CN110003062A - A kind of two Fluorakil 100 of N- phenyl-N- p-toluenesulfonyl and application - Google Patents
A kind of two Fluorakil 100 of N- phenyl-N- p-toluenesulfonyl and application Download PDFInfo
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- CN110003062A CN110003062A CN201910327494.7A CN201910327494A CN110003062A CN 110003062 A CN110003062 A CN 110003062A CN 201910327494 A CN201910327494 A CN 201910327494A CN 110003062 A CN110003062 A CN 110003062A
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- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
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- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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Abstract
The invention belongs to pharmaceutical-chemical intermediate and related chemistry technical fields; a kind of two Fluorakil 100 of N- phenyl-N- p-toluenesulfonyl and application; using two Fluorakil 100 of N- phenyl-N- p-toluenesulfonyl as difluoro acetylation reagent; under the action of metallic catalyst, ligand and alkali; it is reacted in organic solvent with arylboronic acid compound, is efficiently converted into difluoro acetophenone class compound with high selectivity.The synthetic method of difluoro acetophenone class compound of the present invention, reaction step is few, and stabilization is used easily to store NDFTS cheap and easy to get as difluoro acetyl group source, and environmental-friendly, reaction condition is mild, convenient for operation；And target product is obtained with highly selective in high yield, there is preferable industrial production value and practical application value.Further function dough can be carried out using the difluoro acetophenone compound that this method synthesizes to react, and is widely used in the synthesis fields such as medicine, pesticide, bioactive molecule, functional material molecule.
Description
Technical field
The invention belongs to pharmaceutical-chemical intermediate and related chemistry technical field, it is related to a kind of N- phenyl-N- to toluene
Two Fluorakil 100 of sulfonyl and the method for using it to synthesize difluorobenzoethylkederivatives derivatives as novel difluoro acetylation reagent.
Background technique
Difluoro acetophenone compound is a kind of important organic synthesis intermediate, is widely used in synthesizing medicine, pesticide, day
The key areas such as right product, bioactive molecule, organic functional material.Difluoromethyl (- CF contained by it2It H) is drug
A kind of very important structural unit, can assign drug molecule good pharmacokinetic properties, usually as targeting in
Functional end-group.By using a kind of novel difluoro acetylation reagent for efficiently, synthesize difluoro acetophenone with high selectivity
Compound has important practical significance and application value.
Develop that the synthetic method of difluoro acetyl group is introduced into organic molecule is always important synthesis side in organic chemistry
To.Although difference only one fluorine atom between difluoro acetyl group and trifluoroacetyl group, this species diversity will affect one
Molecule whether can readily in conjunction with its target, its effect can have it is more can maintain by force how long.Past tens year,
People have also been developed it is a series of synthesis difluoro acetophenones methods, mainly include Hoesch reaction [E.K.Raja,
D.A.Klumpp, Tetrahedron.Lett., 2011,52,5170], Grignard reaction [H.F.Koch, W.Tumas,
R.Knoll, J.Am.Chem.Soc., 1981,103,5423], alcohol oxidation reaction [Y.Tanaka, T.Ishihara,
T.Konno,J.Fluorine.Chem.2012,137, 99].However the having the obvious disadvantage that property of reaction of these types, such as
Hoesch reaction condition is harsher, and strong acid (hydrochloric acid, trifluoromethanesulfonic acid etc.) is needed to make catalyst；Grignard reaction needs to make
With the metalating reagent to air-sensitive, substrate needs functionalization in advance；Oxidation reaction needs the oxidant of stoichiometry to join
With react, post-process and comparatively laborious be easy to cause environmental pollution.Therefore, high novel of developing low-cost, easy to use, stability
Difluoro acetylation reagent to realize difluoro acetophenone class compound it is succinct, efficiently synthesize be current area research hotspot.
Summary of the invention
The present invention provides a kind of two Fluorakil 100 of N- phenyl-N- p-toluenesulfonyl and application, the difluoro acetophenones
Close object preparation method synthetic route it is short, substrate is easy to get, mild condition, it is environmental-friendly, convenient for operation, good substrate applicability,
High income, and reaction cost is low.
Technical solution of the present invention:
A kind of novel two Fluorakil 100 NDFTS of difluoro acetylation reagent N- phenyl-N- p-toluenesulfonyl, molecular structural formula
It is as follows:
A kind of novel difluoro acetylation reagent N- phenyl-N- p-toluenesulfonyl difluoro acetamide compound (NDFTS)
Preparation method under DMAP and dehydrating agent DCC effect, is reacted using N- phenyl-para toluene sulfonamide as raw material with difluoroacetic acid,
In anhydrous solvent CH2Cl2In at 0 DEG C, react 16 hours, by being filtered, washed, being recrystallized to give NDFTS；
A kind of preparation method of difluoro acetophenone compound, using difluoro acetylation reagent NDFTS as raw material, in alkali, metal
Under the action of catalyst and ligand, and aryl boric acid derivatives reaction, in anhydrous organic solvent, under the conditions of 25-50 DEG C, instead
It answers 16-24 hours and obtains difluoro acetophenone compound, synthetic route is as follows:
R=H, alkyl, OMe, OPh, CO2Me,aryl,vinyl,naphthyl,halides,CF3, NO2,CN
R is selected from hydrogen (H), alkyl (alkyl), methoxyl group (OMe), phenoxy group (OPh), methyl carbonate base (CO2Me), aryl
(aryl), vinyl (vinyl), naphthalene (naphthyl), halogen (halides), trifluoromethyl (CF3), nitro (NO2) and cyanogen
Base (CN)；
The molar ratio of aryl boric acid derivative and metallic catalyst is 1:0.05~1:0.1；
The molar ratio of aryl boric acid derivative and difluoro acetylation reagent NDFTS are 1:1~10:1；
The molar ratio of aryl boric acid derivative and alkali is 1:0~1:10；
The molar ratio of aryl boric acid derivative and ligand is 1:0.05~1:0.4；
Molar concentration of the aryl boric acid derivative in system is 0.01mmol/mL~2mmol/mL.
Organic solvent includes: tetrahydrofuran, glycol dimethyl ether, methylene chloride, ether, acetone, acetonitrile, dimethyl Asia
Sulfone, the tert-butyl alcohol, Isosorbide-5-Nitrae-dioxane, toluene, n,N-Dimethylformamide, n-hexane etc., preferably tetrahydrofuran, Isosorbide-5-Nitrae-dioxy six
Ring, toluene.
Alkali includes: potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium acetate, sodium methoxide, tricresyl phosphate
Potassium, sodium tert-butoxide, cesium carbonate.It is preferred that cesium carbonate, potassium carbonate, tripotassium phosphate.
Metallic catalyst includes: tetrakis triphenylphosphine palladium, palladium acetate, tris(dibenzylideneacetone) dipalladium, palladium chloride, three
Fluoroacetic acid palladium, allyl palladium chloride dimer, palladium acetylacetonate.It is preferred that palladium acetate, tris(dibenzylideneacetone) dipalladium, acetyl
Acetone palladium.
Ligand includes: triphenylphosphine, three (4- aminomethyl phenyl) phosphines, three (2- furyl) phosphines, tricyclohexyl phosphine, 2- (two uncles
Butyl phosphine) biphenyl, (±) -2,2'- be double-(diphenyl phosphine) -1,1'- dinaphthalene, bis- (dicyclohexyl phosphino-) ethane of 1,2-, three positive fourths
Base phosphine, tri-tert-butylphosphine.It is preferred that bis- (dicyclohexyl phosphino-) ethane of tri-tert-butylphosphine, tricyclohexyl phosphine, 1,2-.
Separation method includes: recrystallization, column chromatography etc..The solvent that recrystallization method uses such as, benzene, ethyl alcohol, petroleum ether, second
Nitrile, tetrahydrofuran, chloroform, n-hexane, acetone, ethyl acetate, methylene chloride；With column chromatography method, silica gel or oxygen can be used
Change aluminium as stationary phase, solvent is generally polarity and nonpolar mixed solvent, such as ethyl acetate-light petrol, acetic acid second
Ester-n-hexane, dichloromethane-petroleum ether, methanol-petroleum ether.
Beneficial effects of the present invention: the synthetic route of the preparation method of the difluoro acetophenone compound is short, mild condition, behaviour
Work is easy, substrate is easy to get, is environmental-friendly, reaction cost is low, is expected to realize industrialization, and obtains difluoro acetophenone in high yield and produce
Object；A step functionalization can be carried out using the difluoro acetophenone class compound that this method synthesizes, to be applied to synthesis day
Right product, pharmaceutical intermediate, bioactive molecule and functional material etc..
Detailed description of the invention
Fig. 1 is ((1,1'- biphenyl -4- base) ethyl ketone of the fluoro- 1- of 2,2- bis- in embodiment 11H nuclear magnetic spectrogram.
Fig. 2 is ((1,1'- biphenyl -4- base) ethyl ketone of the fluoro- 1- of 2,2- bis- in embodiment 113C nuclear magnetic spectrogram.
Fig. 3 is the fluoro- 1- of 2,2- bis- (3- tolyl) ethyl ketone in embodiment 21H nuclear magnetic spectrogram.
Fig. 4 is the fluoro- 1- of 2,2- bis- (3- tolyl) ethyl ketone in embodiment 213C nuclear magnetic spectrogram.
Fig. 5 is the fluoro- 1- of 2,2- bis- in embodiment 3 ((4- methoxyl group) phenyl) ethyl ketone1H nuclear magnetic spectrogram.
Fig. 6 is the fluoro- 1- of 2,2- bis- in embodiment 3 ((4- methoxyl group) phenyl) ethyl ketone13C nuclear magnetic spectrogram.
Fig. 7 is 4- in embodiment 4 (2,2- difluoro acetyl group) methyl benzoate1H nuclear magnetic spectrogram.
Fig. 8 is 4- in embodiment 4 (2,2- difluoro acetyl group) methyl benzoate13C nuclear magnetic spectrogram.
Fig. 9 is the fluoro- 1- of 2,2- bis- in embodiment 5 ((4- phenoxy group) phenyl) ethyl ketone1H nuclear magnetic spectrogram.
Figure 10 is the fluoro- 1- of 2,2- bis- in embodiment 5 ((4- phenoxy group) phenyl) ethyl ketone13C nuclear magnetic spectrogram.
Figure 11 is ((1,1'- biphenyl -2- base) ethyl ketone of the fluoro- 1- of 2,2- bis- in embodiment 61H nuclear magnetic spectrogram.
Figure 12 is ((1,1'- biphenyl -2- base) ethyl ketone of the fluoro- 1- of 2,2- bis- in embodiment 613C nuclear magnetic spectrogram.
Figure 13 is the fluoro- 1- of 2,2- bis- (naphthalene -2- base) ethyl ketone in embodiment 71H nuclear magnetic spectrogram.
Figure 14 is the fluoro- 1- of 2,2- bis- (naphthalene -2- base) ethyl ketone in embodiment 713C nuclear magnetic spectrogram.
Specific embodiment
The preparation method for the difluoro acetophenone compound that novel difluoro acetylation reagent NDFTS of the present invention is realized,
Reaction step is less, and raw material is cheap and easy to get, and reaction condition is mild, environmental-friendly, convenient for operation；And products obtained therefrom high income,
Purity is high, the low quality requirement complied fully with as pharmaceutical intermediate of reaction cost, provide skill for subsequent industrialized production
Art is supported and theoretical direction.
Present invention will be further explained below with reference to specific examples.These embodiments are merely to illustrate the present invention and do not have to
In limiting the scope of the invention.Technical staff in the art belongs to this hair to the simple replacement of the invention done or improvement
Within bright protected technical solution.
The fluoro- 1- of the embodiment 1:2,2- bis- (synthesis of (1,1'- biphenyl -4- base) ethyl ketone
In 25mL reactor, it is added palladium acetate (0.0023g, 0.01mmol), potassium carbonate (0.0553g, 0.4mmol),
Tricyclohexyl phosphine (0.0057g, 0.02mmol) and NDFTS (0.0651g, 0.2mmol) after nitrogen is replaced 3 times, are added anhydrous 1,
4- dioxane 2mL is added with stirring 4- biphenylboronic acid (0.0792 g, 0.4mmol), is stirred for 24 hours at 25 DEG C.Column chromatographs (silicon
Glue, 200-300 mesh；Solvent, petroleum ether: ethyl acetate=100:1) obtain the fluoro- 1- of 2,2- bis- ((1,1'- biphenyl -4- base) second
Ketone 0.0409g, yield 88%.
The fluoro- 1- of 2,2- bis- ((1,1'- biphenyl -4- base) ethyl ketone
White solid,1H NMR(500MHz,CDCl3) δ 8.16 (d, J=8.4Hz, 2H), 7.79-7.73 (m, 2H),
7.67-7.63 (m, 2H), 7.53-7.47 (m, 2H), 7.47-7.42 (m, 1H), 6.33 (t, J=53.5Hz, 1H)；13C NMR
(125MHz,CDCl3)δ187.40,187.20,186.99,147.59,139.39,130.28, 130.27,130.25,
130.16,129.09,128.72,127.56,127.35,113.35,111.33,109.32
The synthesis of embodiment 2:2,2- bis- fluoro- 1- (3- tolyl) ethyl ketone
In 25mL reactor, it is added palladium acetate (0.0023g, 0.01mmol), potassium carbonate (0.0553g, 0.4mmol),
Tri-tert-butylphosphine (0.0041g, 0.02mmol) and NDFTS (0.0651g, 0.2mmol) after nitrogen is replaced 3 times, are added anhydrous 1,
4- dioxane 2mL is added with stirring 3- methylphenylboronic acid (0.0544 g, 0.4mmol), is stirred for 24 hours at 50 DEG C.Column chromatography
(silica gel, 200-300 mesh；Solvent, petroleum ether: ethyl acetate=100:1) obtain 2,2- bis- fluoro- 1- (3- tolyl) ethyl ketone
0.0228g, yield 67%.
2,2- bis- fluoro- 1- (3- tolyl) ethyl ketone
Colourless liquid,1H NMR(500MHz,CDCl3) δ 7.87 (d, J=5.7Hz, 2H), 7.48 (d, J=7.6 Hz,
1H), 7.41 (t, J=7.9Hz, 1H), 6.29 (t, J=53.5Hz, 1H), 2.43 (s, 3H)；13C NMR (126MHz,CDCl3)
δ187.87,187.67,187.47,138.93,135.73,131.56,131.54,131.53, 130.00,129.98,
129.96,128.83,126.88,126.86,126.84,113.09,111.08,109.06, 21.31.
The synthesis of the fluoro- 1- of embodiment 3:2,2- bis- ((4- methoxyl group) phenyl) ethyl ketone
Operation is reacted to obtain the fluoro- 1- of 2,2- bis- ((4- methoxyl group) with NDFTS by 4- methoxyphenylboronic acid with embodiment 1
Phenyl) ethyl ketone 0.0336g, 90%.
The fluoro- 1- of 2,2- bis- ((4- methoxyl group) phenyl) ethyl ketone
White solid,1H NMR(500MHz,CDCl3) δ 8.06 (d, J=9.0Hz, 2H), 7.02-6.97 (m, 2H),
6.25 (t, J=53.7Hz, 1H), 3.90 (s, 3H)；13C NMR(126MHz,CDCl3)δ186.25,186.05, 185.86,
164.90,132.19,132.17,132.15,124.48,124.46,124.45,114.28,113.52, 111.50,
109.49,55.63
The synthesis of embodiment 4:4- (2,2- difluoro acetyl group) methyl benzoate
In 25mL reactor, palladium acetylacetonate (0.0031g, 0.005mmol), tricyclohexyl phosphine (0.0057 g,
0.02mmol), cesium carbonate (0.0977g, 0.3mmol) and NDFTS (0.0651g, 0.2mmol) after nitrogen is replaced 3 times, are added
Dry toluene 2mL is added with stirring 4- methoxycarbonyl group phenyl boric acid (0.0540g, 0.3mmol), stirs for 24 hours at 50 DEG C.Column chromatography
(silica gel, 200-300 mesh；Solvent, petroleum ether: ethyl acetate=100:1) obtain 4- (2,2- difluoro acetyl group) benzoic acid first
Ester 0.0395g, yield 92%.
4- (2,2- difluoro acetyl group) methyl benzoate
White solid,1H NMR(500MHz,CDCl3) δ 8.15 (d, J=8.6Hz, 2H), 8.11 (d, J=8.1 Hz,
2H), 6.29 (t, J=53.3Hz, 1H), 3.95 (s, 3H)；13C NMR(125MHz,CDCl3)δ 187.42,187.21,
187.00,165.78,135.35,134.49,129.97,129.55,129.54,129.52, 113.11,111.09,
109.07,52.62.
The synthesis of the fluoro- 1- of embodiment 5:2,2- bis- ((4- phenoxy group) phenyl) ethyl ketone
In 25mL reactor, it is added palladium acetate (0.0023g, 0.01mmol), potassium carbonate (0.0553g, 0.4mmol),
Tricyclohexyl phosphine (0.0113g, 0.04mmol) and NDFTS (0.0651g, 0.2mmol) after nitrogen is replaced 3 times, are added anhydrous four
Hydrogen furans 2mL is added with stirring 4- phenoxy group phenyl boric acid (0.0856 g, 0.4mmol), is stirred for 24 hours at 30 DEG C.Column chromatographs (silicon
Glue, 200-300 mesh；Solvent, petroleum ether: ethyl acetate=100:1) obtain the fluoro- 1- of 2,2- bis- ((4- phenoxy group) phenyl) second
Ketone 0.0443g, yield 89%.
The fluoro- 1- of 2,2- bis- ((4- phenoxy group) phenyl) ethyl ketone
Colourless liquid；1H NMR(500MHz,CDCl3) δ 8.09 (d, J=8.7Hz, 2H), 7.46 (t, J=7.9Hz,
2H), 7.28 (d, J=7.2Hz, 1H), 7.13 (d, J=7.8Hz, 2H), 7.07 (d, J=8.9Hz, 2H), 6.28 (t, J=
53.6Hz,1H)；13C NMR(126MHz,CDCl3)δ186.33,186.13,185.93,163.65, 154.77,132.20,
132.18,132.16,130.22,125.81,125.79,125.20,120.58,117.30, 113.51,111.49,
109.47.
The fluoro- 1- of the embodiment 6:2,2- bis- (synthesis of (1,1'- biphenyl -2- base) ethyl ketone
In 25mL reactor, it is added palladium acetate (0.0023g, 0.01mmol), 1,2- bis- (dicyclohexyl phosphino-) ethane
Anhydrous Isosorbide-5-Nitrae-dioxane is added after nitrogen is replaced 3 times in (0.0043g, 0.01mmol) and NDFTS (0.0651g, 0.2mmol)
2mL is added with stirring 2- biphenylboronic acid (0.0792g, 0.4mmol), is stirred for 24 hours at 50 DEG C.Column chromatographs (silica gel, 200-300
Mesh；Solvent, petroleum ether: ethyl acetate=100:1) obtain the fluoro- 1- of 2,2- bis- ((1,1'- biphenyl -2- base) ethyl ketone
0.0441g, yield 95%.
The fluoro- 1- of 2,2- bis- ((1,1'- biphenyl -2- base) ethyl ketone
Colourless liquid,1H NMR(500MHz,CDCl3) δ 8.96 (d, J=8.5Hz, 1H), 8.10 (d, J=8.6 Hz,
2H), 7.66 (dddd, J=27.4,8.2,6.8,1.4Hz, 2H), 7.42 (d, J=7.5Hz, 1H), 6.42 (t, J=
53.9Hz,1H),2.79(s,3H)；13C NMR(125MHz,CDCl3)δ189.46,189.27, 189.08,143.26,
133.14,131.39,131.36,131.32,131.17,128.78,126.87,126.53, 126.01,125.27,
124.63,113.05,111.03,109.00.
The synthesis of the fluoro- 1- of embodiment 7:2,2- bis- (naphthalene -2- base) ethyl ketone
Operation is reacted to obtain the fluoro- 1- of 2,2- bis- (naphthalene -2- base) ethyl ketone with NDFTS by 1- naphthalene boronic acids with embodiment 6
0.0371g, 90%.
The fluoro- 1- of 2,2- bis- (naphthalene -2- base) ethyl ketone
White solid,1H NMR(500MHz,CDCl3) δ 8.65 (s, 1H), 8.07 (d, J=8.7Hz, 1H), 8.00 (d, J
=8.2Hz, 1H), 7.95 (d, J=8.7Hz, 1H), 7.90 (d, J=8.2Hz, 1H), 7.67 (ddd, J=8.2,6.9,1.3
Hz, 1H), 7.60 (ddd, J=8.1,6.8,1.2 Hz, 1H), 6.41 (t, J=53.6 Hz, 1H)；13C NMR(125 MHz,
CDCl3)δ187.73,187.53,187.33,136.29,132.53,132.50, 132.47,132.28,130.05,
129.64,128.99,128.78,127.91,127.23,124.07,113.41, 111.39,109.38。
Claims (9)
1. a kind of novel two Fluorakil 100 NDFTS of difluoro acetylation reagent N- phenyl-N- p-toluenesulfonyl, which is characterized in that
The molecular structural formula of the NDFTS is as follows:
2. a kind of preparation method of difluoro acetophenone compound, which is characterized in that steps are as follows: with difluoro acetylation reagent
NDFTS is raw material, under the action of alkali, metallic catalyst and ligand, and aryl boric acid derivatives reaction, in anhydrous organic solvent
In, under the conditions of 25-50 DEG C, reaction obtains difluoro acetophenone compound in 16-24 hours, and synthetic route is as follows:
R is selected from hydrogen, alkyl, methoxyl group, phenoxy group, methyl carbonate base, aryl, vinyl, naphthalene, halogen, trifluoromethyl, nitro
And cyano；
The molar ratio of aryl boric acid derivative and metallic catalyst is 1:0.05~1:0.1；
The molar ratio of aryl boric acid derivative and difluoro acetylation reagent NDFTS are 1:1~10:1；
The molar ratio of aryl boric acid derivative and alkali is 1:0~1:10；
The molar ratio of aryl boric acid derivative and ligand is 1:0.05~1:0.4；
Molar concentration of the aryl boric acid derivative in system is 0.01mmol/mL~2mmol/mL.
3. preparation method according to claim 2, which is characterized in that the metallic catalyst is four (triphenylphosphines)
Palladium, palladium acetate, tris(dibenzylideneacetone) dipalladium, palladium chloride, palladium trifluoroacetate, allyl palladium chloride dimer, acetyl
Acetone palladium.
4. preparation method according to claim 2 or 3, which is characterized in that the ligand is triphenylphosphine, three (4- first
Base phenyl) phosphine, three (2- furyl) phosphines, tricyclohexyl phosphine, 2- (di-t-butyl phosphine) biphenyl, (±) -2,2'- pairs-(diphenyl phosphine
Base) -1,1'- dinaphthalene, bis- (dicyclohexyl phosphino-) ethane of 1,2-, tri-n-butyl phosphine, tri-tert-butylphosphine.
5. preparation method according to claim 2 or 3, which is characterized in that the organic solvent is tetrahydrofuran, second two
Diethylene glycol dimethyl ether, methylene chloride, ether, acetone, acetonitrile, dimethyl sulfoxide, the tert-butyl alcohol, 1,4- dioxane, toluene, N, N- diformazan
Base formamide, n-hexane.
6. the preparation method according to claim 4, which is characterized in that the organic solvent is tetrahydrofuran, ethylene glycol
Dimethyl ether, methylene chloride, ether, acetone, acetonitrile, dimethyl sulfoxide, the tert-butyl alcohol, 1,4- dioxane, toluene, N, N- dimethyl
Formamide, n-hexane.
7. according to preparation method described in claim 2,3 or 6, which is characterized in that the alkali be potassium hydroxide, sodium carbonate,
Potassium carbonate, sodium bicarbonate, saleratus, sodium acetate, sodium methoxide, tripotassium phosphate, sodium tert-butoxide, cesium carbonate.
8. the preparation method according to claim 4, which is characterized in that the alkali is potassium hydroxide, sodium carbonate, carbonic acid
Potassium, sodium bicarbonate, saleratus, sodium acetate, sodium methoxide, tripotassium phosphate, sodium tert-butoxide, cesium carbonate.
9. preparation method according to claim 5, which is characterized in that the alkali is potassium hydroxide, sodium carbonate, carbonic acid
Potassium, sodium bicarbonate, saleratus, sodium acetate, sodium methoxide, tripotassium phosphate, sodium tert-butoxide, cesium carbonate.
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| CN110003062B (en) | 2021-04-20 |
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