JPS6261951A - Carbonate having ethynyl group - Google Patents
Carbonate having ethynyl groupInfo
- Publication number
- JPS6261951A JPS6261951A JP60201217A JP20121785A JPS6261951A JP S6261951 A JPS6261951 A JP S6261951A JP 60201217 A JP60201217 A JP 60201217A JP 20121785 A JP20121785 A JP 20121785A JP S6261951 A JPS6261951 A JP S6261951A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- carbonate
- ethynyl group
- ethynyl
- 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
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
- Y02P20/141—Feedstock
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、一般式
（式中、Ｒは水素原子、アルキル基又はアリール基であ
る）
で表わされる新規なエチニル基を有するカルボナート及
びその製造方法に関するものである。Detailed Description of the Invention [Technical Field] The present invention relates to a novel carbonate having an ethynyl group represented by the general formula (wherein R is a hydrogen atom, an alkyl group, or an aryl group) and a method for producing the same. It is.
従来、α−エチニル−ｔ、ｅｒｔ、−アルコールに対し
、銅塩とトリアルキルアミンの存在下で二酸化炭素を反
応させると、α−メチレン−環状カルボナートを与える
ことは知られている（ドイツ特許第１０９８９５３号及
び１１４５６３２号明細書）。この場合の反応は次の式
で表わされる。It has been known that the reaction of α-ethynyl-t, ert, -alcohol with carbon dioxide in the presence of a copper salt and a trialkylamine yields α-methylene-cyclic carbonate (German Patent No. 1098953 and 1145632). The reaction in this case is expressed by the following formula.
（前記式中、Ｒ１、Ｒ２はアルキル基を示す）〔目
的〕
本発明者らは、エチニル基を有するアルコールと二酸化
炭素との反応について種々研究を行っていたところ、プ
ロパギルアルコール又はα−エチニル−５ｅｃ−アルコ
ールに対し二酸化炭素を反応させる時には、意外にも、
前記従来法とは異なり、鎖状構造のエチニル基を有する
カルボナートが得られることを見出した。(In the above formula, R1 and R2 represent an alkyl group)
The present inventors have conducted various studies on the reaction between alcohols having an ethynyl group and carbon dioxide, and found that when carbon dioxide is reacted with propargyl alcohol or α-ethynyl-5ec-alcohol, an unexpected result was found. too,
It has been found that, unlike the conventional method, a carbonate having an ethynyl group in a chain structure can be obtained.
従って、本発明の目的は、新規な鎖状構造のエチニル基
を有するカルボナートを提供することにある。Therefore, an object of the present invention is to provide a carbonate having an ethynyl group with a novel chain structure.
本発明のカルボナートは、次の反応式によって製造され
る。The carbonate of the present invention is produced by the following reaction formula.
１−Ｉ Ｃ＝Ｃ−Ｃ−○！（＋Ｃ○２
■
ＲＲ
（式中、Ｒは水素原子、アルキル基又はアリール基であ
り、アルキル基としては、例えば、メチル、エチル、プ
ロピル等があり、アリール基としては、フェニル、ｉ−
リル等がある）前記反応は、ルテニウム触媒の存在下で
行われ、反応条件としては、二酸化炭素加圧下で、原料
アルコールの重合を抑制するために、比較的低温度、好
ましくは０℃〜室温付近の反応温度が採用される。前記
ルテニウム触媒としては、そのハロゲン化物や、カルボ
ニル錯体が用いられ、助触媒として三級アミン等の有機
塩基を併用するのが望ましい。二酸化炭素加圧としては
１通常１〜５０気圧程度の加圧が採用される。溶媒とし
ては、不活性溶媒、例えばニトリル系溶媒等が用いられ
る。1-I C=C-C-○! (+C○2 ■ RR (wherein, R is a hydrogen atom, an alkyl group, or an aryl group; examples of the alkyl group include methyl, ethyl, and propyl; examples of the aryl group include phenyl, i-
The reaction is carried out in the presence of a ruthenium catalyst, and the reaction conditions are under pressure of carbon dioxide and at a relatively low temperature, preferably from 0°C to room temperature, in order to suppress the polymerization of the raw material alcohol. Reaction temperatures in the vicinity are employed. As the ruthenium catalyst, its halide or carbonyl complex is used, and it is desirable to use an organic base such as a tertiary amine as a co-catalyst. As the pressurization of carbon dioxide, a pressure of about 1 to 50 atmospheres is usually employed. As the solvent, an inert solvent such as a nitrile solvent is used.
