JPS62273937A - Production of 1-iodinated ethyl alkyl carbonate - Google Patents
Production of 1-iodinated ethyl alkyl carbonateInfo
- Publication number
- JPS62273937A JPS62273937A JP61116893A JP11689386A JPS62273937A JP S62273937 A JPS62273937 A JP S62273937A JP 61116893 A JP61116893 A JP 61116893A JP 11689386 A JP11689386 A JP 11689386A JP S62273937 A JPS62273937 A JP S62273937A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- alkyl carbonate
- calcium phosphate
- formula
- chloroethyl
- 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
- 238000004519 manufacturing process Methods 0.000 title description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 8
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 8
- 239000012336 iodinating agent Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- USROXVACOOYSGX-UHFFFAOYSA-N carbonic acid;hydroiodide Chemical class I.OC(O)=O USROXVACOOYSGX-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001516 alkali metal iodide Inorganic materials 0.000 abstract description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 229940098779 methanesulfonic acid Drugs 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 239000011968 lewis acid catalyst Substances 0.000 abstract 1
- 150000002960 penicillins Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- -1 zinc chloride Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 235000009518 sodium iodide Nutrition 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- BDHXJIRTSWHBPR-UHFFFAOYSA-N ethyl 1-iodoethyl carbonate Chemical compound CCOC(=O)OC(C)I BDHXJIRTSWHBPR-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- YVRGKFXJZCTTRB-UHFFFAOYSA-N 1-chloroethyl ethyl carbonate Chemical compound CCOC(=O)OC(C)Cl YVRGKFXJZCTTRB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960002699 bacampicillin Drugs 0.000 description 1
- PFOLLRNADZZWEX-FFGRCDKISA-N bacampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@@H]3N(C2=O)[C@H](C(S3)(C)C)C(=O)OC(C)OC(=O)OCC)=CC=CC=C1 PFOLLRNADZZWEX-FFGRCDKISA-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
- 239000011575 calcium Substances 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical group [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
３−１ 目 的
バカンピシリンは、３位にエステル基
−ＣＯ２ＣＨ−ＯＣＯ２Ｃ２Ｈ５ｔ−有するペニシリン
銹導体であさＨ５
９、経口吸収ａｔ有する有用な抗菌剤である。Detailed Description of the Invention 3-1 Purpose Bacampicillin is a penicillin conductor having an ester group -CO2CH-OCO2C2H5t- at the 3-position and is a useful antibacterial agent with an oral absorption rate of H59.
このエステル化ニは１−ヨードエチル エチルカーボネ
ートヲ使用するのが有利でおることが知られている。It is known that it is advantageous to use 1-iodoethyl ethyl carbonate as the ester.
本発明は、１−ヨードエチル エチルカーボネートなど
の１−ヨードエチル アルキルカーボネート（２）の改
良製法である。The present invention is an improved method for producing 1-iodoethyl alkyl carbonates (2) such as 1-iodoethyl ethyl carbonate.
最近、ｔ−ヨードエチル アルキルカーボネ−） （２
）の製法に関して次の式で示される方法が報告されてい
る（特開昭８１−４０２４６号公＠）。Recently, t-iodoethyl alkyl carbonate) (2
) has been reported (Japanese Unexamined Patent Application Publication No. 81-40246@) as shown by the following formula.
この方法により、１−クロロエチル アルキルカーボネ
ート（１）にルイス酸几とえば塩化亜鉛の存在下、ヨウ
素化剤たとえばヨウ化ナトリウムを反応させると、１−
ヨードエチル アルキルカーボネート（２）が得られる
。According to this method, when 1-chloroethyl alkyl carbonate (1) is reacted with an iodizing agent such as sodium iodide in the presence of a Lewis acid such as zinc chloride, 1-chloroethyl alkyl carbonate (1) is reacted with an iodizing agent such as sodium iodide.
Iodoethyl alkyl carbonate (2) is obtained.
この方法は、吸湿性のため取扱いが困難なルイス酸を触
媒として用いることから、工業的な農法としては問題が
ある。This method is problematic as an industrial farming method because it uses a Lewis acid as a catalyst, which is difficult to handle due to its hygroscopic nature.
