JPH0443911B2 - - Google Patents
Info
- Publication number
- JPH0443911B2 JPH0443911B2 JP23600389A JP23600389A JPH0443911B2 JP H0443911 B2 JPH0443911 B2 JP H0443911B2 JP 23600389 A JP23600389 A JP 23600389A JP 23600389 A JP23600389 A JP 23600389A JP H0443911 B2 JPH0443911 B2 JP H0443911B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- thiol
- reaction
- derivative
- oxazolidone
- 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 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical class O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002169 ethanolamines Chemical class 0.000 claims description 8
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 12
- 150000003573 thiols Chemical class 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- CHEANNSDVJOIBS-MHZLTWQESA-N (3s)-3-cyclopropyl-3-[3-[[3-(5,5-dimethylcyclopenten-1-yl)-4-(2-fluoro-5-methoxyphenyl)phenyl]methoxy]phenyl]propanoic acid Chemical compound COC1=CC=C(F)C(C=2C(=CC(COC=3C=C(C=CC=3)[C@@H](CC(O)=O)C3CC3)=CC=2)C=2C(CCC=2)(C)C)=C1 CHEANNSDVJOIBS-MHZLTWQESA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GTZCNONABJSHNM-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin zinc Chemical compound [Zn].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 GTZCNONABJSHNM-UHFFFAOYSA-N 0.000 description 1
- ARILQDNHZGKJBK-UHFFFAOYSA-N 5-phenyl-1,3-oxazolidin-2-one Chemical compound O1C(=O)NCC1C1=CC=CC=C1 ARILQDNHZGKJBK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229940125681 anticonvulsant agent Drugs 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、光化学的に二酸化炭素を固定化する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for photochemically fixing carbon dioxide.
［従来技術］
二酸化炭素は炭素資源の最終酸化物であるが、
地球上では植物等による炭酸同化作用によつて、
大気中の二酸化炭素の増加が抑えられている。し
かし、近年、エネルギー消費量の増加や森林破壊
等による二酸化炭素濃度の増加及びそれによつて
引き起こされる地球温暖化が深刻な問題となつて
きている。そのためには、二酸化炭素を固定化す
る必要があるが、この場合、生成物は付加価値の
高いものが望ましい。本発明では、二酸化炭素を
２−オキサゾリドン誘導体２として固定化する
が、この化合物は抗けいれん剤等の医薬品の原
料、中間体としての利用が考えられる。従来、２
−オキサゾリドン誘導体の製造は、エタノールア
ミンと炭酸ジエチル、クロル炭酸エチル、または
ホスゲンを作用させて得る方法や有機アンチモン
触媒を用いてエタノールアミン誘導体と二酸化炭
素から直接合成する方法等が考えられてきた。[Prior art] Carbon dioxide is the final oxide of carbon resources,
On earth, carbon dioxide is assimilated by plants, etc.
The increase in carbon dioxide in the atmosphere is being suppressed. However, in recent years, an increase in carbon dioxide concentration due to increased energy consumption, deforestation, etc., and global warming caused thereby have become serious problems. For this purpose, it is necessary to fix carbon dioxide, and in this case, it is desirable that the product has high added value. In the present invention, carbon dioxide is immobilized as a 2-oxazolidone derivative 2, and this compound can be considered to be used as a raw material or intermediate for pharmaceuticals such as anticonvulsants. Conventionally, 2
-Oxazolidone derivatives have been produced by reacting ethanolamine with diethyl carbonate, ethyl chlorocarbonate, or phosgene, or by direct synthesis from ethanolamine derivatives and carbon dioxide using an organic antimony catalyst.
［発明が解決しようとする問題点］
しかしながら、ホスゲンのような試薬は毒性が
極めて高いという欠点がある。また、有機アンチ
モン触媒を用いる系では、高温、高圧を必要とす
るという欠点があつた。[Problems to be Solved by the Invention] However, reagents such as phosgene have the disadvantage of extremely high toxicity. Furthermore, systems using organic antimony catalysts have the drawback of requiring high temperatures and pressures.
［問題点を解決するための手段］
そこで、本発明者らは、ホスゲンなどのカルボ
ニル化剤や有機アンチモンを使用しない方法を研
究、探索した結果、光化学的なチオールの酸化反
応を利用することにより、常温、常圧で、毒性の
低い試薬を用いて二酸化炭素を固定化できること
を見いだし、本発明を完成するに至つた。[Means for Solving the Problems] Therefore, the present inventors researched and searched for a method that does not use carbonylating agents such as phosgene or organic antimony. They discovered that carbon dioxide can be fixed using a low-toxicity reagent at room temperature and pressure, leading to the completion of the present invention.
