CN104447396B - Benzoin oxime derivative and preparation method thereof - Google Patents
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- CN104447396B CN104447396B CN201410728358.6A CN201410728358A CN104447396B CN 104447396 B CN104447396 B CN 104447396B CN 201410728358 A CN201410728358 A CN 201410728358A CN 104447396 B CN104447396 B CN 104447396B
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- WAKHLWOJMHVUJC-FYWRMAATSA-N (2e)-2-hydroxyimino-1,2-diphenylethanol Chemical class C=1C=CC=CC=1C(=N/O)\C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-FYWRMAATSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- WAKHLWOJMHVUJC-UHFFFAOYSA-N benzoin alpha-oxime Natural products C=1C=CC=CC=1C(=NO)C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-UHFFFAOYSA-N 0.000 claims abstract description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012265 solid product Substances 0.000 claims abstract description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims abstract description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012312 sodium hydride Substances 0.000 claims abstract description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 241001597008 Nomeidae Species 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004440 column chromatography Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 229940125904 compound 1 Drugs 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- AZQCFLDDJHERFZ-UHFFFAOYSA-N Br.C#Cc1ccccc1 Chemical compound Br.C#Cc1ccccc1 AZQCFLDDJHERFZ-UHFFFAOYSA-N 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical group CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002024 ethyl acetate extract Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- IIMJBFUBGQRXLJ-UHFFFAOYSA-N CC1=CC=CC=C1.C#C.Br Chemical compound CC1=CC=CC=C1.C#C.Br IIMJBFUBGQRXLJ-UHFFFAOYSA-N 0.000 claims description 3
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 claims description 3
- -1 Isopropyl ester Chemical class 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- BPVHWNVBBDHIQU-UHFFFAOYSA-N 2-bromoethynylbenzene Chemical compound BrC#CC1=CC=CC=C1 BPVHWNVBBDHIQU-UHFFFAOYSA-N 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)OC(C(CC1[C@@](C=C2c3ccc(C)cc3)N=C(C)c3ccccc3)(CC1=C2C#Cc1ccc(*)cc1)C(OC(C)C)=O)=O Chemical compound CC(C)OC(C(CC1[C@@](C=C2c3ccc(C)cc3)N=C(C)c3ccccc3)(CC1=C2C#Cc1ccc(*)cc1)C(OC(C)C)=O)=O 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002690 malonic acid derivatives Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a benzoin oxime derivative and a preparation method thereof. A structural formula of the benzoin oxime derivative is shown in the specification. The preparation method comprises the following steps: reacting malonate with propargyl bromide in anhydrous acetonitrile under the catalysis of sodium hydride to obtain a white solid product; by taking triethylamine as alkali, reacting the white solid product with phenylethynyl bromine or substituted phenylethynyl bromine in anhydrous acetonitrile under the catalysis of Pd(PPh3)2Cl2/CuI to obtain a light brown solid product; reacting the light brown solid product with benzoin oxime in toluene at 95-105 DEG C to obtain the benzoin oxime derivative. A brand new synthetic method of polysubstituted benzoin oxime is provided, and a series of new benzoin oxime derivatives are generated. Compared with normal benzoin oxime derivatives, the benzoin oxime derivative prepared by virtue of the preparation method has relatively complex and diverse structures by virtue of multiple cycles, and presents relatively wide application prospects in chemical industry production and clinic medicines.
Description
Technical field
The present invention relates to organic compound field, be specifically related to a kind of benzoin oxime derivant and preparation method thereof.
Background technology
Benzoinum, benzoin oxime and derivant thereof are widely used in commercial production and scientific research, such as Benzoinum, benzoin oxime
And derivant is organic synthesis and the important intermediate of fine chemistry industry, it is widely used in chemical industry, medicine, spice, chelating agen, painting
The fields such as material.In view of the special significance of Benzoinum, benzoin oxime and derivant thereof, how to go expand benzoin oxime and derive
The synthesis path of thing causes countless organic synthesis man and chemist actively thinks deeply, and has drawn some effectively methods.
Common Benzoinum, benzoin oxime synthetic method have:
One, with Cyanogran., potassium cyanide as catalyst:
With Cyanogran., potassium cyanide as catalyst, benzaldehyde intermolecular occur condensation generate Benzoinum, recycling Benzoinum alkali without
Reacting with oxammonium hydrochloride. under aqueous carbonate potassium effect and prepare benzoin oxime, but Cyanogran., potassium cyanide are poisonous drugs, to human body and
Environmental security has grave danger, in-convenience in use.
Two, with vitamin B1 as catalyst:
By 1.8g vitamin B1,6 L water, 15mL ethanol and the mixing of 15mL benzaldehyde, it is slowly added dropwise 150g/L NaOH,
Regulation pH9-10, shakes up, and at 60-75 DEG C, reflux 75min.Reactant mixture is cooled to room temperature, separates out light yellow knot
Crystalline substance, in ice bath, cooling makes crystallization complete, obtains synthesizing benzoic optimum yields.Again by Benzoinum in alkali Anhydrous potassium carbonate effect
Lower reaction with oxammonium hydrochloride. prepares benzoin oxime.This method productivity is higher, avoids severe toxicity medicine potassium cyanide, the making of Cyanogran. simultaneously
With, environmental protection.
Summary of the invention
The deficiency existed for prior art, the present invention provides a kind of benzoin oxime derivant and preparation method thereof.
The technical solution used in the present invention is:
A kind of benzoin oxime derivant, its structural formula is:
Wherein E1=E2=CO2R, R are straight chained alkyl, branched alkyl, unsaturated alkyl or aryl radical；R1、R2For hydrogen, straight chain
Alkyl, branched alkyl, halogen or alkoxyl and corresponding derivant thereof.
The preparation method of a kind of benzoin oxime derivant, comprises the following steps:
(1) with sodium hydride as catalyst, malonate and propargyl bromide joining ice-water bath in anhydrous acetonitrile, stirring is reacted,
White solid product, i.e. compound 1 is obtained after purifies and separates；
Described sodium hydride, malonate, propargyl bromide the amount of material than for 4-5:1:2.2-3.2；
Described malonate concentration in anhydrous acetonitrile is 0.5-0.8mol/L；
Described malonate is selected from malonates, malonic acid unsaturated alkyl ester, malonic acid aryl radical ester；
Described purifies and separates is the washing that added water by product, is extracted with ethyl acetate, and decompression is spin-dried for, and is the acetic acid of 1:100 by volume ratio
Ethyl ester: petroleum ether column chromatography for separation；
The described response time is more than 5h；
(2) compound 1 is blended in Pd (PPh with phenylacetylene bromide or substituted phenylacetylene bromide3)2Cl2The anhydrous and oxygen-free of/CuI is urged
In change system, make alkali with triethylamine, with anhydrous acetonitrile as solvent, stirring reaction under room temperature, obtain light brown after purifies and separates solid
Body product, i.e. precursor compound 2；
Described compound 1, phenylacetylene bromide or substituted phenylacetylene bromide, Pd (PPh3)2Cl2, the amount of material of triethylamine be
1:2.2-3.2:0.0085-0.014:4-5；
The substituent group of described substituted phenylacetylene bromide is straight chained alkyl, branched alkyl, halogen or alkoxyl and corresponding derivant thereof；
The described compound 1 concentration in anhydrous acetonitrile is 0.32-0.6mol/L；
Described Pd (PPh3)2Cl2In the anhydrous and oxygen-free catalyst system and catalyzing of/CuI, Pd (PPh3)2Cl2With the amount of the material of CuI than for 3:1；
Described purifies and separates is the washing that added water by product, is extracted with ethyl acetate, and decompression is spin-dried for, and is the acetic acid of 1:100 by volume ratio
Ethyl ester: petroleum ether column chromatography for separation；
The described response time is more than 10h；
(3) under conditions of 95-105 DEG C, the precursor compound 2 prepared by step (2) is reacted with benzoin oxime in toluene
More than 10 hours, after being separated by product purification, obtain yellow solid compound 3, i.e. target product benzoin oxime derivant；
The amount of described precursor compound 2 and the material of benzoin oxime is than for 1:1.1-1.5；
The precursor compound 2 concentration in toluene is 0.2-0.5mol/L；
Described purifies and separates is to be washed by products in water, and ethyl acetate extracts, and decompression is spin-dried for, and is the ethyl acetate of 1:30 by volume ratio:
Petroleum ether column chromatography for separation.
Compared with prior art, the invention provides the synthetic method of a kind of brand-new polysubstituted benzoin oxime, generate a series of newly
Benzoin oxime derivant.Relative to common benzoin oxime derivant, benzoin oxime derivant prepared by the present invention has multi-ring depositing
, its structure is the most complicated various, also will show more wide purposes prospect in Chemical Manufacture, clinical medicine.
Detailed description of the invention
Embodiment 1
A kind of benzoin oxime derivant, structural formula is:
A kind of preparation method of benzoin oxime derivant, described preparation method comprises the following steps:
A, precursor synthesize；
B, target product synthesize；
C, purification.
Wherein, a, precursor synthesize, and comprise the following steps:
(1) with 830mmol sodium hydride as catalyst, 200mmol diethyl malonate is joined with 440mmol propargyl bromide
Ice-water bath in 250mL anhydrous acetonitrile, stirring reaction 8 hours, product adds water washing, is extracted with ethyl acetate, and decompression is spin-dried for,
Column chromatography (volume ratio ethyl acetate: petroleum ether=1:100) obtains white solid product, i.e. compound 1；
(2) 80mmol compound 1 and 200mmol phenylacetylene bromide are blended in 1.3gPd (PPh3)2Cl2The anhydrous and oxygen-free of/CuI
In catalyst system and catalyzing, Pd (PPh3)2Cl2With the amount of the material of CuI than for 3:1, make alkali with 320mmol triethylamine, anhydrous with 200ml
Acetonitrile is solvent, and stirring reaction 12 hours under room temperature, products in water washs, and is extracted with ethyl acetate, and decompression is spin-dried for, column chromatography
(volume ratio ethyl acetate: petroleum ether=1:100) obtains light tan solid product, i.e. precursor compound 2.
Wherein b, target product synthesis, comprises the following steps:
Under conditions of 100 DEG C, 0.44g precursor compound 2 and 0.34g benzoin oxime are reacted 12 hours in 3mL toluene,
Obtain compound 3, the i.e. crude product of benzoin oxime derivant.
Wherein, c, purification, comprise the following steps:
The crude product with water washing of benzoin oxime derivant step b prepared, ethyl acetate extracts, and decompression is spin-dried for, column chromatography
(volume ratio ethyl acetate: petroleum ether=1:30) isolated yellow solid product, i.e. benzoin oxime derivant, column chromatography produces
Rate is 65.2%.
Yellow solid product structure is passed through；1H NMR；13C NMR measures.
Yellow solid product:
1H NMR(300MHz,CDCl3) δ 7.96 (s, 1H), 7.93 (s, 1H), 7.81 (s, 1H), 7.78 (s, 1H),
7.54 7.25 (m, 16H), 6.63 (s, 1H), 4.29 4.22 (m, 4H), 3.73 (s, 2H), 3.66 (s,
2H), 1.32-1.27 (t, 6H).
13C NMR(75MHz,CDCl3) δ 196.89,171.49,166.91,144.95,
144.48,143.29,139.96,134.86,134.64,134.44,132.04,131.23,130.46,129.88
,129.15,129.09,129.03,128.87,128.33,128.20,128.00,127.71,127.31,123.53
,119.13,114.09,95.54,87.32,77.31,77.06,76.81,61.83,59.45,40.97,39.03,
14.07。
Embodiment 2
A kind of benzoin oxime derivant, structural formula is:
A kind of preparation method of benzoin oxime derivant, described preparation method comprises the following steps:
A, precursor synthesize；
B, target product synthesize；
C, purification.
Wherein, a, precursor synthesize, and comprise the following steps:
(1) with 800mmol sodium hydride as catalyst, 200mmol Diisopropyl malonate is added with 500mmol propargyl bromide
Ice-water bath in 200ml anhydrous acetonitrile, stirring reaction 10 hours, product adds water washing, is extracted with ethyl acetate, and decompression is revolved
Dry, column chromatography (volume ratio ethyl acetate: petroleum ether=1:100) obtains white solid product, i.e. compound 3；
(2) 80mmol compound 1 is blended in 2.17gPd (PPh with 200mmol to methylbenzene acetylenebromide3)2Cl2/CuI
Anhydrous and oxygen-free catalyst system and catalyzing in, Pd (PPh3)2Cl2Pd (PPh in/CuI3)2Cl2With the amount of the material of CuI than for 3:1, with
Alkali made by 350mmol triethylamine, with 250ml anhydrous acetonitrile as solvent, and stirring reaction 10 hours under room temperature, products in water washs,
Being extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: petroleum ether=1:100) obtains light tan solid and produces
Thing, i.e. precursor compound 3.
Wherein b, target product synthesis, comprises the following steps:
Under conditions of 100 DEG C, 0.47g precursor compound 3 and 0.32g benzoin oxime react 11 hours in 5mL toluene,
Compound 4, the i.e. crude product of benzoin oxime derivant.
Wherein, c, purification, comprise the following steps:
The crude product with water washing of benzoin oxime derivant step b prepared, ethyl acetate extracts, and decompression is spin-dried for, column chromatography
(volume ratio ethyl acetate: petroleum ether=1:30) isolated yellow solid product, i.e. benzoin oxime derivant, column chromatography produces
Rate is 73.6%.
Yellow solid product structure is passed through；1H NMR；13C NMR measures.
Yellow solid product:
1H NMR(300MHz,CDCl3) δ 7.95 (s, 1H), 7.92 (s, 1H), 7.80 (s, 1H), 7.78 (s,
1H), 7.53 7.19 (m, 10H), 7.14 7.06 (m, 4H), 6.60 (s, 1H), 5.12 5.04 (m, 2H),
3.68 (s, 2H), 3.61 (s, 2H), 2.36 (s, 3H), 2.32 (s, 3H), 1.30-1.25 (t, 12H).
13C NMR(75MHz,CDCl3) δ 197.10,171.12,166.54,144.90,
144.51,142.96,138.05,137.15,136.89,134.88,134.37,133.04,131.88,131.05,129.91,129.11,129.01,128.97,1
28.83,128.41,128.30,127.70,120.66,118.93,114.15,95.63,86.86,77.29,77.04,76.78,69.24,59.47,40.98,38.
99,21.58,21.47,21.41,21.21,21.17,21.14。
Claims (8)
1. a benzoin oxime derivant, its structural formula is:
2. the preparation method of benzoin oxime derivant as claimed in claim 1, comprises the following steps:
(1) with sodium hydride as catalyst, malonate and propargyl bromide are joined ice-water bath in anhydrous acetonitrile, stirring reaction 5h
Above, white solid product, i.e. compound 1 are obtained after purifies and separates；Described malonate is diethyl malonate or malonic acid
Diisopropyl ester；
(2) compound 1 is blended in Pd (PPh with phenylacetylene bromide or substituted phenylacetylene bromide3)2Cl2The anhydrous and oxygen-free of/CuI is urged
In change system, making alkali with triethylamine, with anhydrous acetonitrile as solvent, under room temperature, stirring reaction more than 10h, obtains after purifies and separates
Light tan solid product, i.e. precursor compound 2；Described substituted phenylacetylene bromide is to methylbenzene acetylenebromide；
(3) under conditions of 95-105 DEG C, the precursor compound 2 prepared by step (2) is reacted with benzoin oxime in toluene
More than 10 hours, after being separated by product purification, obtain yellow solid compound 3, i.e. target product benzoin oxime derivant.
3. preparation method as claimed in claim 2, it is characterised in that: sodium hydride, diethyl malonate in described step (1)
Or the amount of the material of Diisopropyl malonate, propargyl bromide is than for 4-5:1:2.2-3.2, diethyl malonate or malonic acid two
Isopropyl ester concentration in anhydrous acetonitrile is 0.5-0.8mol/L.
4. preparation method as claimed in claim 2, it is characterised in that: in described step (1), purifies and separates is for add water product
Washing, is extracted with ethyl acetate, and decompression is spin-dried for, and is the ethyl acetate of 1:100 by volume ratio: petroleum ether column chromatography for separation.
5. preparation method as claimed in claim 2, it is characterised in that: compound 1, phenylacetylene bromide in described step (2)
Or to methylbenzene acetylenebromide, Pd (PPh3)2Cl2, the amount of material of triethylamine be 1:2.2-3.2:0.0085-0.014:4-5,
The described compound 1 concentration in anhydrous acetonitrile is 0.32-0.6mol/L.
6. preparation method as claimed in claim 2, it is characterised in that: Pd (PPh in described step (2)3)2Cl2/ CuI's is anhydrous
In anaerobic catalyst system and catalyzing, Pd (PPh3)2Cl2With the amount of the material of CuI than for 3:1；Described purifies and separates is the washing that added water by product,
Being extracted with ethyl acetate, decompression is spin-dried for, and is the ethyl acetate of 1:100 by volume ratio: petroleum ether column chromatography for separation.
7. preparation method as claimed in claim 2, it is characterised in that: precursor compound 2 and Benzoinum in described step (3)
The amount of the material of oxime is than for 1:1.1-1.5, and the precursor compound 2 concentration in toluene is 0.2-0.5mol/L.
8. preparation method as claimed in claim 2, it is characterised in that: described in described step (3), purifies and separates is by product
Washing with water, ethyl acetate extracts, and decompression is spin-dried for, and is the ethyl acetate of 1:30 by volume ratio: petroleum ether column chromatography for separation.
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| CN201410728358.6A CN104447396B (en) | 2014-12-04 | 2014-12-04 | Benzoin oxime derivative and preparation method thereof |
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| CN105622569B (en) * | 2016-01-29 | 2018-05-08 | 安徽师范大学 | A kind of o-hydroxy amine derivative and preparation method thereof |
| CN105968013B (en) * | 2016-05-16 | 2018-08-17 | 安徽师范大学 | A kind of π-copolymer and preparation method thereof |
| CN106748769B (en) * | 2016-11-29 | 2018-08-17 | 安徽师范大学 | A kind of polysubstituted 3- phenyl phenol derivatives and preparation method thereof |
| CN106588666B (en) * | 2016-12-14 | 2018-08-17 | 安徽师范大学 | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof |
| CN106946704B (en) * | 2017-03-15 | 2018-08-17 | 安徽师范大学 | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof |
| CN106946707B (en) * | 2017-03-24 | 2018-08-31 | 安徽师范大学 | Polysubstituted hydrogenation indene derivative of one kind and preparation method thereof |
| CN107641080B (en) * | 2017-09-29 | 2018-12-14 | 安徽师范大学 | A kind of dihydronaphthalene ketones derivant and preparation method thereof containing spirane structure |
| CN108774189B (en) * | 2018-06-08 | 2022-04-19 | 安徽师范大学 | Oxazine phenyl ether derivative and preparation method thereof |
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| CN114014779A (en) * | 2021-12-14 | 2022-02-08 | 安徽师范大学 | Bisaryl oxime ether compound and preparation method thereof |
| CN116217785B (en) * | 2023-03-09 | 2024-06-11 | 核工业北京化工冶金研究院 | Molybdenum separation resin and preparation method and application thereof |
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