JPH0419220B2 - - Google Patents
Info
- Publication number
- JPH0419220B2 JPH0419220B2 JP60201218A JP20121885A JPH0419220B2 JP H0419220 B2 JPH0419220 B2 JP H0419220B2 JP 60201218 A JP60201218 A JP 60201218A JP 20121885 A JP20121885 A JP 20121885A JP H0419220 B2 JPH0419220 B2 JP H0419220B2
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- formula
- carbonate
- carbon atoms
- carbon dioxide
- 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.)
- Expired - Lifetime
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000000468 ketone group Chemical group 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000003822 preparative gas chromatography Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、一般式
（式中、Ｒは炭素数１〜３のアルキル基である）
で表わされる新規なケト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 the general formula (In the formula, R is an alkyl group having 1 to 3 carbon atoms)
The present invention relates to a novel keto group-containing carbonate represented by: and a method for producing the same.
従来、α−エチニル−tert−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 when α-ethynyl-tert-alcohol is reacted with carbon dioxide in the presence of a copper salt and a trialkylamine, α-methylene-cyclic carbonate is obtained (German Patent No. 1098953 and 1145632 specification). 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
（アセチレニツクアルコール）と二酸化炭素との
反応について種々研究を行つていたところ、プロ
パルギルアルコールに対し、炭素数１〜３の低級
アルキルアルコールの存在下、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、鎖状構造のケト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, R 1 and R 2 represent an alkyl group.) [Purpose] The present inventors have conducted various studies on the reaction between alcohol having an ethynyl group (acetylenic alcohol) and carbon dioxide. However, when carbon dioxide is reacted with propargyl alcohol in the presence of a lower alkyl alcohol having 1 to 3 carbon atoms, a carbonate having a chain-like keto group is surprisingly obtained, unlike the conventional method. I discovered that.
従つて、本発明の目的は、新規な鎖状構造のケ
ト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 a novel chain structure and a keto group.
本発明のカルボナートは、次の反応式によつて
製造される。
The carbonate of the present invention is produced by the following reaction formula.
式中、Ｒは炭素数１〜３の低級アルキル基であ
る。 In the formula, R is a lower alkyl group having 1 to 3 carbon atoms.
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
料プロパルギル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、通常10〜50気圧程度の加圧が採用される。低
級アルキルアルコールの使用割合は、プロパギル
アルコール１モル当り１〜10モル、好ましくは50
〜10モルの割合である。 The reaction is carried out in the presence of a ruthenium catalyst, and the reaction conditions include carbon dioxide under pressure and a relatively low temperature, preferably around 0°C to room temperature, in order to suppress the polymerization of the raw material propargyl alcohol. will be adopted. 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 10 to 50 atmospheres is usually employed. The ratio of lower alkyl alcohol used is 1 to 10 mol, preferably 50 mol per mol of propargyl alcohol.
The proportion is ~10 mol.
本発明により得られるケト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
まれるケト基を利用し、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 a keto group obtained by the present invention is a new compound, and by utilizing the keto group contained therein, it can be used as a variety of synthetic intermediates, especially intermediates for pharmaceuticals and agricultural chemicals. can.
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
50ml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〔Ru3（CO）12〕0.2ｍmol、助触媒
としてトリエチルアミン〔（Et）3N〕２ml、エタ
ノール７ml及びプロパルギルアルコール１mlを装
入し、50気圧の二酸化炭素加圧下、室温で45時間
反応を行つた。その結果、式
CH3COCH2OCOOC2H5で表わされるケトカルボ
ナートを、プロパルギルアルコール基準で、転化
率66％及び収率15％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つた。Example A 50 ml autoclave was charged with 0.2 mmol of ruthenium carbonyl [Ru 3 (CO) 12 ] as a catalyst, 2 ml of triethylamine [(Et) 3 N] as a promoter, 7 ml of ethanol, and 1 ml of propargyl alcohol, and heated at 50 atm. The reaction was carried out at room temperature under pressure of carbon dioxide for 45 hours. As a result, the expression
A ketocarbonate represented by CH 3 COCH 2 OCOOC 2 H 5 was obtained with a conversion of 66% and a yield of 15% based on propargyl alcohol. In this case, the product was separated and recovered as follows.
カラムクロマトで触媒ルテニウムを除去したの
ち、分取ガスクロにて単離した。
After removing the catalyst ruthenium using column chromatography, it was isolated using preparative gas chromatography.
また、生成物の構造決定は、次のようにして行
つた。 Further, the structure of the product was determined as follows.
i.r.（neat）1750（OCOO）、1730（Ｃ＝Ｏ）、1270
（Ｃ−Ｏ）
H1n.m.r.（DCCl3）δ1.35（3H、ｔ、CH3CH2O−、
Ｊ＝７Hz）、2.20（3H、ｓ、CH3CO−）、4.32
（2H、ｑ、CH3CH2O−、Ｊ＝７Hz）、4.75
（2H、ｓ、−OCH2CO−）
GC−MS 147（Ｍ＋１）+
実施例 ２
実施例１において、エタノールの代りにメタノ
ールを用いた以外は同様にして実験を行つた。そ
の結果、式CH3COCH2OCOOCH3で表わされる
ケトカルボナートを、パロパルギルアルコール基
準で、収率11％の成績で得た。
ir (neat) 1750 (OCOO), 1730 (C=O), 1270
(C-O) H 1 nmr (DCCl 3 ) δ1.35 (3H, t, CH 3 CH 2 O-,
J=7Hz), 2.20 (3H, s, CH 3 CO−), 4.32
(2H, q, CH 3 CH 2 O−, J = 7Hz), 4.75
(2H, s, -OCH 2 CO-) GC-MS 147 (M+1) + Example 2 The experiment was conducted in the same manner as in Example 1 except that methanol was used instead of ethanol. As a result, a ketocarbonate represented by the formula CH 3 COCH 2 OCOOCH 3 was obtained with a yield of 11% based on paropargyl alcohol.
カラムクロマトで触媒ルテニウムを除去したの
ち、分取ガスクロにて単離した。
After removing the catalyst ruthenium using column chromatography, it was isolated using preparative gas chromatography.
また、生成物の構造決定は、次のようにして行
つた。 Furthermore, the structure of the product was determined as follows.
i.r.（neat）1750（OCOO）、1730（Ｃ＝Ｏ）、1270
（Ｃ−Ｏ）
H1n.m.r.（DCCl3）δ2.18（3H、ｓ、CH3−CO−）、
3.83（3H、ｓ、CH3O−）、4.69（2H、ｓ、−
OCH2CO−）
GC−MS 133（Ｍ＋１）+
実施例 ３
実施例１において、エタノールの代りにｎ−プ
ロパノールを用いた以外は同様にして実験を行つ
た。その結果、式CH3COCH2OCOOOC3H7で表
わされるケトカルボナートを、パロパルギルアル
コール基準で、収率１％の成績で得た。
ir (neat) 1750 (OCOO), 1730 (C=O), 1270
(C-O) H 1 nmr (DCCl 3 ) δ2.18 (3H, s, CH 3 -CO-),
3.83 (3H, s, CH 3 O−), 4.69 (2H, s, −
OCH 2 CO-) GC-MS 133 (M+1) + Example 3 The experiment was conducted in the same manner as in Example 1 except that n-propanol was used instead of ethanol. As a result, a ketocarbonate represented by the formula CH 3 COCH 2 OCOOOC 3 H 7 was obtained with a yield of 1% based on paropargyl alcohol.
カラムクロマトで触媒ルテニウムを除去したの
ち、分取ガスクロにて単離した。
After removing the catalyst ruthenium using column chromatography, it was isolated using preparative gas chromatography.
また、生成物の構造決定は、次のようにして行
つた。 Further, the structure of the product was determined as follows.
i.r.（neat）1750（OCOO）、1730（Ｃ＝Ｏ）、1270
（Ｃ−Ｏ）
H1n.m.r.（DCCl3）δ0.98（3H、ｔ、CH3CH2−、
Ｊ＝８Hz）、1.72（2H、ｍ、CH3−CH2−CH2、
Ｊ＝８Hz）、2.18（3H、ｓ、CH3CO−）、4.14
（2H、ｔ、Ｏ−CH2−CH2、Ｊ＝８Hz）、4.67
（2H、ｓ、−OCH2CO−）
GC−MS 166（Ｍ＋１）+
ir (neat) 1750 (OCOO), 1730 (C=O), 1270
(C-O) H 1 nmr (DCCl 3 ) δ0.98 (3H, t, CH 3 CH 2 −,
J=8Hz), 1.72 (2H, m, CH3 - CH2 - CH2 ,
J=8Hz), 2.18 (3H, s, CH 3 CO−), 4.14
(2H, t, O- CH2 - CH2 , J=8Hz), 4.67
(2H, s, -OCH 2 CO-) GC-MS 166 (M+1) +
Claims (1)
で表わされるケト基を有するカルボナート。 ２ プロパルギルアルコールに、炭素数１〜３の
低級アルキルアルコール中において、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 （式中、Ｒは炭素数１〜３のアルキル基である）
で表わされるケト基を有するカルボナートの製造
方法。[Claims] 1. General formula (In the formula, R is an alkyl group having 1 to 3 carbon atoms)
A carbonate having a keto group represented by: 2 General formula characterized by reacting propargyl alcohol with carbon dioxide in the presence of a ruthenium catalyst in a lower alkyl alcohol having 1 to 3 carbon atoms (In the formula, R is an alkyl group having 1 to 3 carbon atoms)
A method for producing a carbonate having a keto group represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201218A JPS6261950A (en) | 1985-09-11 | 1985-09-11 | Carbonate having keto group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201218A JPS6261950A (en) | 1985-09-11 | 1985-09-11 | Carbonate having keto group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6261950A JPS6261950A (en) | 1987-03-18 |
| JPH0419220B2 true JPH0419220B2 (en) | 1992-03-30 |
Family
ID=16437299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60201218A Granted JPS6261950A (en) | 1985-09-11 | 1985-09-11 | Carbonate having keto group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6261950A (en) |
-
1985
- 1985-09-11 JP JP60201218A patent/JPS6261950A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6261950A (en) | 1987-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |