JPH02282377A - Production of cis-7-decen-4-olide - Google Patents
Production of cis-7-decen-4-olideInfo
- Publication number
- JPH02282377A JPH02282377A JP10337289A JP10337289A JPH02282377A JP H02282377 A JPH02282377 A JP H02282377A JP 10337289 A JP10337289 A JP 10337289A JP 10337289 A JP10337289 A JP 10337289A JP H02282377 A JPH02282377 A JP H02282377A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- oxo
- reaction
- organic solvent
- 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 10
- NKNGVPNCSFZRSM-ONEGZZNKSA-N 5-(3-hexenyl)dihydro-2(3h)-furanone Chemical compound CC\C=C\CCC1CCC(=O)O1 NKNGVPNCSFZRSM-ONEGZZNKSA-N 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052987 metal hydride Inorganic materials 0.000 claims description 4
- 150000004681 metal hydrides Chemical class 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000007273 lactonization reaction Methods 0.000 claims description 3
- JZAOQHBPUGDRPQ-UHFFFAOYSA-N 5-hex-3-ynyloxolan-2-one Chemical compound CCC#CCCC1CCC(=O)O1 JZAOQHBPUGDRPQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006114 decarboxylation reaction Methods 0.000 claims description 2
- 150000003900 succinic acid esters Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 6
- 150000002168 ethanoic acid esters Chemical class 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- -1 4-oxo-7-decynoic acid ester Chemical class 0.000 abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003205 fragrance Substances 0.000 abstract description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 3
- 239000012312 sodium hydride Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 238000005755 formation reaction Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002596 lactones Chemical class 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000010656 jasmine oil Substances 0.000 description 2
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical group COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MHSLDASSAFCCDO-UHFFFAOYSA-N 1-(5-tert-butyl-2-methylpyrazol-3-yl)-3-(4-pyridin-4-yloxyphenyl)urea Chemical compound CN1N=C(C(C)(C)C)C=C1NC(=O)NC(C=C1)=CC=C1OC1=CC=NC=C1 MHSLDASSAFCCDO-UHFFFAOYSA-N 0.000 description 1
- VDHGRVFJBGRHMD-UHFFFAOYSA-N 1-bromopent-2-yne Chemical compound CCC#CCBr VDHGRVFJBGRHMD-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NKNGVPNCSFZRSM-UHFFFAOYSA-N 5-hex-3-enyloxolan-2-one Chemical compound CCC=CCCC1CCC(=O)O1 NKNGVPNCSFZRSM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical group 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XBOWOKOGHZCGDS-WAYWQWQTSA-N ethyl (Z)-4-oxodec-7-enoate Chemical compound CCOC(=O)CCC(=O)CC\C=C/CC XBOWOKOGHZCGDS-WAYWQWQTSA-N 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- XXFQGNXPWZSRRK-UHFFFAOYSA-N sodium;n-chlorobenzenesulfonamide Chemical group [Na+].ClNS(=O)(=O)C1=CC=CC=C1 XXFQGNXPWZSRRK-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ジャスミン油の香気成分から見い出され、従
来の文献に記載のシス−７−デセン−４オリト（γ−ジ
ャスモラクトン）の新規な製法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is a novel method for producing cis-7-decene-4olito (γ-jasmolactone), which is found from the aromatic components of jasmine oil and described in the conventional literature. Regarding the manufacturing method.
更に詳しくは、本発明はジャスミン様の香気をで表され
るシス−７−デセン−４−オリドの新規な製法に関する
。More specifically, the present invention relates to a novel method for producing cis-7-decene-4-olide, which exhibits a jasmine-like aroma.
（従来の技術）
従来、シス−７−デセン−４−オリドを合成する方法と
しては、例えば、Ｈｅ ｌ ｖ、Ｃｈ ｉｍ。(Prior Art) Conventionally, methods for synthesizing cis-7-decene-4-olide include, for example, Helv and Chim.
