74563-00-1

Basic information

• Product Name: α,β-dideuteriobenzhydrol
• Synonyms: α,β-dideuteriobenzhydrol
• CAS NO: 74563-00-1
• Molecular Weight: 186.222
• Mol File: 74563-00-1.mol

Chemical Properties

• CAS DataBase Reference: α,β-dideuteriobenzhydrol(CAS DataBase Reference)
• NIST Chemistry Reference: α,β-dideuteriobenzhydrol(74563-00-1)
• EPA Substance Registry System: α,β-dideuteriobenzhydrol(74563-00-1)

Safety Data

• Hazardous Substances Data: 74563-00-1(Hazardous Substances Data)

Upstream product

• 119-61-9 benzophenone 
• 3129-17-7 diphenylcarbene 

Relevant articles and documents

The epimetallation and carbonation of carbonyl and imino derivatives: Epivanadation route to 2-amino and 2-hydroxy acids

The feasibility of hydrocarboxylating carbonyl and imino derivatives by the two-step process of epimetallation and carbonation has been demonstrated with the model substrates of 9-fluorenone and 9-fluorenone anil. With lithium vanadium dihydride as the epimetallating agent, such hydrocarboxylation has led to a 75% yield of 9-hydroxy-9-fluorenecarboxylic acid and a 65% yield of 9-(N-phenylamino)-9-fluorenecarboxylic acid, respectively. Some initial success in extending the scope of this reaction to other substrates, such as benzophenone, has been achieved by using other epimetallating agents, like the presumed LiV(CH3)2 and Ti(OPri)2. A brief review of the processes and organic synthetic applications of epimetallation and transfer epimetallation of C-C π-bonds is offered as background.

Ruthenium(II) Complex of a Tridentate Azoaromatic Pincer Ligand and its Use in Catalytic Transfer Hydrogenation of Aldehydes and Ketones with Isopropanol

In this work, a new Ru(II) complex with the redox-active pincer 2,6-bis(phenylazo)pyridine ligand (L) is reported which acts as a metal-ligand bifunctional catalyst for transfer hydrogenation reactions. The isolated complex [(L)Ru(PMe2Ph)2(CH3CN)](ClO4)2; [1](ClO4)2 is characterized by a host of spectroscopic measurements and X-ray structure determination. It is diamagnetic and single-crystal X-ray structure analysis reveals that [1]2+ adopts a distorted octahedral geometry where L binds Ru center in meridional fashion. The observed elongation in the coordinated azo bond length (1.29 ?) is attributed to the extensive π-back bonding, dπ(RuII)→π*(azo)L. The complex [1](ClO4)2 acts as an efficient catalyst, which brings about catalytic transfer hydrogenation reactions of a broad array of aldehydes and ketones in isopropanol and in inert conditions. The selectivity of the catalyst for aldehyde reduction over the other reducible functional groups such as nitro, nitrile, ester etc was also investigated. Mechanistic studies, examined by suitable control reactions and isotope labelling experiments, indicate synergistic participation of both ligand and metal centres via the formation of a fleeting Ru?H intermediate and hydrogen walking to the coordinated azo function of L.

Transfer Hydrogenation of Ketones and Imines with Methanol under Base-Free Conditions Catalyzed by an Anionic Metal-Ligand Bifunctional Iridium Catalyst

An anionic iridium complex [Cp*Ir(2,2′-bpyO)(OH)][Na] was found to be a general and highly efficient catalyst for transfer hydrogenation of ketones and imines with methanol under base-free conditions. Readily reducible or labile substituents, such as nitro, cyano, and ester groups, were tolerated under present reaction conditions. Notably, this study exhibits the unique potential of anionic metal-ligand bifunctional iridium catalysts for transfer hydrogenation with methanol as a hydrogen source.

Re(I)-Catalyzed Hydropropargylation of Silyl Enol Ethers Utilizing Dynamic Interconversion of Vinylidene-Alkenylmetal Intermediates via 1,5-Hydride Transfer

Re(I)-catalyzed hydropropargylation reaction of silyl enol ethers was realized utilizing dynamic interconversion of vinylidene-alkenylmetal intermediates, where alkenylmetals underwent 1,5-hydride transfer of the α-hydrogen to generate vinylidene intermediates. Furthermore, this process was found to be in an equilibrium.

The highly reactive benzhydryl cation isolated and stabilized in water ice

Diphenylcarbene (DPC) shows a triplet ground-state lying approximately 3 kcal/mol below the lowest singlet state. Under the conditions of matrix isolation at 25 K, DPC reacts with single water molecules embedded in solid argon and switches its ground state from triplet to singlet by forming a strong hydrogen bond. The complex between DPC and water is only metastable, and even at 3 K the carbene center slowly inserts into the OH bond of water to form benzhydryl alcohol via quantum chemical tunneling. Surprisingly, if DPC is generated in amorphous water ice at 3 K, it is protonated instantaneously to give the benzhydryl cation. Under these conditions, the benzhydryl cation is stable, and warming to temperatures above 50 K is required to produce benzhydryl alcohol. Thus, for the first time, a highly electrophilic and extremely reactive secondary carbenium ion can be isolated in a neutral, nucleophilic environment avoiding superacidic conditions.

Vanadium(I) chloride and lithium vanadium(I) dihydride as selective epimetallating reagents for π- and σ-bonded organic substrates

Subvalent vanadium(I) salts, of empirical formulas, VCl, vanadium(I) chloride and LiVH2, lithium vanadium(I) dihydride, whose efficient preparation, structural constitution and mode of reaction toward certain organic substrates have been described in a preceding article, are here evaluated in their reactions toward a wide variety of π- and σ-bonded organic substrates, namely carbonyl, imine, azo, alkene, 1,3-diene, nitrile π-bonds and C-X, C-O, C-N and N-N σ-bonds. Compared with the high reactivity of CrCl and LiCrH2 reagents in attacking both types of bonds, the VCl and LiVH2 reagents were much milder and selective in epimetallating π-bonds, often forming the 1:1 adduct of LiVH2 and π-bonded substrate as the major product. Finally, the vanadium reagents showed little tendency to cleave C-O, C-S and C-N bonds and a smaller scope in cleaving C-X bonds than their chromium counterparts. Because of their selectivity these vanadium reagents offer the following preparative promise: 1) smooth McMurry carbonyl coupling to their reductive dimers; 2) deoxygenation of epoxides; 3) selective aromatic C-X reduction; 4) high yields of epimetallated carbonyls or imines as intermediates to α-hydroxy and α-amino acids; 5) 1,4-reductions of 1,3-alkadienes; 6) reductive dimerization of nitriles to ketones; 7) 1,4 or 1,n-epimetallations leading to acyloins or indoles; and 8) reductive dimerizations of azines to produce unusual imidazole derivatives. In explaining the greater kinetic stability of the 1:1 LiVH2 adduct with carbonyl or imine substrates it is pointed out that such epimetallated adducts from LiVH2 would likely be diamagnetic, whereas such adducts from LiCrH2 have an unpaired electron on the Cr center and hence would rupture, so that the electron would be on the C center. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Iridium complexes with chiral and achiral β-aminophosphane ligands: Catalysts for >C=O hydrogenation and H/D exchange involving both homo-and heterolytic H2 activation

Chiral and achiral P,N-chelated IrI complexes of the general type [(COD)Ir(P∩NR1R2)]BF4, where COD = η4-1,5-C8H12 and P∩NR1R 2 = (1R,2R)-, (1S,2S)-, or (1R,2S)-Ph2PC 1H(Ph)C2H(Me)NR1R2 (NR 1R2 = NH2, NHMe, NHCH2Ph, NHCHMe2, NMe2), Ph2PCH2CR 2NH2 (R = H, Me), of 2-Ph2PC6H 4NHMe, have been prepared by treating [Ir(COD)2]BF 4 with the required β-aminophosphane in THF. The monolithiated ligands Ph2PCH2CMe2N(Li)H and 2-Ph 2PC6H4N(Li)Me interacted with [{(COD)Ir(μ-Cl))2] to give the neutral alkyl- and arylamido compounds [(COD)-Ir(Ph2PCH2CMe2NH)] and [(COD)Ir(2-Ph2PC6H4NMe)]. All IrI complexes [(COD)Ir(P∩NR1R2)]BF4 acted as catalysts for the direct hydrogenation of alkyl aryl ketones to the corresponding 1-phenylalkanols, if combined with an alkaline or amine base in methanol under H2 (10-50 bar) between 25 and 50 °C. The reaction occurred with modest to moderate enantioselectivity (ca. 20-75% ee) if chelate complexes bearing the various optically active β-aminophosphanes were used as catalysts. The base-free amido complexes [(COD)-Ir(P∩NR)] displayed similar catalytic activity to the combined systems [(COD)Ir(P∩NHR)]BF 4-KOH (P∩NHR = Ph2PCH2CMe 2NH2, 2-Ph2PC6H4NHMe). The ability of both the cationic β-amino- and the neutral β-amidophosphane IrI complexes to undergo oxidative H 2 addition and the observation of H2/D+ as well as H2/D2 exchange processes during catalysis provided evidence for a mechanism involving reversible "[IrIII(H) 2-P∩NHR]+ ? [(η2-H2)-Ir III(H)-P∩NR]+" proton-to-hydride transfer and heterolytic H2 cleavage on amino-dihydride and amido-dihydrogen- monohydride tautomers. The crystal structures of [(COD)Ir{(1S,2S)-Ph 2PCH(Ph)CH(Me)NHCH2Ph}]BF4·2THF, [(COD)Ir{1R,2S-Ph2PCH(Ph)CH(Me)NHMe}]BF4·THF, and the orthometalated 18e IrI complex [(COD)Ir{(1R,2S)-Ph 2PCH(C6H4-o)-CH(Me)NHCHMe2}], which resulted from treatment of [(COD)Ir{(1R,2S)-Ph2PCH(Ph)CH(Me) NHCHMe2}]BF4 with excess KOH, have been determined by single crystal X-ray diffraction studies. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Stereoelectronic Effects in Hydrogen Atom Abstraction from Substituted 1,3-Dioxanes

An EPR technique and a method involving the gas chromatographic determination of the relative rates of consumption of substrates have been employed to measure the relative rates of hydrogen atom abstraction by tert-butoxy radicals from various substituted 1,3-dioxanes.The high relative reactivities of dioxanes equitorially substituted at C-2 as compared with their axially substituted epimers are attributed to the favorable stereoelectronic interactions in the former between the axial C-H bonds and adjacent oxygen lone pairs.The effects of methoxy substituents on the relative reactivities of cyclic ethers have been similarly rationalized.The photoinduced reaction between benzophenone and the methoxydioxane (8) has been shown to be reversible.

Transformation of Carbinols by RuCl2(PPh3)3 and by Some Other Transition-Metal Catalysts

Several platinoid metal catalysts have been shown to promote reductive coupling, dehydration, disproportionation, and dehydrogenation of diarylcarbinols.Mechanistic studies were performed at 180-210 deg C with benzhydrol as substrate and RuCl2(PPh3)3 as catalyst.In aromatic hydrocarbon solvents the main process is reductive coupling.In this medium solvated RuCl2(PPh3)2 is suggested to be the active catalyst.In dimethyl sulfoxide the starting complex is transformed initially into RuCl2(PPh3)(Me2SO)2 and causes chiefly carbinol dehydrogenation.Ruthenium alkoxides are implied as common reaction intermediates in all four catalyses.Ruthenium hydrides are suggested to take part in the reductive coupling, disproportionation, and dehydrogenation processes.Some aliphatic and primary aromatic alcohols that do not react by themselves in the presence of RuCl2(PPh3)3 can both serve as active hydrogen donors and form crossover products in the presence of secondary and tertiary aromatic carbinols.