CN106810461B - Preparation method of α -dimethylamino-p-alkoxy acetophenone compounds - Google Patents
Preparation method of α -dimethylamino-p-alkoxy acetophenone compounds Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000012043 crude product Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- 239000012045 crude solution Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003495 polar organic solvent Substances 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- -1 tetraphenyl guanidine borate Chemical compound 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FUASJQSBFUVWJQ-UHFFFAOYSA-N [N].NC(N)=N Chemical compound [N].NC(N)=N FUASJQSBFUVWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- MKNZKCSKEUHUPM-UHFFFAOYSA-N potassium;butan-1-ol Chemical compound [K+].CCCCO MKNZKCSKEUHUPM-UHFFFAOYSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Chemical group 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of α -dimethylamino p-alkoxy acetophenone compounds, which takes a compound II and metal alkoxide as raw materials to prepare α -dimethylamino p-alkoxy acetophenone compounds I through one-step reaction at 20-110 ℃, and the reaction equation is as follows:
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a preparation method of α -dimethylamino-p-alkoxy acetophenone compounds.
Background
In recent years, the photolatent tertiary amine photolatent alkali becomes a hotspot field of photoinitiator research, and has been successfully developed to be a novel photolatent alkali such as quaternary ammonium salt, α -aminoketone, tetraphenyl guanidine borate and the like, wherein the photolatent alkali can release free tertiary amine, amidine or guanidine nitrogen-containing alkali during ultraviolet irradiation, has stronger alkali catalytic activity, can initiate anion polymerization, can still continuously catalyze the crosslinking curing reaction of epoxy prepolymer or isocyanate prepolymer and a multi-mercapto compound even after the ultraviolet irradiation is stopped, and the application field of the ultraviolet curing technology is greatly widened.
European patent document EP0898202B1 discloses two photoinitiators, namely 2-methyl-2- (4-morpholinyl) -1- (4-methylthiophenyl) acetone (Irgacure 907) and 2-benzyl-2-dimethylamino-1- (4-morpholinyl phenyl) butanone (Irgacure 369), which can be used in the photolatent base curing technology, but the Irgacure 907 has very low photocuring activity, long-time illumination is needed to complete the crosslinking curing process, and the Irgacure369 with relatively good curing performance is easy to generate yellowing phenomenon, so that the application of the Irgacure369 in varnish is limited.
U.S. Pat. No. 5,50774, A discloses a series of α -dimethylamino p-alkoxy acetophenone compounds which can be used as photoinitiators, and the structural use of alkoxy groups in the compounds replaces morpholinyl groups, so that the defect that Irgacure369 is easy to yellow in use is overcome, and the compounds have potential application prospects.
Disclosure of Invention
The technical problem to be solved by the invention is to fill the blank of the preparation process of α -dimethylamino-p-alkoxy acetophenone compounds in the prior art, and further provide a simple, convenient and efficient preparation method of α -dimethylamino-p-alkoxy acetophenone compounds.
Therefore, the technical scheme for realizing the purpose is as follows:
a process for preparing α -dimethylamino-p-alkoxy acetophenone compounds includes reaction between metal alkoxide and compound II at 20-110 deg.C, purifying reaction liquid to obtain compound I, the reaction equation is as follows:
in the formula, R1Is C1-C4Alkyl, M is potassium or sodium, R2Is methyl or ethyl, R3Is hydrogen or methyl.
Preferably, the molar ratio of the metal alkoxide to the compound II is (1.2-1.3): 1.
Preferably, in the absence of a solvent, the purification treatment is: washing the reaction solution with water, and collecting an organic phase to obtain a crude product; dissolving the crude product in R1Adding active carbon into OH such as ethanol, heating to reflux, filtering, collecting filtrate, and concentrating the filtrate to obtain compound I; wherein the mass ratio of the water to the reaction liquid is (6-8) to 1.
Preferably, the compound II is dropwise added into the metal alkoxide to react in the presence of a polar organic solvent; the metal alkoxide is a metal alkoxide solution, and the metal alkoxide solution is a metal alkoxide dissolved by a polar organic solvent; the compound II is a compound II solution, and the compound II solution is the compound II dissolved by a polar organic solvent.
Preferably, the polar organic solvent is DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), R1A mixture of one or more of OH or acetonitrile.
Preferably, the molar concentration of the metal alkoxide solution is 2 to 5 mol/L; the molar concentration of the compound II solution is 1.5-2 mol/L.
Preferably, the temperature of the reaction is 20-70 ℃.
Preferably, the purification treatment is: and (3) distilling the reaction solution under reduced pressure, dissolving residues by toluene or n-hexane, washing by water, collecting an organic phase to obtain a crude product solution, adding activated carbon into the crude product solution, heating to reflux, filtering, collecting filtrate, and concentrating to obtain the compound I.
Preferably, when compound I is a solid, the method further comprises the step of recrystallizing the crude product or the crude solution.
Preferably, the reaction is carried out under an inert gas blanket.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of α -dimethylamino-p-alkoxy acetophenone compounds, which takes a compound II and metal alkoxide as raw materials to prepare α -dimethylamino-p-alkoxy acetophenone compounds I through one-step reaction at 20-110 ℃, and has the advantages of mild reaction conditions, simple and convenient operation, short reaction time, high yield, high product purity and good industrial application prospect.
2. According to the preparation method of the α -dimethylamino-p-alkoxy acetophenone compound, the compound II and the metal alkoxide can react without a solvent, so that the purification operation is simplified, and the product loss is reduced.
3. According to the preparation method of the α -dimethylamino-p-alkoxy acetophenone compound, the compound II solution is dripped into the metal alkoxide solution for reaction, so that the generation of side reaction is favorably inhibited, and the purity and the reaction yield of a target product are improved.
4. According to the preparation method of the α -dimethylamino-p-alkoxy acetophenone compound, the crude product is decolorized by adopting activated carbon, so that red impurities generated by oxidation of a nitrogen-containing compound in the synthesis process can be removed, and the color purity of the product is favorably improved.
Detailed Description
The preparation method of α -dimethylamino-p-alkoxyacetophenone compounds provided by the present invention is described in detail with reference to the following specific examples.
Example 1: preparation of 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) butanone
50g (0.167mol) of 2-benzyl-2-dimethylamino-1- (4-fluorophenyl) butanone is added into a reaction flask, the temperature is raised to 60 ℃, 10.9g (0.202mol) of sodium methoxide is added under continuous stirring, and the mixture reacts for 1h at the temperature of 110 ℃ and 120 ℃. The reaction solution was cooled to 60-80 ℃, washed sequentially with 200ml of water, 100ml of water, and 100ml of water, the organic phase was collected, and the residual water was removed under reduced pressure to obtain 48.5g of crude product. Dissolving the crude product in 150ml 95% ethanol, adding 1.5g active carbon, heating to reflux for decolorizing for 0.5h, filtering to remove active carbon, distilling the filtrate under reduced pressure to 97g, cooling to-10 deg.C, precipitating crystal under stirring, filtering, and filtering to obtain filter cakeDrying at 30 ℃ to obtain 44.2g of 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) butanone as a light yellow solid, wherein the HPLC purity is 99.5 percent, the yield is 85.0 percent, and the melting point is 44.7-46.6 ℃.1HNMR(CDCl3，300MHz)δppm：0.59(t，3H，CH3)，1.71-2.03(m，2H，CH2)，2.31(s，6H，N(CH3)2)，3.11(s，2H，PhCH2)，3.83(s，3H，OCH3)，6.97(d，2H，Ar-H)，6.97-7.22(m，5H，Ar-H)，8.29(d，2H，Ar-H)。
Example 2: preparation of 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) butanone
A250 ml four-necked flask was equipped with a stirrer, a thermometer, a constant pressure dropping funnel and an aeration device. Adding 10.9g of sodium methoxide and 40ml of DMSO into a reaction bottle, stirring and dissolving under the protection of nitrogen, then dropwise adding 80ml of DMSO solution dissolved with 50g of 2-benzyl-2-dimethylamino-1- (4-fluorophenyl) butanone into the reaction bottle, controlling the temperature to be 60-70 ℃ after dropwise adding, reacting for 2h, and replacing a reduced pressure distillation device to remove the DMSO. Dissolving the residue in 150ml of n-hexane, washing with 200ml of water, 100ml of water and 100ml of water in sequence, collecting an organic phase to obtain a crude solution, adding 1.5g of activated carbon into the crude solution, heating to reflux for decoloring, filtering, collecting filtrate, concentrating to 95g, cooling to-10 ℃, stirring to separate out crystals, filtering, and drying a filter cake at 30 ℃ to obtain 43.2g of light yellow solid 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) butanone with the HPLC purity of 99.3% and the yield of 83.1%.
Example 3: preparation of 2-benzyl-2-dimethylamino-1- (4-n-butoxyphenyl) acetone
A250 ml four-necked flask was equipped with a stirrer, a thermometer, a constant pressure dropping funnel and an aeration device. 24.6g (0.219mol) of potassium n-butoxide and 62ml of DMF are added to a reaction flask, 116ml of DMF solution in which 50g (0.175mol) of 2-benzyl-2-dimethylamino-1- (4-fluorophenyl) acetone is dissolved is added dropwise to the reaction flask under nitrogen protection and continuous stirring, after the dropwise addition, the reaction is carried out at 20 to 30 ℃ for 6 hours, and the vacuum distillation device is replaced to remove the DMF. The residue was dissolved in 150ml of toluene, washed with 200ml of water, 100ml of water and 100ml of water in this order,collecting organic phase to obtain crude solution, adding 1.5g of activated carbon into the crude solution, heating to reflux for decoloring, filtering, and concentrating the filtrate to obtain orange yellow liquid 2-benzyl-2-dimethylamino-1- (4-n-butoxyphenyl) acetone 51.6g with HPLC purity of 98.2% and yield of 86.8%.1HNMR(CDCl3，300MHz)δppm：0.90(t，3H，CH3)，1.45-1.52(sextet，2H，CH2)，1.50(s，3H，CH3)，1.71-1.82(quintet，2H，CH2)，2.36(s，6H，NCH3)，3.19(s，2H，PhCH2)，4.06(t，2H，OCH2)，6.84(d，2H，Ar-H)，7.17-7.26(m，5H，Ar-H)，8.37(d，2H，Ar-H)。
Example 4: preparation of 2-benzyl-2-dimethylamino-1- (4-ethoxyphenyl) butanone
A100 ml four-necked flask was equipped with a stirrer, a thermometer, a constant pressure dropping funnel and an aeration device. 2.9g (0.043mol) of sodium ethoxide and 20ml of acetonitrile are added into a reaction flask, 20ml of acetonitrile solution in which 10g (0.033mol) of 2-benzyl-2-dimethylamino-1- (4-fluorophenyl) butanone is dissolved is dropwise added into the reaction flask under the protection of nitrogen and continuous stirring, the reaction is carried out for 1h at 70 ℃ after the dropwise addition is finished, and a reduced pressure distillation device is replaced to remove the acetonitrile. Dissolving the residue in 50ml of toluene, washing with 20ml of water, 20ml of water and 10ml of water in sequence, collecting an organic phase to obtain a crude product solution, adding 0.5g of activated carbon into the crude product solution, heating to reflux for decoloring, filtering, and distilling the filtrate under reduced pressure to obtain 10g of an orange viscous product, namely 2-benzyl-2-dimethylamino-1- (4-ethoxyphenyl) butanone, wherein the HPLC purity is 98.0 percent, and the yield is 93.1 percent.1HNMR(CDCl3，300MHz)δppm：0.68(t，3H，CH3)，1.44(t，3H，CH3)，1.81-2.13(m，2H，CH2，)，2.36(s，6H，NCH3)，3.19(s，2H，PhCH2)，4.10(q，2H，OCH2)，6.84(d，2H，Ar-H)，7.17-7.26(m，5H，Ar-H)，8.37(d，2H，Ar-H)。
Example 5: preparation of 2-p-methylbenzyl-2-dimethylamino-1- (4-isopropoxyphenyl) butanone
The mixture is stirred on a three-mouth bottle of 250mlA thermometer, and a ventilator. 50g (0.16mol) of 2-p-methylbenzyl-2-dimethylamino-1- (4-fluorophenyl) butanone and 18.8g (0.192mol) of potassium isopropoxide are added successively to a reaction flask under nitrogen protection and stirring, and the reaction is carried out at 25 ℃. After the reaction is finished, washing the reaction solution by 200ml of water, 100ml of water and 100ml of water in sequence, collecting an organic phase, removing residual water under reduced pressure to obtain a crude product, dissolving the crude product in 150ml of 95% ethanol, adding 1.5g of activated carbon, heating to reflux for decoloring for 0.5h, filtering to remove the activated carbon, and distilling the filtrate under reduced pressure until no low-boiling-point substances exist to obtain orange yellow liquid 2-p-methylbenzyl-2-dimethylamino-1- (4-isopropoxyphenyl) butanone 52.8g, wherein the HPLC purity is 97.5%, and the yield is 93.5%.1HNMR(CDCl3，300MHz)δppm：0.70(t，3H，CH3)，1.31/1.34(d，6H，2CH3)，1.80-1.87(m，H，CH2)，2.01-2.09(m，1H，CH2)，2.30(s，3H，CH3)，2.36(s，6H，NCH3)，3.15(s，2H，PhCH2)，4.70(heptet，1H，OCH)，6.80/6.83(d，2H，Ar-H)，7.01/7.04(d，2H，Ar-H)，7.11/7.13(d，2H，Ar-H)，8.35/8.38(d，2H，Ar-H)。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (2)
1. A preparation method of 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) butanone is characterized in that 50g of 2-benzyl-2-dimethylamino-1- (4-fluorophenyl) butanone is added into a reaction bottle, the temperature is raised to 60 ℃, 10.9g of sodium methoxide is added under the condition of continuous stirring, and the reaction is carried out for 1h at the temperature of 110 ℃ and 120 ℃; cooling the reaction solution to 60-80 ℃, washing with 200ml of water, 100ml of water and 100ml of water in sequence, collecting an organic phase, and removing residual water under reduced pressure to obtain 48.5g of a crude product; dissolving the crude product in 150ml of 95% ethanol, adding 1.5g of activated carbon, heating to reflux for decoloring for 0.5h, filtering to remove the activated carbon, distilling the filtrate under reduced pressure to 97g, cooling to-10 ℃, precipitating crystals under stirring, filtering, and drying a filter cake at 30 ℃ to obtain 44.2g of 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) butanone.
2. A preparation method of 2-p-methylbenzyl-2-dimethylamino-1- (4-isopropoxyphenyl) butanone is characterized in that a stirrer, a thermometer and an aeration device are assembled on a 250ml three-necked bottle, 50g of 2-p-methylbenzyl-2-dimethylamino-1- (4-fluorophenyl) butanone and 18.8g of potassium isopropoxide are sequentially added into the reaction bottle under the protection of nitrogen and continuous stirring, the reaction is carried out at 25 ℃, after the reaction is finished, 200ml of water, 100ml of water and 100ml of water are sequentially used for washing reaction liquid, an organic phase is collected, residual water is removed under reduced pressure to obtain a crude product, the crude product is dissolved in 150ml of 95% ethanol, 1.5g of activated carbon is added, the mixture is heated to reflux for carrying out decoloration treatment for 0.5h, the activated carbon is removed by filtration, filtrate is distilled under reduced pressure until no low-boiling substances exist, thus, 52.8g of 2-p-methylbenzyl-2-dimethylamino-1- (4-isopropoxyphenyl) butanone was obtained as an orange-yellow liquid.
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| US5077402A (en) * | 1987-03-26 | 1991-12-31 | Ciba-Geigy Corporation | Novel alpha-aminoacetophenones as photoinitiators |
| CN103012081A (en) * | 2011-09-20 | 2013-04-03 | 烟台九目化学制品有限公司 | 4-iodophenylether derivative preparation method |
-
2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077402A (en) * | 1987-03-26 | 1991-12-31 | Ciba-Geigy Corporation | Novel alpha-aminoacetophenones as photoinitiators |
| CN103012081A (en) * | 2011-09-20 | 2013-04-03 | 烟台九目化学制品有限公司 | 4-iodophenylether derivative preparation method |
Non-Patent Citations (1)
| Title |
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| "卤代苯腈与醇盐的亲核取代反应及氰基苯酚的合成研究";孟德素;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20040315(第01期);B014-59，12-13 * |
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