Ａｃｔａ、、６１．９９０−９９７ （１９７８）が提
案されている。該方法によると、アクロレインを（Ｚ）
−３−ヘキセニルマグネシウムブロマイドと縮合反応
させ（Ｚ）−ノナ−１，５−ジエン−３−オールを合成
した後、該化合物をクロム酸酸化して（Ｚ）−ノナ−１
，６−ゲニン−３オンを形成し、次に該化合物をシアン
化ナトリウムと反応させて、（Ｚ）−１−シアノ−６−
ノネン−３−オンを合成し、更に該化合物をｐ−トルエ
ンスルホン酸の存在下にエタノールと反応させてエチル
（Ｚ）−４−オキソ−７−デセノエートを形成し、更に
また該化合物を水素化ホウ素ナトリウムで還元ラクトン
化して（Ｚ）−γ−ジャスモラクトンを合成している。Acta, 61.990-997 (1978). According to the method, acrolein (Z)
After a condensation reaction with -3-hexenylmagnesium bromide to synthesize (Z)-nona-1,5-dien-3-ol, the compound was oxidized with chromic acid to form (Z)-nona-1.
,6-genin-3one and then reacting the compound with sodium cyanide to form (Z)-1-cyano-6-
synthesize nonen-3-one, further react the compound with ethanol in the presence of p-toluenesulfonic acid to form ethyl (Z)-4-oxo-7-decenoate, and further hydrogenate the compound. (Z)-γ-jasmolactone is synthesized by reductive lactonization with sodium boron.
（発明が解決しようとする課題）
しかしながら、上記の従来提案された方法は、式（１）
の化合物を製造する工程数が多く、また目的化合物の収
率も満足できるものではなく、更に反応工程に毒性のあ
るクロム酸を使用しているため安全衛生上問題点があり
、必ずしも満足のいくものではなく解決すべき課題があ
った。(Problem to be Solved by the Invention) However, the previously proposed method described above is based on the formula (1)
The number of steps required to produce the compound is large, and the yield of the target compound is not satisfactory.Furthermore, the use of toxic chromic acid in the reaction process poses safety and health problems, and the process is not always satisfactory. There were problems to be solved, not things.
そこで本発明者らは、上記の課題を解決するため、鋭意
研究を行った結果、後記式（５）の３オキソ−６−ノニ
ン酸エステル類を出発原料に選ぶことにより、毒性の強
いクロム酸を用いることなく短い製造工程数で、香料化
合物として有用な前記式（１）の化合物を好収率、好純
度で合成できることを発見して本発明を完成した。Therefore, in order to solve the above problems, the present inventors conducted intensive research and found that by selecting 3oxo-6-nonynoic acid esters of formula (5) below as a starting material, the highly toxic chromic acid The present invention was completed by discovering that the compound of the formula (1), which is useful as a fragrance compound, can be synthesized in good yield and purity in a short number of production steps without using.
従って、本発明の目的は、従来の合成方法と比較して有
利な方法で、香料化合物として有用な前記式（１）の化
合物を製造する方法を提供することにある。Therefore, an object of the present invention is to provide a method for producing the compound of formula (1) useful as a fragrance compound using a method that is more advantageous than conventional synthesis methods.
（課題を解決するための手段）
本発明によれば、後記式（５）の３−オキソ６−ノニン
酸エステル類を有機溶媒中、塩基の存在下に後記式（６
）のハロゲン化酢酸エステル類と縮合反応させて後記式
（４）の２−（１−オキソ−４−へブチニル）コハク酸
エステル類を合成し、法式（４）の化合物を有機溶媒中
、酸の存在下に加熱し加水分解脱炭酸反応させて後記式
（３）の４−オキソ−７−デシン酸エステル類を合成し
、次に法式（３）の化合物を金属水素化物で環化ラクト
ン化反応させ後記式（２）の７−デシン−４オリドを合
成し、さらに法式（２）の化合物を触媒の存在下に水素
で部分還元させることにより本発明の前記式（１）の化
合物を容易に合成することができる。(Means for Solving the Problems) According to the present invention, 3-oxo-6-nonynoic acid esters of the formula (5) below are added to the 3-oxo-6-nonynoic acid esters of the formula (6) below in an organic solvent in the presence of a base.
) to synthesize 2-(1-oxo-4-hebutynyl)succinic acid esters of the formula (4) described later, and the compound of the formula (4) was reacted with an acid in an organic solvent. 4-oxo-7-decinoic acid esters of the formula (3) described later are synthesized by heating in the presence of a hydrolytic decarboxylation reaction, and then the compound of the formula (3) is cyclized and lactonized with a metal hydride. The compound of the formula (1) of the present invention can be easily synthesized by reacting to synthesize 7-decyne-4 olide of the formula (2) below, and further partially reducing the compound of the formula (2) with hydrogen in the presence of a catalyst. can be synthesized into
本発明の式（１）の化合物の合成法を反応式で示すと、
例えば、以下のように表すことができる。The method for synthesizing the compound of formula (1) of the present invention is shown by a reaction formula:
For example, it can be expressed as follows.
式中、Ｒはメチル基およびエチル基を示し、Ｘはハロゲ
ン原子を示す
上記反応式に従って、本発明の式（１）の化合物の合成
法を以下に詳細に述べる。In the formula, R represents a methyl group or an ethyl group, and X represents a halogen atom. A method for synthesizing the compound of formula (1) of the present invention will be described in detail below according to the above reaction formula.
本発明の出発原料である式（５）の化合物は文献に記載
の化合物であり、例えば、アセト酢酸エステル類ジアニ
オンを２−ペンチニルブロマイドと縮合反応させて容易
に合成することができる。The compound of formula (5), which is the starting material of the present invention, is a compound described in literature, and can be easily synthesized, for example, by condensing an acetoacetate dianion with 2-pentynyl bromide.
式（５）の化合物の具体例としてはメチル−３−オキソ
−６−ノ二ノエートおよびエチル−３−オキソ−６−ノ
二ノエートを挙げることができる。Specific examples of the compound of formula (5) include methyl-3-oxo-6-nondinoate and ethyl-3-oxo-6-nondinoate.
上記反応式において、式（５）の化合物から式（４）の
化合物を合成するには、式（５）の化合物を有機溶媒中
、塩基の存在下に式（６）の化合物と縮合反応させるこ
とにより容易に行うことができる。In the above reaction formula, to synthesize the compound of formula (4) from the compound of formula (5), the compound of formula (5) is subjected to a condensation reaction with the compound of formula (6) in an organic solvent in the presence of a base. This can be easily done.
上記の反応は、例えば、約Ｑ ’Ｏ〜約１００℃、より
好ましくは約り０℃〜約８０°Ｃの温度範囲で、通常約
１時間〜約５０時間、より好ましくは約５時間〜約３０
時間程度で行うことができる。The above reaction is carried out, for example, at a temperature range of about Q'O to about 100°C, more preferably about 0°C to about 80°C, usually for about 1 hour to about 50 hours, more preferably about 5 hours to about 30
It can be done in about an hour.
この反応に使用する式（６）の化合物としては、フッ素
、塩素、臭素、ヨウ素などのノ）ロゲン原子が置換した
酢酸のメチルおよびエチルエステルを例示することがで
き、好ましい具体例としてメチルブロモアセテート、メ
チルクロルアセテ−１・、エチルブロモアセテート、エ
チルクロルアセテートなどを挙げることができる。これ
ら式（６）の化合物の使用量は、例えば、式（５）の化
合物１モルに対して、約１モル〜約３モル、より好まし
くは約１．２モル−約２．０モル程度の範囲内を例示す
ることができる。Examples of the compound of formula (6) used in this reaction include methyl and ethyl esters of acetic acid substituted with chlorogen atoms such as fluorine, chlorine, bromine, and iodine, and a preferred specific example is methyl bromoacetate. , methyl chloroacetate-1., ethyl bromoacetate, ethyl chloroacetate, and the like. The amount of the compound of formula (6) to be used is, for example, about 1 mol to about 3 mol, more preferably about 1.2 mol to about 2.0 mol, per 1 mol of the compound of formula (5). Examples can be given within the range.
