CN107915649B - Preparation method of 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol - Google Patents

Preparation method of 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol Download PDF

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CN107915649B
CN107915649B CN201711271525.9A CN201711271525A CN107915649B CN 107915649 B CN107915649 B CN 107915649B CN 201711271525 A CN201711271525 A CN 201711271525A CN 107915649 B CN107915649 B CN 107915649B
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butylamine
tetrahydronaphthalene
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oxazolidine
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白大昌
代洪雪
杨思琪
李兴伟
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Henan Normal University
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Abstract

The invention discloses a preparation method of 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol, belonging to the technical field of organic synthesis. Nitrone 2 and methylene cyclopropane 3 are subjected to addition reaction in the presence of a rhodium catalyst and an oxidant to generate oxazolidine 4 with a bridged ring structure, and then zinc/acetic acid is subjected to reduction ring opening to obtain 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol 1. The method has the advantages of cheap and easily-obtained raw materials, mild reaction conditions, good atom economy, high selectivity, simple post-treatment and high yield, and provides a rapid synthesis way for the tetrahydronaphthalene-2-alcohol compound.

Description

Preparation method of 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol.
Background
1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalen-2-ol is a very useful synthetic intermediate, widely found in medicine, pesticides and natural product intermediates. The preparation of 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalen-2-ol by bridged ring compounds is a difficult point in the synthesis, and although some methods for preparing compounds containing bridged ring structures have been developed, the methods usually have more steps, low efficiency, high production cost and low flexibility. In the prior art, oxazolidine compounds containing bridged ring structures generally have the defects of high synthesis difficulty, high reaction risk, long reaction steps, low reaction yield, low atom economy and the like.
Therefore, the development of a simpler synthetic method for preparing the 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol has important significance in industrial application.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol. Nitrone 2 and methylene cyclopropane 3 are subjected to addition reaction in the presence of a rhodium catalyst and an oxidant to generate oxazolidine 4 with a bridged ring structure, and then zinc/acetic acid is subjected to reduction ring opening to obtain 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol.
A preparation method of oxazolidine compounds containing bridged ring structures is characterized by comprising the following operations: in an organic solvent, nitrone 2 and methylene cyclopropane 3 are subjected to addition reaction in the presence of a rhodium catalyst and an oxidant to generate oxazolidine 4 with a bridged ring structure, and then the oxazolidine 4 is subjected to reduction ring opening to obtain 1- (Z-4-tert-butylbenzyl) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol 1; the reaction equation is as follows:
Figure BDA0001495686420000021
further, in the above technical solution, the rhodium catalyst is selected from trivalent rhodium salts or rhodium-containing complexes. The trivalent rhodium salt is one or more selected from pentamethylcyclopentadienyl rhodium dichloride and pentamethylcyclopentadienyl rhodium diacetate.
Further, in the above technical solution, the oxidizing agent includes one or more of silver acetate, silver nitrate, silver pivalate, silver carbonate, and silver phenylacetate.
Further, in the above technical solution, the organic solvent is one or more of an alcohol solvent, a nitrile solvent, an ether solvent, and an amide solvent. Preferably a trifluoroethanol solvent.
Further, in the above technical scheme, the molar ratio of the rhodium catalyst to the nitrone is 0.02-1: 1; the molar ratio of the methylene cyclopropane to the nitrone is 0.5-4: 1, preferably in a molar ratio of 2.5: 1; the molar ratio of the oxidant to the nitrone is 1.0-6.0.
Further, in the above technical scheme, the temperature of the addition reaction is 0-100 ℃, and the preferable reaction temperature is 30-50 ℃.
Further, in the above technical solution, the addition reaction is performed under the protection of an inert gas or in air, and the inert gas is nitrogen, argon or helium.
Further, in the above technical means, when 0.1 to 2.0 equivalents of an inorganic base is added, for example, potassium carbonate, sodium acetate, lithium carbonate, etc., and zinc acetate, magnesium methoxide, etc., have no influence on the reaction.
Further, in the above technical scheme, the reduction ring-opening reaction is that acetic acid is added to oxazolidine 4 with bridged ring structure, zinc powder is used for reduction ring-opening, and then nitrogen-oxygen bond is broken to obtain 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol 1.
The invention has the beneficial effects that:
1) reacting nitrone with methylene cyclopropane, and then carrying out reduction ring opening, so that 1- (Z-4-tert-butylbenzyl) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol can be synthesized efficiently and selectively in two steps;
2) the reaction raw materials are convenient to obtain, the substrate is easy to synthesize, the catalyst is also a common catalyst, and a new way is provided for synthesizing the compound on a gram-scale or higher scale;
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1:
adding Cp Rh (OAc)2(7.0mg,0.010mmol,0.050equiv), AgOAc (80mg, 0.500mmol,2.50equiv) were added to a 25mL sealed tube, and magnetons and 1 mL solvent CF were added under nitrogen protection3CH2OH, after stirring for 10 min, nitrone 2(0.200mmol,1.00equiv) and methylene cyclopropane 3(0.500mmol,2.50equiv) were added to the closed tube and the reaction stirred at 40 ℃ for 24h, then filtered through celite and washed with 15mL of ethyl acetate. The organic layer is dried by spinning and is directly subjected to column chromatography to obtain a product 4 with the total yield of 84 percent,1H NMR、13the purity of C NMR was greater than 95%.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝7.8Hz,1H),7.44(s,4H),7.29(s, 1H),7.25(t,J＝7.6Hz,1H),7.18(t,J＝7.3Hz,1H),7.09(d,J＝7.3Hz,1H), 5.46(d,J＝5.5Hz,1H),4.31(d,J＝4.9Hz,1H),2.33(s,1H),2.02(t,J＝10.2 Hz,1H),1.35(s,9H),1.18(s,9H).13CNMR(101MHz,CDCl3)δ150.1,142.4, 136.9,134.0,132.8,129.4,127.6,127.5,125.9,125.3,124.7,123.7,73.3,59.7, 58.8,37.9,34.6,31.4,26.8 HRMS (ESI, m/z): theoretical value C25H32NO[M+H]+362.2478, test value 362.2480.
Zinc powder (25mg), acetic acid (1.0mL) and water (1.5mL) were added to a THF solution (0.5mL) of 4 under argon, stirred at room temperature overnight, dried over anhydrous sodium sulfate, filtered through celite, the solvent was removed under reduced pressure, and purified by column chromatography (PE: EA ═ 10:1) to give product 1 in 69% yield. mp 171 and 173 ℃,1H NMR(400MHz,CDCl3)δ7.85(d,J＝7.2Hz,1H),7.56(d,J＝8.3Hz,2H), 7.42(d,J＝8.4Hz,2H),7.35–7.24(m,2H),7.30(s,1H),7.18(m,1H),5.75 –5.17(br,1H),5.03(s,1H),4.25(s,1H),2.52(dt,J＝14.4Hz,J＝2.8Hz1H),1.84(s,1H),1.82(dt,J＝14.4Hz,J＝2.8Hz,1H),1.34(s,9H),1.28(s, 9H).13C NMR(101MHz,CDCl3)δ150.4,137.7,136.7,134.1,133.8,129.4, 129.2,128.3,128.1,127.4,125.3,124.8,66.0,52.6,50.7,34.6,33.7,31.3, 29.3.HRMS(ESI,m/z):calcdforC25H34NO[M+H]+:364.2635,found 364.2637.
