JPS63222164A - Production of alpha,beta-unsaturated delta-lactones - Google Patents
Production of alpha,beta-unsaturated delta-lactonesInfo
- Publication number
- JPS63222164A JPS63222164A JP5317687A JP5317687A JPS63222164A JP S63222164 A JPS63222164 A JP S63222164A JP 5317687 A JP5317687 A JP 5317687A JP 5317687 A JP5317687 A JP 5317687A JP S63222164 A JPS63222164 A JP S63222164A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- olide
- compound
- reaction
- reacting
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000000422 delta-lactone group Chemical group 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims abstract description 9
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000002253 acid Substances 0.000 abstract description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 239000000796 flavoring agent Substances 0.000 abstract description 2
- 235000019634 flavors Nutrition 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 abstract 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- -1 alcohol compound Chemical class 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 4
- XPTXKXKPWKNYKB-UHFFFAOYSA-N 6-Heptyl-5,6-dihydro-2H-pyran-2-one Chemical compound CCCCCCCC1CC=CC(=O)O1 XPTXKXKPWKNYKB-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DYNKRGCMLGUEMN-UHFFFAOYSA-N 2-methyl-2,3-dihydropyran-6-one Chemical compound CC1CC=CC(=O)O1 DYNKRGCMLGUEMN-UHFFFAOYSA-N 0.000 description 2
- FAPYUVKMJWJMEH-UHFFFAOYSA-N 5-pentyloxolan-2-ol Chemical compound CCCCCC1CCC(O)O1 FAPYUVKMJWJMEH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- KSQKIXDIEWBMGO-UHFFFAOYSA-N 2,5-dihydroxynonanenitrile Chemical compound CCCCC(O)CCC(O)C#N KSQKIXDIEWBMGO-UHFFFAOYSA-N 0.000 description 1
- FZGRTOXOBUQQAD-UHFFFAOYSA-N 2-butyl-2,3-dihydropyran-6-one Chemical compound CCCCC1CC=CC(=O)O1 FZGRTOXOBUQQAD-UHFFFAOYSA-N 0.000 description 1
- HUFRMAUWIZDZIJ-UHFFFAOYSA-N 2-hydroxyhexano-6-lactone Chemical compound OC1CCCCOC1=O HUFRMAUWIZDZIJ-UHFFFAOYSA-N 0.000 description 1
- CRCMEDPBLYDLQH-UHFFFAOYSA-N 2-nonyl-2,3-dihydropyran-6-one Chemical compound CCCCCCCCCC1CC=CC(=O)O1 CRCMEDPBLYDLQH-UHFFFAOYSA-N 0.000 description 1
- VOTUWUFYGAFJPA-UHFFFAOYSA-N 2-octyl-2,3-dihydropyran-6-one Chemical compound CCCCCCCCC1CC=CC(=O)O1 VOTUWUFYGAFJPA-UHFFFAOYSA-N 0.000 description 1
- XHFKKMXWXSWHOZ-UHFFFAOYSA-N 2-pentadecyl-2,3-dihydropyran-6-one Chemical compound CCCCCCCCCCCCCCCC1CC=CC(=O)O1 XHFKKMXWXSWHOZ-UHFFFAOYSA-N 0.000 description 1
- ZFFLYUGDQAHVSE-UHFFFAOYSA-N 2-propyl-2,3-dihydropyran-6-one Chemical compound CCCC1CC=CC(=O)O1 ZFFLYUGDQAHVSE-UHFFFAOYSA-N 0.000 description 1
- KHBGZIAKALJFRO-UHFFFAOYSA-N 2-tetradecyl-2,3-dihydropyran-6-one Chemical compound CCCCCCCCCCCCCCC1CC=CC(=O)O1 KHBGZIAKALJFRO-UHFFFAOYSA-N 0.000 description 1
- LIIXNZRSHIMJDW-UHFFFAOYSA-N 2-undecyl-2,3-dihydropyran-6-one Chemical compound CCCCCCCCCCCC1CC=CC(=O)O1 LIIXNZRSHIMJDW-UHFFFAOYSA-N 0.000 description 1
- NWOULGUVRYNVGI-UHFFFAOYSA-N 3-hydroxy-6-methyloxan-2-one Chemical compound CC1CCC(O)C(=O)O1 NWOULGUVRYNVGI-UHFFFAOYSA-N 0.000 description 1
