JPH01265085A - Production of 3,7,11-trimethyl-2,6,10-dodecatrienoic acid (2,2-dimethyl-1,3-dioxolan-4-yl)methyl ester - Google Patents
Production of 3,7,11-trimethyl-2,6,10-dodecatrienoic acid (2,2-dimethyl-1,3-dioxolan-4-yl)methyl esterInfo
- Publication number
- JPH01265085A JPH01265085A JP32102687A JP32102687A JPH01265085A JP H01265085 A JPH01265085 A JP H01265085A JP 32102687 A JP32102687 A JP 32102687A JP 32102687 A JP32102687 A JP 32102687A JP H01265085 A JPH01265085 A JP H01265085A
- Authority
- JP
- Japan
- Prior art keywords
- dimethyl
- acid
- methyl ester
- dioxolan
- dioxolane
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- GUTBPJMBNXXRIK-UHFFFAOYSA-N (2,2-dimethyl-1,3-dioxolan-4-yl)methyl 3,7,11-trimethyldodeca-2,6,10-trienoate Chemical compound CC(C)=CCCC(C)=CCCC(C)=CC(=O)OCC1COC(C)(C)O1 GUTBPJMBNXXRIK-UHFFFAOYSA-N 0.000 title 1
- -1 (dimethyl-dioxolan-yl) methyl Chemical group 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 claims abstract description 6
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract 3
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 150000004702 methyl esters Chemical class 0.000 claims description 6
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- 238000006052 Horner reaction Methods 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- 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３，７．１１−）ジメチル−２，６，１０−ド
デカトリエン酸（２，２−ジメチル−１，３−ジオキソ
ラン−４−イル）メチルエステル（以下ＫＮＣ−２２５
と略称する）の新規製造法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to 3,7,11-)dimethyl-2,6,10-dodecatrienoic acid (2,2-dimethyl-1,3-dioxolane-4- yl) methyl ester (hereinafter KNC-225
(abbreviated as )).
ＫＮＣ−２２５は裸妃類（Ｄｏｒｉｄ ｎｕｄＬｂｒａ
ｎｃｈ＠）に属するＡｄｃｈｉｄｏｒｉｓ ｏｄｎｅｒ
ｉのメタノール抽出物から得られた化合物で、このもの
は生体外でスタフィロコツカス・アウレウス（Ｓｔａｐ
ｈｙｌｏｃｏｃｃｕａ ａｕｒｅｕｓ）に対して殺菌作
用を示すことが知られている［ Ｔｅｔｒａｈ＠ｄｒｏ
ｎ Ｌｅｔｔｅｒｓ ｖｏｌ、 ２１ 、７９７ （１
９８０）］。KNC-225 is Dorid nudLbra.
Adchidoris odner belonging to nch@)
A compound obtained from the methanol extract of Staphylococcus aureus in vitro.
hylococcua aureus) [Tetrah@dro
n Letters vol, 21, 797 (1
980)].
又、本発明者らはＫＮＣ−２２５が優れた抗炎症作用を
有することを見い出した（本願と同一出願人による同日
付の出願であるｒ３，７．１１−）ジメチル−２、６，
１０−ドデカトリエン酸（２，２−ジメチル−１，３−
ジオキソラン−４−イル）メチルエステルを含有する抗
炎症剤」参照）。In addition, the present inventors have found that KNC-225 has an excellent anti-inflammatory effect (r3,7.11-)dimethyl-2,6,
10-dodecatrienoic acid (2,2-dimethyl-1,3-
anti-inflammatory agents containing dioxolan-4-yl) methyl ester).
ＫＮＣ−２２５の製造法としてはファルネシル酸グリセ
リンエステルと２．２−ジメトキシエタンぐンとを酸触
媒の存在下で反応させて得る方法が知られている（前記
Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ ）。As a method for producing KNC-225, a method is known in which farnesylic acid glycerin ester and 2,2-dimethoxyethane are reacted in the presence of an acid catalyst (the above-mentioned Tetrahedron Letters).