発明者等は、ルイスＩ［−用いなくても好収率ｆｌ−：
１ｌ−）”エチル アルキルヵーポ、？、 −ト（２）
が得られる方法を見出し、本発明を完成した。The inventors have demonstrated that Lewis I [- with good yield fl-:
1l-)”Ethyl alkyl capo, ?, -t (2)
The present invention was completed by discovering a method for obtaining the following.
３−２構成
本発明は式
％式％（１）
を有する化合物をプロトン酸およびリン酸カルシウムの
存在下、ヨウ素化剤と反応させることを特徴とする１式
％式％（２）
を有する１−ヨウ化エチル アルキルカーボネートの製
法である。3-2 Structure The present invention is characterized in that a compound having the formula % (1) is reacted with an iodinating agent in the presence of a protic acid and calcium phosphate. This is a method for producing ethyl alkyl carbonate.
上記式中、Ｒは低級アルキル基を示す。In the above formula, R represents a lower alkyl group.
Ｒの低級アルキル基は、たとえばメチル、エチル、プロ
ピル、インプロピル、ブチル、イソブチル、８−ブチル
ま友はｔ−ブチルがあげられる。Examples of the lower alkyl group for R include methyl, ethyl, propyl, inpropyl, butyl, isobutyl, 8-butyl, and t-butyl.
もしくはトルエンスルホン酸のようなスルホン酸；ギ酸
、酢酸もしくはプロピオン酸のような脂肪酸または塩酸
、硫酸、硝酸、ＩＪ ン酸もしくはヨウ化水素酸のよう
な鉱酸があげられ、好適にはスルホン酸がめげられる。or sulfonic acids such as toluenesulfonic acid; fatty acids such as formic acid, acetic acid or propionic acid; or mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, IJ acid or hydroiodic acid, preferably sulfonic acids. I'm disappointed.
上述したリン酸カルシウムは次とえばＣａ５（ＰＯａ）
２、［Ｃ’ａ３（ＰＯａｈ〕５Ｃａ（ＯＨ）２、Ｃａ（
ＰＯｓ）２１ 次はＣａ２Ｐ２Ｏ７があげられ、好まし
くはＣａ３（ＰＯ４）２ ’！ ７’ｒ−は［Ｃａ５（
ＰＯｔ）２］５Ｃａ（ＯＨ）２ があげられる。The above-mentioned calcium phosphate is then, for example, Ca5 (POa)
2, [C'a3(POah]5Ca(OH)2, Ca(
POs)21 Next is Ca2P2O7, preferably Ca3(PO4)2'! 7'r- is [Ca5(
POt)2]5Ca(OH)2.
上述したヨウ素化剤は、たとえばヨウ化リチウム、ヨウ
化ナトリウムもしくはヨウ化カリウムのようなアルカリ
金属ヨウ化物′！たけヨウ化カルシウムもしくはヨウ化
マグネシウムのようなアルカリ土類金属ヨウ化物があげ
られ、好ましくはアルカリ金属ヨウ化物があげられる。The iodizing agents mentioned above are, for example, alkali metal iodides', such as lithium iodide, sodium iodide or potassium iodide! Examples include alkaline earth metal iodides such as calcium iodide or magnesium iodide, and preferably alkali metal iodides.
本製法においては、溶媒を用いて反応が行われ、その溶
媒は、友とえばペンタン、インペンタン、ヘキサン、ヘ
プタンもしくはオクタンのような脂肪族炭化水素；シク
ロペンタン、シクロヘキサンもしくはメチルシクロヘキ
サンのような脂環式炭化水素；ベンゼン、トルエンもし
くはキシレンのような芳香族炭化水素：塩化メチレン、
クロロホルム、四塩化炭素もしくはトリクロロエチレン
のようなハロゲン化炭化水素：酢酸エテルまたはこれら
の二種以上の混合溶媒があげられ、好ましくはヘキサン
、シクロヘキサン、ベンゼン、クロロホルム、四塩化炭
素または酢酸エチルがあげられる。In this process, the reaction is carried out using a solvent, which may be an aliphatic hydrocarbon such as pentane, impentane, hexane, heptane or octane; a fatty acid such as cyclopentane, cyclohexane or methylcyclohexane. cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene or xylene; methylene chloride;
Halogenated hydrocarbons such as chloroform, carbon tetrachloride, or trichloroethylene; ethyl acetate; or a mixed solvent of two or more thereof; preferred are hexane, cyclohexane, benzene, chloroform, carbon tetrachloride, and ethyl acetate.
