CN1403441A - Prepn of propane diamide compound - Google Patents
Prepn of propane diamide compound Download PDFInfo
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- CN1403441A CN1403441A CN 01130745 CN01130745A CN1403441A CN 1403441 A CN1403441 A CN 1403441A CN 01130745 CN01130745 CN 01130745 CN 01130745 A CN01130745 A CN 01130745A CN 1403441 A CN1403441 A CN 1403441A
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- malonamide
- phosphorus trichloride
- benzene
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Abstract
The present invention provides the preparation process of propane diamide compound. The propane diamide compound is prepared through adding malonic acid, amine and solvent, heating to 60-65 deg.c dropping phosphor trichloride and reaction at the said temperature for 1.5-2 hr. The general reaction expression is 2RNH2+HOOCCH2COOH+PCl3-R-NHCOCH2COLNH-R+H3PO3+HCl. The preparation process of present invention has short reaction period, low reaction temperature and high yield. The propane diamide compound product can be used to release compound parent substance for development inhibitor and development promoter.
Description
Relates to the field of
The present invention relates to a process for producing a malonamide compound, and more particularly to a process for producing a malonamide compound used for a development inhibitor releasing compound precursor and a development accelerator releasing compound precursor for photography.
Background
As is well known, among functional compounds for photography, there is a class of compounds in which a malonamide compound is a parent, and their parent structure can be represented by the following general formula (I): R-NHCOCH2CONH-R
(I)
The compound shown in the general formula (I) is generally prepared by reacting malonic acid with acyl chloride such as thionyl chloride to prepare malonyl chloride, and then reacting the malonyl chloride with arylamine or alkylamine by two steps; or by exchange reaction of diethyl malonate with aromatic amines or alkyl amines as described in us patent 4095984. The former method needs to use thionyl chloride and other acyl chloridizing agents to prepare malonyl chloride, has long reaction time and strong corrosivity, is greatly influenced by natural conditions such as air humidity, and is generally not suitable for use; the latter method generally requires higher reaction temperature, longer reaction time and lower yield.
Objects of the invention
A novel process for synthesizing a malonamide compound, particularly a malonamide compound used as a developer-releasing compound precursor and a developer-releasing accelerator precursor for photography, is provided which enables the synthesis reaction temperature of the malonamide compound to be reduced, the reaction time to be shortened, and the yield to be greatly improved, thereby enabling the production under milder conditions and reducing the cost.
The technical scheme provided by the invention is as follows: a preparation method of a malonamide compound is characterized in that malonic acid, amine and a solvent are added into a reactor, the mixture is heated to 60-65 ℃, phosphorus trichloride is dropwise added, and the mixture reacts for 1.5-2 hours at a constant temperature within the temperature range to obtain malonamide, wherein the general reaction formula of the malonamide is as follows: in the above formulaWherein X ═ H, Cl, Br, F:
L＝-COO-，-NHCO-，-O-，-COOCH(R2)COO-，R2＝C1-C3a linear alkyl group;
R1＝C8-C18straight chain alkyl or substituted alkyl.
The above amines are specifically exemplified as follows:the corresponding representative compounds of malonamide are as follows: 
in a preferred embodiment, the solvent is an organic solvent which does not react with phosphorus trichloride under the above reaction conditions, and is preferably benzene or chlorobenzene.
One preferred scheme is as follows: adding 4-chloro-3-amino-dodecyl benzoate, malonic acid and benzene into a reactor, heating to 60-65 ℃, dropwise adding phosphorus trichloride, continuously reacting at the temperature for 1.5-2 hours after dropwise adding, and evaporating a benzene solvent to obtain a white solid.
One preferred scheme is as follows: adding m-amino-n-octyl benzoate, malonic acid and chlorobenzene into a reactor, heating to 60-65 ℃, then dropwise adding phosphorus trichloride, continuing to react for 1.5-2 hours at the temperature after dropwise adding, and evaporating a chlorobenzene solvent to obtain a white solid.
One preferred scheme is that 4-chloro-3-amino-benzoic acid (α -dodecyl methyl acetate), malonic acid and benzene are added into a reactor, heated to 60-65 ℃, then phosphorus trichloride is added dropwise, the reaction is continued at the temperature for 1.5-2 hours after the addition is finished, and the benzene solvent is evaporated to obtain a white solid.
Examples
Example 1:
synthesis of Compound (1)
170g of 4-chloro-3-amino-dodecyl benzoate, 26g of malonic acid and 1000ml of benzene are added into a 2000ml three-necked flask, the flask is heated to 60 ℃, 37.5ml of phosphorus trichloride is dripped within half an hour, the reaction is continued for 1.5 hours at the temperature after the dripping is finished, and the benzene solvent is distilled off to obtain 183g of white solid, the yield is 98 percent, and the melting point is 94-96 ℃.
The above compounds were synthesized under otherwise identical reaction conditions at temperatures controlled at 62 ℃ and 65 ℃ respectively, and the results were identical.
Results of elemental analysis
C H N
Theoretical value 65.868.033.75
(％)
Found value 66.057.973.57
(％)
Example 2:
synthesis of Compound (2)
24.9g of m-amino-n-octyl benzoate, 5.2g of malonic acid and 150ml of chlorobenzene are added into a 500ml three-necked flask, the mixture is heated to 62 ℃, 5.2ml of phosphorus trichloride is dripped within 1 hour, the reaction is continued for 2.0 hours after the dripping is finished, the chlorobenzene solvent is evaporated out, 26.9g of white solid is obtained, the yield is 95 percent, and the melting point is 72-75 ℃.
The above compounds were synthesized under otherwise identical reaction conditions at temperatures controlled at 60 ℃ and 65 ℃ respectively, and the results were identical.
Results of elemental analysis
C H N
Theoretical value 69.968.134.95
(％)
Found value 69.858.064.87
(％)
Example 3:
synthesis of Compound (3)
Adding 41.1g of 4-chloro-3-amino-benzoic acid (α -dodecyl methyl acetate), 5.2g of malonic acid and 180ml of benzene into a 500ml three-necked bottle, heating to 65 ℃, dropwise adding 5.2ml of phosphorus trichloride within 1 hour, continuing to react for 1.5 hours after dropwise adding, and evaporating the benzene solvent to obtain 40g of white solid, wherein the yield is 90 percent, and the melting point is 66-67 ℃.
The above compounds were synthesized under otherwise identical reaction conditions at temperatures controlled at 60 ℃ and 63 ℃ respectively, and the results were identical.
Results of elemental analysis
C H N
Theoretical value 63.307.633.14
(％)
Found value 63.157.573.32
(％)
Example 4:
synthesis of Compound (5)
42.3g of 4-chloro-3-amino-benzoyloctadecylamine, 5.2g of malonic acid and 190ml of benzene are added into a 500ml three-necked flask, the flask is heated to 65 ℃, 5.2ml of phosphorus trichloride is dropwise added within 1 hour, the reaction is continued for 2.0 hours after the dropwise addition is finished, and the benzene solvent is distilled off to obtain 43.7g of white solid, the yield is 96 percent, and the melting point is 86-87 ℃.
The above compounds were synthesized under otherwise identical reaction conditions at temperatures controlled at 62 ℃ and 60 ℃ respectively, and the results were identical.
Results of elemental analysis
C H N
Theoretical value 69.749.435.26
(％)
Found value 69.559.575.12
(％)
Has the advantages that:
for compound (1)', the data comparing the method provided using the present invention with the method provided using US patent US4095984 is as follows:
synthesis of Compound (1)
Reaction temperature and reaction time yield
The method provided by the invention has the reaction at 60-65 ℃ for 1.5-2 hours and 98%
The reaction is carried out for 2 hours at 4095984220℃ in U.S. Pat. No. 4
The provided method is carried out at 170 ℃ under reduced pressure for 10 hours 81 percent
From the above table it can be seen that the process of the present invention offers significant advantages in terms of reaction temperature, reaction time and yield over the process provided in US4095984, especially a 17% yield increase.
Claims (7)
1. A preparation method of a malonamide compound is characterized in that malonic acid, amine and a solvent are added into a reactor, the mixture is heated to 60-65 ℃, phosphorus trichloride is dropwise added, and the mixture reacts for 1.5-2 hours at a constant temperature within the temperature range to obtain malonamide, wherein the general reaction formula of the malonamide is as follows: in the above formulaWherein X ═ H, Cl, Br, F;
L＝-COO-，-NHCO-，-O-，-COOCH(R2)COO-，R2＝C1-C3a linear alkyl group;
R1＝C8-C18straight chain alkyl or substituted alkyl.
2. The method for synthesizing a malonamide compound according to claim 1, wherein the solvent is an organic solvent which does not react with phosphorus trichloride under the above reaction conditions.
3. The method for synthesizing a malonamide compound according to claim 2, wherein the solvent is benzene or chlorobenzene.
4. The method for synthesizing a malonamide compound according to claim 3,the amine is as follows:
5. the method for synthesizing the malonamide compound according to claim 1, wherein the 4-chloro-3-amino-dodecyl benzoate, malonic acid and benzene are added into a reactor, heated to 60 to 65 ℃, then phosphorus trichloride is added dropwise, the reaction is continued at the temperature for 1.5to 2 hours after the addition, and the benzene solvent is distilled off to obtain a white solid.
6. The method for synthesizing the malonamide compound according to claim 1, wherein the method comprises adding n-octyl meta-amino-benzoate, malonic acid and chlorobenzene into a reactor, heating to 60-65 ℃, dropwise adding phosphorus trichloride, reacting at the temperature for 1.5-2 hours after the dropwise adding is finished, and distilling off the chlorobenzene solvent to obtain a white solid.
7. The method for synthesizing the malonamide compound according to claim 1, wherein 4-chloro-3-amino-benzoic acid (α -dodecyl methyl acetate), malonic acid and benzene are added into a reactor, heated to 60 to 65 ℃, then phosphorus trichloride is added dropwise, the reaction is continued at the temperature for 1.5 to 2 hours after the addition of phosphorus trichloride is completed, and the benzene solvent is distilled off to obtain a white solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011307455A CN1164567C (en) | 2001-08-23 | 2001-08-23 | Prepn of propane diamide compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011307455A CN1164567C (en) | 2001-08-23 | 2001-08-23 | Prepn of propane diamide compound |
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| Publication Number | Publication Date |
|---|---|
| CN1403441A true CN1403441A (en) | 2003-03-19 |
| CN1164567C CN1164567C (en) | 2004-09-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011307455A Expired - Fee Related CN1164567C (en) | 2001-08-23 | 2001-08-23 | Prepn of propane diamide compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295571A (en) * | 2011-06-01 | 2011-12-28 | 郭建行 | Method for synthesis of amide through ammoxidation of methanol or formaldehyde |
-
2001
- 2001-08-23 CN CNB011307455A patent/CN1164567C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295571A (en) * | 2011-06-01 | 2011-12-28 | 郭建行 | Method for synthesis of amide through ammoxidation of methanol or formaldehyde |
| CN102295571B (en) * | 2011-06-01 | 2016-04-27 | 郭建行 | The method of methyl alcohol or ammonioformaldehyde oxidative synthesis acid amides |
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| Publication number | Publication date |
|---|---|
| CN1164567C (en) | 2004-09-01 |
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