CN101391977A - Method for synthesizing 1,3-diiminoisoindole - Google Patents
Method for synthesizing 1,3-diiminoisoindole Download PDFInfo
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- CN101391977A CN101391977A CNA2008100797761A CN200810079776A CN101391977A CN 101391977 A CN101391977 A CN 101391977A CN A2008100797761 A CNA2008100797761 A CN A2008100797761A CN 200810079776 A CN200810079776 A CN 200810079776A CN 101391977 A CN101391977 A CN 101391977A
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- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 7
- 230000002194 synthesizing effect Effects 0.000 title 1
- 239000002904 solvent Substances 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000010189 synthetic method Methods 0.000 claims abstract description 22
- -1 alkali metal salt Chemical class 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052728 basic metal Inorganic materials 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical group [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- 150000003819 basic metal compounds Chemical class 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 229960004249 sodium acetate Drugs 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 229940039748 oxalate Drugs 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 150000001339 alkali metal compounds Chemical class 0.000 abstract 2
- 239000012530 fluid Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- MTKKGHVQPVOXIL-UHFFFAOYSA-N 3h-isoindol-1-amine Chemical group C1=CC=C2C(N)=NCC2=C1 MTKKGHVQPVOXIL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical class C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Indole Compounds (AREA)
Abstract
The invention discloses a synthetic method of 1, 3-di-iminoisoindoline, which comprises the steps that: 1) raw materials, o-phthalonitrile and a catalyst are mixed, added into an alcohols solvent in a reactor and stirred, ammonia gas is introduced, the temperature is raised to 50 to 60 DEG C, then the reaction is carried out for 4 to 6 hours at the temperature to obtain the reaction fluid; wherein, the dosage of the catalyst is 0.01 to 10 percent of the mass of the o-phthalonitrile, the mol ratio between the o-phthalonitrile and the solvent is 1:1 to 15, while the mol ratio between the o-phthalonitrile and the ammonia gas is 1:0.3 to 13, the catalyst is one or the combination of two or more than two of alkali metals and alkali metal compounds, and the alkali metal compounds are inorganic alkali metal salt or alkali metal alkali or organic alkali metal salt; and 2) the reaction fluid is treated with temperature reduction and filtering to obtain 1, 3-diiminoisoindoline products. The method has the advantages of high product yield, simple process, low cost, easy operation and less three wastes.
Description
Technical field
The present invention relates to a kind of 1, the synthetic method of 3-diimino isoindoline.
Background technology
1,3-diimino isoindoline (in other words 1,3-bis-imino isoindoline) is a kind of important organic synthesis intermediate, be mainly used in synthetic phthalocyanine and isoindoline class pigment, phthalocyanin dyestuff (the gorgeous blue IFG of phthalocyanin), also can be used for synthetic tetraazatetradecane porphyrin, with 1,3,4-thiadiazoles reaction forms heterocyclic system and be that part synthesizes metal complex with it.Existing preparation 1, the method of 3-diimino isoindoline mainly is to be that emulsifying agent, ammonium molybdate are catalyzer with stearic acid and oleic acid, urea and Tetra hydro Phthalic anhydride are through imidoization, condensation reaction takes place in the presence of ammonium nitrate then obtain 1, the nitrate of 3-bis-imino isoindoline obtains target product with the sodium hydroxide neutralization at last.Above method all exists yield not high, produces a large amount of waste water and complicated operation, condition harshness, problems such as three wastes difficult treatment.CN1884285A discloses a kind of copper phthalocyanine liquid solid phase mixed type continuous reactor and technology thereof, this reactor is to drop into phthalic anhydride, urea, cuprous chloride and little amount of catalyst continuously, are uninterruptedly produced copper phthalocyanine through copper phthalocyanine liquid solid phase mixed type continuous reactor equipment through automatic feeder by setup parameter, it is characterized in that: liquid-solid phase segmentation reaction, the liquid phase section adopts urea to make solvent, and product mainly is 1-imino-isoindoline and 1,3-diimino isoindoline.This technology is for how improving yield, simplifying the technical scheme that synthesis technique does not provide directiveness.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of 1, the synthetic method of 3-diimino isoindoline, and this synthetic method yield height, technology is simple, low cost, and the three wastes are few.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of 1, the synthetic method of 3-diimino isoindoline, its technical scheme is that described synthetic method comprises the steps: 1. with raw material phthalonitrile and catalyst mix, add in the alcoholic solvent in the reactor, stir, feed ammonia, be warming up to 50 ℃～60 ℃, under this temperature, reacted 4～6 hours, and obtained reaction solution; Wherein, catalyst consumption is 0.01%～10% of a phthalonitrile quality (weight), the mol ratio of phthalonitrile and solvent is 1: 1～15, the mol ratio of phthalonitrile and ammonia is 1: 0.3～13, catalyzer is the wherein a kind of material in basic metal and the basic metal compounds or the combination of two kinds of materials or two or more materials, and the basic metal compounds is inorganic alkaline metal salt or alkali-metal alkali or organic alkali metal salt; 2. above-mentioned reaction solution cooling is filtered, obtain 1,3-diimino isoindoline product.