本製法を以下に説明する。１−クロロエチルアルキルカ
ーポネー）（１）ｉ１〜２１１ｉｉｔ、好ましくは１〜
７倍′Ｎｉ１ｌｉ：の溶媒（先に例示し次溶媒）に浴か
す。この溶液に１〜４当意、好ましくは１〜２当址のヨ
ウ素化剤、０．５〜２当量、好ましくは１〜１．５当に
のカルシウムを含むリン酸カルシウムおよび０．５〜２
当量、好ましくは０．９〜１．５当址のプロトン酸を加
える。この混合液上０〜５０℃、好ましくは２０〜４０
’Ｃで２〜４８時間、好ましくは３〜７時間攪拌する。This manufacturing method will be explained below. 1-chloroethyl alkyl carbonate) (1) i1 to 211iit, preferably 1 to
7 times Ni1li: bathed in a solvent (the following solvent is exemplified above). This solution contains 1 to 4 equivalents, preferably 1 to 2 equivalents of an iodinating agent, 0.5 to 2 equivalents, preferably 1 to 1.5 equivalents of calcium phosphate, and 0.5 to 2 equivalents of calcium phosphate.
Add equivalents, preferably 0.9 to 1.5 equivalents of protic acid. The temperature above this mixed liquid is 0 to 50℃, preferably 20 to 40℃.
Stir at 'C for 2-48 hours, preferably 3-7 hours.
反応液を常法に従って処理すると目的の１−ヨードエチ
ル アルキルヵーボネ−） （２）カｍられる。When the reaction solution is treated according to a conventional method, the desired 1-iodoethyl alkylcarbonate (2) is obtained.
こへに得られる目的物（２）は精製することなくアンピ
シリンなどのエステル化反応に用いることができるが、
必要ならばシリカゲルクロマトグラフィー、蒸留などに
より精製することができる。The target product (2) obtained here can be used in the esterification reaction of ampicillin etc. without purification.
If necessary, it can be purified by silica gel chromatography, distillation, etc.
３−３効果
本発明により、ルイス酸勿用いなくても、プロトン酸お
よびリン酸カルシウムを用いて好収率で１−ヨードエチ
ル アルキルカーボネート（２）が得られる。従って、
この方法は化合＊ （２）のすぐれた工業的製法である
。3-3 Effects According to the present invention, 1-iodoethyl alkyl carbonate (2) can be obtained in good yield using a protonic acid and calcium phosphate without necessarily using a Lewis acid. Therefore,
This method is an excellent industrial method for producing compound * (2).
以下に実施例をあけて本発明を具体的に示す。The present invention will be specifically illustrated with reference to Examples below.
実施例１
１−ヨードエチル インプロビルヵーボネー上
１−クロロエチル インプロビルカーボネー） （５，
Ｓ’）をトルエン（１５ｍＺ）に溶かす。この溶液に沃
化ナトリウム（６，７４，９； １．５当量り、第三リ
ン酸カルシウム（１゜５５ ！９； １当１ｔ）および
メタンスルホン酸（３，６，９； １．２５当量）ｔ−
加え、３０℃で５時間攪拌する。反応液にトルエン（３
５ｍ／）を加え、氷水（３５ｗｔ）で洗う。トルエン溶
液を５％チオ硫酸す） ＩＪウム水溶液（３５−）、５
％炭酸水素ナトリワム水浴ｆｉ （３５ｔｄ）、水（３
５ｄ）の順で洗い、乾燥＜ＭＪｊＳＯａ） Ｌ、、トル
エンを留去すると目的物（ｙ、ｓ ｙ ；収率９６％）
が油状物として得られる。Example 1 1-Iodoethyl Improvir carbonate 1-chloroethyl Improvir carbonate) (5,
Dissolve S') in toluene (15mZ). To this solution were added sodium iodide (6,74,9; 1.5 equivalents), tribasic calcium phosphate (1°55!9; 1 ton) and methanesulfonic acid (3,6,9; 1.25 equivalents). −
Add and stir at 30°C for 5 hours. Toluene (3
5m/) and washed with ice water (35wt). (toluene solution 5% thiosulfate) IJium aqueous solution (35-), 5
% sodium bicarbonate water bath fi (35td), water (3
Wash in the order of 5d) and dry <MJjSOa) L, and when toluene is distilled off, the target product (y, s y ; yield 96%)
is obtained as an oil.
ＮＭＲ（ＣＣ１ｍ）δｐｐｍ ７１．２０ （６Ｈ、（
１、Ｊ ＝６、５ Ｈｚ ） 、 ２．０８（３Ｈ、ｄ
、 Ｊ −６，５［（Ｚ ） 。NMR (CC1m) δppm 71.20 (6H, (
1, J = 6, 5 Hz), 2.08 (3H, d
, J-6,5[(Z).
４．７２ （Ｉ Ｈ、ｈｅｐｔ 、 Ｊ ＝ ８．５
Ｈｚ ） 、 ６．５８ （Ｉ Ｈ、ｑ 、 ８ Ｈｚ
）
実施例１と同様の反応を、次の各溶媒を用いて実施例１
と全く同様（試薬および浴媒蓋、反応条件ならび反厄液
の処理条件）に行うと、次の結果が得られる。4.72 (I H, hept, J = 8.5
Hz), 6.58 (IH,q, 8 Hz
) The same reaction as in Example 1 was carried out using the following solvents.
If the procedure is carried out in exactly the same manner as (reagents and bath medium lid, reaction conditions, and treatment conditions for the anti-toxic liquid), the following results will be obtained.
実施例１〜５で得られるもの一ガスクロマトグラフィー
は目的物のピークのみを示す。Gas chromatography of the products obtained in Examples 1 to 5 shows only the peak of the target product.
実施例６
１−ヨウドエチル エチルカーボ木−ト１−クロロエチ
ル エチルカーポネー）（１）を用いて、実施例１と同
様に反応、処理（試薬、溶媒１反応時間、反応液の処理
条件）すあ・と目的物（７，０１；収率９５％）が油状
物として得られる。Example 6 Using 1-iodoethyl ethylcarbohydrate (1-chloroethyl ethylcarbonate) (1), reaction and treatment were carried out in the same manner as in Example 1 (reagents, solvent 1 reaction time, reaction solution treatment conditions). The desired product (7,01; yield 95%) was obtained as an oil.
ＮＭＲ（ｃｐｃｚ５）δｐｐｍ ： ＩＪ６ （３Ｈ、
ｔ、 Ｊ −７Ｈｚ ） 、 ２．２５ （３Ｈ、ａ
、 Ｊ −６Ｈｚ ） 、 ４．２９（２Ｈ、ｑ 、
Ｊ ＝ ７ Ｈｚ ） 、 ６．８０ （Ｉ Ｈ。NMR (cpcz5) δppm: IJ6 (3H,
t, J -7Hz), 2.25 (3H, a
, J -6Hz), 4.29(2H,q,
J = 7 Hz), 6.80 (IH.
ｑ＊ Ｊ ＝ ６ Ｈｚ ）
水晶のガスクロマトグラフィーは目的物のピークのみを
示す。q* J = 6 Hz) Quartz crystal gas chromatography shows only the peak of the target product.
Claims (1)
存在下、ヨウ素化剤と反応させることを特徴とする、式 ＣＨ＿３ＣＨＩＯＣＯＯＲ を有する１−ヨウ化エチルアルキルカーボネートの製法
。 上記式中、Ｒは低級アルキル基を示す。Claims: A process for the preparation of 1-ethylalkyl iodide carbonates having the formula CH_3CHIOCOOR, characterized in that a compound having the formula CH_3CHClOCOOR is reacted with an iodinating agent in the presence of a protic acid and calcium phosphate. In the above formula, R represents a lower alkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116893A JPH0615509B2 (en) | 1986-05-21 | 1986-05-21 | Method for producing 1-ethyl iodide alkyl carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116893A JPH0615509B2 (en) | 1986-05-21 | 1986-05-21 | Method for producing 1-ethyl iodide alkyl carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62273937A true JPS62273937A (en) | 1987-11-28 |
| JPH0615509B2 JPH0615509B2 (en) | 1994-03-02 |
Family
ID=14698242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61116893A Expired - Fee Related JPH0615509B2 (en) | 1986-05-21 | 1986-05-21 | Method for producing 1-ethyl iodide alkyl carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615509B2 (en) |
-
1986
- 1986-05-21 JP JP61116893A patent/JPH0615509B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0615509B2 (en) | 1994-03-02 |
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