20175-89-7

Upstream product

• 2027-17-0 2-Isopropylnaphthalene 
• 41816-68-6 2-isopropyl-3,4-dihydronaphthalen-1 (2H)-one 
• 79-31-2 isobutyric Acid 
• 130-15-4 [1,4]naphthoquinone 
• 75-30-9 2-iodo-propane 
• 57727-06-7 2-(isopropoxy)-2-oxoacetic acid 
• 94-36-0 dibenzoyl peroxide 
• 30615-19-1 isopropylmercury(II) chloride 
• 4900-63-4 1-methoxy-4-nitronaphthalene 
• 78-84-2 isobutyraldehyde 
• 72-18-4 L-valine 

Relevant academic research and scientific papers

Stereoselective [4+2] cycloaddition of singlet oxygen to naphthalenes controlled by carbohydrates

Stereoselective reactions of singlet oxygen are of current interest. Since enantioselective photooxygenations have not been realized efficiently, auxiliary control is an attractive alternative. However, the obtained peroxides are often too labile for isolation or further transformations into enantiomerically pure products. Herein, we describe the oxidation of naphthalenes by singlet oxygen, where the face selectivity is controlled by carbohydrates for the first time. The synthesis of the precursors is easily achieved starting from naphthoquinone and a protected glucose derivative in only two steps. Photooxygenations proceed smoothly at low temperature, and we detected the corresponding endoperoxides as sole products by NMR. They are labile and can thermally react back to the parent naphthalenes and singlet oxygen. However, we could isolate and characterize two enantiomerically pure peroxides, which are sufficiently stable at room temperature. An interesting influence of substituents on the stereoselectivities of the photooxygenations has been found, ranging from 51:49 to up to 91:9 dr (diastereomeric ratio). We explain this by a hindered rotation of the carbohydrate substituents, substantiated by a combination of NOESY measurements and theoretical calculations. Finally, we could transfer the chiral information from a pure endoperoxide to an epoxide, which was isolated after cleavage of the sugar chiral auxiliary in enantiomerically pure form.

Study of radical decarboxylation toward functionalization of naphthoquinones

In order to obtain functionalized naphthoquinones, a systematic study of the Kochi-Anderson procedure for the alkylation of quinones is presented. While linear amino acids of different lengths were good substrates for this decarboxylation procedure, chira

Progress towards metal-free radical alkylations of quinones under mild conditions

A new method for the radical alkylation of quinones is reported. Lewis basic nitrogen additives increase the efficacy of quinone alkylations from carboxylic acids using catalytic AgNO3 and Selectfluor as a mild oxidant. Electrochemical data sug

Quinone C-H Alkylations via Oxidative Radical Processes

A brief survey of radical additions to quinones is reported. Carboxylic acids, aldehydes, and unprotected amino acids are compared as alkyl radical precursors for the mono- or bis- C-H alkylation of several quinones. Two methods for radical initiation are discussed comparing inorganic persulfates and Selectfluor as stoichiometric oxidants. Kinetic analysis reveals dramatic differences in the rate of radical initiation depending on the identity of the radical precursor and oxidant. Synthetic strategies for efficiently producing alkyl-quinones are discussed in the context of selecting optimum radical precursors and initiators depending on quinone identity and functional groups present.

Homolytic base-promoted aromatic alkylations by alkylmercury halides

Electron transfer chain reactions leading to substitution in electronegatively substituted benzene derivatives can be observed with alkylmercury halides in the presence of proton accepters such as DABCO. Promotion by base involves the abstraction of a proton from the substituted cyclohexadienyl adduct radical to form a radical anion which readily transfers an electron to RHgX with the regeneration of R.. Aromatic substitutions involving t-Bu. are highly regioselective and yield products of only para attack for PhCHO, PhCOCH3, PhCOCMe3, PhCOPh, PhCN, phthalimides, or 1,2-dicyanobenzene. The ortho/para substitution products are observed for isophthaldehyde or 1,3-dicyanobenzene, while 1,4-dicyanobenzene yields the ortho substitution product. At 25-35°C substitution by t-Bu. ortho to an ester group is not observed and m- or p-cyanobenzoate esters yield only products of substitution ortho to the cyano group. With the isopropyl radical substitution ortho to the ester function is observed with diethyl isophthalate. Intramolecular radical cyclizations of the radical adducts of 1-aryl-4-penten-1-ones leading to α-tetralones is also promoted by the presence of DABCO. When the aryl group contains a para ester function, spirocyclizatien occurs leading to a rearrangement acyl radical which can be oxidized by t-BuHgCl to the acyl cation and the carboxylic acid.

