JPS6330481A - Production of pyran derivative - Google Patents
Production of pyran derivativeInfo
- Publication number
- JPS6330481A JPS6330481A JP17262886A JP17262886A JPS6330481A JP S6330481 A JPS6330481 A JP S6330481A JP 17262886 A JP17262886 A JP 17262886A JP 17262886 A JP17262886 A JP 17262886A JP S6330481 A JPS6330481 A JP S6330481A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- product
- compound
- pyran
- dimethyl
- 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 4
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 150000004880 oxines Chemical class 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002304 perfume Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical group C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- OANSOJSBHVENEI-UHFFFAOYSA-N cyclohexene-1-carbaldehyde Chemical compound O=CC1=CCCCC1 OANSOJSBHVENEI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000003205 fragrance Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GPWNWKWQOLEVEQ-UHFFFAOYSA-N 2,4-diaminopyrimidine-5-carbaldehyde Chemical compound NC1=NC=C(C=O)C(N)=N1 GPWNWKWQOLEVEQ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- CHVQGLOTUNUPHU-UHFFFAOYSA-N 4,6-dimethylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1CC(C)=CCC1C=O CHVQGLOTUNUPHU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical group C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- WNJSKZBEWNVKGU-UHFFFAOYSA-N 2,2-dimethoxyethylbenzene Chemical compound COC(OC)CC1=CC=CC=C1 WNJSKZBEWNVKGU-UHFFFAOYSA-N 0.000 description 1
- KPHPTSMXBAVNPX-UHFFFAOYSA-N 4-methylpent-4-en-2-ol Chemical compound CC(O)CC(C)=C KPHPTSMXBAVNPX-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 241001632578 Hyacinthus orientalis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- YNMSDIQQNIRGDP-UHFFFAOYSA-N Phenethyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCCC1=CC=CC=C1 YNMSDIQQNIRGDP-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 241000736148 Styrax Species 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- QUMXDOLUJCHOAY-UHFFFAOYSA-N alpha-methylbenzyl acetate Natural products CC(=O)OC(C)C1=CC=CC=C1 QUMXDOLUJCHOAY-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- -1 diene compound Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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〕
本発明は次の一般式（［）
（式中、Ｒ２は０式又はＣＨ，を示し、Ｒ，、Ｒ，、Ｒ
いＲ，、Ｒ，及びＲ７はＨ又はＣＨ，を示す。ただし馬
及びＲ７がＣＨ８でかつＲ５、Ｒ４及びＲ８がＨである
場合を除く。Ｘ、Ｙ及びＺの何れか１つは二重結合で、
他の２つは単結合を示す〕
で表わされる香料として有用な新規などラン誘導体の製
造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to the following general formula ([) (wherein R2 represents 0 formula or CH, R,, R,, R
R, , R and R7 represent H or CH. However, this excludes cases where horse and R7 are CH8 and R5, R4 and R8 are H. Any one of X, Y and Z is a double bond,
The other two represent single bonds] This invention relates to a method for producing a novel orchid derivative useful as a fragrance.
従来、次式（ａ）
瓜
（式中、Ｒ４、Ｒ，、Ｒ，及びＲ１は前記と同じものを
示す）
で表わされるジエン化合物と一般式山）（式中、Ｒ３は
前記と同じものを示す）で表わされるジェノフィルをデ
ィールスアルダー反応させて得られる次式（ＩＩ）
Ｒ１
（式中、Ｒ，、Ｒ４、Ｒ，、Ｒ，及びＲ７は前記と同じ
ものを示す〕
で表わされる化合物が強いグリーンノートを有すること
が知られている。Conventionally, a diene compound represented by the following formula (a) (where R4, R, , R, and R1 are the same as above) and a general formula (Yama) (wherein R3 is the same as above) have been used. The compound represented by the following formula (II) R1 (wherein R,, R4, R, R, and R7 are the same as above) obtained by subjecting Genophile represented by (shown) to Diels-Alder reaction is strong. Known to have green notes.
しかしながら、上記（ｎ）式の化合物はホルミル基を有
するため安定性に問題があった。However, the compound of the above formula (n) has a problem in stability because it has a formyl group.
そこで、本発明者は、斯かる問題点を解決すべく鋭意研
究を行った結果、化合物（ｎ）に次の一般式（Ｉ）
（式中、Ｒ２は前記と同じものを示す）で表わされる化
合物を反応させて得られる上記−般式（Ｉ）で表わされ
るピラン誘導体は安定性に優れ、かつ持続性のあるグリ
ーンノートを有しておυ、香料組成物の製造原料として
有用であることを見出し、本発明を完成した。Therefore, as a result of intensive research in order to solve such problems, the present inventors found that the compound (n) is represented by the following general formula (I) (wherein R2 is the same as the above). The pyran derivative represented by the above general formula (I) obtained by reacting the compounds has excellent stability and a long-lasting green note, and is useful as a raw material for producing fragrance compositions. They discovered this and completed the present invention.
すなわち、本発明は、（Ｉ）式の化合物と（Ｉｆ）式の
化合物を酸触媒の存在下反応させてピラン誘導体（Ｉ）
を製造する方法である。That is, the present invention provides pyran derivative (I) by reacting a compound of formula (I) and a compound of formula (If) in the presence of an acid catalyst.
This is a method of manufacturing.
本発明方法で得られるピラン誘導体（Ｉ）には、二重結
合の位置によって次の３つの異性体があり、本発明方法
によれば生成物はこれらの混合物として得られる。The pyran derivative (I) obtained by the method of the present invention has the following three isomers depending on the position of the double bond, and according to the method of the present invention, the product is obtained as a mixture of these isomers.
（Ｉａ） （Ｉｂ） （ＩＣ）（
式中、Ｒ２、Ｒ５、Ｒ４，Ｒ，、Ｒ１及びＲ７は前記と
同じものを示す）
従って、本発明方法は次の反応式によって示される。(Ia) (Ib) (IC)(
(In the formula, R2, R5, R4, R, , R1 and R7 are the same as described above.) Therefore, the method of the present invention is represented by the following reaction formula.
（ＩＶ）
（式中、Ｒ，、Ｒ，、Ｒ４，Ｒ５、Ｒ６，Ｒ，は前記と
同じものを示す）
本発明方法において、化合物（ＩＩ）に対する化合物（
Ｉ）のモル比は特に制限されないが、（■）１モルに対
しく０を０．５〜ｚＯモル使用するのが好ましい。酸触
媒としては、強酸が好ましく、例えば硫酸、パラトルエ
ンスルホン酸、塩酸、リン酸等が挙げられる。触媒量は
その種類にもよるが、原料の仕込量に対し０．０１〜１
０％が好ましい。反未から水を除去できる溶媒、例えば
ヘキサン、ベンゼン、トルエン、キシレン等が好適に利
用される。本反応は一般に１０〜２００℃の温度で、好
ましくは５０〜１５０℃の温度で行われ、反応時間は温
度によっても異なるが、１〜２００時間で進行する。(IV) (In the formula, R,, R,, R4, R5, R6, R, are the same as above) In the method of the present invention, the compound (
The molar ratio of I) is not particularly limited, but it is preferable to use 0.5 to zO moles of 0 to 1 mole of (■). The acid catalyst is preferably a strong acid, such as sulfuric acid, para-toluenesulfonic acid, hydrochloric acid, phosphoric acid, and the like. The amount of catalyst depends on the type, but it is 0.01 to 1% of the amount of raw materials charged.
0% is preferred. Solvents that can remove water from the reactor, such as hexane, benzene, toluene, xylene, etc., are preferably used. This reaction is generally carried out at a temperature of 10 to 200°C, preferably 50 to 150°C, and the reaction time varies depending on the temperature, but proceeds for 1 to 200 hours.
本発明方法によれば、生成物は（Ｉａ）、（Ｉｂ）及び
（ｔｃ）の混合物として得られるが、これらは分離する
ことなく香料として使用することができる。According to the process of the invention, the product is obtained as a mixture of (Ia), (Ib) and (tc), which can be used as a perfume without separation.
本発明方法で得られる化合物（Ｉ）は安定性に優れ、持
続性のあるグリーンノートな香気を有しているので、徨
々の香料組成物の調製に使用することができる。Compound (I) obtained by the method of the present invention has excellent stability and a long-lasting green note fragrance, so it can be used in the preparation of various fragrance compositions.
次に実施例を挙げて説明する。 Next, an example will be given and explained.
実施例１
ヘキサン１８０？と濃硫酸１．３ｔの混合液を還流させ
ながら、３，６−シメチルー３−シクロヘキセン−１−
カルバルデヒドと４，６−シメチルー３−シクロヘキセ
ン−１−カルバルデヒドトの混合物１００ｙ−（０，７
２モルつと７９％の純度をｍｆる４−、’チルー４−ペ
ンテンー２−オール１１０５’（０，８７モル〕とを均
一に混合したものを３時間かけて滴下した。反応により
生成する水はヘキサンと共沸させることによシ反応系外
に除去した。滴下終了後ヘキサンを一部留去させること
により内温を９５℃まで上げた。その後、この温度を保
持しながら、共沸脱水反応を６時間行なった。反応物は
５％炙酸ナトリウム水にて洗浄し、その後、ボウ硝水に
て水洗を３回行なった。減圧下、ヘキサンをトッピング
した後、蒸留を行ない、２ｍ１ＨＰ、１００〜１２０°
Ｃの留分１５２９−を得た。Example 1 Hexane 180? 3,6-dimethyl-3-cyclohexene-1- while refluxing a mixture of
A mixture of carbaldehyde and 4,6-dimethyl-3-cyclohexene-1-carbaldehyde 100y-(0,7
A homogeneous mixture of 2 moles of 4-,'chi-4-penten-2-ol 1105 with a purity of 79% (0.87 moles) was added dropwise over 3 hours.The water produced by the reaction was It was removed from the reaction system by azeotroping with hexane.After the dropwise addition, the internal temperature was raised to 95°C by partially distilling off the hexane.Then, while maintaining this temperature, azeotropic dehydration was carried out. was carried out for 6 hours.The reaction product was washed with 5% sodium aqueous solution, and then washed three times with Bowser's salt water.Under reduced pressure, after topping with hexane, distillation was performed, and 2ml of HP, 100% ~120°
A fraction 1529- of C was obtained.
これを精密蒸留により２７１１ Ｈ５’、１００〜１０
４°Ｃの留分８７９−を得た。This was subjected to precision distillation to obtain 2711 H5', 100-10
Fraction 879- was obtained at 4°C.
生成物をガスクロマトグラフィー及びガスマスで測定を
行なったところ、その純度は９９％以上であり、ｍ／ｅ
＝ ２２０の親ピークが認められた。When the product was measured by gas chromatography and gas mass, its purity was over 99%, with m/e
= 220 parent peaks were observed.
更に生成物の元素分析、ＩＨ−ＮＭＲ，ＩＲは次のとお
シである。Furthermore, elemental analysis, IH-NMR, and IR of the product were conducted as follows.
元素分析
計算値（％） ： Ｃ８１，７６、Ｈ１０，９８，０７
，２６実測値（チ） ： Ｃ８１，７３，Ｈ１１，０１
，０７，２６ＩＩ（−ＮＭＲ（ＣＤＣ乃１．ＴＭＳ内部
標準δ）；第１図の複合ピーク
δ０．８〜４．５ 複雑な多重線（２２）りＩＲ（
ａｎ−’）：第２図
２９５０、２８８０．１６７５．１６５０．１４４０．
１３７５゜１３１５．１２２０，１１７０，１１００，
１０６０，１０２０゜８９０．８５０，８１０，７９５
（Ｉａ−１）
（Ｉｂ−１）
（ｆｉｌｅ−１）
これらの結果より、生成物は２，４−ジメチル−６−（
３，６（又は４，６）−ジメチル−３−シクロヘキセン
−１−イル］−３、６−シヒドロー２Ｈ−ビラ：ｚ（ｌ
ａ−１）、４．６−シメチルー２−（：３，６（又は４
，６）−ジメチル−３−シクロヘキセン−１−イル］−
３、６−シヒドロー２Ｈ−ピラン（Ｉｂ−１）及び２−
メチル−６−（３、６（又は４．６）−ジメチル−３−
シクロヘキセン−１−イル〕−４−メチレンテトラヒド
ロビラン（ＩＣ−１）の混合物であることが確認された
。Elemental analysis calculation value (%): C81,76, H10,98,07
,26 actual measurement value (chi): C81,73, H11,01
,07,26II (-NMR (CDC 1.TMS internal standard δ); complex peak δ0.8-4.5 in Figure 1 Complex multiplet (22) IR (
an-'): Fig. 2 2950, 2880.1675.1650.1440.
1375°1315.1220,1170,1100,
1060,1020°890.850,810,795 (Ia-1) (Ib-1) (file-1) From these results, the product is 2,4-dimethyl-6-(
3,6 (or 4,6)-dimethyl-3-cyclohexen-1-yl]-3,6-cyhydro2H-bira:z(l
a-1), 4,6-dimethyl-2-(:3,6(or 4
,6)-dimethyl-3-cyclohexen-1-yl]-
3,6-sihydro-2H-pyran (Ib-1) and 2-
Methyl-6-(3,6 (or 4.6)-dimethyl-3-
It was confirmed that it was a mixture of cyclohexen-1-yl]-4-methylenetetrahydrobilane (IC-1).
実施例２
実施例１の３，６−シメチルー３−シクロヘキセン−１
−カルバルデヒドと４．６−シメチルー３−シクロヘキ
セン−１−カルバルデヒドとの混合物１００？の代わり
に２．４．６−１リメチル−３−シクロヘキセン−１−
カルバルデヒドと３．５．６−１リメチル−３−シクロ
ヘキセン−１−カルバルデヒドとの混合物１１０ｙ−（
０，７２モル）を使用する以外は実施例１と同様に操作
して、精密蒸留後２１Ｈ？、１１０〜１１４℃の留分７
７？を得た。Example 2 3,6-dimethyl-3-cyclohexene-1 of Example 1
-Mixture of carbaldehyde and 4,6-dimethyl-3-cyclohexene-1-carbaldehyde 100? 2.4.6-1-limethyl-3-cyclohexene-1- instead of
110y-(
0.72 mol) was used in the same manner as in Example 1, and after precision distillation, 21H? , 110-114°C fraction 7
7? I got it.
生成物をガスクロマトグラフィー及びガスマスで測定を
行なったとこへその純度は９９チ以上であり、ｍ／ｅ＝
２３４の族ピークが認められた。更に生成物の元素分析
、”Ｈ−Ｎ Ｍ ＲｌＩＲは次のとおりである。When the product was measured by gas chromatography and gas mass, its purity was 99% or higher, and m/e =
234 family peaks were observed. Further elemental analysis of the product, ``H-N M RlIR, is as follows.
元素分析
計算値幅）：Ｃ８１，９９Ｈｌｌ、１８ ０６．８３実
測値（＠： Ｃ８１，９６Ｈｌｌ、２０ ０６．８４Ｌ
Ｈ−ＮＭＲ（ＣＤ（Ｊ、、ＴＭＳ内部標準δ）：第３図
の複合ピーク
δ０．８〜１．３ シクロヘキセン環、ＣＨ，Ｘ２及
びピラン環０−Ｃ−ＣＨ。Elemental analysis calculated value range): C81,99Hll, 18 06.83 Actual value (@: C81,96Hll, 20 06.84L
H-NMR (CD (J, TMS internal standard δ): complex peak δ 0.8-1.3 in Figure 3 cyclohexene ring, CH, X2 and pyran ring 0-C-CH.
δ１．５〜４．３ 複雑な多重線（Ｉ５Ｂ）ＩＲ（ｍ
−’ ）：第４図
２９５０．２９００，２８７０，１６８０，１６５０，
１４５０゜１３８０．１３２０，１１７０，１１１５，
１０５５，１０２０゜９６０．８９０，８１５
（Ｉａ−２）
（Ｉｂ−２）
（Ｉ［Ｃ−２）
これらの結果より、生成物は、２．＋−１メチル−６−
（２，４，６（又は３，５．６）−トリメチル−３−シ
クロヘキセン−１−イル”ｌ−３。δ1.5~4.3 Complex multiplet (I5B) IR (m
-' ): Fig. 4 2950.2900, 2870, 1680, 1650,
1450°1380.1320,1170,1115,
1055,1020°960.890,815 (Ia-2) (Ib-2) (I[C-2) From these results, the product is 2. +-1 methyl-6-
(2,4,6 (or 3,5.6)-trimethyl-3-cyclohexen-1-yl"l-3.
６−ジヒドｏ−２Ｈ−ピラフ （ｌａ−２）、４，６−
シメチルー２−［２，４，６（又は３，５．６）−トリ
メチル−３−シクロヘキセン−１−イル〕−３，６−シ
ヒドロー２Ｈ−ビラン（Ｉｂ−２）及び２−メチル−６
−（２，４，６（又は３，５．６）−トリメチル−３−
シクロヘキセン−１−イル］−４−メチレンテトラヒド
ロピラン（ＩＣ−２）の混合物でちることが確認された
。6-dihydro-2H-pilaf (la-2), 4,6-
Cymethyl-2-[2,4,6 (or 3,5.6)-trimethyl-3-cyclohexen-1-yl]-3,6-cyhydro-2H-bilane (Ib-2) and 2-methyl-6
-(2,4,6(or 3,5.6)-trimethyl-3-
It was confirmed that a mixture of cyclohexen-1-yl]-4-methylenetetrahydropyran (IC-2) was used.