- FJHWWAFZOCILBV-UHFFFAOYSA-N 3-hydroxy-6-nonyloxan-2-one Chemical compound CCCCCCCCCC1CCC(O)C(=O)O1 FJHWWAFZOCILBV-UHFFFAOYSA-N 0.000 description 1
- NLDGWCCPRWYBAS-UHFFFAOYSA-N 3-hydroxy-6-pentyloxan-2-one Chemical compound CCCCCC1CCC(O)C(=O)O1 NLDGWCCPRWYBAS-UHFFFAOYSA-N 0.000 description 1
- LDEIGBGMYXTCGI-UHFFFAOYSA-N 5-butyloxolan-2-ol Chemical compound CCCCC1CCC(O)O1 LDEIGBGMYXTCGI-UHFFFAOYSA-N 0.000 description 1
- ZHDOFGHVOHPUIL-UHFFFAOYSA-N 5-methyloxolan-2-ol Chemical compound CC1CCC(O)O1 ZHDOFGHVOHPUIL-UHFFFAOYSA-N 0.000 description 1
- YBAKFVHKAJNLRW-UHFFFAOYSA-N CCCCC1CCC(O)C(=O)O1 Chemical compound CCCCC1CCC(O)C(=O)O1 YBAKFVHKAJNLRW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WHFBEAHOEDIAOX-UHFFFAOYSA-N decane-2,5-diol Chemical compound CCCCCC(O)CCC(C)O WHFBEAHOEDIAOX-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WQGRORNFTHKGRO-UHFFFAOYSA-N heptadecane-2,5-diol Chemical compound CCCCCCCCCCCCC(O)CCC(C)O WQGRORNFTHKGRO-UHFFFAOYSA-N 0.000 description 1
- ZXPWFWWSCFIFII-UHFFFAOYSA-N heptadecanenitrile Chemical compound CCCCCCCCCCCCCCCCC#N ZXPWFWWSCFIFII-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- NEDIAPMWNCQWNW-UHFFFAOYSA-N massoia lactone Chemical compound CCCCCC1CC=CC(=O)O1 NEDIAPMWNCQWNW-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- VMUTVYRBWACMMQ-UHFFFAOYSA-N tetradecane-2,5-diol Chemical compound CCCCCCCCCC(O)CCC(C)O VMUTVYRBWACMMQ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、バター乃至ミルク様の香気を有する香料化合
物として有用な公知物質であるα２．β−不飽和δ−ラ
クトンの新規な製法に間する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to α2. A new method for producing β-unsaturated δ-lactones is developed.
更に詳しくは、本発明は下記式（１）
但し式中、Ｒはアルキル基を示す、
で表されるα、β−不飽和δ−ラクトンの新規な製法に
間する。More specifically, the present invention is directed to a novel method for producing an α,β-unsaturated δ-lactone represented by the following formula (1), where R represents an alkyl group.
（従来の技術）
従来、上記式（１）で表されるα、β−不飽和δ−ラク
トンの製法に間して、例えば下記反応工程図で示した合
成方法（２−ドデセン−５−オリドの合成例）が知られ
ている（特公昭４６−４１１８３）。(Prior art) Conventionally, in the production of α,β-unsaturated δ-lactone represented by the above formula (1), for example, the synthesis method (2-dodecene-5-olide) shown in the reaction process diagram below has been used. Synthesis example) is known (Japanese Patent Publication No. 46-41183).
クシＢ「＋／νへ７、式）１０ □
（Ａ） ＣＢ）
（Ｃ）
（Ｄン（Ｅ）
上記反応工程区の方法によれば、式（Ａ）のプロパギル
ブロマイドと式（Ｂ）のオクタナールとをリホルマトス
キー反応で、式（Ｃ）のアルコール化合物を形成せしめ
、これにエチルマグネシウムブロマイドを作用させて、
式（Ｄ）のグリ・二アール試薬とした後、オートクレー
ブ中において、いでリンドラ−触媒を用いて部分還元し
て、これを蒸留しながらラクトン化して上記式（１）化
合物に包含される式（Ｇ）の２−ドデセン−５−オリド
を合成している。Comb B "7 to +/ν, formula) 10 □ (A) CB) (C)
(D-(E)) According to the method of the above reaction step, propargyl bromide of formula (A) and octanal of formula (B) are subjected to a reformatoski reaction to form an alcohol compound of formula (C), By acting with ethylmagnesium bromide,
After preparing the Gly-Nial reagent of formula (D), it is partially reduced using a Lindlar catalyst in an autoclave, and then lactonized while distilling to obtain the formula ( G) 2-dodecene-5-olide is synthesized.
（発明が解決しようとする問題点）
上記従来提案の方法における問題点としては、例えば、
工程数が長く、反応手段が極めて煩雑である点、又、各
段とも副生成物が生成し易くそれぞれの化合物を純度良
く得られない点、更に工業的に適さないリホマトスキー
反応を用いている点など多くの問題点がある。(Problems to be solved by the invention) Problems in the conventionally proposed method described above include, for example:
The number of steps is long and the reaction means are extremely complicated. Also, by-products are easily produced in each stage, making it difficult to obtain each compound in high purity. Furthermore, the Lihomatosky reaction is used, which is not suitable for industrial use. There are many problems such as.
（問題点を解決するための手段）
その結果、市場で安価且つ容易に入手可能なδて、工程
数が短く、そして、副生成物を伴うこと但し式中、Ｒは
アルキル基を示す、
で表されるアルキルラクトールをシアン化カリウム、シ
アン化ナトリウムもしくはシアン化水素と反応させて、
下記式（３）
但し式中、Ｒは上記したと同義１
、下記式（２）
但し式中、Ｒはアルキル基を示す、
で表される２−ヒドロキシ−アルキル−５−オリドを塩
基の存在下にメシルクロリドと反応させて、下記式（１
）
但し式中、Ｒは上記したと同義、
で表されるα、β−不飽和δ−ラクトン類を容易な操作
で工業的に高純度且つ安価に合成できることを発見した
。(Means for solving the problem) As a result, δ, which is inexpensive and easily available on the market, requires a short number of steps and produces by-products, provided that in the formula, R represents an alkyl group. Reacting the represented alkyl lactol with potassium cyanide, sodium cyanide or hydrogen cyanide,
Formula (3) below, where R has the same meaning as above 1, Formula (2) below, where R represents an alkyl group. By reacting with mesyl chloride, the following formula (1
) In the formula, R has the same meaning as above, and it has been discovered that α,β-unsaturated δ-lactones represented by the following can be synthesized industrially with high purity and at low cost by easy operations.
従って、本発明の目的は、上記従来提案の方法ある。Therefore, the object of the present invention is to provide the above-mentioned conventionally proposed method.
本発明の上記式（１）化合物の製造を上記式（４）化合
物の製造例を含めて卦赫修嚢４工程図で示すと以下のよ
うに表すことができる。The production of the above formula (1) compound of the present invention can be expressed as follows when the production of the above formula (4) compound is shown in a four-step diagram.
本発明の２−アルケン−５−オリドの製造方法を上記工
程図に従って、以下に説明する。The method for producing 2-alkene-5-olide of the present invention will be explained below according to the above process diagram.
上記式（４）のアルキルラクトールから、上記式（３）
のアルキルシアンヒドリンを合成するには、例えば、式
（４）化合物をシアン化ナトリウム、シアン化カリウム
もしくはシアン化水素と反ル、のどとき溶媒及び酢酸、
プロピオン酸、硫酸上記反応の反応温度及び反応時間は
、適宜に選択して行うことができるが、例えば、約００
〜約１００”Ｃ程度の範囲の温度で、約４〜約１０時間
程度の範囲の反応時間を好ましく例示することができる
。この反応に使用するシアン化ナトリウム、シアン化カ
リウムもしくはシアン化水素の使用量としては、例えば
式（４）化合物１モルに対して、約１〜約５モル程度の
範囲を好ましくあげることができる。又、上記のごとき
溶媒の使用量には特別の制限はなく、適宜に選択すれば
良いが使用量も適宜選択して行うことができ墨が、例え
ばシアン化ナトリウム、シアン化カリウムもしくはシア
ン化水素に対して、約０．５〜ｒ１３モル倍抽出し、水
洗浄を行い、濃縮することにより式（３）化合物を容易
に得ることができる。From the alkyl lactol of the above formula (4), the above formula (3)
To synthesize the alkyl cyanohydrin, for example, the compound of formula (4) is mixed with sodium cyanide, potassium cyanide or hydrogen cyanide, a solvent and acetic acid,
Propionic acid, sulfuric acid The reaction temperature and reaction time of the above reaction can be suitably selected, but for example, about 0.0
Preferred examples include a reaction time of about 4 to about 10 hours at a temperature of about 100" C. The amount of sodium cyanide, potassium cyanide or hydrogen cyanide used in this reaction is as follows: For example, the amount of the solvent used can be preferably about 1 to about 5 mol per 1 mol of the compound of formula (4).Also, there is no particular restriction on the amount of the solvent used, and it can be selected as appropriate. However, the amount used can be selected appropriately.The black ink can be extracted by extracting about 0.5 to 13 moles of sodium cyanide, potassium cyanide, or hydrogen cyanide, washing with water, and concentrating it to obtain the formula ( 3) The compound can be easily obtained.
ここで得ることのできる上記式（３）化合物中、Ｒの好
ましいアルキルの具体例としては、例えば０１〜Ｃ１５
のアルキル基を例示することができる。In the compound of formula (3) that can be obtained here, specific examples of preferable alkyl for R include, for example, 01 to C15
The alkyl group can be exemplified.
次に、上述で得られた式（３）アルキルシアンヒドリン
から式（２）の２−ヒドロキシ−アルキル−５−オリド
を合成するには、式（３）化合物を酸の存在下に加熱反
応させることにより容易に合成することができる。Next, in order to synthesize the 2-hydroxy-alkyl-5-olide of formula (2) from the alkylcyanhydrin of formula (3) obtained above, the compound of formula (3) is subjected to a heating reaction in the presence of an acid. It can be easily synthesized by
反応は、例えば約３０”〜約１５０°Ｃ１より好ましく
は約５０°Ｃ〜約１００”Ｃ程度の広い範囲で行うこと
ができる。又、反応時間は、例えば約０．５〜約６時閏
程度の範囲で行うことができる。この反応に使用する酸
としては例えば、塩酸、硫酸、リン酸のごとき酸を例示
することができる。これらの酸の使用量には、特別の制
限はなく広い範囲で使用可能であるが、例えば、式（３
）化合物に対して約０．２〜約５モル程度の範囲上述の
ようにして合成することの出来る式（２）化合物から、
式（１）のα、β−不飽和δ−ラクトンを合成するには
、まず式（２）化合物を塩基の存在下に、メシルクロリ
ドと反応してメシレートを形成せしめ、引き続き反応を
続けて脱メタンスルホン酸反応することにより容易に合
成することができる。The reaction can be carried out in a wide range, for example, from about 30" to about 150°C, more preferably from about 50°C to about 100"C. Further, the reaction time can be set, for example, in a range of about 0.5 to about 6 hours. Examples of acids used in this reaction include hydrochloric acid, sulfuric acid, and phosphoric acid. The amount of these acids to be used is not particularly limited and can be used within a wide range.
) from the compound of formula (2) that can be synthesized as described above, in a range of about 0.2 to about 5 mol based on the compound,
To synthesize the α,β-unsaturated δ-lactone of formula (1), the compound of formula (2) is first reacted with mesyl chloride in the presence of a base to form mesylate, and then the reaction is continued to remove the compound. It can be easily synthesized by reaction with methanesulfonic acid.
メシレート形成反応は、例えば、約−１０°〜約５０°
Ｃ程度、より好ましくは約００〜約３０°Ｃ程度の範囲
で、約１〜約７時間程度、より好ましくは約２〜約３時
間程度の範囲の反応時間で行うことができる。上記反応
に使用するメシルクロリドの使用量としては、例えば、
約１〜約６モル程度の範囲、より好ましくは約１．２〜
約３モル程度の範囲を例示することができる。又、この
反応に使用する塩基としては、例えば、ピリジン、ジメ
チルアミン、ジエチルアミン、ジメチルホルムアミド、
ジメチルアセトアミド、トリエチルアミン、トリエタノ
ールアミンなどのごとき、塩基を例示することができる
。これらの塩基の使用量には、特別の制限はなく多量に
使用しても差し支えないが、例えば、メシルクロリドに
対して約１〜約５０モル程度の範囲を好ましく例示する
ことができる。The mesylate formation reaction is, for example, about -10° to about 50°
The reaction can be carried out at a temperature of about 100°C to about 30°C, more preferably about 00°C to about 30°C, and for a reaction time of about 1 to about 7 hours, more preferably about 2 to about 3 hours. The amount of mesyl chloride used in the above reaction is, for example,
The range is about 1 to about 6 moles, more preferably about 1.2 to about 6 moles.
A range of about 3 moles can be exemplified. In addition, examples of the base used in this reaction include pyridine, dimethylamine, diethylamine, dimethylformamide,
Examples include bases such as dimethylacetamide, triethylamine, triethanolamine, and the like. The amount of these bases to be used is not particularly limited and may be used in large amounts, but for example, a range of about 1 to about 50 moles relative to mesyl chloride is preferably exemplified.
反応終了後は、反応生成物を単離してから、脱メタンス
ルホン酸反応を行ってもよいが、通常は単離することな
く、脱メタンスルホン酸反応に移ることができる。After completion of the reaction, the reaction product may be isolated and then subjected to the demethanesulfonic acid reaction, but usually the reaction product can be moved to the demethanesulfonic acid reaction without isolation.
上述のようにして得られたメシレートを単離することな
く脱メタンスルホン酸反応を行うには、メシレート形成
後、反応温度を例えば、約７０”〜約２００” Ｃ程度
の範囲、より好ましくは約１００°〜約１５０”Ｃ程度
の範囲に上昇させ、約１〜約８時間程度、より好ましく
は、約３〜約５時間程度の範囲の反応時間で行うことが
できる。In order to carry out the demethanesulfonic acid reaction without isolating the mesylate obtained as described above, after forming the mesylate, the reaction temperature is adjusted to a range of, for example, about 70" to about 200" C, more preferably about The temperature can be raised to about 100[deg.] to about 150''C for a reaction time of about 1 to about 8 hours, more preferably about 3 to about 5 hours.
反応終了後は、反応生成物中にエーテルのごとき有機溶
媒を注入して抽出し、エーテル層を水洗浄して、濃縮し
、例えば蒸留のごとき手段で精製して、式（１）化合物
を得ることができる。・又、上述で得られたメシレート
を単離してから脱メタンスルホン酸反応を行う場合は、
上述のメシレート形成反応に用いたと同様の塩基を使用
し、又上述の脱メタンスルホン酸反応と同一条件を採用
して、式（１）化合物を合成することもできる。After the reaction is completed, an organic solvent such as ether is injected into the reaction product for extraction, and the ether layer is washed with water, concentrated, and purified by means such as distillation to obtain the compound of formula (1). be able to. -Also, when performing the demethanesulfonic acid reaction after isolating the mesylate obtained above,
The compound of formula (1) can also be synthesized by using the same base as used in the mesylate formation reaction described above and by employing the same conditions as in the demethanesulfonic acid reaction described above.
１〜Ｃ１５のアルキル基を好ましく例示することができ
る。これらの化合物の具体例としては、例えば、２−ヘ
キセン−５−オリド、２−へブテン−５−オリド、２−
オクテン−５−オリド、−ノネン−５−オリド、２−デ
セン−５−オリド、２−ウンデセン−６−オリド、２−
ドデセン−５−オリド、２−トリデセン−５−オリド、
２−テトラデセン−５−オリド、２−ペンタデセン−６
−オリド、２−へキサデセン−５−オリド、２−へブタ
デセン−６−オリド、２−オクタデセン−６−オリド、
２−ノナデセン−５−オリド、２−エイコセン−５−オ
リドなどを好ましく例示す、ることかできる。Preferred examples include 1 to C15 alkyl groups. Specific examples of these compounds include 2-hexene-5-olide, 2-hebutene-5-olide, 2-
Octene-5-olide, -nonene-5-olide, 2-decene-5-olide, 2-undecene-6-olide, 2-
Dodecene-5-olide, 2-tridecene-5-olide,
2-tetradecene-5-olide, 2-pentadecene-6
-olide, 2-hexadecen-5-olide, 2-hebutadecen-6-olide, 2-octadecen-6-olide,
Preferred examples include 2-nonadecene-5-olide and 2-eicosene-5-olide.
以下本発明の実施態様を実施例をあげて更に詳細に説明
する。Hereinafter, embodiments of the present invention will be described in more detail by way of examples.
（実施例）
（１）２．５−ジヒドロキシ−ノナンニトリル式％式％
エタノール４７５ｇ、シアン化カリウム６３゜５ｇ （
０，９８モル）、２−ヒドロキシ−５−ブチルテトラヒ
ドロフラン１００ｇ （０，６３モル）中にかくはんし
なからｏ” ｃ、ａｏ分間で酢酸８５．５ｇ （０１，
４２５モル）を加えた。更に同温で１時間かくはん後、
反応混合物は氷水中に注入、エーテル抽出、水洗、炭酸
水素ナトリウム水溶液洗浄を順次行った後、溶媒を除去
して１１２ｇ（収率９６％）の油状の標記化合物を得た
。(Example) (1) 2.5-dihydroxy-nonanenitrile formula% formula% Ethanol 475g, potassium cyanide 63°5g (
85.5 g of acetic acid (01,
425 mol) was added. After further stirring at the same temperature for 1 hour,
The reaction mixture was poured into ice water, extracted with ether, washed with water, and washed with an aqueous sodium bicarbonate solution, and then the solvent was removed to obtain 112 g (yield: 96%) of the title compound as an oil.
