38445-62-4

Upstream product

• 67-56-1 methanol 
• 1193-18-6 3-methylcyclohexen-2-one 
• 21378-21-2 3-methylcyclohex-2-en-1-ol 
• 75411-49-3 3-methyl-2-cyclohexen-1-yl acetate 
• 94059-92-4 6,6-dimethoxyhex-1-yne 
• 91988-32-8 4-iodobutyraldehyde dimethyl acetal 
• 90498-69-4 Acetat des 1-Methyl-cyclohexen-⁽²⁾-ols-⁽¹⁾ 
• 94059-90-2 (E)-6,6-dimethoxy-2-methyl-1-trimethylsilylhex-1-ene 
• 94059-91-3 (Z)-6,6-dimethoxy-2-methyl-1-trimethylsilylhex-1-ene 
• 74-88-4 methyl iodide 
• 29882-07-3 4-chlorobutanal dimethyl acetal 

Downstream Products

• 1219117-58-4 C₁₀H₁₉O₃PS 
• 52204-64-5 trans-3-methyl-1-methoxycyclohexane 
• 52204-64-5 cis-3-methyl-1-methoxycyclohexane 
• 1193-18-6 3-methylcyclohexen-2-one 

Relevant academic research and scientific papers

Molybdenum(II)- and tungsten(II)-catalyzed allylic substitution

The molybdenum(II) complexes Mo(CO)5(OTf)2 (7a), [Mo(CO)4Br2]2 (8a), their tungsten(II) congeners 7b and 8b, and bimetallic complex Mo(CO)3(MeCN)2(SnCl3)Cl (9a) have been found to catalyze the C-C bond-forming allylic substitution with silyl enol ethers derived from β-dicarbonyls (e.g., 16 + 30 → 46) or from simple ketones (e.g., 16 + 32 → 50), aldehydes, and esters as nucleophiles under mild conditions (room temperature, 1-2 h). Methanol, as a prototype oxygen nucleophile, reacts in a similar fashion (e.g., 16 + MeOH → 43). Mechanistic and stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-controlled process.

Reaction of cyclic allylic acetates with aliphatic alcohols in the presence of cerium(III) chloride

The reactions of selected allylic acetates with methanol, ethanol, n-propyl alcohol, isopropyl alcohol and tert-butyl alcohol in the presence of catalytic amounts of cerium(III) chloride are described. Allylic alkyl ethers, bis-allylic ethers and 1,3-dienes were obtained depending on the structure of the acetates.

The reaction of cyclic allylic alcohols with aliphatic alcohols in the presence of cerium(III) chloride

Cyclic secondary and tertiary allylic alcohols react with primary aliphatic alcohols in the presence of cerium(III) chloride heptahydrate to give alkyl allylic ethers. When secondary or tertiary aliphatic alcohols are used 1,3-dienes are obtained from allylic alcohols heaving the 3-methyl-2-en-1-ol moiety (3-8, 13-15).

Regioselectivity in the gas - phase nucleophilic attack on O - protonated 3-methyl-2-cyclohexen-1-ol and 1-methyl-2-cyclohexen-1-ol

