1988-21-2

Upstream product

• 98-54-4 para-tert-butylphenol 
• 25891-31-0 triformylamine 
• 939-97-9 4-tert-Butylbenzaldehyde 
• 2565-30-2 formyl chloride 
• 64-18-6 formic acid 
• 253185-03-4 tert-butylbenzene 
• 556-63-8 lithium formate 

Downstream Products

• 14103-27-6 p-tert.-Butyl-phenyl-1,1-dimethyl-butyl-ether 
• 14041-81-7 4-tert-butylphenyl benzoate 
• 1392408-48-8 4-(tert-butyl)phenyl 1-benzyl-1H-indole-3-carboxylate 
• 1426654-58-1 (4-(tert-butyl)phenyl)(1-methyl-1H-indol-3-yl)methanone 

Relevant academic research and scientific papers

The formyloxyl radical: Electrophilicity, C-H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes

In the past the formyloxyl radical, HC(O)O, had only been rarely experimentally observed, and those studies were theoretical-spectroscopic in the context of electronic structure. The absence of a convenient method for the preparation of the formyloxyl radical has precluded investigations into its reactivity towards organic substrates. Very recently, we discovered that HC(O)O is formed in the anodic electrochemical oxidation of formic acid/lithium formate. Using a [CoIIIW12O40]5- polyanion catalyst, this led to the formation of phenyl formate from benzene. Here, we present our studies into the reactivity of electrochemically in situ generated HC(O)O with organic substrates. Reactions with benzene and a selection of substituted derivatives showed that HC(O)O is mildly electrophilic according to both experimentally and computationally derived Hammett linear free energy relationships. The reactions of HC(O)O with terminal alkenes significantly favor anti-Markovnikov oxidations yielding the corresponding aldehyde as the major product as well as further oxidation products. Analysis of plausible reaction pathways using 1-hexene as a representative substrate favored the likelihood of hydrogen abstraction from the allylic C-H bond forming a hexallyl radical followed by strongly preferred further attack of a second HC(O)O radical at the C1 position. Further oxidation products are surmised to be mostly a result of two consecutive addition reactions of HC(O)O to the CC double bond. An outer-sphere electron transfer between the formyloxyl radical donor and the [CoIIIW12O40]5- polyanion acceptor forming a donor-acceptor [D+-A-] complex is proposed to induce the observed anti-Markovnikov selectivity. Finally, the overall reactivity of HC(O)O towards hydrogen abstraction was evaluated using additional substrates. Alkanes were only slightly reactive, while the reactions of alkylarenes showed that aromatic substitution on the ring competes with C-H bond activation at the benzylic position. C-H bonds with bond dissociation energies (BDE) ≤ 85 kcal mol-1 are easily attacked by HC(O)O and reactivity appears to be significant for C-H bonds with a BDE of up to 90 kcal mol-1. In summary, this research identifies the reactivity of HC(O)O towards radical electrophilic substitution of arenes, anti-Markovnikov type oxidation of terminal alkenes, and indirectly defines the activity of HC(O)O towards C-H bond activation.

Palladium-Catalyzed Carbonylative Synthesis of Aryl Formates under Mild Conditions

Aryl formates have been extensively applied as CO sources in CO-free carbonylation reactions. However, there are no catalytic synthetic procedures for their preparation. In this manuscript, we developed a convenient palladium-catalyzed procedure for the synthesis of aryl formates. Good yields were achieved under mild reaction conditions with formic acid as the formyl source. A formyl meeting: A convenient palladium-catalyzed carbonylation procedure for the synthesis of aryl formates is developed. Good yields are achieved under mild reaction conditions with formic acid as the formyl source.

Palladacycle-catalyzed carbonylation of aryl iodides or bromides with aryl formates

An efficient palladacycle-catalyzed aromatic carbonylation reaction of aryl formates with aryl iodides or bromides has been developed. Commercially available and easily prepared aryl formates were employed as carbonyl sources without the use of external carbon monoxide. The present catalytic system shows broad functional group tolerance and affords aryl benzoate derivatives in good to excellent yields. Copyright

O-acylation of substituted phenols with various alkanoyl chlorides under phase-transfer catalyst conditions

Esterification of several types of mono-and disubstituted phenols with various mono-and dialkanoyl chlorides was performed in phase-transfer catalysis conditions, using tetrabutylammonium chloride in a mixture of aqueous NaOH and dichloromethane. The process is particularly efficient (almost quantitative yields) as well as rapid (only 5 min reaction time, at a temperature of0°C). Taylor & Francis Group, LLC.

One-pot synthesis of phenols from aromatic aldehydes by Baeyer-Villiger oxidation with H2O2 using water-tolerant Lewis acids in molecular sieves

The heterogeneous oxidation systems Sn-Beta/H2O2 and Al-Beta/H2O2 were both active for the Baeyer-Villiger oxidation of aromatic aldehydes. With alkoxy substituents in ortho and especially in para position, the corresponding formate ester was the primary reaction product with excellent selectivity. The highest selectivity toward the ester was obtained with the Sn-Beta catalyst in dioxane as solvent. High selectivities of the corresponding phenol could be obtained by employing ethanol or aqueous acetonitrile as solvent with Sn-Beta. Al-Beta was more efficient as catalyst for both Baeyer-Villiger oxidation and ester hydrolysis and, thus achieved high yields for the corresponding alcohol. However, this was a less selective catalyst than Sn-Beta zeolite. Sn-Beta was a chemoselective catalyst when the aldehyde reactant contained olefinic groups in an alkyl chain. With these reactants, the Al-zeolite gave no activity. Other classical BV oxidants, e.g., peracids, also yielded the epoxidation products. Thus, Sn-Beta catalysts open a new entry to aromatic phenols with unsaturated alkyl substituents that are interesting intermediates in the chemical industry.

Orthoamides, LVI [1]. A new method of wide scope for the preparation of aryl formates

Aryl formates 4a-u, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 are prepared by formylation of hydroxyarenes 3a-u, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25 with N,N-diformylacetamide (1) or triformamide (2), respectively, in fairly good yields. The reactions can be catalyzed by sodium diformamide or praseodymium(III) triflate. The thiolformate 28 was obtained analogously from 1-thionaphthol (27).

Bisphosphonic acids and esters

The present invention relates to hitherto unknown compounds of the formula I STR1 in which R1 is a straight or branched, saturated or unsaturated aliphatic or alicyclic C1 -C10 hydrocarbon radical, an aryl or an aryl-C1 -C4 -alkyl radical, R1 if desired being unsubstituted or substituted with straight or branched C1 -C4 -alkyl, amino, C1 -C4 -alkamino, di-(C1 -C4 -alkyl)-amino, carboxy, C1 -C4 -alkoxycarbonyl, hydroxy, C1 -C4 -alkoxy, phenoxy, mercapto, C1 -C4 -alkylthio, phenylthio, halogen, trifluoromethyl; R2 stands for hydrogen, C1 -C8 -alkyl, aryl-C1 -C4 -alkyl or halogen; X is O or S, and n is an integer from 0 to 2; with the proviso that R2 cannot be hydrogen or methyl if n=O and R1 is methyl. The compounds of the invention are valuable in the human and veterinary practice.