すなわち、本発明は、ルテニウム錯体や亜鉛錯
体を光増感剤として用いたチオールの酸化反応、
及びチオールとホスフインとの酸化還元反応を駆
動力とする脱水縮合反応を利用して、エタノール
アミン誘導体１と炭酸ガスを反応させることによ
り、２−オキサゾリドン誘導体２を得る方法を提
供するものである。 That is, the present invention relates to a thiol oxidation reaction using a ruthenium complex or a zinc complex as a photosensitizer,
The present invention also provides a method for obtaining 2-oxazolidone derivative 2 by reacting ethanolamine derivative 1 with carbon dioxide gas using a dehydration condensation reaction using a redox reaction between thiol and phosphine as a driving force.
本発明では以下のスキームに示す反応サイクル
が動くことによつて、二酸化炭素の固定化が達成
される。この反応系において、可視光を照射する
ことによりまず光増感剤（Sensitizern+）が励起
（Sensitizern+*）される。次に、チオール
（ArSH）から励起された光増感剤へ電子が移動
し、チオールはジスルフイド（ArSSAr）に酸化
され、増感剤は還元型（Sensitizer(n-1)+）にな
る。酸素存在下で還元型増感剤は再び酸化され、
はじめの状態（Sensitizern+）に戻る。一方、エ
タノールアミン誘導体１と二酸化炭素は容易に反
応し、比較的安定なカルバメート３を生成する。
また、ジスルフイドとホスフインからはイオウ−
リン中間体４が生成する。この中間体４とカルバ
メート３は容易に反応し、中間体５を生成する。
さらに、中間体５は分子内環化反応を起こし、最
終生成物（２−オキサゾリドン誘導体；２）とな
る。このとき、ホスフインは不可逆的にホスフイ
ンオキシド（R3P＝０）となり、またジスルフイ
ドはチオールに戻る。以上のようにして、前記の
反応サイクルが動く。 In the present invention, fixation of carbon dioxide is achieved by the reaction cycle shown in the following scheme. In this reaction system, the photosensitizer (Sensitizer n+ ) is first excited (Sensitizer n+* ) by irradiation with visible light. Next, electrons are transferred from the thiol (ArSH) to the excited photosensitizer, the thiol is oxidized to disulfide (ArSSAr), and the sensitizer becomes a reduced form (Sensitizer (n-1)+ ). In the presence of oxygen, the reduced sensitizer is oxidized again,
Return to the initial state (Sensitizer n+ ). On the other hand, ethanolamine derivative 1 and carbon dioxide easily react to produce relatively stable carbamate 3.
In addition, sulfur is produced from disulfide and phosphine.
Phosphorus intermediate 4 is produced. This intermediate 4 and carbamate 3 readily react to produce intermediate 5.
Furthermore, intermediate 5 undergoes an intramolecular cyclization reaction to become the final product (2-oxazolidone derivative; 2). At this time, phosphine irreversibly becomes phosphine oxide (R 3 P=0), and disulfide returns to thiol. The reaction cycle described above operates in the manner described above.
光増感剤としては、トリス（２，2′−ビピリジ
ル）ルテニウム（）クロリド、亜鉛テトラフエ
ニルポルフインを用いることができる。また、チ
オールには、メルカプトピリジン、４−ニトロチ
オフエノール、チオフエノールを用いることがで
きる。ホスフインとしては、トリフエニルホスフ
イン、トリ−ｎ−ブチルホスフインの使用が可能
である。さらに、エタノールアミン誘導体には、
２−アミノ−１−フエニルエタノール１を用いる
ことができる。また、反応溶媒はアセトニトリル
のような非プロトン性溶媒が使用できる。 As the photosensitizer, tris(2,2'-bipyridyl)ruthenium() chloride and zinc tetraphenylporphine can be used. Moreover, mercaptopyridine, 4-nitrothiophenol, and thiophenol can be used as the thiol. As the phosphine, triphenylphosphine and tri-n-butylphosphine can be used. Furthermore, ethanolamine derivatives include
2-amino-1-phenylethanol 1 can be used. Furthermore, an aprotic solvent such as acetonitrile can be used as the reaction solvent.
本発明における反応は、第三級アミンの存在下
で行うことが望ましい。チオールは解離型の方が
電子伝達を起こしやすいため、第三級アミンはチ
オールの中和剤として用いている。また、一部、
カルバメート３の中和剤としても作用する。第三
級アミンとしては、トリエチルアミンなどが使用
できる。第三級アミンの使用量は、エタノールア
ミン誘導体１の1.5倍程度である。また、光増感
剤の量はエタノールアミン誘導体の1/100（モル
比）以上で、２−オキサゾリドン誘導体の最終収
率はほぼ一定となる。２−オキサゾリドン誘導体
の最終収率は、チオールの増加とともに高くなる
が、メルカプトピリジンやチオフエノールでは、
ある濃度以上では飽和してくる。しかしながら、
４−ニトロチオフエノールの場合には、飽和は見
られず収率は単調に増加する。全体として、トリ
−ｎ−ブチルホスフイを用いた場合の方が、収率
は高かつた。トリ−ｎ−ブチルホスフイン系で
は、チオールとしてチオフエノールを用いた場合
が特に収率が高く、メルカプトピリジンや４−ニ
トロチオフエノールでは高収率は得られなかつ
た。 The reaction in the present invention is preferably carried out in the presence of a tertiary amine. Tertiary amines are used as thiol neutralizers because thiols are more likely to undergo electron transfer in their dissociated form. Also, some
It also acts as a neutralizer for carbamate 3. Triethylamine and the like can be used as the tertiary amine. The amount of tertiary amine used is about 1.5 times that of ethanolamine derivative 1. Further, when the amount of photosensitizer is 1/100 (mole ratio) or more of the ethanolamine derivative, the final yield of the 2-oxazolidone derivative becomes almost constant. The final yield of 2-oxazolidone derivatives increases with increasing thiol, but with mercaptopyridine and thiophenol,
Above a certain concentration, it becomes saturated. however,
In the case of 4-nitrothiophenol, no saturation is observed and the yield increases monotonically. Overall, the yield was higher when tri-n-butylphosphide was used. In the tri-n-butylphosphine system, the yield was particularly high when thiophenol was used as the thiol, whereas a high yield could not be obtained using mercaptopyridine or 4-nitrothiophenol.
一方、トリフエニルホスフイン系では、何れの
チオールを用いても収率は低かつた。 On the other hand, in the case of triphenylphosphine, the yield was low regardless of which thiol was used.
［発明の効果］
本発明によれば、大気中の二酸化炭素濃度を減
少させて地球温暖化を防ぐとともに付加価値の高
い物質を得ることができる。[Effects of the Invention] According to the present invention, it is possible to reduce the carbon dioxide concentration in the atmosphere, prevent global warming, and obtain a substance with high added value.
［実施例］
次に本発明を実施例により、更に詳細に説明す
る。[Example] Next, the present invention will be explained in more detail with reference to Examples.
実施例
２−アミノ−１−フエニルエタノール（４×
10-2M）、トリエチルアミン（６×10-2M）のア
セトニトリル溶液（５ml）に二酸化炭素を室温で
40分間通し、その後、トリス（２，2′−ビピリジ
ル）ルテニウム（）クロリド（８×10-4M）、
トリ−ｎ−ブチルホスフイン（２×10-1M）、チ
オフエノール（８×10-3M）を添加し、光照射を
開始する。反応容器は、空気と接するように一部
オープンにしてあるものを用いた（直径：18mm）。
光源として500W超高圧水源ランプ（UVカツト
オフフイルター：Ｙ−45及びIRカツトオフフイ
ルター：IRA−25S）を用い、25℃で撹拌しなが
ら反応させた。生成する５−フエニル−２−オキ
サゾリドンは、高速液体クロマトグラフイー
（ODSカラムを使用、展開溶媒：水／アセトニト
リル＝60／40）で定量した。Example 2-amino-1-phenylethanol (4x
10 -2 M), triethylamine (6 x 10 -2 M) in acetonitrile (5 ml) at room temperature.
for 40 minutes, then tris(2,2'-bipyridyl)ruthenium() chloride (8 x 10 -4 M),
Tri-n-butylphosphine (2×10 −1 M) and thiophenol (8×10 −3 M) are added, and light irradiation is started. The reaction vessel used was one that was partially open so that it could come into contact with air (diameter: 18 mm).
