【発明の詳細な説明】
本発明は，つぎの式（Ａ）
で表される，（7Z,10Z）−ヘキサデカジエナール（Ｉ）
を含有することを特徴とする香料組成物に関する．
上記化合物Ｉは,Kempがキュウリから分離して報告した
既知物質である（J.Am.Oil Chem.Soc.1975,52,300）．
しかし,Iのもつ香気および香味，さらには香料としての
利用については，いままでに記載されたことがなく，ま
たそれを示唆する記事もない．そして,Iはいままでに合
成されたことがない．
本発明者のうちの分析グループ（梶原ら）は，海藻中の
緑藻に属するアナアオサ（Ulva pertusa）の揮発性成
分を研究し，ひとつの主要な成分として,Iを単離した．
そして,Iを初めて合成して，その構造を確認した．
一方，応用グループはＩがアナアオサの香気に大きく寄
与する物質であることを知見した．そして,Iの香気およ
び香味を詳しく調べた結果,Iがアナアオサの香気および
香味に限定されずに，多くの用途に活用できる香料とし
て非常に有用な化合物であることを見いだした．
従来の認識によれば，高級直鎖状脂肪属の不飽和アルデ
ヒドにおいて，その炭素数が14ないし15以上になると，
炭素数の増加にともなって，それぞれがもつ特徴的な香
気香味およびその強さが順次減少するものとかんがえら
れてきた．しかし，意外にも炭素数が16で２個のシス型
の不飽和結合をもつＩは，香気香味が予期した以上に強
い．この理由は，おそらく２個のシス型不飽和結合によ
るものであろう．炭素数が14ないし15以上のシス型不飽
和高級アルデヒドの官能特性については，いままで香料
分野ではほとんど注目されていないところである．
本発明者の研究によれば,Iはチーズ，チキン，煮干しお
よび貝に共通する，あぶらっぽい香気および香味（fatt
y note）を強くもっている．さらに，シトラスあるいは
オレンジを連想させる香気および香味をもあわせ持つた
めに，食品香料に限らず香粧品香料の香料組成物に配合
して，香気香味付与あるいは改良補強剤としてはば広く
利用できることがわかった．
たとえば，食品香料ではＩのもつ特徴を生かして，従来
のチーズ用の香料組成物にＩを0.1から１％添加するこ
とが好ましく，これによって脂肪を強く連想させる香料
組成物をつくることができる．また，香粧品香料では，
セッケンやシャンプー用香料組成物に0.05から１％添加
することによって，天然物から抽出した花のにおいの自
然さを強調できる．このように,Iを配合することによっ
て，いままでにはない香料組成物をつくることができ
る．
以下，合成によるＩの製造例，つづいて香料組成物の実
施例を述べて，本発明の有用性を明らかにする．
〈化合物Ｉの製造例〉
Ｉの製造例は，工程１から３までに分けて，それぞれを
つぎのように反応式で示すことができる．
工程１の説明；液体アンモニウムに金属ナトリウムを溶
解し，これにアセチレンガスを吹き込み，さらにエチレ
ンオキサイドを滴下して３−ブチノール（II）を得た．
これと2,3−ジハイドロピランと反応させてピラニルエ
ーテル（III）としたのち，さらに臭化ペンチルと反応
させて,9-（２−テトラハイドロピラニロキシ）−６−
ノニン（IV,9-THP・0-6−ノニン）を合成した．
そして,30％リン酸とメタノールの混合液中で脱ピラニ
ルエーテル化したのち，リンドラー（Lindlar）触媒と
キノリンの存在下で水素添加をおこない，（3Z）−ノネ
ノール（VI）を得た．これをピリジン中でトシル化した
のち，ヨウ化ナトリウムと暗所で反応させて，ヨウ素誘
導体（VIII）にした．つぎに，トリフェニルホスフィン
と反応させて，ホスホニウム塩（IX）を得た．
工程２の説明;1,6−ヘキサンジオール（Ｘ）を,47％臭
化水素酸によってモノブロミネーションをおこない，さ
らにピラニルエーテル（X II）としたのち，テトラハイ
ドロフラン（THF）中で金属マグネシウムを用いて調製
したグリニヤル試薬と，トリエチル−オルソホーメート
との反応でアセタール（X III）を合成し，水とアセト
ン混合液中で脱アセタール反応によりアルデヒド（X I
V）を得た．
工程３の説明；ホスホニウム塩（IX）とアルデヒド（X
IV）を,THFとヘキサメチルホスホルアミド（HMPA）の混
合液中で,n−ブチルリチウム（BuLi）と−78℃でウィテ
ィッヒ（Wittig）反応をおこなった．生成物（X V）を3
0％リン酸とメタノールの混合液で脱ピラニルエーテル
化して，さらにコリンズ（Collins）酸化して，目的物
である（7Z,10Z）−ヘキサデカジエナール（Ｉ）を得
た．
以上が合成方法の概略であるが，つぎに具体例を述べ
る．
〈具体的製造例〉
工程１から３をさらに細分して，段階アからソまでの15
段階にわけて，以下それぞれを具体的に説明する．
工程1:段階アからクまで．
ア.3−ブチノール（II）の製法．
−40℃で液体アンモニア（700ml）に金属ナトリウム（3
2g,1.4モル）を溶解し，アセチレンガスを吹き込み，こ
れにエチレンオキサイド（51g,1.2モル）を滴下して，
−33℃で24時間攪拌した．ふたたび−40℃に冷却して塩
化アンモニウム（75g,1.4モル）を加え，室温に戻して
アンモニアを気化させた．残渣に水を加え，エーテルで
抽出した.2N−塩酸および飽和食塩水で洗浄後，硫酸ナ
トリウムで乾燥させ減圧蒸留によってIIを得た（18g,収
率44％）.bp77℃/80mm.
イ.4-（２−テトラハイドロピラニロキシ）−１−ブチ
ン（III）の製法．
上のII（20g,0.29モル）と2,3−ジハイドロピラン（36
g,0.43モル）および触媒量の濃硫酸を室温で反応させ
た．エーテルを加え，飽和食塩水さらに飽和炭酸水素ナ
トリウムで洗浄し，硫酸ナトリウムで乾燥させ，減圧蒸
留してIIIを得た（39.1g,収率88％）.bp106℃/24mm.
ウ.9-（２−テトラハイドロピラニロキシ）−６−ノニ
ン（IV）の製法．
−40℃で液体アンモニア（700ml）に，金属ナトリウム
（9.0g）を溶解して，これに上のIIIを滴下した．さら
に，臭化ペンチル（67.3g,0.44モル）を滴下して，−33
℃で24時間攪拌した．ふたたび−40℃に冷却して塩化ア
ンモニウム（31g,0.58モル）を加え，室温に戻してアン
モニアを気化させた．残渣に水を加え，エーテルで抽出
した.2N−塩酸および飽和食塩水で洗浄後，硫酸ナトリ
ウムで乾燥させ，減圧蒸留してIVを得た（44.1g,収率77
％）.bp117℃/1mm.
エ.3−ノニノール（Ｖ）の製法．
リン酸（108ml）とメタノール（325ml）の混合液中に，
上のIVを滴下して室温で攪拌した．飽和食塩水を加えな
がら，減圧下でメタノールを留去したのちエーテルで抽
出した．エーテル層を飽和食塩水および飽和炭酸水素ナ
トリウム水で洗浄後，硫酸ナトリウムで乾燥させて減圧
蒸留してＶを得た（25.2g,収率91％）.bp98℃/5mm.
オ．（3Z）−ノネノール（VI）の製法．
ｎ−ヘキサン（1L），キノリン（2.5ml），リンドラー
触媒（2g）およびＶ（7g,50ミリモル）に，水素ガス
（1.5L）を吹き込み，反応終了後ガラスフィルターで濾
別し，食塩で飽和した3N−塩酸および飽和食塩水で洗浄
し，減圧蒸留してVIを得た（5.6g,収率78％）.bp84℃/1
mm.
カ．（3Z）−（ノネン−１−イル）−トシレート（VI
I）の製法．
０℃でピリジン（100ml）中にVI（3.95g,27.8ミリモ
ル）とｐ−トルエンスルホン酸クロライド（p-TsCl,10.
5g,55ミリモル）を加え,24時間攪拌した.1.3Lの冷2N−
塩酸に注ぎ込み，エーテルで抽出した．飽和食塩水およ
び飽和炭酸水素ナトリウム水で洗浄後，硫酸ナトリウム
で乾燥させ減圧濃縮してVIIを得た（7.6g,収率92％）．
キ．（3Z）‐１−ヨウドノネン（VIII）の製法．
暗所にてアセトン（50ml）にVII（7.6g）とヨウ化ナト
リウム（7.5g,50ミリモル）を加え，室温で67時間攪拌
した．冷暗所下で冷水に反応混合物を注ぎこみ，エーテ
ル抽出した.12％亜硫酸水素ナトリウム水および飽和食
塩水で洗浄後，硫酸ナトリウムで乾燥させて減圧濃縮し
てVIIIを得た（5.5g,収率85％）．
ク．（3Z）−（ノネン−１−イル）−トリフェニルホス
ホニウム−ヨウダイド（IX）の製法．
窒素気流中の暗所下で，ベンゼン（100ml）にトリフェ
ニルホスフィン（6.3g,24ミリモル）を溶解して,1時間
還流ののちにVIII（5.5g）を加え,43時間80℃で攪拌し
た．室温に戻して，ベンゼンを留去してエーテルで洗浄
した．残った油状物をジクロロメタンに溶解して減圧濃
縮した．さらに，減圧下55℃で乾燥させて粗結晶を得
た．酢酸メチルから再結晶させてIXを得た（8.7g,収率7
7％）.mp86℃．
工程2:段階ケからシまで．
ケ.6−ブロモヘキサノール（X I）の製法．
トルエン（500ml）中に,1,6−ヘキサンジオール（X,59
g,0.50モル）と47％臭化水素酸（105ml,0.9モル）を加
え,90℃で14時間反応させた．有機層を飽和食塩水で洗
浄し，硫酸ナトリウムで乾燥後，減圧下に濃縮した．濃
縮物を塩化カルシウムに吸着させて精製した（67.8g,収
率75％）．
コ.6-（２−テトラハイドロピラニロキシ）−１−ブロ
モヘキサン（X II）の製法．
X I（46.4g,0.26モル）と2,3−ジハイドロピラン（32.8
g,0.39モル）を触媒量の濃硫酸の存在下で室温で攪拌し
た．反応生成物にエーテルを加え，飽和食塩水および飽
和炭酸水素ナトリウム水で洗浄して，硫酸ナトリウムで
乾燥後，減圧濃縮してX IIを得た（67.5g,収率99％）．
サ.7-（２−テトラハイドロピラニロキシ）−ヘプタン
ジエチルアセタール（X III）の製法．
窒素気流中,THF（70ml）に金属マグネシウム（5.5g,0.2
2モル）とヨード（少量）を加え,THF（70ml）に溶解し
たX II（54g,0.2モル）を滴下して,40℃で１時間攪拌
し,95℃でトリエチル−オルソホーメート（50g,0.34モ
ル）を加え,48時間攪拌した．室温で水（150ml）を加
え，しばらく攪拌ののちにヘキサンで抽出した．これを
飽和食塩水および炭酸水素ナトリウム水で洗浄後，硫酸
ナトリウムで乾燥させ減圧濃縮してX IIIを得た（58g,
収率99％）．
シ.7-（２−テトラハイドロピラニロキシ）−ヘプタナ
ール（X IV）の製法．
アセトン（210ml）と水（140ml）の混合溶媒にシュウ酸
（31.0g,0.25モルえ）を加え，さらにX III（24g,83ミ
リモル）を加えて30℃で35分間攪拌した．炭酸水素ナト
リウム（25g）で中和し，減圧下でアセトンを留去し，
残りをエーテルで抽出して飽和食塩水および飽和炭酸水
素ナトリウム水で洗浄後，硫酸ナトリウムで乾燥させ減
圧濃縮してX IVを得た（9.4g,収率53％）．
工程3:段階スからソまで．
ス.1-（２−テトラハイドロピラニロキシ）−（7Z,10
Z）−ヘキサデカジエン（X V）の製法．
IX（17.0g,33ミリモル）をTHF（500ml）に溶解し，窒素
気流中，−78℃でn-BuLi（28ml,42ミリモル）を加えて2
0分間攪拌したのち,HMPA（43ml）とX IV（7.0g,33ミリ
モル）を加えて,0℃以下で１時間攪拌した．水を加えた
のち減圧下でTHFを留去し，食塩で水層を飽和にしてエ
ーテルで抽出した．減圧濃縮後,n−ヘキサンに溶解し
て，飽和食塩水で洗浄し硫酸ナトリウムで乾燥させた．
減圧濃縮したのちに，シリカゲルカラム（溶出剤,n−ヘ
キサン）で処理してX Vを得た（4.4g,収率41％）．
セ．（7Z,10Z）−ヘキサデカジエノール（X VI）の製
法．
リン酸（80ml）とメタノール（200ml）の混合液に，上
のX V（4.4g）を加えて室温で攪拌した．減圧下でメタ
ノールを留去し，残りをエーテルで抽出した．これを希
炭酸水素ナトリウム水および飽和食塩水で洗浄後，硫酸
ナトリウムで乾燥させたのちに，シリカゲルカラムで処
理してX VIを得た（2.8g,収率86％）．
ソ．（7Z,10Z）−ヘキサデカジエナール（Ｉ）の製法．
ジクロロメタン（145ml）にピリジン（9.2g）を加え，
室温で攪拌したのち三酸化クロム（5.8g,58ミリモル）
を加えて15分間攪拌した.X VI（2.1g）を加え，さらに1
5分間攪拌したのち，フロリジルカラムを通し濾過して
残渣をエーテルで洗い込み，有機層を集めて希酸と飽和
食塩水で洗浄後，硫酸ナトリウムで乾燥させた．これを
シリカゲルカラムで処理をしてＩを得た（1.65g,収率77
％）．
このようにして，初めて合成によって得られたＩの分析
データをつぎに示す．
合成Ｉは，海藻アナアオサから分離されたＩと同じ香気
香味を示した．
H-NMR:−ＣHＯ（δ 9.67,1H,t,J＝1.7Hz）,2（−ＣH＝
ＣH−）（δ 5.30,4H,m），−CH＝CH−ＣH2−CH＝CH−
（δ 2.80,2H,t,J＝5.5Hz），−CH2−ＣH2‐CHO（δ
2.45,2H,m）,2（＝CH−ＣH2−）（δ 1.98,4H,m），−
ＣH2−（δ 1.30,12H,m）,CH3−（δ 0.90,3H,t,J＝7
Hz）．
IR（cm-1）:2725（CHO）,1730（Ｃ＝Ｏ）,1660（Ｃ＝
Ｃ）．
MS:m/z 236（6.5％,M＋）,151（3.5）,137（4.7）,123
（5.7）,109（15.7）,98（44.9）,81（69.4）,67（10
0）,55（40.8）,41（14.9）．
なお，上記段階で示した化合物のうち,X VとX VIは新規
化合物である．
化合物Ｉは，冒頭で述べたように特徴的な香気香味をも
つため，この官能特性を利用した香料組成物の製造例
を，以下の実施例で具体的に記述するが，本発明はこれ
に限定されるものではない．
〈実施例〉
実施例1.
チーズフレーバーをつぎの成分で調製した（重量比）．
ブチル ブチリルラクテート 2.0
３−メチルブタン酸 0.5
エチル ブチレート 1.5
ブタン酸 4.0
デカン酸 1.0
２−ヘプタノン 1.0
２−ウンデカノン 0.5
乳酸 1.0
エタノール 8.0プロピレングリコール 80.5
計 100.0
上記組成物と，上記組成物100gに対してＩを1g加えたも
のを熟練した調香師６名で官能評価をおこなった．その
結果,Iを加えた組成物のほうがよりチェダーチーズ様の
香気および香味を強く示し,Iの添加によってチェダー特
有の華やかさと天然らしさが増強したことを指摘した．
実施例2.
シトラスタイプの香料をつぎの各成分を混合して調製し
た．
ジャスミンベース 4.0
ローズベース 1.0
α−アミルシンナムアルデヒド 1.0
ジメチル アンスラニレート 2.0
ターピネオール 5.0
リナロール 15.0
リナリル アセテート 5.0
オクタナール 10％＊ 2.0
ノナナール 10％＊ 1.0
デカナール 50％＊ 2.0
レモンオイル 5.0
ライムオイル 5.0d−リモネン 52.0
計 100.0
＊エタノール中
上記組成物と，上記組成物100gにＩの10％エタノール溶
液を2g加えたものを，熟練した調香師６名で官能評価を
おこなった．全員がＩを加えた組成物の方が，シトラス
の天然らしさおよびフレッシュな香気に富み，さらに匂
いだちの強さと拡散性がより優れていることを指摘し
た．
実施例3.
ローズタイプの香料をつぎのように各成分を混合して調
製した．
ロジノール 10
フェニルエチルアルコール 20
シンナミルアルコール ６
ゲラニオール 20
シトロネロール 14
リナロール ６
ハイドロキシシトロネラール ５
リナリル アセテート ４
オイゲノール ４
ゼラニウムオイル（アフリカン） 10フェニルエチル アセテート 1
計 100
上記組成物と，上記組成物100gに対してＩの１％エタノ
ール溶液6gを加えたものを，熟練した調香師６名で官能
評価をおこなった．その結果,Iを加えた組成物のほう
が，ローズ特有の華やかさと天然らしさが強く付与さ
れ，匂いだちおよび拡散性がともにより優れていること
が指摘された．DETAILED DESCRIPTION OF THE INVENTION The present invention provides the following formula (A): Represented by (7Z, 10Z) -hexadecadienal (I)
The present invention relates to a fragrance composition comprising: The above compound I is a known substance reported by Kemp after being separated from cucumber (J. Am. Oil Chem. Soc. 1975, 52 , 300).
However, the fragrance and flavor of I, and its use as a fragrance, have never been described before, and there is no article suggesting it. And I has never been synthesized before. An analysis group (Kajiwara et al.) Of the present inventors studied the volatile components of Ulva pertusa, which belongs to green algae in seaweed, and isolated I as one of the main components.
Then, I was synthesized for the first time, and its structure was confirmed. On the other hand, the application group found that I is a substance that greatly contributes to the aroma of Anahusa. As a result of detailed investigation of the aroma and flavor of I, it was found that I is a very useful compound as a perfume that can be used for many purposes without being limited to the aroma and flavor of Anahusa. According to conventional recognition, in unsaturated aldehydes of higher linear aliphatics, when the number of carbon atoms is 14 to 15 or more,
It has been considered that the characteristic aroma and flavor of each of them and its intensity gradually decrease as the carbon number increases. However, surprisingly, I, which has 16 carbon atoms and two cis-type unsaturated bonds, has a stronger aroma and flavor than expected. The reason for this is probably due to the two cis unsaturated bonds. The organoleptic properties of cis-unsaturated higher aldehydes having 14 to 15 or more carbon atoms have received little attention in the perfume field until now. According to the research conducted by the present inventor, I is oily aroma and flavor (fatt) common to cheese, chicken, anchovies and shellfish.
y note). Furthermore, it has been found that it has aroma and flavor reminiscent of citrus or orange, and therefore it can be widely used as an aroma and flavor enhancer or an improving and reinforcing agent by being added to a flavor composition of not only food flavors but also cosmetic flavors. It was. For example, in food flavors, it is preferable to add 0.1 to 1% of I to the conventional flavor composition for cheese by making the best use of the characteristics of I, whereby a flavor composition strongly associated with fat can be prepared. In the case of cosmetics and fragrances,
The natural odor of flowers extracted from natural products can be emphasized by adding 0.05 to 1% to the fragrance composition for soap and shampoo. Thus, by blending I, a fragrance composition that has never existed can be made. Hereinafter, the usefulness of the present invention will be clarified by describing an example of producing I by synthesis and then an example of a fragrance composition. <Production Example of Compound I> The production example of I can be divided into steps 1 to 3 and each can be represented by the following reaction formula. Description of Step 1; Metallic sodium was dissolved in liquid ammonium, acetylene gas was blown into the solution, and ethylene oxide was added dropwise to obtain 3-butynol (II).
This is reacted with 2,3-dihydropyran to form pyranyl ether (III) and then further reacted with pentyl bromide to give 9- (2-tetrahydropyranyloxy) -6-
Nonin (IV, 9-THP.0-6-nonin) was synthesized. After depyranyl etherification in a mixture of 30% phosphoric acid and methanol, hydrogenation was carried out in the presence of Lindlar catalyst and quinoline to obtain (3Z) -nonenol (VI). This was tosylated in pyridine and then reacted with sodium iodide in the dark to give an iodine derivative (VIII). Next, triphenylphosphine Was reacted with to obtain a phosphonium salt (IX). Description of step 2; 1,6-hexanediol (X) was monobrominated with 47% hydrobromic acid, and then pyranyl ether (X II) was prepared, and then metal magnesium was added in tetrahydrofuran (THF). The acetal (X III) was synthesized by the reaction of the Grignard reagent prepared by using a triethyl-orthoformate, and the aldehyde (XI
I got V). Description of step 3; phosphonium salt (IX) and aldehyde (X
IV) was subjected to Wittig reaction with n-butyllithium (BuLi) at -78 ℃ in a mixture of THF and hexamethylphosphoramide (HMPA). 3 products (XV)
Depyranyl etherification was carried out with a mixed solution of 0% phosphoric acid and methanol, and further Collins oxidation was carried out to obtain (7Z, 10Z) -hexadecadienal (I) as a target. The above is an outline of the synthesis method. Next, a concrete example will be described. <Specific manufacturing example> Steps 1 to 3 are further subdivided into 15
Each step will be explained in detail below. Process 1: From stage a to c. A. Preparation of 3-butynol (II). Liquid ammonia (700 ml) at −40 ° C.
2 g, 1.4 mol) was dissolved, acetylene gas was blown into it, and ethylene oxide (51 g, 1.2 mol) was added dropwise thereto,
The mixture was stirred at -33 ° C for 24 hours. The mixture was cooled to -40 ° C again, ammonium chloride (75 g, 1.4 mol) was added, and the mixture was returned to room temperature to vaporize ammonia. Water was added to the residue and the mixture was extracted with ether.The extract was washed with 2N-hydrochloric acid and saturated brine, dried over sodium sulfate, and distilled under reduced pressure to give II (18 g, yield 44%). Bp 77 ° C / 80 mm. A method for producing 4- (2-tetrahydropyranyloxy) -1-butyne (III). II above (20 g, 0.29 mol) and 2,3-dihydropyran (36
g, 0.43 mol) and a catalytic amount of concentrated sulfuric acid were reacted at room temperature. Ether was added, washed with saturated brine and saturated sodium hydrogen carbonate, dried over sodium sulfate, and distilled under reduced pressure to obtain III (39.1 g, yield 88%). Bp 106 ° C / 24 mm. Preparation of 2-tetrahydropyranyloxy) -6-nonine (IV). Metallic sodium (9.0 g) was dissolved in liquid ammonia (700 ml) at −40 ° C., and the above III was added dropwise thereto. Further, pentyl bromide (67.3g, 0.44mol) was added dropwise to give a -33
The mixture was stirred at ℃ for 24 hours. The mixture was cooled again to −40 ° C., ammonium chloride (31 g, 0.58 mol) was added, and the mixture was returned to room temperature to vaporize ammonia. Water was added to the residue, and the mixture was extracted with ether. The extract was washed with 2N-hydrochloric acid and saturated brine, dried over sodium sulfate, and distilled under reduced pressure to give IV (44.1 g, yield 77
%). Bp 117 ° C./1 mm. D. Method for producing 3-noninol (V). In a mixed solution of phosphoric acid (108 ml) and methanol (325 ml),
The above IV was added dropwise and stirred at room temperature. Methanol was distilled off under reduced pressure while adding saturated saline, followed by extraction with ether. The ether layer was washed with saturated saline and saturated aqueous sodium hydrogen carbonate, dried over sodium sulfate and distilled under reduced pressure to give V (25.2 g, yield 91%). Bp 98 ° C / 5 mm. Method for producing (3Z) -nonenone (VI). Hydrogen gas (1.5 L) was blown into n-hexane (1 L), quinoline (2.5 ml), Lindlar catalyst (2 g) and V (7 g, 50 mmol), and after the reaction was completed, it was filtered with a glass filter and saturated with sodium chloride. Washed with saturated 3N-hydrochloric acid and saturated brine, and distilled under reduced pressure to give VI (5.6g, yield 78%). Bp 84 ℃ / 1
mm. (3Z)-(nonen-1-yl) -tosylate (VI
Method I). VI (3.95 g, 27.8 mmol) and p-toluenesulfonic acid chloride (p-TsCl, 10.
5 g, 55 mmol) was added and stirred for 24 hours.
It was poured into hydrochloric acid and extracted with ether. The extract was washed with saturated saline and saturated aqueous sodium hydrogen carbonate, dried over sodium sulfate and concentrated under reduced pressure to give VII (7.6 g, yield 92%). G. Method for producing (3Z) -1-iodononene (VIII). VII (7.6 g) and sodium iodide (7.5 g, 50 mmol) were added to acetone (50 ml) in the dark, and the mixture was stirred at room temperature for 67 hours. The reaction mixture was poured into cold water in a cool dark place and extracted with ether. The extract was washed with 12% aqueous sodium hydrogen sulfite solution and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain VIII (5.5 g, yield 85 %). Ku. A method for producing (3Z)-(nonen-1-yl) -triphenylphosphonium-iodide (IX). Triphenylphosphine (6.3 g, 24 mmol) was dissolved in benzene (100 ml) in a dark place in a nitrogen stream, and after refluxing for 1 hour, VIII (5.5 g) was added and stirred at 80 ° C for 43 hours. ． The mixture was returned to room temperature, benzene was distilled off and washed with ether. The remaining oil was dissolved in dichloromethane and concentrated under reduced pressure. Further, it was dried at 55 ° C under reduced pressure to obtain crude crystals. Recrystallization from methyl acetate gave IX (8.7 g, yield 7
7%). Mp86 ° C. Process 2: From stage K to Shi. K. Method for producing 6-bromohexanol (XI). In toluene (500 ml), 1,6-hexanediol (X, 59
g, 0.50 mol) and 47% hydrobromic acid (105 ml, 0.9 mol) were added and reacted at 90 ° C for 14 hours. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrate was adsorbed on calcium chloride for purification (67.8 g, yield 75%). C. Method for producing 6- (2-tetrahydropyranyloxy) -1-bromohexane (XII). XI (46.4g, 0.26mol) and 2,3-dihydropyran (32.8
g, 0.39 mol) was stirred at room temperature in the presence of catalytic amount of concentrated sulfuric acid. Ether was added to the reaction product, washed with saturated saline and saturated aqueous sodium hydrogen carbonate, dried over sodium sulfate, and concentrated under reduced pressure to give X II (67.5 g, yield 99%). Preparation of 7- (2-tetrahydropyranyloxy) -heptane diethyl acetal (XIII). Metallic magnesium (5.5g, 0.2g) in THF (70ml) under nitrogen stream
2 mol) and iodine (small amount) were added, X II (54 g, 0.2 mol) dissolved in THF (70 ml) was added dropwise, and the mixture was stirred at 40 ° C for 1 hour and triethyl-orthoformate (50 g, 50 ° C) at 95 ° C. 0.34 mol) was added and stirred for 48 hours. Water (150 ml) was added at room temperature, the mixture was stirred for a while, and then extracted with hexane. This was washed with saturated brine and aqueous sodium hydrogen carbonate, dried over sodium sulfate, and concentrated under reduced pressure to give XIII (58 g,
Yield 99%). Preparation of 7- (2-tetrahydropyranyloxy) -heptanal (X IV). Oxalic acid (31.0 g, 0.25 mol) was added to a mixed solvent of acetone (210 ml) and water (140 ml), X III (24 g, 83 mmol) was further added, and the mixture was stirred at 30 ° C for 35 minutes. Neutralize with sodium hydrogen carbonate (25g), distill off acetone under reduced pressure,
The residue was extracted with ether, washed with saturated brine and saturated aqueous sodium hydrogen carbonate solution, dried over sodium sulfate, and concentrated under reduced pressure to give XIV (9.4 g, yield 53%). Process 3: From stage S to S. Su. 1- (2-tetrahydropyranyloxy)-(7Z, 10
Z) -hexadecadiene (XV) manufacturing method. IX (17.0 g, 33 mmol) was dissolved in THF (500 ml), and n-BuLi (28 ml, 42 mmol) was added at -78 ° C in a nitrogen stream to add 2
After stirring for 0 minutes, HMPA (43 ml) and XIV (7.0 g, 33 mmol) were added, and the mixture was stirred at 0 ° C or lower for 1 hour. After adding water, the THF was distilled off under reduced pressure, the aqueous layer was saturated with sodium chloride and extracted with ether. After concentration under reduced pressure, the residue was dissolved in n-hexane, washed with saturated brine and dried over sodium sulfate.
After concentration under reduced pressure, XV was obtained by treating with a silica gel column (eluent, n-hexane) (4.4 g, yield 41%). C. Preparation of (7Z, 10Z) -hexadecadienol (X VI). The above XV (4.4 g) was added to a mixed solution of phosphoric acid (80 ml) and methanol (200 ml), and the mixture was stirred at room temperature. Methanol was distilled off under reduced pressure, and the rest was extracted with ether. This was washed with dilute aqueous sodium hydrogen carbonate solution and saturated brine, dried over sodium sulfate, and then treated with a silica gel column to obtain XVI (2.8 g, yield 86%). S. (7Z, 10Z) -Production method of hexadecadienal (I). Pyridine (9.2g) was added to dichloromethane (145ml),
After stirring at room temperature, chromium trioxide (5.8g, 58mmol)
And stirred for 15 minutes. Add X VI (2.1 g) and add 1 more
After stirring for 5 minutes, the mixture was filtered through a Florisil column, the residue was washed with ether, the organic layers were combined, washed with dilute acid and saturated saline, and dried over sodium sulfate. This was treated with a silica gel column to obtain I (1.65 g, yield 77
%). The analytical data of I obtained by synthesis for the first time in this way are shown below. Synthetic I showed the same aroma and flavor as I isolated from the seaweed Anahusa. H-NMR: -C H O (δ 9.67,1H, t, J = 1.7Hz), 2 (-C H =
C H -) (δ 5.30,4H, m), - CH = CH-C H2 -CH = CH-
(Δ 2.80,2H, t, J = 5.5Hz), -CH2-C H2- CHO (δ
2.45,2H, m), 2 (= CH-C H2 -) (δ 1.98,4H, m), -
C H2 − (δ 1.30,12H, m), C H3 − (δ 0.90,3H, t, J = 7
Hz). IR (cm-1): 2725 (CHO), 1730 (C = O), 1660 (C =
C). MS: m / z 236 (6.5%, M +), 151 (3.5), 137 (4.7), 123
(5.7), 109 (15.7), 98 (44.9), 81 (69.4), 67 (10
0), 55 (40.8), 41 (14.9). Of the compounds shown in the above steps, XV and XVI are new compounds. Since the compound I has a characteristic aroma and flavor as described at the beginning, a production example of a fragrance composition utilizing this sensory characteristic will be specifically described in the following examples. It is not limited. <Example> Example 1. A cheese flavor was prepared with the following components (weight ratio). Butyl butyryl lactate 2.0 3-Methylbutanoic acid 0.5 Ethyl butyrate 1.5 Butanoic acid 4.0 Decanoic acid 1.0 2-Heptanone 1.0 2-Undecanone 0.5 Lactic acid 1.0 Ethanol 8.0 Propylene glycol 80.5 Total 100.0 I was added to the above composition and 100 g of the above composition. Sensory evaluation was performed by 6 skilled perfumers with 1 g added. As a result, it was pointed out that the composition to which I was added exhibited a stronger cheddar cheese-like aroma and flavor, and that the addition of I enhanced the brilliance and naturalness peculiar to Cheddar. Example 2 A citrus-type fragrance was prepared by mixing the following components. Jasmine base 4.0 Rose base 1.0 α-amylcinnamaldehyde 1.0 Dimethyl anthranilate 2.0 Terpineol 5.0 Linalool 15.0 Linalyl acetate 5.0 Octanal 10% * 2.0 Nonanal 10% * 1.0 Decanaal 50% * 2.0 Lemon oil 5.0 Lime oil 5.0 d-Limonene 52.0 Total 100.0 * The above composition in ethanol and 100 g of the above composition added with 2 g of a 10% ethanol solution of I were subjected to sensory evaluation by 6 trained perfumers. All of them pointed out that the composition to which I was added was rich in the naturalness and fresh aroma of citrus, and more excellent in the intensity and diffusivity of smell. Example 3 A rose type fragrance was prepared by mixing the components as follows. Rosinol 10 Phenylethyl Alcohol 20 Cinnamyl Alcohol 6 Geraniol 20 Citronellol 14 Linalool 6 Hydroxycitronellal 5 Linalyl Acetate 4 Eugenol 4 Geranium Oil (African) 10 Phenylethyl Acetate 1 Total 100 For the above composition and 100 g of the above composition Sensory evaluation was performed by 6 trained perfumers with the addition of 6 g of a 1% ethanol solution of I. As a result, it was pointed out that the composition to which I was added strongly gave the gorgeousness and naturalness peculiar to rose, and was more excellent in the smell and the diffusibility.