JPS6281335A - Production of tricyclo(5.3.1.03,8)undec-4-ene - Google Patents

Production of tricyclo(5.3.1.03,8)undec-4-ene

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Publication number
JPS6281335A
JPS6281335A JP60221561A JP22156185A JPS6281335A JP S6281335 A JPS6281335 A JP S6281335A JP 60221561 A JP60221561 A JP 60221561A JP 22156185 A JP22156185 A JP 22156185A JP S6281335 A JPS6281335 A JP S6281335A
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JP
Japan
Prior art keywords
formula
tricyclo
reaction
palladium
metal catalyst
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
Application number
JP60221561A
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Japanese (ja)
Other versions
JP2782512B2 (en
Inventor
Naotake Takaishi
高石　尚武
Kimihiko Hori
公彦 堀
Masatomo Ando
安藤　正知
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
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Kao Corp
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Filing date
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Priority to JP60221561A priority Critical patent/JP2782512B2/en
Publication of JPS6281335A publication Critical patent/JPS6281335A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

PURPOSE:To carry out dehydrohalogenation reaction and decarbonylation reaction at a stroke, by treating a tricyclo[5.3.1.0<3>,<8>]undecane-3-carbonyl halide in the presence of a transition metal catalyst and tertiary amine. CONSTITUTION:A tricyclo[5.3.1.0<3>,<8>]undecane-3-carbonyl halide expressed by formula I (X is halogen) is treated in the presence of 0.01-20mol%, particularly 0.1-5mol%, based on the raw materials compound expressed by formula I, transition metal catalyst, e.g. palladium chloride, palladium chloride, palladium bromide, rhodium oxide or rhodium chloride, and 1-10 equivalents, particularly 1-2 equivalents, based on the raw material compound expressed by formula I, tertiary amine, e.g. pyrdine, triethylamine or qinoline, to carry out de hydrohalogenation reaction and decarbonylation reaction at a stroke in one operation and afford the aimed compound expressed by formula II. USE:An intermediate for producing perfumes and perfume component having comphoric fragrance with woody feeling.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は式（１）、 で表わされるトリシフａ（５，３，１，０”、”　　：
］］ウンデカー４−エの喪造法に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to trisiph a(5,3,1,0"," expressed by formula (1)):
]] Concerning the mourning method of Undekar 4-e.

〔従来の技術及びその問題点〕[Conventional technology and its problems]

トリシクロ（５，３，１，０”、”　　）ウンデカン骨
格を有する化合物の中には香気成分として知られている
ものが多い（特開昭５３−１１１０４９〜１１１０５２
号、特公昭５６−４５３８号）。例えば今までに次の式
（３）、（４）、（５）、（６）、（力で表わされる化
合物等が知られているうこれらはいずれもｆ＊［の強い
芳容を有し、香料の基剤として極めて有用な化合物であ
る。Many compounds having a tricyclo(5,3,1,0'','') undecane skeleton are known as aroma components (Japanese Patent Laid-Open No. 111049-111052)
No., Special Publication No. 56-4538). For example, compounds represented by the following formulas (3), (4), (5), (6), and , is an extremely useful compound as a base for fragrances.

しかしながら、これら化合＊を合成するうえで重要な中
間体であるトリシフＯ（５，３，１゜Ｏｊ・６　〕〕ウ
ンデカー４−エン１）を大量に、かつ収率良く合成する
方法はなく、高石らが化合物（６）の構造を確認するた
めに次に示す反応式に従って化合物（９）へ導いた際に
中間体として化合物＋１）の合成を行なっているのみで
ある〔ケミストリー・レターズ（ｅｈｅｍ、　Ｌｅｔｔ
、　ｌ　８２５　（１９７８１）。However, there is no method for synthesizing trisifu O (5,3,1゜Oj・6]]undec-4-ene 1), which is an important intermediate for synthesizing these compounds*, in large quantities and with good yield. In order to confirm the structure of compound (6), Takaishi et al. led to compound (9) according to the reaction formula shown below, and only synthesized compound +1) as an intermediate [Chemistry Letters (ehem , Lett
, l 825 (19781).

（式中、Ｔｓはトシル基を示す） しかし、この反応は上式から明らかな如く、化合物の構
造を決定するだめに、わざわざ多段階の反応を用いて化
合物（２）を導いたものであって、化合物（２）を合成
するための実用的な方法とは云えない。(In the formula, Ts represents a tosyl group.) However, as is clear from the above formula, this reaction intentionally used a multi-step reaction to derive compound (2) in order to determine the structure of the compound. Therefore, it cannot be called a practical method for synthesizing compound (2).

従って、前記式（３）〜（９）で示される化合物等のト
リシクロ（５，３，１，０’・６　〕ウンデカン誘導体
を合成する際の共通中間体として有用な前記式（１）で
示されるトリシクロ（：５．３．１．０”、’　　］］
ウンデカー４−エン金簡に、かつ高収率で、しかも大量
に合成できる喪失が所望されていた。Therefore, the compound represented by the above formula (1) is useful as a common intermediate in the synthesis of tricyclo(5,3,1,0'・6]undecane derivatives such as the compounds represented by the above formulas (3) to (9). tricyclo(:5.3.1.0”,' ]]
There was a desire for a compound that could be synthesized into undec-4-ene gold strips in high yield and in large quantities.

〔問題点を解決するための手段〕[Means for solving problems]

斯かる実状において、本発明者は鋭意研究の結果、トリ
シクロ（５，３，１，０”−）ウンデカ−４−エン（１
）を−回の操作で一挙に製造しうる方法を見出し、本発
明を完成した。Under such circumstances, the present inventor has conducted extensive research and found that tricyclo(5,3,1,0''-)undec-4-ene(1
) was discovered in one operation, and the present invention was completed.

すなわ゛ち本発明は、 （式中、Ｘはハロゲン原子を示す） で表わされる公知のトリシクロ（５，３，１゜０３・”
〕ｒ）ンｆカンー３−カルボン酸ハロゲン化物（特公昭
５６−１８５８８号公報）を遷移金属触媒及び三級アミ
ン類の存在下処理し、脱ハロゲン化水素、脱カル余キシ
ル化反応を一挙に行なうことを特徴とする前記式ｉｌｌ
で示される化合物の製造法を提供するものである。In other words, the present invention is directed to the well-known tricyclo(5,3,1゜03.''
[r) Kan-3-carboxylic acid halide (Japanese Patent Publication No. 56-18588) is treated in the presence of a transition metal catalyst and tertiary amines to simultaneously perform dehydrohalogenation and decalcification and xylation reactions. Said formula ill characterized in that it performs
The present invention provides a method for producing a compound represented by:

遷移金属触媒としては、例えばパラジウム金属触媒ロジ
ウム金属触媒等が好適なものとして挙げられる。パラジ
ウム金属触媒としては、例えば塩化パラジウム、臭化パ
ラジウム、酢酸パラジウム等の２価のパラジウム、パラ
ジウムブラック、パラジウム付活性炭、テトラキス（ト
リフェニルホスフィン）パラジウム等の０価のパラジウ
ム等が挙げられる。また、ロジウム金属触媒としては、
例えば金属ロジウム、酸化ロジウム、塩化ロジウム、ク
ロロトリス（）！ｊ、ｙエニルホスフイン）ロジウム（
Ｉ）、ヒドリドカルボニルトリス（トリフェニルホスフ
ィン）ロジウムｔＩ）　等の金属ロジウム、酸化物、錯
体等が挙げられる。遷移金属触媒は、原料化合物（２）
に対してその０．０１〜２０モルチ、特に０．１〜５七
ル優となるように使用するのが好ましい。Suitable transition metal catalysts include, for example, palladium metal catalysts and rhodium metal catalysts. Examples of the palladium metal catalyst include divalent palladium such as palladium chloride, palladium bromide, and palladium acetate, and zero-valent palladium such as palladium black, palladium-attached activated carbon, and tetrakis(triphenylphosphine)palladium. In addition, as a rhodium metal catalyst,
For example, metal rhodium, rhodium oxide, rhodium chloride, chlorotris ()! j, y enylphosphine) rhodium (
I), metal rhodium such as hydridocarbonyltris(triphenylphosphine)rhodium tI), oxides, complexes, and the like. The transition metal catalyst is a raw material compound (2)
It is preferable to use it in an amount of 0.01 to 20 mole, particularly 0.1 to 57 mole, per mol.

また、反応中に生成するハロゲン化水素の除去試薬とし
て使用される三級アミン類は、例えばピリジン、トリエ
チルアミン、トリブチルアミン、ピコリン、キノリン等
が挙げられる。三級アはン類は、原料化合物（２）に対
して１〜１０当量、荷に１〜２当竜使用するのが好まし
い。Furthermore, examples of tertiary amines used as a reagent for removing hydrogen halide generated during the reaction include pyridine, triethylamine, tributylamine, picoline, and quinoline. The tertiary amines are preferably used in an amount of 1 to 10 equivalents based on the raw material compound (2), and 1 to 2 equivalents in weight.

反応は一般には無溶媒で行なうことができるが、反応に
不活性な溶媒の存在下行なうこともできる。The reaction can generally be carried out without a solvent, but it can also be carried out in the presence of a solvent that is inert to the reaction.

反応温度は、０〜２００℃、特に１００−１５０℃が好
ましい。The reaction temperature is preferably 0 to 200°C, particularly 100 to 150°C.

〔作用及び発明の効果〕[Action and effect of invention]

本発明方法によれば、香料を製造するだめの中間体とし
て、また木様点のあるカン７ア一様の香気を有しそれ自
身も香料成分とし一〇有用な化合物であるトリシクロＣ
５，３，１，０’・８　〕〕ウンデカー４−エを容易に
、かつ高収率で製造することができる。According to the method of the present invention, tricycloC, which is a useful compound, can be used as an intermediate for producing perfumes, and has a woody point-like aroma and is itself a perfume ingredient.
5,3,1,0'·8]] Undecor 4-e can be produced easily and in high yield.

〔央痛例〕[Central pain case]

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 トリシクロ［５，３，１，０”・６　〕〕ウンデカンー
３−カルボンｆａｌｌ化吻（４，２ｙ、　　２０．０ｍ
ｍａｌｌ及びトリーｎ−ブチルアミン（４，４７，２２
，０ｍｍｏｌ　）の７昆合物に臭化パラジウム（５２η
、０．２ｍｍｏｌ　）を加え、反応温１ｆ１３０℃で２
時間加熱攪拌する。反応混合物をＩＮ塩酸で処理してア
ミンを除去した後、エーテルで抽出し、抽出液ｔ−無水
硫酸ナトリウムで乾燥させ溶媒を留去する。残渣を減圧
蒸留したところ、トリシクロ［：５．３゜１　、０”ｌ
”　　）　’）７ｆ−）ｙ−４−ｃンｉ３．ＯＦ　（１
９，９ｍｍａｌ　ｌ得た。本化合物は、木様点のあるカ
ンファー陣の香２１．を有していた。Example 1 Tricyclo[5,3,1,0"・6]]undecane-3-carbon fall proboscis (4,2y, 20.0m
mall and tri-n-butylamine (4,47,22
, 0 mmol) of the heptadol complex was added with palladium bromide (52η
, 0.2 mmol) was added, and the reaction temperature was 1f130°C.
Heat and stir for an hour. The reaction mixture was treated with IN hydrochloric acid to remove the amine, extracted with ether, the extract was dried over anhydrous sodium sulfate, and the solvent was distilled off. When the residue was distilled under reduced pressure, tricyclo[:5.3゜1, 0"l
” ) ')7f-)y-4-cni3.OF (1
9.9 mmal was obtained. This compound has a camphor group aroma with woody points.21. It had

収率　９９チ 沸点　１３８〜ｂ Ｉ　Ｒ（Ｎｃａ　ｔ　ｌ　（７Ｆ！’−”３０２０．１
６４０ ’ｉ（−ＮＭＲ（Ｃ１）ＣＬ、溶媒、ＴＭＳ内部傾準、
δ）１．１〜Ｚ２　ｔ　１４Ｈ，ｒｎｌ、５．４〜５．
５　（Ｌ　Ｈ，ｍ　ｌ、５．８〜５．９（ＩＨ，ｍ） ｕｃ−ＮＭｌｔ　ｔ　ＣＬ）Ｃｇ、　ｍ媒、ＴＭＳ内部
標準、δ）２３．４９（ｄｉ、２４．８０ｆｔ＋、２５
．０２ｆｔ＋、２８．５４（ｄｉ、２８．６４（ｄ）、
３１．４１（ｄ）、３２．１６（ｔｌ、３２−７９ｆｔ
）、３３．７５ｆｔ＋、１２２．３１（ｄ）、１３５．
０８（ｄｌこれらのスペクトルの結果は、いずｔＬも文
献値〔ケミストリー・レターズ（Ｃｈｅｍ、　Ｌｅｔｔ
、　ｌ　８２５（１９７８１１と一致した。Yield: 99cm Boiling point: 138~b IR(Ncatl (7F!'-"3020.1
640'i(-NMR(C1)CL, solvent, TMS internal tilt,
δ) 1.1~Z2 t 14H, rnl, 5.4~5.
5 (L H, ml, 5.8-5.9 (IH, m) uc-NMlt t CL) Cg, m medium, TMS internal standard, δ) 23.49 (di, 24.80 ft+, 25
．． 02ft+, 28.54(di, 28.64(d),
31.41(d), 32.16(tl, 32-79ft
), 33.75ft+, 122.31(d), 135.
08 (dl) The results of these spectra are both tL and literature values [Chemistry Letters (Chem, Lett
, l 825 (matched with 197811).

以上 ！’　　ｈ”ｃ　　？ｌｌｉ　　ｉＥ　　ｔＢ　（自発
）昭和６０年１１月５日 特１負庁長官宇賀道部殿 １、　　°ｌＧ件の表示 昭和６０年特許願第２２１５６１号 ２、　発明の名称 トリシクロ（５，３，１，０）ウンデカ−４−エンの製
造法３、　補）Ｅをする者 ・１９件との関係　　　出願人 名　称　　（０９１）花王株式会社 ４、代理人 住　所　東京都中央区日本橋人形町１丁目３番６号（〒
１０３）５、　補正命令のトＩ付　　　　　　　　　　
　　　　　′−−−−□−−ｊ自　　発 ６、補正の対象 明細書の「発明の詳細な説明」の欄 ７、補正の内容 （１）明細書中、第５頁第９行 「脱カルボキシル化反応」 とあるを 「脱カルボニル化反応」 と訂正する。that's all! ' h”c ?lli iE tB (Spontaneous) November 5, 1985 Mr. Michibu Uga, Commissioner of the Special 1 Negative Agency 1, °lG indication 1985 Patent Application No. 221561 2, Name of the invention Tricyclo (5 , 3, 1, 0) Process for producing undeca-4-ene 3, Supplementary) Person conducting E/Relationship with 19 cases Applicant name (091) Kao Corporation 4, Agent address Nihonbashi Doll, Chuo-ku, Tokyo Town 1-3-6 (〒
103) 5. Correction instruction with G.I.
'-----□--j Spontaneous 6, "Detailed Description of the Invention" column 7 of the specification subject to amendment, Contents of the amendment (1) In the specification, page 5, line 9, "Decarboxylation "reaction" is corrected to "decarbonylation reaction".

（２）同、第５頁第１３行 「触媒ロジウム金属触媒等」 とあるを ［触媒、ロジウム金属触Ｉｔ’ｄ等」 と訂正する。(2) Same, page 5, line 13 "Catalyst rhodium metal catalyst etc." A certain thing [Catalyst, rhodium metal catalyst, etc.] I am corrected.

手続補正書（自発） 昭和６１年１０月２４日 １、　事件の表示 昭和６０手　特　許　　願第２２１５６１　号２、発明
の名称。Procedural amendment (voluntary) October 24, 1985 1. Indication of the case 1985 Patent Application No. 221561 2. Title of the invention.

トリシクロ（５，３，１，０”−）ウンデカ−４−エン
の製造法３　補正をする者 ２１９件との関係　　　出願人 １下　　　所 名　称　（０９１）花王株式会社 ４　　代　　理　　人 ・阪　　　　　　　ｌ 住　所　同　　　　上　　　　　　　　　　１１−一一
一一一６、　補正の対象 明細書の「発明の詳細な説明」の欄 ７、　補正の内容 （１）　　明細書中、第４頁第５行および第４頁第５〜
６行 「化合物（２）」とあるを 「化合物（１）」と訂正する。Process for producing tricyclo(5,3,1,0”-)undec-4-ene 3 Relationship with 219 amendments Applicant 1 Name (091) Kao Corporation 4 Agent Saka l Address Same as above 11-11116, "Detailed description of the invention" column 7 of the specification subject to amendment, Contents of amendment (1) Page 4, line 5 and page 4 of the description 5th~
In line 6, "Compound (2)" should be corrected to "Compound (1)."

Claims (1)

【特許請求の範囲】 １、式（２） ▲数式、化学式、表等があります▼（２） （式中、Ｘはハロゲン原子を示す） で表わされるトリシクロ〔５．３．１．０＾３＾，＾８
〕ウンデカン−３−カルボン酸ハロゲン化物を遷移金属
触媒及び三級アミン類の存在下処理し、脱ハロゲン化水
素、脱カルボニル化反応を一挙に行なうことを特徴とす
る式（１） ▲数式、化学式、表等があります▼（１） で表わされるトリシクロ〔５．３．１．０＾３＾，＾８
〕ウンデカ−４−エンの製造法。[Claims] 1. Tricyclo[5.3.1.0^3] represented by formula (2) ▲Mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, X represents a halogen atom) ^, ^8
] Formula (1) characterized by treating undecane-3-carboxylic acid halide in the presence of a transition metal catalyst and tertiary amines to perform dehydrohalogenation and decarbonylation reactions at once ▲Mathematical formula, chemical formula , tables, etc.▼(1) Tricyclo [5.3.1.0^3^,^8
] A method for producing undec-4-ene.
JP60221561A 1985-10-04 1985-10-04 Method for producing tricyclo [5.3.1.0 [top 3] '[top 8]] undec-4-ene Expired - Lifetime JP2782512B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60221561A JP2782512B2 (en) 1985-10-04 1985-10-04 Method for producing tricyclo [5.3.1.0 [top 3] '[top 8]] undec-4-ene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60221561A JP2782512B2 (en) 1985-10-04 1985-10-04 Method for producing tricyclo [5.3.1.0 [top 3] '[top 8]] undec-4-ene

Publications (2)

Publication Number Publication Date
JPS6281335A true JPS6281335A (en) 1987-04-14
JP2782512B2 JP2782512B2 (en) 1998-08-06

Family

ID=16768654

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Country Link
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