CN105037126A - Synthetic method of salicylic acid compound - Google Patents
Synthetic method of salicylic acid compound Download PDFInfo
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- CN105037126A CN105037126A CN201510033305.7A CN201510033305A CN105037126A CN 105037126 A CN105037126 A CN 105037126A CN 201510033305 A CN201510033305 A CN 201510033305A CN 105037126 A CN105037126 A CN 105037126A
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Abstract
The invention discloses a method of selectively achieving hydroxylation at an o-position of an oriented group to synthesize a salicylic acid compound with low-cost copper as a catalyst under the effect of a N,O-bidentate oriented group. The method includes the following steps: (1) adding aromatic acylaminopyridine-1-oxide, basic cupric carbonate, potassium carbonate, water and DMPU successively into a reaction tube; (2) performing a reaction at 105-115 DEG C for 20-30 h; (3) performing extraction, concentration and chromatographic separation to obtain an o-position hydroxylated product; (3) dissolving the o-position hydroxylated product in an ethanol solution of NaOH, performing a reaction at 85-95 DEG C for 20-30 h; and (4) after the reaction is finished, adding diluted hydrochloric acid to neutralize residual NaOH, and performing extraction, concentration and column chromatography to obtain the salicylic acid compound. The method is mild in reaction conditions, is good in tolerance of functional groups, and can selectively achieve the hydroxylation of a C-H bond at the o-position with the oriented group being easily to remove. The raw materials are low in cost and are easy to obtain. The method is simple in operations and is high in yield and good in suitable range.
Description
Technical field
The present invention relates to a kind of method being activated salicylate compounds by C-H, fragrant amidopyridine-1-oxide compound optionally realizes under copper catalysis
n,
othe hydroxylation at-bidentate guiding base ortho position, then guiding base is removed obtain salicylic acid compounds.
Background technology
Whitfield's ointment and derivative thereof are prevalent in medicine and natural product, as Ya Sha can, Metoclopramide Tablets, flecainide acetate etc.In addition, the phenolic hydroxyl group that salicylic acid compounds contains can also be converted into other functional groups such as ether, ester easily, in organic synthesis, also have good application prospect.Therefore, the synthesis of salicylic acid compounds causes the extensive concern of people.In the last few years, owing to not needing the pre-activate of c h bond, effectively can shorten the reactions steps of organic synthesis, the direct functionalization of c h bond causes the broad interest of people.The introducing of the salicylic acid compounds hydroxyl of previous literature report is mainly hydrolyzed realization again by first obtaining ester group intermediate, does not meet the requirement of Atom economy.(
org.Lett.
2012,
14, 2874;
org.Lett.
2012,
14, 4210;
angew.Chem.Int.Ed.
2012,
51, 13070.) and about the hydroxylating of the c h bond directly realized without ester hydrolysis, be realize hydroxylated very efficient method, but only have several sections of reports about this type of reaction, and the metal of catalysis be also confined to precious metal palladium (
j.Am.Chem.Soc.
2009,
131, 14654.), make the range of application of reacting have very strong limitation.Therefore developing a kind of take cheap metal as catalyzer, and the method that the hydroxylation realizing c h bond without hydrolysis of ester group carrys out salicylate compounds will be the breakthrough very large to previous methods.
Summary of the invention
Technical problem to be solved by this invention is with c h bond direct functionalization salicylate compounds severe reaction conditions, has the problems such as limitation, there is provided a kind of synthetic method of salicylic acid compounds, the method is catalyzer with cheap metal and simply efficient.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A synthetic method for salicylic acid compounds, step is as follows:
(1) in reaction tubes, add fragrant amidopyridine-1-oxide compound, ventilation breather, salt of wormwood successively, water and DMPU, 105 ~ 115
oreact 20 ~ 30 hours under the condition of C, reaction terminates rear extraction, and concentrated, TLC separation obtains the product of vicinal hydroxyl groups; The chemical formula of fragrance amido class pyridine-1-oxide compound is
, wherein R is in phenyl ring C2-C4 position, and R is hydrogen atom, methyl, methoxyl group, trifluoromethyl, the tertiary butyl, fluorine, bromine, iodine, phenyl or first sulfonyl;
(2) product of the vicinal hydroxyl groups obtained is dissolved in the ethanolic soln of NaOH, 85 ~ 95
oreact 20 ~ 30 hours under the condition of C, add NaOH in dilute hydrochloric acid He unnecessary, extraction after reaction terminates, concentrate, column chromatography obtains salicylic acid compounds; Reaction equation is as follows:
In described step (1), the ratio of the amount of substance of fragrant amidopyridine-1-oxide compound, ventilation breather and salt of wormwood is 3.5 ~ 4.5:0.8 ~ 1.2:0.8 ~ 1.2, with 1mmol fragrance amidopyridine-1-oxide compound for benchmark, needs H
2o70 ~ 80 μ L, DMPU1 ~ 5mL.
In described step (1), extraction employing adds dilute hydrochloric acid cancellation reaction, then reaction solution dichloromethane extraction, adopts anhydrous sodium sulfate drying, adopts underpressure distillation to concentrate, and adopts the method for TLC separation to carry out chromatographic separation.
In described step (2), the consumption of the ethanolic soln of sodium hydroxide is with fragrant amidopyridine-1-oxide compound for benchmark, and needed for 1mmol fragrance amidopyridine-1-oxide compound, the ethanolic soln of sodium hydroxide is 0.8 ~ 1.5mL.
In described step (2), the concentration of the ethanolic soln of sodium hydroxide is 2.5 ~ 3.5mol/L.
In described step (2), extraction adopts dichloromethane extraction, adopts anhydrous sodium sulfate drying, adopts underpressure distillation to concentrate, and adopts the method for pillar layer separation to carry out chromatographic separation.
Beneficial effect of the present invention: (1) the invention provides a kind of novel
n,
ocarry out the method for salicylate compounds as the hydroxylation at the realization of catalyst selectivity guiding base ortho position using cheap copper under the effect of-bidentate guiding base; (2) with the ventilation breather of cheapness for catalyzer, reaction conditions is gentle, and functional group's tolerance is good; (3) reaction optionally can realize the hydroxylation of ortho position c h bond; (4) base that leads can be introduced easily and remove; (5) present method raw material and catalyzer are all cheap and easy to get, and reaction conditions is gentle, easy and simple to handle, has good productive rate and the scope of application; (6) productive rate of the corresponding salicylic acid compounds of present method gained is up to 82%.
Embodiment
For the ease of understanding, below will be described in detail the present invention by specific embodiment.Obviously, the invention is not restricted to above embodiment, many distortion can also be had, all distortion that those of ordinary skill in the art can directly derive from the disclosure of invention or associate, all should protection scope of the present invention be thought.
Embodiment 1
The salicylic preparation method of the present embodiment is as follows:
(1) preparation of o-hydroxy formamido group pyridine-1-oxide compound
By benzene carbon amide yl pyridines-1-oxide compound (0.2mmol, 42.8mg), anhydrous Cu (OH)
2cO
3(0.05mmol, 11.1mg), anhydrous K
2cO
3(0.05mmol, 6.9mg), adds in Shrek pipe, and then adds 15 μ LH
2o, 0.5mLDMPU and air atmosphere 110
oreact 24h under C, after reaction terminates, add dilute hydrochloric acid (5mL, 1N) cancellation reaction, then reaction solution CH
2cl
2(5 × 4mL) extracts, then uses saturated aqueous common salt (5 × 3mL) to wash, anhydrous sodium sulfate drying, TLC separation (CH
2cl
2/ CH
3oH) the product 34mg of vicinal hydroxyl groups is obtained, productive rate 74%.
Fusing point 211-212
oc.
1hNMR (400MHz, CDCl
3)
δ12.60 (s, 1H), 8.57 (d,
j=8.3Hz, 1H), 8.41 (dd,
j=6.2Hz, 1H), 8.03 (dd,
j=7.8Hz,
j=1.4Hz, 1H), 7.48-7.44 (m, 2H), 7.17-7.14 (m, 1H), 7.04-6.97 (m, 2H).
13cNMR (100MHz, CDCl
3)
δ163.5,156.6,144.5,137.4,134.3,131.2,127.2,119.6,119.1,117.9,117.1,114.7.HRMS (positiveESI) CalcdforC
12h
11n
2o
3(M+H) 231.0764, Found231.0766.
(2) salicylic preparation
By the vicinal hydroxyl groups product (0.2mmol, 46mg) obtained, NaOH (3mmol, 120mg) is placed in Shrek pipe, adds 1mL ethanol, 90
oconfined reaction 24h under C.Reaction terminates rear decompression removing ethanol, adds dilute hydrochloric acid (5mL, 1N) and neutralizes unnecessary alkali, then mixed solution CH
2cl
2(5 × 4mL) extracts, anhydrous sodium sulfate drying, pillar layer separation (CH
2cl
2/ CH
3oH) Whitfield's ointment 25mg is obtained, productive rate 91%.
1HNMR(400MHz,CDCl
3)
δ10.37(s,1H),7.94(dd,
J=8.0Hz,
J=1.7Hz,1H),7.56-7.52(m,1H),7.02(dd,
J=8.4Hz,
J=0.84Hz,1H),6.97-6.93(m,1H).
13CNMR(100MHz,CDCl
3)
δ175.0,162.2,137.1,131.0,119.6,117.9,111.3.
Embodiment 2
The preparation method of the 2-hydroxyl-6-tolyl acid of the present embodiment is as follows:
(1) preparation of 2-(2-hydroxyl-6-methylbenzoylamin. o) pyridine-1-oxide compound
By the method described in embodiment 1 step (1), unlike substrate used and reagent be: 2-methylbenzoylamin. o pyridine-1-oxide compound (0.2mmol, 45.6mg), anhydrous Cu (OH)
2cO
3(0.05mmol, 11.1mg), anhydrous K
2cO
3(0.05mmol, 6.9mg), H
2o15 μ L, DMPU0.5mL and air atmosphere 110
oreact 24h. under C and obtain 2-(2-hydroxyl-6-methylbenzoylamin. o) pyridine-1-oxide compound 25mg, solid, productive rate 51%.
Fusing point 198-199
oc.
1hNMR (400MHz, CDCl
3)
δ10.97 (s, 1H), 10.61 (s, 1H), 8.46 (d,
j=7.9Hz, 1H), 8.40 (d,
j=5.9Hz, 1H), 7.49-7.45 (m, 1H), 7.23-7.15 (m, 1H), 6.82 (d,
j=8.1Hz, 1H), 6.77 (d,
j=7.4Hz, 1H), 2.36 (s, 3H).
13cNMR (100MHz, CDCl
3)
δ165.5,154.9,143.8,138.7,137.3,131.3,127.5,121.9,121.6,119.2,114.1,113.8,20.4.HRMS (positiveESI) CalcdforC
13h
13n
2o
3(M+H) 245.0921, Found245.0922.
(2) preparation of 2-hydroxyl-6-tolyl acid
By the method described in embodiment 1 step (2), unlike substrate used and reagent be: 2-(2-hydroxyl-6-methylbenzoylamin. o) pyridine-1-oxide compound (0.2mmol, 49mg), NaOH (3mmol, 120mg) be placed in Shrek pipe, add 1mL ethanol, 90
oconfined reaction 24h under C.Reaction terminates rear decompression removing ethanol, adds dilute hydrochloric acid (5mL, 1N) and neutralizes unnecessary alkali, then mixed solution CH
2cl
2(5 × 4mL) extracts, anhydrous sodium sulfate drying, pillar layer separation (CH
2cl
2/ CH
3oH) 2-hydroxyl-6-tolyl acid is obtained.
Embodiment 3
The preparation method of the 2-hydroxy-5-methyl yl benzoic acid of the present embodiment is as follows:
(1) preparation of 2-(2-hydroxy-5-methyl base benzamido) pyridine-1-oxide compound
By the method described in embodiment 1 step (1), unlike substrate used and reagent be: by substrate 3-methylbenzoylamin. o pyridine-1-oxide compound (0.2mmol, 45.6mg), anhydrous Cu (OH)
2cO
3(0.05mmol, 11.1mg), anhydrous K
2cO
3(0.05mmol, 6.9mg), H
2o15 μ L, DMPU0.5mL and air atmosphere 110
oreact 24h. under C and obtain 2-(2-hydroxy-5-methyl base benzamido) pyridine-1-oxide compound 28mg, solid, productive rate 58%.
Fusing point 225-226
oc.
1hNMR (400MHz, CDCl
3)
δ12.57 (brs, 1H), 11.80 (brs, 1H), 8.62 (dd,
j=8.4Hz,
j=1.6Hz, 1H), 8.46 (d,
j=6.2Hz, 1H), 7.87 (d,
j=1.8Hz, 1H), 7.54-7.49 (m, 1H), 7.33 (dd,
j=8.3Hz,
j=2.1Hz, 1H), 7.23-7.19 (m, 1H), 7.03 (d,
j=8.3Hz, 1H), 2.32 (s, 3H).
13cNMR (100MHz, CDCl
3)
δ163.4,154.2,144.4,137.4,135.0,130.9,128.4,127.2,119.1,117.4,116.9,114.7,19.9.HRMS (positiveESI) CalcdforC
13h
13n
2o
3(M+H) 245.0921, Found245.0921.
(2) preparation of 2-hydroxy-5-methyl yl benzoic acid
By the method described in embodiment 1 step (2), unlike substrate used and reagent be: 2-(2-hydroxy-5-methyl base benzamido) pyridine-1-oxide compound (0.2mmol, 48.3mg), NaOH (3mmol, 120mg) be placed in Shrek pipe, add 1mL ethanol, 90
oconfined reaction 24h under C.Reaction terminates rear decompression removing ethanol, adds dilute hydrochloric acid (5mL, 1N) and neutralizes unnecessary alkali, then mixed solution CH
2cl
2(5 × 4mL) extracts, anhydrous sodium sulfate drying, pillar layer separation (CH
2cl
2/ CH
3oH) 2-hydroxy-5-methyl yl benzoic acid is obtained.
Embodiment 4
The benzoic preparation method of 2-hydroxy-4-methyl of the present embodiment is as follows:
(1) preparation of 2-(2-hydroxy-4-methyl benzamido) pyridine-1-oxide compound
By the method described in embodiment 1 step (1), unlike substrate used and reagent be: by substrate 4-methylbenzoylamin. o pyridine-1-oxide compound (0.2mmol, 45.6mg), anhydrous Cu (OH)
2cO
3(0.05mmol, 11.1mg), anhydrous K
2cO
3(0.05mmol, 6.9mg), H
2o15 μ L, DMPU0.5mL and air atmosphere 110
oreact 24h. under C and obtain 2-(2-hydroxy-4-methyl benzamido) pyridine-1-oxide compound 34mg, solid, productive rate 70%.
Fusing point 200-201
oc,
1hNMR (400MHz, CDCl
3)
δ12.58 (brs, 1H), 11.93 (brs, 1H), 8.62 (d,
j=8.3Hz, 1H), 8.47 (d,
j=6.2Hz, 1H), 7.97 (d,
j=8.3Hz, 1H), 7.53-7.49 (m, 1H), 7.22-7.19 (m, 1H), 6.88-6.87 (m, 2H), 2.36 (s, 3H).
13cNMR (100MHz, CDCl
3)
δ163.4,156.4,144.9,144.5,137.4,131.1,127.2,120.9,119.0,117.2,115.4,114.6,21.1.HRMS (positiveESI) CalcdforC
13h
13n
2o
3(M+H) 245.0921, Found245.0922.
2) the benzoic preparation of 2-hydroxy-4-methyl
By the method described in embodiment 1 step (2), unlike substrate used and reagent be: 2-(2-hydroxy-4-methyl benzamido) pyridine-1-oxide compound (0.2mmol, 49mg), NaOH (3mmol, 120mg) be placed in Shrek pipe, add 1mL ethanol, 90
oconfined reaction 24h under C.Reaction terminates rear decompression removing ethanol, adds dilute hydrochloric acid (5mL, 1N) and neutralizes unnecessary alkali, then mixed solution CH
2cl
2(5 × 4mL) extracts, anhydrous sodium sulfate drying, pillar layer separation (CH
2cl
2/ CH
3oH) 2-hydroxy-4-methyl phenylformic acid is obtained.
Embodiment 5
The preparation method of the 2-hydroxyl-4-methoxybenzoic acid of the present embodiment is as follows:
(1) preparation of 2-(2-hydroxyl-4-Methoxybenzamido) pyridine-1-oxide compound
By the method described in embodiment 1 step (1), unlike substrate used and reagent be: by anhydrous for substrate 4-Methoxybenzamido pyridine-1-oxide compound (0.35mmol, 85.4mg) Cu (OH)
2cO
3(0.08mmol, 17.76mg), anhydrous K
2cO
3(0.08mmol, 17.76mg), H
2o24.5 μ L, DMPU0.35mL and air atmosphere 105
oreact 30h under C and obtain 2-(2-hydroxyl-4-Methoxybenzamido) pyridine-1-oxide compound 70.9mg, solid, productive rate 78%.
Fusing point 247-248
oc,
δ12.62 (brs, 1H), 11.62 (brs, 1H), 8.62 (dd,
j=8.4Hz,
j=1.5Hz, 1H), 8.46 (d,
j=6.1Hz, 1H), 7.57 (d,
j=3.1Hz, 1H), 7.55-7.51 (m, 1H), 7.24-7.20 (m, 1H), 7.17 (dd,
j=8.9Hz,
j=3.2Hz, 1H), 7.08 (d,
j=8.9Hz, 1H), 3.84 (s, 3H).
13cNMR (100MHz, CDCl
3)
δ163.1,152.3,150.3,144.3,137.4,127.3,121.5,119.3,118.2,117.9,114.7,113.6,55.4.HRMS (positiveESI) CalcdforC
13h
13n
2o
4(M+H) 261.0870, Found261.0871.
(2) preparation of 2-hydroxyl-4-methoxybenzoic acid
By the method described in embodiment 1 step (2), unlike substrate used and reagent be: 2-(2-hydroxyl-4-Methoxybenzamido) pyridine-1-oxide compound (0.2mmol, 52mg), NaOH (2.25mmol, 90mg) be placed in Shrek pipe, add 0.9mL ethanol, 85
oconfined reaction 30h under C.Reaction terminates rear decompression removing ethanol, adds dilute hydrochloric acid (5mL, 1N) and neutralizes unnecessary alkali, then mixed solution CH
2cl
2(5 × 4mL) extracts, anhydrous sodium sulfate drying, pillar layer separation (CH
2cl
2/ CH
3oH) 2-hydroxyl-4-methoxybenzoic acid is obtained.
Embodiment 6
The preparation method of the 2-hydroxyl-4-trifluoromethylbenzoic acid of the present embodiment is as follows:
(1) preparation of 2-(2-hydroxyl-4-trifluoromethylbenzoyl is amino) pyridine-1-oxide compound
By the method described in embodiment 1 step (1), unlike substrate used and reagent be: by substrate 4-trifluoromethylbenzoyl aminopyridine-1-oxide compound (0.45mmol, 126.9mg), anhydrous Cu (OH)
2cO
3(0.12mmol, 26.64mg), anhydrous K
2cO
3(0.05mmol, 16.56mg), H
2o36 μ L, DMPU2.25mL and air atmosphere 115
oreact 20h under C and obtain 2-(2-hydroxyl-4-trifluoromethylbenzoyl is amino) pyridine-1-oxide compound 69.7mg, solid, productive rate 52%.
Fusing point 237-238
oc,
1hNMR (400MHz, CDCl
3)
δ12.7 (brs, 2H), 8.61 (dd,
j=8.4Hz,
j=1.4Hz, 1H), 8.49 (d,
j=6.2Hz, 1H), 8.28 (d,
j=8.2Hz, 1H), 7.56-7.52 (m, 1H), 7.39 (d,
j=8.4Hz, 1H), 7.34 (s, 1H), 7.27-7.23 (m, 1H).
13cNMR (100MHz, CDCl
3)
δ162.2,156.7,144.15,137.4,133.6 (d,
j c-F=31.8Hz), 132.7,127.3,123.4 (d,
j c-F=255.7Hz), 121.5,119.6,115.8,114.9,113.7.
19fNMR (376MHz, CDCl
3)
δ-60.03.HRMS (positiveESI) CalcdforC
13h
10f
3n
2o
3(M+H) 299.0638, Found299.0639.
(2) preparation of 2-hydroxyl-4-trifluoromethylbenzoic acid
By the method described in embodiment 1 step (2), unlike substrate used and reagent be: 2-(2-hydroxyl-4-trifluoromethylbenzoyl is amino) pyridine-1-oxide compound (0.2mmol, 60mg), NaOH (3.85mmol, 154mg) be placed in Shrek pipe, add 1.1mL ethanol, 95
oconfined reaction 20h under C.Reaction terminates rear decompression removing ethanol, adds dilute hydrochloric acid (5mL, 1N) and neutralizes unnecessary alkali, then mixed solution CH
2cl
2(5 × 4mL) extracts, anhydrous sodium sulfate drying, pillar layer separation (CH
2cl
2/ CH
3oH) 2-hydroxyl-4-trifluoromethylbenzoic acid is obtained.
Claims (6)
1. a synthetic method for salicylic acid compounds, is characterized in that, step is as follows:
(1) in reaction tubes, fragrant amidopyridine-1-oxide compound, ventilation breather, salt of wormwood is added successively, water and DMPU, react 20 ~ 30 hours under the condition of 105 ~ 115 DEG C, and reaction terminates rear extraction, concentrated, TLC separation obtains the product of vicinal hydroxyl groups; The chemical formula of fragrance amido class pyridine-1-oxide compound is
, wherein R is in phenyl ring C2-C4 position, and R is hydrogen atom, methyl, methoxyl group, trifluoromethyl, the tertiary butyl, fluorine, bromine, iodine, phenyl or first sulfonyl;
(2) product of the vicinal hydroxyl groups obtained is dissolved in the ethanolic soln of NaOH, 85 ~ 95
oreact 20 ~ 30 hours under the condition of C, add NaOH in dilute hydrochloric acid He unnecessary, extraction after reaction terminates, concentrate, column chromatography obtains salicylic acid compounds.
2. the synthetic method of salicylic acid compounds according to claim 1, it is characterized in that: in described step (1), the ratio of the amount of substance of fragrant amidopyridine-1-oxide compound, ventilation breather and salt of wormwood is 3.5 ~ 4.5:0.8 ~ 1.2:0.8 ~ 1.2, with 1mmol fragrance amidopyridine-1-oxide compound for benchmark, need H
2o70 ~ 80 μ L, DMPU1 ~ 5mL.
3. the synthetic method of salicylic acid compounds according to claim 1, it is characterized in that: in described step (1), extraction employing adds dilute hydrochloric acid cancellation reaction, then reaction solution dichloromethane extraction, adopt anhydrous sodium sulfate drying, adopt underpressure distillation to concentrate, adopt the method for TLC separation to carry out chromatographic separation.
4. the synthetic method of salicylic acid compounds according to claim 1, it is characterized in that: in described step (2), the consumption of the ethanolic soln of sodium hydroxide is with fragrant amidopyridine-1-oxide compound for benchmark, and needed for 1mmol fragrance amidopyridine-1-oxide compound, the ethanolic soln of sodium hydroxide is 4.5 ~ 5.5mL.
5. the synthetic method of salicylic acid compounds according to claim 4, is characterized in that: in described step (2), the concentration of the ethanolic soln of sodium hydroxide is 2.5 ~ 3.5mol/L.
6. the synthetic method of salicylic acid compounds according to claim 1, it is characterized in that: in described step (2), extraction adopts dichloromethane extraction, adopt anhydrous sodium sulfate drying, adopt underpressure distillation to concentrate, adopt the method for pillar layer separation to carry out chromatographic separation.
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Citations (2)
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GB1078786A (en) * | 1964-12-18 | 1967-08-09 | Dow Chemical Co | Preparation of salicylic acids |
CN101585762A (en) * | 2009-06-06 | 2009-11-25 | 浙江大学宁波理工学院 | Method for synthesizing 2-(4-cyclopropoxycarbonylphenyl)-2-methylpropanoic acid |
-
2015
- 2015-01-23 CN CN201510033305.7A patent/CN105037126A/en active Pending
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GB1078786A (en) * | 1964-12-18 | 1967-08-09 | Dow Chemical Co | Preparation of salicylic acids |
US3337616A (en) * | 1964-12-18 | 1967-08-22 | Dow Chemical Co | Preparation of salicylic acids |
DE1276652B (en) * | 1964-12-18 | 1968-09-05 | Dow Chemical Co | Process for the preparation of salicylic acid derivatives |
CN101585762A (en) * | 2009-06-06 | 2009-11-25 | 浙江大学宁波理工学院 | Method for synthesizing 2-(4-cyclopropoxycarbonylphenyl)-2-methylpropanoic acid |
Non-Patent Citations (3)
Title |
---|
JAMES ROANE AND OLAFS DAUGULIS: "Copper-Catalyzed Etherification of Arene C-H Bonds", 《ORG. LETT.》 * |
LIN-BAO ZHANG等: "Copper-Mediated Direct Alkoxylation of Arenes Using an N,O-Bidentate Directing System", 《J. ORG. CHEM.》 * |
李刘艳等: "N,O-双齿导向基作用下铜催化酰胺的直接羟基化反应", 《河南省化学会2014年学术年会论文摘要集》 * |
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