上記の反応に使用する塩基の具体例としては、例えば、
水素化ナトリウム、ソジウムメトキシド、ソジウムエト
キシド、ソジウムアミドなどを挙げることができ、その
使用量は、例えば、式（５）の化合物１モルに対して、
約１モル〜約３モル、より好ましくは約１．２モル−約
２．０モル程度の範囲内を挙げることができる。また、
この反応に使用する有機溶媒の種類としては、例えば、
テトラヒドロフラン、メタノール、エタノール、ベンゼ
ン、トルエン、ジメトキシエタンなどを挙げることがで
きる。これらの有機溶媒の使用量には特別な制約はなく
、例えば、式（５）の化合物に対して、約２〜約５０重
量倍程度の範囲をより好ましく例示できる。Specific examples of the base used in the above reaction include, for example:
Sodium hydride, sodium methoxide, sodium ethoxide, sodium amide, etc. can be mentioned, and the amount used is, for example, per 1 mole of the compound of formula (5).
The amount can be in the range of about 1 mol to about 3 mol, more preferably about 1.2 mol to about 2.0 mol. Also,
Examples of the types of organic solvents used in this reaction include:
Examples include tetrahydrofuran, methanol, ethanol, benzene, toluene, dimethoxyethane, and the like. There is no particular restriction on the amount of these organic solvents to be used, and a more preferable range is, for example, about 2 to about 50 times the weight of the compound of formula (5).
反応終了後は常法に従って洗浄、抽出、乾燥、濃縮、必
要により蒸留などの精製手段を用いることにより式（４
）の化合物を好収率、好純度で得ることができる。この
ようにして得られる式（４）の化合物の好ましい具体例
としては、例えば、ジメチル２−（１−オキソ−４−へ
ブチニル）サクシネート、ジエチル２−（ｌ−オキソ−
４−へブチニル）サクシネートを挙げることができる。After the reaction is completed, the formula (4
) can be obtained in good yield and purity. Preferred specific examples of the compound of formula (4) obtained in this way include dimethyl 2-(1-oxo-4-hebutynyl)succinate, diethyl 2-(l-oxo-
4-hebutynyl) succinate may be mentioned.
上述のようにして得ることのできる式（４）の化合物か
ら式（３）の化合物を合成するには、式（４）の化合物
を有機溶媒中、酸の存在下に加熱し、加水分解脱炭酸反
応を行うことにより容易に合成することができる。To synthesize the compound of formula (3) from the compound of formula (4) that can be obtained as described above, the compound of formula (4) is heated in an organic solvent in the presence of an acid to undergo hydrolytic desorption. It can be easily synthesized by carrying out a carbonic acid reaction.
この反応は、例えば、約３０°Ｃ〜約１００℃程度の温
度範囲内で、約１時間〜約５０時間程度の反応時間で行
うことができる。This reaction can be carried out, for example, within a temperature range of about 30° C. to about 100° C., and for a reaction time of about 1 hour to about 50 hours.
上記反応に使用する酸の例示としては、例えば、塩酸、
硫酸、臭化水素酸、リン酸などを挙げることができる。Examples of acids used in the above reaction include hydrochloric acid,
Sulfuric acid, hydrobromic acid, phosphoric acid, etc. can be mentioned.
これら酸の使用量としては、例えば、式（４）の化合物
１モルに対して、約１モル〜約１０モル程度の範囲内を
挙げることができる。またこの反応で用いる有機溶媒の
種類としては、例えば、メタノール、エタノールなどを
挙げることができ、その使用量は式（４）の化合物に対
して、約１〜約２０重量倍程度の範囲をより好ましく例
示することができる。式（３）の化合物の具体例として
はメチル４−オキソ−７−ゾシノエート、エチル４−オ
キソ−７−ゾシノエートを挙げることができる。The amount of these acids to be used is, for example, within the range of about 1 mol to about 10 mol per 1 mol of the compound of formula (4). Examples of the organic solvent used in this reaction include methanol and ethanol, and the amount used is about 1 to about 20 times the weight of the compound of formula (4). Preferred examples can be given. Specific examples of the compound of formula (3) include methyl 4-oxo-7-zosinoate and ethyl 4-oxo-7-zosinoate.
上記した方法で得ることのできる式（３）の化合物から
式（２）の化合物を合成するには、式（３）の化合物を
金属水素化物で環化ラクトン化反応させることにより容
易に行うことができる。The compound of formula (2) can be easily synthesized from the compound of formula (3) that can be obtained by the above method by subjecting the compound of formula (3) to a cyclization and lactonization reaction with a metal hydride. I can do it.
上記の反応は、約−３０°Ｃ〜約８０°Ｃ程度の温度範
囲内で、通常約１時間〜約３０時間程度の範囲内で行う
ことができる。The above reaction can be carried out within a temperature range of about -30°C to about 80°C, and usually for about 1 hour to about 30 hours.
この反応に使用する金属水素化物の具体例としては、例
えば、水素化ホウ素すトリウムを挙げることができる。A specific example of the metal hydride used in this reaction is, for example, sodium borohydride.
この化合物の使用量は、例えば、式（３）の化合物１モ
ルに対して、約０．２５モル〜約０．５モル程度の範囲
内を好ましく例示することができる。またこの反応は溶
媒の存在下で行うことができ、使用する溶媒の種類とし
ては、例えば、エタノール、メタノール、イングロパノ
ール、ジグリム、水などを例示することができる。The amount of this compound to be used is preferably within the range of about 0.25 mol to about 0.5 mol, for example, per 1 mol of the compound of formula (3). Further, this reaction can be carried out in the presence of a solvent, and examples of the type of solvent used include ethanol, methanol, ingropanol, diglyme, and water.
これら溶媒の使用量は、式（３）の化合物に対して、約
２〜約５０重量倍程度の範囲内を好ましく挙げることが
できる。The amount of these solvents to be used is preferably about 2 to about 50 times the weight of the compound of formula (3).
反応終了後は常法に従って、洗浄、乾燥、濃縮、必要に
より、例えば、カラムクロマトグラフィーなどの手段を
用いて精製することにより式（２）の化合物を好収率、
好純度で得ることができる。After the reaction is completed, the compound of formula (2) can be obtained in good yield by washing, drying, concentrating, and, if necessary, purifying using means such as column chromatography according to conventional methods.
It can be obtained with good purity.
前記反応式において、上述のようにして得ることのでき
る式（２）の化合物から本発明の式（１）の化合物を合
成するには、式（２）の化合物を触媒の存在下に水素で
部分還元することにより容易に行うことができる。In the above reaction formula, to synthesize the compound of formula (1) of the present invention from the compound of formula (2) that can be obtained as described above, the compound of formula (2) is reacted with hydrogen in the presence of a catalyst. This can be easily achieved by partial reduction.
上記の反応は、例えば、約１〜約２０°Ｃ程度の温度範
囲で行うことができ、より好ましくは約Ｊｏ０ｃ〜約３
０ ’Ｏ程度の範囲がしばしば採用される。反応時間に
は特別な制約はなく、理論量の水素吸収があったところ
を反応の終点とすればよい。The above reaction can be carried out, for example, at a temperature range of about 1 to about 20°C, more preferably about Jo0c to about 3°C.
A range of around 0'O is often adopted. There is no particular restriction on the reaction time, and the end point of the reaction may be the point at which the theoretical amount of hydrogen has been absorbed.
水素圧は、例えば、約１ｋｇ／ｃｍ２〜約５０ｋｇ ／
ｃ ｍ ”程度の範囲で行うことができ、好ましくは
約５ｋｇ／ｃｍ２−約１０ｋｇ／ｃｍ２程度の範囲がし
ばしば採用される。The hydrogen pressure is, for example, about 1 kg/cm2 to about 50 kg/cm2.
It can be carried out within a range of approximately 5 kg/cm 2 to approximately 10 kg/cm 2 , and is often employed preferably.
上記反応に用いる触媒の具体例としては、リンドラ−型
触媒、Ｐ２−ニッケル触媒などを挙げることができる。Specific examples of catalysts used in the above reaction include Lindlar type catalysts and P2-nickel catalysts.