Our radiolytic study of the occurrence in the gas phase of concerted SN2' reactions on several open-chain allylic oxonium ions generated in the gas phase from the attack of gaseous GA+ acids (GA+ = CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) on suitable substrates is now continued with cyclic allylic alcohols, such as 3-methyl-2-cyclohexen-1-ol (1) and 1-methyl-2-cyclohexen-1-ol (2), with both MeOH and NMe3 as neutral nucleophiles.With MeOH as the nucleophile, the substitution reaction exclusively takes place on 1 as the starting compound, whereas when the substrate is 2 it is accompanied by extensive elimination.With NMe3, only the elimination reaction is observed in the same systems.The analysis of the isomeric distribution of the substitution and elimination products allows definition of the corresponding reaction patterns.As for open-chain oxonium ions, the nucleophilic attack on O-protonated 1 and 2 is preceded by significant intramolecular interconversion.Partial unimolecular dissociation of the same ionic intermediates also takes place.After careful evaluation of the extent of these side processes, it is demonstrated that the O-protonated 1 undergoes the concerted SN2 process with MeOH almost exclusively ( 99percent).With O-protonated 2, however, the concerted SN2' pathway (84-95percent) prevails over the classical SN2 one (6-17percent).Concomitant (E2) and elimination (E2') pathways involve attack of the selected nucleophiles on the oxonium ions from 1 and 2.Their relative extent (E2'/E2:1.78-1.96 (1); 1.43-1.70 (2)) appears only slightly dependent on the nature of the ionic substrate, the nucleophile (whether MeOH or NMe3), and the leaving group (whether H2O or MeOH).The effects of both intrinsic structural factors and experimental conditions in determining the SN2'/SN2 and E2'/E2 branchings in the selected oxonium ions is discussed and compared with related gas-phase data. - Keywords: cyclohexenols; elimination reactions; gas-phase chemistry; mechanistic studies; nucleophilic substitutions

On the mechanism of alcoholysis of allylic and benzylic alcohols and of epoxides in the presence of ceric ammonium nitrate

The methanolysis of allylic alcohols, benzylic tertiary alcohols and epoxides in the presence of a catalytic amount of ceric ammonium nitrate (CAN) is shown to be catalysed by protons generated from the oxidation of methanol. This reaction is also catalysed by Lewis acids.

Allylic Substitution Catalyzed by a New Molybdenum Complex

A new molybdenum(II) complex (E), generated in situ from Mo(CO)6 by sequential treatment with PhCH2(Et)3N+Cl- and CF3SO3Ag (3 equiv.), has been found to catalyze the substitution of allylic acetates with MeOH (4 -> 5 8; 9

Alcoholyses and acetolyses of allylic and tertiary benzylic alcohols catalyzed by 2,3-dichloro-5,6-dicyanobenzoquinone

Allylic and tertiary benzylic alcohols can be converted into their corresponding ethers and acetates selectively and efficiently in the presence of catalytic amounts of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ).

Synthesis of Alkyl Allylic Ethers and 1,3-Dienes by the Reaction of Conjugated Cyclohexenones with Sodium Borohydride-Cerium(III) Chloride in Aliphatic Alcohols

The reaction of conjugated cyclohexenones 1,3-containing 3-methyl-2-en-1-one moiety with NaBH4/CeCl3*7H2O in primary aliphatic alcohols (MeOH, EtOH, n-PrOH) affords alkyl allylic ethers and 1,3-dienes.In isopropanol or tert-butanol only 1,3-dienes are obtained.Ketones 4-6 containing 2-methyl-2-en-1-one moiety are reduced under the same conditions to the corresponding allylic alcohols irrespective of the alcohol used.Key words: reduction, α,β-unsaturated ketones, allylic alcohols, alkyl allylic ethers, sodium borohydride, cerium(III) chloride

Cerium(IV), as a selective and efficient catalyst for alcoholyses of allylic and tertiary benzylic alcohols

An efficient and selective method is described for the catalytic conversion of allylic, and tertiary benzylic alcohols into their corresponding ethers in the presence of Ce(IV) under solvolytic and non- solvolytic conditions.

Controlling the Outcome of a Carbocation-initiated Cyclisation

The Z- and E-vinylsilanes, 6,6-dimethoxy-2-methyl-1-trimethylsilylhex-1-ene (6), gave only 3-methoxy-1-methylcyclohexene (7) on treatment with zinc bromide, and the allylsilane, 6,6-dimethoxy-2-methyl-3-trimethylsilylhex-1-ene (8), gave only 5-methoxy-1-methylcyclohexene (9) on treatment with tin(IV) chloride.Taken together with an earlier result, these results show that the silyl group completely controls the outcome of this carbocationic cyclisation.The syntheses of the two starting materials, (6) and (8), illustrate the usefulness of the silyl-cuprate reagent in the costruction of specific vinyl- and allyl-silanes.