Naphthalene anti-psoriatic agents

Psoriasis in mammals is relieved by topically administering naphthalenes of the formula: STR1 wherein: R1 is lower alkoxy or optionally substituted phenoxy; R2 is hydrogen, lower alkyl, optionally substituted phenyl or optionally substituted phenyl-lower-alkyl; R3 is hydrogen, lower alkyl, lower alkoxy, halo, optionally substituted phenyl, optionally substituted phenyl-lower-alkyl or optionally substituted phenyl-lower-alkoxy, and m is 1 or 2; X and Y are different and are selected from the group consisting of hydrogen, R4 and -C(O)W, wherein W is alkyl of one to seven carbon atoms, optionally substituted phenyl or optionally substituted benzyl; and R4 is lower alkyl or optionally substituted phenyl-lower-alkyl.

METHOD FOR TREATING DISEASE STATES IN MAMMALS WITH NAPHTHALENE LIPOXYGENASE-INHIBITTNG AGENTS

Psoriasis in mammals is relieved by topically administering naphthalenes of the formula: wherein: R1 is lower alkoxy or optionally substituted phenoxy, R2 is the same as R1, or R2 is hydrogen, lower alkyl, optionally substituted phenyl or optionally substituted phenylalkyl, R3 is hydrogen, lower alkyl, lower alkoxy, halo, optionally substituted phenyl, optionally substituted phenyl-lower-alkyl or optionally substituted phenyl-lower-alkoxy, and m is 1 or 2; both X groups are the same and X is either -C(O)OR4 or -C(O)NR5R6 , wherein R4 is alkyl, phenyl or benzyl optionally substituted with one or two lower alkyl groups, lower alkoxy groups or halo; and R5 and R6 are independently hydrogen, lower alkyl, cycloalkyl or phenyl optionally substituted with one or two lower alkyl groups, lower alkoxy groups or halo. The compounds of this invention are also useful for the treatment of disease-states caused by lipoxygenase activity in mammals, particularly 5-lipoxygenase activity, when administered systemically.

Naphthalene lipoxygenase-inhibiting agents

Psoriasis in mammals is relieved by topically administering naphthalenes of the formula: STR1 wherein: R1 is lower alkoxy or optionally substituted phenoxy; R2 is hydrogen, lower alkyl, optionally substituted phenyl or optionally substituted phenylalkyl; R3 is hydrogen, lower alkyl, lower alkoxy, halo, optionally substituted phenyl, optionally substituted phenyl-lower-alkyl or optionally substituted phenyl-lower-alkoxy, and m is 1 or 2; X and Y are different and are either R4 or --C(O)W wherein R4 is lower alkyl or optionally substituted phenyl-lower-alkyl; W is --OR5 or --NR6 R7, wherein R5 is alkyl, optionally substituted phenyl or optionally substituted benzyl; and R6 and R7 are independently hydrogen, lower alkyl, cycloalkyl or optionally substituted phenyl. The compounds of this invention are also useful for the treatment of disease-states caused by lipoxygenase activity in mammals, particularly 5-lipoxygenase activity, when administered systemically.

A New Selective Method for the Homolytic Alkylation and Carboxylation of Quinones by Monoesters of Oxalic Acid

Alkyl and alkoxycarbonyl radicals were generated by oxidative decarboxylation of oxalic acid monoesters by persulfate; they were then utilized for the selective substitution of quinones.

HOMOLYTIC ALKYLATION OF NAPHTHOQUINONE AND METHYL-NAPHTHOQUINONE. ENTHALPIC, STERIC AND POLAR EFFECTS.

The homolytic methylation of naphthoquinone to obtain menadione has been investigated by three sources of methyl radical: t-BuOOH, DMSO and H2O2, acetone and H2O2.Moreover the homolytic alkylation of naphthoquinone and 2-methylnaphthoquinone has been investigated by using alkyl iodides as sources of alkyl radicals.