（２）実施例（１）の２−ヒドロキシ−５−ブチル−テ
トラヒドロフランの代わりに、２−ヒドロキシ−５−メ
チル−テトラヒドロフラン、２−ヒドロキシ−５−ペン
チル−テトラヒドロフラン、２−ヒドロキシ−５−ヘプ
チル−テトラヒドロフラン、２−ヒドロキシ−６−ノニ
ルーテトラヒドロフラン、２−ヒドロキシ−５−ドデシ
ル−テトラヒドロフラン、２−ヒドロキシ−５−テトラ
デシル−テトラヒドロフランを用いた他は実施例（１）
に準じて行って、各種の式（３）化合物を合成した。そ
の結果を表−１に示した。(2) Instead of 2-hydroxy-5-butyl-tetrahydrofuran in Example (1), 2-hydroxy-5-methyl-tetrahydrofuran, 2-hydroxy-5-pentyl-tetrahydrofuran, 2-hydroxy-5-heptyl- Example (1) except that tetrahydrofuran, 2-hydroxy-6-nonyl-tetrahydrofuran, 2-hydroxy-5-dodecyl-tetrahydrofuran, and 2-hydroxy-5-tetradecyl-tetrahydrofuran were used.
Various compounds of formula (3) were synthesized according to the following procedure. The results are shown in Table-1.
表−１
２，５−ジヒドロキシ−ヘキサンニド ８５リル
２．５−ジヒドロキシ−デカンニトリ ９６ル
２．５−ジヒドロキシードデカンニド ９５リル
２．５−ジヒドロキシ−テトラデカン ９８ニトリル
２．５−ジヒドロキシ−ヘプタデカン ９２ニトリル
２．５−ジヒドロキシーノナデカンニ ９６ニリル
（３）２−ヒドロキシ−５−ブチル−ノナン−５−オリ
ド式（２）の合成。Table 1 2,5-dihydroxy-hexannido 85lyl 2,5-dihydroxy-decane nitri 96lyl 2,5-dihydroxydedecannide 95lyl 2,5-dihydroxy-tetradecane 98 nitrile 2,5-dihydroxy-heptadecane 92 nitrile 2 .5-Dihydroxynonadecanni 96nilyl (3) Synthesis of 2-hydroxy-5-butyl-nonane-5-olide formula (2).
２．５−ジヒドロキシ−ノナンニトリル式（３％式％ ３０分閏下前え、同温で１５分間撹拌を続けた。2.5-dihydroxy-nonanenitrile formula (3% formula% Before cooling for 30 minutes, stirring was continued for 15 minutes at the same temperature.
冷浸、エーテル抽出、食塩水洗浄後、溶媒を除去して、
減圧蒸留すると沸点１２０°〜１３５°Ｃ／２〜３ｍｍ
Ｈｇで７６ｇ（収率６８％）の留分を得た。After cooling, ether extraction, and saline washing, the solvent was removed.
When distilled under reduced pressure, the boiling point is 120° to 135°C/2 to 3 mm.
A fraction of 76 g (68% yield) was obtained using Hg.
ＩＲ；３４００．１７４０．１１２０ｃｍＭ５；１８６
（４）実施例（３）の２，５−ジヒドロキシノナンニト
リルの代わりに、２，６−シヒドロキシーヘキサンニト
リル、２，５−ジヒドロキシ−デカンニトリル、２，５
−ジヒドロキシ−ドデカンニトリル、２，５−ジヒドロ
キシ−テトラデカンニトリル、２，５−ジヒドロキシ−
ヘプタデカンニトリル、２，５−ジヒドロキシ−ノナデ
カンニトリルを用いた他は、実施例（３）と同様に行、
って、各種の式（２）化合物を合成した。その結果を表
−２に示した。IR; 3400.1740.1120cmM5; 186 (4) Instead of 2,5-dihydroxynonanenitrile in Example (3), 2,6-cyhydroxyhexanenitrile, 2,5-dihydroxy-decanenitrile, 2, 5
-dihydroxy-dodecanenitrile, 2,5-dihydroxy-tetradecanenitrile, 2,5-dihydroxy-
The same procedure as in Example (3) was carried out except that heptadecane nitrile and 2,5-dihydroxy-nonadecane nitrile were used.
