JPS6317822B2 - - Google Patents
Info
- Publication number
- JPS6317822B2 JPS6317822B2 JP60201219A JP20121985A JPS6317822B2 JP S6317822 B2 JPS6317822 B2 JP S6317822B2 JP 60201219 A JP60201219 A JP 60201219A JP 20121985 A JP20121985 A JP 20121985A JP S6317822 B2 JPS6317822 B2 JP S6317822B2
- Authority
- JP
- Japan
- Prior art keywords
- alkyl group
- formula
- carbon dioxide
- carbamate ester
- general 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.)
- Expired
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- -1 Carbamate ester Chemical class 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 238000004440 column chromatography Methods 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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、R1は水素原子又はアルキル基、R2はア
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バミン酸
エステル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 1 is a hydrogen atom or an alkyl group, and R 2 is an alkyl group.) The present invention relates to a novel keto group-containing carbamate ester represented by the following formula 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
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、プロパギルアルコール又はα−エチ
ニル−sec−アルコールに対し、第１級又は第２
級アミンの存在下、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バミン酸エステルが得られ
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 were conducting various studies on the reaction between alcohols having an ethynyl group and carbon dioxide, and found that propargyl alcohol or For α-ethynyl-sec-alcohol, primary or secondary
It has been surprisingly found that when carbon dioxide is reacted in the presence of a class amine, a carbamic acid ester having a chain-like keto group can be obtained, unlike the conventional method described above.
従つて、本発明の目的は、新規な鎖状構造のケ
ト基を有するカルバミン酸エステルを提供するこ
とにある。 Therefore, an object of the present invention is to provide a carbamate ester having a novel chain structure and a keto group.
本発明のカルバミン酸エステルは、次の反応式
によつて製造される。
The carbamate ester of the present invention is produced by the following reaction formula.
式中、R1は水素原子又はアルキル基であり、
R2はアルキル基である。アルキル基としては、
例えば、メチル、エチル、プロピル等がある。
（R2）2NHは第２級アミンを表わす。 In the formula, R 1 is a hydrogen atom or an alkyl group,
R 2 is an alkyl group. As an alkyl group,
Examples include methyl, ethyl, propyl, etc.
(R 2 ) 2 NH represents a secondary amine.
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、通常１〜50
気圧程度の加圧が採用される。 The reaction is carried out in the presence of a ruthenium catalyst, and the reaction conditions include a relatively low temperature, preferably around 0°C to room temperature, in order to suppress the polymerization of the raw alcohol under pressurized carbon dioxide. 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. Carbon dioxide pressurization is usually 1 to 50
Pressurization of about atmospheric pressure is used.
本発明により得られるケト基を有する鎖状構造
のカルバミン酸エステルは、新規化合物であり、
溶剤、燃料添加剤、高分子原料及び種々の合成中
間体として利用することができる。
The carbamate ester with a chain structure having a keto group obtained by the present invention is a new compound,
It can be used as a solvent, fuel additive, polymer raw material, and various synthetic intermediates.
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、アミン
としてジエチルアミン〔HN（C2H5）2〕２ml、溶
媒としてシア化メチル（CH3CN）７ml、アセチ
レニツクアルコールとしてプロパギルアルコール
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
CH3COCH2OCON（C2H5）2で表わされるカルバ
ミン酸エステルを、原料アルコール基準で、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つた。Example In a 50 ml autoclave, 0.2 mmol of ruthenium carbonyl [Ru 3 (CO) 12 ] as a catalyst, 2 ml of diethylamine [HN(C 2 H 5 ) 2 ] as an amine, 7 ml of methyl siaide (CH 3 CN) as a solvent, 1 ml of propargyl alcohol was charged as acetylene alcohol, and the reaction was carried out at room temperature for 45 hours under a carbon dioxide pressure of 50 atmospheres. As a result, the expression
The yield of carbamate ester represented by CH 3 COCH 2 OCON (C 2 H 5 ) 2 is calculated based on the raw material alcohol.
I got it with a score of 27%. 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）1730（Ｃ＝０）、1705（NCOO）
H1n.m.r.（DCCl3）δ1.16（6H、ｔ、CH3、Ｊ＝４
Hz）、2.18（3H、ｓ、CH3CO）、3.41（4H、ｑ、
−CH2−、Ｊ＝４Hz）、4.72（2H、ｓ、−
COCH2O−）
ir (neat) 1730 (C = 0), 1705 (NCOO) H 1 nmr (DCCl 3 ) δ1.16 (6H, t, CH 3 , J = 4
Hz), 2.18 (3H, s, CH 3 CO), 3.41 (4H, q,
−CH 2 −, J=4Hz), 4.72(2H, s, −
COCH 2 O−)
Claims (1)
R2はアルキル基である） で表わされるケト基を有するカルバミン酸エステ
ル。 ２ 一般式 （式中、R1は水素原子又はアルキル基、R2はア
ルキル基である） で表わされるα−エチニルアルコールを、一般式
（R2）2NH（式中、R2はアルキル基である）で表わ
される第２級アミン中において、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、R1、R2は前記と同じ意味を有する。） で表わされるケト基を有するカルバミン酸エステ
ルの製造方法。[Claims] 1. General formula (In the formula, R 1 is a hydrogen atom or an alkyl group,
R 2 is an alkyl group) Carbamate ester having a keto group. 2 General formula (In the formula , R 1 is a hydrogen atom or an alkyl group, R 2 is an alkyl group) A general formula characterized by reacting carbon dioxide in the presence of a ruthenium catalyst in a secondary amine represented by (In the formula, R 1 and R 2 have the same meanings as above.) A method for producing a carbamate ester having a keto group represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201219A JPS6261961A (en) | 1985-09-11 | 1985-09-11 | Carbamic acid ester having keto group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201219A JPS6261961A (en) | 1985-09-11 | 1985-09-11 | Carbamic acid ester having keto group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6261961A JPS6261961A (en) | 1987-03-18 |
| JPS6317822B2 true JPS6317822B2 (en) | 1988-04-15 |
Family
ID=16437314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60201219A Granted JPS6261961A (en) | 1985-09-11 | 1985-09-11 | Carbamic acid ester having keto group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6261961A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0566706U (en) * | 1992-02-17 | 1993-09-03 | 株式会社キーエンス | Programmable control device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2955223B2 (en) * | 1994-12-28 | 1999-10-04 | 花王株式会社 | Absorbent articles |
| JP4261853B2 (en) * | 2001-09-19 | 2009-04-30 | 株式会社日本触媒 | Water absorbent resin, water absorbent resin particles, and production method thereof |
| JP2003136621A (en) * | 2001-11-01 | 2003-05-14 | Kurabo Ind Ltd | Highly absorbent composites and diapers |
| JP4711616B2 (en) * | 2003-11-25 | 2011-06-29 | ユニ・チャーム株式会社 | Absorbent articles |
| JP4758669B2 (en) * | 2004-03-29 | 2011-08-31 | 株式会社日本触媒 | Amorphous crushed particulate water-absorbing agent |
| JP5078131B2 (en) * | 2007-03-27 | 2012-11-21 | 旭化成ケミカルズ株式会社 | Absorbent composite with ultrafast absorption capability |
| JP5417133B2 (en) * | 2009-06-17 | 2014-02-12 | 花王株式会社 | Absorbent articles |
| JP5592185B2 (en) * | 2010-07-21 | 2014-09-17 | 株式会社リブドゥコーポレーション | Absorbent articles |
-
1985
- 1985-09-11 JP JP60201219A patent/JPS6261961A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6261961A (en) | 1987-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |