CN115246757B - Preparation method of aryl acetamide compound - Google Patents
Preparation method of aryl acetamide compound Download PDFInfo
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- CN115246757B CN115246757B CN202210015959.7A CN202210015959A CN115246757B CN 115246757 B CN115246757 B CN 115246757B CN 202210015959 A CN202210015959 A CN 202210015959A CN 115246757 B CN115246757 B CN 115246757B
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- -1 aryl acetamide compound Chemical class 0.000 title claims abstract description 41
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- OAHKWDDSKCRNFE-UHFFFAOYSA-N phenylmethanesulfonyl chloride Chemical compound ClS(=O)(=O)CC1=CC=CC=C1 OAHKWDDSKCRNFE-UHFFFAOYSA-N 0.000 claims abstract description 19
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 7
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims abstract description 6
- 235000011009 potassium phosphates Nutrition 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000003513 alkali Substances 0.000 claims 3
- 239000003446 ligand Substances 0.000 claims 3
- 239000002904 solvent Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 239000012039 electrophile Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 238000005810 carbonylation reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005910 aminocarbonylation reaction Methods 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- YTFJQDNGSQJFNA-UHFFFAOYSA-L benzyl phosphate Chemical compound [O-]P([O-])(=O)OCC1=CC=CC=C1 YTFJQDNGSQJFNA-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/06—Formation or introduction of functional groups containing nitrogen of amide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an aryl acetamide compound, which comprises the following steps: palladium acetate, 1, 3-bis (diphenylphosphine) propane, molybdenum carbonyl, potassium phosphate, water, benzyl sulfonyl chloride and nitroarene are reacted at 120 ℃ for 16 hours, and after the reaction is completed, the aryl acetamide compound is obtained through post treatment. According to the preparation method, benzyl sulfonyl chloride is used as an electrophile, nitroarene is used as a nitrogen source, and molybdenum carbonyl is used as a carbonyl source and a reducing agent, so that the operation is simple, the initial raw materials of the reaction are cheap and easy to obtain, the tolerance range of the substrate functional group is wide, and the reaction efficiency is high. Can synthesize various aryl acetamide compounds according to actual needs, is convenient to operate and widens the practicability of the method.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of an aryl acetamide compound.
Background
Transition metal catalyzed carbonylation reactions are an important class of efficient and convenient means of synthesizing carbonyl-containing compounds by inserting one or more CO molecules into a parent compound (Chem 2019,5,526-552). Since the pioneering work of Heck and its colleagues in 1974, palladium-catalyzed carbonylation reactions have undergone rapid development and have received increasing attention for their wide use in academic and large-scale industrial synthesis (j. Org. Chem.1974,39, 3318-3326). Although this conversion shows significant advantages in organic chemistry, the electrophiles used in the carbonylation reactions are primarily concentrated in C (sp 2 ) On electrophiles, such as aryl halides or pseudohalides. C (sp) 3 ) The use of electrophiles always presents challenges because of the presence of C (sp 3 ) X bonds are difficult to oxidatively add to the metal center in the presence of CO. In this respect, the benzyl substrate provides a good choice and becomesAnd is more attractive. In recent years, various benzyl compounds such as benzyl chloride/bromide, benzyl acetate/carbonate, benzyl phosphate, benzyl amine and benzyl ammonium salts have been developed. However, there are often disadvantages in such reactions such as a narrow range of substrates and waste generated during the pre-activation step. Therefore, the development of different benzyl substrates as electrophiles in carbonylation reactions is of great interest and urgent need.
On the other hand, sulfonyl chloride has many uses and has received much attention in organic synthesis due to its inexpensive, readily available and easy-to-handle nature (chem. Soc. Rev.2020,49, 4307-4359). The sulfonyl chloride can rapidly release SO under the action of the transition metal catalyst 2 As coupling reagents, have been successfully used in various cross-coupling and C-H functionalization reactions. However, there are very limited reports of the use of sulfonyl chloride as a carbon coupling reagent in carbonylation reactions, and further development is still needed. In addition, compared with the conventional amine compounds, the nitroarene has the advantages of good stability, easy availability and low price, so that the nitroarene becomes a promising nitrogen source in recent years, and the aminocarbonylation reaction taking the nitroarene as a nitrogen substitute is also reported.
