JPH0262872A - Delta-valerolactone derivative - Google Patents
Delta-valerolactone derivativeInfo
- Publication number
- JPH0262872A JPH0262872A JP63212828A JP21282888A JPH0262872A JP H0262872 A JPH0262872 A JP H0262872A JP 63212828 A JP63212828 A JP 63212828A JP 21282888 A JP21282888 A JP 21282888A JP H0262872 A JPH0262872 A JP H0262872A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- reaction
- valerolactone
- tables
- formula
- 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
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical class O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 title description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001361 allenes Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 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
Landscapes
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（２）−数式
％式％
（式中、
Ｒは水素原子又は
本発明は、
δ−バレロラクトン誘導体
Ｈ２
および
Ｈ２
また、アレンは、パラジウム触媒存在下で、二酸化炭素
と反応して、鎖状エステルを与えることが知られている
。この場合の反応は、次の式で表わされる。Detailed Description of the Invention (2) -Formula %Formula % (wherein R is a hydrogen atom or the present invention refers to δ-valerolactone derivatives H2 and H2). It is known that the reaction gives a chain ester.The reaction in this case is represented by the following formula.
３ ＣＨ２＝Ｃ＝ＣＨ２＋ ＣＯ２ およびその製造方法に関するものである。3 CH2=C=CH2+ CO2 and its manufacturing method.
従来、ブタジェン等の１，３−ジエンは、パラジウム触
媒存在下で、二酸化炭素と反応して、δ−バレロラクト
ン誘導体を与えることが知られている。この場合の反応
は、次の式で表わされる。It has been known that 1,3-dienes such as butadiene react with carbon dioxide in the presence of a palladium catalyst to give a δ-valerolactone derivative. The reaction in this case is expressed by the following formula.
２ ＣＨ２＝ＣＨ−ＣＨ＝ＣＨ２＋ ＣＯ２〔目
的〕
本発明者らは、１，２−ジエン類と二酸化炭素の反応に
ついて種々研究を行っていたところ、触媒としてパラジ
ウムのかわりに、ニッケルを用いた場合には、意外にも
、前記従来技術とは異なり、δ−バレロラクトン誘導体
が得られることを見出した。2 CH2=CH-CH=CH2+ CO2
] The present inventors conducted various studies on the reaction between 1,2-dienes and carbon dioxide, and found that, unexpectedly, when nickel was used instead of palladium as a catalyst, the above-mentioned prior art It has been found that a δ-valerolactone derivative can be obtained.
従って、本発明の目的は、新規なδ−バレロラクトン誘
導体を提供することにある。Therefore, an object of the present invention is to provide novel δ-valerolactone derivatives.
本発明のδ−バレロラクトン誘導体は、次の反応式によ
って製造される。The δ-valerolactone derivative of the present invention is produced by the following reaction formula.
２ＣＨ２＝Ｃ＝ＣＨ２＋ ＣＯ２
Ｈ２
および
２ ＣＨ２＝Ｃ＝ＣＨＣＨ３＋ ＣＯ２Ｈ２
＼ ／
前記反応は一ニッケル触媒の存在下で行われ、反応条件
としては、二酸化炭素圧１〜５０気圧、好ましくは、５
〜２０気圧、反応温度５０〜１２０°Ｃ１好ましくは、
７０〜１００°Ｃの条件が採用される。前記ニッケル触
媒としては、低原子価、三級ホスフィン錯体が用いられ
る。2CH2=C=CH2+ CO2 H2 and 2 CH2=C=CHCH3+ CO2H2 \ / The reaction is carried out in the presence of a nickel catalyst, and the reaction conditions include carbon dioxide pressure of 1 to 50 atm, preferably 5
~20 atm, reaction temperature 50~120°C1 Preferably,
Conditions of 70-100°C are employed. As the nickel catalyst, a low valence, tertiary phosphine complex is used.
本発明により得られるδ−バレロラク・トン誘導体は新
規化合物であり、合成中間体および高分子原料として利
用することができる。The δ-valerolac ton derivative obtained by the present invention is a new compound and can be used as a synthetic intermediate and a polymer raw material.
〔実施例１〕
５０ｍ１のオートクレーブ中に、触媒として、Ｎ１ （
ＣＯＤ）２ （ＣＯＤはシクロオクタジエンの略）
０．３１１１１０１． ＤＰＥ （ジフェニルホスフィ
ノエタン） ０ 、６１１１１１１０１、溶媒として、
アセトニトリル（ＣＨ３ＣＮ）ｌ Ｏｗ＋ｆｆｉ、１，
２−ジエンとしてアレン（ＣＨ２＝Ｃ＝ＣＨ２）３０１
１１１１１０１を装入し、１５気圧の二酸化炭素加圧下
、８０°Ｃで４５時間反応を行った。[Example 1] In a 50 ml autoclave, N1 (
COD)2 (COD is an abbreviation for cyclooctadiene)
0.3111101. DPE (diphenylphosphinoethane) 0, 611111101, as a solvent,
Acetonitrile (CH3CN)l Ow+ffi, 1,
Allen (CH2=C=CH2) 301 as 2-diene
1111101 was charged, and the reaction was carried out at 80°C for 45 hours under a carbon dioxide pressure of 15 atm.
その結果、式
Ｈ２
で表されるδ−バレロラクトン誘導体を、アレン基準で
、収率２０％の成績で得た。As a result, a δ-valerolactone derivative represented by formula H2 was obtained with a yield of 20% based on allene.
〔実施例２〕
実施例１のアレンのかわりに、１．スープタジェン（Ｃ
Ｈ２＝Ｃ＝ＣＨＣＨ３）３０１１１０１を用いて反応を
行った。[Example 2] Instead of allene in Example 1, 1. Souptagen (C
The reaction was carried out using H2=C=CHCH3)3011101.
その結果、式
で表わされるδ−バレロラクトン誘導体が、１゜２−ブ
タジェン基準で、収率１１％の成績で得られた。As a result, a δ-valerolactone derivative represented by the formula was obtained with a yield of 11% based on 1°2-butadiene.
δ−バレロラクトン誘導体は、反応液から、溶媒を留去
した後、分取ガスクａにて単離し、赤外、ＩＨＮＭＲ，
およびＧＣ−ＭＳスペクトルにより同定した。After distilling off the solvent from the reaction solution, the δ-valerolactone derivative was isolated using a preparative Gasc a, and subjected to infrared, IHNMR,
and identified by GC-MS spectrum.
特許出願人 工業技術院長 飯塚幸三＼ ／Patent applicant Kozo Iizuka, Director of the Agency of Industrial Science and Technology
Claims (2)
基である）で表わされる１，２−ジエンを、ニッケル触
媒存在下、二酸化炭素と反応させることを特徴とする ▲数式、化学式、表等があります▼ および ▲数式、化学式、表等があります▼ の製造方法。(2) ▲ characterized by reacting a 1,2-diene represented by the general formula H_2C=C=CHR (in the formula, R is a hydrogen atom or a methyl group) with carbon dioxide in the presence of a nickel catalyst. There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63212828A JP2753563B2 (en) | 1988-08-26 | 1988-08-26 | δ-Valerolactone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63212828A JP2753563B2 (en) | 1988-08-26 | 1988-08-26 | δ-Valerolactone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0262872A true JPH0262872A (en) | 1990-03-02 |
| JP2753563B2 JP2753563B2 (en) | 1998-05-20 |
Family
ID=16629036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63212828A Expired - Lifetime JP2753563B2 (en) | 1988-08-26 | 1988-08-26 | δ-Valerolactone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2753563B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594653A (en) * | 2022-10-25 | 2023-01-13 | 西华大学（Cn） | Polysubstituted beta-alkenyl valerolactone compound, preparation method and application |
-
1988
- 1988-08-26 JP JP63212828A patent/JP2753563B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594653A (en) * | 2022-10-25 | 2023-01-13 | 西华大学（Cn） | Polysubstituted beta-alkenyl valerolactone compound, preparation method and application |
| CN115594653B (en) * | 2022-10-25 | 2024-03-29 | 江西力田维康科技有限公司 | Polysubstituted beta-alkenyl valerolactone compound, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2753563B2 (en) | 1998-05-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |