CN102659580B - Preparation method and crystallization method of 2, 3, 5-tri-methyl hydroquinone diester new crystal - Google Patents
Preparation method and crystallization method of 2, 3, 5-tri-methyl hydroquinone diester new crystal Download PDFInfo
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- CN102659580B CN102659580B CN201210113838.2A CN201210113838A CN102659580B CN 102659580 B CN102659580 B CN 102659580B CN 201210113838 A CN201210113838 A CN 201210113838A CN 102659580 B CN102659580 B CN 102659580B
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- 239000013078 crystal Substances 0.000 title claims abstract description 41
- -1 2, 3, 5-tri-methyl hydroquinone diester Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000002425 crystallisation Methods 0.000 title abstract description 14
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 238000001228 spectrum Methods 0.000 claims abstract 2
- JXLWCZWBHZGUEE-UHFFFAOYSA-N (4-acetyloxy-2,3,5-trimethylphenyl) acetate Chemical compound CC(=O)OC1=CC(C)=C(OC(C)=O)C(C)=C1C JXLWCZWBHZGUEE-UHFFFAOYSA-N 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000006194 liquid suspension Substances 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 abstract description 6
- IWAOTYDFIQQFPL-UHFFFAOYSA-N acetic acid;2,3,5-trimethylbenzene-1,4-diol Chemical compound CC(O)=O.CC(O)=O.CC1=CC(O)=C(C)C(C)=C1O IWAOTYDFIQQFPL-UHFFFAOYSA-N 0.000 abstract 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001757 thermogravimetry curve Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical class C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a preparation method and a crystallization method of a 2, 3, 5-trimethylhydroquinone diacetate new crystal. The crystal uses a powder X ray diffraction atlas, a differential scanning calorimetric curve characteristic endothermic peak, a thermo-gravimetric analysis curve and an infrared light spectrum. The preparation method comprises the following steps: when the temperature is 50-80 DEG C, dissolving 2, 3, 5-trimethylhydroquinone diacetate of which the purity is larger than or equal to 97 percent into a C1-C3 low-molecular weight organic solvent to form solution, and the concentration of the 2, 3, 5-trimethylhydroquinone diacetate in the organic solvent is 0.5-2.5 g/ml; cooling the solution to 30-40 DEG C; dropwise adding a melting-out agent of which the volume is 1-5 times of that of the organic solvent into a suspension; continuously agitating for 0.5-2 hours after the completion of dropwise adding; and separating and vacuum-drying to obtain the 2, 3, 5-tri-methyl hydroquinone diester type-B crystal. The degree of crystallinity of a product is high, the crystal is good in crystal habit, larger in grain size, smooth in crystal surface and higher in bulk density, the subsequent operation is facilitated in the crystallization process, and meanwhile, the quality of a 2, 3, 5-trimethylhydroquinone diacetate product is effectively improved.
Description
Invention field
The invention belongs to chemical engineering crystallization technique field, particularly a kind of crystallization method of preparing 1,4-diacetoxy-2,3,5-trimethylbenzene new crystal and improving the quality of products.
Background of invention
1,4-diacetoxy-2,3,5-trimethylbenzene, full name TMHQ-DA, English name trimethylhydroquinone diacetate, is called again Isosorbide-5-Nitrae-diacetoxy-2,3,5-trimethylbenzene, molecular formula is C
13h
160
4, molar mass is 236.268gmol
-1, structural formula is as follows:
1,4-diacetoxy-2,3,5-trimethylbenzene is synthesising complex E (V
e) a kind of important intermediate, be also simultaneously active chroman compounds on the pharmacology important intermediate in synthetic, and as antioxidant, use widely.V
ein fields such as medicine, food, healthcare products, makeup, livestock industry, be widely used.V
ebecome of many uses on world market, the great main vitamins kind of volume of production and marketing, same V
c, V
athe three large pillar products that become together VITAMIN series, domestic and abroad market prospect is wide.
At present, more existing reports about 1,4-diacetoxy-2,3,5-trimethylbenzene synthetic method on domestic and foreign literature.US5969176, and in patent families, reported the synthesis technique that 1,4-diacetoxy-2,3,5-trimethylbenzene is different.In patent US5969176, in order to obtain the solid of 1,4-diacetoxy-2,3,5-trimethylbenzene, after reaction mixture is filtered, filtrate is mixed with frozen water, suction filtration at 5 ℃, obtain 2, the purity of 3,5-Trimethylhydroquinone diester product is 94% left and right, and yield is 95% left and right.These methods are lowered the temperature reaction product, and add a large amount of dissolved agent (as, water etc.), and to promote 1,4-diacetoxy-2,3,5-trimethylbenzene crystallization, although the yield of product is higher, purity is not very high.And in order to obtain enough colds, energy consuming ratio is more serious.
In EP0916642 and patent families, reported the method for 1,4-diacetoxy-2,3,5-trimethylbenzene crystallization in the mixed solvent of acetic acid and water.In patent EP0916642, the mass ratio of acetic acid and water is 40/60～70/30, and strength of solution is 10～35% (massfractions), crystallization terminal temperature is 10～18 ℃, 2,3, the purity of 5-Trimethylhydroquinone diester is up to 99.9%, but yield is only 60% left and right.These methods are in order to improve the purity of 1,4-diacetoxy-2,3,5-trimethylbenzene product, the starting point concentration that has reduced solution, solvent-oil ratio is larger, and the solvent treatment ability of unit volume is declined, meanwhile, magma amount to be separated is larger, has increased the load of centrifugation.And the yield that finally obtains product is lower and unstable, the circulation ratio of experiment is not strong.
Outside upper performance constraint, checking by experiment, in document, the product ubiquity crystal size of the whole bag of tricks gained is less, easily coalescent, magma is sticky, filtration difficulty, and mother liquor contains serious problem, these shortcomings can have a strong impact on the purity of final 1,4-diacetoxy-2,3,5-trimethylbenzene product.As shown in Figure 6, PXRD as shown in Figure 7 for the SEM photo of the 1,4-diacetoxy-2,3,5-trimethylbenzene product obtaining according to method described in the patents such as US5969176, EP0916642.Above-mentioned crystallization method is difficult to " purity " and " yield " these two indexs to be optimized simultaneously.
Summary of the invention
The present invention is directed to the deficiency of existing crystallization technique, proposed a kind of crystallization method of preparing 1,4-diacetoxy-2,3,5-trimethylbenzene new crystal and improving the quality of products.
The new crystal of a kind of 1,4-diacetoxy-2,3,5-trimethylbenzene crystal of the present invention:
X-ray powder diffraction is in diffraction angle 2 θ=12.7 ± 0.2,13.8 ± 0.2,14.9 ± 0.2,15.7 ± 0.2,17.8 ± 0.2,18.6 ± 0.2,20.1 ± 0.2,20.4 ± 0.2,23.4 ± 0.2,24.1 ± 0.2,25.9 ± 0.2,27.2 ± 0.2,32.7 ± 0.2,33.5 ± 0.2,34.7 ± 0.2,36.6 ± 0.2,40.7 ± 0.2 and 42.5 ± 0.2 degree places have PXRD characteristic peak.As shown in Figure 1.
Poor formula scanning calorimetric curve has a DSC fusing endotherm(ic)peak at 110 ± 1 ℃.As shown in Figure 2.Test condition: 20～140 ℃, temperature rise rate is 5 ℃/min, protection nitrogen: 100ml/min.
Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before.As shown in Figure 3.Test condition: 30～300 ℃, temperature rise rate is 10 ℃/min, protection nitrogen: 20ml/min.
Infrared spectra is 3488 ± 2, and 3435 ± 2,2992 ± 2,2934 ± 2,2876 ± 2,2410 ± 2,2128 ± 2,2078 ± 2,2041 ± 2,1757 ± 2,1624 ± 2,1578 ± 2,1482 ± 2,1435 ± 2,1371 ± 2,1231 ± 2,1207 ± 2,1203 ± 2,1186 ± 2,1079 ± 2,1043 ± 2,1015 ± 2,916 ± 2,858 ± 2,824 ± 2,759 ± 2,734 ± 2,638 ± 2,593 ± 2,561 ± 2 and 531 ± 2cm
-1there is characteristic peak at place.As shown in Figure 4.
The new crystal of 1,4-diacetoxy-2,3,5-trimethylbenzene crystal of the present invention is named as crystal form B, and its preparation method is:
Any type of purity is more than or equal to 97% 1,4-diacetoxy-2,3,5-trimethylbenzene, is dissolved in C1～C3 lower molecular weight organic solvent and forms solution, temperature is 50～80 ℃, and 1,4-diacetoxy-2,3,5-trimethylbenzene is 0.5～2.5g/ml in the concentration of organic solvent; Then solution is cooled to 30～40 ℃; In suspension, drip dissolved agent again, the volume of dissolved agent is 1～5 times of organic solvent volume; After dropwising, dissolved agent continues to stir 0.5～2h; The solid-liquid suspension of gained is separated, and vacuum-drying, obtains 1,4-diacetoxy-2,3,5-trimethylbenzene Type B crystal.
Described C1～C3 lower molecular weight organic solvent is selected from a kind of of methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone or acetonitrile.
Described dissolved agent is water, normal hexane or hexanaphthene.The temperature of the dissolved agent adding is 30～40 ℃, and time for adding is 1～5h.
Described suspension after separating, the drying conditions of product is that temperature is that 40～60 ℃, vacuum tightness are 0.08～0.1MPa.
The preparation method's of 1,4-diacetoxy-2,3,5-trimethylbenzene crystal formation of the present invention advantage is that operational condition is simple and easy to control.By PXRD collection of illustrative plates and SEM photo, can confirm, product degree of crystallinity is high, the brilliant inveterate habit of crystal, and for bar-shaped, and granularity is large, plane of crystal is bright and clean, and bulk density is higher.These advantages are conducive to the subsequent operations (as filtered, washing and dry etc.) of crystallisation process, have also effectively improved the quality of 1,4-diacetoxy-2,3,5-trimethylbenzene product.
Accompanying drawing explanation
Fig. 1: the PXRD collection of illustrative plates of 1,4-diacetoxy-2,3,5-trimethylbenzene B crystal formation;
Fig. 2: the DSC collection of illustrative plates of 1,4-diacetoxy-2,3,5-trimethylbenzene B crystal formation;
Fig. 3: the TGA collection of illustrative plates of 1,4-diacetoxy-2,3,5-trimethylbenzene B crystal formation;
Fig. 4: the FTIR collection of illustrative plates of 1,4-diacetoxy-2,3,5-trimethylbenzene B crystal formation;
Fig. 5: the SEM photo of 1,4-diacetoxy-2,3,5-trimethylbenzene B crystal formation (amplifying 15 times);
Fig. 6: the SEM photo of the 1,4-diacetoxy-2,3,5-trimethylbenzene product that bibliographical information technique obtains (amplifying 100 times);
Fig. 7: the PXRD collection of illustrative plates of the 1,4-diacetoxy-2,3,5-trimethylbenzene product that bibliographical information technique obtains.
Embodiment
Embodiment 1:
By 50g purity, be 99.5% 2, 3, 5-Trimethylhydroquinone diester solid adds in 50ml methyl alcohol, be heated to 60 ℃, make its dissolve complete, then solution is cooled to 40 ℃, under agitation dropping temperature is the water 100ml of 40 ℃, time for adding is 1h, continue to stir 1h, the suspension that vacuum filtration is separating obtained, at 40 ℃, vacuum tightness is dry gained filter cake under 0.08MPa, obtain colourless bar-shaped 2, 3, 5-Trimethylhydroquinone diester Type B crystal 47.47g, its purity of gas chromatographic analysis is 99.8%, 2, 3, the yield of 5-Trimethylhydroquinone diester is 95.23%.Product degree of crystallinity is high, and crystal size is large, any surface finish, and bulk density is larger.The stereoscan photograph of product as shown in Figure 5.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.7, and 13.8,14.9,15.7,17.7,18.7,20.2,20.4,23.2,24.0,25.9,27.2,32.6,33.5,34.7,36.6,40.7 and 42.5 degree places have characteristic peak; DSC locates to have fusing endotherm(ic)peak at 110.64 ℃; Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before; FTIR collection of illustrative plates is 3490,3434, and 2993,2934,2877,2409,2128,2078,2040,1757,1624,1577,1481,1436,1371,1230,1207,1202,1186,1079,1043,1016,917,858,823,759,736,638,593,560 and 530cm
-1place has charateristic avsorption band.
Embodiment 2:
By 50g purity, be 99.5% 2, 3, 5-Trimethylhydroquinone diester solid adds in 100ml ethanol, be heated to 70 ℃, make its dissolve complete, then solution is cooled to 30 ℃, under agitation dropping temperature is the hexanaphthene 150ml of 30 ℃, time for adding is 2h, continue to stir 2h, the suspension that vacuum filtration is separating obtained, at 50 ℃, vacuum tightness is dry gained filter cake under 0.09MPa, obtain colourless bar-shaped 2, 3, 5-Trimethylhydroquinone diester Type B crystal 47.20g, its purity of gas chromatographic analysis is 99.9%, 2, 3, the yield of 5-Trimethylhydroquinone diester is 94.78%.Product degree of crystallinity is high, and crystal size is large, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.6, and 13.8,14.9,15.8,17.7,18.7,20.3,20.5,23.2,24.0,25.9,27.2,32.5,33.5,34.7,36.6,40.7 and 42.5 degree places have characteristic peak; DSC locates to have fusing endotherm(ic)peak at 110.87 ℃; Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before; FTIR collection of illustrative plates is 3489,3435, and 2992,2933,2876,2409,2128,2077,2040,1757,1624,1577,1482,1436,1371,1231,1207,1203,1186,1080,1043,1016,917,858,823,761,736,638,593,561 and 531cm
-1place has charateristic avsorption band.
Embodiment 3:
By 75g purity, be 99.0% 2, 3, 5-Trimethylhydroquinone diester solid adds in 50ml n-propyl alcohol, be heated to 80 ℃, make its dissolve complete, then solution is cooled to 35 ℃, under agitation dropping temperature is the normal hexane 100ml of 35 ℃, time for adding is 3h, continue to stir 1h, the suspension that vacuum filtration is separating obtained, at 60 ℃, vacuum tightness is dry gained filter cake under 0.1MPa, obtain colourless bar-shaped 2, 3, 5-Trimethylhydroquinone diester Type B crystal 69.94g, its purity of gas chromatographic analysis is 99.4%, 2, 3, the yield of 5-Trimethylhydroquinone diester is 93.63%.Product degree of crystallinity is high, and crystal size is large, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.5, and 13.7,14.9,15.6,17.8,18.7,20.2,20.4,23.2,24.0,25.9,27.3,32.6,33.5,34.7,36.6,40.7 and 42.5 degree places have characteristic peak; DSC locates to have fusing endotherm(ic)peak at 110.34 ℃; Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before; FTIR collection of illustrative plates is 3488,3433, and 2994,2934,2877,2409,2128,2078,2040,1757,1624,1576,1481,1436,1371,1230,1208,1203,1186,1079,1043,1016,917,858,823,759,736,639,593,562 and 530cm
-1place has charateristic avsorption band.
Embodiment 4:
By 125g purity, be 98.5% 2, 3, 5-Trimethylhydroquinone diester solid adds in 50ml acetonitrile, be heated to 80 ℃, make its dissolve complete, then solution is cooled to 38 ℃, under agitation dropping temperature is the water 250ml of 38 ℃, time for adding is 5h, continue to stir 1.5h, the suspension that vacuum filtration is separating obtained, at 55 ℃, vacuum tightness is dry gained filter cake under 0.1MPa, obtain colourless bar-shaped 2, 3, 5-Trimethylhydroquinone diester Type B crystal 120.28g, its purity of gas chromatographic analysis is 99.1%, 2, 3, the yield of 5-Trimethylhydroquinone diester is 96.81%.Product degree of crystallinity is high, and crystal size is large, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.7, and 13.8,14.9,15.7,17.7,18.7,20.3,20.5,23.2,24.0,25.9,27.2,32.6,33.5,34.7,36.6,40.7 and 42.5 degree places have characteristic peak; DSC locates to have fusing endotherm(ic)peak at 110.17 ℃; Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before; FTIR collection of illustrative plates is 3490,3434, and 2993,2934,2877,2409,2128,2078,2040,1757,1624,1577,1481,1436,1371,1230,1207,1202,1186,1079,1044,1016,917,858,823,759,736,638,594,560 and 529cm
-1place has charateristic avsorption band.
Embodiment 5:
By 100g purity, be 98% 2, 3, 5-Trimethylhydroquinone diester solid adds in 50ml acetone, be heated to 50 ℃, make its dissolve complete, then solution is cooled to 35 ℃, under agitation dropping temperature is the normal hexane 50ml of 35 ℃, time for adding is 1.5h, continue to stir 1h, the suspension that vacuum filtration is separating obtained, at 55 ℃, vacuum tightness is the lower dry gained filter cake of 0.09MPa, obtain colourless bar-shaped 2, 3, 5-Trimethylhydroquinone diester Type B crystal 87.53g, its purity of gas chromatographic analysis is 98.9%, 2, 3, the yield of 5-Trimethylhydroquinone diester is 88.33%.Product degree of crystallinity is high, and crystal size is large, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.8, and 13.8,14.9,15.6,17.7,18.7,20.1,20.3,23.2,24.0,25.9,27.2,32.6,33.7,34.8,36.6,40.7 and 42.7 degree places have characteristic peak; DSC locates to have fusing endotherm(ic)peak at 110.03 ℃; Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before; FTIR collection of illustrative plates is 3488,3435, and 2993,2934,2878,2409,2129,2078,2040,1758,1624,1577,1480,1436,1371,1233,1207,1202,1186,1079,1043,1016,918,858,823,759,735,638,592,562 and 531cm
-1place has charateristic avsorption band.
Embodiment 6:
By 90g purity, be 97% 2, 3, 5-Trimethylhydroquinone diester solid adds in 50ml Virahol, be heated to 80 ℃, make its dissolve complete, then solution is cooled to 36 ℃, under agitation dropping temperature is the hexanaphthene 50ml of 36 ℃, time for adding is 2h, continue to stir 0.5h, the suspension that vacuum filtration is separating obtained, at 50 ℃, vacuum tightness is dry gained filter cake under 0.08MPa, obtain 2, 3, 5-Trimethylhydroquinone diester Type B crystal 79.79g, its purity of gas chromatographic analysis is 98.4%, 2, 3, the yield of 5-Trimethylhydroquinone diester is 89.94%.Product degree of crystallinity is high, and crystal size is large, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.7, and 13.8,15.0,15.7,17.8,18.8,20.2,20.4,23.4,24.0,25.7,27.1,32.6,33.6,34.8,36.6,40.6 and 42.5 degree places have characteristic peak; DSC locates to have fusing endotherm(ic)peak at 109.83 ℃; Thermogravimetric analysis is presented at fusing endotherm(ic)peak and occurs there is no weightlessness before; FTIR collection of illustrative plates is 3486,3433, and 2992,2934,2875,2409,2128,2078,2039,1756,1624,1576,1480,1436,1370,1230,1207,1201,1186,1078,1043,1016,915,856,822,759,733,637,592,559 and 529cm
-1place has charateristic avsorption band.
The crystallization method that the present invention is open and proposition is prepared 1,4-diacetoxy-2,3,5-trimethylbenzene new crystal and improved the quality of products, those skilled in the art can be by using for reference content herein, and the links such as appropriate change raw material, processing parameter realize.Method of the present invention and product are described by preferred embodiment, person skilled obviously can be within not departing from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and content.
Claims (4)
1. the new crystal of 1,4-diacetoxy-2,3,5-trimethylbenzene, is characterized in that: X-ray powder diffraction is in diffraction angle 2 θ=12.7 ± 0.2,13.8 ± 0.2,14.9 ± 0.2,15.7 ± 0.2,17.8 ± 0.2,18.6 ± 0.2,20.1 ± 0.2,20.4 ± 0.2,23.4 ± 0.2,24.1 ± 0.2,25.9 ± 0.2,27.2 ± 0.2,32.7 ± 0.2,33.5 ± 0.2,34.7 ± 0.2,36.6 ± 0.2,40.7 ± 0.2 and 42.5 ± 0.2 degree places have PXRD characteristic peak; Differential scanning calorimetric curve has been located a fusing endothermic characteristics peak at 110 ± 1 ℃; Infared spectrum is 3488 ± 2, and 3435 ± 2,2992 ± 2,2934 ± 2,2876 ± 2,2410 ± 2,2128 ± 2,2078 ± 2,2041 ± 2,1757 ± 2,1624 ± 2,1578 ± 2,1482 ± 2,1435 ± 2,1371 ± 2,1231 ± 2,1207 ± 2,1203 ± 2,1186 ± 2,1079 ± 2,1043 ± 2,1015 ± 2,916 ± 2,858 ± 2,824 ± 2,759 ± 2,734 ± 2,638 ± 2,593 ± 2,561 ± 2 and 531 ± 2cm
-1there is charateristic avsorption band at place.
2. prepare as claimed in claim 12 for one kind, 3, the method of the new crystal of 5-Trimethylhydroquinone diester, is characterized in that: by purity be more than or equal to 97% 2,3,5-Trimethylhydroquinone diester, be dissolved in C1～C3 lower molecular weight organic solvent and form solution, temperature is 50～80 ℃, 2,3,5-Trimethylhydroquinone diester is 0.5～2.5g/mL in the concentration of organic solvent; Then solution is cooled to 30～40 ℃; In suspension, drip dissolved agent again, the volume of dissolved agent is 1～5 times of organic solvent volume; After dropwising, dissolved agent continues to stir 0.5～2h; The solid-liquid suspension of gained is separated, and vacuum-drying, obtains 1,4-diacetoxy-2,3,5-trimethylbenzene Type B crystal; Described C1～C3 lower molecular weight organic solvent is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone or acetonitrile.
3. preparation method as claimed in claim 2, is characterized in that described dissolved agent is water, normal hexane or hexanaphthene; The temperature of the dissolved agent adding is 30～40 ℃, and time for adding is 1～5h.
4. preparation method as claimed in claim 2, the drying conditions that it is characterized in that product is that temperature is that 40～60 ℃, vacuum tightness are 0.08～0.1MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2250066A1 (en) * | 1971-11-05 | 1973-05-10 | Kuraray Co | METHOD FOR PRODUCING 2,3,5TRIMETHYLHYDROQUINONE |
| DE2250065A1 (en) * | 1971-11-05 | 1973-05-10 | Kuraray Co | METHOD FOR PURIFYING 2,3,5TRIMETHYLHYDROQUINONE |
| CN1219531A (en) * | 1997-11-12 | 1999-06-16 | 大赛璐化学工业株式会社 | Hydroquinone diester derivatives and method for producing the same |
| CN1234389A (en) * | 1998-04-21 | 1999-11-10 | 德古萨－于尔斯股份公司 | Noval process for preparing 2,3,5-trimethyl-hydroquinone diester |
| US6369263B1 (en) * | 1998-12-28 | 2002-04-09 | Daicel Chemical Industries, Ltd. | Process for producing hydroquinone diester derivative |
| CN1137081C (en) * | 1996-12-27 | 2004-02-04 | 大赛璐化学工业株式会社 | Method for producing trimethylhydroquinone diester |
-
2012
- 2012-04-18 CN CN201210113838.2A patent/CN102659580B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2250066A1 (en) * | 1971-11-05 | 1973-05-10 | Kuraray Co | METHOD FOR PRODUCING 2,3,5TRIMETHYLHYDROQUINONE |
| DE2250065A1 (en) * | 1971-11-05 | 1973-05-10 | Kuraray Co | METHOD FOR PURIFYING 2,3,5TRIMETHYLHYDROQUINONE |
| CN1137081C (en) * | 1996-12-27 | 2004-02-04 | 大赛璐化学工业株式会社 | Method for producing trimethylhydroquinone diester |
| CN1219531A (en) * | 1997-11-12 | 1999-06-16 | 大赛璐化学工业株式会社 | Hydroquinone diester derivatives and method for producing the same |
| CN1234389A (en) * | 1998-04-21 | 1999-11-10 | 德古萨－于尔斯股份公司 | Noval process for preparing 2,3,5-trimethyl-hydroquinone diester |
| US6369263B1 (en) * | 1998-12-28 | 2002-04-09 | Daicel Chemical Industries, Ltd. | Process for producing hydroquinone diester derivative |
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