Based on this, we developed a benzyl sulfonyl chloride as C (sp 3 ) Electrophiles, in nitroarenes as the abundant and more stable nitrogen precursors, synthesize a variety of aryl acetamides by palladium catalyzed aminocarbonylation reactions. The reaction opens up a new way for the carbonylation reaction of benzyl sulfonyl chloride as an electrophile.
Disclosure of Invention
The invention provides a preparation method of an aryl acetamide compound, which has the advantages of simple steps, low-cost and easily-obtained reaction raw materials, compatibility with various functional groups, good reaction applicability, and provides a new direction for the synthesis of the aryl acetamide compound by taking benzyl sulfonyl chloride as an electrophile, nitroarene as a nitrogen source and molybdenum carbonyl as a carbonyl source and a reducing agent.
A process for the preparation of an aryl acetamide compound comprising the steps of: reacting palladium catalyst, 1, 3-bis (diphenylphosphine) propane, molybdenum carbonyl, potassium phosphate, benzyl sulfonyl chloride and nitroarene at 110-130 ℃ for 12-20 hours, and after the reaction is completed, carrying out post-treatment to obtain the aryl acetamide compound;
the structure of the benzyl sulfonyl chloride is shown as a formula (II):
the structure of the nitroarene is shown in a formula (III):
the structure of the aryl acetamide compound is shown as a formula (I):
ar in the formulae (I) to (III) 1 And Ar is a group 2 Independently selected from substituted or unsubstituted aryl;
the substituent on the aryl is C 1 ～C 2 Alkyl, C 1 ～C 6 Alkoxy, trifluoromethyl, trifluoromethoxy, cyano, methylthio, C 1 ～C 6 Alkoxycarbonyl, C 1 ～C 6 One or more of alkylthio, phenoxy or halogen.
The molar ratio of the palladium catalyst to the 1, 3-bis (diphenylphosphine) propane to the potassium phosphate is 0.05:0.05:2;
Ar 1 ，Ar 2 the substitution position on the aryl group of (a) may be para or meta.
The reaction formula is as follows:
in the invention, the optional post-treatment process comprises: filtering, mixing with silica gel, and purifying by column chromatography to obtain corresponding aryl acetamide compound, wherein column chromatography purification is common technical means in the field.
Preferably Ar 1 In order to substitute or unsubstituted phenyl, the substituent on the phenyl is one or more of methyl, cyano, methoxycarbonyl, trifluoromethyl, trifluoromethoxy or Cl, at this time, the benzyl sulfonyl chloride is easily obtained, and the yield of the reaction is high.
Preferably Ar 2 The substituent on the phenyl is methyl, ethyl, methylthio, trifluoromethyl, methoxy, phenoxy, trifluoromethoxy, F or Cl. At this time, the nitroaromatic hydrocarbon is easily obtained, and the yield of the reaction is high.
The benzylsulfonyl chloride and nitroaromatic hydrocarbon used to prepare the aryl acetamide compound are relatively inexpensive and widely available in nature, preferably, benzylsulfonyl chloride on a molar basis: nitroaromatics: palladium catalyst=1-2:1:0.05-0.1; as a further preference, the benzylsulfonyl chloride is present in molar amounts: nitroaromatics: palladium catalyst=2:1:0.05.
Preferably, the reaction time is 16 hours, and the reaction time is too long to increase the reaction cost, but on the contrary, it is difficult to ensure the completion of the reaction.
Preferably, the reaction is carried out in acetonitrile in an amount to provide good dissolution of the starting materials, with 0.2mmol nitroaromatic hydrocarbon using an amount of acetonitrile of about 1 to 2mL.
Preferably, the palladium catalyst is palladium acetate, and among a plurality of palladium catalysts, palladium acetate is relatively inexpensive, and the reaction efficiency is relatively high when palladium acetate is used as the catalyst.
As a further preferred aspect, the aryl acetamide compound is one of the compounds of formula (I-1) -formula (I-5):
the compounds represented by the formulae (I-1) to (I-5) are known compounds.
In the preparation method, the benzyl sulfonyl chloride, the nitroaromatic hydrocarbon, the molybdenum carbonyl, the palladium acetate, the 1, 3-bis (diphenylphosphine) propane and the potassium phosphate are generally commercially available products, and can be conveniently obtained from the market.
Compared with the prior art, the invention has the beneficial effects that: the benzylsulfonyl chloride is used as an electrophile, the nitroarene is used as a nitrogen source, and meanwhile, the molybdenum carbonyl is used as a carbonyl source and a reducing agent, so that the preparation method is simple, the operation is easy, the post-treatment is simple and convenient, the reaction starting materials are cheap and easy to obtain, the tolerance range of the substrate functional group is wide, and the reaction efficiency is high. Can synthesize various aryl acetamide compounds according to actual needs, and has strong practicability.
Detailed Description
The invention is further described below in connection with specific embodiments.
Examples 1 to 15
Palladium acetate, 1, 3-bis (diphenylphosphine) propane, molybdenum carbonyl, potassium phosphate, benzyl sulfonyl chloride (II) and nitroarene (III) are added into a 15mL sealed tube according to the raw material ratio of the table 1, acetonitrile (1 mL) is then added, the mixture is uniformly mixed and stirred, the reaction is carried out according to the reaction conditions of the table 2, after the reaction is completed, the mixture is filtered, the silica gel is stirred, and the corresponding aryl acetamide compound (I) is obtained through column chromatography purification, wherein the reaction process is shown as the following formula:
TABLE 1 amounts of raw materials to be added in examples 1 to 15
TABLE 2
In tables 1 and 2, T is the reaction temperature, T is the reaction time, ph is phenyl, OMe is methoxy, CN is cyano, me is methyl, et is ethyl, SMe is methylthio, OPh is phenoxy, CF 3 Is trifluoromethyl, OCF 3 Is trifluoromethoxy.
Structure confirmation data for the compounds prepared in examples 1 to 5:
nuclear magnetic resonance of the aryl acetamide Compound (I-1) obtained in example 1 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.42–7.37(m,4H),7.33–7.32(m,3H),7.29–7.25(m,2H),7.21(brs,1H),7.07(t,J＝7.4Hz,1H),3.72(s,2H).
13 C NMR(101MHz,CDCl 3 )δ169.3,137.7,134.6,129.6,129.4,129.1,127.8,124.6,120.0,45.0.
nuclear magnetic resonance of the aryl acetamide Compound (I-2) obtained in example 2 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.42–7.38(m,2H),7.34–7.32(m,4H),7.30–7.29(m,1H),7.02(brs,1H),6.81(d,J＝9.0Hz,2H),3.76(s,3H),3.72(s,2H).
13 C NMR(101MHz,CDCl 3 )δ169.1,156.7,134.7,130.8,129.7,129.4,127.8,121.9,114.2,55.6,44.8.
nuclear magnetic resonance of the aryl acetamide Compound (I-3) obtained in example 3 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.42–7.38(m,3H),7.35–7.31(m,4H),7.24–7.22(m,2H),7.17(brs,1H),3.73(s,2H).
13 C NMR(101MHz,CDCl 3 )δ169.2,136.3,134.3,129.64,129.56,129.4,129.1,127.9,121.2,44.9.
nuclear magnetic resonance of the aryl acetamide Compound (I-4) obtained in example 4 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,DMSO-d 6 )δ10.14(s,1H),7.79(d,J＝8.2Hz,2H),7.52(d,J＝8.2Hz,2H),7.46(d,J＝8.4Hz,2H),7.09(d,J＝8.3Hz,2H),3.74(s,2H),2.23(s,3H).
13 C NMR(101MHz,DMSO-d 6 )δ167.8,141.9,136.5,132.3,132.2,130.3,129.1,119.2,118.9,109.4,43.1,20.4.
nuclear magnetic resonance of the aryl acetamide Compound (I-5) obtained in example 5 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ8.04(d,J＝8.2Hz,2H),7.41(d,J＝8.2Hz,2H),7.30(d,J＝8.4Hz,2H),7.17(brs,1H),7.08(d,J＝8.3Hz,2H),3.92(s,3H),3.75(s,2H),2.29(s,3H).
13 C NMR(101MHz,CDCl 3 )δ168.1,166.9,139.8,135.0,134.5,130.4,129.62,129.60,129.5,120.1,52.3,44.7,21.0.
Claims (6)
1. a process for the preparation of an aryl acetamide compound comprising the steps of: reacting palladium catalyst, ligand, molybdenum carbonyl, alkali, benzyl sulfonic acid chloride and nitroarene at 110-130 deg.c for 12-20 hr, and post-treatment to obtain the aryl acetamide compound;
the structure of the benzyl sulfonyl chloride is shown as a formula (II):
the structure of the nitroarene is shown in a formula (III):
the structure of the aryl acetamide compound is shown as a formula (I):
ar in the formulae (I) to (III) 1 And Ar is a group 2 Independently selected from substituted or unsubstituted aryl;
the substituent on the aryl is C 1 ～C 2 Alkyl, C 1 ～C 6 Alkoxy, trifluoromethyl, trifluoromethoxy, cyano, methylthio, C 1 ～C 6 Alkoxycarbonyl, C 1 ～C 6 One or more of alkylthio, phenoxy or halogen;
acetonitrile is used as a solvent in the reaction;
the ligand is 1, 3-bis (diphenylphosphine) propane;
the alkali is potassium phosphate.
2. The method for producing a thioester compound according to claim 1, characterized in that Ar 1 And the substituent on the phenyl is one or more of methyl, cyano, methoxycarbonyl, trifluoromethyl, trifluoromethoxy or Cl.
3. The method for producing a thioester compound according to claim 1, characterized in that Ar 2 The substituent on the phenyl is methyl, ethyl, methylthio, trifluoromethyl, methoxy, phenoxy, trifluoromethoxy, F or Cl.
4. The process for producing an arylacetamide compound according to claim 1, characterized in that the benzylsulfonic acid chloride is contained in a molar amount: nitroaromatics: molybdenum carbonyl: palladium catalyst: ligand: alkali=1-2:1:1.5-2:0.05-0.1:0.05-0.1:1.5-2.
5. The method for producing an arylacetamide compound according to claim 1, wherein said palladium catalyst is palladium acetate.
6. The method for producing an arylacetamide compound according to claim 1, characterized in that said arylacetamide compound is one of the compounds represented by the formulae (I-1) - (I-5):
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| CN104961644A (en) * | 2015-05-20 | 2015-10-07 | 上海交通大学 | Method used for preparing N-aryl amide compound |
| CN107827705A (en) * | 2017-11-20 | 2018-03-23 | 温州大学 | A kind of single arylation method of dichloro benzene-like compounds |
| CN112812032A (en) * | 2021-01-19 | 2021-05-18 | 浙江理工大学 | Preparation method of acetamide compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104961644A (en) * | 2015-05-20 | 2015-10-07 | 上海交通大学 | Method used for preparing N-aryl amide compound |
| CN107827705A (en) * | 2017-11-20 | 2018-03-23 | 温州大学 | A kind of single arylation method of dichloro benzene-like compounds |
| CN112812032A (en) * | 2021-01-19 | 2021-05-18 | 浙江理工大学 | Preparation method of acetamide compound |
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