Showing papers on "Diazomethane published in 1972"
TL;DR: Aryl(chloromethyl)thallium dichlorides with diazomethane have been obtained by treatment of arylthalliam dichloride with tetramerethyltin this paper.
26 citations
TL;DR: In this paper, a 0.2 M solution of trimethylanilinium hydroxide in methanol and injecting the solution into a gas chromatograph was used to form methyl esters.
Abstract: Fatty acid methyl esters may be formed by dissolving the fatty acids in a 0.2 M solution of trimethylanilinium hydroxide in methanol and injecting the solution into a gas chromatograph. The reaction is rapid and quantitative, and the reagent appears to be less hazardous than diazomethane.
20 citations
TL;DR: The most predominant species of lamb liver phosphatidylinositol is the monoenoic followed by the tetraenoic (17%).
Abstract: 1. Two methods for the fractionation of phosphatidylinositol into molecular species were developed. In addition to preserving the fatty acid moiety of the molecule, the first method preserves the phosphorus, and the second preserves both the phosphorus and inositol ring. 2. In the first method, phosphatidylinositol was oxidized with periodate and the products reacted with diazomethane. I.r. examination showed that the main product was identical with dimethylphosphatidic acid. Fractionation to molecular species was carried out on thin layers impregnated with silver nitrate. The fatty acid composition of the species was determined by gas-liquid chromatography, and their distribution in lamb liver phosphatidylinositol was studied by a method using [(3)H]methanol. 3. In the second method, phosphatidylinositol was acetylated under mild reaction conditions. The major product was the triacetylated derivative of this phospholipid. This was reacted with diazomethane and the methylated-triacetylated phosphatidylinositol was fractionated into molecular species on silver nitrate-impregnated thin layers. Solvent mixtures containing acetone and distilled chloroform were found most suitable for this purpose. The fatty acid composition of the molecular species was determined by g.l.c., and their distribution in lamb liver phosphatidylinositol was studied by a method using [1-(14)C]acetic anhydride during the acetylation reaction. 4. Results from both methods agree fairly well. The most predominant species of lamb liver phosphatidylinositol is the monoenoic (60%) followed by the tetraenoic (17%). The di- and tri-enoic species existed as minor components.
17 citations
TL;DR: In this article, a new compound was synthesized by methylation of 2,3,3',4,4'-penta-O-acetylsucrose with diazomethane and boron trifluoride with subsequent deacetylation.
Abstract: 1',6,6'-Tri-O-methylsucrose, a new compound, has been synthesized by methylation of 2,3,3',4,4'-penta-O-acetylsucrose with diazomethane and boron trifluoride with subsequent deacetylation. 2,3,3',4,4'-Penta-O-methylsucrose has been obtained in improved yield from the tri-O-trityl derivative by reduction with lithium in liquid ammonia. A major product of the incomplete methylation of 11,6,6'-tri-O-tritylsucrose was the 2,3,3',4'-tetra-O-methyl derivative, and after reductive detritylation 2,3,3',4'-tetra-O-methylsucrose, a new compound, was isolated and identified by examination of its hydrolysis products.
14 citations
TL;DR: In this article, a treatment of 5-arylideneisorhodanines with GRIGNARD reagents, effects addition of the reagent to the double bound of the lateral chain to yield products, proved to have structure 2.
Abstract: Treatment of 5-arylideneisorhodanines 1 with GRIGNARD reagents, effects addition of the reagent to the double bound of the lateral chain to yield products, proved to have structure 2.
The thiono group in 1 and 2 condenses with aniline to yield the corresponding 5-substituted-4-phenylimino-2-thiazolidinones 3 and 4.
Alkylation of 1 and 2 with alkyl halides or with ethereal diazomethane results in the formation of the S-alkyl derivatives 5 and 6, respectively.
14 citations
13 citations
TL;DR: In this article, two parallel, first-order processes were used to decompose Δ3-1,3,4-Oxadiazolin-2-ones in moderate temperatures, either neat or in solution.
Abstract: Δ3-1,3,4-Oxadiazolin-2-ones are decomposed at moderate temperatures, either neat or in solution, by two parallel, first-order processes. One of these results in the formation of the appropriate diazomethane and carbon dioxide while the other leads to ketone, nitrogen, and carbon monoxide. Rates of these competing processes are reported along with some solvent effects and substituent effects on the product ratios.
