WO2012100403A1 - 芳基1,2-二醇转化为酮的环境友好性氧化新工艺 - Google Patents
芳基1,2-二醇转化为酮的环境友好性氧化新工艺 Download PDFInfo
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- WO2012100403A1 WO2012100403A1 PCT/CN2011/002210 CN2011002210W WO2012100403A1 WO 2012100403 A1 WO2012100403 A1 WO 2012100403A1 CN 2011002210 W CN2011002210 W CN 2011002210W WO 2012100403 A1 WO2012100403 A1 WO 2012100403A1
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- Prior art keywords
- hydrogen peroxide
- bromine
- compound
- hydrogen
- oxidation
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 150000002576 ketones Chemical class 0.000 title description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 46
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 41
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 41
- 229910052794 bromium Inorganic materials 0.000 claims description 41
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- -1 α-(1-hydroxycyclohexyl)-benzene-nonanol Chemical compound 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 229940126214 compound 3 Drugs 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- 229940125904 compound 1 Drugs 0.000 claims description 3
- 229940125898 compound 5 Drugs 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010411 cooking Methods 0.000 claims description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims 2
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 claims 2
- IDIFZGIIUVTIIR-UHFFFAOYSA-N 2-hydroxy-2-(1H-indol-2-yl)-1-phenylpropan-1-one Chemical compound OC(C(=O)C1=CC=CC=C1)(C)C=1NC2=CC=CC=C2C=1 IDIFZGIIUVTIIR-UHFFFAOYSA-N 0.000 claims 1
- AMLVBKKHVPSTBT-UHFFFAOYSA-N [Br].OO Chemical compound [Br].OO AMLVBKKHVPSTBT-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 3
- 238000003847 radiation curing Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 18
- 150000002009 diols Chemical class 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000004809 thin layer chromatography Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- 238000005502 peroxidation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NEPTUHIWSNKWGB-UHFFFAOYSA-N 1-(4-methoxyphenyl)-2-methylpropane-1,2-diol Chemical group COC1=CC=C(C(O)C(C)(C)O)C=C1 NEPTUHIWSNKWGB-UHFFFAOYSA-N 0.000 description 2
- IHBQQMPFWYZRPM-UHFFFAOYSA-N 1-[hydroxy(phenyl)methyl]cyclohexan-1-ol Chemical group C1CCCCC1(O)C(O)C1=CC=CC=C1 IHBQQMPFWYZRPM-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UPFQJMVQJWHPOL-UHFFFAOYSA-N 2-methyl-1-phenylpropane-1,2-diol Chemical group CC(C)(O)C(O)C1=CC=CC=C1 UPFQJMVQJWHPOL-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000008282 halocarbons Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IZGNAMNBBIETLY-UHFFFAOYSA-N 2-hydroxy-1-(4-methoxyphenyl)-2-methylpropan-1-one Chemical group COC1=CC=C(C(=O)C(C)(C)O)C=C1 IZGNAMNBBIETLY-UHFFFAOYSA-N 0.000 description 1
- XGAAUANKDSTWFH-UHFFFAOYSA-N 2-hydroxy-1-phenyl-2-sulfanylpropan-1-one Chemical group OC(C(=O)C1=CC=CC=C1)(C)S XGAAUANKDSTWFH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- OKKQVRHLNHSUOR-UHFFFAOYSA-N OC1(CCCCC1)C1=C(C(C2=CC3=CC=CC=C3C2=C1)=O)C1=CC=CC=C1 Chemical group OC1(CCCCC1)C1=C(C(C2=CC3=CC=CC=C3C2=C1)=O)C1=CC=CC=C1 OKKQVRHLNHSUOR-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- YWIBETYWGSNTAE-UHFFFAOYSA-N [Br].Br Chemical compound [Br].Br YWIBETYWGSNTAE-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the invention relates to the technical field of radiation curing photopolymerization initiators, in particular to a new environmentally friendly process technology for the oxidation of a plurality of specific aryl 1,2 diol compounds to form corresponding aryl hydroxy ketones.
- Compound 1 Chinese name is 2-hydroxy-2-mercapto-1-phenyl-1-propanone; the corresponding English name is 2-hydroxy-2-methyl- 1 -phenyl- 1 -propanone; corresponding compound registration number It is 7473-98-5.
- Compound 2 Chinese name is (1-hydroxycyclohexyl)phenyl-fluorenone; the corresponding English name is (1-hydroxycyclohex l)phenyl-methanone; the corresponding compound registration number is 947-19-3.
- Compound 3 Chinese name is 2-hydroxy-1-(4-decyloxyphenyl)-2-methyl-1-propanone; the corresponding English name is 2-hydroxy- 1 -(4-methoxyphenyl)-2- Methyl-1 -propanone; The corresponding compound registration number is 15482-17-4.
- compound 1-3 can be prepared by oxidation of the corresponding aryl 1,2-diol with bromine (Br 2 ) as an oxidizing agent; or bromine as an oxidation catalyst with hydrogen peroxide ( Commonly known as hydrogen peroxide, H 2 0 2 ) is prepared by oxidation of the terminal oxidant.
- bromine commonly known as hydrogen peroxide, H 2 0 2
- H 2 0 2 hydrogen peroxide
- the object of the present invention is to propose a novel process for the preparation of compound 1-3 from the corresponding aryl 1,2-diol with bromine as the oxidant or bromine as the catalyst and hydrogen peroxide as the terminal oxidant.
- aryl 1,2-diol precursors are in turn the following compounds 4-6:
- Compound 4 Chinese name is 2-methyl-1-phenyl-1,2-propanediol; the corresponding English name is 2-methyl- 1 -phenyl- 1 ,2-propanediol; the corresponding compound registration number is 20907- 13 -5.
- Compound 5 Chinese name is ⁇ -(1-hydroxycyclohexyl)-benzene-nonanol; the corresponding English name is ⁇ -(1-hydroxycyclohexyl)-benzene-methanol; the compound registration number of the phase is 1135-72-4 .
- the general chemical reaction scheme of the new oxidation reaction process is as shown in any of the following diagrams.
- the process consists of two steps: In the first step, the diol compound 4-6 is oxidized under bromine (Br 2 ) to form product 1-3 while releasing hydrogen bromide (HBr) by-product.
- the reaction temperature is preferably room temperature
- the solvent is preferably a halogenated hydrocarbon dichloromethane
- the oxidizing agent bromine is preferably used in an amount of 1-3 equivalents, but the reaction temperature and the solvent and the amount of bromine used are not restrictive conditions, and the limiting condition of this step is use. Bromine is used as an oxidant for this step.
- the second step is to recycle the hydrogen bromide by-product and the hydrogen peroxide (H 2 0 2 ) aqueous phase to recover the bromine.
- the reaction temperature is preferably room temperature
- the stoichiometric ratio of hydrogen bromide and hydrogen peroxide is preferably from 2/1 to 1/1
- the concentration of the hydrogen peroxide reagent is preferably from 10 to 50%.
- the process is only one step, that is, the "one-pot” method, using bromine as a catalyst, the diol compound 4-6 and hydrogen peroxide are reacted to obtain the product 1-3.
- the reaction temperature is preferably room temperature
- the solvent is preferably a halogenated hydrocarbon dichloromethane
- the catalyst bromine is preferably used in an amount of 0.05 to 0.70 equivalent
- the hydrogen peroxide is preferably used in an amount of 1 to 20 equivalents.
- a beneficial improvement in performing the specific operation of the process is to use a catalytic amount of hydrogen bromide as the starting catalyst species, which is feasible because hydrogen bromide can be hydrogen peroxide oxidized in situ to generate bromine in situ. Catalytic oxidation function.
- reaction temperature the initial form of the catalyst (bromine or hydrogen bromide), the equivalent ratio of hydrogen bromide to hydrogen peroxide, and the concentration of hydrogen peroxide are non-limiting conditions.
- the limiting condition of this step is the use of peroxidation.
- a catalytic oxidation system such as hydrogen/bromine or hydrogen peroxide/hydrogen bromide achieves conversion from starting materials 4-6 to products 1-3.
- the first step oxidation reaction two falling boxes
- the second step the aqueous phase obtained by the above reaction and the aqueous solution which absorbed the acid gas are combined and placed in a flask, and 2 equivalents of hydrogen peroxide (30% aqueous solution) are slowly added dropwise, and the brown liquid which is immediately formed is immediately For the recovery of bromine.
- Hydrogen peroxide / bromine system 1662 g of diol 4 was dissolved in 20 liters of dichloromethane, 2 equivalents of hydrogen peroxide (30% strength in water) were added, and water was added to adjust the volume of the aqueous phase to the organic phase.
- Hydrogen (30% strength aqueous solution) promotes the reaction to completion.
- the reaction system was diluted with an equal volume of water, and the organic phase was separated by shaking. The solvent was distilled off, and the residue was evaporated to dryness to give a pale oily hydroxy ketone product 1 about 1433 g.
- Hydrogen peroxide / hydrobromic acid system 1662 g of diol 4 was dissolved in 20 liters of dichloromethane, 2 equivalents of hydrogen peroxide (30% strength aqueous solution) was added, and 243 g of hydrobromine was slowly added at room temperature. Acid (0.3 eq, 0.5M aqueous solution), pay attention to sufficient cooling to maintain the reaction at room temperature, and follow the progress of the reaction with a thin layer color method. 0.5-2 equivalent hydrogen peroxide (30% aqueous solution) can be added. ) Promote complete reaction. The reaction system was diluted with an equal volume of water, and the organic phase was separated by shaking. The solvent was distilled off, and the residue was distilled under reduced pressure to give a crude oily hydroxy ketone product 1 about 1336 g.
- Example 2 Oxidation of diol 5 to form hydroxyketone product 2
- the second step the aqueous phase obtained by the above reaction and the aqueous solution which absorbed the acid gas are combined and placed in a flask, and 2 equivalents of hydrogen peroxide (30% aqueous solution) are slowly added dropwise, and the brown liquid which is immediately formed is immediately For the recovery of bromine.
- Hydrogen peroxide / bromine system 2063 g of diol 5 was dissolved in 20 liters of dichloromethane, 2 equivalents of hydrogen peroxide (30% strength aqueous solution) was added, and water was added to adjust the volume of the aqueous phase to the organic phase. One part, slowly add 480 g of bromine (0.3 eq.) at room temperature, pay attention to sufficient cooling to maintain the reaction at room temperature, and follow the progress of the reaction by thin layer chromatography. 0.5-2 equivalent peroxidation can be added. Hydrogen (30% strength aqueous solution) promotes the reaction to completion. The reaction system was diluted with an equal volume of water, the organic phase was separated by shaking, and the solvent was evaporated. The residue was evaporated under reduced pressure to give a white solid hydroxy ketone product 2 about 1655 g.
- the product 3 spectrum characterization data is as follows:
- the second step the aqueous phase obtained by the above reaction and the aqueous solution which absorbed the acid gas are combined and placed in a flask, and 2 equivalents of hydrogen peroxide (30% aqueous solution) are slowly added dropwise, and the brown liquid which is immediately formed is immediately For the recovery of bromine.
- Hydrogen peroxide / bromine system Dissolve 1962 g of diol 6 in 20 liters of dichloromethane, add 2 equivalents of hydrogen peroxide (30% strength in water), add water to adjust the volume of the aqueous phase to the organic phase of three One part, slowly add 480 g of bromine (0.3 eq.) at room temperature, pay attention to sufficient cooling to maintain the left stirring reaction at room temperature, trace the progress of the reaction by thin layer chromatography, and add 0.5-2 equivalent of peroxidation. Hydrogen (30% strength aqueous solution) promotes the reaction to completion. The reaction system was diluted with an equal volume of water, the organic phase was separated by shaking, and the solvent was evaporated to give a white solid hydroxy ketone product 3 about 1221 g.
- Hydrogen peroxide / hydrobromic acid system 1962 g of diol 6 was dissolved in 20 liters of dichloromethane, 2 equivalents of hydrogen peroxide (30% strength aqueous solution) was added, and 243 g of hydrobromic acid was slowly added at room temperature. (0.3 eq., 0.5 ⁇ ice solution), pay attention to sufficient cooling to maintain the reaction at room temperature, and follow the progress of the reaction by thin layer chromatography. 0.5-2 equivalent of hydrogen peroxide (30% aqueous solution) can be added. Promote complete reaction. The reaction system was diluted with an equal volume of water, and the organic phase was separated by shaking. The solvent was distilled away, and the residue was evaporated under reduced pressure to give a white solid hydroxy ketone product 3 about 1109 g.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
芳基 1,2-二醇转化为酮的环境友好性氧化新工艺
【技术领域】
本发明涉及辐射固化光聚合引发剂技术领域, 特别涉及若干具体芳基 1,2 二醇类化合物氧化生成相应芳基说羟基酮的新的环境友好性工艺技术。
【背景技术】
下述三个具体的芳基羟基酮化合物 1-3在工业上是重要的含烯不饱和体系 紫外光辐射光聚合固化引发剂:
书
化合物 1: 中文名称为 2-羟基 -2-曱基 -1-苯基 -1-丙酮; 相应的英文名称为 2-hydroxy-2-methyl- 1 -phenyl- 1 -propanone; 相应的化合物注册号为 7473-98-5。
化合物 2: 中文名称为 (1-羟基环己基)苯基-曱酮; 相应的英文名称为 (1- hydroxycyclohex l)phenyl-methanone; 相应的化合物注册号为 947- 19-3。
化合物 3: 中文名称为 2-羟基 -1- ( 4-曱氧基苯基) -2-甲基 -1-丙酮; 相应的 英文名称为 2-hydroxy- 1 -(4-methoxyphenyl)-2-methyl- 1 -propanone; 相应的化合 物注册号为 15482-17-4。
化合物 1-3传统的生产工艺以所谓的弗瑞德-克拉夫茨反应 ( Friedel-Crafts Reactions ) 为基础, 该工艺常常使用超过当量的三氯化铝和氯气等危险化学 品, 产生大量的固体废物和废酸废碱, 环保压力巨大。 近年来, 专利文献 US2009/0018354A1和 US2005/0203315A1分别披露了该类化合物自相应的芳基 1,2-二醇氧化制备的新工艺, 但是, 其工艺分别使用了重金属钯(Pd )和铜 ( Cu )衍生的氧化催化剂, 该类催化剂不仅难于大规模制备, 价格高昂, 而且 由此引发的重金属污染风险仍然非常突出。
本项专利申请现已首次发现化合物 1-3可以自相应的芳基 1,2-二醇以溴素 ( Br2 )为氧化剂氧化制备; 或以溴素为氧化催化剂, 而以过氧化氢(俗称双 氧水, H202 )为终端氧化剂氧化制备。 该工艺的突出特点是产率高, 经济价值 显著, 而且具有高度的绿色环保环境友好性。
【发明内容】
1
确认本
本发明的目的是提出化合物 1-3 自相应的芳基 1,2-二醇以溴素为氧化剂, 或以溴素为催化剂, 以过氧化氢为终端氧化剂氧化制备的新工艺。 这些芳基 1,2-二醇前体依次是下述化合物 4-6:
化合物 4: 中文名称为 2-甲基 -1-苯基 -1, 2-丙二醇; 相应的英文名称为 2- methyl- 1 -phenyl- 1 ,2-propanediol; 相应的化合物注册号为 20907- 13-5。
化合物 5: 中文名称为 α- ( 1-羟基环己基) -苯-曱醇; 相应的英文名称为 α- ( 1 -hydroxycyclohexyl)-benzene-methanol; 相症的化合物注册号为 1135-72-4。
化合物 6: 中文名称为 1- ( 4-曱氧基苯基) -2-曱基 -1, 2-丙二醇; 相应的 英文名称为 1 -(4-methoxyphenyl)-2-methyl- 1 ,2-propanediol; 相应的化合物注册 号为 261930-06-7。
该氧化反应新工艺的通用化学反应流程是如下图示 ^和 ?中的任意一种。 工艺 包含两步: 第一步即二醇化合物 4-6在溴素(Br2 )氧化下生成产物 1-3同时放出溴化氢(HBr )副产物。 反应温度优选室温, 溶剂优选卤代烃二氯 甲烷, 氧化剂溴素的使用量优选 1-3 当量, 但是反应温度和溶剂以及溴素的使 用量均非限制性条件, 本步限制性条件是使用了溴素作为该步反应的氧化剂。: 第二步即溴化氢副产物和过氧化氢(H202 )水相反应回收溴素循环使用。 反应 温度优选室温, 溴化氢和过氧化氢的化学当量比例优选 2/1至 1/1, 过氧化氢试 剂的浓度优选 10-50%。
工艺 只有一步, 即 "一锅煮" 的方式, 以溴素为催化剂, 将二醇化合物 4-6和过氧化氢反应制得产物 1-3。 反应温度优选室温, 溶剂优选卤代烃二氯曱 烷, 催化剂溴素的使用量优选 0.05-0.70 当量, 过氧化氢的用量优选 1-20 当 量。 执行该工艺具体操作时的一个有益改进是使用催化量的溴化氢为起始催化 剂物种, 这是可行的, 因为溴化氢可以原位地被过氧化氢氧化从而原位地生成 溴素执行催化氧化功能。 但是反应温度, 催化剂的起始形式 (溴素或溴化 氢), 溴化氢和过氧化氢的当量比以及过氧化氢的浓度均非限制性条件, 本步 限制性条件是使用了过氧化氢 /溴素或过氧化氢 /溴化氢这样的催化氧化系统实 现了自原料 4-6到产物 1-3的转化。
第一步: 氧化反应 二墜化盒物
+ 产整化合物
4或 5或 6 1载 2或 3 溴化氢 第二步: 回收溴素 溴化氢 + 过: 溴素 + 水
"一锅煮"工艺
(催化 ¾) 在 或 两种工艺中, 主干副产物均为水, 这是迄今为止本领域内所有已 知文献方法所无法比拟的优势, 因此该技术具有优越的绿色环境友好性和经济 成本竟争力。
【具体实施方式】
下面结合具体实施例进一步说明本工艺流程:
实施例一: 二醇 4氧化生成羟基酮产物 1
工艺
第一步: 将 1662克二醇 4溶解在 20升二氯曱烷中, 在室温下緩緩加入 1598克溴素(1 当量) , 注意维持此温度搅拌反应, 反应体系溢出的气体用水 吸收, 用薄层色谱法跟踪反应进程直至完成。 加入等体积的水, 振摇分离有机 相, 蒸馏回收溶剂, 残余物减压蒸馏得到无色油状羟基酮产物 1约 1562克。
产物 1波谱表征数据如下:
产物 1的核磁共振氢谙 1H NMR (CDC13, ppm单位): 8.01 (d, 2H), 7.56 (t, 1H), 7.46 (t, 2H), 4.12 (br, 1H), 1.61 (s, 6H);
产物 1的核磁共振碳谘 13C NMR (CDCls, ppm单位): 204.7, 133.8, 132.8, 129.6, 128.3, 76.3, 28.3。
第二步: 将上述反应后处理得到的水相和吸收了酸气的水溶液合并置于烧 瓶中, 緩緩滴加入 2 当量的过氧化氢(30%浓度的水溶液) , 即刻生成的棕色 液体即为回收后的溴素。
工艺
过氧化氢 /溴素体系: 将 1662克二醇 4溶解在 20升二氯甲烷中, 加入 2当 量的过氧化氢(30%浓度的水溶液) , 加入水调节水相体积至有机相的三分之 一, 在室温下緩緩加入 480克溴素(0.3 当量) , 注意充分冷却以维持在室温 温度左右搅拌反应, 用薄层色谱法跟踪反应进輊, 可适当补加 0.5-2 当量过氧 化氢(30%浓度的水溶液)促进反应完全。 反应体系用等体积水稀释, 振摇分 离有机相, 蒸馏回收溶剂, 残余物减压蒸榴得到无色油状羟基酮产物 1约 1433 克。
过氧化氢 /氢溴酸体系: 将 1662克二醇 4溶解在 20升二氯曱烷中, 加入 2 当量的过氧化氢(30%浓度的水溶液) , 在室温下緩緩加入 243克氢溴酸(0.3 当量, 0.5M浓度水溶液) , 注意充分冷却以维持在室温温度左右搅拌反应, 用 薄层色 i普法跟踪反应进程, 可适当补加 0.5-2 当量过氧化氢(30%浓度的水溶 液)促进反应完全。 反应体系用等体积水稀释, 振摇分离有机相, 蒸馏回收溶 剂, 残余物減压蒸馏得到无色油状羟基酮产物 1约 1336克。 实施例二: 二醇 5氧化生成羟基酮产物 2
工艺
第一步: 将 2063克二醇 5溶解在 20升二氯甲烷中, 在室温下緩緩加入 1598克溴素(1 当量) , 注意维持此温度搅袢反应, 反应体系溢出的气体用水 吸收, 用薄层色錯法跟踪反应进程直至完成。 加入等体积的水, 振摇分离有机 相, 蒸傭回收溶剂, 残余物减压蒸馏得到白色固体羟基酮产物 2约 1817克£ 产物 2波镨表征数据如下:
产物 2的核磁共振氢诸 1H NMR (CDC13, ppm单位): 8.01-8.00 (d, 2H), 7.55- 7.43 (m, 3H), 3.41 (s, 1H), 2.07-2.04 (m, 2H), 1.82-1.66 (m, 8H);
产物 2的核磁共振碳谱 13C NMR (CDCI3, ppm单位): 205.5, 135.2, 132.3, 129.5, 128.2, 78.7, 35.3, 25.3, 21.4。
第二步: 将上述反应后处理得到的水相和吸收了酸气的水溶液合并置于烧 瓶中, 緩緩滴加入 2 当量的过氧化氢(30%浓度的水溶液) , 即刻生成的棕色 液体即为回收后的溴素。
工艺 5:
过氧化氢 /溴素体系: 将 2063克二醇 5溶解在 20升二氯曱烷中, 加入 2当 量的过氧化氢(30%浓度的水溶液) , 加入水调节水相体积至有机相的三分之 一, 在室温下緩緩加入 480克溴素(0.3 当量) , 注意充分冷却以维持在室温 温度左右搅拌反应, 用薄层色谱法跟踪反应进程, 可适当补加 0.5-2 当量过氧 化氢(30%浓度的水溶液)促进反应完全。 反应体系用等体积水稀释, 振摇分 离有机相, 蒸馏回收溶剂, 残余物減压蒸熘得到白色固体羟基酮产物 2约 1655 克。
过氧 ^氢 /氢溴酸体系: 将 2063克二醇 5溶解在 20升二氯甲烷中, 加入 2 当量的过氧化氢(30%浓度的水溶液) , 在室温下緩緩加入 243克氢溴酸(0.3 当量, 0.5M浓度水溶液) , 注意充分冷却以维持在室温温度左右搅拌反应, 用 薄层色谱法跟踪反应进程, 可适当补加 0.5-2 当量过氧化氢(30%浓度的水溶 液)促进反应完全。 反应体系用等体积水稀释, 振摇分离有机相, 蒸馏回收溶 剂, 残余物减压蒸馏得到白色固体羟基酮产物 2约 1587克。 实施例三: 二醇 6氧化生成羟基酮产物 3
工艺
第一步: 将 1962克二醇 6溶解在 20升二氯曱烷中, 在室温下緩緩加入 1598克溴素(1 当量) , 注意维持此温度搅拌反应, 反应体系溢出的气体用水 吸收, 用薄层色谱法跟踪反应进程直至完成。 加入等体积的水, 振摇分离有机 相, 蒸馏回收溶剂, 残余物减压蒸愤得到白色固体羟基酮产物 3约 372克。
产物 3波谱表征数据如下:
产物 3的核磁共振氢谱 lH NMR (CDCI3, ppm单位): 8.06 (d, 2H, J = 7 Hz), 6.94 (d, 2H, J = 7 Hz), 4.28 (s, 1H), 3.87 (s, 3H), 1.62 (s, 6H)。
第二步: 将上述反应后处理得到的水相和吸收了酸气的水溶液合并置于烧 瓶中, 緩緩滴加入 2 当量的过氧化氢(30%浓度的水溶液) , 即刻生成的棕色 液体即为回收后的溴素。
工艺 Β··
过氧化氢 /溴素体系: 将 1962克二醇 6溶解在 20升二氯曱烷中, 加入 2当 量的过氧化氢(30%浓度的水溶液) , 加入水调节水相体积至有机相的三分之 一, 在室温下緩緩加入 480克溴素(0.3 当量) , 注意充分冷却以维持在室温 温度左 搅拌反应, 用薄层色谱法跟踪反应进程, 可适当补加 0.5-2 当量过氧 化氢(30%浓度的水溶液)促进反应完全。 反应体系用等体积水稀释, 振摇分 离有机相, 蒸镏回收溶剂, 残余物减压蒸餾得到白色固体羟基酮产物 3约 1221 克。
过氧化氢 /氢溴酸体系: 将 1962克二醇 6溶解在 20升二氯甲烷中, 加入 2 当量的过氧化氢(30%浓度的水溶液) , 在室温下緩緩加入 243克氢溴酸( 0.3 当量, 0.5Μ浓度氷溶液) , 注意充分冷却以维持在室温温度左右搅拌反应, 用 薄层色谱法跟踪反应进程, 可适当补加 0.5-2 当量过氧化氢(30%浓度的水溶 液)促进反应完全。 反应体系用等体积水稀释, 振摇分离有机相, 蒸馏回收溶 剂, 残余物减压蒸馏得到白色固体羟基酮产物 3约 1109克。
需要强调的是, 上述列举的实施例仅是一些优选的示例性试验, 不应被视 为是限定性工艺条件。 本发明申请所涵盖的工艺创新范围应以权利要求书记载 为准。
Claims
1、 一种将 2-曱基小苯基 -1, 2-丙二醇(编号化合物 4)氧化生成 2-羟基 -2-甲 基 -1-苯基 -1-丙酮(编号化合物 1)的新的工艺条件, 该工艺条件的核心限制性 ^件 是使用溴素为氧化剂。
2、 一种将 α- (1-羟基环己基) -苯 -曱醇(编号化合物 5)氧化生成(1-羟基环 £ 基)苯基 -曱酮(编号化合物 2)的新的工艺条件, 该工艺条件的核心限制性奈件是 使用溴素为氧化剂。
3、 一种将 1- (4-曱 苯基) -2-甲基 -1, 2-丙二醇(编号化合物 6)氧化生成 2-羟基 -1- (4-甲氧基苯基) -2-曱基 -1-丙酮(编号化合物 3)的新的工艺条件, 该工 艺条件的核心限制性条件是使用溴素为氧化剂。
4、 上述权力要求 1-3条中的反应工艺通式如下 式所描述, 该通式的核心限制 性条件是在其第一步里使用溴素为氧化剂。 在其第二步里使用过氧化氢(俗称双氧 水)氧化第一步生成的溴化氢副产物从而有效实现了溴素的回收。 第一步: 氧化反 i +
; + 漠
. (A)
第二步: 回收^
溴化氢 + 过氧化氢 溴素 + 水
5、 一种将 2-曱基 -1-苯基 -1, 2-丙二醇(编号化合物 4)氧化生成 2-羟基- 2-曱基 -1-苯基 -1-丙酮(编号化合物 1)的新的工艺条件, 该工艺条件的核心限 制性条件是使用过氧化氢 /渙素或过氧化氢 /溴化氢这样的催化氧化系统, 也即 是使用溴素为实盾氧 催化剂, 以过氧化氢(俗称双氧水)为终端氧化剂氧化 原位生成的溴化氢副产物生成溴素从而有效实现了催化氧化循环。
6、 一种将 α- (1-羟基环己基) -苯 -曱醇(编号化合物 5)氧化生成(1-羟 基环己基)苯基 -甲酮(编号化合物 2)的新的工艺条件, 该工艺条件的核心限 制性条件是使用过氧化氢 /溴素或过氧化氢 /溴化氢这样的催化氧化系统, 也 : 是使用溴素为实质氧化催化剂, 以过氧化氢(俗称双氧水)为终端氧化剂氧化 原位生成的溴化氢副产物生成溴素从而有效实现了催化氧化循环。
7、 一种将 1- ( 4-曱氧基苯基) -2-甲基 -1 , 2-丙二醇(编号化合物 6 )氧化 生成 2-羟基小(4-曱氧基苯基) -2-曱基 -1-丙酮(编号化合物 3 )的新的工艺条: 件, 该工艺条件的核心限制性条件是使用过氧化氢 /溴素或过氧化氢 /溴化氢i 样的催化氧化系统, 也即是使用溴素为实质氧化催化剂, 以过氧化氢(俗称双 氧水)为终端氧化剂氧化原位生成的溴化氢副产物生成溴素从而有效实现了催 化氧化循环。
8、 上述权力要求 5-7条中的反应工艺通式如下 式所描述, 该通式的核心限制 性 是使用了过氧化氢 /溴素或过氧化氢 /溴化氢这样的催化氧化系统实现了催化辈 化循环。
"一锅煮"工艺
产 化合物
2或 3 + 水
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