Thus, various compounds of formula (2) were synthesized. The results are shown in Table-2.
表−２
式（２）化合物 収率％２−ヒドロキシ
ーヘキサン−５−オリド ６５２−ヒドロキシ−デカン
−５−オリド ６８２−ヒドロキシ−ドデカン−５−
オリド ６５２−ヒドロキシ−テトラデカン−５−オ
７０リド
２−ヒドロキシ−ヘプタデカン−５−オ ７２リド
２−ヒドロキシ−ノナデカン−５−オリ ７２ ド
（５）２−ノネン−５−オリド式（１）の合成。Table 2 Formula (2) Compound Yield% 2-hydroxy-hexane-5-olide 652-hydroxy-decane-5-olide 682-hydroxy-dodecane-5-
Olido 652-hydroxy-tetradecan-5-o
70 Lido 2-Hydroxy-heptadecan-5-olide 72 Lido 2-hydroxy-nonadecane-5-olide 72 Do(5) 2-Nonene-5-olide Synthesis of formula (1).
２−ヒドロキシ−５−ブチル−ノナン−６−オリド式（
２）２８ｇ （０，１５モル）、トリエチルアミン２３
ｇ （０，２３） 、ジメチルホルムアミド７３ｇ中に
、０°Ｇ、１時間でメタンスルホニルクロリド２０．８
ｇ （０，１８モル）を加えた。同温で１間熱撹拌後、
１３００〜１３５・′″Ｃで６時間反応した。冷浸、水
洗浄、エーテル抽出、炭酸水素ナトリウム水溶液洗浄、
水洗浄を順次行った後、乾燥後減圧蒸留した。2-hydroxy-5-butyl-nonane-6-olide formula (
2) 28g (0.15 mol), triethylamine 23
g (0,23), methanesulfonyl chloride 20.8 in 73 g dimethylformamide at 0°G for 1 hour.
g (0.18 mol) was added. After stirring for 1 hour at the same temperature,
Reaction was carried out at 1300 to 135·''C for 6 hours. Cooling, water washing, ether extraction, sodium bicarbonate aqueous solution washing,
After sequentially washing with water, it was dried and then distilled under reduced pressure.
湘点；１０５＠〜１０８°Ｃ／２ｍｍＨｇＩＲおよびＮ
ＭＲの分析結果は、標準品と一致した。Xiang point; 105@~108°C/2mmHgIR and N
The MR analysis results were consistent with the standard product.
（６）実施例（６）の２−ヒドロキシ−ノナン−５−オ
リドの代わりに２−ヒドロキシ−ヘキサン−６−オリド
、２−ヒドロキシ−デカン−５−オリド、２−ヒドロキ
シ−ドデカン−５−オリド、２−ヒドロキシ−テトラデ
カン−５−オリド、２−ヒドロキシ−ヘプタ−デカン−
５−オリド、２−ヒドロキシ−ノナデカン−５−オリド
を用いた他は、実施例（５）に準じて行って各種の式（
１）化合物を合成した。その結果を表−３に示した表−
３
式（１）化合物 収率％２−ヘキ
センー５−オリド ５５２−デセン−５−
オリド ７０２−ドデセン−５−オリド
７．２２−テトラデセン−５−オリド
７０２−へブタデセン−５−オリド
７５２−ノナデセン−５−オリド ７８これ
ら化合物のＩＲ及びＮＭＲの分析結果は棟準品と一致し
た。(6) 2-hydroxy-hexane-6-olide, 2-hydroxy-decane-5-olide, 2-hydroxy-dodecane-5-olide instead of 2-hydroxy-nonane-5-olide in Example (6) , 2-hydroxy-tetradecane-5-olide, 2-hydroxy-hepta-decane-
Various formulas (
1) A compound was synthesized. The results are shown in Table 3.
3 Formula (1) compound Yield% 2-hexene-5-olide 552-decene-5-
olide 702-dodecene-5-olide 7.22-tetradecene-5-olide
702-hebutadecen-5-olide
752-Nonadecene-5-olide 78 The IR and NMR analysis results of these compounds were consistent with the standard product.
（発明の効果）
本発明によれば、バター乃至ミルク様の香気を有する香
料物質として有用な２−アルケン−５−オリド類を工業
的に安価且つ容易に製造できる方法を提供することがで
きる。(Effects of the Invention) According to the present invention, it is possible to provide a method for industrially producing 2-alkene-5-olides, which are useful as flavor substances having a butter-like or milk-like aroma, at low cost and easily.
すなわち、下記式（１）
但し式中、Ｒはアルキル基を示す、
で表されるα、β−不飽和δ−ラクトンを市場で容易に
人手出来るγ−アルキルラクトンを水素化して容易に合
成できるアルキルラクトール（２−ヒドロキシ−６−ア
ルキル−テトラヒドロフラン）を原料として、工程数が
短く、そして副生、酸物を伴うことなく高純度で且つ筒
車な操作で製造できる方法を提供することができる。That is, the α,β-unsaturated δ-lactone represented by the following formula (1), where R represents an alkyl group, can be easily synthesized by hydrogenating a γ-alkyl lactone that can be easily obtained on the market. To provide a method that uses alkyl lactol (2-hydroxy-6-alkyl-tetrahydrofuran) as a raw material, has a short number of steps, produces high purity without producing by-products or acids, and can be produced by simple operation. can.
ほか１名1 other person
Claims (1)
基の存在下にメシルクロリドと反応せしめることを特徴
とする下記式（１） ▲数式、化学式、表等があります▼（１） 但し式中、Ｒは上記したと同義、 で表されるα，β−不飽和δ−ラクトン類の製法。 ２、該式（２）化合物が、下記式（４） ▲数式、化学式、表等があります▼（４） 但し式中、Ｒはアルキル基を示す、 で表されるアルキルラクトールをシアン化カリウム、シ
アン化ナトリウムもしくはシアン化水素と反応させて、
下記式（３） ▲数式、化学式、表等があります▼（３） 但し式中、Ｒは上記したと同義、 で表されるアルキルシアンヒドリンを形成せしめ、次い
で該式（３）化合物を酸と反応させて形成されることを
特徴とする特許請求の範囲第１項記載の製法。[Claims] 1. The following formula (2) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (2) However, in the formula, R represents an alkyl group, 2-hydroxy-alkyl-5-olide represented by The following formula (1) is characterized by reacting with mesyl chloride in the presence of a base ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) However, in the formula, R has the same meaning as above, and α represented by , a method for producing β-unsaturated δ-lactones. 2. The compound of formula (2) has the following formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) However, in the formula, R represents an alkyl group. By reacting with sodium chloride or hydrogen cyanide,
The following formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (3) However, in the formula, R has the same meaning as above, and an alkylcyanohydrin represented by is formed, and then the compound of formula (3) is acidified. The manufacturing method according to claim 1, characterized in that it is formed by reacting with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5317687A JPH082891B2 (en) | 1987-03-10 | 1987-03-10 | Process for producing α, β-unsaturated δ-lactones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5317687A JPH082891B2 (en) | 1987-03-10 | 1987-03-10 | Process for producing α, β-unsaturated δ-lactones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222164A true JPS63222164A (en) | 1988-09-16 |
| JPH082891B2 JPH082891B2 (en) | 1996-01-17 |
Family
ID=12935553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5317687A Expired - Lifetime JPH082891B2 (en) | 1987-03-10 | 1987-03-10 | Process for producing α, β-unsaturated δ-lactones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082891B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467424A (en) * | 2013-08-22 | 2013-12-25 | 南京华安药业有限公司 | Synthesizing method of 2,5-dihydroxyvaleric acid delta lactone |
| WO2015128552A1 (en) | 2014-02-27 | 2015-09-03 | Charabot | Method for producing lactones from a strain of aureobasidium pullulans |
-
1987
- 1987-03-10 JP JP5317687A patent/JPH082891B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467424A (en) * | 2013-08-22 | 2013-12-25 | 南京华安药业有限公司 | Synthesizing method of 2,5-dihydroxyvaleric acid delta lactone |
| WO2015128552A1 (en) | 2014-02-27 | 2015-09-03 | Charabot | Method for producing lactones from a strain of aureobasidium pullulans |
| US10196659B2 (en) | 2014-02-27 | 2019-02-05 | Charabot | Method for producing lactones from a strain of Aureobasidium pullulans |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082891B2 (en) | 1996-01-17 |
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