CN1489567A - 1,3-二酮的纯化方法 - Google Patents
1,3-二酮的纯化方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000000746 purification Methods 0.000 title claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- -1 indyl Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical group CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000006193 alkinyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002618 bicyclic heterocycle group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- UPIJOAFHOIWPLT-UHFFFAOYSA-N methyl 4-tert-butylbenzoate Chemical class COC(=O)C1=CC=C(C(C)(C)C)C=C1 UPIJOAFHOIWPLT-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229960001679 octinoxate Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种1,3-二酮的纯化方法,包括将1,3-二酮与土金属或者碱土金属络合剂在有机溶剂中反应,分离、洗涤和分解得到的络合物和分离纯化的1,3-二酮。
Description
本发明涉及一种1,3-二酮的纯化或者从包含所述1,3-二酮的反应混合物中分离纯净1,3-二酮的新方法。
依照本发明,所述方法包括:
a)将1,3-二酮与土金属(earth metal)或者碱土金属络合剂在有机溶剂中反应形成一种络合物,
b)分离所述络合物,
c)用有机溶剂洗涤所述络合物,
d)分解所述络合物,和
e)分离被纯化的1,3-二酮。
在优选的方面,本发明涉及式R1CO-CH2-CO-R2表示的1,3-二酮的纯化或者分离,其中R1和R2独立地为脂肪族、芳香族或者杂环部分。由R1和/或R2代表的脂肪族部分的实例为饱和脂肪族部分,例如C1-20烷基,和不饱和脂肪族部分,如C2-20链烯基或者链炔基(alkinyl groups),其可为直链或支链且可被或者不被如卤素、羟基、低级烷氧基或低级烷酰氧基取代。
芳香族部分R1和R2的实例为单和双环部分,如未取代或者取代的苯基和萘基。杂环部分的实例为包含一个或多个氮原子、硫原子和/或者氧原子作为杂原子的单和双环杂环,如吡啶基、嘧啶基、噻吩基、呋喃基、噻唑基、吲哚基、喹啉基和异喹啉基。
特别优选地,本发明的1,3-二酮是4-叔丁基-4′-甲氧基-二苯甲酰基甲烷或异丙基二苯甲酰基甲烷,也分别被称为PARSOL1789和EUSOLEX8020,广泛在化妆品防晒组合物中用作UV过滤剂(UV filter)。4-叔丁基-4′-甲氧基-二苯甲酰基甲烷通常是由4-叔丁基苯甲酸衍生物与4-甲氧基苯乙酮通过羟醛(aldol)缩合制备,缩合产物粗品用甲醇重结晶而纯化。用本发明的方法可以得到高纯度的二酮如4-叔丁基-4′-甲氧基-二苯甲酰基甲烷。这特别重要,因为少量的杂质会给产物带入颜色,而这在化妆品组合物中是不希望的。
本发明纯化方法中使用的有机溶剂可为任何一种能溶解将要纯化的1,3-二酮的有机溶剂,且对络合剂呈惰性。典型的溶剂为芳香烃,例如苯,优选甲苯。本发明中使用的其他溶剂的实例为脂肪醇类例如甲醇和乙醇,醚例如乙醚、甲基叔丁基醚,四氢呋喃和二氧六环,和氯代烃例如二氯甲烷,氯仿和氯苯。
土金属或者碱土金属络合剂可为能与1,3-二酮形成络合物的所述金属的任何衍生物。典型的实例为硼、铝、钙和镁的卤化物,特别是三氟化硼,三氯化铝,氯化钙和氯化镁,以及硼酸。优选络合剂是三氟化硼。
纯化方法可通过向1,3-二酮粗品在合适有机溶剂的溶液中添加络合剂,或者向包含1,3-二酮的反应混合物中添加络合剂来进行。合适地,使用等摩尔量的1,3-二酮和络合剂,优选使用稍微过量,如10%摩尔过量的络合剂。1,3-二酮与络合剂反应后,就形成了固体沉淀的络合物,其可以被分离出来,用合适的溶剂洗涤,合适地使用与溶解粗品产物相同的溶剂或者使用1,3-二酮制备反应中的溶剂进行洗涤。洗涤后,固体沉淀可以用含碱的水性介质处理而分解,从而产生高纯度的1,3-二酮。所用碱可为溶于水性介质的任何碱,如氨水,碱金属氢氧化物(alkali hydroxides)、碱金属碳酸盐或者碱金属碳酸氢盐,例如NaOH,KOH,Na2CO3或NaHCO3。优选氨水。合适地使用与1,3-二酮络合物等摩尔量或者稍微过量,如10%摩尔过量的碱。1,3-二酮络合物的分解合适地在溶剂,例如前面说明的溶剂,特别地是烷醇例如甲醇中进行。在本发明的另一个实施方案中,纯净二酮可用酸处理络合物而得到,所用酸溶于水性介质且能与络合剂如草酸形成络合物。
本发明通过下列实施例进行更详细的说明。
实施例1
a)36g(1.2mol)的80%氨基钠(sodium amide)和300g无水甲苯加到充满氮气的圆底烧瓶中。将混合物加热到50℃,在1.5小时内加入150.2g(1mol)乙酰苯甲醚在309g甲苯中的溶液。加液完毕后,混合物在50℃保持15分钟,然后在该温度下,在1小时50分钟内加入192.3g(1mol)对叔丁基苯甲酸甲酯(按照美国专利4,387,089制备)。混合物继续在50℃搅拌1小时,然后在100℃下加热1小时,然后产物以固体沉淀的形式分离出来。混合物放置12小时,然后加入300ml冰-水,接着加入100ml纯净盐酸和250ml冰-水的混合物。分离出各相,有机相用水洗涤两次,用硫酸钠干燥。
b)向步骤a)得到的有机相中,滴加140ml(1.1mol)三氟化硼乙醚络合物(boron trifluoride diethyl etherate)。加入完成后,溶液变成深棕色。5分钟后,出现沉淀,混合物变成红棕色。然后将混合物120℃(回流温度)下加热1小时。颜色又发生变化,从红棕色变到粉紫色。将混合物冷却至室温,滤出沉淀,用600ml叔丁基甲醚洗涤。高真空干燥后,得到240g的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的BF3络合物,为黄绿荧光固体产物。
c)向装配回流冷凝器、搅拌器和油浴的6升三颈反应烧瓶中,加入240g(0.67mol)步骤b)申得到的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的BF3络合物、3.5升甲醇和50g氨水(25%)。混合物在搅拌下加热到70℃(回流温度)过夜。形成透明的溶液。用冰浴冷却后,形成沉淀,将沉淀滤出,用1升甲醇水溶液(75%)洗涤。高真空干燥后,得到196g的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷,m.p.85.5℃。HPLC检测纯度:99.7%。
实施例2
a)浓缩实施例1步骤a)得到的部分有机相,在高真空下干燥,得到5g棕色半结晶物质,其中包含70%的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷(用HPLC检测)。所述物质溶解在15毫升乙醇中,加热到60℃。在另一个烧瓶中,0.72g的AlCl3溶解在15ml乙醇中,引起放热反应。将所述溶液缓慢加到第一种溶液中。用2ml氨水(25%)处理该合并的黄色溶液,立即形成浅黄色晶体。反应在60℃下再搅拌15分钟,冷却,过滤。用水和乙醇洗涤残留物且在高真空干燥。得到4.3g相应的Al+3-络合物,为淡橙色晶体。MS:954(M+);645(100%)。
b)向装配有回流冷凝器、搅拌器和油浴的250ml三颈反应烧瓶中,加入4.1g实施例2步骤a)得到的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的Al+3-络合物溶解在50ml甲醇和1ml氨水(25%)中的溶液。将混合物加热到回流,加入0.82g草酸二水合物,过滤热溶液。将滤液冷却,沉淀出4-叔丁基-4′-甲氧基-二苯甲酰基甲烷。滤出沉淀,高真空干燥得到2.33g上文提及的纯净产物。用少量水处理滤液,沉淀出4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的第二部分,过滤该第二部分并干燥得到另外1克纯净产物。
实施例3
利用MgCl2代替AlCl3,按照实施例2a)描述的类似方法,得到4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的MgCl2络合物,从其中得到类似于实施例2b)中的纯净、白色的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷。
实施例4
利用CaCl2代替AlCl3,按照实施例2a)描述的类似方法,得到4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的CaCl2络合物,从其中得到类似实施例2b中的纯净、白色的4-叔丁基-4′-甲氧基-二苯甲酰基甲烷。
Claims (10)
1.一种1,3-二酮的纯化方法,包括:
a)将1,3-二酮与土金属或碱土金属络合剂在有机溶剂中反应形成络合物,
b)分离所述络合物,
c)用有机溶剂洗涤所述络合物,
d)分解所述络合物,和
e)分离纯化的1,3-二酮。
2.根据权利要求1的方法,其中络合剂是三氟化硼。
3.根据权利要求1或2的方法,其中反应中使用的有机溶剂是芳香烃。
4.根据权利要求3的方法,其中芳香烃是甲苯。
5.根据权利要求1-4中任一项所述的方法,其中用氨水溶液进行处理而分解络合物。
6.根据权利要求1-5中任一项所述的方法,其中1,3-二酮是式R1-CO-CH2-CO-R2的化合物,其中R1和R2独立地为脂肪族、芳香族或杂环部分。
7.根据权利要求6的方法,其中R1和R2独立地为苯基或取代的苯基。
8.根据权利要求7的方法,其中R1为对-叔丁基苯基且R2为对-甲氧基苯基。
9.制备纯净的1,3-二酮的方法,基本上如上文描述,尤其是参考实施例描述的方法。
10.4-叔丁基-4′-甲氧基-二苯甲酰基甲烷的BF3络合物。
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KR (1) | KR100618742B1 (zh) |
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DE102013101575B4 (de) | 2012-12-21 | 2019-06-06 | L’AIR LIQUIDE Société Anonyme pour l’Etude et l’Exploitation des Procédés Georges Claude | Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten |
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GB868106A (en) * | 1956-10-16 | 1961-05-17 | Despic Aleksandar | Unsaturated ª- diketones |
BE577999A (zh) * | 1958-04-25 | |||
US3919275A (en) * | 1970-05-28 | 1975-11-11 | Us Agriculture | Chelated beta dicarbonyl compounds |
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JP2004517954A (ja) | 2004-06-17 |
US6844470B2 (en) | 2005-01-18 |
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EP1355871A1 (en) | 2003-10-29 |
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