実施例３
実施例１の７９％の純度を有する４−メチル−４−ペン
テン−２−オール１１０５’（０，８７モル）の代わり
に、９８チ純度を有する３−メチル−３−ブテン−１−
オール７６５’ （０，８７モル）を使用する以外は実
施例１と同様に操作して、精密蒸留後２朋Ｈ１，１１３
〜１２０℃の留分５４？を得た。Example 3 Instead of 4-methyl-4-penten-2-ol 1105' (0,87 mol) with a purity of 79% in Example 1, 3-methyl-3-butene-1 with a purity of 98% −
The same procedure as in Example 1 was carried out except that all 765' (0.87 mol) was used, and after precision distillation, 2 H1,113
~120°C fraction 54? I got it.
生成物をガスクロマトグラフィー及びガスマスで測定を
行なったところ、その純度は９９％以上であり、 ｍ／
ｅ＝ ２０６の親ピークが認められた。When the product was measured by gas chromatography and gas mass, its purity was over 99%, m/
A parent peak of e=206 was observed.
更に生成物の元素分析、ＩＨ−ＮＭＲ１丁Ｒは次のとお
りである。Furthermore, the elemental analysis of the product, IH-NMR 1 column R, is as follows.
元素分析
計算値（チ） ： Ｃ８１，５０Ｈｌｏ、７５ ０７．
７６実測値（％） ： Ｃ８１，４５Ｈｌｏ、７６ ０
７．７９’Ｈ，ＮＭＲ（ＣＤＣβ１．ＴＭＳ内部標準δ
）：第５図び（Ｉａ） （Ｉｂ）のピラン環。Elemental analysis calculation value (chi): C81,50Hlo, 75 07.
76 Actual value (%): C81,45Hlo, 76 0
7.79'H, NMR (CDCβ1.TMS internal standard δ
): Pyran ring in Figures 5 and (Ia) and (Ib).
δ０．８〜１．１ シクロヘキセン環−ＣＦ２ （３
Ｈ）δ１．２〜４．３ 複雑な多重線 （Ｉ７Ｈ）Ｉ
Ｒ（副−１）：第６図
２９５０、２９００．１６７５．１４４０．１３８０．
１１６０゜１１２０、１０１０．８８５．８５０．７８
０（Ｉａ−３）
（［ｂ−３）
（ＩＣ−３）
これらの結果より、生成物は、４−メチル−６−（３，
６（又は４，６）−ジメチル−３−シクロヘキセン−１
−イル）−３，６−シヒドロー２Ｈ−ビラ：’ （Ｉａ
−３）、４−メチル−２−１： ３ 、６ （又１ｉ４
．６）−ジメチル−３−シクロヘキセン−１−イル］−
３、６−シヒドロー２Ｈ−ピラン（［ｂ−３）及び２−
（３，６（又は４，６）−ジメチル−３−シクロヘキセ
ン−１−イルツー４−メチレンテトラヒドロピラン（［
０−３）の混合物であることが確認された。δ0.8-1.1 cyclohexene ring-CF2 (3
H) δ1.2~4.3 Complex multiplet (I7H)I
R (sub-1): Figure 6 2950, 2900.1675.1440.1380.
1160°1120, 1010.885.850.78
0(Ia-3) ([b-3) (IC-3) From these results, the product is 4-methyl-6-(3,
6(or 4,6)-dimethyl-3-cyclohexene-1
-yl)-3,6-sihydro2H-bira:' (Ia
-3), 4-methyl-2-1: 3, 6 (also 1i4
．． 6)-dimethyl-3-cyclohexen-1-yl]-
3,6-sihydro2H-pyran ([b-3) and 2-
(3,6 (or 4,6)-dimethyl-3-cyclohexen-1-yltu-4-methylenetetrahydropyran ([
It was confirmed that it was a mixture of 0-3).
実施例４
ヒアシンス調調合香料
重量部
ガルパナム油 ３ベン
ジルアセテート １００フエニル
アセトアルデヒドジメチルアセタール ５フエ
ニルエチルアルコール ４００フエニル
エチルアセテート１０
フェニルエチルフェニルアセｆ−ト ４０フエ
ニルエチルサリシレート ２００フエニル
エチルシンナメー） ８０シンナミツ
クアルコール ５０スチラツクスレ
ジノイド ２０オイゲノール
２０インドール
２ジヤスミンベース ２
０上記調合香料９５０部に実施例２で得た化合物を５０
部加えることによシ、ナチュラルでフレッシュなグリー
ン感の強調されたヒアシンス調調合香料が得られた。Example 4 Parts by Weight of Hyacinth Mixed Fragrance Galpanum oil 3 Benzyl acetate 100 Phenyl acetaldehyde dimethyl acetal 5 Phenylethyl alcohol 400 Phenylethyl acetate 10 Phenylethyl phenylacet 40 Phenylethyl salicylate 200 Phenylethyl cinname) 80 Cinnamic Alcohol 50 Styrax Resinoid 20 Eugenol
20 indole
2 diasmine base 2
0 50 parts of the compound obtained in Example 2 was added to 950 parts of the above blended fragrance.
By adding this amount, a hyacinth-like blended fragrance with an emphasized natural and fresh green feeling was obtained.
第１図は実施例１の生成物のＩＨ−Ｎ Ｍ Ｒスペクト
ル、第２図は同生成物のＩＲスペクトル、第３図は実施
例２の生成物のＩＨ−Ｎ Ｍ Ｒスペクトル、第４図は
同生成物のＩＲスペクトル、第５図は実施例３の生成物
の’Ｈ−ＮＭＲスペクトル、第６図は同生成物のＩＲス
ペクトルである。
以上Figure 1 is the IH-N MR spectrum of the product of Example 1, Figure 2 is the IR spectrum of the same product, Figure 3 is the IH-N MR spectrum of the product of Example 2, and Figure 4 is the IH-N MR spectrum of the product of Example 2. is the IR spectrum of the same product, FIG. 5 is the 'H-NMR spectrum of the product of Example 3, and FIG. 6 is the IR spectrum of the same product. that's all
Claims (1)
又はＣＨ＿３を示す。ただしＲ＿５及びＲ＿７がＣＨ＿
３でかつＲ＿３、Ｒ＿４及びＲ＿６がＨである場合を除
く） で表わされる化合物を酸触媒の存在下反応させることを
特徴とする一般式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｒ＿１はＣＨ＿２又はＣＨ＿３を示し、Ｘ、Ｙ
及びＺの何れか１つは二重結合で、他の２つは単結合を
示す。Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿５、Ｒ＿６及びＲ
＿７は前記と同じものを示す） で表わされるピラン誘導体の製造方法。[Claims] 1. A compound represented by the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, R_2 represents H or CH_3) and the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_3, R_4, R5, R_6 and R_7 are H
Or indicates CH_3. However, R_5 and R_7 are CH_
3 and R_3, R_4 and R_6 are H) General formula (III) characterized by reacting a compound represented by the following in the presence of an acid catalyst ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III ) (In the formula, R_1 represents CH_2 or CH_3, X, Y
Any one of and Z is a double bond, and the other two are single bonds. R_2, R_3, R_4, R_5, R_6 and R
_7 indicates the same thing as above) A method for producing a pyran derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17262886A JPS6330481A (en) | 1986-07-22 | 1986-07-22 | Production of pyran derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17262886A JPS6330481A (en) | 1986-07-22 | 1986-07-22 | Production of pyran derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6330481A true JPS6330481A (en) | 1988-02-09 |
Family
ID=15945401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17262886A Pending JPS6330481A (en) | 1986-07-22 | 1986-07-22 | Production of pyran derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6330481A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04187806A (en) * | 1990-11-21 | 1992-07-06 | Nissan Motor Co Ltd | Controller for internal combustion engine |
| US6438338B1 (en) | 2000-10-19 | 2002-08-20 | Xerox Corporation | Extended life recycleable silencer assembly |
-
1986
- 1986-07-22 JP JP17262886A patent/JPS6330481A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04187806A (en) * | 1990-11-21 | 1992-07-06 | Nissan Motor Co Ltd | Controller for internal combustion engine |
| US6438338B1 (en) | 2000-10-19 | 2002-08-20 | Xerox Corporation | Extended life recycleable silencer assembly |
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