテートと決定した。
（ｂ）：
マススペクトル
ｍ／z152（M+，14％），134（Ｍ―H2O，50），
119（92），106（91），93（72），91（74），84（34）
，79
（83），77（42），68（100），67（79），55（76），5
3
（43），41（55），39（39）
1H―NMR
δ1.49ppm（1H，ｓ，OH），1.65（3H，ｓ，
C7H3），4.13（2H，ｓ，C9H2OH），4.89，5.04
（2H，２×ｄ，＝C9H2），5.38（1H，ｍ，C2H）
（ｂ）のマススペクトルにはｍ／z152に分子
イオンピーク、134に脱水、119に水とメチル基の
両者の脱離に基づくフラグメントイオンが認めら
れ、 1H―NMRスペクトルにはδ1.49ppmに水酸
基のプロトン、1.65にC7ビニルメチル、4.13に水
酸基付け根のメチレン、4.89、5.04に末満メチレ
ン、5.38にC2位オレフインプロトンが認められた
ことから１―ｐ―メンテングリコールジアセテー
トと決定した。
精留により得た（）および（ｂ）からなる
混合物136.1gを2N―NaOH／EtOH1000mlを用い
て80℃、１時間加水分解し、加水分解後エタノー
ルを回収し、水200mlを加え、エーテル500mlで３
回抽出し、水200mlで３回洗浄後、無水硫酸ナト
リウムで乾燥、エーテルを留去して１―ｐ―メン
テングリコール108.1gを得た。続いて10倍量
（1081g）の酢酸を加え、４時間115℃にて加熱還
流した後、常法に処理し水200mlを加え、炭酸ナ
トリウムでアルカリ性にし、ヘキサン1000mlで５
回抽出し、水200mlで３回洗浄後、無水硫酸ナト
リウムで乾燥し、ヘキサンを留去し、２時間蒸留
（100〜145℃／１mmHg）して純度98％の１―ｐ―
メンテングリコールモノアセテート（）を
130.8g得た。
◇１―ｐ―メンテングリコールモノアセテート
（）の分子内環化反応
反応の１例を示す。１―ｐ―メンテングリコー
ルモノアセテート（）100gをヘキサン1000ml
に溶解し、酸性硫酸水素カリウム50gを加えて水
浴で２時間60℃に激しく撹拌しながら加熱した。
反応終了後、炭酸ナトリウム水溶液で中和し、ヘ
キサン2500mlで３回抽出、無水硫酸ナトリウムで
乾燥後、溶媒を65℃で留去して油分98.8gを得た。
◇（）の分離操作の実施例
上記油分9.90gを減圧下に蒸留115〜125℃／１
mmHg）を行い、ガスクマトグラフイー純度95％
の（）を9.25g得た。
分析結果
９―アセトキシ―１，８―シネオール（）：
マススペクトル
ｍ／z197（Ｍ―CH3，１％），152（Ｍ―AcOH，
１），140（13），139（100），124(3)，121(3)，117(3
)，
112(2)，109(4)，95（13），84(4)，82(7)，81(5)，71
(4)，43（30）
1H―NMR
δ1.06ppm（3H，ｓ，C9H3），1.27（3H，ｓ，
C12H3），2.06（3H，ｓ，C9H2―Ｏ―CO―CH3），
3.87，4.12（2H，２×ｄ，C9H2―Ｏ―CO―
CH3），
13C―NMRは第２表に示した。[Table] Analysis results (a): Mass spectrum m/z194 (M + , 1%), 152(2), 134 (M-Ac,
73), 119 (M-AcOH-CH 3 , 91), 106 (100), 91
(58), 84 (39), 79 (50), 77 (24), 68 (52), 55
(2),
43 (79), 41 (27), 39 (17) 1 H-NMR δ1.64ppm (3H, s, C 7 H 3 ), 2.08 (3H, s,
C 9 H 2 ―0―CO―CH 3 ), 4.56 (2H, s, C 9 H 2 ―
0-CO-CH 3 ), 4.92, 5.02 (2H, 2×s, =
The mass spectrum of C 9 H 2 ), 5.36 (1H, brs, = C 2 H) (a) has a molecular ion peak at m/z 194, 134
1 H-
The NMR spectrum shows vinyl methyl at the 7 -position at δ1.64ppm, methyl of the acetoxyl group at 2.08, methylene at the base of the acetoxyl group at 4.56, terminal methylene at the C10 - position at 4.92 and 5.02, and an olefin proton at the C2 - position at 5.36. Therefore, it was determined to be 1,8-p-mentadiene-9-acetate. (b): Mass spectrum m/z152 (M + , 14%), 134 (MH 2 O, 50),
119 (92), 106 (91), 93 (72), 91 (74), 84 (34)
,79
(83), 77 (42), 68 (100), 67 (79), 55 (76), 5
3
(43), 41 (55), 39 (39) 1 H-NMR δ1.49ppm (1H, s, OH), 1.65 (3H, s,
C 7 H 3 ), 4.13 (2H, s, C 9 H 2 OH), 4.89, 5.04
(2H, 2×d, = C 9 H 2 ), 5.38 (1H, m, C 2 H) The mass spectrum of (b) shows a molecular ion peak at m/z 152, dehydration at 134, and water and methyl groups at 119. Fragment ions due to the elimination of both were observed in the 1 H-NMR spectrum, with a proton of the hydroxyl group at δ1.49ppm, C7 vinyl methyl at 1.65, methylene at the base of the hydroxyl group at 4.13, terminal methylene at 4.89 and 5.04, Since an olefin proton at C2 position was observed at 5.38, it was determined to be 1-p-mentene glycol diacetate. 136.1 g of a mixture consisting of () and (b) obtained by rectification was hydrolyzed using 1000 ml of 2N-NaOH/EtOH at 80°C for 1 hour, ethanol was recovered after hydrolysis, 200 ml of water was added, and the mixture was diluted with 500 ml of ether. 3
The extract was extracted twice, washed three times with 200 ml of water, dried over anhydrous sodium sulfate, and the ether was distilled off to obtain 108.1 g of 1-p-mentene glycol. Next, 10 times the amount (1081 g) of acetic acid was added, heated under reflux at 115°C for 4 hours, treated in the usual manner, added 200 ml of water, made alkaline with sodium carbonate, and diluted with 1000 ml of hexane.
Extracted twice, washed three times with 200 ml of water, dried over anhydrous sodium sulfate, distilled off the hexane, and distilled for 2 hours (100-145°C/1 mmHg) to obtain a 1-p-
Menthene glycol monoacetate ()
Obtained 130.8g. ◇Intramolecular cyclization reaction of 1-p-mentene glycol monoacetate () An example of the reaction is shown below. 100g of 1-p-mentene glycol monoacetate () and 1000ml of hexane
50 g of acidic potassium hydrogen sulfate was added, and the mixture was heated at 60° C. for 2 hours with vigorous stirring in a water bath.
After the reaction was completed, the mixture was neutralized with an aqueous sodium carbonate solution, extracted three times with 2500 ml of hexane, dried over anhydrous sodium sulfate, and the solvent was distilled off at 65°C to obtain 98.8 g of oil. ◇Example of separation operation in () 9.90g of the above oil was distilled under reduced pressure at 115-125℃/1
mmHg), gas chromatography purity 95%
9.25g of () was obtained. Analysis results 9-acetoxy-1,8-cineole (): Mass spectrum m/z 197 (M-CH 3 , 1%), 152 (M-AcOH,
1), 140(13), 139(100), 124(3), 121(3), 117(3
),
112(2), 109(4), 95(13), 84(4), 82(7), 81(5), 71
(4), 43 (30) 1 H―NMR δ1.06ppm (3H, s, C 9 H 3 ), 1.27 (3H, s,
C 12 H 3 ), 2.06 (3H, s, C 9 H 2 —O—CO—CH 3 ),
3.87, 4.12 (2H, 2×d, C 9 H 2 -O-CO-
CH 3 ), 13 C-NMR are shown in Table 2.
【表】
９―ヒドロキシ―１，８―シネオール（）：
マススペクトル
ｍ／z155（Ｍ―CH3，0.2％），152（Ｍ―H2O，
0.2），139（100），121(3)，95（19），81(5)，71(8)
，
43（37）
1H―NMR
δ1.07ppm（3H，ｓ，C8H3），1.27（3H，ｓ，
C10H3），1.68（1H，ｓ，OH），3.39，3.61（2H，
２×ｄ，Ｊ＝10.5Hz，C9H2OH）
13C―NMRは第３表に示した。[Table] 9-Hydroxy-1,8-cineole (): Mass spectrum m/z155 (M-CH 3 , 0.2%), 152 (M-H 2 O,
0.2), 139 (100), 121 (3), 95 (19), 81 (5), 71 (8)
，
43 (37) 1 H―NMR δ1.07ppm (3H, s, C 8 H 3 ), 1.27 (3H, s,
C 10 H 3 ), 1.68 (1H, s, OH), 3.39, 3.61 (2H,
2×d, J=10.5Hz, C 9 H 2 OH) 13 C—NMR is shown in Table 3.
【表】
◇（）から（）への加水分解条件
反応油98.8mgを2N―NaOH／EtOH1mlを用い
て１時間80℃で還流し、加水分解を行い、加水分
解後エタノールを回収し、水２mlを加え、ヘキサ
ン10mlで３回抽出し、水５mlで２回洗浄後、無水
硫酸ナトリウムで乾燥、ヘキサンを留去して加水
分解生成物80.9mgを得た。
◇（）の分離操作
加水分解生成物は固定相にシリカゲル、移動相
にヘキサン―エーテル混合溶媒（列例えば３：２
で溶出）を用いるカラムクロマトグラフイーで精
製し、液体ガスクロマトグラフイー単一ピークの
（）を76.1mgを得た。
以上のことから、天然製油中最も豊富で低廉な
価格安定して供給されているテレビン油の主成分
である２―ピネン、２(10)―ピネンから容易に得ら
れる１，８―ｐ―メンタジエン（）を出発物質
として（）の四酢酸鉛酸化、それに次ぐ酸性硫
酸水素塩による（）分子内環化反応の２工程
で、目的化合物である（）が収率約90％で得ら
れ、（）は加水分解で定量的に９―ヒドロキシ
―１，８―シネオール（）に転換しうるので本
研究は（）の経済的な合成経路を確立し得た。
（）のマススペクトルには分子イオンピークは
認められないがｍ／z197に脱メチル、152に脱酢
酸に基づくフラグメントイオンが認められ、 1H
―NMRスペクトルにはδ1.06ppm、1.27にC7，
C10位のメチル基、2.06にアセトキシ基のメチル、
3.87、4.12にアセトキシル基付け根のメチレンプ
ロトンが認められ、さらに 13C―NMRスペクト
ルにはδ22.02ppm、24.29、27.27に３個のメチル
基、69.90にアセトキシル基付け根のメチレン炭
素、70.08、74.40にエーテル付け根C1、C8位の四
級炭素、170.99にアセトキシル基のカルボニル炭
素が観測され、他の炭素も第２表に示したよう
に、矛循なく帰属されたことから、９―アセトキ
シ―１，８―シネオールと決定した。
（）はmp62〜63℃、〔α〕22 2＝＋0.70（Ｃ＝0.5，
CHCl3）を示す白色針状結晶で、マススペクトル
には分子イオンピークは認められないが、ｍ／
z115に脱メチル、152に脱水に基ずくフラグメン
トイオンが認められ、 1H―NMRスペクトルに
はδ1.07ppm、1.27にC7、C10位のメチル基、1.68
に水酸基のプロトン、3.39、3.61に水酸基付け根
のメチレンプロトンが認められ、さらに 13C―
NMRスペクトルにはδ23.77ppm、27.39にC7、
C10位のメチル基、69.14に水酸基付け根のメチレ
ン、70.14、75.63にエーテル付け根のC1、C8位の
四級炭素が認められ、他の炭素も第３表に示した
ように矛循なく帰属されたことから、９―ヒドロ
キシ―1.8―シネオールと決定した。
（発明の効果）
本発明によれば、１，８―ｐ―メンタジエンの
四酢酸鉛酸化による１―ｐ―メンテングリコール
モノアセテートの合成、それに次ぐ酸性硫酸水素
カリウムによる分子内環化反応の２工程で、１，
８―シネオール―９―置換体が高収率で得られ
る。この化合物は、除草剤、農薬（松喰虫の忌避
剤）等の中間体として有用である。[Table] ◇Hydrolysis conditions from () to () 98.8 mg of reaction oil was refluxed at 80°C for 1 hour using 1 ml of 2N-NaOH/EtOH to perform hydrolysis, recover ethanol after hydrolysis, and add 2 ml of water. was added, extracted three times with 10 ml of hexane, washed twice with 5 ml of water, dried over anhydrous sodium sulfate, and distilled off the hexane to obtain 80.9 mg of a hydrolyzed product. ◇ Separation operation for () The hydrolyzed product is prepared using silica gel as the stationary phase and a hexane-ether mixed solvent (column, e.g. 3:2) as the mobile phase.