これらの触媒の使用量は適宜に変更できるが、式（２）
の化合物に対して、好ましくは約１〜約３０重量％程度
、より好ましくは約２〜約１０重量％程度である。Although the amount of these catalysts used can be changed as appropriate, formula (2)
It is preferably about 1 to about 30% by weight, more preferably about 2 to about 10% by weight, based on the compound.
また上お反応は有機溶媒の存在下で行うことができ、使
用する有機溶媒の具体例としてはメタノール、エタノー
ル、ヘキサン、トルエンなどを挙げることができる。こ
れらの有機溶媒の使用量は特別の制約はないが、式（２
）の化合物に対して、約２〜約５０重量倍程度を例示す
ることができる。Further, the reaction can be carried out in the presence of an organic solvent, and specific examples of the organic solvent used include methanol, ethanol, hexane, and toluene. There is no particular restriction on the amount of these organic solvents used, but the formula (2
) can be exemplified in an amount of about 2 to about 50 times the weight of the compound.
反応終了後、使用した触媒を濾別し、減圧下に蒸留を行
って、式（１）の化合物を好収率、好純度で取得するこ
とができる。After the reaction is completed, the used catalyst is filtered off and distilled under reduced pressure to obtain the compound of formula (1) in good yield and purity.
以下に本発明について、実施例を挙げて詳細に説明する
。The present invention will be described in detail below with reference to Examples.
（実施例）
実施例１
ジメチル２−（１−オキソ−４−へブチニル）サクシネ
ート［（４）の化合物］の合成フラスコに６０％の水素
化ナトリウム１４．５ｇ （０，３６モル）およびテト
ラヒドロフラン５００ｍ１を仕込む。氷水冷却下（５〜
１０°Ｃ）、３０分間でメチル３−オキソ−６一ノ二ノ
エート５５ｇ （０，３０モル）のテトラヒドロフラン
溶液１００ｍ１を滴下し、さらに３０分間撹拌する。Examples Example 1 Synthesis of dimethyl 2-(1-oxo-4-hebutynyl)succinate [compound (4)] 14.5 g (0.36 mol) of 60% sodium hydride and 500 ml of tetrahydrofuran were added to a flask. Prepare. Cooled with ice water (5~
10 DEG C.), 100 ml of a solution of 55 g (0.30 mol) of methyl 3-oxo-6-inodinoate in tetrahydrofuran was added dropwise over 30 minutes, and the mixture was stirred for a further 30 minutes.
次に、５〜１０°Ｃで３０分間を要して、メチルブロモ
アセテート５５ｇ （０，３６モル）のテトラヒドロフ
ラン溶液１００ｍ１を滴下する。滴下後、更に室温で２
０時間撹拌して反応させる。反応終了後、反応生成物を
中和、エーテル抽出、洗浄、乾燥、濃縮する。得られた
残渣を蒸留することにより純粋な式（４）の化合物６１
ｇを得た。Next, 100 ml of a solution of 55 g (0.36 mol) of methyl bromoacetate in tetrahydrofuran is added dropwise over a period of 30 minutes at 5-10°C. After dropping, add 2 more at room temperature.
Stir and react for 0 hours. After the reaction is completed, the reaction product is neutralized, extracted with ether, washed, dried, and concentrated. Pure compound 61 of formula (4) is obtained by distilling the obtained residue.
I got g.
収率、８０％
沸点＝１４０°Ｃ！−１５０℃／ｌｍｍＨｇ実施例２
メチル４−オキソ−７−ゾシノエート［式（３）の化合
物］の合成。Yield, 80% Boiling point = 140°C! -150°C/lmmHg Example 2 Synthesis of methyl 4-oxo-7-zosinoate [compound of formula (3)].
