CN109851507B - Application of scandium-containing rare earth catalyst in catalysis of para-alkylation reaction of aromatic amine - Google Patents
Application of scandium-containing rare earth catalyst in catalysis of para-alkylation reaction of aromatic amine Download PDFInfo
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- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 27
- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 27
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- -1 aromatic primary amine Chemical class 0.000 claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 229910052717 sulfur Chemical group 0.000 claims abstract description 5
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 25
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- SMVIAQFTVWDWDS-UHFFFAOYSA-N 2-bromo-n-methylaniline Chemical compound CNC1=CC=CC=C1Br SMVIAQFTVWDWDS-UHFFFAOYSA-N 0.000 claims description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims description 3
- LDVAIJZDACHGML-UHFFFAOYSA-N 2-fluoro-n-methylaniline Chemical compound CNC1=CC=CC=C1F LDVAIJZDACHGML-UHFFFAOYSA-N 0.000 claims description 3
- FTMGWGRYZSQTMF-UHFFFAOYSA-N 2-prop-1-en-2-ylthiophene Chemical compound CC(=C)C1=CC=CS1 FTMGWGRYZSQTMF-UHFFFAOYSA-N 0.000 claims description 3
- YBBLSBDJIKMXNQ-UHFFFAOYSA-N 3,4-dihydro-2h-1,4-benzothiazine Chemical compound C1=CC=C2NCCSC2=C1 YBBLSBDJIKMXNQ-UHFFFAOYSA-N 0.000 claims description 3
- WCMSFBRREKZZFL-UHFFFAOYSA-N 3-cyclohexen-1-yl-Benzene Chemical compound C1CCCC(C=2C=CC=CC=2)=C1 WCMSFBRREKZZFL-UHFFFAOYSA-N 0.000 claims description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 3
- UGUYQBMBIJFNRM-UHFFFAOYSA-N but-2-en-2-ylbenzene Chemical compound CC=C(C)C1=CC=CC=C1 UGUYQBMBIJFNRM-UHFFFAOYSA-N 0.000 claims description 3
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 claims description 3
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- ANGVCCXFJKHNDS-UHFFFAOYSA-N pent-1-en-2-ylbenzene Chemical compound CCCC(=C)C1=CC=CC=C1 ANGVCCXFJKHNDS-UHFFFAOYSA-N 0.000 claims description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940067157 phenylhydrazine Drugs 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- BHFSXGLQLQHDCH-UHFFFAOYSA-N 1-bromo-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(Br)=C1 BHFSXGLQLQHDCH-UHFFFAOYSA-N 0.000 claims description 2
- WQDGTJOEMPEHHL-UHFFFAOYSA-N 1-chloro-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(Cl)C=C1 WQDGTJOEMPEHHL-UHFFFAOYSA-N 0.000 claims description 2
- XCTSGGVBLWBSIJ-UHFFFAOYSA-N 1-methoxy-4-prop-1-en-2-ylbenzene Chemical compound COC1=CC=C(C(C)=C)C=C1 XCTSGGVBLWBSIJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 136
- 239000000203 mixture Substances 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 238000004440 column chromatography Methods 0.000 description 21
- 239000007788 liquid Substances 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000006519 CCH3 Chemical group 0.000 description 6
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005913 hydroamination reaction Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to application of a scandium-containing rare earth catalyst in catalyzing para-selective alkylation reaction of aromatic amine, wherein the scandium-containing rare earth catalyst has the following structural formula:
the aromatic amine is aromatic primary amine or aromatic secondary amine. The invention also discloses a preparation method of the para-alkylated aromatic amine, which comprises the following steps: aromatic amine of formula (1) and olefin of formula (2) are catalyzed by scandium-containing rare earth catalyst in organic solventReacting at 60-150 ℃ to obtain the para-alkylated aromatic amine, wherein the reaction route is as follows:
wherein R is1Is hydrogen, an aromatic radical or C1‑C10An alkyl group; r2Is hydrogen, C1‑C4Alkyl radical, C1‑C4Alkoxy, aryl or halogen; and R is2Cannot be substituted in the para position; x is methylene or sulfur atom, and n1 is any one of values of 0-4; r3Is C1‑C20Alkyl, aryl or with R5The number n2 of the methylene groups is any value of 1-4; r4Is hydrogen, C1‑C20Alkyl, aryl, thienyl, benzofuranyl, or substituted aryl; r5Is hydrogen, methyl or methylene; r6Is hydrogen.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to application of a scandium-containing rare earth catalyst in catalyzing para-alkylation reaction of aromatic amine.
Background
Aromatic amine and its derivatives are widely used in drugs, fluorescent dyes, natural products and organic functional materials. However, currently most aromatic amines are prepared by multi-step functional group transformations. If the direct addition of simple aromatic amines to unsaturated olefins can be achieved, such compounds can be synthesized simply and efficiently. In the conventional Friedel-crafts alkylation reaction, stoichiometric or catalytic amount of Lewis acid is generally used as a catalyst, so that acid-base adducts are easily formed when the Lewis acid reacts with aromatic amine substrates with stronger alkalinity, and the reaction cannot be carried out.
Although different types of transition metal (ruthenium, rhodium, iridium, zinc, gold, yttrium and titanium) catalysts or bronsted acids and ionic liquids have been used as catalysts for the alkylation of aromatic amines and olefins, the chemoselectivity and regioselectivity of the reaction are very poor, usually giving hydroamination products and ortho-alkylation products of aromatic amines, with only very small amounts of para-alkylation products of aromatic amines. And can only realize para-specific alkylation reaction of tertiary aromatic amine and similar active olefin substrates such as alpha, beta-unsaturated aldehyde ketone and the like. The existing synthesis method does not realize the para-specific alkylation reaction of aromatic primary amine and secondary amine with various inactive olefins by using one catalyst. The amount of the catalyst used in the above method is relatively large, and usually 20% or more.
Patent CN201710441715 discloses a rare earth metal complex based on diimine ligand and its application, using scandium-containing catalyst to catalyze the reaction of olefin and aromatic amine, but the process in this patent cannot achieve para-alkylation of aromatic amine.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an application of a scandium-containing rare earth catalyst in catalyzing para-position alkylation reaction of aromatic amine, and the invention discloses a new application of the scandium-containing rare earth catalyst, which can catalyze para-position selective alkylation reaction of aromatic amine and a plurality of olefins in situ.
The first purpose of the invention is to disclose the application of scandium-containing rare earth catalyst in catalyzing aromatic amine para-selective alkylation reaction, wherein the scandium-containing rare earth catalyst has the following structural formula:
Further, the reaction is an addition reaction of aromatic amine and olefin, and the reaction temperature is 60-150 ℃.
Further, the structural formula of the aromatic amine is shown as formula (1), and the structural formula of the olefin is shown as formula (2):
R1is hydrogen, an aromatic radical or C1-C10An alkyl group;
R2is hydrogen, C1-C4Alkyl radical, C1-C4Alkoxy, aryl or halogen; and R is2Cannot be substituted in the para position;
x is methylene or sulfur atom, and n1 is any one of values of 0-4;
R3is C1-C20Alkyl, aryl or with R5The number n2 of the methylene groups is any value of 1-4;
R4is hydrogen, C1-C20Alkyl, aryl, thienyl, benzofuranyl, or substituted aryl;
R5is hydrogen, methyl or methylene;
R6is hydrogen.
Further, the dosage of the scandium-containing rare earth catalyst is 1-20mol% of the olefin.
It is a second object of the present invention to provide a process for the preparation of para-alkylated aromatic amines comprising the steps of:
reacting aromatic amine of formula (1) with olefin of formula (2) in organic solvent at 60-150 ℃ under the catalysis of scandium-containing rare earth catalyst and cocatalyst to obtain the para-alkylated aromatic amine, wherein the scandium-containing rare earth catalyst has the following structural formula:
the reaction route is as follows:
R1is hydrogen, an aromatic radical or C1-C10An alkyl group;
R2is hydrogen, C1-C4Alkyl radical, C1-C4Alkoxy, aryl or halogen; and R is2Cannot be substituted in the para position;
x is methylene or sulfur atom, and n1 is any one of values of 0-4;
R3is C1-C20Alkyl, aryl or with R5The number n2 of the methylene groups is any value of 1-4;
R4is hydrogen, C1-C20Alkyl, aryl, thienyl, benzofuranyl, or substituted aryl;
R5is hydrogen, methyl or methylene;
R6is hydrogen.
Further, in the present invention, aryl is preferably phenyl.
Further, in the present invention, the substituent in the substituted aryl group is preferably C1-C10Alkoxy, halogen.
Further, in the present invention, halogen is F, Cl, Br or I.
Further, the cocatalyst is [ PhNHMe2][B(C6F5)4]、[Ph3C][B(C6F5)4]Or B (C)6F5)3。
Further, the amount of the co-catalyst is 1 to 20mol% of the total reactants. Preferably, the amount of co-catalyst is 10-15 mol% of the total reactants; more preferably, the amount of cocatalyst is 10 mol% of the total reactants.
