CN102659580A - 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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- 239000013078 crystal Substances 0.000 title claims abstract description 43
- -1 2, 3, 5-tri-methyl hydroquinone diester Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000002425 crystallisation Methods 0.000 title abstract description 13
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 17
- 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
- 239000006194 liquid suspension Substances 0.000 claims abstract description 3
- 238000001228 spectrum Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 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 3
- 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 description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 238000001757 thermogravimetry curve Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 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
- 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 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
- 238000004581 coalescence Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- DETAHNVSLBCZAA-ARJGXJLFSA-N photo product Chemical compound C[C@@H]([C@]12O)[C@@H](OC(C)=O)[C@@]3(OC(C)=O)C(C)(C)C3[C@@H]2C2[C@]3(COC(C)=O)C[C@]4(O)[C@H]1C2[C@@]3(C)C4=O DETAHNVSLBCZAA-ARJGXJLFSA-N 0.000 description 1
- 238000012545 processing Methods 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
- 238000009987 spinning Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012795 verification Methods 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 is defined as a type-B crystal by using 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: 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, wherein the temperature is 50-80 DEG C, 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 an obtained solid-liquid suspension and vacuum-drying to obtain the 2, 3, 5-tri-methyl hydroquinone diester type-B crystal. The PXRD (Powder X Ray Diffraction) atlas and a SEM (Scanning Electron Microscope) picture can confirm that 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 preparation 2,3,5-Trimethylhydroquinone diester new crystal and the crystallization method that improves the quality of products.
Background of invention
2,3,5-Trimethylhydroquinone diester, full name 2,3,5-Trimethylhydroquinone diacetate esters, English name trimethylhydroquinone diacetate is called 1 again, 4-diacetoxy-2,3,5-trimethylbenzene, molecular formula is C
13H
160
4, molar mass is 236.268gmol
-1, structural formula is following:
2,3,5-Trimethylhydroquinone diester is synthesising complex E (V
E) a kind of important intermediate, simultaneously also be active chroman compounds on the pharmacology important intermediate in synthetic, and use as inhibitor widely.V
EBe widely used in fields such as medicine, food, healthcare products, makeup, livestock industry.V
EBecome of many uses on the world market, the great main vitamins kind of volume of production and marketing, same V
C, V
ABecome three big pillar products of VITAMINs series together, domestic and abroad market prospect is wide.
At present, have some on the domestic and foreign literature about 2,3, the report of 5-Trimethylhydroquinone diester compound method.US5969176, and reported 2,3, the synthesis technique that 5-Trimethylhydroquinone diester is different in the patent families.In patent US5969176, in order to obtain 2,3, the solid of 5-Trimethylhydroquinone diester; After reaction mixture filtered, will filtrate and mix with frozen water, at 5 ℃ of following suction filtrations, obtain 2; 3, the purity of 5-Trimethylhydroquinone diester product is about 94%, and yield is about 95%.These methods are lowered the temperature reaction product, and add a large amount of dissolved agent (like, water etc.), and to promote 2,3, the crystallization of 5-Trimethylhydroquinone diester is separated out, 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.
Reported 2,3 in EP0916642 and the patent families, 5-Trimethylhydroquinone diester crystalline method 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), and the crystallization terminal temperature is 10～18 ℃, 2,3, and the purity of 5-Trimethylhydroquinone diester is up to 99.9%, but yield is merely about 60%.These methods are in order to improve 2,3, the purity of 5-Trimethylhydroquinone diester product; Reduced initial concentration of solution, solvent-oil ratio is bigger, makes the solvent treatment ability drop of unit volume; Meanwhile, treat that isolating magma amount is bigger, increased the load of spinning.And the yield that finally obtains product is lower and unstable, and the circulation ratio of experiment is not strong.
Outside last performance constraint, through experimental verification, the product ubiquity crystal size of the whole bag of tricks gained is less in the document, coalescence easily; Magma is sticky, and filtration difficulty, mother liquor contain serious problem; It is final 2,3 that these shortcomings can have a strong impact on, the purity of 5-Trimethylhydroquinone diester product.According to method described in the patents such as US5969176, EP0916642 obtain 2,3, the SEM photo of 5-Trimethylhydroquinone diester product is as shown in Figure 6, PXRD is as shown in Figure 7.Above-mentioned crystallization method is difficult to " purity " and " yield " these two indexs are optimized simultaneously.
Summary of the invention
The present invention is directed to the deficiency of existing crystallization technique, proposed a kind of preparation 2,3,5-Trimethylhydroquinone diester new crystal and the crystallization method that improves the quality of products.
Of the present invention a kind of 2,3,5-Trimethylhydroquinone diester crystalline new crystal:
The 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 the PXRD characteristic peak.As shown in Figure 1.
Difference 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 the fusing endotherm(ic)peak and occurs there is not weightlessness before.As shown in Figure 3.Test condition: 30～300 ℃, temperature rise rate is 10 ℃/min, protection nitrogen: 20ml/min.
Ir 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 the place.As shown in Figure 4.
Of the present invention 2,3,5-Trimethylhydroquinone diester crystalline new crystal is named and is crystal form B, and its preparation method is:
With any type of purity more than or equal to 97% 2,3,5-Trimethylhydroquinone diester is dissolved in C1～C3 lower molecular weight organic solvent and forms 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-s, drip the dissolved agent again, the volume of dissolved agent is 1～5 times of organic solvent volume; After dropwising, the dissolved agent continues to stir 0.5～2h; The solid-liquid suspension of gained is separated, and vacuum-drying obtains 2,3,5-Trimethylhydroquinone diester 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 that adds is 30～40 ℃, and the dropping time is 1～5h.
Described suspension-s after separating, the drying conditions of product are that temperature is that 40～60 ℃, vacuum tightness are 0.08～0.1MPa.
Of the present invention 2,3, the preparing method's of 5-Trimethylhydroquinone diester crystal formation advantage is that operational condition is simple and easy to control.Can confirm that through PXRD collection of illustrative plates and SEM photo product percent crystallinity is high, the brilliant inveterate habit of crystalline, for bar-shaped, and granularity is big, plane of crystal is bright and clean, and bulk density is higher.These advantages help the subsequent operations (like filtration, washing and drying etc.) of crystallisation process, have also effectively improved 2,3, the quality of 5-Trimethylhydroquinone diester product.
Description of drawings
Fig. 1: 2,3, the PXRD collection of illustrative plates of 5-Trimethylhydroquinone diester B crystal formation;
Fig. 2: 2,3, the DSC collection of illustrative plates of 5-Trimethylhydroquinone diester B crystal formation;
Fig. 3: 2,3, the TGA collection of illustrative plates of 5-Trimethylhydroquinone diester B crystal formation;
Fig. 4: 2,3, the FTIR collection of illustrative plates of 5-Trimethylhydroquinone diester B crystal formation;
Fig. 5: 2,3, the SEM photo of 5-Trimethylhydroquinone diester B crystal formation (amplifying 15 times);
Fig. 6: bibliographical information technology obtain 2,3, the SEM photo of 5-Trimethylhydroquinone diester product (amplifying 100 times);
Fig. 7: bibliographical information technology obtain 2,3, the PXRD collection of illustrative plates of 5-Trimethylhydroquinone diester product.
Embodiment
Embodiment 1:
With 50g purity be 99.5% 2,3,5-Trimethylhydroquinone diester solid adds in the 50ml methyl alcohol, heat temperature raising to 60 ℃; Make its dissolving fully, then solution is cooled to 40 ℃, under agitation dropping temperature is 40 ℃ water 100ml, and the dropping time is 1h; Continue to stir 1h, the suspension-s that vacuum filtration is separating obtained is dry gained filter cake under the 0.08MPa at 40 ℃, vacuum tightness, obtains colourless bar-shaped 2; 3,5-Trimethylhydroquinone diester Type B crystal 4 7.47g, its purity of gas chromatographic analysis is 99.8%; 2,3, the yield of 5-Trimethylhydroquinone diester is 95.23%.Product percent crystallinity is high, and crystal size is big, any surface finish, and bulk density is bigger.The stereoscan photograph of product is as shown in Figure 5.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.7,13.8,14.9,15.7, and 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 the fusing endotherm(ic)peak at 110.64 ℃; Thermogravimetric analysis is presented at the fusing endotherm(ic)peak and occurs there is not weightlessness before; The 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
-1The place has charateristic avsorption band.
Embodiment 2:
With 50g purity be 99.5% 2,3,5-Trimethylhydroquinone diester solid adds in the 100ml ethanol, heat temperature raising to 70 ℃; Make its dissolving fully, then solution is cooled to 30 ℃, under agitation dropping temperature is 30 ℃ hexanaphthene 150ml, and the dropping time is 2h; Continue to stir 2h, the suspension-s that vacuum filtration is separating obtained is dry gained filter cake under the 0.09MPa at 50 ℃, vacuum tightness, obtains colourless bar-shaped 2; 3,5-Trimethylhydroquinone diester Type B crystal 4 7.20g, its purity of gas chromatographic analysis is 99.9%; 2,3, the yield of 5-Trimethylhydroquinone diester is 94.78%.Product percent crystallinity is high, and crystal size is big, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.6,13.8,14.9,15.8, and 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 the fusing endotherm(ic)peak at 110.87 ℃; Thermogravimetric analysis is presented at the fusing endotherm(ic)peak and occurs there is not weightlessness before; The 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
-1The place has charateristic avsorption band.
Embodiment 3:
With 75g purity be 99.0% 2,3,5-Trimethylhydroquinone diester solid adds in the 50ml n-propyl alcohol, heat temperature raising to 80 ℃; Make its dissolving fully, then solution is cooled to 35 ℃, under agitation dropping temperature is 35 ℃ normal hexane 100ml, and the dropping time is 3h; Continue to stir 1h, the suspension-s that vacuum filtration is separating obtained is dry gained filter cake under the 0.1MPa at 60 ℃, vacuum tightness, obtains colourless bar-shaped 2; 3,5-Trimethylhydroquinone diester Type B crystal 6 9.94g, its purity of gas chromatographic analysis is 99.4%; 2,3, the yield of 5-Trimethylhydroquinone diester is 93.63%.Product percent crystallinity is high, and crystal size is big, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.5,13.7,14.9,15.6, and 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 the fusing endotherm(ic)peak at 110.34 ℃; Thermogravimetric analysis is presented at the fusing endotherm(ic)peak and occurs there is not weightlessness before; The 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
-1The place has charateristic avsorption band.
Embodiment 4:
With 125g purity be 98.5% 2,3,5-Trimethylhydroquinone diester solid adds in the 50ml acetonitrile, heat temperature raising to 80 ℃; Make its dissolving fully, then solution is cooled to 38 ℃, under agitation dropping temperature is 38 ℃ water 250ml, and the dropping time is 5h; Continue to stir 1.5h, the suspension-s that vacuum filtration is separating obtained is dry gained filter cake under the 0.1MPa at 55 ℃, vacuum tightness, obtains 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 percent crystallinity is high, and crystal size is big, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.7,13.8,14.9,15.7, and 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 the fusing endotherm(ic)peak at 110.17 ℃; Thermogravimetric analysis is presented at the fusing endotherm(ic)peak and occurs there is not weightlessness before; The 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
-1The place has charateristic avsorption band.
Embodiment 5:
With 100g purity be 98% 2,3,5-Trimethylhydroquinone diester solid adds in the 50ml acetone, heat temperature raising to 50 ℃; Make its dissolving fully, then solution is cooled to 35 ℃, under agitation dropping temperature is 35 ℃ normal hexane 50ml, and the dropping time is 1.5h; Continue to stir 1h, the suspension-s that vacuum filtration is separating obtained is the following dry gained filter cake of 0.09MPa at 55 ℃, vacuum tightness, obtains 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 percent crystallinity is high, and crystal size is big, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.8,13.8,14.9,15.6, and 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 the fusing endotherm(ic)peak at 110.03 ℃; Thermogravimetric analysis is presented at the fusing endotherm(ic)peak and occurs there is not weightlessness before; The 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
-1The place has charateristic avsorption band.
Embodiment 6:
With 90g purity be 97% 2,3,5-Trimethylhydroquinone diester solid adds in the 50ml Virahol, heat temperature raising to 80 ℃; Make its dissolving fully, then solution is cooled to 36 ℃, under agitation dropping temperature is 36 ℃ hexanaphthene 50ml, and the dropping time is 2h; Continue to stir 0.5h, the suspension-s that vacuum filtration is separating obtained is dry gained filter cake under the 0.08MPa at 50 ℃, vacuum tightness, obtains 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 percent crystallinity is high, and crystal size is big, even particle size distribution.
The PXRD collection of illustrative plates of product is in diffraction angle 2 θ=12.7,13.8,15.0,15.7, and 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 the fusing endotherm(ic)peak at 109.83 ℃; Thermogravimetric analysis is presented at the fusing endotherm(ic)peak and occurs there is not weightlessness before; The 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
-1The place has charateristic avsorption band.
The present invention is open and propose preparation 2,3,5-Trimethylhydroquinone diester new crystal and the crystallization method that improves the quality of products, and those skilled in the art can be through using for reference this paper content, and links such as appropriate change raw material, processing parameter realize.Method of the present invention and product are described through preferred embodiment; Person skilled obviously can be in not breaking away 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 present invention's technology.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as and are included in spirit of the present invention, scope and the content.
Claims (8)
1. one kind 2,3, the new crystal of 5-Trimethylhydroquinone diester is characterized in that: the 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 the PXRD characteristic peak.
2. as claimed in claim 12,3, the new crystal of 5-Trimethylhydroquinone diester is characterized in that differential scanning calorimetric curve located a fusing endothermic characteristics peak at 110 ± 1 ℃.
3. as claimed in claim 12,3, the new crystal of 5-Trimethylhydroquinone diester is characterized in that infared spectrum 3488 ± 2,3435 ± 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-1 place charateristic avsorption band is arranged.
4. like claim 1,2 or 3 described 2,3, the new crystal of 5-Trimethylhydroquinone diester is characterized in that being defined as 2,3, and the new crystal of 5-Trimethylhydroquinone diester is the Type B crystal.
One kind to prepare claim 4 described 2,3, the new crystalline method of 5-Trimethylhydroquinone diester; It is characterized in that: with purity 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-s, drip the dissolved agent again, the volume of dissolved agent is 1～5 times of organic solvent volume; After dropwising, the dissolved agent continues to stir 0.5～2h; The solid-liquid suspension of gained is separated, and vacuum-drying obtains 2,3,5-Trimethylhydroquinone diester Type B crystal.
6. preparation method as claimed in claim 5 is characterized in that 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.
7. preparation method as claimed in claim 5 is characterized in that described dissolved agent is water, normal hexane or hexanaphthene; The temperature of the dissolved agent that adds is 30～40 ℃, and the dropping time is 1～5h.
8. preparation method as claimed in claim 5, 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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|---|---|---|---|---|
| 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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