In the technique scheme, carry out step 2. before, preferably with above-mentioned reaction solution elder generation distilling off solvent, and then cooling filters, the solvent that distills out can recycle.Above-mentioned catalyzer can be inorganic alkaline metal salt, and catalyzer can be selected the wherein a kind of material in alkaline carbonate and the alkali metal hydrocarbonate or the combination of two kinds of materials or two or more materials for use.Above-mentioned catalyzer can be basic metal, can select sodium Metal 99.5 etc. for use.Above-mentioned catalyzer can be alkali-metal alkali, and catalyzer can be selected wherein a kind of in potassium hydroxide and the sodium hydroxide or the combination of the two for use.Above-mentioned inorganic alkaline metal salt as catalyzer can be salt of wormwood, sodium bicarbonate etc., and catalyzer can be selected wherein a kind of in salt of wormwood and the sodium bicarbonate or the combination of the two for use.Above-mentioned organic alkali metal salt as catalyzer can be alkali metal formate, alkali metal acetate, basic metal oxalate, basic metal alcohols salt etc., and catalyzer can be selected their the wherein a kind of material or the combination of two kinds of materials or two or more materials for use.Above-mentioned organic alkali metal salt as catalyzer can be sodium formiate, sodium-acetate, sodium methylate, sodium oxalate, sodium ethylate, potassium oxalate etc., and catalyzer can be selected their the wherein a kind of material or the combination of two kinds of materials or two or more materials for use.Above-mentioned solvent can for carbonatoms less than 10 alcohols or alcohol solution, solvent can be selected methyl alcohol, ethanol, ethylene glycol for use.Above-mentioned catalyst consumption can be 0.1%～5% of phthalonitrile quality, and the mol ratio of above-mentioned phthalonitrile and solvent is 1: 9～15, and the mol ratio of above-mentioned phthalonitrile and ammonia is 1: 1～3.
Synthetic method of the present invention makes 1, and the yield of 3-diimino isoindoline is 107%, and purity (content) is 97.5% (HPLC).Its yield height, technology is simple, and low cost is operated easyly, and the three wastes are few.
Embodiment
Embodiment 1:1, the synthetic method of 3-diimino isoindoline comprises the steps: 1. to add the methyl alcohol 68ml through drying treatment in the dry 250ml four-hole bottle of whipping appts is housed, raw material phthalonitrile 18g (140mmol) and sodium formiate 0.2g are mixed, add in the solvent methanol, stir, feed the about 6735ml of ammonia (density of ammonia under the normal conditions is 0.7081g/L), the flow of ammonia can be at 20～50L/h, slowly be warming up to 60 ℃, tail gas absorbs with dilute hydrochloric acid, reaction is 5.5 hours under this temperature, and reaction obtains reaction solution after finishing.The consumption proportion of above-mentioned each material is, the consumption of catalyzer sodium formiate is 1.1% of a phthalonitrile quality, and the mol ratio of phthalonitrile and solvent methanol is 1: 12, and the mol ratio of phthalonitrile and ammonia is 1: 2.2. with above-mentioned reaction solution distilling off solvent methyl alcohol, cooling (can down to 25 ℃ of room temperatures) is filtered, obtain 1 at last, 3-diimino isoindoline product (outward appearance: the off-white color crystallization) 19.2g, productive rate is 107%, recording fusing point is 195.6～197.1 ℃ (consistent with literature value), and purity (content) is 97.8% (HPLC).The solvent methanol that above-mentioned steps distills out in 2. can recycle.It is as follows to the present invention relates to the experimental equation formula:
Embodiment 2:1, the synthetic method of 3-diimino isoindoline comprises the steps: 1. to add the ethanol 486ml through drying treatment in the dry four-hole bottle of whipping appts is housed, raw material phthalonitrile 128g (1mol) and sodium hydroxide 1.5g are mixed, add in the etoh solvent, stir, feed the about 240.5L of ammonia, slowly be warming up to 50 ℃, reaction is 6 hours under this temperature, and reaction obtains reaction solution after finishing.The consumption proportion of above-mentioned each material is, the consumption of catalyzer sodium hydroxide is 1.1% of a phthalonitrile quality, and the mol ratio of phthalonitrile and etoh solvent is 1: 8.32, and the mol ratio of phthalonitrile and ammonia is 1: 10.2. with above-mentioned reaction solution distilling off solvent ethanol, cooling (can down to room temperature) is filtered, and obtains 1 at last, 3-diimino isoindoline product 135.7g, and productive rate is 106.1%, and recording fusing point is 194.7～196.2 ℃, and purity (content) is 97.1% (HPLC).The etoh solvent that above-mentioned steps distills out in 2. can recycle.
Embodiment 3: by embodiment 1 operation that feeds intake, different is to change methyl alcohol into ethanol 300ml, change sodium formiate into sodium hydroxide 1.5g, after reaction finishes, distillating filtering gets product 19.09g, and productive rate is 106.1%, content is 98.1% (HPLC), and recording fusing point is 194.7～196.2 ℃ (consistent with literature value).
Embodiment 4: by embodiment 1 operation that feeds intake, different is that methyl alcohol is changed into ethylene glycol and changes sodium formiate into sodium methylate, after reaction finishes, distillating filtering gets product 19.18g, and productive rate is 106.6%, content is 98%, and fusing point is 195.8～197.1 ℃ (consistent with literature value).
Embodiment 5: by embodiment 1 operation that feeds intake, different is to change sodium formiate 0.2g into sodium Metal 99.5 0.1g, after reaction finishes, distillating filtering gets product 19.31g, and productive rate is 107.3%, purity (content) is 97.6% (HPLC), and fusing point is 195.1～197.6 ℃ (consistent with literature value).
Embodiment 6:1,1. the synthetic method of 3-diimino isoindoline comprises the steps: raw material phthalonitrile and catalyst mix, adds in the alcoholic solvent, stirs, and feeds ammonia, is warming up to 55 ℃, reaction is 4 hours under this temperature, obtains reaction solution; Wherein, catalyst consumption is 3% (can also select 0.01% or 5% or 10% for use) of phthalonitrile quality, the mol ratio of phthalonitrile and solvent is 1: 10 (can also select for use 1: 1 or 1: 5 or 1: 15), and the mol ratio of phthalonitrile and ammonia is 1: 3 (can also select for use 1: 0.3 or 1: 6 or 1: 13).Catalyzer is the wherein a kind of material in basic metal and the basic metal compounds or the combination of two kinds of materials or two or more materials, and the basic metal compounds is inorganic alkaline metal salt or alkali-metal alkali or organic alkali metal salt.2. with above-mentioned reaction solution distilling off solvent, cooling is filtered, and obtains 1,3-diimino isoindoline product.The solvent cycle that above-mentioned steps distills out in is 2. used.Productive rate is 106%～107%, and purity (content) is 97%～97.6% (HPLC), and fusing point is 194.5～197.6 ℃.
Above-mentioned catalyzer can be inorganic alkaline metal salt, and catalyzer can be selected the wherein a kind of material in alkaline carbonate and the alkali metal hydrocarbonate or the combination of two kinds of materials or two or more materials for use.Above-mentioned catalyzer can be basic metal, can select sodium Metal 99.5 etc. for use.Above-mentioned catalyzer can be alkali-metal alkali, and catalyzer can be selected wherein a kind of in potassium hydroxide and the sodium hydroxide or the combination of the two for use.Above-mentioned inorganic alkaline metal salt as catalyzer can be salt of wormwood, sodium bicarbonate etc., and catalyzer can be selected wherein a kind of in salt of wormwood and the sodium bicarbonate or the combination of the two for use.Above-mentioned organic alkali metal salt as catalyzer can be alkali metal formate, alkali metal acetate, basic metal oxalate, basic metal alcohols salt etc., and catalyzer can be selected their the wherein a kind of material or the combination of two kinds of materials or two or more materials for use.Above-mentioned organic alkali metal salt as catalyzer can be sodium formiate, sodium-acetate, sodium methylate, sodium oxalate, sodium ethylate, potassium oxalate etc., and catalyzer can be selected their the wherein a kind of material or the combination of two kinds of materials or two or more materials for use.Such as, catalyzer can be sodium Metal 99.5 and salt of wormwood and sodium ethylate three's combination.Also such as, catalyzer can be the combination of potassium hydroxide and sodium-acetate.Above-mentioned solvent can for carbonatoms less than 10 alcohols or alcohol solution, solvent can be selected methyl alcohol or ethanol or the ethylene glycol or their aqueous solution separately for use.
The various embodiments described above are that content of the present invention is further specified, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to the foregoing description, and all technology that realizes based on foregoing all belong to protection scope of the present invention.
Claims (10)
1, a kind of 1, the synthetic method of 3-diimino isoindoline is characterized in that described synthetic method comprises the steps:
1. with raw material phthalonitrile and catalyst mix, add in the alcoholic solvent in the reactor, stir, feed ammonia, be warming up to 50 ℃～60 ℃, under this temperature, reacted 4～6 hours, obtain reaction solution; Wherein, catalyst consumption is 0.01%～10% of a phthalonitrile quality, the mol ratio of phthalonitrile and solvent is 1: 1～15, the mol ratio of phthalonitrile and ammonia is 1: 0.3～13, catalyzer is the wherein a kind of material in basic metal and the basic metal compounds or the combination of two kinds of materials or two or more materials, and the basic metal compounds is inorganic alkaline metal salt or alkali-metal alkali or organic alkali metal salt;
2. above-mentioned reaction solution cooling is filtered, obtain 1,3-diimino isoindoline product.
2, synthetic method according to claim 1, it is characterized in that carrying out step 2. before, with above-mentioned reaction solution elder generation distilling off solvent, and then cooling filters, the solvent cycle that distills out is used.
3, synthetic method according to claim 1 is characterized in that above-mentioned catalyzer is an inorganic alkaline metal salt, and catalyzer is selected the wherein a kind of material in alkaline carbonate and the alkali metal hydrocarbonate or the combination of two kinds of materials or two or more materials for use.
4, synthetic method according to claim 1 is characterized in that above-mentioned catalyzer is a basic metal, selects sodium Metal 99.5 for use.
5, synthetic method according to claim 1 is characterized in that above-mentioned catalyzer is alkali-metal alkali, and catalyzer is selected wherein a kind of in potassium hydroxide and the sodium hydroxide or the combination of the two for use.
6, synthetic method according to claim 3 is characterized in that above-mentioned inorganic alkaline metal salt as catalyzer is salt of wormwood, sodium bicarbonate, and catalyzer is selected wherein a kind of in salt of wormwood and the sodium bicarbonate or the combination of the two for use.
7, synthetic method according to claim 1, it is characterized in that above-mentioned organic alkali metal salt as catalyzer is alkali metal formate, alkali metal acetate, basic metal oxalate, basic metal alcohols salt, catalyzer is selected their the wherein a kind of material or the combination of two kinds of materials or two or more materials for use.
8, synthetic method according to claim 7, it is characterized in that above-mentioned organic alkali metal salt as catalyzer is sodium formiate, sodium-acetate, sodium methylate, sodium oxalate, sodium ethylate, potassium oxalate, catalyzer is selected their the wherein a kind of material or the combination of two kinds of materials or two or more materials for use.
9, synthetic method according to claim 1 is characterized in that above-mentioned solvent is a carbonatoms less than 10 alcohols or alcohol solution, and solvent is selected methyl alcohol, ethanol, ethylene glycol for use.
10, synthetic method according to claim 1, it is characterized in that above-mentioned catalyst consumption is 0.1%～5% of a phthalonitrile quality, the mol ratio of above-mentioned phthalonitrile and solvent is 1: 9～15, and the mol ratio of above-mentioned phthalonitrile and ammonia is 1: 1～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100797761A CN101391977A (en) | 2008-11-17 | 2008-11-17 | Method for synthesizing 1,3-diiminoisoindole |
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| CNA2008100797761A CN101391977A (en) | 2008-11-17 | 2008-11-17 | Method for synthesizing 1,3-diiminoisoindole |
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