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Method for the preparation of symmetrical pincer ligands of the m-terphenyl compound type

A compound, benzoyl technology, applied in the field of compounds of the formula ABA, can solve the problems of high processing costs, unfavorable, expensive ligand systems, etc., and achieve the effects of reducing the formation of by-products, low direct synthesis, and reduced consumption

Inactive Publication Date: 2020-03-10
EVONIK OPERATIONS GMBH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Toxic by-products (e.g. bromine compounds) often occur during the reaction, which are difficult to separate from the desired product and expensive to dispose of
In addition, the product has to be prepared in a very large number of steps, which is likewise very disadvantageous (see schematic figure 1 and 2 )
Increasingly rare raw materials make ligand systems expensive to prepare via palladium-catalyzed cross-coupling or chemical oxidants
[0021] The preparation of symmetrical pincer ligands is very complicated by traditional methods
Requires many different reagents and solvents and additionally generates a very large amount of waste which should be avoided from an ecological and economic point of view

Method used

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  • Method for the preparation of symmetrical pincer ligands of the m-terphenyl compound type
  • Method for the preparation of symmetrical pincer ligands of the m-terphenyl compound type
  • Method for the preparation of symmetrical pincer ligands of the m-terphenyl compound type

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Experimental program
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preparation example Construction

[0119] Preparative liquid chromatography for the separation of mixtures of substances was performed using 60 M silica gel (0.040-0.063 mm) (Machery-Nagel GmbH & Co. KG, Düren) at a maximum pressure of 2 bar. All eluents used (ethyl acetate (technical purity), cyclohexane (technical purity)) were purified by distillation on a rotary evaporator beforehand.

[0120] Thin film chromatography (TLC) on ready-made PSC silica gel plates at 60 F 254 (Merck KGaA, Darmstadt). Detection of the different substances first under UV light and then by means of staining with the cerium / molybdophosphoric acid reagent (5.6 g of molybdophosphoric acid, 2.2 g of cerium(IV) sulfate tetrahydrate and 13.3 g of concentrated sulfuric acid in 200 ml of water) and then Carry out by heating with a hot hair dryer.

[0121] Gas Chromatography (GC / GCMS)

[0122] Gas chromatography (GC) analysis of product mixtures and pure substances was performed with the aid of a gas chromatograph GC-2010 (Shimadzu, Ja...

Embodiment 1

[0144] 2,2''-dihydroxy-5,5''-dimethyl-2'- N,N -Dimethylamino-3,3'',4'-trimethoxy[1,1';5' 1'']terphenyl (1)

[0145] The electrolysis was carried out according to AAV1 using 1.38 g (10 mmol, 2.0 equiv) of 4-methylguaiacol and 0.76 g (5 mmol, 1.0 equiv) of 3-( N , N -Dimethylamino)anisole. The current intensity is 15 mA, and the charge is 1929.7 C (4F per 3-( N , N -Dimethylamino)anisole). The crude product was prepurified by column chromatography on silica gel 60 using a gradient of eluent mixture of 95:5, then 9:1 and finally 4:1 (cyclohexane (CH):ethyl acetate (EE)). The fractions obtained were tested for the presence of product and re-used on silica gel 60 with eluents 1:1:0.01, then 1:1:0.02 (dichloromethane (DCM):cyclohexane (CH):methanol ( MeOH)) purification. Additional purification of the mixed fractions was by bulb distillation (150 °C, 180 °C, 190 °C and 205 °C for 10 -3 mbar) to proceed. The product was obtained as a yellow oil.

[0146]

[0147] ...

Embodiment 2

[0155] 2,2''-dihydroxy-3,3'',4'-trimethoxy-5,5'',2'-trimethyl[1,1';5'1'']terphenyl (2 )

[0156] The electrolysis was carried out according to AAV1, using 1.45 g (10.5 mmol, 2.0 equiv) of 4-methylguaiacol and 639 mg (5.23 mmol, 1.0 equiv) of 3-methylanisole. Current density of 2.8 mA / cm 2 , with a charge of 2 F per 4-methylguaiacol (Q = 2018 C). After separation of the solvent, the product mixture was purified by column chromatography on silica gel 60 using eluent 9:1 (CH:EE). The product was obtained as a yellow oily substance.

[0157]

[0158] Yield: 68 mg (0.17 mmol, 3%)

[0159] GC (hard method, HP-5): t R = 21.35 min

[0160] R f (Cy:EA = 4:1) = 0.39

[0161]

[0162]

[0163] HRMS (ESI, positive mode): m / z C 24 h 26 o 5 (M+Na + ): Calculated: 417.1678; Measured: 417.1670

[0164] Melting point: 67.7°C (crystallized from DCM).

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Abstract

The present invention relates to a process for the preparation of symmetrical pincer ligands of the m-terphenyl compound type. In particular, the present invention relates to a process for the preparation of a compound of formula ABA by reacting a compound of formula (A) with a compound of formula (B), wherein X=-OR' or -NHR'; and R'=H or protecting group functional group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from hydrogen, (C 1 -C 12 )‑Alkyl, O‑(C 1 -C 12 )-Alkyl, (C 6 -C 20 )‑aryl, O‑(C 6 -C 20 )-aryl, wherein the group R 1 to R 4 Two of can also be linked by covalent bonds, and halogen, characterized in that the reaction is carried out electrochemically.

Description

technical field [0001] The present invention relates to a process for the preparation of compounds of formula ABA, [0002] [0003] It is obtained by making the compound of formula (A) [0004] [0005] react with a compound of formula (B), [0006] [0007] where X = -OH or -NR'R''; and R' = H or a protecting group functional group and R'' = H or a protecting group functional group, and R' and R'' may be linked to each other by a covalent bond and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from hydrogen, hydrocarbyl and hydrocarbyl with heteroatoms, wherein the group R 1 to R 8 Adjacent groups of can be linked by covalent bonds, characterized in that the reaction is carried out electrochemically. [0008] In the present invention, an adjacent group refers to a group that is bonded on directly adjacent carbon atoms. In the case of compound (A), for example the group R 1 and R 2 . Examples of such groups are eg -O-(CH 2 ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C43/23C07C217/84C25B3/10B01J31/22C25B3/29
CPCB01J31/2213C07C43/23C07C217/84B01J2531/0244C25B3/29C07C41/30C07C213/08C07C269/06Y02P20/55B01J31/0271
Inventor K.M.迪巴拉R.弗兰克D.弗里达格S.R.瓦尔德福格尔B.埃尔斯勒A.维贝
Owner EVONIK OPERATIONS GMBH
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