2785-97-9

Usage

Uses

Used in Organic Synthesis:
LITHIUM 2,6-DIMETHOXYPHENYL is used as a reagent in the preparation of aryl lithium compounds, which are crucial intermediates in organic synthesis. Its strong nucleophilic character allows it to participate in a range of reactions, making it a valuable component in the synthesis of complex organic molecules.
Used in Chemical Research:
In the field of chemical research, LITHIUM 2,6-DIMETHOXYPHENYL serves as a versatile tool for studying the reactivity and selectivity of nucleophilic aromatic substitution and other related reactions. Its use can provide insights into reaction mechanisms and help in the development of new synthetic methodologies.
Used in Pharmaceutical Industry:
LITHIUM 2,6-DIMETHOXYPHENYL is utilized in the synthesis of pharmaceutical compounds, particularly those containing aryl groups. Its ability to form aryl lithium intermediates can facilitate the construction of complex molecular structures, which are often found in drug molecules.
Used in Material Science:
In material science, LITHIUM 2,6-DIMETHOXYPHENYL can be employed in the development of new materials with specific properties, such as organic conductors or polymers with tailored characteristics. LITHIUM 2,6-DIMETHOXYPHENYL's reactivity and ability to form aryl lithium species make it a useful building block in the synthesis of novel materials.

InChI:InChI=1/C8H9O2.Li/c1-9-7-4-3-5-8(6-7)10-2;/h3-5H,1-2H3;/rC8H9LiO2/c1-10-6-4-3-5-7(11-2)8(6)9/h3-5H,1-2H3

Upstream product

• 16932-45-9 1-bromo-2,6-dimethoxybenzene 
• 151-10-0 1,3-Dimethoxybenzene 
• 124-38-9 carbon dioxide 

Downstream Products

• 3657-22-5 N-tert.-Butyl-N-(2,6-dimethoxy-phenyl)-hydroxylamin 
• 3416-29-3 2,6-Dimethoxyphenyl-t-butyl-nitroxid-Radikal 
• 19177-22-1 Bis-(2,6-dimethoxy-phenyl)-nitroxid 
• 21163-52-0 7-<2.6-Dimethoxy-phenyl>-cycloheptatrien-(1.3.5) 
• 16932-44-8 2-iodo-1,3-dimethoxybenzene 
• 120011-51-0 Benzyl-bis-(2,6-dimethoxy-phenyl)-phosphane 
• 76638-71-6 6-hydroxymethyl-2,2',5,6'-tetramethoxy-4-methylbenzophenone 
• 76638-72-7 6-hydroxymethyl-2,2',5,6'-tetramethoxy-3-methylbenzophenone 
• 2734-70-5 2,6-dimethoxyaniline 
• 85473-72-9 tris[2,6-di(methoxy)phenyl]arsine 
• 151-10-0 1,3-Dimethoxybenzene 
• 76504-82-0 2α-(2,6-dimethoxybenzoyl)-7-oxabicyclo<2.2.1>heptane-3α-carboxylic acid 
• 76504-82-0 2β-(2,6-dimethoxybenzoyl)-7-oxabicyclo<2.2.1>heptane-3β-carboxylic acid 
• 64655-64-7 Bis(2,6-dimethoxyphenyl)phenylmethanol 

Relevant academic research and scientific papers

A substituted 2, 3 - dihydrobenzo [d] [1, 3] oxa phosphorus mixed cyclopentadiene ligand preparation method

The invention relates to a preparation method of a substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand. The preparation method of the substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand comprises the following concrete steps: (b) in presence of alkali and a hydroxymethylation reagent, carrying out hydroxymethylation on a compound show in a formula II to obtain a compound shown in a formula C; (c) in presence of a halogenating reagent, carrying out halogenating reaction on the compound shown in the formula C to obtain a compound shown in a formula D; (d) in presence of Lewis acid or Bronsted acid and alkali, carrying out demethylation cyclization reaction on a compound shown in the formula D to obtain a compound shown in a formula E; and (e) in presence of a reducing agent, carrying out reduction reaction on the compound shown in the formula E to obtain the ligand shown in a formula I, wherein groups in each formula are defined in the specification. The invention also discloses a compound shown in the formula II and a preparation method thereof. The preparation method of the substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand is simple in steps, mild in reaction conditions and applicable to industrial production.

