JPS62212377A - Oxamate compound and production thereof - Google Patents
Oxamate compound and production thereofInfo
- Publication number
- JPS62212377A JPS62212377A JP61053079A JP5307986A JPS62212377A JP S62212377 A JPS62212377 A JP S62212377A JP 61053079 A JP61053079 A JP 61053079A JP 5307986 A JP5307986 A JP 5307986A JP S62212377 A JPS62212377 A JP S62212377A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- lower alkyl
- oxamate
- alkyl group
- hydrogen atom
- 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
- -1 Oxamate compound Chemical class 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 10
- 229910052763 palladium Inorganic materials 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000001766 physiological effect Effects 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- UKUXKKFOPDVTIM-UHFFFAOYSA-N 4-methylmorpholine-2,3-dione Chemical compound CN1CCOC(=O)C1=O UKUXKKFOPDVTIM-UHFFFAOYSA-N 0.000 abstract 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001414 amino alcohols Chemical class 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KHKPJEQCLYWOCD-UHFFFAOYSA-N CC#N.I.I Chemical compound CC#N.I.I KHKPJEQCLYWOCD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 241000723267 Diospyros Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101700012268 Holin Proteins 0.000 description 1
- 206010051602 Laziness Diseases 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- PLQCPDHNBLXOEO-UHFFFAOYSA-N oxazine-3,4-dione Chemical compound O=C1C=CONC1=O PLQCPDHNBLXOEO-UHFFFAOYSA-N 0.000 description 1
- PRAYXGYYVXRDDW-UHFFFAOYSA-N piperidin-2-ylmethanol Chemical compound OCC1CCCCN1 PRAYXGYYVXRDDW-UHFFFAOYSA-N 0.000 description 1
- HVVNJUAVDAZWCB-UHFFFAOYSA-N prolinol Chemical compound OCC1CCCN1 HVVNJUAVDAZWCB-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、一般式（Ｉ）
（式中、Ｒ１は水素原子、低級アルキル基、低級アルケ
ニル基またはフェニル基を、 Ｒ２は低級アルキル基ま
たはフェニル基を、Ｒ３は水素原子または低級アルキル
基を示す。但し、Ｒ１とＲ２が結合して環を形成してい
てもよい）で示されるオキサメート化合物およびその製
造法に関する。Detailed Description of the Invention The present invention is based on the general formula (I) (wherein R1 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a phenyl group, R2 is a lower alkyl group or a phenyl group, and R3 is hydrogen) The present invention relates to an oxamate compound represented by an atom or a lower alkyl group (provided that R1 and R2 may be bonded to form a ring) and a method for producing the same.
一般式（Ｉ）で示されるオキサメート化合物は浬々の生
理活性を有するオキサメート系医薬等の中間体としてそ
の利用が多いに期待される新規化合物であって、本発明
者が初めて見出した新規化合物であり、該化合物は、一
般式■（式中、Ｒ＋、ＲｚおよびＲ３は前記と同じ怠味
を有する）
で示されるアミノアルコール類を、パラジウム系触媒、
銅塩および酸素の存在下、−酸化炭素と反応させること
により容易に製造することができる。The oxamate compound represented by the general formula (I) is a novel compound that is expected to be widely used as an intermediate for oxamate-based drugs, etc., which have numerous physiological activities, and is a novel compound discovered for the first time by the present inventor. The compound is a compound in which an amino alcohol represented by the general formula (1) (wherein R+, Rz and R3 have the same laziness as above) is reacted with a palladium-based catalyst,
It can be easily produced by reacting with -carbon oxide in the presence of a copper salt and oxygen.
この反応における原料である一般式佃で示されるアミノ
アルコールにおいて、置換基Ｒ１として具体的には水素
原子、メチル、エチル、プロピロ、ブチル、ヘキシル、
エチレン、アリル、ブテン、ヘキセン、フェニルなどが
例示され、好ましくは水素原子または低級アルキル基で
ある。また、Ｒ２として具体的には上記と同様の低級ア
ルキル基またはフェニル基、好ましくは低級アルキル基
が、Ｒａとして具体的には水素原子または上記と同様の
低級アルキル基が例示され、Ｒ１とＲ２とが結合して窒
素原子を含む４員環、５員環、６員環などを形成してい
てもよい。In the amino alcohol represented by the general formula Tsukuda, which is a raw material in this reaction, the substituent R1 is specifically a hydrogen atom, methyl, ethyl, propyro, butyl, hexyl,
Examples include ethylene, allyl, butene, hexene, phenyl, etc., and preferably a hydrogen atom or a lower alkyl group. Further, R2 is specifically exemplified by the same lower alkyl group or phenyl group as above, preferably a lower alkyl group, and Ra is specifically exemplified by a hydrogen atom or the same lower alkyl group as above, and R1 and R2 are may be combined to form a 4-, 5-, or 6-membered ring containing a nitrogen atom.
本反応において、触媒としては２価のパラジウム系触媒
が使用され、該パラジウム系触媒としては従来より公知
の柿々のものが適用可能であるが、ＰｄＸｚ（Ｘ：塩素
、臭素等のハロゲン原子２、Ｐｄ’（ＯＡｃ）２あるい
はこれらの錯体たとえばＰｄＣｚｚ （ＭｅＣＮ）ｚ
、ＰｄＣ／ｚ（ＰＥｔａ）が好ましく使用される。In this reaction, a divalent palladium-based catalyst is used as a catalyst, and conventionally known persimmons can be used as the palladium-based catalyst, but PdXz (X: halogen atoms such as chlorine and bromine) , Pd'(OAc)2 or complexes thereof such as PdCzz (MeCN)z
, PdC/z(PEta) are preferably used.
かかる触媒の使用量は原料アミノアルコールに対して通
常０．１〜２０モル％、好ましくは１〜１０モル％であ
る。The amount of such a catalyst used is usually 0.1 to 20 mol%, preferably 1 to 10 mol%, based on the raw material amino alcohol.
また、本反応においては銅塩の共存は必須であり、該銅
塩としてはハロゲン化銅（たとえばＯｕＩ 、 ＯｕＣ
／ 、 Ｃｕ０ｚ２． （３ｕＢｒ 、 ０ｕＢｒ ２
）、酸化銅（たとえばＣｕｚＯ、ＯｕＯ）、硫酸銅（
たとえばＣｕ（８０４）ｚ 、 Ｃｕ８０４）が汐Ｕ示
されるが、ハロゲン化銅が好ましく使用される。かかる
銅塩は通常パラジウム系触媒に対して当所以上使用され
、その上限については特に制限されないが、経済性等の
理由から一般的には２０当量倍までである。In addition, the coexistence of a copper salt is essential in this reaction, and the copper salt may include copper halides (e.g. OuI, OuC
/ , Cu0z2. (3uBr, 0uBr 2
), copper oxide (e.g. CuzO, OuO), copper sulfate (
For example, Cu(804)z, Cu804) is shown, but copper halides are preferably used. Such a copper salt is usually used in an amount exceeding a certain amount for a palladium-based catalyst, and the upper limit thereof is not particularly limited, but is generally up to 20 equivalents for reasons such as economical efficiency.
一酸化炭素は理論的には原料アミノアルコールに対して
２当Ｍｋ倍必聾であるが、一般的にはそれより過剰貝で
、かつ５〜２０００Ｍ、好ましくは２０〜１００ ＃／
ｃｄの加圧下で反応を行う。Theoretically, carbon monoxide must be 2 equivalents Mk to the raw material amino alcohol, but generally it is in excess of that and 5 to 2000M, preferably 20 to 100#/
The reaction is carried out under pressure of cd.
酸素は反応系における分圧として２〜２０船侃、好まし
くは８〜１５＃肩となる範囲で使用される。Oxygen is used at a partial pressure in the reaction system of 2 to 20 degrees, preferably 8 to 15 degrees.
反応は通常溶媒中で行われ、溶媒としては反応に不活性
であれば特に制限されないが、アセトニトリル、低級ア
ルコール（たとえばメタノール、エタノール、フタノー
ル、アミルアルコール）が好ましく使用される。The reaction is usually carried out in a solvent, and the solvent is not particularly limited as long as it is inert to the reaction, but acetonitrile and lower alcohols (eg, methanol, ethanol, phthanol, amyl alcohol) are preferably used.
この反応において、脱水剤たとえばトリメトキシメタン
などを使用することは有効であるが、必ずしも必要とす
るものではない。In this reaction, it is effective to use a dehydrating agent such as trimethoxymethane, but it is not always necessary.
反応温度は０〜１００℃の範囲であればよいが、本反応
は室温においても十分に反応が進行するため、楢端に高
温にする必要はない。The reaction temperature may be in the range of 0 to 100°C, but since the reaction proceeds satisfactorily even at room temperature, there is no need to raise the temperature to a high temperature.
かくして、上記反応によれば一般式の）で示されるアミ
ノアルコールから一工程でダブルカルボニル化が容易に
進行して目的とする一般式（Ｉ）で示されるオキサメー
ト化合物を好収率で得ることができ、かくして得られた
オキサメート化合物は撞々の生理活性を有するオキサメ
ート系医薬等の中間体としてその利用が多い（ζ期待さ
れる。Thus, according to the above reaction, double carbonylation can easily proceed in one step from the amino alcohol represented by the general formula () to obtain the desired oxamate compound represented by the general formula (I) in a good yield. The oxamate compounds obtained in this way are often used as intermediates for oxamate-based pharmaceuticals, etc., which have a wide range of physiological activities (ζ is expected).
以下、実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
実施例Ｉ
ＬＯｘｌ容オートクレーブにアセトニトリル２耐、Ｎ−
メチルエタノールアミンｌ、 Ｑ ｍｍＯ／ 。Example I Acetonitrile 2 resistant, N-
Methylethanolamine l, Q mmO/.
ジクロルパラジウム−アセトニトリル錯体０．０５ｍ
ｍｏ ｌおよびヨウ化第１９Ａ Ｏ，２５ｍｆｎＯ／を
仕込み、−酸化炭素と酸素をＣＯ圧４０彬−１０２圧５
＃肩となるように封入し、室温で２０時間攪拌する。Dichloropalladium-acetonitrile complex 0.05m
mol and 19A iodide, 25mfnO/, -carbon oxide and oxygen at CO pressure 40 - 102 pressure 5
# Seal the mixture so that it forms a shoulder, and stir at room temperature for 20 hours.
反応終了後、反応系を常圧に戻したのち濾過して触媒を
除き、ろ液を塩化メチレン−エーテルを用いてカラムク
ロマトで処理して４−メチル−Ｔ−Ｊｌ／ ホリン２
＋ ８−ジオンを０．７３ ｍｍｏｆ（対アミノアルコ
ール収率７８％）得た。これをベンゼンから再結晶した
。After the reaction was completed, the reaction system was returned to normal pressure, filtered to remove the catalyst, and the filtrate was treated with column chromatography using methylene chloride-ether to obtain 4-methyl-T-Jl/holin 2.
+ 0.73 mmof (yield based on amino alcohol: 78%) of 8-dione was obtained. This was recrystallized from benzene.
ｎｉ、 ｐ ： ９０〜９１℃
ＩＲ（ＫＢｒ）： １７５０ （８，ｃ＝ｏ＞ 、１６
８６＜Ｓ、ｃ＝０）、１３５２（ｉｎ）、１１９０（ｍ
）、１１０５６（Ｗ）ｔ’
１Ｈ−ＮＭＲ（ＣＤＯ／３）： ６３．１３ （８，
８Ｈ、−ＣＨａ ） 。ni, p: 90-91°C IR (KBr): 1750 (8, c=o>, 16
86<S, c=0), 1352 (in), 1190 (m
), 11056(W)t' 1H-NMR (CDO/3): 63.13 (8,
8H, -CHa).
８．７０ （ｔ 、 Ｊ ＝７．０Ｈｚ 、 ２Ｈ、Ｎ
−ＣＨ２−） 。8.70 (t, J = 7.0Hz, 2H, N
-CH2-).
４．５１ （Ｌ 、 Ｊ ＝７．０Ｈｚ 、 ２Ｈ−０
−ＣＨ２−）実施ｔ！／！ｌ ２
１ＯＩ１１容オートクレーブにメタノール２震ｌ。4.51 (L, J = 7.0Hz, 2H-0
-CH2-) Implementation t! /! Add 2 liters of methanol to a 1 OI 11 volume autoclave.
Ｎ−ブチルエタノールアミンｌ、 Ｑ ｍｍｏｌ、ジク
ロルパラジウム−アセトニトリル錯体０．１ ｍｍＯ／
および塩化第１銅９．５ ｍｍｏｌを仕込み、−膜化炭
素と酸素をＣＯ圧８０＃／ｄ、０２圧５＃肩となるよう
に封入し、室温で２０時間攪拌する。N-butylethanolamine l, Q mmol, dichloropalladium-acetonitrile complex 0.1 mmO/
Then, 9.5 mmol of cuprous chloride were added, carbon film and oxygen were sealed so that the CO pressure was 80#/d and the pressure was 5#, and the mixture was stirred at room temperature for 20 hours.
反応終了後、実施例１と同様に後処理して４−ブチルモ
ルホリン−２，８−ジオン０．８６ ｍｍｏｌ （収＄
８６％）を得、これをエーテルから再結晶した。After completion of the reaction, post-treatment was carried out in the same manner as in Example 1 to obtain 0.86 mmol of 4-butylmorpholine-2,8-dione (yield $
86%), which was recrystallized from ether.
１６８２（８，Ｃ＝Ｏ）、１４８２（→、 １４５４（
Ｗ）、１８６０ｔ１１，１１８０（ｎｌ）、１０１０６
４Ｈ’’Ｈ−ＮＭ Ｒ（ＯＤＯＡＦ ａ ） ： δ
０．７３〜１．９０（１１１，７Ｈ。1682(8,C=O), 1482(→, 1454(
W), 1860t11, 1180(nl), 10106
4H''H-NMR(ODOAFa): δ
0.73-1.90 (111,7H.
寸ＣＨｚ′ｎ０Ｈａ ） 、 ８．５７（ｑ 、Ｊ＝６
．９Ｈｚ 。Dimension CHz'n0Ha), 8.57 (q, J=6
．． 9Hz.
２Ｈ、Ｎ−ＯＨ２−） 、 ８．６５ （ｔ 、 Ｊ＝
５．２Ｈｚ 、２Ｈ，−Ｎ−ＯＨ２） 、 ４．５１
（ｃ、 Ｊ ＝５．２Ｈｚ 、２Ｈ，０−ＣＨｚ−）
実施例８
１０ｍ１容オートクレーブにアセトニトリル２ゴ、Ｎ−
エチルエタノールアミン１．Ｑ ｍｍｏｆ 。2H, N-OH2-), 8.65 (t, J=
5.2Hz, 2H, -N-OH2), 4.51
(c, J = 5.2 Hz, 2H, 0-CHz-) Example 8 In a 10 ml autoclave, add 2 g of acetonitrile, N-
Ethylethanolamine1. Qmmof.
ジヨウ化パラジウム−アセトニトリル錯体０．０６ｒｎ
ｒｎｏ／およびヨウ化第１０４０．５ ｍｍｏｚを仕込
み、−酸化炭素と酸素をＣＯ圧８０峰−９０２圧５ ＃
／ｃｄとなるように封入し、４０℃で２０時間攪拌する
。Palladium diiodide-acetonitrile complex 0.06rn
rno/ and 1040.5 mmoz of iodide, - carbon oxide and oxygen at CO pressure 80 - 902 pressure 5 #
/cd, and stirred at 40°C for 20 hours.
以下、実施例１と同様に後処理して４−エチルモルホリ
ン−２，８−ジオンをｏ、 ｓ ６ ｍｍｏｒ（収率８
６％）得た。これをエーテルから再結晶した。Thereafter, 4-ethylmorpholine-2,8-dione was post-treated in the same manner as in Example 1 to obtain o, s 6 mmor (yield: 8
6%) obtained. This was recrystallized from ether.
ｍ、ｐニア０〜７０．５℃
ＩＲ（ＫＢｒ）： １７５４（Ｓ 、ｃ＝ｕ）、ｔｓｓ
２（ｓ、ｃ＝０） 、１４８８（Ｗ）、１４４４（Ｗ５
．１８６８（ｆＴＩ。m, pnia 0-70.5℃ IR (KBr): 1754 (S, c=u), tss
2 (s, c=0), 1488 (W), 1444 (W5
．． 1868 (fTI.
１８１４（Ｗ５．１１７８（ｒｒｌ）、１０５８（Ｗ５
ｃ＊ ’’Ｈ−ＮＭＲ（ＯＤＣ／ａ）： ａ １．２
１ （ｔ 、Ｊ＝７．４Ｈｚ 、８Ｈ。1814(W5.1178(rrl), 1058(W5
c*''H-NMR (ODC/a): a 1.2
1 (t, J=7.4Hz, 8H.
−ＣＨａ）、 ３．５４（Ｊ＝７．４Ｈｚ、２ｆ■、
Ｎ −ＣＨ２−） 、 ８．６７ （ｔ 、 Ｊ＝５．
８Ｈｚ 、 ２Ｈ。-CHa), 3.54 (J=7.4Hz, 2f■,
N -CH2-), 8.67 (t, J=5.
8Hz, 2H.
Ｎ−ＣＨ２−） 、 ４．５１（ｔ＝ 、Ｊ＝５．３Ｈ
ｚ 。N-CH2-), 4.51 (t=, J=5.3H
z.
２Ｈ，０−ｅＨｚ −）
実施例４
Ｎ−メチルエタノールアミンに代えて２−ヒドロキシメ
チルピロリジンを使用し、ＣＯ圧を８０ ＃／ｃｄとす
る以外は実施例１と同様に反応、後処理してヘキサヒド
ロ−ＩＨ−ピロロ〔２，１−ｃ：＋〔ｔ、ａ〕−オキサ
ジン−８，４−ジオン０、６４ ｍｍｏｒ （収率６４
％）を得た。2H,0-eHz -) Example 4 The reaction and post-treatment were carried out in the same manner as in Example 1, except that 2-hydroxymethylpyrrolidine was used in place of N-methylethanolamine and the CO pressure was 80 #/cd. Hexahydro-IH-pyrrolo[2,1-c:+[t,a]-oxazine-8,4-dione 0,64 mmor (yield 64
%) was obtained.
これをベンゼン−ヘキサン混合溶媒から再結晶した。This was recrystallized from a benzene-hexane mixed solvent.
ｍ−Ｐ ：１８５〜１８７℃
ＩＲ（ＫＢｒ）： １７５６（８，０＝０）、１６８８
（Ｓ、Ｃ＝０）、１４５０Ｍ、１８９６（Ｗ）、１１６
２（Ｗ）。m-P: 185-187°C IR (KBr): 1756 (8,0=0), 1688
(S, C=0), 1450M, 1896 (W), 116
2 (W).
１１９２（Ｆｎ）、１０４８（Ｗ）、１００２１００２
（’’Ｈ−ＮＭＲ（ＯＤＯ／ ａ ） ：δ１−８６〜
２．８８ （ｍ 、 ４ Ｈ、−ＣＨ２−） １２．９
９〜８．７４ （ｍ ｌ ２Ｈ、Ｎ−ＣＨ２−） 。1192 (Fn), 1048 (W), 10021002
(''H-NMR (ODO/a): δ1-86~
2.88 (m, 4H, -CH2-) 12.9
9-8.74 (ml 2H, N-CH2-).
８．９２〜４．６０ （ｍ、３Ｈ，０−ＪＥＩ（２−、
Ｎ −ＣＨ２−）
マススペクト７Ｌ、 ： ｍ／ｅ １５５ （Ｍ＋）
、 １１１（Ｍ＋−ＣＯ２）
実施例５
１０１１１容オートクレーブにアセトニトリル２ｍ１．
２−ヒドロキシメチルピペリジン１． Ｏｍｍｏ／１酢
順パラジウム０．１ ｍｍｏＩ！およびヨウ化第１銅Ｑ
、５ ｍｍｏｌを仕込み、ＣＯ圧８０ ｋｑ／ａＡ 、
０２圧５＃４肩、５０℃で２０時間攪拌した。以下、実
施例１と同様に処理してオクタヒドロピリジノ（２，１
−Ｃ）（１，４）オキサジン−３，４−ジオン０．７６
ｍｍｏｊ（収率７６つ）を得た。8.92-4.60 (m, 3H, 0-JEI (2-,
N -CH2-) Mass spectrum 7L: m/e 155 (M+)
, 111 (M+-CO2) Example 5 2 ml of acetonitrile was added to a 10111 volume autoclave.
