Henry Gilman's research while affiliated with Saint Louis University and other places
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Publications (35)
Classically, organometallic chemistry is considered to deal with substances containing a direct carbon-metal bond. The scope of this field however expands as the definition of a metallic element is liberalized. If both physical properties such as high thermal and electrical conductivity, remarkable cohesiveness and luster, and chemical characterist...
The interaction of quinoline and allylmagnesium chloride in tetrahydrofuran with subsequent hydrolysis and isolation in a nitrogen atmosphere led to 2-allyl-1,2-dihydroquinoline (I). Compound I is thermally isomerized to 2-n-propylquinoline (II) and is transformed into 2-propenylquinoline (III) plus some II by hot nitrobenzene oxidation. The identi...
Several new N-substituted phenothiazine derivatives were prepared by heating a mixture of phenothiazine and an aryl or heterocyclic halide in the presence of sodium carbonate and copper powder. Many of these derivatives were oxidized to sulfoxides and sulfones using hydrogen peroxide in ethanol and hydrogen peroxide in glacial acetic acid, respecti...
o-Methoxyphenol and m-methoxyphenol were metalated with n-butyllithium, and, upon carbonation, were found to give a mixture of isomeric acids which were separated and identified. The directive influence of the hydroxyl vs. the methoxyl group is discussed. The 2-tetrahydropyranyl ethers of m-methoxyphenol and p-bromophenol were prepared and their me...
Benzeneboronic acid and o-hydroxybenzeneboronic acid anhydride were cleaved with n-butyllithium and the products characterized by carbonation. Benzeneboronic acid gave either 1-butaneboronic acid, benzoic acid or benzene, or a combination, the products depending upon the temperature at which the cleavage was run. o-Hydroxybenzeneboronic acid anhydr...
A number of new aromatic boronic acids have been synthesized for testing in brain tumor therapy. Some observations are reported on difficulties in the determination of melting point and purification and on the influence of the solvent used for recrystallization upon the transition: acid ⇄anhydride. A tentative characterization of the aromatic boron...
Lithium does not add directly to phenazine in tetrahydrofuran. An improved yield of 5-methyl-10-phenyl-5,10-dihydrophenazine was obtained when tetrahydrofuran was used in place of ethylene glycol dimethyl ether. 5,10-Diphenyl-5,10-dihydrophenazine has been prepared and its structure conclusively established by stepwise degradation to known compound...
A number of alkyl derivatives of dibenzo-p-dioxin(I) have been prepared. These include the 2-(II), 2,7(8)-di-t-butyl-dibenzo-p-dioxin(III); 2-(IV), 2,3-di-(V), 2,3,7,8-tetra-(VI), and a hexaisopropyldibenzo-p-dioxin(VII); and 2-benzyl-dibenzo-p-dioxin(VIII). Also obtained in the study were ethyl dibenzo-p-dioxin-2-dithiocarboxylate(IX), methyl dibe...
A wide variety of polyaryls containing an aza-aromatic heterocycle have been screened as liquid scintillator solutes. In general this heterocycle appears to be less effective than other nitrogen heterocycles, but some striking effects of the dialkylamino derivatives are observed. A number of the compounds are previously unreported, and details of t...
In a study of the substitutions! chemistry of phenanthridinone it was found that this system could be chlorinated, iodinated and sulfonated readily at the 2-position. A nitro group could be introduced easily into the 4-position only if the 2-position was blocked. However, nitration and bromination of 2-acetammophenanthridinone may have led to the 1...
The preparation of 6-substituted phenanthridines and their 5,6-dihydro derivatives by the organometallic alkylation of phenanthridine has been examined. It was found that not only do organolithium compounds (n-butyl- and o-tolyllithium) attack phenanthridine readily, but active Grignard reagents such as benzylmagnesium chloride can also add to the...
ortho-, meta- and para-hydroxybenzeneboronic acids and/or anhydrides were prepared by the reaction of tri-n-butyl borate with the corresponding organolithium compounds. The properties of the three "isomers" (boronic acid or anhydride), including anhydride formation ability, were found to vary considerably. The preparation of 2-(m-bromophenoxy)-tetr...
Condensation of p-terphenyl-4-yllithium and 4,4′-biphenylenedilithium with 2-, 3- and 4-methylcyclohexanone, followed by dehydration, has been used to synthesize monomethyltetrahydro-p-quaterphenyls and dimethyloctahydro-p-quaterphenyls, respectively. The corresponding p-quaterphenyl derivatives are formed by dehydrogenation with chloranil. The eff...
Allylmagnesium bromide readily added in a 1,2-manner to the structurally related systems, N-diphenylmethyleneaniline (I), fluorenone anil (VIII) and 6-phenylphenanthridine (IX). The structure of the product from I was demonstrated by an unambiguous synthesis. The mechanism of 1,2-addition to the azomethine linkage is discussed and an explanation is...
Direct preparations for 2-chloro- (II), 2,7-dichloro- (III), 2,7-dibromo- (VI) and 2,3,7,8-tetrabromo-dibenzo-p-dioxin (VIII) from dibenzo-p-dioxin (I) are reported. The 1-bromo-dibenzo-p-dioxin (IV) and the 2-iodo-dibenzo-p-dioxin (IX) are obtained by indirect methods. II, IV, VI, VIII and IX are new compounds. Structure proofs for these and 2,8-d...
In the interaction between allylmagnesium bromide and certain aza-aromatic heterocycles, the following reactivity series was observed: pyridine < quinoline ≃ isoquinoline < phenanthridine ≃ N-benzylideneaniline ≃ acridine < quinoxaline. Proof of structure of the resulting allyl derivatives was accomplished by synthesis, degradation and infrared ana...
1-Hydroxythianthrene was prepared in greatly improved yield by a modification of an earlier procedure. The treatment of the phenol with nitric acid (sp. gr. 1.2) in glacial acetic acid at reflux temperature resulted in the formation of 2,4-dinitro-1-hydroxythianthrene-5(or 10)-oxide in 61-65% yield. Reduction of the sulfoxide with hydrogen bromide...
Thianthrene-5-dioxide was metalated in the 4- and/or 4,6-positions by n-butyllithium. Phenyllithium metalated the sulfone in the 4,6-positions. Metalation of thianthrene was checked and 1-thianthrenecarboxylic acid and 1-aminothianthrene were obtained in greater purity, and the orientation of the lithium atom in the thianthrenyllithium was establis...
The action of some organometallic compounds on thianthrene-5-oxide was studied. The reported conversion of this sulfoxide to dibenzothiophene, by the action of n-butyllithium at low temperature, was found to be a very rapid reaction. Methyllithium reduced thianthrene-5-oxide to give a 60% yield of thianthrene, while ethyl- and n-butyl-magnesium bro...
Thianthrene was oxidized to thianthrene-5-oxide in good yields by treatment with negatively substituted benzenediazonium salts in glacial acetic acid. The best results were obtained with o- and p-nitrobenzenediazonium sulfates. Thianthrene was prepared in improved yields by a modification of an earlier procedure.
One molar equivalent of bromine and thianthrene gave 2-bromothianthrene in fair yield, while two molar equivalents of bromine and thianthrene gave a mixture of 2,7- and 2,8-dibromothianthrene. The same isomeric mixture was obtained by the action of bromine on thianthrene-5-oxide, and of hydrobromic acid on thianthrene-5,10-dioxide. Bromine did not...
The action of hydrohalic acids on 10-ethylphenothiazine-5-oxide was studied. With hydrochloric acid 3-chloro-10-ethylphenothiazine was obtained in improved yield. Hydrobromic acid gave a compound which was shown to be 3-bromo10-ethylphenothiazine; hydriodic acid produced 10-ethylphenothiazine and a salt of 10-ethylphenothiazine-5-oxide and hydriodi...
Diphenyldiallyltin, triphenylallyltin, and diphenyldi-4-pentenyltin have been prepared for the first time. Diphenyldiallyllead and triphenyl-4-pentenyltin were too unstable to be obtained pure. The free-radical-catalyzed addition of triphenylsilane or triphenylgermane to olefinic organotin and organolead compounds was unsuccessful. Only starting ma...
Citations
... There are many classical methods available, e.g., via the Schmidt reaction [13][14][15][16], the Ullmann reaction [17], and the Beckmann rearrangement reaction [18,19], dienonephenol rearrangement [20], and intramolecular rearrangement reaction [21]. In addition, phenanthridinones can be constructed through dichromate oxidation [22], internal cyclisation of a benzyne intermediate [23][24][25], and other conventional methods [26,27]. However, these classical reactions have their limitations due to the requirement of additional steps for the synthesis of the key starting materials, and the generally poor to moderate overall yields. ...
... [27] Phenazines can be conveniently modified by various synthetic methods to form disubstituted 5,10dihydrophenazines which are highly electron-rich and redoxactive compounds. [28][29][30][31] Dihydrophenazine derivatives, especially 5,10-diaryl-5,10-dihydrophenazines, are readily able to form very persistent radical cation species under specific conditions, such as irradiation, heat, electrolysis, and chemical reactions. [32][33][34][35] Because of their remarkable redox activity and ability to generate stable radical cations, dihydrophenazines feature unique optical, electronic, magnetic, and chemocatalytic properties. ...
... All the other compounds were the best available reagent grade and used without further purification. Thianthrene 5-oxide was prepared from thianthrene following the literature protocol, [16] and its purity was confirmed by 1 H NMR spectroscopy. ...
... All other chemical reagents were obtained from TCI Ltd and used as received. The monomers 2,8-dibromothianthrene-5,5',10,10'-tetraoxide, [51,52] 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene, [19,45] and 2,7-bis(4,4',5,5'-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene [46] were prepared in accordance with the reported methods. ...
... Unless otherwise stated, all reagents were obtained from commercial sources and were used without further purification. The compounds 10-ethyl- phenothiazine-5-oxide (7) [11], phenothiazine-5-oxide (5) [11], and phenothiazine-5,5-dioxide (6) [12] were all made using literature methods. ...
... [10][11][12][13][14][15][16][17][18][19][20] The addition of organolithium compounds to the C=N bond of pyridine and related nitrogen heterocycles is a well-established reaction. [21][22][23][24] In particular, organolithium reagents undergo 1,2-addition to pyridine and quinoline. 25 In some cases addition is followed by electrophilic addition at position 5 of pyridine to give 2,5-disubstituted 2,5-dihydropyridines, 26,27 which are known to be unstable. ...
... synthesised by Dr.J.B. Greig according to the method ofGilman and Dietrich (1957). 1,2,3,4-tetrachlorodibenzo-p-dioxin was prepared from catechol (Fluorochem Ltd) and pentachloronitrobenzene (Lancaster Synthesis Ltd), with potassium carbonate and acetone catalysis under nitrogen, according to the method ofPohland and Yang (1972). ...
... Even after three cycles of such dissolution and freeze-drying process, the CSA aerogel still possesses compression strength of no less than 0.10 MPa, which is acceptable considering that many recently reported aerogel materials show their strengths are lower than this value [50][51][52]. The probable cause for such decline in mechanical property is the hydrolysis of CS molecular chains in acidic solution during the repeated dissolution process that has led to the decrease of molecular weight, since some other studies on CS have also reached similar conclusions [53][54][55]. Compared with other chitin/chitosan aerogels [12,37,56], the advantages of such electrostatic assembled CSA aerogel include not only rapid self-healing capacity, but also easy processability as well as excellent sustainability. ...
... Our calculations suggest that the ν(BO) mode is also manifested by the rather strong bands observed in the range of 1457−1370 cm −1 . Santucci et al. 79 and Faniran and Shurvell 78 have assigned the band in the spectral range between 1103 and 1082 cm −1 to the Figure S1). The −BO 2 out-of-plane and in-plane deformations give rise to the absorptions at approximately 631 and 590 cm −1 . ...
... Among various organic transformations in water, [2] Suzuki-Miyaura (S-M) cross-coupling [3] and Aldol condensation (AC) reactions [4] occupy esteemed positions as both reactions tend to enrich molecular diversity by formation of C À C and C=C bonds, respectively. However, cascade reactions involving Suzuki-Miyaura cross-coupling and Aldol condensation reactions in one pot in an aqueous environment for the generation of biarylchalcones (C 6 -C 6 -C=C-CO-C 6 ) is an important but still challenging transformation because of oxidative scission of the double bond in the presence of palladium catalysts, [5] the dehydroboration of boronic acids with water at elevated temperatures, [6] and the formation of b-arylated ketones as a side product. [7] Biarylchalcones have gained significance in the field of medicinal chemistry because of their anticancer activities [8] ( Figure 1). ...