It was purified by column chromatography using (elution) and liquid gas chromatography to obtain 76.1 mg of a single peak (). From the above, 2-pinene, the main component of turpentine oil, which is the most abundant, inexpensive, and stably supplied natural oil, 1,8-p-mentadiene ( ) as a starting material, the target compound () was obtained in approximately 90% yield through two steps: lead tetraacetate oxidation of (), followed by intramolecular cyclization reaction () with acidic hydrogen sulfate, and (). can be quantitatively converted to 9-hydroxy-1,8-cineole () by hydrolysis, so this study was able to establish an economical synthetic route for (). In the mass spectrum of (), no molecular ion peak is observed, but fragment ions due to demethylation at m/z 197 and deacetic acid at m/z 152 are observed.
-NMR spectrum shows δ1.06ppm, C 7 at 1.27,
Methyl group at C 10 position, methyl acetoxy group at 2.06,
Methylene protons at the base of the acetoxyl group are observed at 3.87 and 4.12, and δ22.02ppm in the 13 C-NMR spectrum, three methyl groups at 24.29 and 27.27, methylene carbon at the base of the acetoxyl group at 69.90, and ether at 70.08 and 74.40. The carbonyl carbon of the acetoxyl group was observed at the base C1 , the quaternary carbon at the C8 position, and the carbonyl carbon at 170.99, and other carbons were also assigned without contradiction as shown in Table 2, so 9-acetoxy-1 ,8-Cineole was decided. () is mp62-63℃, [α] 22 2 = +0.70 (C = 0.5,
It is a white needle crystal that shows CHCl 3 ), and no molecular ion peak is observed in the mass spectrum, but m/
Fragment ions due to demethylation at z115 and dehydration at 152 are observed, δ1.07ppm in the 1 H-NMR spectrum, methyl group at C7 and C10 positions at 1.27, and 1.68
A proton of the hydroxyl group is observed in , a methylene proton at the base of the hydroxyl group is observed in 3.39 and 3.61, and 13 C―
NMR spectrum shows δ23.77ppm, C7 at 27.39,
A methyl group at the C10 position, methylene at the hydroxyl group at 69.14, C1 at the ether base at 70.14 and 75.63, and a quaternary carbon at the C8 position, and the other carbons are also consistent as shown in Table 3. Based on the assignment, it was determined to be 9-hydroxy-1.8-cineole. (Effects of the Invention) According to the present invention, there are two steps: synthesis of 1-p-mentene glycol monoacetate by lead tetraacetic acid oxidation of 1,8-p-mentadiene, followed by intramolecular cyclization reaction with acidic potassium hydrogen sulfate. So, 1,
8-cineole-9-substituted product is obtained in high yield. This compound is useful as an intermediate for herbicides, agricultural chemicals (pine beetle repellent), and the like.
Claims (1)
して１―ｐ―メンテングリコールモノアセテート
とし、次いで酸性硫酸水素塩による分子内環化反
応を行うことを特徴とする１，８―シネオール―
９―置換体の製造方法。[Claims] 1. General formula: (In the formula, A represents an acyl group having 1 to 4 carbon atoms.) A 1,8-cineole-9-substituted product represented by: 2 1,8-Cineol- characterized by oxidizing 1,8-p-mentadiene with lead tetraacetate to produce 1-p-mentene glycol monoacetate, and then performing an intramolecular cyclization reaction with acidic hydrogen sulfate.
9-Method for producing substituted product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62085833A JPS63253081A (en) | 1987-04-09 | 1987-04-09 | 1,8-cineole-9-substituted compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62085833A JPS63253081A (en) | 1987-04-09 | 1987-04-09 | 1,8-cineole-9-substituted compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63253081A JPS63253081A (en) | 1988-10-20 |
| JPH0257553B2 true JPH0257553B2 (en) | 1990-12-05 |
Family
ID=13869853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62085833A Granted JPS63253081A (en) | 1987-04-09 | 1987-04-09 | 1,8-cineole-9-substituted compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63253081A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19608316C2 (en) * | 1996-02-22 | 2000-11-09 | Ivoclar Ag Schaan | Functionalized bicyclic (meth) acrylates, process for their preparation and their use #### |
-
1987
- 1987-04-09 JP JP62085833A patent/JPS63253081A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63253081A (en) | 1988-10-20 |
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