CN1263727C - Method of preparing 1-nitryl-2-ethyl anthraquinone - Google Patents
Method of preparing 1-nitryl-2-ethyl anthraquinone Download PDFInfo
- Publication number
- CN1263727C CN1263727C CN 03159203 CN03159203A CN1263727C CN 1263727 C CN1263727 C CN 1263727C CN 03159203 CN03159203 CN 03159203 CN 03159203 A CN03159203 A CN 03159203A CN 1263727 C CN1263727 C CN 1263727C
- Authority
- CN
- China
- Prior art keywords
- anthraquinone
- ethyl
- nitro
- ethyl anthraquinone
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- GROCBQWLHMMTLP-UHFFFAOYSA-N 2-ethyl-1-nitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C(CC)=CC=C3C(=O)C2=C1 GROCBQWLHMMTLP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- -1 filter Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 5
- 239000012043 crude product Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 2
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CUMCMYMKECWGHO-UHFFFAOYSA-N 3-methyl-1,2-oxazole Chemical compound CC=1C=CON=1 CUMCMYMKECWGHO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides new technology for preparing 1-nitro-2-ethyl anthraquinone by an organic solvent, which comprises the steps: 2-ethyl anthraquinone is dissolved in an organic solvent of halogenated hydrocarbon and is nitrified in fuming nitric acid and concentrated sulfuric acid; after the solvent is distilled off, a crude product of 1-nitro-2-ethyl anthraquinone is obtained through filtration, washing and drying; the crude product of 1-nitro-2-ethyl anthraquinone is heated in a sodium sulfite solution and a sodium hydroxide solution, and 1-nitro-2-ethyl anthraquinone with the purity of more than 99.8% is obtained through filtration, washing and drying. The method has the advantages of easy control of temperature, little amount of nitric acid, little side effect, easy treatment of the product, little amount of waste acid, etc. The solvent can be recycled, and the device needs no special material. The present invention has large industrial production value.
Description
Technical field the present invention relates to the preparation method of fine chemistry industry dyestuff intermediate.
Background technology 1-nitro-2-ethyl-anthraquinone is the important source material of preparation high-quality vat and dispersed dye; can also prepare anthraquinone [1 with it; 2-c] methyl-isoxazole; and then can prepare 1-amino-2-ethanoyl or 1; the dispersed dye that 4-diamino-2-ethanoyl anthraquinone etc. are important and the intermediate of vat dyes; therefore, has very important application prospect.
At present, the preparation method of domestic and international known 1-nitro-2～EAQ and homologue thereof mainly contains: the vitriol oil is done pure nitric acid nitrating method (chemical abstracts C.A.6,359 of medium
4), be that 2-ethyl-anthraquinone is dissolved in the vitriol oil, directly add pure nitric acid and carry out nitrated; It is that 2-ethyl-anthraquinone is dissolved in the vitriol oil that mixed acid nitrifying (chemical abstracts C.A.51,13833i＜1957 〉) is arranged in addition, adds nitration mixture and carries out nitrated; Also having high pressure nitrofication process (Pol.46428＜1960 〉), is after itself and hydrogen fluoride, saltpetre are mixed, to pressurize in autoclave and react.After pure nitric acid nitrating and mixed acid nitrifying carry out nitrated end of a period, need thin up just can separate out product, this can cause a large amount of spent acid.Simultaneously, because nitric acid is excessive more, side reaction and by product also can be more, purify for separation and bring bigger trouble.The high pressure nitrofication process is had relatively high expectations to the conversion unit material, has increased the cost of this method.
Summary of the invention the invention provides the novel process that a kind of organic solvent method prepares 1-nitro-2-ethyl-anthraquinone.At first the 2-ethyl-anthraquinone of 1 times of content more than 98.5% is dissolved in the 5-10 organic solvent (halohydrocarbon: methylene dichloride, ethylene dichloride, trichloroethane, chloroform, tetracol phenixin, chlorobenzene, dichlorobenzene) doubly, add 0.2-0.5 times of nitrosonitric acid, add the 0.5-5.0 times of vitriol oil again, reacted 2-12 hour down at 0-45 ℃, steaming solvent (in order to recycling) after reaction finishes filters, be washed to neutrality, drying makes the thick product of 1-nitro-2-ethyl-anthraquinone; Then, thick product is suspended in the sodium sulfite solution, the mol ratio that makes 1-nitro-2-ethyl-anthraquinone and S-WAT is 1: 1.1-2.5, add sodium hydroxide, the weight ratio that makes 1-nitro-2-ethyl-anthraquinone and sodium hydroxide is 1: 0.1-0.35 is heated to 90-98 ℃, reacted 4-10 hour, heat filtering, hot wash filter cake, drying obtains purity at the 1-nitro-2-ethyl-anthraquinone more than 99.8%.
Present method has easy temperature control system, and nitric acid dosage is few, and side reaction is few, and product is handled easily, and the spent acid amount is little, and equipment does not need advantages such as special substance, and bigger industrial value is arranged.
Embodiment
Embodiment 1
Get 4.8 gram 2-ethyl-anthraquinone and be dissolved in the methylene dichloride of 20-45 milliliter, add the nitric acid 0.4-1.5 milliliter and the 1.8-2.3 milliliter vitriol oil, 25-40 ℃ stirring reaction 2-8 hour.Reaction finishes, and steams methylene dichloride wherein, filters, and is washed to neutrality, drying.To make 1-nitro-2-ethyl-anthraquinone crude product and be suspended in the sodium sulfite solution, add sodium hydroxide solution in 90-98 ℃ of reaction 4-10 hour, filtered while hot, with an amount of hot wash several times, drying.Obtain pure 1～nitro-2-ethyl-anthraquinone 5.2g.Productive rate is about 93%.
Embodiment 2
Get 4.8 gram 2-ethyl-anthraquinone and be dissolved in the chlorobenzene of 45-70 milliliter, add the nitric acid 0.8-2.0 milliliter and the 1.0-1.8 milliliter vitriol oil, 0-20 ℃ stirring reaction 6-12 hour.Reaction finishes, and steams chlorobenzene wherein, filters, and is washed to neutrality, drying.To make 1-nitro-2-ethyl-anthraquinone crude product and be suspended in and contain in the 1.5-2.5g sodium sulfite solution, and add 0.15g left and right sides sodium hydroxide, solution is in 90-98 ℃ of reaction 4-10 hour, and filtered while hot is with an amount of hot wash filter cake several times, drying.Obtain pure 1-nitro-2-ethyl-anthraquinone 5.5g.Productive rate is about 98%.
Claims (2)
1, a kind of method for preparing 1-nitro-2-ethyl-anthraquinone by 2-ethyl-anthraquinone and nitric acid and sulfuric acid reaction, it is characterized in that this method is that the 2-ethyl-anthraquinone of 1 times of content more than 98.5% is dissolved in the 5-10 halohydrocarbon doubly, add 0.2-0.5 times of nitrosonitric acid, add the 0.5-5.0 times of vitriol oil again, reacted 2-12 hour down at 0-45 ℃, after reaction finishes, steam solvent, filter, filter cake is washed to neutrality, drying obtains the thick product of 1-nitro-2-ethyl-anthraquinone; Then thick product is suspended in the sodium sulfite solution, the mol ratio that makes 1-nitro-2-ethyl-anthraquinone and S-WAT is 1: 1.1-2.5, add sodium hydroxide, the weight ratio that makes 1-nitro-2-ethyl-anthraquinone and sodium hydroxide is 1: 0.1-0.35, be heated to 90-98 ℃, and reacted 4-10 hour, heat filtering, the hot wash filter cake, drying makes purity at the 1-nitro-2-ethyl-anthraquinone more than 99.8%.
2,, it is characterized in that halohydrocarbon is methylene dichloride, ethylene dichloride, trichloroethane, chloroform, tetracol phenixin, chlorobenzene or dichlorobenzene according to the preparation method of the described 1-nitro-2-ethyl-anthraquinone of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03159203 CN1263727C (en) | 2003-09-02 | 2003-09-02 | Method of preparing 1-nitryl-2-ethyl anthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03159203 CN1263727C (en) | 2003-09-02 | 2003-09-02 | Method of preparing 1-nitryl-2-ethyl anthraquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1519223A CN1519223A (en) | 2004-08-11 |
| CN1263727C true CN1263727C (en) | 2006-07-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03159203 Expired - Fee Related CN1263727C (en) | 2003-09-02 | 2003-09-02 | Method of preparing 1-nitryl-2-ethyl anthraquinone |
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| CN (1) | CN1263727C (en) |
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| CN104497617B (en) * | 2014-11-29 | 2016-08-24 | 萧县凯奇化工科技有限公司 | A kind of reducing dye palm fibre GG and preparation method |
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- 2003-09-02 CN CN 03159203 patent/CN1263727C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1519223A (en) | 2004-08-11 |
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Address after: 226131 chemical industry area, Ling Yang Industrial Complex Area, Linjiang New District, Haimen, Jiangsu Patentee after: Haimen Wuyang Chemical Co., Ltd. Patentee after: Dalian University of Technology Address before: 226103 Jiangsu Province Haimen City riverside town Patentee before: Haimen Jianbin No. 2 Chemical Plant Patentee before: Dalian University of Technology |
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