本発明により得られるエチニル基を有する鎖状構造のカ
ルボナートは、新規化合物であり、それに含まれる三重
結合及びケト基を利用し５種々の合成中間体、殊に、医
薬や農薬の中間体として利用することができる。The carbonate having a chain structure having an ethynyl group obtained by the present invention is a new compound, and by utilizing the triple bond and keto group contained therein, it can be used as a variety of synthetic intermediates, especially intermediates for pharmaceuticals and agricultural chemicals. can do.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例
５０ｍ Ｑのオートクレーブ中に、触媒としてルテニウ
ムカルボニル（Ｒｕ ３ （Ｃｏ） １２ ）０．２ｍ
ｍｏ Ｑ、助触媒として１〜リエチルアミン（（Ｅｊ）
３ Ｎ）２ｍΩ、溶媒としてシア化メチル（Ｃｌｌ
３ ＣＮ）７ｍ Ｑ及び反応基質としてプロパギルアル
コール］、ｍＱを装入し、５０気圧の二酸化炭素加圧下
、室温で４５時間反応を行った。Example 5 In an autoclave of 0mQ, 0.2m of ruthenium carbonyl (Ru 3 (Co) 12 ) was added as a catalyst.
mo Q, 1 to ethylamine ((Ej) as cocatalyst
3 N) 2 mΩ, methyl siade (Cll
3CN)7mQ and propargyl alcohol] and mQ as reaction substrates were charged, and the reaction was carried out at room temperature under a carbon dioxide pressure of 50 atm for 45 hours.
その結果、式ＣＩｌ ３ＣＯＣＩ＋ ２０ＣＯＣＩＩ
２ＣミＣＨ＋で表わされるカルボナートを、原料アルコ
ール基準で、転化率６９％及び収率２７％の成績で得た
。この場合、生成物の分離回収は次のようにして行った
。As a result, the formula CIl 3COCI+ 20COCII
A carbonate represented by 2CmiCH+ was obtained with a conversion rate of 69% and a yield of 27% based on the starting alcohol. In this case, the product was separated and recovered as follows.
カラ１１クロマトで触媒ルテニウムを除去したのち、分
取ガスクロにて、昨離した。After removing the catalyst ruthenium using Color 11 chromatography, it was separated using preparative gas chromatography.
また、生成物の構造決定は、次のようにして行った。Further, the structure of the product was determined as follows.
ｉ、ｒ、（ｎｅａｊ） ３２７０（ＩＩｃ−Ｅ）、 ２
＋４０（Ｃ＝Ｃ）、＋７５０ （ＯＣＯＯ）、１７２５
（Ｃ＝０）、１２８０（Ｃ−０）ＩＩ’ ｒ＋、ｍ、ｒ
、 （ＤＣＣＱ ３ ）δ２．２４（３＋１、Ｓ、Ｃ１
１３）、２．５９（ＩＩＩ、ｔ、、ＩＩｃ 、Ｊ”２
１１ｚ）、４．７９（２＋１゜Ｓ、ＤＣＩＩ ２０）、
４．８７（２＋１． ｄ、ＤＣＩＩ ２Ｃａ 。i, r, (neaj) 3270 (IIc-E), 2
+40 (C=C), +750 (OCOO), 1725
(C=0), 1280(C-0)II' r+, m, r
, (DCCQ 3 ) δ2.24 (3+1, S, C1
13), 2.59 (III, t, , IIc, J”2
11z), 4.79 (2+1°S, DCII 20),
4.87 (2+1.d, DCII 2Ca.
、１ ＝ ２１１ｚ）
ＧＣＭＳ １５７（Ｍ＋１）十実施例２
実施例１において、アルコールとして、式＋１ｃ三Ｃ（
ＣＩｌ Ｊ） ＩＩ −Ｏｌｌで表わされるものを用い
た以外は同様にして反応を行った。その結果、式％式％, 1 = 211z) GCMS 157 (M+1) 10 Example 2 In Example 1, as the alcohol, the formula +1c3C (
The reaction was carried out in the same manner except that the compound represented by CIl J) II-Oll was used. As a result, the formula % formula %
Claims (2)
る） で表わされるエチニル基を有するカルボナート。(1) Carbonate having an ethynyl group represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a hydrogen atom, an alkyl group, or an aryl group).
る） で表わされるα−エチニルアルコールに、ルテニウム触
媒の存在下、二酸化炭素を反応させることを特徴とする
一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは前記と同じ意味を有する） で表わされるエチニル基を有するカルボナートの製造方
法。(2) In the presence of a ruthenium catalyst, carbon dioxide is added to α-ethynyl alcohol represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R is a hydrogen atom, an alkyl group, or an aryl group) A method for producing a carbonate having an ethynyl group represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, R has the same meaning as above), which is characterized by reacting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201217A JPS6261951A (en) | 1985-09-11 | 1985-09-11 | Carbonate having ethynyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201217A JPS6261951A (en) | 1985-09-11 | 1985-09-11 | Carbonate having ethynyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6261951A true JPS6261951A (en) | 1987-03-18 |
| JPH0236565B2 JPH0236565B2 (en) | 1990-08-17 |
Family
ID=16437282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60201217A Granted JPS6261951A (en) | 1985-09-11 | 1985-09-11 | Carbonate having ethynyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6261951A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1003167A3 (en) * | 1989-02-10 | 1991-12-17 | Enichem Sintesi | Dimethylcarbonate synthesis method by means of dehydrogenating carbonylation |
-
1985
- 1985-09-11 JP JP60201217A patent/JPS6261951A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1003167A3 (en) * | 1989-02-10 | 1991-12-17 | Enichem Sintesi | Dimethylcarbonate synthesis method by means of dehydrogenating carbonylation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0236565B2 (en) | 1990-08-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |