CN100537544C - Method for preparing compound of 1, 2 (dodecyl) 4 hydroxide methylene - 3, 5 pyrazole - Google Patents
Method for preparing compound of 1, 2 (dodecyl) 4 hydroxide methylene - 3, 5 pyrazole Download PDFInfo
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- CN100537544C CN100537544C CNB2006101022018A CN200610102201A CN100537544C CN 100537544 C CN100537544 C CN 100537544C CN B2006101022018 A CNB2006101022018 A CN B2006101022018A CN 200610102201 A CN200610102201 A CN 200610102201A CN 100537544 C CN100537544 C CN 100537544C
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Abstract
This invention discloses a method for preparing 1, 2-di (dodecyl)-4-hydroxymethylene-3, 5-pyrazolin diketone compound. The method comprises: (1) adding dodecyl aldehyde, CaO, hydrazine hydrate and alcohol into a reactor, and reflux-reacting for 1-2 h to obtain intermediate A; (2) reflux-reacting intermediate A with absolute ether and LiAlH4 for 1-2 h, and neutralizing to obtain intermediate B; (3) reflux-reacting intermediate B with NaH and diethyl malonate in an organic solvent for 4-5 h, removing ethanol, and neutralizing to obtain intermediate C; (4) reacting intermediate C and ethylorthoformate in acetic anhydride at 70-90 deg.C for 2-3 h to obtain 1,2-di(dodecyl)-4-hydroxymethylene-3,5-pyrazolin diketone compound. This method has such advantages as advanced process, simple post-treatment and high product purity.
Description
Technical field
The present invention relates to a kind of preparation method of pyrazoline cyclohexadione compounds, particularly a kind of 1 of thermally developable material that is used for, 2-two (dodecyl)-4-hydroxyl methene-3, the preparation method of 5-pyrazoline dione compounds.
Background technology
As everyone knows, with in the nucleator, a kind of pyrazoline derovatives is arranged at various types of thermally developable materials, its structural formula is as follows:
This compound appears on the Japanese Patent of calendar year 2001 the earliest, its patent No. is JP2001209144, this patent is one piece and uses patent, disclose this compound and be used for thermally developable material as a kind of nucleator, but do not disclose the synthetic of this compound, relevant synthetic method is not seen any disclosed document and patent yet.
Summary of the invention
It is a kind of 1 that problem to be solved by this invention provides, 2-two (dodecyl)-4-hydroxyl methene-3, and the preparation method of 5-pyrazoline dione compounds, this preparation method's technology is simple, the product yield height.
The technical scheme that addresses the above problem is:
A kind of 1,2-two (dodecyl)-4-hydroxyl methene-3, the preparation method of 5-pyrazoline dione compounds is characterized in that, this preparation method may further comprise the steps:
1. add lauric aldehyde, calcium oxide, hydrazine hydrate and alcohol in reaction vessel, back flow reaction 1～2 hour obtains intermediate A;
2. intermediate A and anhydrous diethyl ether and lithium aluminum hydride back flow reaction are 1～2 hour, and neutralization obtains intermediate B;
3. intermediate B and sodium hydride, diethyl malonate back flow reaction 4～5 hours in organic solvent is removed the ethanol of generation, and neutralization obtains intermediate C;
4. intermediate C and triethyl orthoformate reacted in aceticanhydride 2～3 hours, and temperature of reaction is 70～90 ℃, obtained 1,2-two (dodecyl)-4-hydroxyl methene-3,5-pyrazoline dione compounds.
Above-mentioned 1,2-two (dodecyl)-4-hydroxyl methene-3, the preparation method of 5-pyrazoline dione compounds, described alcohol is methyl alcohol or ethanol.
Above-mentioned 1,2-two (dodecyl)-4-hydroxyl methene-3, the preparation method of 5-pyrazoline dione compounds, described organic solvent is chlorobenzene, toluene or dimethylbenzene.
2. above-mentioned 1,2-two (dodecyl)-4-hydroxyl methene-3, the preparation method of 5-pyrazoline dione compounds, described alcohol adopts dehydrated alcohol, and described organic solvent adopts chlorobenzene.
This preparation method's concrete reaction formula is as follows:
Beneficial effect
Preparation method provided by the invention, the synthesis technique advanced person, aftertreatment is simple, the product purity height that obtains.
Embodiment
The present invention is further illustrated below in conjunction with specific examples.
Embodiment 1
In the 1000mL there-necked flask, add 105 milliliters of lauric aldehyde, calcium oxide 45 grams, 15 milliliters of hydrazine hydrates (content 85%) and dehydrated alcohol 120mL, back flow reaction 2 hours, cooling is separated out 64 gram intermediate A, yield 73%;
64 gram intermediate A and 17.5 gram lithium aluminum hydrides back flow reaction 2 hours in 600 milliliters of anhydrous diethyl ethers add 10% aqueous sodium hydroxide solution and emit up to no obvious hydrogen, cool off, and separate out 60 and restrain white solids, are intermediate B, yield 93%;
60 gram intermediate B and 17.5 restrain 30% sodium hydride, 39 milliliters of diethyl malonates back flow reaction 5 hours in 140 milliliters of chlorobenzenes, remove the ethanol that generates in the reaction under reduced pressure, extract with 265 milliliters of methylene dichloride and 265 ml waters, adding 2N hydrochloric acid accent pH value in the extraction liquid is 4, separate out 43 gram intermediate C, yield 60%;
34 gram intermediate C and 40 milliliters of triethyl orthoformates reacted 2 hours in 80 milliliters of aceticanhydrides, and temperature of reaction is 70 ℃, removes excessive aceticanhydride under reduced pressure, and white crystals is separated out in cooling, filtered, and obtained 16.3 gram NA-1, yield 45%.
Ultimate analysis:
Theoretical value: C%:72.41, H%:11.21, N%:6.03;
Measured value: C%:72.31, H%:11.16, N%:6.13.
1H-NMR:d, 0.9 (6H, the CH3 on the dodecyl), 1.28 (32H, the CH2 on the dodecyl), 1.58 (4H, the CH on the dodecyl
2), 2.35 (4H, the CH on the dodecyl
2), 6.60 (1H, the hydrogen on the methene).
Embodiment 2
In the 500mL there-necked flask, add 53 milliliters of lauric aldehyde, calcium oxide 23 grams, 8 milliliters of hydrazine hydrates (content 85%) and methyl alcohol 80mL, back flow reaction 1.5 hours, cooling is separated out 30 gram intermediate A, yield 68%;
30 gram intermediate A and 8.4 gram lithium aluminum hydrides back flow reaction 1 hour in 250 milliliters of anhydrous diethyl ethers add 15% potassium hydroxide aqueous solution and emit up to no obvious hydrogen, cool off, and separate out 28 and restrain white solids, are intermediate B, yield 92%;
The sodium hydride of 28 gram intermediate B and 8.4 grams 30%, 18 milliliters of diethyl malonates were 70 milliliters of reflux in toluene reactions 4.5 hours, remove the ethanol that generates in the reaction under reduced pressure, extract with 120 milliliters of trichloromethanes and 120 ml waters, adding 1N sulfuric acid accent pH value in the extraction liquid is 4.5, separate out 19.7 gram intermediate C, yield 59%;
17 gram intermediate C and 20 milliliters of triethyl orthoformates reacted 2.5 hours in 40 milliliters of aceticanhydrides, and temperature of reaction is 80 ℃, removes excessive aceticanhydride under reduced pressure, and white crystals is separated out in cooling, filtered, and obtained 7.8 gram NA-1, yield 43%.
Ultimate analysis:
Theoretical value: C%:72.41, H%:11.21, N%:6.03;
Measured value: C%:72.38, H%:11.17, N%:6.33.
1H-NMR:d, 0.9 (6H, the CH on the dodecyl
3), 1.28 (32H, the CH on the dodecyl
2), 1.58 (4H, the CH on the dodecyl
2), 2.35 (4H, the CH on the dodecyl
2), 6.60 (1H, the hydrogen on the methene).
Embodiment 3
In the 500mL there-necked flask, add 60 milliliters of lauric aldehyde, calcium oxide 26 grams, 10 milliliters of hydrazine hydrates (content 85%) and dehydrated alcohol 70mL, back flow reaction 1 hour, cooling is separated out 35 gram intermediate A, yield 70%;
35 gram intermediate A and 10 gram lithium aluminum hydrides back flow reaction 2 hours in 350 milliliters of anhydrous diethyl ethers add 10% aqueous sodium hydroxide solution and emit up to no obvious hydrogen, cool off, and separate out 32 and restrain white solids, are intermediate B, yield 91%;
32 gram intermediate B and 10 restrain 30% sodium hydride, 21 milliliters of diethyl malonates back flow reaction 4 hours in 80 milliliters of dimethylbenzene, remove the ethanol that generates in the reaction under reduced pressure, extract with 150 ml n-hexanes and 100 ml waters, the glacial acetic acid of adding 50% accent pH value is 5 in the extraction liquid, separate out 22 gram intermediate C, yield 58%;
17 gram intermediate C and 20 milliliters of triethyl orthoformates reacted 3 hours in 40 milliliters of aceticanhydrides, and temperature of reaction is 90 ℃, removes excessive aceticanhydride under reduced pressure, and white crystals is separated out in cooling, filtered, and obtained 8 gram NA-1, yield 44%.
Ultimate analysis:
Theoretical value: C%:72.41, H%:11.21, N%:6.03;
Measured value: C%:72.47, H%:11.26, N%:5.98.
1H-NMR:d, 0.9 (6H, the CH on the dodecyl
3), 1.28 (32H, the CH on the dodecyl
2), 1.58 (4H, the CH on the dodecyl
2), 2.35 (4H, the CH on the dodecyl
2), 6.60 (1H, the hydrogen on the methene).
Embodiment 4
In the 500mL there-necked flask, add 80 milliliters of lauric aldehyde, calcium oxide 35 grams, 12 milliliters of hydrazine hydrates (content 85%) and methyl alcohol 120mL, back flow reaction 2 hours, cooling is separated out 46 gram intermediate A, yield 69%;
46 gram intermediate A and 13 gram lithium aluminum hydrides back flow reaction 1.5 hours in 450 milliliters of anhydrous diethyl ethers add 15% potassium hydroxide aqueous solution and emit up to no obvious hydrogen, cool off, and separate out 41 and restrain white solids, are intermediate B, yield 89%;
41 gram intermediate B and 12 restrain 30% sodium hydride, 27 milliliters of diethyl malonates back flow reaction 4 hours in 100 milliliters of chlorobenzenes, remove the ethanol that generates in the reaction under reduced pressure, extract with 180 milliliters of methylene dichloride and 120 ml waters, adding 2N hydrochloric acid accent pH value in the extraction liquid is 4, separate out 29 gram intermediate C, yield 59%;
17 gram intermediate C and 20 milliliters of triethyl orthoformates reacted 3 hours in 40 milliliters of aceticanhydrides, and temperature of reaction is 75 ℃, removes excessive aceticanhydride under reduced pressure, and white crystals is separated out in cooling, filtered, and obtained 7.4 gram NA-1, yield 41%.
Ultimate analysis:
Theoretical value: C%:72.41, H%:11.21, N%:6.03;
Measured value: C%:72.53, H%:11.19, N%:6.15.
1H-NMR:d, 0.9 (6H, the CH on the dodecyl
3), 1.28 (32H, the CH on the dodecyl
2), 1.58 (4H, the CH on the dodecyl
2), 2.35 (4H, the CH on the dodecyl
2), 6.60 (1H, the hydrogen on the methene).
Claims (3)
1.1 the preparation method of 2-two (dodecyl)-4-hydroxyl methene-3,5-pyrazoline dione compounds is characterized in that it may further comprise the steps:
1. add lauric aldehyde, calcium oxide, hydrazine hydrate and alcohol in reaction vessel, back flow reaction 1～2 hour obtains intermediate A;
(n)C
11H
23—CH＝＝N—N＝＝CH—C
11H
23(n)；
2. intermediate A and anhydrous diethyl ether and lithium aluminum hydride back flow reaction are 1～2 hour, and neutralization obtains intermediate B:
(n)C
12H
25—NH—NH—C
12H
25(n)
3. intermediate B and sodium hydride, diethyl malonate back flow reaction 4～5 hours in organic solvent is removed the ethanol of generation, and neutralization obtains intermediate C:
4. intermediate C and triethyl orthoformate reacted in aceticanhydride 2～3 hours, and temperature of reaction is 70～90 ℃, obtained 1,2-two (dodecyl)-4-hydroxyl methene-3,5-pyrazoline dione compounds:
2. preparation method according to claim 1 is characterized in that, described alcohol is methyl alcohol or ethanol.
3. preparation method according to claim 1 and 2 is characterized in that, described organic solvent is chlorobenzene, toluene or dimethylbenzene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101022018A CN100537544C (en) | 2006-11-30 | 2006-11-30 | Method for preparing compound of 1, 2 (dodecyl) 4 hydroxide methylene - 3, 5 pyrazole |
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|---|---|---|---|
| CNB2006101022018A CN100537544C (en) | 2006-11-30 | 2006-11-30 | Method for preparing compound of 1, 2 (dodecyl) 4 hydroxide methylene - 3, 5 pyrazole |
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|---|---|
| CN1958573A CN1958573A (en) | 2007-05-09 |
| CN100537544C true CN100537544C (en) | 2009-09-09 |
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| CNB2006101022018A Expired - Fee Related CN100537544C (en) | 2006-11-30 | 2006-11-30 | Method for preparing compound of 1, 2 (dodecyl) 4 hydroxide methylene - 3, 5 pyrazole |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654130A (en) * | 1996-03-14 | 1997-08-05 | Minnesota Mining And Manufacturing Company | 2-substituted malondialdehyde compounds as co-developers for black-and-white photothermographic and thermographic elements |
| JP2000284397A (en) * | 1999-03-30 | 2000-10-13 | Fuji Photo Film Co Ltd | Heat developable photosensitive material |
| EP1258774A2 (en) * | 2001-05-08 | 2002-11-20 | Konica Corporation | Photothermographic recording material |
| JP2003140298A (en) * | 2001-10-31 | 2003-05-14 | Fuji Photo Film Co Ltd | Heat developable photosensitive material |
-
2006
- 2006-11-30 CN CNB2006101022018A patent/CN100537544C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654130A (en) * | 1996-03-14 | 1997-08-05 | Minnesota Mining And Manufacturing Company | 2-substituted malondialdehyde compounds as co-developers for black-and-white photothermographic and thermographic elements |
| JP2000284397A (en) * | 1999-03-30 | 2000-10-13 | Fuji Photo Film Co Ltd | Heat developable photosensitive material |
| EP1258774A2 (en) * | 2001-05-08 | 2002-11-20 | Konica Corporation | Photothermographic recording material |
| JP2003140298A (en) * | 2001-10-31 | 2003-05-14 | Fuji Photo Film Co Ltd | Heat developable photosensitive material |
Non-Patent Citations (2)
| Title |
|---|
| 肼与羰基化合物的反应及其机理研究. 赵建霞.山东师范大学硕士学位论文. 2006 |
| 肼与羰基化合物的反应及其机理研究. 赵建霞.山东师范大学硕士学位论文. 2006 * |
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Effective date of registration: 20110620 Address after: 071054 Kennan street, Hebei, Baoding, No. 6 Co-patentee after: Baoding Lucky Chemical Co., Ltd. Patentee after: Chinese Lekai Film Group Co Address before: 071054 Kennan street, Hebei, Baoding, No. 6 Patentee before: Chinese Lekai Film Group Co |
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Address after: South Street, New District Hebei city of Baoding province Chinese lucky number 6 Patentee after: China Lucky Group Corporation Patentee after: Baoding Lucky Chemical Co., Ltd. Address before: 071054 Kennan street, Hebei, Baoding, No. 6 Patentee before: Chinese Lekai Film Group Co Patentee before: Baoding Lucky Chemical Co., Ltd. |
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