Further, the dosage of the scandium-containing rare earth catalyst is 1-20mol% of the olefin. Preferably, the scandium-containing rare earth catalyst is used in an amount of 10-15 mol% of the olefin; more preferably, the scandium-containing rare earth catalyst is used in an amount of 10 mol% of the olefin.
Preferably, the reaction temperature is 100-120 ℃; more preferably, the reaction temperature is 120 ℃.
Preferably, the aromatic amine is N-methylaniline, 2-bromo-N-methylaniline, 2-methyl-N-methylaniline, 2-fluoro-N-methylaniline, indoline, N-ethylaniline, 3, 4-dihydro-2H-1, 4-benzothiazine, diphenylamine, aniline, o-methoxyaniline, o-chloroaniline or phenylhydrazine.
Preferably, the olefin is α -methylstyrene, 4-methoxy- α -methylstyrene, 4-chloro- α -methylstyrene, 3-bromo- α -methylstyrene, α -propylstyrene, 1-diphenylethylstyrene, 2-isopropenylthiophene, 2- (α -methylvinyl) benzofuran, 2-phenylbut-2-ene or 1-phenylcyclohexene.
Further, the scandium-containing rare earth catalyst and the cocatalyst are reacted at 20-30 ℃, after the reaction is completed, the aromatic amine of the formula (1) and the olefin of the formula (2) are added for reaction at 60-150 ℃.
Further, the molar ratio of the aromatic amine of formula (1) to the olefin of formula (2) is 1.5: 1.0.
Further, the organic solvent is one or more of toluene, chlorobenzene, bromobenzene and tetrahydrofuran.
Taking N-methylaniline and alpha-methylstyrene as reactants as examples, the reaction principle of the invention is as follows: during the reaction, cation scandium active species are firstly generated, and the compound catalyzes intermolecular hydroamination reaction and then carries out further rearrangement reaction to selectively generate para-position alkylation products.
By the scheme, the invention at least has the following advantages:
the invention discloses a new application of a scandium-containing rare earth catalyst, breaks through the limitation that the traditional Friedel-crafts alkylation reaction can not realize the hydrogenation alkylation reaction of aromatic amine and olefin, and improves the regioselectivity and chemical selectivity of C-H functional group of aromatic amine catalyzed by a transition metal catalyst. The method realizes the para-specific alkylation reaction of aromatic primary amine or secondary amine and various olefins by using the rare earth catalyst for the first time, and has wide application range to substrates, high tolerance of functional groups and high regioselectivity.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples, the scandium-containing rare earth catalysts used have the following structural formula:
"tolumen" in the reaction equation represents toluene. "10 mol%" means that it accounts for 10% of the total number of moles of olefins.
Example 1
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (61mg, yield 91%).
HRMS (ESI) calculated m/z C16H19NNa+[M+Na]+248.1410; found 248.1400.
1H NMR(400MHz,CDCl3,298K)δ＝7.18(m,4H,o-Ph,m-Ph),7.08(m,1H,p-Ph),6.99(m,2H,m-PhN),6.47(m,2H,o-PhN),3.40(brs,1H,NH),2.74(s,3H,NCH3),1.57(s,6H,CMe2)。
13C{1H}NMR(101MHz,CDCl3,298K)δ＝151.5(i-Ph),147.1(i-PhN),139.8(p-PhN),128.0(m-Ph),127.7(m-PhN),126.9(o-Ph),125.5(p-Ph),112.3(o-PhN),42.3(CMe2),31.1(NHCH3),31.0(CMe2)。
Example 2
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 15 minutes. After completion of the reaction, N-methylaniline (48mg) and 4-methoxy-. alpha. -methylstyrene (44mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (70mg, yield 92%).
HRMS (ESI) calculated m/z C17H21NNaO[M+Na]+278.1515; found 278.1526.
1HNMR(400MHz,CDCl3,298K)δ＝7.18(m,2H,o-Ph),7.08(m,2H,m-PhN),6.82(m,2H,m-Ph),6.56(m,2H,o-PhN),3.80(m,4H,OMe,NHCH3),2.83(s,3H,NHCH3),1.64(s,6H,CMe2)。
13CNMR(101MHz,CDCl3,298K)δ＝157.3(p-Ph),147.1(i-PhN),143.7(i-Ph),140.0(p-PhN),127.8(o-Ph),127.6(m-Ph),113.3(m-PhN),112.2(o-PhN),55.3(OMe),41.6(CMe2),31.2(CMe2),31.0(NHCH3)。
Example 3
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 4-chloro-. alpha. -methylstyrene (46mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (64mg, yield 89%).
HRMS (ESI) calculated m/z C16H19ClN[M+H]+260.1201; found 260.1205.
1H NMR(400MHz,CDCl3,298K)δ＝7.17(m,4H,o-Ph,m-Ph),7.02(m,2H,m-PhN),6.51(m,2H,o-PhN),3.57(brs,1H,NHCH3),2.79(s,3H,NHCH3),1.61(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝150.1(i-Ph),147.3(i-PhN),138.9(p-PhN),131.2(p-Ph),128.3(o-Ph),128.0(m-PhN),127.5(m-Ph),112.2(o-PhN),42.0(CMe2),31.0(CMe2),30.9(NHCH3)。
Example 4
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 3-bromo-. alpha. -methylstyrene (59mg) were added to the mixture, and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (77mg, yield 85%).
HRMS (ESI) calculated m/z C16H19BrN[M+H]+304.0695; found 304.0709.
1H NMR(400MHz,CDCl3,298K)δ＝7.40(m,1H,2-Ph),7.27(m,1H,4-Ph),7.11(m,2H,5-Ph),7.02(m,2H,m-PhN),6.52(m,2H,o-PhN),3.58(brs,1H,NHCH3),2.79(s,3H,NHCH3),1.61(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝154.0(1-Ph),147.4(i-PhN),138.6(p-PhN),129.9(2-Ph),129.6(5-Ph),128.6(4-Ph),127.6(m-PhN),125.8(6-Ph),122.3(3-Ph),112.2(o-PhN),42.3(CMe2),30.9(CMe2),30.8(NHCH3)。
Example 5
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and α -propylstyrene (44mg) were added thereto, and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (66mg, yield 87%).
HRMS (ESI) calculated m/z C18H24N[M+H]+254.1903; found 254.1916.
1H NMR(400MHz,CDCl3,298K):δ＝7.22(m,4H,o-Ph,m-Ph),7.13(m,1H,p-Ph),7.00(m,2H,m-PhN),6.52(m,2H,o-PhN),3.57(brs,1H,NHCH3),2.80(s,3H,NHCH3),2.01(t,3JHH＝8.3Hz,2H,CCH2),1.58(s,3H,CCH3),1.11(m,2H,CH2CH3),0.87(t,3JHH＝7.3Hz,3H,CH2CH3)。
13C{1H}NMR(101MHz,CDCl3,298K):δ＝150.7(i-Ph),147.1(i-PhN),138.8(p-PhN),128.2(m-PhN),127.9(m-Ph),127.4(o-Ph),125.4(p-Ph),112.1(o-PhN),45.6(CCH3),44.5(CCH2),31.0(NHCH3),27.9(CCH3),18.2(CH2CH3),15.0(CH2CH3)。
Example 6
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 1, 1-diphenylethylstyrene (54mg) were added thereto, and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (70mg, yield 81%).
HRMS (ESI) calculated m/z C21H22N[M+H]+288.1747; found 288.1756.
1H NMR(400MHz,CDCl3,298K):δ＝7.21(m,4H,m-Ph),7.15(m,2H,p-Ph),7.10(m,4H,o-Ph),6.89(m,2H,m-PhN),6.46(m,2H,o-PhN),3.53(brs,1H,NHCH3),2.73(s,3H,NHCH3),2.12(s,3H,CCH3)。
13C{1H}NMR(101MHz,CDCl3,298K):δ＝149.8(i-Ph),147.3(i-PhN),137.7(p-PhN),129.5(m-PhN),128.8(o-Ph),127.8(m-Ph),125.8(p-Ph),111.8(o-PhN),51.8(CCH3),30.8(NHCH3),30.6(CCH3)。
Example 7
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 2-isopropenylthiophene (37mg) were added thereto, and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (67mg, yield 88%).
HRMS (ESI) calculated m/z C14H17NNaS[M+H]+254.0974; found 254.0973.
1H NMR(400MHz,CDCl3,298K)δ7.16(m,3H,m-Ph,2-C4H3),6.92(m,1H,3-C4H3),6.83(m,1H,4-C4H3),6.57(m,2H,o-PhN),3.65(brs,1H,NHCH3),2.84(s,3H,NHCH3),1.77(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝157.6(1-C4H3),147.6(i-PhN),138.7(p-PhN),127.1(m-PhN),126.2(3-C4H3),123.3(4-C4H3),123.0(2-C4H3),112.1(o-PhN),40.9(CMe2),32.3(CMe2),30.9(NHCH3)。
Example 8
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 2- (. alpha. -methylvinyl) benzofuran (47mg) were added, and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (74mg, yield 93%).
HRMS (ESI) calculated m/z C18H19NNaO[M+Na]+288.1359; found 288.1357.
1H NMR(400MHz,CDCl3,298K)δ＝7.39(m,1H,4-C8H6),7.28(m,1H,6-C8H6),7.07(m,4H,2-C8H6,5-C8H6,m-PhN),6.43(m,2H,o-PhN),6.35(m,1H,7-C8H6),3.48(brs,1H,NHCH3),2.68(s,3H,NHCH3),1.63(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝166.4(1-C8H6),154.9(8-C8H6),147.8(i-PhN),135.7(p-PhN),128.8(3-C8H6),127.0(m-PhN),123.3(2-C8H6),122.4(5-C8H6),120.5(4-C8H6),112.3(o-PhN),111.2(6-C8H6),101.3(7-C8H6),39.9(CMe2),30.9(NHCH3),28.6CMe2)。
Example 9
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 2-phenylbut-2-ene (40mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (56mg, yield 78%).
HRMS (ESI) calculated m/z C17H22N[M+H]+240.1747; found 240.1758.
1H NMR(400MHz,CDCl3,298K)δ＝7.20(m,4H,o-Ph,m-Ph),7.11(m,1H,p-Ph),7.00(m,2H,m-PhN),6.49(m,2H,o-PhN),3.56(brs,1H,NHCH3),2.75(s,3H,NHCH3),2.08(q,3JHH＝7.4Hz,2H,CCH2CH3),1.55(s,3H,CMe),0.72(t,3JHH＝7.3Hz,3H,CCH2CH3)。
13C NMR(101MHz,CDCl3,298K)δ＝150.4(i-Ph),147.0(i-PhN),138.4(p-PhN),128.2(m-PhN),127.8(m-Ph),127.5(o-Ph),125.3(p-Ph),112.0(o-PhN),45.7(CMe),34.2(CCH2CH3),30.9(NHCH3),27.1(CMe),9.3(CCH2CH3)。
Example 10
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-methylaniline (48mg) and 1-phenylcyclohexene (47mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (58mg, yield 73%).
HRMS (ESI) calculated m/z C19H24N[M+H]+266.1903; found 266.1904.
1H NMR(400MHz,CDCl3,298K)δ＝7.24(m,4H,o-Ph,m-Ph),7.08(m,3H,p-Ph,m-PhN),6.53(m,2H,o-PhN),3.55(brs,1H,NHCH3),2.78(s,3H,NHCH3),2.23(m,4H,2-C6H10),1.55(m,4H,3-C6H10),1.48(m,2H,4-C6H10)。
13C NMR(101MHz,CDCl3,298K)δ＝149.6(i-Ph),146.9(i-PhN),137.4(p-PhN),128.2(o-Ph),128.1(m-PhN),127.2(m-Ph),125.2(p-Ph),112.4(o-PhN),45.6(1-C6H10),37.4(2-C6H10),30.9(NHCH3),26.6(4-C6H10),23.1(3-C6H10)。
Example 11
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, 2-bromo-N-methylaniline (83mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (75mg, yield 82%).
HRMS (ESI) calculated m/z C16H19BrN[M+H]+304.0695; found 304.0692.
1H NMR(400MHz,CDCl3,298K)δ＝7.38(m,1H,3-PhN),7.30(m,4H,o-Ph,m-Ph),7.22(m,1H,p-Ph),7.10(m,1H,5-PhN),6.59(m,1H,6-PhN),4.28(brs,1H,NHCH3),2.90(s,3H,NHCH3),1.69(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝150.7(p-Ph),143.9(1-PhN),140.4(4-PhN),130.6(3-PhN),128.1(m-PhN),127.2(5-PhN),126.8(o-Ph),125.7(p-Ph),110.5(6-PhN),109.5(2-PhN),42.2(CMe2),31.0(CMe2),30.8(NHCH3)。
Example 12
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, 2-methyl-N-methylaniline (55mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (66mg, yield 91%).
HRMS (ESI) calculated m/z is For C17H22N[M+H]+240.1747; found 240.1749.
1H NMR(400MHz,CDCl3,298K)δ＝7.24(m,4H,o-Ph,m-Ph),7.14(m,1H,p-Ph),7.03(m,1H,5-PhN),6.90(m,1H,3-PhN),6.52(m,1H,6-PhN),3.45(brs,1H,NHCH3),2.86(s,3H,NHCH3),2.07(s,3H,PhCH3),1.64(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.6(i-Ph),145.2(1-PhN),139.2(4-PhN),128.8(3-PhN),128.0(m-Ph),126.9(o-Ph),125.4(p-Ph),125.3(5-PhN),121.7(2-PhN),108.8(6-PhN),42.2(CMe2),31.1(CMe2),31.0(NHCH3),17.8(PhCH3)。
Example 13
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, 2-fluoro-N-methylaniline (56mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (60mg, yield 82%).
HRMS (ESI) calculated m/z is For C16H19F[M+H]+244.1496; found 244.1490.
1H NMR(400MHz,CDCl3,298K)δ＝7.23(m,4H,o-Ph,m-Ph),7.16(m,1H,p-Ph),6.89(m,1H,5-PhN),6.83(m,1H,3-PhN),6.59(m,1H,6-PhN),3.81(brs,1H,NHCH3),2.84(s,3H,NHCH3),1.63(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.4(d,JFC＝238.0Hz,2-PhN),150.8(i-Ph),139.8(d,JFC＝5.2Hz,4-PhN),135.5(d,JFC＝12.0Hz,1-PhN),128.1(m-Ph),126.8(o-PhN),125.7(p-Ph),122.5(d,JFC＝3.0Hz,5-PhN),113.3(d,JFC＝18.8Hz,3-PhN),111.08(d,JFC＝3.8Hz,6-PhN),42.3(CMe2),30.9(CMe2),30.5(NHCH3)。
Example 14
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, indoline (54mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (59mg, yield 83%).
HRMS (ESI) calculated m/z C17H20N[M+H]+238.1590; found 238.1594.
1H NMR(400MHz,CDCl3,298K)δ＝7.25(m,4H,o-Ph,m-Ph),7.16(m,1H,p-Ph),6.97(m,1H,3-Ph),6.90(m,1H,5-Ph),6.55(m,1H,6-Ph),3.65(brs,1H,NH),3.52(t,3JHH＝8.3Hz,2H,NHCH2CH2),2.96(t,3JHH＝8.3Hz,2H,NHCH2CH2),1.64(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.6(i-Ph),149.4(1-Ph),141.5(4-Ph),129.4(2-Ph),128.0(m-Ph),126.9(o-Ph),125.5(5-Ph),125.4(p-Ph),123.5(3-Ph),108.9(6-Ph),47.7(NHCH2CH2),42.5(CMe2),31.2(CMe2),30.1(NHCH2CH2)。
Example 15
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, N-ethylaniline (55mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (64mg, yield 89%).
HRMS (ESI) calculated m/z is For C17H22N[M+H]+240.1747; found 240.1755.
1H NMR(400MHz,CDCl3,298K)δ＝7.31(m,4H,o-Ph,m-Ph),7.21(m,1H,p-Ph),7.10(m,2H,m-PhN),6.58(m,2H,o-PhN),3.46(brs,1H,NHCH2),3.18(q,3JHH＝7.1Hz,2H,CH2CH3),1.70(s,6H,CMe2),1.29(t,3JHH＝7.2Hz,3H,CH2CH3)。
13C NMR(101MHz,CDCl3,298K)δ＝151.4(i-Ph),146.2(i-PhN),139.4(p-PhN),127.9(m-Ph),127.6(m-PhN),126.8(o-Ph),125.4(p-Ph),112.4(o-PhN),42.1(CMe2),38.6(CH2CH3),31.0(CMe2),15.0(CH2CH3)。
Example 16
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, 3, 4-dihydro-2H-1, 4-benzothiazine (68mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (79mg, yield 91%).
HRMS (ESI) calculated m/z is For C17H19NNaS[M+Na]+292.1130; found 292.1137.
1H NMR(400MHz,CDCl3,298K)δ＝7.28(m,4H,o-Ph,m-Ph),7.19(m,1H,p-Ph),6.95(m,1H,3-Ph),6.72(m,1H,5-Ph),6.39(m,1H,6-Ph),3.80(brs,1H,NH),3.60(m,2H,NHCH2CH2),3.07(m,2H,NHCH2CH2),1.64(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.0(i-Ph),140.7(4-Ph),139.5(1-Ph),128.0(m-Ph),126.8(o-Ph),125.6(p-Ph),125.5(3-Ph),124.6(5-Ph),115.3(6-Ph),115.2(2-Ph),42.4(NHCH2CH2),42.2(CMe2),30.9(CMe2),26.4(NHCH2CH2)。
Example 17
This example provides a method for preparing para-alkylated aromatic secondary amines, the reaction scheme and specific steps are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, diphenylamine (42mg) and alpha-methylstyrene (35mg) were added thereto and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (79mg, yield 91%).
HRMS (ESI) calculated m/z C21H22N[M+H]+288.1747; found 288.1753.
1H NMR(400MHz,CDCl3,298K)δ＝7.26(m,4H,o-Ph,m-Ph),7.22(m,2H,7-Ph),7.16(m,1H,p-Ph),7.12(m,2H,3-Ph),7.02(m,2H,2-Ph),6.97(m,2H,6-Ph),6.88(m,1H,8-Ph),5.61(brs,1H,NH),1.67(s,6H,CMe2)。
13CNMR(101MHz,CDCl3,298K)δ＝151.0(i-Ph),143.7(4-Ph),143.6(5-Ph),140.7(1-Ph),129.4(7-Ph),128.1(m-Ph),127.8(3-Ph),126.9(o-Ph),125.7(p-Ph),120.7(8-Ph),117.8(6-Ph),117.5(2-Ph),42.5(CMe2),31.0(CMe2)。
Example 18
This example provides a method for preparing para-alkylated aromatic primary amines, the reaction scheme and specific steps of which are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, aniline (42mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (55mg, yield 87%).
HRMS (ESI) calculated m/z C15H18N[M+H]+212.1434; found 212.1435.
1H NMR(400MHz,CDCl3,298K)δ＝7.24(m,4H,o-Ph,m-Ph),7.15(m,1H,p-Ph),7.01(m,2H,m-PhN),6.59(m,2H,o-PhN),3.54(brs,2H,NH2),1.63(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.3(i-Ph),144.1(i-PhN),141.1(p-PhN),128.0(m-Ph),127.8(m-PhN),126.9(o-Ph),125.5(p-Ph),114.9(o-PhN),42.3(CMe2),31.0(CMe2)。
Example 19
This example provides a method for preparing para-alkylated aromatic primary amines, the reaction scheme and specific steps of which are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, o-anisidine (55mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (65mg, yield 90%).
HRMS (ESI) calculated m/z is For C16H19NNaO[M+Na]+264.1359; found 264.1369.
1H NMR(400MHz,CDCl3,298K)δ＝7.27(m,4H,o-Ph,m-Ph),7.18(m,1H,p-Ph),6.72(m,1H,3-Ph),6.65(m,2H,5-Ph),3.76(s,3H,OCH3),3.45(s,2H,NH2),1.68(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.3(i-Ph),147.1(2-Ph),141.4(4-Ph),133.8(1-Ph),128.0(o-Ph),126.8(m-Ph),125.5(p-Ph),119.2(3-Ph),114.6(6-Ph),109.9(5-Ph),55.5(OCH3),42.7(CMe2),31.1(CMe2)。
Example 20
This example provides a method for preparing para-alkylated aromatic primary amines, the reaction scheme and specific steps of which are as follows:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, o-chloroaniline (55mg) and α -methylstyrene (35mg) were added, and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (57mg, yield 79%).
HRMS (ESI) calculated m/z is For C17H21NNa[M+Na]+262.1566; found 262.1570.
1H NMR(400MHz,CDCl3,298K)δ＝7.33(m,4H,o-Ph,m-Ph),7.29(m,1H,p-Ph),6.95(m,2H,m-PhN),3.47(brs,2H,NH2),2.27(s,6H,PhCH3),1.78(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.5(i-Ph),140.4(i-PhN),140.3(p-PhN),128.0(m-Ph),126.9(m-PhN),126.8(o-Ph),125.4(p-Ph),121.3(o-PhN),42.1(CMe2),31.1(CMe2),18.0(PhCH3)。
Example 21
This example provides a method for preparing a para-alkylated hydrazine product, which comprises the following steps:
l1(17mg), [ PhNHMe ] was weighed2][B(C6F5)4](24mg) was dissolved in toluene and reacted at room temperature for 30 minutes. After completion of the reaction, phenylhydrazine (49mg) and α -methylstyrene (35mg) were added and the mixture was heated at 120 ℃ for 36 hours. After completion of the reaction, toluene was drained to obtain an oily residue, which was subjected to column chromatography to obtain a pale yellow oily liquid (73mg, yield 91%).
HRMS (ESI) calculated m/z is For C15H18N2Na[M+Na]+249.1362; found 249.1367.