上記ＫＮＣ−２２５の製造はＡｄｅｈｉｄｏｒｉｓ ｏ
ｄｎｅｒｉ中に存在するファルネシル酸グリセリンエス
テルの構造確認のために行われたものであシ、かかる製
造法は抽出物たるファルネシル酸グリセリンエステルを
原料とする製造法であって工業的製造法とはなシ難い。The above KNC-225 is manufactured by Adehidoris o.
This was carried out to confirm the structure of farnesylic acid glycerol ester present in Dneri, and this manufacturing method uses farnesylic acid glycerol ester, which is an extract, as a raw material and is not an industrial manufacturing method. It's difficult.
本発明者らはＫＮＣ−２２５の安価で容易な工業的製造
法を種々検討した結果本発明を完成するに至った。かか
る本発明によるＫＮＣ−２２５の製造法はゲラニルアセ
トンとジアルコキシホスホノ酢ｉ（２，２−ジメチル１
．３−ジオキソラン−４−イル）メチルエステルとを用
いてＨｏｒｎｅｒ反応（Ｂｅｒ、９５．５８１（＋６２
）〕として知られている方法に従って合成する方法であ
る。下記に一般式で示す。The present inventors have completed the present invention as a result of various studies on inexpensive and easy industrial manufacturing methods for KNC-225. The method for producing KNC-225 according to the present invention includes geranyl acetone and dialkoxyphosphonoacetic acid (2,2-dimethyl
．． Horner reaction (Ber, 95.581 (+62
)]. The general formula is shown below.
（式中Ｒはアルキル基、アリール基又はアラルキル基を
示す）
Ｒの定義中、アルキル基はメチル基、エチル差等炭素数
１〜２０のアルキル基を、アリール基はフェニル基、ト
リル基等を、アラルキル基はベンジル基等を包含する。(In the formula, R represents an alkyl group, an aryl group, or an aralkyl group.) In the definition of R, an alkyl group is an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, and an aryl group is a phenyl group, a tolyl group, etc. , aralkyl groups include benzyl groups and the like.
ジアルコキシホスホノ酢酸（２，２−ジメチル−１，３
ジオキソラン−４−イル）メチルエステルはつぎのよう
にして合成できる。２．２−ジメチル−１，３−ジオキ
ソラン−４−メタノール（公知化合物）とこれに対して
約０．５〜１．２当量、好ましくは０．８〜１、Ｏ当量
のモノハロゲン酢酸ハライド、好ましくはモノクロル酢
酸クロリドとを不活性溶媒の存在下又は不存在下に該モ
ノハロゲン酢酸ハライドに対して約１．０当量ないしは
溶媒量のピリジン、トリエチルアミンなどの有機第３級
塩基の存在下、０℃〜室温で１−１０時間反応させるこ
とによルモノハロダン酢酸（２，２−ジメチル−１゜３
−ジオキソラン−４−イル）メチルエステルを得ること
ができる。不活性の溶媒としては例えばトルエン、ベン
ゼン、ｎ−ヘキサンナトの炭化水素系溶媒：四塩化炭素
、クロロホルム、ジクロルメタン、ジクロルエタン、ト
リクレンなどのハロダン化炭化水素系溶媒；ジエチルエ
ーテル、１−ブチルメチルエーテル、ジイソグロビルエ
ーテル、テトラヒドロフラン、ジメトキシエタンなどの
エーテル系溶媒などを使用できる。つき゛に（ＲＯ）５
Ｐ（式中Ｒは前記定義のとおりである）で表わされる亜
リン酸エステルとこれに対して約０．５〜１．２当量、
好ましくは０．８〜１．０当量のモノハロダン酢酸（２
，２−ジメチル−１，３−ジオキノラン−４−イル）メ
チルエステルとヲ１００’〜２００℃で１〜５時間反応
させることによシジアルコキシホスホノ酢酸（２，２−
ジメチル−１，３−ジオキソラン−４−・イル）メチル
エステルを得ることができる。Dialkoxyphosphonoacetic acid (2,2-dimethyl-1,3
Dioxolan-4-yl) methyl ester can be synthesized as follows. 2.2-dimethyl-1,3-dioxolane-4-methanol (known compound) and about 0.5 to 1.2 equivalents, preferably 0.8 to 1,0 equivalents of monohalogen acetic acid halide, Preferably, monochloroacetic acid chloride is added in the presence or absence of an inert solvent and in the presence of an organic tertiary base such as pyridine or triethylamine in an amount of about 1.0 equivalent to the solvent amount relative to the monohalogen acetic acid halide. By reacting for 1-10 hours at ℃ to room temperature, monohalodaneacetic acid (2,2-dimethyl-1゜3