A 500 W ultra-high pressure water source lamp (UV cut-off filter: Y-45 and IR cut-off filter: IRA-25S) was used as a light source, and the reaction was carried out at 25° C. with stirring. The produced 5-phenyl-2-oxazolidone was quantified by high performance liquid chromatography (using an ODS column, developing solvent: water/acetonitrile = 60/40).
生成物の単離は、まず反応溶液の溶媒を減圧下
で留去し、残査をカラムクロマトグラフイー（シ
リカゲルカラム、展開溶媒：ヘキサン／酢酸エチ
ル＝１／２）で分離した。単離した白黄色の残査
をクロロホルム／ヘキサンから再結晶することに
より、白色結晶を得た（単難収率：90％）。 To isolate the product, first, the solvent of the reaction solution was distilled off under reduced pressure, and the residue was separated by column chromatography (silica gel column, developing solvent: hexane/ethyl acetate = 1/2). The isolated white-yellow residue was recrystallized from chloroform/hexane to obtain white crystals (single yield: 90%).
融点：87.5〜89℃（文献値：88〜90℃）
1H NMR（重クロロホルム中）δ 3.54（ｔ，
1H，Ｊ＝8.2Hz，−CHaHb−），3.98（ｔ，1H，
Ｊ＝8.7Hz，−CHaHb−），5.61（ｔ，1H，Ｊ＝
8.2Hz，−CHPh−），6.48（br.s，1H，D2O交換
可能，−NH−），7.39（ｓ，5H，芳香族）
IR（KBr） 3460（str.，NH伸縮），3000
（wk.，族，CH伸縮），1750（v.str.，CO伸縮） Melting point: 87.5-89℃ (literature value: 88-90℃) 1 H NMR (in deuterated chloroform) δ 3.54 (t,
1H, J=8.2Hz, −CHaHb−), 3.98(t, 1H,
J=8.7Hz, -CHaHb-), 5.61(t, 1H, J=
8.2Hz, -CHPh-), 6.48 (br.s, 1H, D 2 O exchangeable, -NH-), 7.39 (s, 5H, aromatic) IR (KBr) 3460 (str., NH stretching), 3000
(wk., family, CH stretching), 1750 (v.str., CO stretching)
第１図は、二酸化炭素固定反応系について示し
た図であり、１はエタノールアミン誘導体を示し
たものであり、２は２−オキサゾリドン誘導体を
示したものであり、３はカルバメートを示したも
のであり、４及び５は中間体を示したものであ
る。
Figure 1 is a diagram showing a carbon dioxide fixation reaction system, where 1 shows an ethanolamine derivative, 2 shows a 2-oxazolidone derivative, and 3 shows a carbamate. 4 and 5 indicate intermediates.
Claims (1)
ミン及び酸素の存在下、可視光を照射することに
より、エタノールアミン誘導体と二酸化炭素を反
応させることを特徴とする２−オキサゾリドン誘
導体の製造方法。1. A method for producing a 2-oxazolidone derivative, which comprises reacting an ethanolamine derivative with carbon dioxide by irradiating visible light in the presence of a photosensitizer, thiol, phosphine, tertiary amine, and oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23600389A JPH0399070A (en) | 1989-09-12 | 1989-09-12 | Preparation of 2-oxazolidone derivative by photochemical carbon dioxide immobilization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23600389A JPH0399070A (en) | 1989-09-12 | 1989-09-12 | Preparation of 2-oxazolidone derivative by photochemical carbon dioxide immobilization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0399070A JPH0399070A (en) | 1991-04-24 |
| JPH0443911B2 true JPH0443911B2 (en) | 1992-07-20 |
Family
ID=16994358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23600389A Granted JPH0399070A (en) | 1989-09-12 | 1989-09-12 | Preparation of 2-oxazolidone derivative by photochemical carbon dioxide immobilization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0399070A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000487A (en) * | 2010-10-19 | 2011-04-06 | 上海海事大学 | Method for capturing carbon dioxide |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468865A (en) * | 1994-05-03 | 1995-11-21 | Celgene Corporation | Stereopreferential synthesis of 3-(1-phenylprop-2-yl)-5-phenyloxazolidinones |
| CN102057109B (en) * | 2008-07-16 | 2013-06-05 | 株式会社小松制作所 | Cab for construction machine |
-
1989
- 1989-09-12 JP JP23600389A patent/JPH0399070A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000487A (en) * | 2010-10-19 | 2011-04-06 | 上海海事大学 | Method for capturing carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0399070A (en) | 1991-04-24 |
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