フラスコに６規定の塩酸２００ｇ、メタノール４００ｇ
およびジメチル２−（ｌ−オキソ−４へブチニル）サク
シネート６０ｇ （０，２３６モル）を仕込み、す７ラ
ツクス（７５°Ｃ）させながら１５時間撹拌し反応させ
る。反応終了後、生成物を食塩水中に注入し、エーテル
抽出する。エテル層を水洗浄、乾燥、濃縮する。更に得
られた残渣を蒸留することにより、純粋な式（３）の化
合物３４．７ｇを得た。200g of 6N hydrochloric acid and 400g of methanol in a flask
and 60 g (0,236 mol) of dimethyl 2-(l-oxo-4-hebutynyl)succinate were charged, and the mixture was stirred and reacted for 15 hours at a temperature of 7 lux (75°C). After the reaction is complete, the product is poured into brine and extracted with ether. The ether layer is washed with water, dried, and concentrated. Further, the obtained residue was distilled to obtain 34.7 g of pure compound of formula (3).
収率ニア５％ 沸点：１１２°Ｃ！−１１５°Ｏ／ｌｍｍＨｇ実施例３ ７−デシン−４−オリド［式（２）の化合物］の合成。Yield near 5% Boiling point: 112°C! -115°O/lmmHg Example 3 Synthesis of 7-decyne-4-olide [compound of formula (2)].
フラスコに水素化ホウ素ナトリウム３．０ｇ（０，０８
モル）および９５％エチルアルコール１００ｍ１を仕込
む。この中に、氷水冷却下（５〜１０℃）３０分間でメ
チル４−オキソ−７−ゾシノエート３０ｇ（０，１５モ
ル）の９５％エチルアルコール溶液５０ｍ１を滴下する
。滴下後、さらに室温で１５時間撹拌して反応させる。3.0 g (0.08 g) of sodium borohydride in a flask
mol) and 100 ml of 95% ethyl alcohol. 50 ml of a 95% ethyl alcohol solution containing 30 g (0.15 mol) of methyl 4-oxo-7-zosinoate is added dropwise to this mixture over a period of 30 minutes while cooling with ice water (5 to 10 DEG C.). After the dropwise addition, the reaction mixture is further stirred at room temperature for 15 hours.
反応終了後、反応生成物を中和し、エーテル抽出する。After the reaction is completed, the reaction product is neutralized and extracted with ether.
エーテル層を洗浄、乾燥、濃縮する。得られた残渣をシ
リカゲルカラムクロマトグラフィー（ｎ−ヘキサン：酢
酸エチル： ３ ： １）で精製することにより、純粋
な式（２）の化合物１６．４ｇを得た。Wash, dry, and concentrate the ether layer. The obtained residue was purified by silica gel column chromatography (n-hexane:ethyl acetate: 3:1) to obtain 16.4 g of pure compound of formula (2).
収率：６６％
沸点：１２３°０−１２８°Ｏ／ ｌ ｍ ｍ Ｈｇ実
施例４
シス−７−デセン−４−オリド［式（１）の化合物Ｊの
合成。Yield: 66% Boiling point: 123°0-128°O/l m m Hg Example 4 Synthesis of cis-7-decene-4-olide [Compound J of formula (1).
３００ｍ１のオートクレーブに７−デシン−４オリドロ
ｇ（３６ミリモル）、メタノール１００ｍ１、リンドラ
−触媒０．６ｇおよびキノリン０．６ｇを仕込む。室温
で、水素圧０．５〜５ｋｇ ／ ｃ ｍ ”の条件で水
素添加反応を行う。理論量の水素吸収があったところで
反応を終了する。反応終了後、反応生成物を釜出し、触
媒を濾別する。A 300 ml autoclave is charged with 7-decyne-4olidrog (36 mmol), 100 ml of methanol, 0.6 g of Lindlar catalyst and 0.6 g of quinoline. The hydrogenation reaction is carried out at room temperature and at a hydrogen pressure of 0.5 to 5 kg/cm.The reaction is terminated when the theoretical amount of hydrogen has been absorbed.After the reaction is complete, the reaction product is taken out of the pot and the catalyst is removed. Filter.
濾液を洗浄、乾燥、濃縮した後、蒸留することにより純
粋な式（１）の化合物５ｇを得た。The filtrate was washed, dried, concentrated, and then distilled to obtain 5 g of pure compound of formula (1).
