CN114163369A - Preparation method of sulfur/oxygen ester group-containing aromatic hydrocarbon compound - Google Patents
Preparation method of sulfur/oxygen ester group-containing aromatic hydrocarbon compound Download PDFInfo
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- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/26—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to carbon atoms of six-membered aromatic rings
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Abstract
The invention discloses a preparation method of a sulfur/oxygen ester group-containing aromatic hydrocarbon compound, which comprises the following steps: A. reacting substituted benzoyl chloride with tert-butyl mercaptan to obtain substituted tert-butyl thioester benzoate; B. reacting substituted bromobenzene with isopropyl magnesium chloride Grignard reagent, cooling, and adding di-tert-butyl dicarbonate to react to obtain substituted tert-butyl benzoate; C. carrying out reflux reaction on the substituted tert-butyl benzoate and a Lawson reagent to obtain substituted tert-butyl benzoate disulfide; D. and (2) reacting the substituted tert-butyl benzoate or substituted tert-butyl benzoate with TMPMgCl. LiCl, and then carrying out demetallization reaction by using an iodine simple substance to obtain substituted 2-iodobenzoic acid tert-butyl thioester or substituted 2-iodobenzoic acid tert-butyl ester. The aromatic hydrocarbon compound containing the sulfur/oxygen ester group obtained by the method has various forms, simple, green and efficient preparation process, low cost, high speed and easy operation, provides an important material source for modification of the aromatic hydrocarbon compound containing the sulfur/oxygen ester group, and has important application value.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a sulfur/oxygen ester group-containing aromatic hydrocarbon compound.
Background
The aromatic hydrocarbon compound containing sulfur/oxygen ester group is widely existed in natural products, and the unique biological activity of the aromatic hydrocarbon compound enables the aromatic hydrocarbon compound to be widely applied to various pesticides, such as insecticide methyl isoxathion, acaricide fenpyroximate, bactericide alafenac-S-methyl and the like. In order to achieve versatile synthesis or subsequent functionalization of sulfur/oxy ester group-containing aromatic compounds, organic chemistry workers have made beneficial attempts in this field. However, the sulfur-containing organic compounds generally have the characteristics of malodor, easy oxidation, possibility of poisoning metal catalysts and the like, so that the synthesis of the sulfur/oxygen ester group-containing aromatic compounds is difficult, and related synthesis reports are few.
Therefore, a series of sulfur/oxygen ester group-containing aromatic hydrocarbon compounds are prepared by developing a simple, green and efficient method, an important material source can be provided for modification of the sulfur/oxygen ester group-containing aromatic hydrocarbon compounds, and the method has an important application value.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a preparation method of a sulfur/oxygen ester group-containing aromatic hydrocarbon compound, and solves the technical problems that the sulfur/oxygen ester group-containing aromatic hydrocarbon compound is difficult to synthesize and is difficult to obtain in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention provides a preparation method of a sulfur/oxygen ester group-containing aromatic hydrocarbon compound, wherein the structural formula of the sulfur/oxygen ester group-containing aromatic hydrocarbon compound is as follows:
wherein X is S or O; y is S or O; z is F, Cl, Br, I, CN, NO2、CF3COOEt, alkyl or alkoxy, Z can be mono-substituted or poly-substituted, and the substitution position on the aromatic ring is not limited;
the preparation method of the sulfur/oxygen ester group-containing aromatic hydrocarbon compound comprises the following steps:
A. reacting substituted benzoyl chloride and tert-butyl mercaptan under the action of organic base and a first organic solvent to obtain substituted tert-butyl thioester benzoate; the reaction formula is as follows:
B. carrying out bromine-magnesium exchange reaction on substituted bromobenzene and isopropyl magnesium chloride Grignard reagent under the action of a second organic solvent, cooling to 0-5 ℃ after the reaction is finished, and adding di-tert-butyl dicarbonate to continue the reaction to obtain substituted tert-butyl benzoate; the reaction formula is as follows:
C. carrying out reflux reaction on the substituted tert-butyl benzoate and excessive Lawson reagent in a third organic solvent to obtain substituted tert-butyl benzoate disulfide; the reaction formula is as follows:
D. reacting substituted tert-butyl benzoate or substituted tert-butyl benzoate with TMPMgCl LiCl under the action of a fourth organic solvent, and performing a demetallization reaction by using an iodine simple substance after the reaction is finished to obtain substituted 2-iodobenzoic acid tert-butyl thioester or substituted 2-iodobenzoic acid tert-butyl ester; the reaction formula is as follows:
compared with the prior art, the invention has the beneficial effects that:
the aromatic hydrocarbon compound containing the sulfur/oxygen ester group obtained by the method has various forms, simple, green and efficient preparation process, low cost, high speed and easy operation, can be subsequently subjected to oriented ortho-position C-H activation or oriented metallization so as to be functionalized, provides an important material source for modification of the aromatic hydrocarbon compound containing the sulfur/oxygen ester group, and has important application value.
Drawings
FIG. 1 shows tert-butyl 3-chlorobenzoate synthesized in example 1 of the present invention1H NMR characterization spectrum;
FIG. 2 is a diagram of tert-butyl 3-chlorobenzoate synthesized in example 2 of the present invention1H NMR characterization spectrum;
FIG. 3 shows the synthesis of tert-butyl 3-chlorobenzenethioate of example 3 of the present invention1H NMR characterization spectrum;
FIG. 4 shows the synthesis of tert-butyl 3-chloro-2-iodobenzoate according to example 4 of the present invention1H NMR characterization spectrum;
FIG. 5 is a photograph of tert-butyl 3-chloro-2-iodobenzoate synthesized in example 5 of this invention1H NMR characterization spectrum.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a sulfur/oxygen ester group-containing aromatic hydrocarbon compound, wherein the structural formula of the sulfur/oxygen ester group-containing aromatic hydrocarbon compound is as follows:
wherein X is S or O; y is S or O; z is F, Cl, Br, I, CN, NO2、CF3COOEt, alkyl or alkoxy, Z can be mono-substituted or poly-substituted, and the substitution position on the aromatic ring is not limited.
The preparation method of the sulfur/oxygen ester group-containing aromatic hydrocarbon compound comprises the following steps:
A. reacting substituted benzoyl chloride and tert-butyl mercaptan under the action of organic base and a first organic solvent to obtain substituted tert-butyl thioester benzoate; the reaction formula is as follows:
wherein Z is F, Cl, Br, I, CN, NO2、CF3COOEt, hydrocarbyl or alkoxy, Z may beThe substituent can be mono-substituted or poly-substituted, and the substituent position on the aromatic ring is not limited;
B. carrying out bromine-magnesium exchange reaction on substituted bromobenzene and isopropyl magnesium chloride Grignard reagent under the action of a second organic solvent, cooling to 0-5 ℃ after the reaction is finished, and adding di-tert-butyl dicarbonate to continue the reaction to obtain substituted tert-butyl benzoate; the reaction formula is as follows:
wherein Z is F, Cl, Br, I, CN, NO2、CF3COOEt, alkyl or alkoxy, Z can be mono-substituted or poly-substituted, and the substitution position on the aromatic ring is not limited;
C. carrying out reflux reaction on the substituted tert-butyl benzoate and an excessive Lawesson reagent (Lawesson reagent) in a third organic solvent to obtain substituted tert-butyl methyl dithionate; the reaction formula is as follows:
wherein Z is F, Cl, Br, I, CN, NO2、CF3COOEt, alkyl or alkoxy, Z can be mono-substituted or poly-substituted, and the substitution position on the aromatic ring is not limited;
D. reacting substituted tert-butyl benzoate or substituted tert-butyl benzoate with TMPMgCl.LiCl (TMP: 2,2,6, 6-tetramethyl piperidyl) under the action of a fourth organic solvent, and performing demetallization reaction by using an iodine simple substance after the reaction is finished to obtain substituted tert-butyl 2-iodobenzoate or substituted tert-butyl 2-iodobenzoate; the reaction formula is as follows:
wherein Y is S or O; z is F, Cl, Br, I, CN, NO2、CF3COOEt, hydrocarbyl or alkoxy, Z may beMonosubstitution or polysubstitution can be carried out, and the substitution position on the aromatic ring is not limited.
In the invention, in the synthesis process of the substituted benzoic acid tert-butyl thioester, the molar ratio of the substituted benzoyl chloride to the tert-butyl mercaptan to the triethylamine is 1: (1.1-1.5): (1.3-1.7), further 1: 1.2: 1.5; the organic base is diethylamine or triethylamine, and the first organic solvent is at least one of tetrahydrofuran or diethyl ether; the reaction temperature is room temperature, and the reaction time is 0.5-2 h, further 1 h; during the reaction, the reaction was monitored by TLC; after the reaction is finished, quenching with sodium hypochlorite, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, concentrating the organic phase, and performing column chromatography on a crude product to obtain the substituted benzoic acid tert-butyl thioester.
In the invention, in the synthesis process of the substituted tert-butyl benzoate, the reaction is carried out under the anhydrous and oxygen-free conditions; the molar ratio of the substituted bromobenzene to the isopropyl magnesium chloride to the di-tert-butyl dicarbonate is 1: (1.1-1.3): (1.1-1.3), further 1: 1.2: 1.2; the second organic solvent is at least one of tetrahydrofuran or diethyl ether; the temperature of the bromine-magnesium exchange reaction is room temperature, the time is 0.5-2 h, and further 1 h; during the continued reaction by adding di-tert-butyl dicarbonate, the reaction was monitored by TLC; after the reaction is finished, quenching the product by using citric acid aqueous solution, extracting the aqueous phase by using ethyl acetate, combining the organic phases, drying the organic phases by using anhydrous sodium sulfate, concentrating the organic phases, and carrying out column chromatography on a crude product to obtain the substituted tert-butyl benzoate. In the process, a novel KNOCHEL magnesium reagent is used, and the magnesium reagent has good tolerance to a series of sensitive groups on an aromatic ring, so that the method can greatly expand the application range of the substrate.
In the invention, in the synthesis process of the substituted tert-butyl methyl dithionate, the molar ratio of the substituted tert-butyl benzoate to the Lawson reagent is 1: (3-5), further 1: 3; the third organic solvent is toluene; the temperature of the reflux reaction is 120-150 ℃, further 130 ℃, and the time is 5-10 hours, further 7 hours; after the reaction is finished, saturated ammonium chloride is used for quenching, ethyl acetate is used for extracting the water phase, organic phases are combined and dried by anhydrous sodium sulfate, and the organic phase is concentrated to obtain the substituted benzyl disulfide tert-butyl ester.
In the invention, in the synthesis process of substituted 2-iodobenzoic acid tert-butyl thioester or substituted 2-iodobenzoic acid tert-butyl ester, the reaction is carried out under the anhydrous and oxygen-free conditions; the molar ratio of the substituted tert-butyl benzoate or substituted tert-butyl benzoate to TMPMgCl. LiCl and iodine is 1: (1.1-1.2): (1.8-2.5), further 1: 1.2: 2; the fourth organic solvent is at least one of tetrahydrofuran or diethyl ether, the temperature of the reaction of the substituted tert-butyl benzoate or the substituted tert-butyl benzoate and TMPMgCl. LiCl is room temperature, the time is 2-3 h, and the reaction is monitored by GC; the demetallization reaction is carried out at room temperature for 1-3 hours; after the demetallization reaction is finished, quenching the reaction by using a saturated ammonium chloride solution, extracting a water phase by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating the organic phases, and separating a crude product by using column chromatography to obtain substituted 2-iodobenzoic acid tert-butyl thioester or substituted 2-iodobenzoic acid tert-butyl ester. In the process, a KNOCHEL magnesium reagent is used, the reagent can tolerate a series of sensitive groups and can realize good ortho-position metallization and subsequent functionalization, so that the application range of the substrate is greatly widened.
EXAMPLE 13 Synthesis of tert-Butylthiobenzoate
3-chlorobenzoyl chloride (20mmol), t-butylmercaptan (24mmol) and triethylamine (30mmol) were added to the reaction tube, 10mL of tetrahydrofuran was added slowly, the mixture was stirred at room temperature for 1 hour, and the reaction was monitored by TLC. After the reaction is finished, quenching with sodium hypochlorite, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, concentrating the organic phase, and performing column chromatography on a crude product to obtain 4.509g (light yellow oily liquid) of the 3-chlorobenzoic acid tert-butyl thioester with the yield of 98.8 percent and the purity of more than or equal to 95 percent. FIG. 1 shows tert-butyl 3-chlorobenzoate synthesized in example 1 of the present invention1H NMR characterization spectrum.
1H NMR(400MHz,CDCl3):δ(ppm)7.29-7.25(m,1H),7.71(d,J＝8Hz,1H),7.41(d,J＝8Hz,1H),7.81(s,1H),1.50(s,9H).
HRMS(ESI)m/z[M+H]+Calcd for C11H14ClOS(229.0448),found:229.0450.
EXAMPLE 23 Synthesis of tert-butyl chlorobenzoate
To a solution of m-chlorobromobenzene (40mmol) in THF was added 48mmol of isopropyl magnesium chloride Grignard reagent under anhydrous and oxygen-free conditions, and the mixture was reacted at room temperature for 1 hour. After completion of the bromo-magnesium exchange reaction, the mixed system was cooled to 0-5 ℃ and 48mmol of di-tert-butyl dicarbonate was added thereto, and the reaction was monitored by TLC. After the reaction is finished, quenching the reaction product by using citric acid aqueous solution. The aqueous phase was extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, the organic phase was concentrated and the crude product was column chromatographed to give 10.354g (white solid) of the product tert-butyl 3-chlorobenzoate with a yield of 61% and a purity of 95% or more. FIG. 2 is a diagram of tert-butyl 3-chlorobenzoate synthesized in example 2 of the present invention1H NMR characterization spectrum. Mp 46 ℃.
1H NMR(400MHz,CDCl3):δ(ppm)7.29-7.25(m,1H),7.79(d,J＝8Hz,1H),7.41(d,J＝8Hz,1H),7.87(s,1H),1.51(s,9H).
HRMS(ESI)m/z[M+H]+Calcd for C11H14ClO2(213.0677),found:213.0667.
EXAMPLE 33 Synthesis of t-butyl chlorobenzoate
The tert-butyl 3-chlorobenzoate (20mmol) obtained in example 1 was reacted with an excess (60mmol) of Lawson's reagent (Lawesson's reagent) in 108mL of toluene solvent at 130 ℃ under heating and refluxing for 7 hours. After the reaction is finished, saturated ammonium chloride is used for quenching, ethyl acetate is used for extracting a water phase, organic phases are combined and dried by anhydrous sodium sulfate, and the organic phase is concentrated to obtain 2.235g (red oily liquid) of the product 3-chlorobenzyl tert-butyl disulfide, wherein the yield is 30.5 percent, and the purity is more than or equal to 95 percent. FIG. 3 shows the synthesis of tert-butyl 3-chlorobenzenethioate of example 3 of the present invention1H NMR characterization spectrum.
1H NMR(400MHz,CDCl3):δ(ppm)7.32-7.28(m,1H),7.75(d,J＝8Hz,1H),7.47(d,J＝8Hz,1H),7.86(s,1H),1.70(s,9H).
HRMS(ESI)m/z[M+H]+Calcd for C11H14ClS2(245.0220),found:245.0225.
EXAMPLE 43 Synthesis of tert-butyl-2-iodobenzoate
To the tert-butyl 3-chlorobenzoate (2mmol) obtained in example 1 was added 2.4mL (1 mol/L concentration) of TMPMgCl. LiCl in THF under anhydrous and oxygen-free conditions, and the reaction was followed by GC at room temperature for 2 hours. After the reaction is finished, adding an iodine simple substance (4mmol) into the system, carrying out demetallization reaction for 2h at room temperature, and then quenching the reaction by using a saturated ammonium chloride solution. The aqueous phase is extracted by ethyl acetate, the organic phases are combined and dried by anhydrous sodium sulfate, the organic phase is concentrated, and the crude product is separated by column chromatography to obtain 0.428g (light yellow oily liquid) of the product substituted 2-iodobenzoic acid tert-butyl thioester, the yield is 60 percent, and the purity is more than or equal to 95 percent. FIG. 4 shows the synthesis of tert-butyl 3-chloro-2-iodobenzoate according to example 4 of the present invention1H NMR characterization spectrum.
1H NMR(400MHz,CDCl3):δ(ppm)7.34-7.25(m,2H),7.50(d,J＝4Hz,1H),1.62(s,9H).
HRMS(ESI)m/z[M+H]+Calcd forC11H13ClIOS(354.9415),found:354.9420.
EXAMPLE 53 Synthesis of tert-butyl chloro-2-iodobenzoate
To tert-butyl 3-chlorobenzoate (2mmol) obtained in example 2 was added slowly in an anhydrous oxygen-free systemA solution of commercially available TMPMgCl. LiCl in THF was slowly added at 2.4mL (concentration 1mol/L) and reacted at room temperature for 2, with monitoring of the reaction by GC. After the reaction is finished, adding an iodine simple substance (4mmol) into the system, carrying out demetallization reaction for 2h at room temperature, and then quenching the reaction by using a saturated ammonium chloride solution. The aqueous phase was extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, the organic phase was concentrated and the crude product was isolated by column chromatography to give the product tert-butyl 3-chloro-2-iodobenzoate 0.513g (white crystals) in 75.77% yield with a purity of 95% or more. FIG. 5 is a photograph of tert-butyl 3-chloro-2-iodobenzoate synthesized in example 5 of this invention1H NMR characterization spectrum.
Mp:124℃.
1H NMR(400MHz,CDCl3):δ(ppm)7.24-7.16(m,2H),7.38(d,J＝4Hz,1H),1.52(s,9H).
HRMS(ESI)m/z[M+H]+Calcd for C11H13ClIO2(338.9643),found:338.9649.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing a sulfur/oxygen ester group-containing aromatic hydrocarbon compound, which is characterized in that the structural formula of the sulfur/oxygen ester group-containing aromatic hydrocarbon compound is as follows:
wherein X is S or O; y is S or O; z is F, Cl, Br, I, CN, NO2、CF3COOEt, alkyl or alkoxy, Z may be monosubstituted or may be monosubstitutedIs polysubstituted, and the substitution position on the aromatic ring is not limited;
the preparation method of the sulfur/oxygen ester group-containing aromatic hydrocarbon compound comprises the following steps:
A. reacting substituted benzoyl chloride and tert-butyl mercaptan under the action of organic base and a first organic solvent to obtain substituted tert-butyl thioester benzoate; the reaction formula is as follows:
B. carrying out bromine-magnesium exchange reaction on substituted bromobenzene and isopropyl magnesium chloride Grignard reagent under the action of a second organic solvent, cooling to 0-5 ℃ after the reaction is finished, and adding di-tert-butyl dicarbonate to continue the reaction to obtain substituted tert-butyl benzoate; the reaction formula is as follows:
C. carrying out reflux reaction on the substituted tert-butyl benzoate and excessive Lawson reagent in a third organic solvent to obtain substituted tert-butyl benzoate disulfide; the reaction formula is as follows:
D. reacting substituted tert-butyl benzoate or substituted tert-butyl benzoate with TMPMgCl LiCl under the action of a fourth organic solvent, and performing a demetallization reaction by using an iodine simple substance after the reaction is finished to obtain substituted 2-iodobenzoic acid tert-butyl thioester or substituted 2-iodobenzoic acid tert-butyl ester; the reaction formula is as follows:
2. the method for preparing sulfur/oxygen ester group-containing aromatic hydrocarbon compound according to claim 1, wherein the molar ratio of substituted benzoyl chloride to tert-butyl mercaptan and triethylamine in the synthesis process of the substituted benzoic acid tert-butyl thioester is 1: (1.1-1.5): (1.3-1.7).
3. The method for preparing sulfur/oxygen ester group-containing aromatic hydrocarbon compound according to claim 1, wherein in the synthesis process of the substituted tert-butyl benzoate, the organic base is diethylamine or triethylamine, and the first organic solvent is at least one of tetrahydrofuran or diethyl ether; the reaction temperature is room temperature, and the reaction time is 0.5-2 h.
4. The method for preparing sulfur/oxygen ester group-containing aromatic hydrocarbon compound according to claim 1, wherein in the synthesis process of the substituted tert-butyl benzoate, the molar ratio of the substituted bromobenzene to the isopropyl magnesium chloride to the di-tert-butyl dicarbonate is 1: (1.1-1.3): (1.1-1.3).
5. The method for preparing sulfur/oxygen ester group-containing aromatic hydrocarbon compound according to claim 1, wherein in the synthesis process of the substituted tert-butyl benzoate, the second organic solvent is at least one of tetrahydrofuran or diethyl ether; the temperature of the bromine-magnesium exchange reaction is room temperature, and the time is 0.5-2 h.
6. The method according to claim 1, wherein the molar ratio of tert-butyl benzoate to Lawson's reagent in the synthesis of said substituted tert-butyl benzoate disulfide is 1: (3-5).
7. The method according to claim 1, wherein the third organic solvent is toluene during the synthesis of the substituted tert-butyl benzenedithionate; the temperature of the reflux reaction is 120-150 ℃, and the time is 5-10 h.
8. The method for preparing a sulfur/oxygen ester group-containing aromatic hydrocarbon compound according to claim 1, wherein during the synthesis of the substituted tert-butyl 2-iodobenzoate or the substituted tert-butyl 2-iodobenzoate, the molar ratio of the substituted tert-butyl benzoate or the substituted tert-butyl benzoate to TMPMgCl. LiCl and iodine is 1: (1.1-1.2): (1.8-2.5).
9. The method for preparing a thio/oxycarbonyl ester-containing aromatic hydrocarbon compound as claimed in claim 1, wherein in the synthesis process of the substituted tert-butyl 2-iodobenzoate or the substituted tert-butyl 2-iodobenzoate, the fourth organic solvent is at least one of tetrahydrofuran or diethyl ether, and the reaction temperature of the substituted tert-butyl benzoate or the substituted tert-butyl benzoate and TMPMgCl. LiCl is room temperature and the reaction time is 2-3 h.
10. The method for preparing a thio/oxycarbonyl aromatic hydrocarbon compound as claimed in claim 1, wherein in the synthesis process of the substituted tert-butyl 2-iodobenzoate or tert-butyl 2-iodobenzoate, the demetallization reaction is performed at room temperature for 1-3 hours.
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| US11078157B1 (en) * | 2018-01-31 | 2021-08-03 | University Of Oregon | Compound embodiments that release H2S by reaction with a reactive compound and methods of making and using the same |
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| CN1500813A (en) * | 1996-07-10 | 2004-06-02 | ��Ļ���Ű˾ | Polymerization with living characteristics |
| CN105164128A (en) * | 2013-03-13 | 2015-12-16 | 艾伯维公司 | Processes for the preparation of an apoptosis-inducing agent |
| US11078157B1 (en) * | 2018-01-31 | 2021-08-03 | University Of Oregon | Compound embodiments that release H2S by reaction with a reactive compound and methods of making and using the same |
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| "2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide", pages 3 * |
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| KU, YI-YIN ET AL.: "Development of a Convergent Large-Scale Synthesis for Venetoclax, a First-in-Class BCL-2 Selective Inhibitor", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 84, no. 8, pages 4814 - 4829, XP055617498, DOI: 10.1021/acs.joc.8b02750 * |
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