-dioxolan-4-yl) methyl ester can be obtained. Examples of inert solvents include hydrocarbon solvents such as toluene, benzene, and n-hexanato; halodanated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, and trichlene; diethyl ether, 1-butyl methyl ether, and dichloromethane; Ether solvents such as isoglobil ether, tetrahydrofuran, dimethoxyethane, etc. can be used. Tsuki ni (RO) 5
A phosphite represented by P (wherein R is as defined above) and about 0.5 to 1.2 equivalents thereof,
Preferably 0.8 to 1.0 equivalents of monohalodane acetic acid (2
, 2-dimethyl-1,3-dioquinolan-4-yl) methyl ester and cydialkoxyphosphonoacetic acid (2,2-
Dimethyl-1,3-dioxolan-4-.yl)methyl ester can be obtained.
サラにジアルコキシホスホノ酢ｆｆ１（２，２−ジメチ
ル−１，３−ジオキソラン−４−イル）メチルエステル
に対して０．８〜１．５当量、好ましくは１．０〜１．
１当景の水素化ナトリウム、ナトリウムメチラートなど
の塩基とをベンゼン、トルエン等の炭化水素系溶媒、ジ
エチルエーテル、ジイソグロビルエーテル、テトラヒド
ロフラン、ジメトキシエタン等のエーテル系溶媒などの
溶媒の存在下、ｏ℃〜室温で反応させ喪のちその反応混
合物にジアルコキシホスホノ酢ｒｉ（２，２−ジメチル
−１，３−ジオキンラン−４−イル）メチルエステルに
対して０、８〜１．２当量のゲラニルアセトンを加えて
０〜１００℃で反応させると本発明化合物であるＫＮＣ
−２２５を得ることができる。上記の合成反応によって
得られたＫＮＣ−２２５の分離“精製は通常の方法によ
り行なうことができる。例えば分子蒸留によるかあるい
はカラムクロマトグラフィーに付することによってＫＮ
Ｃ−２２５を分離取得することができる。0.8 to 1.5 equivalents, preferably 1.0 to 1.5 equivalents based on dialkoxyphosphonoacetic acid ff1 (2,2-dimethyl-1,3-dioxolan-4-yl) methyl ester.
1. A base such as sodium hydride or sodium methylate in the presence of a solvent such as a hydrocarbon solvent such as benzene or toluene, or an ether solvent such as diethyl ether, diisoglobyl ether, tetrahydrofuran, or dimethoxyethane. , 0.8 to 1.2 equivalents relative to dialkoxyphosphonoacetic acid (2,2-dimethyl-1,3-dioquinran-4-yl) methyl ester were added to the reaction mixture at 0°C to room temperature. When geranylacetone is added and reacted at 0 to 100°C, the compound of the present invention, KNC
-225 can be obtained. Separation and purification of KNC-225 obtained by the above synthetic reaction can be carried out by conventional methods. For example, KNC-225 can be purified by molecular distillation or by column chromatography.
C-225 can be obtained separately.
以下に本発明を実施例によシ具体的に説明する。 The present invention will be specifically explained below using examples.
なお本発明はこれらの実施例により限定されるものでは
ない。Note that the present invention is not limited to these Examples.
実施例１
２．２−ジメチル−１，３−ジオキソラン−４−メタノ
ール ３７０．５ｆＩ（２，７１ｍｏｌ ）とピリジン
２２１．２Ｊ＋ （２，８ｍｏｌ ）とをジイソゾロビ
ルエーテル７００＋ｄに混合し、氷冷したのちモノクロ
ロ酢酸クロリド ３０７１１（２，７１ｍｏｌ ）をゆ
ツ＜９１０℃以下に反応温度を保つように滴下した。滴
下終了後さらに１時間攪拌したのち、反応液を水にあけ
、ついで５％硫酸水溶液、水、１０％炭酸水素ナトリウ
ム水の順で洗浄した。反応混合物よシジイソグロビルエ
ーテルを蒸発除去し、得られた残留物を減圧蒸留し、８
３℃１０．１■Ｈｇの留分を５０５．５ｇ得た。このも
のはＧＬＣ分析によると純度９３％のモノクロロ酢酸２
．２−ジメチル−１，３ジオキソラン−４−メタノール
エステルであった。Example 1 370.5 fI (2,71 mol) of 2.2-dimethyl-1,3-dioxolane-4-methanol and 221.2 J+ (2,8 mol) of pyridine were mixed in diisozorobyl ether 700+d and cooled on ice. Thereafter, monochloroacetic acid chloride 30711 (2,71 mol) was added dropwise so as to keep the reaction temperature below 910°C. After the addition was completed, the mixture was stirred for an additional hour, and then poured into water, and then washed with a 5% aqueous sulfuric acid solution, water, and 10% aqueous sodium bicarbonate in this order. Diisoglobil ether was removed by evaporation from the reaction mixture, and the resulting residue was distilled under reduced pressure.
505.5 g of a fraction of 10.1 ■Hg at 3°C was obtained. According to GLC analysis, this product has a purity of 93% monochloroacetic acid 2.
．． It was 2-dimethyl-1,3 dioxolane-4-methanol ester.
得られたモノクロロ酢酸２．２−ジメチル−１，３ジオ
キソラン−４−メタノールエステル８９．７１（０，４
ｍｏｌ）とトリエチルホスファイト６６．５Ｎ（０，４
ｍｏｌ ） ｔ−混合し、１３０℃に加熱して３．５時
間攪拌した。反応終了後減圧蒸留して１４５℃１０．２
＋ｗＨｇの留分を１２３．６．９得た。このものはＧＬ
Ｃ分析によると純度９５．７％のジェトキシホスホノ２
．２−ジメチル−１，３ジオキソラン−４−メチルアセ
テートであった。The obtained monochloroacetic acid 2,2-dimethyl-1,3 dioxolane-4-methanol ester 89.71 (0,4
mol) and triethyl phosphite 66.5N (0,4
mol) t-mixed, heated to 130°C and stirred for 3.5 hours. After the reaction is completed, distill it under reduced pressure to 145℃10.2
+wHg fraction 123.6.9 was obtained. This one is GL
Jetoxyphosphono2 with a purity of 95.7% according to C analysis
．． It was 2-dimethyl-1,3 dioxolane-4-methyl acetate.
ついで得られたジェトキシホスホノ２．２−−）メチル
−１，３−ジオキソラン−４−メチルアセテ−） １
２１．５１（０，３９ｍｏｌ）’ｉ水素化ナトリウム（
６０％） ３１．２Ｊｉｌ （０，３９ｍｏｌ ）の
トルエン１！溶液へ室温下で滴下し、さらにゲラニルア
セトン７６Ｊｉ’（０，３９ｍｏｌ）を加え一夜攪拌し
た。Then the obtained jetoxyphosphono2.2-)methyl-1,3-dioxolane-4-methylacetate) 1
21.51 (0.39 mol)'i Sodium hydride (
60%) 31.2 Jil (0.39 mol) of toluene 1! This was added dropwise to the solution at room temperature, and geranylacetone 76Ji' (0.39 mol) was further added and stirred overnight.
反応終了後水にあけたのち、水洗した。有機層よりトル
エンを減圧蒸留除去し、ついで減圧蒸留し１７０℃／
０．１ ｓｍＨｇの留分を８７．２．９’得た。このも
のの分析結果をつぎに示す。After the reaction was completed, it was poured into water and then washed with water. Toluene was removed from the organic layer by distillation under reduced pressure, and then distilled under reduced pressure at 170°C/
A 0.1 smHg fraction of 87.2.9' was obtained. The results of this analysis are shown below.
Ｈ’ ＮＭＲ（６０ＭＨｚ ）δＣＤＣＬ５ＭＳ
１．３ （ｄ、Ｊ−０，５Ｈｚ、６Ｈ）、１．６ （ｂ
ｒｏａｄｔ ９Ｈ）ｔｌ、８０〜２．２５（ｍ、 １１
Ｈ） 、 ３．３０〜４．２０（ｍ、５Ｈ）。H' NMR (60MHz) δCDCL5MS 1.3 (d, J-0.5Hz, 6H), 1.6 (b
roadt 9H) tl, 80-2.25 (m, 11
H), 3.30-4.20 (m, 5H).
５．０５（ｂｒｏａｄ、２Ｈ）、 ５．６１ （ａ、Ｉ
Ｈ）この分析結果よシ上記留分がＫＮＣ−２２５である
ことを確認した。ＧＬＣ分析の結果、該留分中のこの化
合物の純度は９７．４％であった。5.05 (broad, 2H), 5.61 (a, I
H) The analysis results confirmed that the above fraction was KNC-225. As a result of GLC analysis, the purity of this compound in the fraction was 97.4%.
本発明によってＫＮＣ−２２５の安価で容易な工業的製
造法が提供される。The present invention provides an inexpensive and easy industrial method for producing KNC-225.
Claims (2)
示す） で表わされるジアルコキシホスホノ酢酸（２，２−ジメ
チル−１，３−ジオキソラン−４−イル）メチルエステ
ルとを塩基触媒の存在下で反応させることを特徴とする
３，７，１１−トリメチル−２，６，１０−ドデカトリ
エン酸（２，２−ジメチル−１，３−ジオキソラン−４
−イル）メチルエステルの製造法。(1) Geranylacetone and dialkoxyphosphonoacetic acid (2,2-dimethyl-1 , 3-dioxolan-4-yl) methyl ester in the presence of a base catalyst. 1,3-dioxolane-4
-yl) methyl ester production method.
１，３−ジオキソラン−４−イル）メチルエステルを、
２，２−ジメチル−１，３−ジオキソラン−４−メタノ
ールとモノハロゲン酢酸ハライドとを有機第３級塩基の
存在下反応させて、モノハロゲン酢酸（２，２−ジメチ
ル−１，３−ジオキソラン−４−イル）メチルエステル
を得、ついでこれと一般式（ＲＯ）＿３Ｐ（式中Ｒは前
記定義のとおりである）で表わされる亜リン酸エステル
とを反応させることにより製造する特許請求の範囲第１
項記載の製造法。(2) Dialkoxyphosphonoacetic acid (2,2-dimethyl-
1,3-dioxolan-4-yl) methyl ester,
2,2-dimethyl-1,3-dioxolane-4-methanol and monohalogen acetic acid halide are reacted in the presence of an organic tertiary base to form monohalogen acetic acid (2,2-dimethyl-1,3-dioxolane- 4-yl) methyl ester and then reacting this with a phosphite ester represented by the general formula (RO)_3P (wherein R is as defined above). 1
Manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32102687A JPH01265085A (en) | 1987-12-17 | 1987-12-17 | Production of 3,7,11-trimethyl-2,6,10-dodecatrienoic acid (2,2-dimethyl-1,3-dioxolan-4-yl)methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32102687A JPH01265085A (en) | 1987-12-17 | 1987-12-17 | Production of 3,7,11-trimethyl-2,6,10-dodecatrienoic acid (2,2-dimethyl-1,3-dioxolan-4-yl)methyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01265085A true JPH01265085A (en) | 1989-10-23 |
Family
ID=18127966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32102687A Pending JPH01265085A (en) | 1987-12-17 | 1987-12-17 | Production of 3,7,11-trimethyl-2,6,10-dodecatrienoic acid (2,2-dimethyl-1,3-dioxolan-4-yl)methyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01265085A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013227579A (en) * | 2006-07-28 | 2013-11-07 | Givaudan Sa | Method of using organic compounds |
-
1987
- 1987-12-17 JP JP32102687A patent/JPH01265085A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013227579A (en) * | 2006-07-28 | 2013-11-07 | Givaudan Sa | Method of using organic compounds |
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