CN106317087A - 金属乙酰丙酮化物的制备方法 - Google Patents
金属乙酰丙酮化物的制备方法 Download PDFInfo
- Publication number
- CN106317087A CN106317087A CN201610693379.8A CN201610693379A CN106317087A CN 106317087 A CN106317087 A CN 106317087A CN 201610693379 A CN201610693379 A CN 201610693379A CN 106317087 A CN106317087 A CN 106317087A
- Authority
- CN
- China
- Prior art keywords
- solution
- zinc
- days
- preparation
- copper
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 title abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 4
- CTHCTLCNUREAJV-UHFFFAOYSA-N heptane-2,4,6-trione Chemical compound CC(=O)CC(=O)CC(C)=O CTHCTLCNUREAJV-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 abstract 1
- MBBQAVVBESBLGH-UHFFFAOYSA-N methyl 4-bromo-3-hydroxybutanoate Chemical compound COC(=O)CC(O)CBr MBBQAVVBESBLGH-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 13
- 150000002148 esters Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000006073 displacement reaction Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal alkoxide Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VMKYTTSJFPJNOS-UHFFFAOYSA-N 2-ethylsulfanylethyl 2-methylprop-2-enoate Chemical compound CCSCCOC(=O)C(C)=C VMKYTTSJFPJNOS-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 208000016444 Benign adult familial myoclonic epilepsy Diseases 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- ZHVZTRUUPYIJTQ-UHFFFAOYSA-N bis(3-hydroxypropyl) benzene-1,4-dicarboxylate Chemical compound OCCCOC(=O)C1=CC=C(C(=O)OCCCO)C=C1 ZHVZTRUUPYIJTQ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 208000016427 familial adult myoclonic epilepsy Diseases 0.000 description 1
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- GVOLZAKHRKGRRM-UHFFFAOYSA-N hafnium(4+) Chemical compound [Hf+4] GVOLZAKHRKGRRM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003317 samarium compounds Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- AWSFICBXMUKWSK-UHFFFAOYSA-N ytterbium(3+) Chemical compound [Yb+3] AWSFICBXMUKWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了金属乙酰丙酮化物的制备方法，取一定量的六水合硝酸锌和三水合硝酸铜按锌：铜的原子比100:1加入一定体积的无水乙醇配成溶液，加入一定体积10ml的乙酰丙酮，磁力搅拌均匀为A溶液；在10ml‑15ml无水乙醇加入2.5g氢氧化钠搅拌溶解得B溶液；最后在搅拌条件下，将B溶液缓慢加入A溶液，充分搅拌，静止10‑20天，得到两种晶体：一水.二乙酰丙酮合锌C10H16O5Zn和二乙酰丙酮合铜C10H14CuO4。
Description
技术领域
本发明属于乙酰丙酮化物的制备技术领域，尤其涉及金属乙酰丙酮化物的制备方法。
背景技术
酯交换是在数种工业方法中交换有机基团的重要方法。它例如在大规模合成聚酯中使用。在这一应用中，二酯经历与二醇的酯交换，形成大分子。另一实例是通过用短链脂族醇(典型地甲醇或乙醇)酯交换植物油或动物脂肪，生产生物柴油(脂肪酸甲酯，FAME)。
而且在其他工业方法，例如(i)分子内酯交换导致内酯和大环，(ii)生产特殊活性药物成分(API)(的中间体)，(iii)由丙交酯生产聚乳酸(PLA)，(iv)由碳酸亚乙酯和甲醇共-合成碳酸二甲酯和乙二醇中，酯交换是关键的步骤。
通常在催化剂存在下进行酯交换反应，所述催化剂尤其包括无机酸，金属氢氧化物，金属氧化物，金属醇盐(异丙醇铝，四烷氧基钛，有机锡烷氧化物等)，非离子碱(胺，二甲基氨基吡啶，胍等)和脂酶(J.Otera和J.Nishikido,Esterification,p.52-99,Wiley2010)。然而，在各酯或醇反应物内的不饱和键，胺，额外的羟基或其他官能团存在下，这些常规催化剂的活性可能受到妨碍。强无机酸，例如硫酸或甲磺酸例如通常导致缓慢的反应速度，和所得酯交换产物典型地伴随着形成高浓度副产物。所述高浓度副产物通常来自于醇脱水，得到最终污染产物的烯烃和醚。在丙烯酸酯情况下，在最终反应混合物内也发现迈克尔加成产物(醇加成到C＝C双键上)和显著量的聚合物产物。
类似于酸催化剂，碱金属醇盐催化剂(例如，甲醇钠或叔丁醇钾)促进非所需的副反应，而且它们因反应溶液中存在水而失活。因此，催化剂应当连续加入到反应混合物中，同时随后必须除去它，以避免在蒸馏或其他热处理产物过程中醇盐-促进的聚合或降解，特别是若产物是不饱和酯，例如丙烯酸酯的话。
钛(Ti)和锡的醇盐通常具有较高的选择性，但遭受特定的缺点。钛酸酯催化剂尤其对水敏感(通常在含有大于500ppm水的混合物中失活)，从而使得添加更多的催化剂到反应中的相同需求变得必要。另外，在所得产物储存过程中，Ti化合物可导致非所需的变色(泛黄)，所述变色因包括除了Ti(IV)化合物以外还存在Ti(III)化合物，和/或钛倾向于形成络合物在内的因素而引起。还意识到，锡化合物是人类潜在的致癌物质，因此它们在最终产物内的存在是非所需的。因此，强烈地除去是重要的和应当有效地弃置残渣。
由于采用常规催化剂具有这些问题，因此，需要在其他官能团存在下，具有高活性和选择性且对水具有降低的敏感性的改进的酯交换催化剂。
现有技术中通过使用金属乙酰丙酮化物催化剂用以生产各种酯化合物，进行了满足这一需求的已有步骤。如此制备的酯的实例包括(甲基)丙烯酸酯(US4202990,US7071351,US2004/0249191)或更具体的甲基丙烯酸烯丙酯(WO2009003746)，(甲基)丙烯酸异戊二烯酯(DE102008043810)，甲基丙烯酸乙基硫代乙酯(FR2707290)。也公开了生产脂族低聚碳酸酯多羟基化合物(US7060778,US2006/0052572,US6350895)，α-酮基羧酸酯(US6222063)，蜡单体(US5856611)，双(3-羟丙基)对苯二甲酸酯单体(US5840957)和聚对苯二甲酸乙二酯树脂(US3528946,US3528945)。优选的金属主要是锆(US4202990,WO2009003746,US7071351,US2004/0249191,US5856611,FR2707290)，而且还公开了其他金属，例如镱(III)(US7060778,US2005/006539)，钇/钐化合物(US6350895)，镧(US5840957,EP1064247)，铪(IV)(US5037978)，铈和铅(US3532671)。
国内合成乙酰丙酮盐的方法很多，主要以一步催化合成和多步合成为主。一步催化合成工艺简单，成本低，但需要加入催化剂；多步合成工艺相对复杂，成本高。
发明内容
本发明的目的在于提供金属乙酰丙酮化物的制备方法，旨在解决目前合成乙酰丙酮盐中一步催化合成法需要加入催化剂，使工序繁琐；多步合成工艺法则相对非常复杂，成本高的问题。
本发明提供的金属乙酰丙酮化物的制备方法包括以下步骤：
取六水合硝酸锌8.0-10.0g和三水合硝酸铜0.06-0.09g按锌：铜的原子比100:1加入30ml的无水乙醇配成溶液，加入10ml的乙酰丙酮，磁力搅拌均匀为A溶液；
在15ml无水乙醇加入约2.5g氢氧化钠搅拌溶解得B悬浊液；
在搅拌条件下，将B溶液缓慢加入A溶液，充分搅拌，静止10天，出现无色透明，挑出晶体在显微镜熔点测定仪下观察并测熔点(137℃)，晶体为六棱柱棒状晶体，单晶XRD测试为一水.二乙酰丙酮合锌C10H16O5Zn；继续静止15-20天，出现深蓝色晶体，挑出晶体在显微镜熔点测定仪下观察并测熔点(315℃)，晶体为长方体晶体，单晶XRD测试为二乙酰丙酮合铜C10H14CuO4。
国内合成乙酰丙酮盐的方法很多，主要以一步催化合成和多步合成为主。一步催化合成工艺简单，成本低，但需要加入催化剂；多步合成工艺相对复杂，成本高。本发明提及的同一体系制备金属乙酰丙酮化物得到两种单晶的制备方法未见报道，而且合成工艺极其简单，实验原料成本低廉，实验设备简单，能耗低。
附图说明
图1是本发明实施例提供的金属乙酰丙酮化物的制备方法流程图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
下面结合附图及具体实施例对本发明的应用原理作进一步描述。
如图1所示：本发明提供的金属乙酰丙酮化物的制备方法包括以下步骤：
S101：取六水合硝酸锌8.0-10.0g和三水合硝酸铜0.06-0.09g按锌：铜的原子比100:1加入30ml的无水乙醇配成溶液，加入10ml的乙酰丙酮，磁力搅拌均匀为A溶液；
S102：在15ml无水乙醇加入约2.5g氢氧化钠搅拌溶解得B悬浊液；
S103:在搅拌条件下，将B溶液缓慢加入A溶液，充分搅拌，静止10天，出现无色透明，挑出晶体在显微镜熔点测定仪下观察并测熔点(137℃)，晶体为六棱柱棒状晶体，单晶XRD测试为一水.二乙酰丙酮合锌C10H16O5Zn；继续静止15-20天，出现深蓝色晶体，挑出晶体在显微镜熔点测定仪下观察并测熔点(315℃)，晶体为长方体晶体，单晶XRD测试为二乙酰丙酮合铜C10H14CuO4。
下面结合分析数据对本发明进一步说明。
A为单晶衍射分析数据一水.二乙酰丙酮合锌(淡蓝色)
A
Table 1 Crystal data and structure refinement for 123.
Table 2 Fractional Atomic Coordinates(×104)and Equivalent IsotropicDisplacement Parametersfor 123.Ueq is defined as1/3 of of the trace ofthe orthogonalised UIJ tensor.
Table 3 Anisotropic Displacement Parametersfor 123.TheAnisotropic displacement factor exponent takes the form:
-2π2[h2a*2U11+2hka*b*U12+…].
Table 4 Bond Lengths for 123.
Table 5 Bond Angles for 123.
Table 6 Hydrogen Bonds for 123.
Table 7 Torsion Angles for 123.
Table 8 Hydrogen Atom Coordinatesand Isotropic DisplacementParametersfor 123.
B为单晶衍射分析数据二乙酰丙酮合铜C10H14CuO4(黑色)：
B
Table 1 Crystal data and structure refinement for A.
Table 2 Fractional Atomic Coordinates(×104)and Equivalent IsotropicDisplacement Parametersfor A.Ueq is defined as 1/3of of the trace ofthe orthogonalised UIJ tensor.
Table 3 Anisotropic Displacement Parametersfor A.TheAnisotropic displacement factor exponent takes the form:
-2π2[h2a*2U11+2hka*b*U12+…].
Table 4 Bond Lengths for A.
Table 5 Bond Angles for A.
Table 6 Hydrogen Atom Coordinatesand Isotropic DisplacementParametersfor A.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (3)
1.金属乙酰丙酮化物的制备方法，其特征在于，该金属乙酰丙酮化物的制备方法包括以下步骤：
取六水合硝酸锌8.0-10.0g和三水合硝酸铜0.06-0.09g按锌：铜的原子比100:1加入30ml的无水乙醇配成溶液，加入10ml的乙酰丙酮，磁力搅拌均匀为A溶液；
在10ml-15ml无水乙醇加入2.5g氢氧化钠搅拌溶解得B溶液；
最后在搅拌条件下，将B溶液缓慢加入A溶液，充分搅拌，静止10天-20天，得到两种晶体：一水.二乙酰丙酮合锌C10H16O5Zn和二乙酰丙酮合铜C10H14CuO4。
2.如权利要求1所述的金属乙酰丙酮化物的制备方法，其特征在于，所述静止10天-20天，得到两种晶体：一水.二乙酰丙酮合锌C10H16O5Zn和二乙酰丙酮合铜C10H14CuO4中，具体包括：
静止10天，出现无色透明六棱柱棒状晶体一水.二乙酰丙酮合锌C10H16O5Zn，利用显微镜熔点测定仪测试该晶体熔点并进行单晶XRD测试；
继续静止到15天-20天，出现深蓝色长方体晶体二乙酰丙酮合铜C10H14CuO4，利用显微镜熔点测定仪测试该晶体熔点并进行单晶XRD测试。
3.如权利要求2所述的金属乙酰丙酮化物的制备方法，其特征在于，所述无色透明六棱柱棒状晶体一水.二乙酰丙酮合锌C10H16O5Zn熔点为137℃；深蓝色长方体晶体二乙酰丙酮合铜C10H14CuO4熔点为：315℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610693379.8A CN106317087A (zh) | 2016-08-19 | 2016-08-19 | 金属乙酰丙酮化物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610693379.8A CN106317087A (zh) | 2016-08-19 | 2016-08-19 | 金属乙酰丙酮化物的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106317087A true CN106317087A (zh) | 2017-01-11 |
Family
ID=57743776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610693379.8A Pending CN106317087A (zh) | 2016-08-19 | 2016-08-19 | 金属乙酰丙酮化物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106317087A (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299392A (zh) * | 1998-03-12 | 2001-06-13 | 罗狄亚化学公司 | 乙酰丙酮锌－水合物作为卤化聚合物的稳定剂的用途及其制备方法 |
| CN101503343A (zh) * | 2009-03-27 | 2009-08-12 | 北京化工大学 | 一种乙酰丙酮金属化合物的合成方法 |
-
2016
- 2016-08-19 CN CN201610693379.8A patent/CN106317087A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299392A (zh) * | 1998-03-12 | 2001-06-13 | 罗狄亚化学公司 | 乙酰丙酮锌－水合物作为卤化聚合物的稳定剂的用途及其制备方法 |
| CN101503343A (zh) * | 2009-03-27 | 2009-08-12 | 北京化工大学 | 一种乙酰丙酮金属化合物的合成方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103140287B (zh) | 使用混合盐乙酰丙酮化物催化剂的酯交换方法 | |
| Petrus et al. | Solvothermal alcoholysis routes for recycling polylactide waste as lactic acid esters | |
| Abreu et al. | New multi-phase catalytic systems based on tin compounds active for vegetable oil transesterificaton reaction | |
| Roy et al. | Cu-based catalysts show low temperature activity for glycerol conversion to lactic acid | |
| Finn et al. | Next-generation water-soluble homogeneous catalysts for conversion of glycerol to lactic acid | |
| Huang et al. | Activation of commercial CaO for biodiesel production from rapeseed oil using a novel deep eutectic solvent | |
| Scotti et al. | Copper–zirconia catalysts: Powerful multifunctional catalytic tools to approach sustainable processes | |
| Liu et al. | Simultaneous production of lactic acid and propylene glycol from glycerol using solid catalysts without external hydrogen | |
| Qu et al. | Hydrogenation of carboxylic acids, esters, and related compounds over heterogeneous catalysts: A step toward sustainable and carbon-neutral processes | |
| JPWO2007088702A1 (ja) | 脂肪酸アルキルエステルの製造方法および脂肪酸アルキルエステルの製造装置 | |
| CN102218320A (zh) | 一种用于加氢反应的催化剂及其制备方法和用途 | |
| US20100139152A1 (en) | Heterogeneous catalysts for mono-alkyl ester production, method of making, and method of using same | |
| CN101918131A (zh) | 用于环氧化大豆脂肪酸/脂肪酸酯的酯化的催化剂及其使用方法 | |
| Li et al. | Cascade strategy for atmospheric pressure CO2 fixation to cyclic carbonates via silver sulfadiazine and Et4NBr synergistic catalysis | |
| Melchiorre et al. | Homogeneous catalysis and heterogeneous recycling: a simple Zn (ii) catalyst for green fatty acid esterification | |
| Akiri et al. | Synthesis of MCM-41 immobilized (phenoxy) imine palladium (II) complexes as recyclable catalysts in the methoxycarbonylation of 1-hexene | |
| TWI395617B (zh) | Method for producing ester condensates | |
| CN101898946A (zh) | 一种催化甘油氢解的方法 | |
| Nunes et al. | A 5-(2-Pyridyl) tetrazolate Complex of Molybdenum (VI), Its Structure, and Transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins | |
| Calmanti et al. | One-Pot Tandem Catalytic Epoxidation—CO2 Insertion of Monounsaturated Methyl Oleate to the Corresponding Cyclic Organic Carbonate | |
| CN106317087A (zh) | 金属乙酰丙酮化物的制备方法 | |
| Kotyrba et al. | Synthesis of Propylene Carbonate by Urea Alcoholysis—Recent Advances | |
| CN110382114A (zh) | 制备有机锌催化剂的方法，通过该方法制备的有机锌催化剂以及采用该催化剂制备聚碳酸亚烷基酯树脂的方法 | |
| JP2016002546A (ja) | アリルアルコールからアクリル酸製造用不均一系触媒、これを用いたアリルアルコールからアクリル酸を製造する方法 | |
| Smith et al. | Recent advances on the valorization of glycerol into alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170111 |