12 citations
TL;DR: The conditions required for qualitative and quantitative methylation of saturated and unsaturated aliphatic and aromatic polybasic acids with diazomethane were studied in this article, where it was found to be advantageous to replace diethyl ether by dioxan as the solvent for both sample and reagent for the quantitativemethylation of alophatic saturated and aromatic acids.
12 citations
TL;DR: A re-examination of some recently reported studies by Ito et al. as discussed by the authors showed that diazomethane has no effect on barbituric acid, 1-methylbarbiturric acid, and 5-ethyl-and 5-phenyl barbiturate acids.
Abstract: A re-examination of some recently reported studies by Ito etal. (1) of the action of diazomethane on barbituric acid, 1-methylbarbituric acid, and 5-ethyl- and 5-phenylbarbituric acids has resulted...
11 citations
10 citations
TL;DR: The arylhydrazono-malodinitriles 9 react with GRIGNARD reagents to yield the imino derivatives 10.==================�============龍円��============\/\/\/\/\/\/£££€££/$££$££ £££
Abstract: The arylhydrazones of ethyl α-oxo-cyanoacetate 1a–e and the α-arylhydrazones of β-phenyl-α,β-diketopropionitrile 2a–e, react with GRIGNARD reagents at room temperature to yield the cyanocarbinols 3a–h. On the other hand, 1 and 2 react with phenylmagnesium bromide in refluxing ether-benzene mixture, to yield the imino derivatives 4a–d. 3a–e are dehydrated by hot acetic acid to yield compounds 5a–d. Similar treatment of 41–d affords the α-arylazo-β-phenylchalcones 6a–d which react with hydroxylamine to yield isoxazoline derivatives 7a–d.
Treatment of 1b, d with ethereal diazomethane results in the formation of the N-methylarylhydrazones 8a, b.
The arylhydrazono-malodinitriles 9 react with GRIGNARD reagents to yield the imino derivatives 10.
TL;DR: In this article, the S2 symmetry of 5 was established by the reaction of Quinones and α-Dicarbonyl Compounds with Diazoalkanes, which was shown to be the dehydrogenation product 5 of 2.
Abstract: p-Benzochinon liefert mit atherischer Diazomethanlosung, wie zuerst v. Pechmann fand, sofort ein beim Abfiltrieren meistens verpuffendes Addukt 2 (oder 4), das sich im Reaktionsgemisch langsam, mit Alkali rascher in ein schwerlosliches Produkt umwandelte, welches er fur ein Isomeres hielt. Es wird nun gezeigt, das es ein Dehydrierungsprodukt (5) des Addukts 2 ist. Zugabe von Dehydrierungsmittel erhoht die Ausbeute an 5 erheblich. 5 entsteht auch uber zersetzliche Addukte hinweg aus Mono-, am besten aus 2.5-Dihalogen-benzochinonen 7 mit Diazomethan, was die S2-Symmetrie fur 5 beweist. Diazoathan reagiert analog; Diazoessigester liefert den Diester 14, der durch Hydrolyse und Decarboxylierung ebenfalls 5 ergibt.
Reactions of Quinones and α-Dicarbonyl Compounds with Diazoalkanes, XX
On the Structure of the Products Obtained by H. v. Pechmann from the Reaction of Diazoalkanes with p-Benzoquinone and of some Derivatives
p-Benzoquinone reacts with diazomethane to form the instable adduct 2 (or 4) first obtained by v. Pechmann. Upon standing in the reaction mixture 2 is slowly converted via a redox process into a very stable product, which is shown to be the dehydrogenation product 5 of 2. The conversion is catalyzed by alkali, and the addition of a dehydrogenating agent greatly improves the yield. 5 is also formed by the reaction of mono- or better 2.5-dihaloquinones 7 with diazomethane, a route which establishes the S2 symmetry of 5. Diazoethane shows analogous behavior towards 1 and 7. Diazoacetic ester gives the diester 14, which by hydrolysis and decarboxylation also affords 5.