example 2:
adding Cp Rh (OAc)2(7.0mg,0.010mmol,0.050equiv),AgNO2(85mg, 0.500mmol,2.50equiv) was added to a 25mL sealed tube, and magnetons and 1 mL of CF solvent were added under nitrogen protection3CH2OH, after stirring for 10 min, nitrone 2(0.200mmol,1.00equiv) and methylene cyclopropane 3(0.500mmol,2.50equiv) were added to the closed tube and the reaction was stirred at 50 ℃ for 24h, then filtered through celite and washed with 15mL of ethyl acetate. The organic layer is dried by spinning and is directly subjected to column chromatography to obtain a product 4 with the total yield of 85 percent,1H NMR、13the purity of C NMR was greater than 95%.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝7.8Hz,1H),7.44(s,4H),7.29(s, 1H),7.25(t,J＝7.6Hz,1H),7.18(t,J＝7.3Hz,1H),7.09(d,J＝7.3Hz,1H), 5.46(d,J＝5.5Hz,1H),4.31(d,J＝4.9Hz,1H),2.33(s,1H),2.02(t,J＝10.2 Hz,1H),1.35(s,9H),1.18(s,9H).13CNMR(101MHz,CDCl3)δ150.1,142.4, 136.9,134.0,132.8,129.4,127.6,127.5,125.9,125.3,124.7,123.7,73.3,59.7, 58.8,37.9,34.6,31.4,26.8 HRMS (ESI, m/z): theoretical value C25H32NO[M+H]+362.2478, test value 362.2480.
Zinc powder (25mg), acetic acid (1.5mL) and water (0.5mL) were added to a THF solution (0.5mL) of 4 under an argon atmosphere, stirred at room temperature overnight, dried over anhydrous sodium sulfate, filtered through celite, the solvent was removed under reduced pressure, and purified by column chromatography (PE: EA ═ 10:1) to give product 1 in 71% yield. mp 171 and 173 ℃,1H NMR(400MHz,CDCl3)δ7.85(d,J＝7.2Hz,1H),7.56(d,J＝8.3Hz,2H), 7.42(d,J＝8.4Hz,2H),7.35–7.24(m,2H),7.30(s,1H),7.18(m,1H),5.75 –5.17(br,1H),5.03(s,1H),4.25(s,1H),2.52(dt,J＝14.4Hz,J＝2.8Hz1H),1.84(s,1H),1.82(dt,J＝14.4Hz,J＝2.8Hz,1H),1.34(s,9H),1.28(s, 9H).13C NMR(101MHz,CDCl3)δ150.4,137.7,136.7,134.1,133.8,129.4, 129.2,128.3,128.1,127.4,125.3,124.8,66.0,52.6,50.7,34.6,33.7,31.3, 29.3.HRMS(ESI,m/z):calcdforC25H34NO[M+H]+:364.2635,found 364.2637.
example 3:
adding Cp Rh (OAc)2(7.0mg,0.010mmol,0.050equiv),Ag2CO3(55mg, 0.200mmol,1.00equiv) was added to a 25mL sealed tube, and magnetons and 1 mL of CF solvent were added under nitrogen protection3CH2OH, after stirring for 10 min, nitrone 2(0.200mmol,1.00equiv) and methylene cyclopropane 3(0.500mmol,2.50equiv) were added to the closed tube and the reaction was stirred at 30 ℃ for 24h, filtered through celite and washed with 15mL of ethyl acetate. The organic layer is dried by spinning and is directly subjected to column chromatography to obtain a product 4 with the total yield of 81 percent,1H NMR、13the purity of C NMR was greater than 95%.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝7.8Hz,1H),7.44(s,4H),7.29(s, 1H),7.25(t,J＝7.6Hz,1H),7.18(t,J＝7.3Hz,1H),7.09(d,J＝7.3Hz,1H), 5.46(d,J＝5.5Hz,1H),4.31(d,J＝4.9Hz,1H),2.33(s,1H),2.02(t,J＝10.2 Hz,1H),1.35(s,9H),1.18(s,9H).13CNMR(101MHz,CDCl3) Delta 150.1,142.4, 136.9,134.0,132.8,129.4,127.6,127.5,125.9,125.3,124.7,123.7,73.3,59.7, 58.8,37.9,34.6,31.4,26.8 HRMS (ESI, m/z): theoretical valuesC25H32NO[M+H]+362.2478, test value 362.2480.
Zinc powder (25mg), acetic acid (1.0mL) and water (0.5mL) were added to a THF solution (0.5mL) of 4 under argon, stirred at room temperature overnight, dried over anhydrous sodium sulfate, filtered through celite, the solvent was removed under reduced pressure, and purified by column chromatography (PE: EA ═ 10:1) to give product 1 in 69% yield. mp 171 and 173 ℃,1H NMR(400MHz,CDCl3)δ7.85(d,J＝7.2Hz,1H),7.56(d,J＝8.3Hz,2H), 7.42(d,J＝8.4Hz,2H),7.35–7.24(m,2H),7.30(s,1H),7.18(m,1H),5.75 –5.17(br,1H),5.03(s,1H),4.25(s,1H),2.52(dt,J＝14.4Hz,J＝2.8Hz1H),1.84(s,1H),1.82(dt,J＝14.4Hz,J＝2.8Hz,1H),1.34(s,9H),1.28(s, 9H).13C NMR(101MHz,CDCl3)δ150.4,137.7,136.7,134.1,133.8,129.4, 129.2,128.3,128.1,127.4,125.3,124.8,66.0,52.6,50.7,34.6,33.7,31.3, 29.3.HRMS(ESI,m/z):calcdforC25H34NO[M+H]+:364.2635,found 364.2637。

