WO2000014056A1 - Procede de production de o-alkyl-n-cyanoimidate - Google Patents
Procede de production de o-alkyl-n-cyanoimidate Download PDFInfo
- Publication number
- WO2000014056A1 WO2000014056A1 PCT/JP1999/004896 JP9904896W WO0014056A1 WO 2000014056 A1 WO2000014056 A1 WO 2000014056A1 JP 9904896 W JP9904896 W JP 9904896W WO 0014056 A1 WO0014056 A1 WO 0014056A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- alkyl
- cyanamide
- orthoacetate
- producing
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C261/00—Derivatives of cyanic acid
- C07C261/04—Cyanamides
Definitions
- the present invention relates to a process for producing 0-alkyl-N-cyanoimidates useful as pharmaceutical and agricultural chemical intermediates. More specifically, the present invention relates to 0-alkyl-1-N-cyanoimidates by reacting orthoacetate with cyanamide. The present invention relates to a method for producing 0-alkyl-N-cyanomidite, characterized in that the reaction is initiated in the presence of an alkaline catalyst in producing the compound.
- An object of the present invention is to produce 0-alkyl-N-cyanoimidates easily and with a high yield on an industrial scale even at a low-cost iron or stainless steel reactor without selecting a reaction vessel. It is an object of the present invention to provide a method for producing N-cyanimide (hereinafter sometimes abbreviated as CAIM).
- the present inventors have conducted intensive studies in order to solve the above problems, and as a result, In the production of 0-alkyl-N-cyanoimides by the reaction of chloroacetate with cyanamide, the reaction is initiated in the presence of an alkaline catalyst to form 0-alkyl-N-cyanoides.
- the present inventors have found that a medium can be easily produced in high yield, and have completed the present invention.
- FIG. 1 is a graph showing the relationship between the reaction time, the production rate (%) of 0-alkyl-1-N-cyanoimidate (C AIM), and the pH in one embodiment of the reaction of the present invention.
- Cyanamide contains less than about 5% water, depending on the process. It is very difficult to remove this moisture.
- the CAIM itself formed by the reaction is an acidic substance, which dissolves in the reaction medium, thereby lowering the pH of the reaction system (see the following reaction formula (3)).
- the pH can be kept at, for example, 8.5 or more (about 5 minutes) as shown in FIG. Since water can be consumed according to the above reaction formula, it is extremely advantageous that a reaction vessel made of iron or stainless steel (not glass lining) can be used.
- an alkaline catalyst for example, triethanolamine
- the pH can be kept at, for example, 8.5 or more (about 5 minutes) as shown in FIG. Since water can be consumed according to the above reaction formula, it is extremely advantageous that a reaction vessel made of iron or stainless steel (not glass lining) can be used.
- the orthoacetate should be as pure as possible. Sufficiently p H of purified by Aru orthoacetate ester, 6. a 5 (per orthoacetate es Terumoru 1. 5x 10- 7). If an acidic reaction occurs, it is necessary to add more alkaline catalyst.
- the amount of orthoacetate used is 0.8 to 2 moles, preferably 0.9 to 1.2 moles, more preferably 0.95 to 1.04 moles relative to cyanamide. However, if water is contained in cyanamide, an extra amount of orthoacetate is required to match the water content.
- Cyanamide is used after being dissolved or dispersed in an appropriate solvent such as alcohol. If possible, the crystals may be reacted with orthoacetate. It is desirable to use the cyanamide having as little moisture as possible, and usually 5% or less, preferably 2% or less with respect to the cyanamide. Particularly preferably, it is 1% or less. It also contains some acid-reactive stabilizers such as phosphoric acid, but it requires the use of alkaline catalysts. Alkaline catalysts include alcoholic substances which do not react with cyanamide, orthoacetate and alcohol, for example, sodium alcoholates such as sodium methylate, amines such as triethanolamine, pyridine and the like. Aromatic amines. Considering economy and ease of handling, triethanolamine is most preferable. Triethanolamine can be recycled because it is distilled off as a distillate when the 0-alkyl-1-N-cyanoimidate is concentrated.
- the amount of the alkali catalyst used depends on the cyanamide and orthoacetate used, but the amount of the alkali should be such that the pH of the reaction solution at the start of the reaction is 8.0 or more, preferably in the range of 8.5 to 9.5. It is.
- the reaction temperature is 40 ° C to 100 ° C, preferably 60 ° C to 80 ° C.
- the reaction time is 3 hours to 24 hours, preferably 4 hours to 12 hours. After the reaction, confirm that no cyanamide remains in the reaction solution.
- Isolation of the produced 0-alkyl-N-cyanomidate is carried out by distillation, provided that the temperature in the vessel does not exceed 100 ° C, preferably 60 ° C to 80 ° C, particularly preferably the distillate temperature. It is better to carry out the process under reduced pressure such that the temperature is 50 ° C or less. If the temperature in the tank does not exceed 100 ° C, almost no decomposition of 0_alkyl-N-cyanoimidate formed in the tank is observed.
- Example 2 The reaction was carried out in the same manner as in Example 1 except that the alkaline substance in Example 1 was changed to a 50% aqueous sodium hydroxide solution (the pH of the reaction solution was 9.3 when cyanamide was added). 480 mol, a reaction rate of 95.9%) was obtained. Distillation was carried out in the same manner as in Example 1 to obtain 43.7 g (0.471 mol: 88.2% yield based on cyanamide) of 0-alkyl-N-cyanoimidate having a purity of 99.1%.
- reaction was carried out in the same manner as in Example 1 except that the reaction time in Example 1 was changed to 4 hours, and 76.7 g (reaction rate: 89.3%) of a reaction solution was obtained. In addition, this anti The reaction-completed solution was analyzed by gas chromatography, and as a result, about 0.04% by weight of triethylamine was confirmed.
- the reaction was carried out in the same manner as in Example 1 except that 0.05 g of sulfuric acid was used for triethylamine in Example 1 and the reaction time was 4 hours, to obtain a reaction solution of 78.7 g (conversion rate: 91.6%). .
- reaction solution is heated and reacted at 67 ° C.
- triethanolamine is added so that the pH does not become 7 or less, and the pH is maintained in the range of 7.0 to 8.0.
- total amount of triethanolamine added was 2.8 g
- 86.6 g of a reaction solution was obtained. Analysis of this reaction mixture revealed that the purity of the 0-alkyl-N-cyanomidet was 51.0% (conversion 90.0%).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99943232A EP1113002A4 (en) | 1998-09-09 | 1999-09-09 | PROCESS FOR PRODUCING O-ALKYL-N-CYANOIMIDATE |
US09/786,629 US6613925B1 (en) | 1998-09-09 | 1999-09-09 | Process for producing O-alkyl-N-cyanoimidate |
JP2000568816A JP4049534B2 (ja) | 1998-09-09 | 1999-09-09 | O−アルキル−n−シアノアセトイミデ−トの製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10/270499 | 1998-09-09 | ||
JP10/270500 | 1998-09-09 | ||
JP27049998 | 1998-09-09 | ||
JP27050098 | 1998-09-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000014056A1 true WO2000014056A1 (fr) | 2000-03-16 |
Family
ID=26549243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/004896 WO2000014056A1 (fr) | 1998-09-09 | 1999-09-09 | Procede de production de o-alkyl-n-cyanoimidate |
Country Status (4)
Country | Link |
---|---|
US (1) | US6613925B1 (ja) |
EP (1) | EP1113002A4 (ja) |
JP (1) | JP4049534B2 (ja) |
WO (1) | WO2000014056A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8663088B2 (en) | 2003-09-15 | 2014-03-04 | Covidien Lp | System of accessories for use with bronchoscopes |
US8764725B2 (en) | 2004-02-09 | 2014-07-01 | Covidien Lp | Directional anchoring mechanism, method and applications thereof |
US8905920B2 (en) | 2007-09-27 | 2014-12-09 | Covidien Lp | Bronchoscope adapter and method |
US9055881B2 (en) | 2004-04-26 | 2015-06-16 | Super Dimension Ltd. | System and method for image-based alignment of an endoscope |
EP1904027B1 (fr) * | 2005-06-23 | 2018-01-31 | Rhodia Chimie | Ingredient concentre pour le traitement et/ou modification de surfaces, et son utilisation dans des compositions cosmetiques |
US10582834B2 (en) | 2010-06-15 | 2020-03-10 | Covidien Lp | Locatable expandable working channel and method |
US10952593B2 (en) | 2014-06-10 | 2021-03-23 | Covidien Lp | Bronchoscope adapter |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0211553A (ja) * | 1988-05-04 | 1990-01-16 | Skw Trostberg Ag | N‐シアンエタンイミド酸エステルの製造方法 |
JPH07173128A (ja) * | 1993-12-17 | 1995-07-11 | Kuraray Co Ltd | N−シアノエタンイミド酸エステルの製造方法 |
JPH10130220A (ja) * | 1996-10-31 | 1998-05-19 | Nippon Carbide Ind Co Inc | O−アルキル−n−シアノイミデートの製造法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3219054A1 (de) | 1982-05-21 | 1983-11-24 | Skw Trostberg Ag, 8223 Trostberg | Verfahren zur erhoehung der lagerstabilitaet waessriger cyanamidloesungen |
JP3306312B2 (ja) | 1996-08-20 | 2002-07-24 | 日本カーバイド工業株式会社 | O−アルキル−n−シアノイミデートの製造法 |
-
1999
- 1999-09-09 WO PCT/JP1999/004896 patent/WO2000014056A1/ja not_active Application Discontinuation
- 1999-09-09 EP EP99943232A patent/EP1113002A4/en not_active Withdrawn
- 1999-09-09 US US09/786,629 patent/US6613925B1/en not_active Expired - Fee Related
- 1999-09-09 JP JP2000568816A patent/JP4049534B2/ja not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0211553A (ja) * | 1988-05-04 | 1990-01-16 | Skw Trostberg Ag | N‐シアンエタンイミド酸エステルの製造方法 |
JPH07173128A (ja) * | 1993-12-17 | 1995-07-11 | Kuraray Co Ltd | N−シアノエタンイミド酸エステルの製造方法 |
JPH10130220A (ja) * | 1996-10-31 | 1998-05-19 | Nippon Carbide Ind Co Inc | O−アルキル−n−シアノイミデートの製造法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1113002A4 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9089261B2 (en) | 2003-09-15 | 2015-07-28 | Covidien Lp | System of accessories for use with bronchoscopes |
US10383509B2 (en) | 2003-09-15 | 2019-08-20 | Covidien Lp | System of accessories for use with bronchoscopes |
US8663088B2 (en) | 2003-09-15 | 2014-03-04 | Covidien Lp | System of accessories for use with bronchoscopes |
US8764725B2 (en) | 2004-02-09 | 2014-07-01 | Covidien Lp | Directional anchoring mechanism, method and applications thereof |
US9055881B2 (en) | 2004-04-26 | 2015-06-16 | Super Dimension Ltd. | System and method for image-based alignment of an endoscope |
US10321803B2 (en) | 2004-04-26 | 2019-06-18 | Covidien Lp | System and method for image-based alignment of an endoscope |
EP1904027B1 (fr) * | 2005-06-23 | 2018-01-31 | Rhodia Chimie | Ingredient concentre pour le traitement et/ou modification de surfaces, et son utilisation dans des compositions cosmetiques |
US9668639B2 (en) | 2007-09-27 | 2017-06-06 | Covidien Lp | Bronchoscope adapter and method |
US9986895B2 (en) | 2007-09-27 | 2018-06-05 | Covidien Lp | Bronchoscope adapter and method |
US8905920B2 (en) | 2007-09-27 | 2014-12-09 | Covidien Lp | Bronchoscope adapter and method |
US10390686B2 (en) | 2007-09-27 | 2019-08-27 | Covidien Lp | Bronchoscope adapter and method |
US10980400B2 (en) | 2007-09-27 | 2021-04-20 | Covidien Lp | Bronchoscope adapter and method |
US10582834B2 (en) | 2010-06-15 | 2020-03-10 | Covidien Lp | Locatable expandable working channel and method |
US10952593B2 (en) | 2014-06-10 | 2021-03-23 | Covidien Lp | Bronchoscope adapter |
Also Published As
Publication number | Publication date |
---|---|
US6613925B1 (en) | 2003-09-02 |
EP1113002A1 (en) | 2001-07-04 |
JP4049534B2 (ja) | 2008-02-20 |
EP1113002A4 (en) | 2003-01-02 |
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