Nickel-Catalyzed Cross-Coupling of Organolithium Reagents with (Hetero)Aryl Electrophiles

Nickel-catalyzed selective cross-coupling of aromatic electrophiles (bromides, chlorides, fluorides and methyl ethers) with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene (NHC) complex allows the reaction with a variety of (hetero)aryllithium compounds, including those prepared via metal-halogen exchange or direct metallation, whereas a commercially available electron-rich nickel-bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product. These reactions proceed rapidly (1 h) under mild conditions (room temperature) while avoiding the undesired formation of reduced or homocoupled products. Nickel-catalyzed cross-coupling of aromatic electrophiles with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene complex allows reaction with a variety of (hetero)aryllithium compounds, whereas a commercially available electron-rich nickel bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product.

PHOSPHORUS LIGANDS AND METHODS OF USE

In one embodiment, the application discloses ligands, such as a ligand from a dihydrobenzo [1,3] oxaphosphole scaffold, and palladium or other transition metal complexes comprising the ligands and methods for performing cross coupling reactions and asymmetric cross coupling reactions with high selectivity and efficiency, under aqueous micellar catalysis conditions.

Ortho-lithiations reassessed: The advantages of deficiency catalysis in hydrocarbon media

Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODMA), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many cases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.

Concepts for stereoselective acrylate insertion

Various phosphinesulfonato ligands and the corresponding palladium complexes [{((PaO)PdMeCl)-μ-M}n] ([{( X1-Cl)-μ-M}n], (PaO) = κ2- P,O-Ar2PC6H4SO2O) with symmetric (Ar = 2-MeOC6H4, 2-CF3C6H4, 2,6-(MeO)2C6H3, 2,6-(iPrO)2C 6H3, 2-(2′,6′-(MeO)2C 6H3)C6H4) and asymmetric substituted phosphorus atoms (Ar1 = 2,6-(MeO)2C6H 3, Ar2 = 2′-(2,6-(MeO)2C 6H3)C6H4; Ar1 = 2,6-(MeO)2C6H3, Ar2 = 2-cHexOC 6H4) were synthesized. Analyses of molecular motions and dynamics by variable temperature NMR studies and line shape analysis were performed for the free ligands and the complexes. The highest barriers of ΔGa = 44-64 kJ/mol were assigned to an aryl rotation process, and the flexibility of the ligand framework was found to be a key obstacle to a more effective stereocontrol. An increase of steric bulk at the aryl substituents raises the motional barriers but diminishes insertion rates and regioselectivity. The stereoselectivity of the first and the second methyl acrylate (MA) insertion into the Pd-Me bond of in situ generated complexes X1 was investigated by NMR and DFT methods. The substitution pattern of the ligand clearly affects the first MA insertion, resulting in a stereoselectivity of up to 6:1 for complexes with an asymmetric substituted phosphorus. In the consecutive insertion, the stereoselectivity is diminished in all cases. DFT analysis of the corresponding insertion transition states revealed that a selectivity for the first insertion with asymmetric (P aO) complexes is diminished in the consecutive insertions due to uncooperatively working enantiomorphic and chain end stereocontrol. From these observations, further concepts are developed.

Synthesis and spectroscopic properties of rosamines with cyclic amine substituents

(Chemical Equation Presented) There is a close structural similarity between rosamines A and rhodamines B, yet a diversity of structures in the rosamine class and their spectral properties have yet to be explored in depth. This manuscript describes a concise, scalable, solution-phase method to obtain rosamines 1-5 and 12-15, which include some water-soluble derivatives. In one test case (for 15) an illustrative protein conjugate was also formed. Throughout these products were isolated and purified, and the syntheses were found to be scalable. Further, the rosamines with these cyclic amine substituents display solvent-dependent fluorescence intensities, and high quantum yields in chlorinated hydrocarbons. In some cases the nature of the cyclic amine substituent was shown to modulate the fluorescence of the parent molecules in pH-dependent ways. The ring size of those amine substituents also correlated with some of their spectroscopic properties. Several water-soluble rosamines were prepared from some of the addition products 1-5, and one of these, 15, was efficiently conjugated to avidin via an amide linkage. The spectroscopic properties of 15 and 15-avidin in aqueous media were very similar.

QUINOLINE DERIVATIVES AS EP4 ANTAGONISTS

The invention is directed to quinoline derivatives as prostaglandin E type receptor antagonists useful for the treatment of EP4 mediated diseases or conditions, such as acute and chronic pain, osteoarthritis, rheumatoid arthritis and cancer. The derivatives have the following structure of formula (I): wherein A and B represents either a nitrogen atom or a CH group with the proviso that they cannot both simultaneously be CH, Q can represent a nitrogen or a carbon atom, and Y and Z are either a nitrogen atom., a N(O) group or a C(R5) group. Pharmaceutical compositions comprising the derivatives of formula (I) are also included.

Bis(2,6-dimethoxyphenyl)tellurium dihalides (CI, Br or I) and dithiocyanate: Crystal structure and temperature-dependent NMR spectra

Tris(2,6-dimethoxyphenyl)telluronium chloride hydrate, [R3Te]Cl-;)H2O la [R = 2,6-(MeO)2C6H3, n = 2-2.5] was prepared by the reaction of RLi and TeCl4. It decomposed in hot 0.1 M hydrochloric acid to give R2TeCI2 3a, exclusively, from which R2TeX2 (X = Br 3b, 13c or SCN 3d) were derived by halogen exchange. The X-ray crystallographic analyses of 3a-3d showed that these compounds have a twofold axis (except for 3d) with essentially pseudo-trigonal bypyramidal co-ordination with two R groups and a lone pair of electrons occupying the equatorial sites and two halogen atoms the apical sites. The thiocyanate groups in 3d bind to the tellurium atom via sulfur. No intermolecular Te ...X secondary bond was observed for 3a-3d. The Te-C bond distances of 3a-3c [2.09 ±0.01 A] are somewhat shorter than those reported for phenyl derivatives, and those of 3d [2.042(3) and 2.073(2) A] are the shortest ever reported. The C-Te-C bond angle is much larger [107.6(2)-104.37(9)°] than those reported. The X-Te-X bond angles are very close to 180°. The Te ...O distances of 3a-3d [2.880-3.323 A] are significantly shorter than the sum of the O and Te van der Waals radii [3.60 A]. The 'H NMR spectra of 3a-3c were halogen-, solvent-, and temperature-dependent showing that the rotation of R-Te bonds was restricted due to the barrier between R groups and halogen atoms. The activation energies AG? decreased in the order 3a (90 kJ mol-1 in DMSO-d6) > 3b (80 kJ mol-1 in DMSO-d6) > 3d (>65 kJ mor' in CDCl3) > 3c (60 kJ mol-1 in CDC13) > 3d (59 kJ mol-1 in CD3CN). The Royal Society of Chemistry 2000.

Phosphosulfonate herbicides

This invention pertains to phosphosulfonates, having the general formula STR1 wherein Y is phenyl, naphthyl, benzyl, a (C5 -C8)cycloalkyl, a 5-membered heteroaromatic ring, a 6-membered heteraromatic ring, a fused 5,6-membered heteroaromatic ring, or a fused 6,6-membered heteroaromatic ring; and X is oxygen or sulfur; and R1 and R2 are each independently selected from substituted or unsubstituted alkyl, alkoxy, alkylthio, alkenyloxy, alkynyloxy, haloalkoxy, cyanoalkoxy, alkoxyalkoxy, cycloalkyloxy, cycloalkylalkoxy, alkylideneiminooxy, chloro, amino, phenyl or phenoxy; or R1 and R2 are both alkoxy, taken together with the phosphorus atom to form a 6-membered oxygen-containing ring; compositions containing these compounds and their use as herbicides.

REAKTIONSWAERMEN ISOMERER (LITHIOARYL)ETHER MIT s-BUOH

The enthalpies of (2-lithioaryl) ethers and that of 8-lithio-1-methoxynaphthyllithium in di-n-butyl ether are lower than those of their 4-lithio isomers by ca. 20 and 28 kJ/(mol RLi), respectively.