Claims (4)

  1. a process for the preparation of 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalen-2-ol, characterized in that it comprises the following steps: nitrone 2 and methylene cyclopropane 3 are subjected to addition reaction in a trifluoroethanol solvent in the presence of a rhodium catalyst and an oxidant to generate oxazolidine 4 with a bridged ring structure, and then the oxazolidine 4 is subjected to reduction ring opening to obtain 1- (Z-4-tert-butylbenzyl) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-ol 1; the reaction equation is as follows:
    Figure FDA0002225648310000011
    the rhodium catalyst is selected from: pentamethylcyclopentadienylrhodium diacetate; the oxidant is selected from silver acetate, silver nitrate or silver carbonate.
  2. 2. The process for the preparation of 1- (Z-4-tert-buty-lidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalen-2-ol according to claim 1, characterized in that: the molar ratio of the rhodium catalyst, the nitrone 2 and the methylene cyclopropane 3 is 0.02-1: 1: 2.5; the temperature of the addition reaction is 30-50 ℃.
  3. 3. The process for the preparation of 1- (Z-4-tert-buty-lidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalen-2-ol according to claim 1, characterized in that: the addition reaction is carried out under the protection of inert gas, and the inert gas is selected from nitrogen, argon or helium.
  4. 4. The process for the preparation of 1- (Z-4-tert-buty-lidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalen-2-ol according to claim 1, characterized in that: the reduction ring-opening reaction is that acetic acid is added into oxazolidine 4 with a bridged ring structure, zinc powder is used for reduction ring-opening, and then a nitrogen-oxygen bond is broken to obtain 1- (Z-4-tert-butylbenzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol 1.
CN201711271525.9A 2017-12-05 2017-12-05 Preparation method of 1- (Z-4-tert-butyl benzylidene) -4-tert-butylamine-1, 2,3, 4-tetrahydronaphthalene-2-alcohol Expired - Fee Related CN107915649B (en)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Nitrone Directing Groups in Rhodium(III)-Catalyzed C@HActivation of Arenes: 1,3-Dipoles versus Traceless Directing Groups;Fang Xie等;《Angew. Chem. Int. Ed.》;20161110;第55卷;参见Scheme2和scheme7 *
Optically Active Isoxazolidines via Asymmetric Cycloaddition Reactions of Nib-ones with Alkenes: Applications in Organic Synthesis;Martyn Frederickson等;《Terahedron》;19971231;第53卷(第2期);第403-425页 *

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