1H NMR(400MHz,CDCl3,298K)δ＝7.23(m,4H,o-Ph,m-Ph),7.15(m,1H,p-Ph),7.01(m,2H,m-PhN),6.59(m,2H,o-PhN),3.54(brs,2H,NHNH2),1.63(s,6H,CMe2)。
13C NMR(101MHz,CDCl3,298K)δ＝151.3(i-Ph),144.1(i-PhN),141.1(p-PhN),128.0(m-Ph),127.8(m-PhN),126.9(o-Ph),125.5(p-Ph),114.9(o-PhN),42.3(CMe2),31.0(CMe2)。
In the above examples, the amount of catalyst L1 used was not only 10 mol%, but also adjusted between 1 and 20 mol%. Co-catalysts other than PhNHMe may be used2][B(C6F5)4][ Ph ] can also be used3C][B(C6F5)4]Or B (C)6F5)3The amount of the catalyst is not only 10 mol%, but also 1-20 mol%. The reaction temperature can also be adjusted between 60 ℃ and 150 ℃.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The application of the scandium-containing rare earth catalyst in catalyzing para-selective alkylation reaction of aromatic amine, wherein the reaction is addition reaction of aromatic amine and olefin, and the structural formula of the scandium-containing rare earth catalyst is as follows:
R1is hydrogen, phenyl or C1-C10An alkyl group;
R2is hydrogen, C1-C4Alkyl radical, C1-C4Alkoxy, phenyl or halogen; and R is2Cannot be substituted in the para position;
x is methylene or sulfur atom, and n1 is any one of values of 0-4;
R3is C1-C20Alkyl, phenyl or with R5The number n2 of the methylene groups is any value of 1-4;
R4is hydrogen, C1-C20Alkyl, phenyl, thienyl, benzofuranyl or substituted aryl, wherein the substituent of the substituted aryl is C1-C10 alkoxy or halogen;
R5is hydrogen, methyl or methylene;
R6is hydrogen.
2. Use according to claim 1, characterized in that: the reaction temperature is 60-150 ℃.
3. Use according to claim 1 or 2, characterized in that: the dosage of the scandium-containing rare earth catalyst is 1-20mol% of the olefin.
4. A process for the preparation of para-alkylated aromatic amines comprising the steps of:
reacting aromatic amine of formula (1) with olefin of formula (2) in organic solvent at 60-150 ℃ under the catalysis of scandium-containing rare earth catalyst and cocatalyst to obtain the para-alkylated aromatic amine, wherein the scandium-containing rare earth catalyst has the following structural formula:
The reaction route is as follows:
R1is hydrogen, phenyl or C1-C10An alkyl group;
R2is hydrogen, C1-C4Alkyl radical, C1-C4Alkoxy, phenyl or halogen; and R is2Cannot be substituted in the para position;
x is methylene or sulfur atom, and n1 is any one of values of 0-4;
R3is C1-C20Alkyl, phenyl or with R5The number n2 of the methylene groups is any value of 1-4;
R4is hydrogen, C1-C20Alkyl, phenyl, thienyl, benzofuranyl or substituted aryl, wherein the substituent of the substituted aryl is C1-C10 alkoxy or halogen;
R5is hydrogen, methyl or methylene;
R6is hydrogen.
5. The method of claim 4, wherein: the amount of the cocatalyst is 1-20mol% of the olefin.
6. The method of claim 4, wherein: the dosage of the scandium-containing rare earth catalyst is 1-20mol% of the total reactants.
7. The method of claim 4, wherein: the aromatic amine isN-methylaniline, 2-bromo-N-methylaniline, 2-methyl-N-methylaniline, 2-fluoro-N-methylaniline, indoline, methyl ethyl phenyl methyl phenyl ethyl methyl phenyl ethyl methyl ethyl phenyl ethyl methyl ethyl methyl ethyl methyl ethyl methyl ethyl,N-ethylaniline, 3, 4-dihydro-2H-1, 4-benzothiazine, diphenylamine, aniline, o-methoxyaniline, o-chloroaniline or phenylhydrazine.
8. The method of claim 4, wherein: the olefin is alpha-methylstyrene, 4-methoxy-alpha-methylstyrene, 4-chloro-alpha-methylstyrene, 3-bromo-alpha-methylstyrene, alpha-propylstyrene, 1-diphenylethylstyrene, 2-isopropenylthiophene, 2- (alpha-methylvinyl) benzofuran, 2-phenylbut-2-ene or 1-phenylcyclohexene.
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| CN107312034A (en) * | 2017-06-13 | 2017-11-03 | 苏州大学 | Rare earth metal complex and its application based on diimide ligand |
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| CN107312034A (en) * | 2017-06-13 | 2017-11-03 | 苏州大学 | Rare earth metal complex and its application based on diimide ligand |
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