収率：８３％
沸点：１０６°Ｃ！−１１０℃／１ｍｍＨｇ（発明の効
果）
本発明は、前記式（１）で表されるシス−７−デセン−
４−オリド（γ−ジャスモラクトン）の新規な製法を提
供するにある。該製法は、入手容易な式（５）の３−オ
キソ−６−ノニン酸エステル類を出発原料として、短い
製造工程で好収率、好純度に式（１）の化合物を合成す
るものである。Yield: 83% Boiling point: 106°C! -110°C/1mmHg (Effect of the invention) The present invention provides cis-7-decene-
An object of the present invention is to provide a new method for producing 4-olide (γ-jasmolactone). This production method uses readily available 3-oxo-6-nonynoic acid esters of formula (5) as starting materials to synthesize the compound of formula (1) in good yield and purity in a short manufacturing process. .
また、法式（１）の化合物はジャスミン油に含まれてお
り、ジャスミン様の香料組成物の調合素材として有用で
ある。Furthermore, the compound of formula (1) is contained in jasmine oil and is useful as a compounding material for jasmine-like fragrance compositions.
Claims (1)
３−オキソ−６−ノニン酸エステル類を有機溶媒中、塩
基の存在下に下記式（６） ▲数式、化学式、表等があります▼（６） 式中、Ｒはメチル基およびエチル基を示し、Ｘはハロゲ
ン原子を示す で表されるハロゲン化酢酸エステル類と縮合反応させて
下記式（４） ▲数式、化学式、表等があります▼（４） 式中、Ｒはメチル基およびエチル基を示す、で表される
２−（１−オキソ−４−ヘプチニル）コハク酸エステル
類を形成させ、該式（４）の化合物を有機溶媒中、酸の
存在下に加熱し加水分解脱炭酸反応させて下記式（３） ▲数式、化学式、表等があります▼（３） 式中、Ｒはメチル基およびエチル基を示す、で表される
４−オキソ−７−デシン酸エステル類を形成させ、次に
該式（３）の化合物を金属水素化物で環化ラクトン化反
応させ下記式（２）▲数式、化学式、表等があります▼
（２） で表される７−デシン−４−オリドを形成させ、更に該
式（２）の化合物を触媒の存在下に水素で部分還元させ
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） で表されるシス−７−デセン−４−オリドの製法。[Claims] 1. 3-oxo-6-nonine represented by the following formula (5) ▲ Numerical formula, chemical formula, table, etc. ▼ (5) In the formula, R represents a methyl group or an ethyl group. Acid esters are prepared in an organic solvent in the presence of a base using the following formula (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) In the formula, R represents a methyl group and an ethyl group, and X represents a halogen atom. A condensation reaction with a halogenated acetic acid ester represented by the following formula (4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (4) In the formula, R represents a methyl group or an ethyl group. -(1-oxo-4-heptynyl)succinic acid esters are formed, and the compound of formula (4) is heated in an organic solvent in the presence of an acid to cause a hydrolytic decarboxylation reaction to form the following formula (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) In the formula, R represents a methyl group and an ethyl group. The compound is subjected to a cyclization and lactonization reaction with a metal hydride to form the following formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
The following formula (1) is characterized by forming 7-decyne-4-olide represented by (2) and further partially reducing the compound of formula (2) with hydrogen in the presence of a catalyst. There are chemical formulas, tables, etc. ▼ (1) Manufacturing method of cis-7-decene-4-olide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10337289A JP2787468B2 (en) | 1989-04-25 | 1989-04-25 | Production method of cis-7-decene-4-olide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10337289A JP2787468B2 (en) | 1989-04-25 | 1989-04-25 | Production method of cis-7-decene-4-olide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02282377A true JPH02282377A (en) | 1990-11-19 |
| JP2787468B2 JP2787468B2 (en) | 1998-08-20 |
Family
ID=14352279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10337289A Expired - Fee Related JP2787468B2 (en) | 1989-04-25 | 1989-04-25 | Production method of cis-7-decene-4-olide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2787468B2 (en) |
-
1989
- 1989-04-25 JP JP10337289A patent/JP2787468B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2787468B2 (en) | 1998-08-20 |
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