CN1113876C - Preparation of N-formyl morpholine, N-formyl piperazine and their homologues - Google Patents
Preparation of N-formyl morpholine, N-formyl piperazine and their homologues Download PDFInfo
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- CN1113876C CN1113876C CN 98121037 CN98121037A CN1113876C CN 1113876 C CN1113876 C CN 1113876C CN 98121037 CN98121037 CN 98121037 CN 98121037 A CN98121037 A CN 98121037A CN 1113876 C CN1113876 C CN 1113876C
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- formyl
- piperazine
- morpholine
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- salt
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Abstract
The present invention relates to N-formyl morpholine, N-formyl piperazine and a preparation method of homologous compounds thereof. The present invention is characterized in that morpholine, piperazine and organic acid react in the temperature of 60 to 220 DEG C, which generates corresponding salt; after the salt is dewatered, a product is obtained, and the product is fatty acid whose organic acid is C1 to C16. The present invention has the advantages of moderate reaction conditions, short time, simple reaction devices, high yield rate, no three waste, and easy purifying separation.
Description
The present invention relates to the chemical industry technology, the preparation method of a kind of N-formyl morpholine, N-formyl piperazine is provided especially.
N-formyl morpholine, N-formyl piperazine have a lot of use in organic synthesis, can be used as reaction raw materials and also can be used as reaction intermediate, and the method for existing preparation N-formyl morpholine, N-formyl piperazine mainly can reduce following three kinds:
1. in the presence of catalyzer, carry out carbonylation reaction with CO, this method need be carried out under High Temperature High Pressure, and catalyzer is also relatively more expensive, as Jpn.Kokai Tokkyo Koho JP 8242,660;
2. contain the acyl group permutoid reaction of acyl compounds with dimethyl formamide etc., this is a reasonable reaction, but the required reagent of reaction itself is very expensive, and solvent load is big, the three wastes are many, and the resultant purifying is difficult, as Kraus, and Menahem, A.et al, Synthesis, 361 (1973);
3. (1) morpholine and methyl-formiate reaction is carried out under the condition of base catalysis;
(2) methyl-formiate joins in the piperazine hexahydrate, and reflux heats up and boils off alcohol, underpressure distillation, and productive rate 78% is as " Chemical Industry Press under the organic volume of practical fine chemicals handbook.
The condition that above-mentioned these methods have is harsh, production cost is high, and the purifying products that has is difficult, and reaction yield is not too high again, and the raw material sources that also have are easy inadequately.
The object of the present invention is to provide the preparation method of a kind of N-formyl morpholine, N-formyl piperazine, its reaction conditions relaxes, and the time is short, and reaction unit is simple and easy, and productive rate is high and do not have the three wastes, and purifies and separates is easy.
The invention provides the preparation method of a kind of N-formyl morpholine, N-formyl piperazine, its reaction formula is as follows:
1.
2.
Generate corresponding salt with organic acid reactions such as morpholine, piperazine and formic acid, can obtain corresponding product behind the dehydration of salt.The available organic acid is C
1～C
16Lipid acid, the dehydration of its reaction can steam the method for water with direct heating, entrainer evaporations such as also available benzene, toluene, normal hexane, hexanaphthene, butanols or amylalcohol carry out.Dehydration technology is routinely carried out, and dewatering unit can be with common matrass, also available rectifying column.By underpressure distillation get final product high purity product.
Method of the present invention, reaction raw materials is simple, the reaction yield height, another product is a water, does not have other by product, the institute so that and product separation, do not pollute.Below by embodiment in detail the present invention is described in detail.
The preparation of embodiment 1 N-formyl morpholine
In having 250 milliliters common matrass of feeding device, add 78.1 gram morpholines and 52.3 gram (content is 88.0%) formic acid; oil bath is heated to 100～200 ℃; steam the water postcooling; underpressure distillation; obtain reaction product 105.7 grams; stratographic analysis wherein N-formyl morpholine content is 99.0%, is that benchmark calculates with the morpholine, and its molar yield is 90%.Gas chromatographic analysis is produced 103 gas chromatographs with Shanghai analytical instrument factory, chromatographic condition: PEG2 ten thousand packed columns, 2 meters of column lengths, 3 millimeters of internal diameters, 140 ℃ of column temperatures, 150 ℃ of flame ionization ditector temperature of vaporization chamber, carrier gas is a high pure nitrogen, and flow velocity is 15ml/min, hydrogen 80ml/min, air 200ml/min, quantitative with normalization method.
The preparation of embodiment 2 N-formyl piperazines
The formic acid that in having 250 milliliters of matrasss of feeding device, adds 194.4 gram piperazines and 52.3 grams (content 88.0%); add 20 milliliters of benzene; oil bath is heated to 60～150 ℃; steam the water postcooling, underpressure distillation obtains 102.4 products that restrain; use gas chromatographic analysis; the content of N-formyl piperazine wherein is 98.0%, is that benchmark calculates with the piperazine, and its molar yield is 87.7%.Chromatographiccondition, instrument are the same.
Embodiment 3
Preparation
In having 250 milliliters matrass of feeding device, add 76.8 gram palmitinic acids and 26.1 gram morpholines, 20 milliliters of benzene, oil bath is heated to about 100 ℃, azeotropic cools off after having taken off water, obtain crude product, can obtain product 82.8 grams with recrystallization reagent recrystallization, molar yield is 85%.
Embodiment 4
Preparation
In having 250 milliliters matrass of feeding device, add 76.8 gram palmitinic acids and 25.8 gram piperazines, 20 milliliters of benzene, oil bath is heated to about 100 ℃, azeotropic cools off after having taken off water, obtain crude product, can obtain product 82.6 grams with recrystallization reagent recrystallization, molar yield is 85%.
Claims (3)
1. the preparation method of N-formyl morpholine or N-formyl piperazine is characterized in that: at the corresponding salt that 60～220 ℃ of reactions generate, obtain corresponding product with morpholine or piperazine and organic acid behind the dehydration of salt, wherein said organic acid is C
1～C
16Lipid acid.
2. by the preparation method of the described N-formyl morpholine of claim 1, N-formyl piperazine, it is characterized in that: dehydration of salt steams the water method with direct heating.
3. by the preparation method of the described N-formyl morpholine of claim 1, N-formyl piperazine, it is characterized in that: dehydration of salt benzene,toluene,xylene, normal hexane, hexanaphthene, butanols or amylalcohol entrainer azeotropic dehydration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98121037 CN1113876C (en) | 1998-12-04 | 1998-12-04 | Preparation of N-formyl morpholine, N-formyl piperazine and their homologues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98121037 CN1113876C (en) | 1998-12-04 | 1998-12-04 | Preparation of N-formyl morpholine, N-formyl piperazine and their homologues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1256272A CN1256272A (en) | 2000-06-14 |
| CN1113876C true CN1113876C (en) | 2003-07-09 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98121037 Expired - Fee Related CN1113876C (en) | 1998-12-04 | 1998-12-04 | Preparation of N-formyl morpholine, N-formyl piperazine and their homologues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1113876C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262293B (en) * | 2014-09-18 | 2016-04-13 | 四川之江高新材料股份有限公司 | The preparation method of Low acid N-N-formyl morpholine N- |
| CN106746127A (en) * | 2016-08-19 | 2017-05-31 | 江苏好收成韦恩农化股份有限公司 | A kind of ethofumesate produces waste water reclaiming recovery process |
-
1998
- 1998-12-04 CN CN 98121037 patent/CN1113876C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1256272A (en) | 2000-06-14 |
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