2-Hydroxymethylpiperidine 1. Ommo/1 vinegar order palladium 0.1 mmoI! and cuprous iodide Q
, 5 mmol, CO pressure 80 kq/aA,
The mixture was stirred at 50° C. for 20 hours under 02 pressure 5 #4 shoulder. Hereinafter, the same treatment as in Example 1 was performed to obtain octahydropyridino (2,1
-C) (1,4)oxazine-3,4-dione 0.76
mmoj (yield 76 pieces) was obtained.
コレラベンゼン−エーテルで再結晶してｎ上２６８〜６
９℃の結晶を得た。Recrystallized from cholera benzene-ether on n268-6
Crystals at 9°C were obtained.
ＩＲ（ＫＢｒ）： ８９６０（＠、８８８０（Ｗ）、
１７６０（８，０＝ｏ）、１６８６（＋８．ｃ＝ｏ＞
、１４４０（ｍ）、１８９６（Ｗ）、１８５２１ｍ、１
２９６（Ｗ５゜１２０８Ｍ、１０９２（Ｗ）、１０４４
１０４４ｌ１’’Ｈ−ＮＭＲ（ＯＤＣｌ ３） ：δ１
．１６〜２．１７（ｔｎ、６Ｈ。IR (KBr): 8960 (@, 8880 (W),
1760 (8,0=o), 1686 (+8.c=o>
, 1440 (m), 1896 (W), 18521 m, 1
296 (W5゜1208M, 1092 (W), 1044
1044l1''H-NMR (ODCl3): δ1
．． 16-2.17 (tn, 6H.
−ＣＨ２−） 、 ２．５０〜８．０７ （ｎｔ 、
Ｂ（。-CH2-), 2.50-8.07 (nt,
B(.
Ｎ−ＣＨ−）、８．４８〜８．９９（ＩＨ。N-CH-), 8.48-8.99 (IH.
Claims (2)
ケニル基またはフェニル基を、Ｒ＿２は低級アルキル基
またはフェニル基を、Ｒ＿３は水素原子または低級アル
キル基を示す。 但し、Ｒ＿１とＲ＿２が結合して環を形成していてもよ
い） で示されるオキサメート化合物。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a hydrogen atom, lower alkyl group, lower alkenyl group, or phenyl group, R_2 is a lower alkyl group or phenyl group, and R_3 is a hydrogen atom. or a lower alkyl group.However, R_1 and R_2 may be combined to form a ring) An oxamate compound represented by the following.
ケニル基またはフェニル基を、Ｒ＿２は低級アルキル基
またはフェニル基を、Ｒ＿３は水素原子または低級アル
キル基を示す。 但し、Ｒ＿１とＲ＿２が結合して環を形成していてもよ
い） で示されるアミノアルコール類を、パラジウム系触媒、
銅塩および酸素の存在下、一酸化炭素と反応させること
を特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２およびＲ＿３は前記と同じ意味
を有する） で示されるオキサメート化合物の製造法。(2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a hydrogen atom, lower alkyl group, lower alkenyl group, or phenyl group, R_2 is a lower alkyl group or phenyl group, and R_3 is a hydrogen atom. or a lower alkyl group.However, R_1 and R_2 may combine to form a ring).
The general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_1, R_2 and R_3 have the same meanings as above), which is characterized by reacting with carbon monoxide in the presence of copper salts and oxygen. A method for producing oxamate compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61053079A JPH0672143B2 (en) | 1986-03-11 | 1986-03-11 | Method for producing oxamate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61053079A JPH0672143B2 (en) | 1986-03-11 | 1986-03-11 | Method for producing oxamate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62212377A true JPS62212377A (en) | 1987-09-18 |
| JPH0672143B2 JPH0672143B2 (en) | 1994-09-14 |
Family
ID=12932794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61053079A Expired - Lifetime JPH0672143B2 (en) | 1986-03-11 | 1986-03-11 | Method for producing oxamate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672143B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118422A (en) * | 1976-08-23 | 1978-10-03 | Texaco Development Corp. | Polyols from 2,3-morpholinediones |
-
1986
- 1986-03-11 JP JP61053079A patent/JPH0672143B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118422A (en) * | 1976-08-23 | 1978-10-03 | Texaco Development Corp. | Polyols from 2,3-morpholinediones |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672143B2 (en) | 1994-09-14 |
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