JPS63222141A - Production of adamantoyl-substituted olefins - Google Patents
Production of adamantoyl-substituted olefinsInfo
- Publication number
- JPS63222141A JPS63222141A JP62054924A JP5492487A JPS63222141A JP S63222141 A JPS63222141 A JP S63222141A JP 62054924 A JP62054924 A JP 62054924A JP 5492487 A JP5492487 A JP 5492487A JP S63222141 A JPS63222141 A JP S63222141A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- olefins
- adamantoyl
- solvent
- 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
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 1-adamantanecarboxylic acid halide Chemical class 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract 4
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- 229910052763 palladium Inorganic materials 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- MIBQYWIOHFTKHD-UHFFFAOYSA-N adamantane-1-carbonyl chloride Chemical compound C1C(C2)CC3CC2CC1(C(=O)Cl)C3 MIBQYWIOHFTKHD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- HVLVTNMBNVQLQH-UHFFFAOYSA-N C1C(C2)CC(C3)CC2CC13C(=O)C=CC1=CC=CC=C1 Chemical compound C1C(C2)CC(C3)CC2CC13C(=O)C=CC1=CC=CC=C1 HVLVTNMBNVQLQH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100024829 DNA polymerase delta catalytic subunit Human genes 0.000 description 1
- 101000868333 Homo sapiens Cyclin-dependent kinase 1 Proteins 0.000 description 1
- 101000909198 Homo sapiens DNA polymerase delta catalytic subunit Proteins 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical class C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 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
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000000534 ion trap mass spectrometry Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアダマントイル置換オレフィン類、更に詳しく
は、次の一般式（Ｉ）
（式中、Ｒは炭素数１〜２０のアルキル基、アルコキシ
基の炭素数が１〜１０のアルコキシカルボニル基、アル
キル基の炭素数が１〜５のＮ、Ｎ−シアルキルアミノカ
ルボニル基、シアノ基又は）工二ル基を示す）
で表わされるアダマントイル置換オレフィン類の工業的
製造法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to adamantyl-substituted olefins, more specifically, the following general formula (I) (wherein R is an alkyl group having 1 to 20 carbon atoms, an alkoxy an adamantyl-substituted adamantyl group represented by an alkoxycarbonyl group in which the group has 1 to 10 carbon atoms, an N, N-sialkylaminocarbonyl group, a cyano group, or an engineering group in which the alkyl group has 1 to 5 carbon atoms. This article relates to an industrial method for producing olefins.
アダマントイル置換オレフィン類及びこれよシ銹導され
る誘導体には生理活性を有する多くの化合物がある。例
えばアダマントイル置換アクリル酸は抗ウィルス作用を
有しく Ｃｏ１１ｅｃｔ−Ｃｚｅｃｈ。Adamantyl-substituted olefins and their derivatives include many biologically active compounds. For example, adamantyl-substituted acrylic acid has antiviral activity.
Ｃｈｅｍ、 Ｃｏｍｍｕｎ、、 ３７ 、３９５０
（１９７２） ） 、また（１）式中Ｒがエトキシカル
ボニル基で表わされるβ−（ｌ−アダマントイル）アク
リル酸エチルから導かれる次式（Ｖ）、
Ｃ００Ｃｔ穐
（式中、Ｐｈはフェニル基を示す）
で表わされる化合物は抗炎症作用を有しく Ｃｏ１１ｅ
ｃｔ、 Ｃｚｅｃｈ、 Ｃｈｅｍ、 Ｃｏｍｍｕｎ、、
３９ 、６２４（１９７４））、次式（Ｍ）、
で表わされる化合物は除草剤として有効である（西独特
許公開ＤＥ ２７３８６４０）ことが知られている。Chem, Commun,, 37, 3950
(1972) ), and the following formula (V) derived from ethyl β-(l-adamantoyl)acrylate in which R is an ethoxycarbonyl group in the formula (1), C00Ct (in the formula, Ph represents a phenyl group) The compound represented by ) has an anti-inflammatory effect.
ct, Czech, Chem, Commun,,
39, 624 (1974)), the compound represented by the following formula (M) is known to be effective as a herbicide (West German Patent Publication DE 2738640).
このように、アダマントイル置換オレフィン類は、それ
自体において又は合成中間体として有用な化合物である
が、従来、これは次に示すようなりイテイヒ（Ｗｉｔｔ
ｔｇ ）反応によって製造されていた。すなわち、この
方法を、β−（１−７ダマントイル）アクリル酸エチル
の製造（Ｃｏ１１ｅｃｔ。Thus, adamantoyl-substituted olefins are useful compounds in themselves or as synthetic intermediates, but conventionally they have been treated as follows:
tg) was produced by reaction. That is, this method was applied to the production of ethyl β-(1-7 damantoyl)acrylate (Colect.
Ｃｚｅｃｈ、 Ｃｈｅｍ、 Ｃｏｍｍｕｎ、、 ３３
、８８０（１９６８） ）を例に挙げて示せば次のとお
りである。Czech, Chem, Commun,, 33
, 880 (1968)) is as follows.
以下余白
（Ｉｔ／）
しかしながら、この方法は多工程を要するため実用的で
なく、簡便で高収率にて大量にアメマントイル置換オレ
フィン類を製造することのできる工業的方法の提供が望
まれていた。Margin below (It/) However, this method is not practical because it requires multiple steps, and there has been a desire to provide an industrial method that is simple and can produce amemantoyl-substituted olefins in large quantities with high yield. .
斯かる実状にシいて、本発明者らは鋭意研究を行った結
果、１−アダマンタンカルボン酸ノ１０グ／化物から一
工程でアダマントイル置換オレフィン類を製造すること
に成功した。Under these circumstances, the present inventors conducted intensive research and succeeded in producing adamantoyl-substituted olefins in one step from 10 g/m of 1-adamantanecarboxylic acid.
本発明方法は次の反応式によって示される。The method of the present invention is shown by the following reaction formula.
υ
（ｎ） （ｌｉｔ）
υ
１式中、Ｘはハロゲン原子を示し、Ｒは前記の意味を有
する）
すなわち、本発明は、１−アダマンタンカルボン酸ハロ
ゲン化物（ＩＩ）に、ノＱラゾウム触媒及び第三級アミ
ン類の存在下、オレフィン類（１）を反応せしめてアダ
マントイル置換オレフィン類（１）を製造する方法であ
る。υ (n) (lit) υ 1 In the formula, This is a method for producing adamantoyl-substituted olefins (1) by reacting olefins (1) in the presence of tertiary amines.
本発明において、ノ９ラゾウム触媒としては、例えば酢
酸／Ｑ ？ゾウム、塩化ノｑラゾウム、臭化ノＱラゾウ
ム等の２価のノＱラゾウム；ノＱラゾウムブラック、ノ
Ｑラゾウム付活性炭、テトラキス（トリフェニルホスフ
ィン）ノｑラゾウム等の０価のＩＱラゾウム等が挙げら
れる。これらは原料（ｎ）に対してα０１〜２０モルチ
、特に０．１〜５モル−使用するのが好ましい。In the present invention, the 9-razome catalyst is, for example, acetic acid/Q? Bivalent rhazoum, such as rhazoum chloride, rhazoum bromide, etc.; rhazoum black, activated carbon with rhazoum, zero-valent IQ rhazoum, such as tetrakis(triphenylphosphine) rhazoum, etc. can be mentioned. It is preferable to use α01 to 20 mol, particularly 0.1 to 5 mol, of these based on the raw material (n).
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としては、例えばビリシン、
トリエチルアミン、トリブチルアミン、Ｎ、Ｎ−ジメチ
ルアニリン、Ｎ、Ｎ−ジエチルアニリン等が挙げられる
。これらは原料（ＩＩ）に対して、１〜１０当量、特に
１〜４当量使用するのが好ましい。In addition, examples of tertiary amines used as reagents for removing hydrogen halides generated during the reaction include bilysin,
Examples include triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like. These are preferably used in an amount of 1 to 10 equivalents, particularly 1 to 4 equivalents, based on raw material (II).
オレフィン類（Ｉｎ）は原料（旧に対し１〜１０当量、
特に１〜２当量使用するのが好ましい。反応は溶媒の存
在又は不存在下の何れでも行うことができるが、一般に
はキシレン等の溶媒中行うのが好ましい。反応温度は０
〜２００℃、特に１００〜１５０℃が好ましい。Olefins (In) are raw materials (1 to 10 equivalents relative to the former,
In particular, it is preferable to use 1 to 2 equivalents. Although the reaction can be carried out in the presence or absence of a solvent, it is generally preferable to carry out the reaction in a solvent such as xylene. The reaction temperature is 0
-200°C, especially 100-150°C is preferred.
本発明方法によれば、それ自体で、また生理活性物質を
製造する丸めの中間体として有用なアダマントイル置換
オレフィン類を簡便かつ高収率で、しかも大量に製造す
ることができる。According to the method of the present invention, adamantoyl-substituted olefins, which are useful by themselves or as rounding intermediates for producing physiologically active substances, can be produced simply, in high yield, and in large quantities.
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゜ １−アダマンタンカルボン酸塩化物（２，Ｏｆ 。Example 1゜ 1-Adamantanecarboxylic acid chloride (2, Of.
１０．０ミリモル）、アクリル酸エチル（１，２ｔ。10.0 mmol), ethyl acrylate (1.2 t.
ＩＺＯミリモル）及びＮ、Ｎ−ジメチルペンゾルアミン
（１，４ｔ 、 １０．０ミリモル）の混合物に、酢酸
、ｅラジウム（２２ｑ、０．１ミリモル）を加え、反応
温度１３０℃で４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
、抽出液を無水硫酸ナトリウムで乾燥させ、溶媒を留去
する。残渣をシリカゲルカラムクロマトグラフィー処理
することによシ、黄色結晶β−（１−アメマントイル）
アクリル酸エチルを１．４Ｆ（５，３ミリモル）得た。Acetic acid and e-radium (22q, 0.1 mmol) were added to a mixture of IZO mmol) and N,N-dimethylbenzolamine (1.4t, 10.0 mmol), and the mixture was heated and stirred at a reaction temperature of 130°C for 4 hours. do. Reaction mixture IN
After removing the amine by treatment with hydrochloric acid, extraction is performed with ether, the extract is dried over anhydrous sodium sulfate, and the solvent is distilled off. By treating the residue with silica gel column chromatography, yellow crystals of β-(1-amemantoyl) were obtained.
1.4F (5.3 mmol) of ethyl acrylate was obtained.
収１４５３％
融点 ６３．８〜６４．５℃
ＩＲ（ＫＢｒ）ｃｙ＋＋ １７４０．１７１０”Ｈ
−ＮＭＲ（ＣＤＣ２，溶媒、ＴＭＳ内部標準、δ）１．
３ （３Ｈ，ｔ 、Ｊ＝７．１Ｈｚ ） 、 １．７＝
２．１ （１５Ｈ，ｍ）。Yield 1453% Melting point 63.8-64.5℃ IR (KBr)cy++ 1740.1710"H
-NMR (CDC2, solvent, TMS internal standard, δ)1.
3 (3H,t, J=7.1Hz), 1.7=
2.1 (15H, m).
４．３（２Ｈ，ｑ、Ｊ＝７．１Ｈｚ） ？６．７ （Ｉ
Ｈ，ｄ 、Ｊ＝＝１５．８Ｈり、７．５（ＩＨ，ｄ、Ｊ
＝１５．４Ｈｚ）”Ｃ−ＮＭＲ（ＣＤＣ２５ｉｌ！媒、
ＣＨＣｔｓ内部標準、δ）１４．１（ｑ）、２７．８（
ｄ）、３６．４（ｔ）、３７．５（ｔ）。4.3 (2H, q, J=7.1Hz)? 6.7 (I
H, d, J==15.8H, 7.5(IH, d, J
=15.4Hz)"C-NMR (CDC25il! medium,
CHCts internal standard, δ) 14.1 (q), 27.8 (
d), 36.4(t), 37.5(t).
４５．９（Ｓ）、６Ｌ２（ｔ）、１３１．３（ｄ）、１
３５．２（ｄ）、１６５．７（Ｓ）、２０３．１（Ｓ）
マススペクトル ｍ／ｅ（相対強度）
２６２（１，Ｍ”）、１３５（１００）、９３（１０）
ｔ７９（１１）。45.9(S), 6L2(t), 131.3(d), 1
35.2(d), 165.7(S), 203.1(S)
Mass spectrum m/e (relative intensity) 262 (1, M”), 135 (100), 93 (10)
t79(11).
実施例２
スチレン（１，：Ｍ、ＩＺＯミリモル）を用いて、反応
温度１３０℃で３時間加熱攪拌した以外は、実施例１と
同様の操作により、β−（１−アダマントイル）スチレ
ンｔＬ８ｔ （６，６ミＩＪ−ｖ−ル）４た。Example 2 β-(1-adamantoyl)styrene tL8t ( 6,6 mi IJ-v-le) 4.
収率 ６６％
融点 ９０．７〜９１．７℃
１Ｒ（ＫＢｒ）ｃｍ １６９０，１６２０，１５８
０゜’Ｈ−ＮＭＲ（ＣＤＣ／ｓ溶媒、ＴＭＳ内部標準、
δ）１．８−１．９（１２Ｈ，ｍ）、２．１（３Ｈ，ｂ
８）、７．２（ＩＨ，ｄ、Ｊ−１５，４Ｈｚ）、７．４
（３Ｈ，ｂｓ）、７．６（２Ｈ，ｂｓ）、７．７（ＩＨ
，ｄ、Ｊ＝１５．４Ｈ２）”Ｃ−ＮＭＲ（ＣＤ Ｃ４ｆ
ｆＪ 媒、 ＣＨＣＬｓ 内部１１１ｋ ＊δ）２＆１
（ｔ）、３６．７（ｔ）、３８．１（ｔ）、４５．６（
ｓ）。Yield 66% Melting point 90.7-91.7°C 1R(KBr)cm 1690,1620,158
0°'H-NMR (CDC/s solvent, TMS internal standard,
δ) 1.8-1.9 (12H, m), 2.1 (3H, b
8), 7.2 (IH, d, J-15, 4Hz), 7.4
(3H, bs), 7.6 (2H, bs), 7.7 (IH
, d, J=15.4H2)"C-NMR (CD C4f
fJ medium, CHCLs internal 111k *δ)2&1
(t), 36.7(t), 38.1(t), 45.6(
s).
１２０．４（ｄ）、１２８．３（ｄ）、１２＆９（ｄ）
。120.4(d), 128.3(d), 12&9(d)
.
１３０．１（ｄ）、１３５．２（ｓ）、１４Ｚ８（ｄ）
。130.1(d), 135.2(s), 14Z8(d)
.
２０３．８（ｓ）
マススペクトルｍ／ｅ（相対強度）
２６６（３，Ｍ＋）、２３８（５１）、１３５（１００
）。203.8 (s) Mass spectrum m/e (relative intensity) 266 (3, M+), 238 (51), 135 (100
).
７９（２０）、７７（１４）。79(20), 77(14).
実施例３
キシレン中ζＮ、Ｎ−ゾメチルアクリルアミド（１，２
ｆ、ＩＺＯミリモル）を用いて、反応温度１３０℃で１
２時間加熱攪拌した以外は、実施例１と同様の操作を行
ない、β−（１−アダマントイル）−Ｎ、Ｎ−ジメチル
アクリルアミドを０．６ｔ（２，５ミリモル）得た。Example 3 ζN,N-zomethylacrylamide (1,2
f, IZO mmol) at a reaction temperature of 130°C.
The same operation as in Example 1 was performed except that the mixture was heated and stirred for 2 hours to obtain 0.6 t (2.5 mmol) of β-(1-adamantoyl)-N,N-dimethylacrylamide.
収率 ２５％
融点 ９＆０〜９＆５℃
１Ｒ（ＫＢｒ）ｍ １７００，１６６０，１６４０
１Ｈ−ＮＭＲ（ＣＤＣ＆溶媒、ＴＭＳ内部標準、δ）１
．７＝２．１（１５Ｈ，ｍ）、＆０５（３Ｈ，ｓ）、３
．１３（３Ｈ，ｓ）、７．３（ＩＨ，ｄ、Ｊ＝１４．７
Ｈｚ）、７．５（ＩＨ，ｄ、Ｊ＝１５．０Ｈｚ）
”Ｃ−ＮＭＲ（ＣＤ ＣＡｓ 溶媒ｖ ＣＨＣ２ｓ 内
部１１準ｖ ’ ）２７．８（ｄ）、３６．５（ｔ）、
３７．６（ｔ）、４ａ９（ｓ）。Yield 25% Melting point 9&0~9&5℃ 1R(KBr)m 1700,1660,1640
1H-NMR (CDC & solvent, TMS internal standard, δ) 1
．． 7=2.1 (15H, m), &05 (3H, s), 3
．． 13 (3H, s), 7.3 (IH, d, J = 14.7
Hz), 7.5 (IH, d, J = 15.0 Hz) ``C-NMR (CD CAs solvent v CHC2s internal 11 quasi v') 27.8 (d), 36.5 (t),
37.6(t), 4a9(s).
１３１．１（ｄ）、１３３．０（ｄ）、１６５．３（ｓ
）。131.1(d), 133.0(d), 165.3(s
).
２０３．９（ｓ）
マススペクトルｍ／ｅ（相対強度）
２６１（４，Ｍ”）、１３５（１００）、１２６（２６
）。203.9 (s) Mass spectrum m/e (relative intensity) 261 (4, M”), 135 (100), 126 (26
).
９３（１５）、７９（１６）。93(15), 79(16).
実施例４ １−アダマンタンカルボン酸塩化物（ＺＯｆ 。Example 4 1-adamantanecarboxylic acid chloride (ZOf.
１０．０ミリモル）、アクリロニトリル（１，１Ｆ 。10.0 mmol), acrylonitrile (1,1F).
１２．０ミリモル）、トリーｎ−ブチルアミン（２，２
Ｆ、１０．０ミリモル）の混合物に、臭化ノ９ラゾウム
（２７１１１Ｐ、 ０．１ミリモル）を加え、反応温度
１１０℃で５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
出液を無水硫酸ナトリウムで乾燥させ、溶媒を留去する
。残渣をシリカゲルカラムクロマトグラフィー処理（ヘ
キサン／エーテル＝２０／１）後、ヘキサンから再結晶
することにより、β−（１−アメマントイル）アクリロ
ニトリルを１．４ ｆ （６゜４ミリモル）得た。12.0 mmol), tri-n-butylamine (2,2
No9razoum bromide (27111P, 0.1 mmol) was added to a mixture of F, 10.0 mmol), and the mixture was heated and stirred at a reaction temperature of 110° C. for 5 hours. The reaction mixture is treated with IN hydrochloric acid to remove the amine, extracted with ether, the extract is dried over anhydrous sodium sulfate, and the solvent is distilled off. The residue was treated with silica gel column chromatography (hexane/ether = 20/1) and then recrystallized from hexane to obtain 1.4 f (6° 4 mmol) of β-(1-amemantoyl)acrylonitrile.
収率 ６４％
融点 ８０．１〜８０．５℃
ＩＲ（ＫＢｒ）ｍ ３１００，１７２０．１６３０
”Ｈ−ＮＭＲ（ＣＤＣｔｓｌ媒Ｉ Ｔ Ｍ Ｓ内部標準
、δ）１．６〜２．１ （１５Ｈ，ｍ） 、 ６．４（
ＩＨ，ｄ 、Ｊ ＝１＆８Ｈｚ）、７．４（ＩＨ，ｄ、
Ｊ＝１５．８Ｈｚ）”Ｃ−ＮＭＲ（ＣＤＣｌｓｆａｇ、
ＣＨＣＡｍ内部標準、δ）２７．５（ｄ）、３６．２（
ｔ）、３７．１（ｔ）、４５．６（ｓ）。Yield 64% Melting point 80.1-80.5°C IR(KBr)m 3100,1720.1630
"H-NMR (CDCtsl media ITMS internal standard, δ) 1.6-2.1 (15H, m), 6.4 (
IH, d, J = 1 & 8 Hz), 7.4 (IH, d,
J=15.8Hz)"C-NMR (CDClsfag,
CHCAm internal standard, δ) 27.5(d), 36.2(
t), 37.1(t), 45.6(s).
１１０．６（ｄ）、１１６．４（ｓ）、１４０．７（ｄ
）。110.6(d), 116.4(s), 140.7(d
).
２００．２（８）
マススペクトルｍ／ｅ（相対強度）
２１５（２，Ｍ”）、１３５（１００）、９３（１５）
。200.2 (8) Mass spectrum m/e (relative intensity) 215 (2, M”), 135 (100), 93 (15)
.
以上that's all
Claims (1)
に、パラジウム触媒及び第三級アミン類の存在下、一般
式（III） ＣＨ＿２＝ＣＨ−Ｒ（III） （式中、Ｒは炭素数１〜２０のアルキル基、アルコキシ
基の炭素数が１〜１０のアルコキシカルボニル基、アル
キル基の炭素数が１〜５のＮ，Ｎ−ジアルキルアミノカ
ルボニル基、シアノ基又はフェニル基を示す） で表わされるオレフィン類を反応せしめることを特徴と
する一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは前記と同じものを示す） で表わされるアダマントイル置換オレフィン類の製造法
。[Claims] 1. A 1-adamantanecarboxylic acid halide represented by the following general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (wherein, X represents a halogen atom) , in the presence of a palladium catalyst and tertiary amines, the general formula (III) CH_2=CH-R(III) (wherein, R is an alkyl group having 1 to 20 carbon atoms, and the alkoxy group has 1 to 10 carbon atoms) alkoxycarbonyl group, N,N-dialkylaminocarbonyl group whose alkyl group has 1 to 5 carbon atoms, cyano group or phenyl group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing adamantyl-substituted olefins represented by (I) (in the formula, R is the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62054924A JPS63222141A (en) | 1987-03-10 | 1987-03-10 | Production of adamantoyl-substituted olefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62054924A JPS63222141A (en) | 1987-03-10 | 1987-03-10 | Production of adamantoyl-substituted olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63222141A true JPS63222141A (en) | 1988-09-16 |
Family
ID=12984165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62054924A Pending JPS63222141A (en) | 1987-03-10 | 1987-03-10 | Production of adamantoyl-substituted olefins |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63222141A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004052832A1 (en) * | 2002-12-11 | 2006-04-13 | 旭硝子株式会社 | Fluorinated adamantane derivatives |
-
1987
- 1987-03-10 JP JP62054924A patent/JPS63222141A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004052832A1 (en) * | 2002-12-11 | 2006-04-13 | 旭硝子株式会社 | Fluorinated adamantane derivatives |
| JP4534765B2 (en) * | 2002-12-11 | 2010-09-01 | 旭硝子株式会社 | Fluorinated adamantane derivative and method for producing the same |
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