JPH02221255A - Production of alkenyl isothiocyanate - Google Patents
Production of alkenyl isothiocyanateInfo
- Publication number
- JPH02221255A JPH02221255A JP4031389A JP4031389A JPH02221255A JP H02221255 A JPH02221255 A JP H02221255A JP 4031389 A JP4031389 A JP 4031389A JP 4031389 A JP4031389 A JP 4031389A JP H02221255 A JPH02221255 A JP H02221255A
- Authority
- JP
- Japan
- Prior art keywords
- thiocyanate
- alkenyl
- formula
- isothiocyanate
- expressed
- 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
Links
- -1 alkenyl isothiocyanate Chemical class 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 3
- 239000012442 inert solvent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000796 flavoring agent Substances 0.000 abstract description 4
- 235000019634 flavors Nutrition 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000002304 perfume Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000002085 irritant Substances 0.000 abstract 1
- 231100000021 irritant Toxicity 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- DBISBKDNOKIADM-UHFFFAOYSA-N 5-isothiocyanato-1-pentene Chemical compound C=CCCCN=C=S DBISBKDNOKIADM-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- SKIHGKNFJKJXPX-UHFFFAOYSA-N 4-isothiocyanato-1-butene Chemical compound C=CCCN=C=S SKIHGKNFJKJXPX-UHFFFAOYSA-N 0.000 description 4
- 244000195452 Wasabia japonica Species 0.000 description 4
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000000760 Wasabia japonica Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- DDXWRFXSAYFRRE-UHFFFAOYSA-N pent-4-enyl thiocyanate Chemical compound C=CCCCSC#N DDXWRFXSAYFRRE-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BYKYMPVVZNUAEX-UHFFFAOYSA-N 2-pent-4-enylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCC=C)C(=O)C2=C1 BYKYMPVVZNUAEX-UHFFFAOYSA-N 0.000 description 1
- WRFHVMFZOJHYGN-UHFFFAOYSA-N 6-isothiocyanatohex-1-ene Chemical compound C=CCCCCN=C=S WRFHVMFZOJHYGN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、イソチオシアン酸アルケニルの製造方法に関
する。本発明の製造方法によって製造されるイソチオシ
アン酸アルケニルは、わさび様の刺激臭およびグリーン
感を有しており、食品、化粧品、トイレタリー製品等に
添加する香料組成物の素材として有用である。特に人工
わさび香料において、天然のわさびにより近づいた香味
を想起させるのに有用な素材である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing alkenyl isothiocyanates. The alkenyl isothiocyanate produced by the production method of the present invention has a wasabi-like pungent odor and a green feel, and is useful as a material for fragrance compositions added to foods, cosmetics, toiletry products, etc. In particular, it is a useful material for artificial wasabi flavorings to evoke a flavor closer to natural wasabi.
［従来の技術およびその問題点］
イソチオシアン酸アルケニルは沢わさびの香気成分とし
て存在するが、わさびには、微量しか含有されていない
ので、工業的には化学的合成により生産される。[Prior Art and its Problems] Alkenyl isothiocyanate exists as an aromatic component in wasabi wasabi, but since wasabi contains only a trace amount, it is industrially produced by chemical synthesis.
イソチオシアン酸アルケニルの製造法としては、例えば
、出発原料の４−ベンテノールを、三臭化リンを用いて
ハライドとし、次いでフタルイミドカリウムを作用させ
てＮ−（４−ペンテニル）フタルイミドに導き、この化
合物をヒドラジツリシスに付してアミンとし、最後に、
クロロホルム中、チオホスゲンを作用させることにより
、イソチオシアン酸４−ペンテニルを製造する方法が知
られている（＾ｅｔａ Ｃｈｅｗ、 ５ｃａｎｄ、 １
０．１３８５゜（１９５Ｂ）を参照。）。しかしながら
、この方法は、製造工程が長く、その総収率が低いとい
う欠点を有している。さらに、試薬の７タルイミドカリ
ウムが高価であること、また催涙性で強力な中毒性ガス
であるチオホスゲンを使用しているため安全性に欠ける
など、工業的には満足できるものでない。As a method for producing alkenyl isothiocyanate, for example, the starting material 4-bentenol is converted into a halide using phosphorus tribromide, and then potassium phthalimide is reacted to convert it into N-(4-pentenyl)phthalimide. was subjected to hydrazitolysis to give the amine, and finally,
A method for producing 4-pentenyl isothiocyanate by reacting thiophosgene in chloroform is known (^eta Chew, 5cand, 1
See 0.1385° (195B). ). However, this method has the disadvantages of a long manufacturing process and a low overall yield. Furthermore, the reagent, heptatalimide potassium, is expensive, and the use of thiophosgene, a lachrymatory and powerfully toxic gas, lacks safety, making it unsatisfactory from an industrial perspective.
一方、イソチオシアン酸アリル（アリル芥子油）は、ハ
ロゲン化アリルをアルコール中、チオシアン酸塩と反応
させ、次いで加熱して異性化することにより製造される
ことが知られている（香料化学総覧（ｎ） 、 １４２
Ｂ頁（奥田治著、広用書店）を参照。）。しかしながら
、この方法では、主鎖の炭素原子が４個以上であるアル
ケニルの場合チオシアン酸アルケニルの生成で反応は終
了してしまい、加熱しても転位反応は起らない。On the other hand, allyl isothiocyanate (allyl mustard oil) is known to be produced by reacting allyl halide with thiocyanate in alcohol, followed by isomerization by heating (Comprehensive Fragrance Chemistry (n ), 142
See page B (written by Osamu Okuda, Koyo Shoten). ). However, in this method, in the case of alkenyl having four or more carbon atoms in the main chain, the reaction ends with the formation of alkenyl thiocyanate, and no rearrangement reaction occurs even when heated.
［問題点を解決するための手段］
本発明者はかかる問題点を克服すべく、鋭意検討した結
果、類似技術の全く知られていない新規転位反応を利用
するイソチオシアン酸アルケニルの製法を完成するに至
った。[Means for Solving the Problems] In order to overcome these problems, the inventors of the present invention have made extensive studies and have completed a method for producing alkenyl isothiocyanates that utilizes a novel rearrangement reaction in which similar technology is completely unknown. It's arrived.
本発明によれば、
不活性溶媒中、好ましくは、塩基の存在下、式（式中、
ＲおよびＲ２は各々独立して水素原子または低級アルキ
ル基を示し、Ｘはハロゲン原子を示し、Ｙは幹部分の炭
素数が２〜１０である直鎖状または分枝鎖状Ｑアルキレ
ン基を示す。）で表わされるアルケニルハライドをチオ
シアン酸塩と反応させ、得られたチオシアン酸アルケニ
ルを極性非プロトン溶媒中で異性化することを特徴とす
る式（１）
（式中、Ｒ１，Ｒ２およびＹは、前述したものと同一意
義を有する。）
で表わされるイソチオシアン酸アルケニルの製造方法が
提供される。According to the invention, in an inert solvent, preferably in the presence of a base, the formula (wherein
R and R2 each independently represent a hydrogen atom or a lower alkyl group, X represents a halogen atom, and Y represents a linear or branched Q alkylene group having 2 to 10 carbon atoms in the trunk. . ) is reacted with a thiocyanate, and the resulting alkenyl thiocyanate is isomerized in a polar aprotic solvent (wherein R1, R2 and Y are Provided is a method for producing an alkenyl isothiocyanate represented by:
本発明において、不活性溶媒としては、特に限定される
ことはないが、例えばメタノール、ベンゼン、トルエン
、テトラヒドロフラン、塩化メチレンなどが望ましく、
これらのうち１種または２種以上が混合して用いられる
。In the present invention, the inert solvent is not particularly limited, but preferably methanol, benzene, toluene, tetrahydrofuran, methylene chloride, etc.
One or a mixture of two or more of these may be used.
また、極性非プロトン溶媒としては、特に限定されるこ
とはないが、例えば、Ｎ、Ｎ’−ジメチルホルムアミド
、ヘキサメチルリン酸トリアミド、ジメチルスルホキシ
ド、１．３−ジメチル−２−イミダゾリジノンなどが望
ましく、これらのうち１種または２種以上が混合して用
いられる。第１工程で不活性溶媒として極性非プロトン
溶媒を使用する場合は、溶媒を取り換えることなく、第
２工程を実施することができる。In addition, the polar aprotic solvent is not particularly limited, but examples thereof include N,N'-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. Desirably, one or a mixture of two or more of these is used. If a polar aprotic solvent is used as the inert solvent in the first step, the second step can be carried out without replacing the solvent.
本発明の製造方法において、好ましくは、塩基が用いら
れ、例えば、炭酸カルシウム、炭酸カリウム、炭酸ナト
リウム、炭酸水素ナトリウム、ピリジン、トリエチルア
ミンなどの弱塩基が好適に用いられるが、特にこれらに
限定されるものではない。In the production method of the present invention, a base is preferably used, and weak bases such as calcium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, and triethylamine are preferably used, but are particularly limited to these. It's not a thing.
この塩基は、式（ＩＩ）のアルケニルハライドに対して
０．１〜２当量、好ましくは０．１−０．５当量の割合
で使用される。This base is used in an amount of 0.1 to 2 equivalents, preferably 0.1 to 0.5 equivalents, relative to the alkenyl halide of formula (II).
本発明において反応は通常、５０〜２００”Ｃ１好まし
くは７０〜１６０℃の温度で、１〜６時間行なわれる。In the present invention, the reaction is generally carried out at a temperature of 50 to 200" C1, preferably 70 to 160 DEG C., for 1 to 6 hours.
本発明の製造方法において出発化合物として使用される
式（ＩＩ）のうちω−アルケニルハライドは、公知化合
物であって、例えば、特開昭５５−１１８４２５に記載
のα、ω−ジハロゲノ炭化水素を脱ハロゲン化して七ノ
ハロゲノ炭化水素とする方法によって製造される。ハラ
イドとしては、ヨウ化物が好ましく、臭化物や塩化物を
使用する場合は、本発明の異性化の段階で、さらに、ア
ルカリ金属のヨウ化物を加えるのが望ましい。Of the formula (II) used as a starting compound in the production method of the present invention, the ω-alkenyl halide is a known compound, for example, it is described in JP-A No. 55-118425, which removes α,ω-dihalogeno hydrocarbons. It is produced by halogenation to form heptanohalogeno hydrocarbons. As the halide, iodide is preferred, and when bromide or chloride is used, it is desirable to further add an alkali metal iodide in the isomerization step of the present invention.
反応終了後、目的生成物は常法に従って反応混合物中か
ら採取され、例えば蒸留やシリカゲルクロマトグラフィ
ーあるいはこれらを併用して精製される。シリカゲルク
ロマトグラフィーによる場合は、溶離剤として酢酸エチ
ル、ヘキサン等が適当に混合して用いられる。After completion of the reaction, the desired product is collected from the reaction mixture according to a conventional method and purified using, for example, distillation, silica gel chromatography, or a combination thereof. In the case of silica gel chromatography, an appropriate mixture of ethyl acetate, hexane, etc. is used as an eluent.
以下、実施例をあげて、本発明をさらに具体的に説明す
るが、これらに限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例 １
イソチオシアン酸４−ペンテニル
５−ブロモ−１−ペンテン５３．とチオシアン酸ナトリ
ウム３５．を、メタノール２００ ｍｌに溶解し、３時
間還流した。メタノールを除去した後、イソペンタンで
抽出した。イソペンタン層を無水硫酸ナトリウムで乾燥
した後、減圧濃縮してチオシアン酸４−ペンテニルの粗
油３ｇ、を得た。チオシアン酸４−ペンテニルの粗油３
８．をＮ、Ｎ’−ジメチルホルムアミド１１４ｇに溶解
し、ヨウ化カリウム５８ｇと炭酸カルシウム１．５ｇを
加えて撹拌しながら、２時間、還流した。反応液をその
まま減圧蒸留（廊点：８３℃／９６１ｍ＋） Ｌ、次い
で、シリカゲルカラムクロマトグラフィー（ヘキサン：
酢酸エチ／ｌ／−１０：１）により分離精製したところ
、イソチオシアン酸４−ペンテニ、ルｌｕｇが得られた
。収率２４％。Example 1 4-pentenyl isothiocyanate 5-bromo-1-pentene53. and sodium thiocyanate35. was dissolved in 200 ml of methanol and refluxed for 3 hours. After removing methanol, it was extracted with isopentane. The isopentane layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 3 g of crude oil of 4-pentenyl thiocyanate. Crude oil of 4-pentenyl thiocyanate 3
8. was dissolved in 114 g of N,N'-dimethylformamide, 58 g of potassium iodide and 1.5 g of calcium carbonate were added, and the mixture was refluxed for 2 hours while stirring. The reaction solution was directly distilled under reduced pressure (temperature: 83°C/961m+), and then subjected to silica gel column chromatography (hexane:
Separation and purification using ethyl acetate/l/-10:1) gave 4-pentenyl isothiocyanate. Yield 24%.
ＩＲ（ｎｅａｔ） ：
３０７０．２９７０．２９３０．２８６０．２８３０．
２１８０゜２０８０．１６４Ｇ、 １４４５．１４１５
．１３４５．１３０５．９９０．９１０ ａｍ−’
’ＨＮＭＲＣＣＤＣｌ ３）δ：
１．８０ （２Ｈ，ｓ、−ＣＨ２−ＣＨ２ＮＣ３）、２
．２０ （２Ｈ。IR(neat): 3070.2970.2930.2860.2830.
2180°2080.164G, 1445.1415
．． 1345.1305.990.910 am-''HNMRCCCDCl 3) δ: 1.80 (2H,s, -CH2-CH2NC3), 2
．． 20 (2H.
Ｌｄｄｄ、Ｊ−７，２，６，８，１，５，１，１Ｈｚ８
Ｃ！！２−ＣＨ−ＣＨ２）、３．５３ （２Ｈ，ｔ、Ｊ
−８，８Ｈｚ、−ＣＨ２ＮＣ３）、５．０８ （ＬＨ。Lddd, J-7, 2, 6, 8, 1, 5, 1, 1Hz8
C! ! 2-CH-CH2), 3.53 (2H,t,J
-8.8Hz, -CH2NC3), 5.08 (LH.
ｄｄｔ、Ｊ＝ｌＯ，３，１，８，１，１Ｈｚ、−ＣＨ−
ＣＩＩＨ） 、５．１０（ｌＨ，ｄｄＬ、Ｊ＝１７．０
．１．８．１．５）１ｚ、−Ｃ１ｌ−Ｃ１ｌｌｌ）、５
．７８（ＩＨ，ｄｄｔ、Ｊ−１７，０，ｌＯ，３，６，
８Ｈ２，−ＣｊＱ−ＯＨ２）１３ＣＮＭＲ（ＣＤ０ｇ３
）δ：
２９．１．３０．５．４４．３．１１Ｂ、３．１３０．
６．１３８．１
ＭＳ（ｍ／ｚ）：
１２７ （Ｍ 、２Ｅｉ）、１２Ｂ（２４） 、９９
（２４）、８６（４）、８５（２２）、７２（２７）、
７０（２４）、６９（５） 、０８（１０）、（ｉ７（
３２）、Ｇｏ（６） 、５８（８） 、５５（１５）、
５３（１Ｂ）実施例 ２
イソチオシアン酸４−ペンテニル
ヨウ化４−ペンテニル１６ｇ：を、■、３−ジメチルー
２−イミダゾリジノン１６ｇに溶解し、チオシアン酸カ
リウム８ｇと炭酸カルシウム２．７ｇを加え、混合溶液
を７５℃で１時間、加熱撹拌した。次いで、内温を１５
５℃まで加温上昇させて、６時間、加熱撹拌した。不溶
物を除去した後、塩化メチレンで抽出し粗油２９．を得
た。粗油を減圧蒸留したところイソチオシアン酸４−ペ
ンテニル２．１ｇが得られた。収率２０％。沸点８３℃
／９６龍 生成物の分析結果は実施例１で得られたも
のと一致した。ddt, J=lO, 3, 1, 8, 1, 1 Hz, -CH-
CIIH), 5.10 (lH, ddL, J=17.0
．． 1.8.1.5) 1z, -C1l-C1ll), 5
．． 78 (IH, ddt, J-17, 0, lO, 3, 6,
8H2,-CjQ-OH2)13CNMR(CD0g3
) δ: 29.1.30.5.44.3.11B, 3.130.
6.138.1 MS (m/z): 127 (M, 2Ei), 12B(24), 99
(24), 86 (4), 85 (22), 72 (27),
70(24), 69(5), 08(10), (i7(
32), Go(6), 58(8), 55(15),
53 (1B) Example 2 16 g of 4-pentenyl isothiocyanate 4-pentenyl iodide was dissolved in 16 g of 3-dimethyl-2-imidazolidinone, and 8 g of potassium thiocyanate and 2.7 g of calcium carbonate were added and mixed. The solution was heated and stirred at 75° C. for 1 hour. Next, reduce the internal temperature to 15
The temperature was raised to 5°C, and the mixture was heated and stirred for 6 hours. After removing insoluble materials, extraction was performed with methylene chloride to obtain crude oil 29. I got it. When the crude oil was distilled under reduced pressure, 2.1 g of 4-pentenyl isothiocyanate was obtained. Yield 20%. Boiling point 83℃
/96 Dragon The analytical results of the product were consistent with those obtained in Example 1.
実施例 ３
イソチオシアン酸３−ブテニル
４−ブロモ−１−ブテン１０ｇおよびチオシアン酸ナト
リウム７．２ｇの混合溶液にＮ、Ｎ’−ジメチルホルム
アミド３０ｇを加え、１００℃で、１．５時間加熱撹拌
した。不溶物を除き、減圧蒸留して、チオシアン酸３−
ブテニルとＮ、Ｎ’−ジメチルホルムアミドの混合物３
５．を得た。これに、ヨウ化ナトリウム１３ｇと炭酸カ
ルシウム０．７ｇを加え、撹拌下、２時間還流した。次
いで不溶物を除いた後、シリカゲルカラムクロマトグラ
フィー（ヘキサン：酢酸エチル−１０：１）で分離精製
したところイソチオシアン酸３−ブテニル１．０ｇが得
られた。収率１２％。Example 3 30 g of N,N'-dimethylformamide was added to a mixed solution of 10 g of 3-butenyl isothiocyanate 4-bromo-1-butene and 7.2 g of sodium thiocyanate, and the mixture was heated and stirred at 100° C. for 1.5 hours. Insoluble materials were removed and distilled under reduced pressure to obtain 3-thiocyanic acid.
Mixture of butenyl and N,N'-dimethylformamide 3
5. I got it. To this, 13 g of sodium iodide and 0.7 g of calcium carbonate were added, and the mixture was refluxed for 2 hours while stirring. After removing insoluble matter, the residue was separated and purified by silica gel column chromatography (hexane:ethyl acetate-10:1) to obtain 1.0 g of 3-butenyl isothiocyanate. Yield 12%.
Ｉ Ｒ（ｎｅａｔ） ：
３０７０．２９９０．２９７０．２９３０．２９００．
２８６０．２１８０．２０８０．１６４０．１４４５．
１４３０．１４１Ｏ１１３４０，１２６５，１０１０，
９８５，９２０ｃｍ−’ＩＨＮＭＲ（ＣＤ０ｇ３）δ：
２．４６（乱Ｅ−Ｃ１１−Ｃ！！２）、３．５７（２１
１，ｔ、Ｊ−６，７１１ｚ。I R (neat): 3070.2990.2970.2930.2900.
2860.2180.2080.1640.1445.
1430.141O11340,1265,1010,
985,920cm-'IHNMR (CD0g3) δ: 2.46 (random E-C11-C!!2), 3.57 (21
1,t, J-6,711z.
−Ｃ！！２ＮＣ８）、５．１８（１１１，ｄｄｔ、Ｊ−
１０Ｊ、１．５．１．２）１ｚ。-C! ! 2NC8), 5.18 (111, ddt, J-
10J, 1.5.1.2) 1z.
−Ｃ１１−ＣｕＩ２）、５．２１（ＩＩＩ、ｄａｔ、Ｊ
−１７，０，１，５，１，５Ｈｚ、−ＣＨ−ＣＨＨ）
、５．８０（ＩＨ，ｄａｔ、Ｊ−１７，０，ｌＯ，３゜
８．８Ｈ２，−Ｃ！！−ＣＨ２）
’ＣＮＭＲ（ＣＤＣｆＩ３）δ：
３４．１．４４．５．１１ｇ、６．１Ｂ１．８．１３３
゜ＯＭＳ （ｍ／ｚ） ：
１１３ （Ｍ 、１００） 、８５（２４）、７４（
１５）、７３（１０）、７２（１００） 、６Ｇ（９）
、５５（７１）、５３（１Ｂ）［発明の効果］
本発明によれば、イソチオシアン酸アルケニルは、比較
的簡易で、操業上安全な、しかも工業上コストの低い製
造方法を用いて製造することができる。-C11-CuI2), 5.21(III, dat, J
-17,0,1,5,1,5Hz, -CH-CHH)
, 5.80 (IH, dat, J-17,0, lO, 3°8.8H2, -C!!-CH2) 'CNMR (CDCfI3) δ: 34.1.44.5.11g, 6.1B1 .8.133
゜OMS (m/z): 113 (M, 100), 85 (24), 74 (
15), 73 (10), 72 (100), 6G (9)
, 55(71), 53(1B) [Effects of the Invention] According to the present invention, alkenyl isothiocyanates can be produced using a production method that is relatively simple, operationally safe, and industrially inexpensive. Can be done.
本発明の方法によって製造される化合物としては、例え
ば、イソチオシアン酸３−ブテニル、イソチオシアン酸
４−ペンテニル、イソチオシアン酸５−へキセニルなど
が挙げられる。Examples of the compounds produced by the method of the present invention include 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, and 5-hexenyl isothiocyanate.
これらの化合物は、わさび様の刺激臭とグリーンな香味
を有し、食品、化粧品、トイレタリー製品などに添加す
る香料組成物の素材として有用である。These compounds have a pungent wasabi-like odor and a green flavor, and are useful as materials for flavor compositions added to foods, cosmetics, toiletry products, and the like.
Claims (1)
たは低級アルキル基を示し、Ｘはハロゲン原子を示し、
Ｙは幹部分の炭素数が２〜１０である直鎖状または分枝
鎖状のアルキレン基を示す。）で表わされるアルケニル
ハライドをチオシアン酸塩と反応させ、得られたチオシ
アン酸アルケニルを極性非プロトン溶媒中で異性化する
ことを特徴とする式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＾１、Ｒ＾２およびＹは、前述したものと同
一意義を有する。） で表わされるイソチオシアン酸アルケニルの製造方法。[Claims] In an inert solvent, the formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 and R^2 each independently represent a hydrogen atom or a lower alkyl group. , X represents a halogen atom,
Y represents a linear or branched alkylene group having 2 to 10 carbon atoms in the trunk. ) is characterized by reacting an alkenyl halide represented by thiocyanate with a thiocyanate and isomerizing the resulting alkenyl thiocyanate in a polar aprotic solvent (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( I) A method for producing an alkenyl isothiocyanate represented by the following formula (wherein R^1, R^2 and Y have the same meanings as described above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4031389A JPH0670004B2 (en) | 1989-02-22 | 1989-02-22 | Method for producing alkenyl isothiocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4031389A JPH0670004B2 (en) | 1989-02-22 | 1989-02-22 | Method for producing alkenyl isothiocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02221255A true JPH02221255A (en) | 1990-09-04 |
| JPH0670004B2 JPH0670004B2 (en) | 1994-09-07 |
Family
ID=12577128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4031389A Expired - Lifetime JPH0670004B2 (en) | 1989-02-22 | 1989-02-22 | Method for producing alkenyl isothiocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670004B2 (en) |
-
1989
- 1989-02-22 JP JP4031389A patent/JPH0670004B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0670004B2 (en) | 1994-09-07 |
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