JPS5933571B2 - Synthesis method of dihydrolavandural - Google Patents
Synthesis method of dihydrolavanduralInfo
- Publication number
- JPS5933571B2 JPS5933571B2 JP11692275A JP11692275A JPS5933571B2 JP S5933571 B2 JPS5933571 B2 JP S5933571B2 JP 11692275 A JP11692275 A JP 11692275A JP 11692275 A JP11692275 A JP 11692275A JP S5933571 B2 JPS5933571 B2 JP S5933571B2
- Authority
- JP
- Japan
- Prior art keywords
- synthesis method
- dihydrolavandural
- methylbutylidene
- alkylamine
- prenyl chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000001308 synthesis method Methods 0.000 title claims 2
- JKXQKGNGJVZKFA-UHFFFAOYSA-N 1-chloro-3-methylbut-2-ene Chemical compound CC(C)=CCCl JKXQKGNGJVZKFA-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 150000004705 aldimines Chemical class 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 3-methylbutylidene Chemical group 0.000 description 1
- FQNODTJXVHJRNF-UHFFFAOYSA-N CC(C)CC=NC(C)(C)C Chemical compound CC(C)CC=NC(C)(C)C FQNODTJXVHJRNF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
ジヒドロラバンジユラールの合成方法に関するもので
あり、反応式で示せば次の如くなる。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for synthesizing dihydrolabandural, and the reaction formula is as follows.
ノー、だ・ Ｘｔ＝放。 まず、Ｎ−（３−メチルブチ
リデン）アルキルアミンと塩化プレニルとからのジヒド
ロラバンジユラールアルドイミンの合成につき説明する
。No, no. Xt = release. First, the synthesis of dihydrolabanduralaldimine from N-(3-methylbutylidene)alkylamine and prenyl chloride will be explained.
実施例１のように、Ｎ−（３＝メチルブチリデン）アル
キルアミンを−１５℃のような低温でリチウムジアルキ
ルアミドと混合し、次いでこれにプレニルクロライドを
低温で反応させるとジヒドロラバンジユラールアルドイ
ミンであるＮ−〔２−イソプロピルー５−メチルー４−
ヘキセニリデン〕アルキルアミンを生成する。 反応さ
せるプレニルクロライドは、Ｎ−（３一メチルブリデン
）−アルキルアミンに対し、当モル以上好ましく２モル
の比で低温で反応させる。As in Example 1, mixing N-(3=methylbutylidene)alkylamine with lithium dialkylamide at a low temperature such as -15°C and then reacting it with prenyl chloride at a low temperature yields dihydrolavanduralaldo. imine N-[2-isopropyl-5-methyl-4-
Hexenylidene]alkylamine is produced. The prenyl chloride to be reacted is reacted at a low temperature in a molar ratio of at least the same molar amount, preferably 2 molar to N-(3-methylbridene)-alkylamine.
この際使用される触媒としてのリチウムジアルキルアミ
ドは、そのアルキル基としてはブチル、プロピル、エチ
ル等の低級アルキル基よりなるものが使用でき、炭化水
素、エーテル等の不活性溶媒の存在下に反応させること
が好ましい。 次にかくして得られたジヒドロラバンジ
ユラールアルドイミンの加水分解は、無機酸、有機酸と
反応させることによつて達成され容易にジヒドロラバン
ジユラールを得ることができる。The lithium dialkylamide used as a catalyst in this case can have a lower alkyl group such as butyl, propyl, or ethyl as its alkyl group, and is reacted in the presence of an inert solvent such as a hydrocarbon or ether. It is preferable. Next, hydrolysis of the dihydrolabanduralaldimine thus obtained can be achieved by reacting it with an inorganic acid or an organic acid to easily obtain dihydrolabandural.
得られるジヒドロラバンジユラールは香料原料の外、
各種有機合成原料としての用途が期待される。The obtained dihydrorabandillal is not only used as a fragrance raw material, but also as a fragrance material.
It is expected to be used as a raw material for various organic synthesis.
実施例 １
（１）ジヒドロラバンジユラールアルドイミンの合 成
１５゜Ｃに冷却された１．０７（１０ｍｍ０１）のジイ
ソプロピルアミンを含むヘキサン溶液を１５％のｎ−ブ
チルリチウムイキサン溶液４．３７に加え１５分攪拌後
、５ｍ１の乾燥エーテルに溶解した新たに蒸留した１．
４ｙ（１０ｍｍ０１）のＮ−（３−メチルブチリデン）
−ｔブチルアミンを攪拌下１５分かかつて滴下した。Example 1 (1) Synthesis of dihydrolavanduralaldimine A hexane solution containing 1.07 (10 mm 01) diisopropylamine cooled to 15°C was added to 4.37 ml of a 15% n-butyllithium ixane solution. After stirring for 15 minutes, freshly distilled 1.
4y (10mm01) N-(3-methylbutylidene)
-t-butylamine was added dropwise under stirring for 15 minutes.
更に−１５℃で５時間攪拌した。かくして得られた溶液
を５ｍ１の乾燥エーテルに溶解したプレニルクロライド
２１７（２０ｍｍ０１）に加え−１５℃で１時間、次い
で２０℃で２時間反応した。The mixture was further stirred at -15°C for 5 hours. The solution thus obtained was added to prenyl chloride 217 (20 mm01) dissolved in 5 ml of dry ether and reacted at -15°C for 1 hour and then at 20°C for 2 hours.
反応生成液を砕氷上に注ぎ次いでオレンジ色の油層を分
離し、水層はエーテルで２度抽出した。有機層を合せ水
洗し無水芒硝で乾燥した後、溶媒及び未反応プレニルク
ロライド及びＮ（３−メチルブチリデン）−オーブチル
アミンを回収後、１．８ｙのジヒドロラバンジユラール
アルドイミンを蒸留分取した。The reaction product solution was poured onto crushed ice, the orange oil layer was separated, and the aqueous layer was extracted twice with ether. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. After recovering the solvent, unreacted prenyl chloride, and N(3-methylbutylidene)-obutylamine, 1.8y of dihydrolabanduralaldimine was fractionated by distillation. .
（Ｂ．ｐ．８ｌ〜８４℃／５詣Ｈｇ）（収率９０％）、
このアルドイミンはＭＡＳＳ．ＮＭＲ．ＩＲ等によつて
同定した。）２）加水分解
５ｍ１のエーテルに溶解したジヒドロラバンジユラール
アルドイミン０．６７（３ｍｍ０１）に水１２ｍ１に溶
解した蓚酸０．８ｙを２０℃で１５分間かけて攪拌下に
滴下した。(B.p. 8l~84°C/5 pilgrims Hg) (yield 90%),
This aldoimine is MASS. NMR. Identified by IR etc. )2) Hydrolysis 0.8y of oxalic acid dissolved in 12ml of water was added dropwise to 0.67 (3mm01) of dihydrolabandiduralaldimine dissolved in 5ml of ether with stirring at 20°C over 15 minutes.
Claims (1)
塩化プレニルとをリチウムジアルキルアミドの存在下に
反応して得られるジヒドロラバンジユラールアルドイミ
ンを加水分解することを特徴とするジヒドロラバンジユ
ラールの合成法。1 A dihydrorabane dural, which is obtained by hydrolyzing a dihydrorabane dural aldimine obtained by reacting N-(3-methylbutylidene)-alkylamine and prenyl chloride in the presence of lithium dialkylamide. Synthesis method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11692275A JPS5933571B2 (en) | 1975-09-27 | 1975-09-27 | Synthesis method of dihydrolavandural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11692275A JPS5933571B2 (en) | 1975-09-27 | 1975-09-27 | Synthesis method of dihydrolavandural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5242813A JPS5242813A (en) | 1977-04-04 |
| JPS5933571B2 true JPS5933571B2 (en) | 1984-08-16 |
Family
ID=14698982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11692275A Expired JPS5933571B2 (en) | 1975-09-27 | 1975-09-27 | Synthesis method of dihydrolavandural |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5933571B2 (en) |
-
1975
- 1975-09-27 JP JP11692275A patent/JPS5933571B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5242813A (en) | 1977-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yamaguchi et al. | Regioselective Preparation of Allylgermanes. | |
| JPS5933571B2 (en) | Synthesis method of dihydrolavandural | |
| JP4399885B2 (en) | Method for producing 4-methyltetrafluorobenzyl alcohol derivative | |
| JPS5840938B2 (en) | Method for producing substituted or unsubstituted α-oxysuccinic acid ester | |
| JPS6212770B2 (en) | ||
| US3928334A (en) | Process for the production of cefamandole | |
| US2510732A (en) | Method of making 6-methyldihydrocodeine | |
| JPS5944315B2 (en) | Method for producing 2-pentynyl ether | |
| JPS6210494B2 (en) | ||
| JPH029013B2 (en) | ||
| JPS5811414B2 (en) | Method for producing substituted acetophenone | |
| JP3696529B2 (en) | Method for producing aldol compound | |
| JPS6039068B2 (en) | Synthesis method of 5-alkylamino-P-menthen-1 | |
| JPH0146495B2 (en) | ||
| JP2687955B2 (en) | Method for producing 1,4,5,8-tetrahydroxyanthraquinone | |
| JP3634874B2 (en) | Trifluoromethylacetylene derivative, method for producing the same, and method for producing the intermediate | |
| JPS5919535B2 (en) | Method for producing r-ionone and its derivatives | |
| JP2521100B2 (en) | Halogenoalkylfurfuryl alcohols and process for producing the same | |
| JPS625137B2 (en) | ||
| JPS5858335B2 (en) | Alpha - Chikanacetone no Seizouhou | |
| JPS63258836A (en) | Method for producing ethene derivatives | |
| JPH0753679B2 (en) | Process for producing 3-hydroxy-4-phenyl-2-butanone | |
| JPS591432A (en) | Production method of triacontyl halide | |
| JPH05163190A (en) | Production of 5-methylene-2-substituted-2-cyclopentene-1-one | |
| JPS5931499B2 (en) | α. Production method of ω-iminonitrile |