TL;DR: In this paper, the behavior of 2,4-dimethoxypyrimidine (3), 4,6-dimethyl-oxy-6-oxopyridine (4), 2, 4, 6-dimethyltimethyl-trimethoxymidine (5), and 6-chloro-2, 4-dimETHoxypyrimidine (6) were studied by p.m.r. spectrometry.
Abstract: 1-Ethyl-1,6-dihydro-2,4-dimethoxy-5-methyl-6-oxopyrimidine (1a) and 1,5-diethyl-1,6-dihydro-2,4-dime-thoxy-6-oxopyrimidine (2a) are shown to be the correct positional isomers, respectively, for the major O,O-dimethyl derivatives isolated from the reaction products of 1-ethyl-5-methylbarbituric acid (1) and the new 1,5-diethylbarbituric acid (2) with excess diazomethane. In addition to the above compounds, the behavior of 2,4-dimethoxypyrimidine (3), 4,6-dimethoxypyrimidine (4), 2,4,6-trimethoxypyrimidine (5), and 6-chloro-2,4-dimethoxypyrimidine (6) were studied by p.m.r. spectrometry in various solvents. The relatively new shift reagent, Eu(fod)3 was used in these studies because of its affinity for weak electron donors such as ethers.
TL;DR: In this article, a new and convenient method for the synthesis of 4-indolecarboxylic acid (4-CARB) was proposed, which was started with the reduction of 3-nitrophthalimide (4) with sodium borohydride, followed by hydrolysis of the product to obtain 3-hydroxy-4-nitropthalide (6) and it was saponified to the desired 1.
Abstract: As a new and convenient method for the synthesis of 4-indolecarboxylic acid (1), the synthesis was started with the reduction of 3-nitrophthalimide (4) with sodium borohydride, followed by hydrolysis of the product to obtain 3-hydroxy-4-nitrophthalide (6). Treatment of 6 with 2 moles of diazomethane gave 2-methoxycarbonyl-6-nitrostyrene oxide (7) whose reductive cyclization afforded methyl 4-indolecarboxylate (2) and it was saponified to the desired 1.
01 Jan 1972
TL;DR: In this article, a 3-necked flask equipped with a stirrer and a thermometer is used to add a few mg of d -mannose to 100 ml of acetic anhydride followed by 8 drops of 70% perchloric acid.
Abstract: Publisher Summary This chapter discusses the methylation of diazomethane–boron trifluoride etherate. The use of diazomethane–boron trifluoride etherate reagent to methylate partially acylated sugars gives the methyl ethers of aldoses in yields between 70% and 90% and without acyl migration. The procedure is exemplified by the preparation of 2-O-methyl- d -mannose. methylating agents (3-5), frequently gives rise to acyl migration. In a 3-necked flask equipped with a stirrer and a thermometer, a few mg of d -mannose is added to 100 ml of acetic anhydride followed by 8 drops of 70% perchloric acid. To this yellow solution, 26.4 g of d -mannose is added portion-wise with continuous stirring during 20 min, while the temperature is kept at 40°–45°. Lastly, the solution is evaporated to dryness, and the residue (9.52 g) is crystallized and recrystallized from anhydrous ether.
TL;DR: In this article, 6-Phenyl-3-methylmercapto-5-oxo-4,5-dihydro-1,2,4-triazine 4a reacts with phenylmagnesium bromide to form 5, 1a and 2g.
Abstract: 3-Mercapto-5,6-diphenyl-1,2,4-triazine 1a reacts with GRIGNARD reagents to give 2b–g. 6-Phenyl-3-mercapto-5-oxo-4,5-dihydro-1,2,4-triazine 4a reacts with phenylmagnesium bromide to form 5, 1a and 2g. 6-Phenyl-3-methylmercapto-5-oxo-4,5-dihydro-1,2,4-triazine 4b reacts with phenylmagnesium bromide to give 1b. Compound 1b reacts with methyl- and /or ethylmagnesium iodide to give 2h and 2c respectively. Compounds 1b, 4b and 2h react with hydrogen peroxide to give 6, 7 and 3a respectively. The reactivity of the CN in position 4,5 in 1a has been further illustrated by its ready reduction with p-thiocresol to give 2a. The action of ethereal diazomethane on 1a gives 1b.
TL;DR: The action of Me2NHAlCl3 on acylferrocenes is a convenient route to ferrocenylimmonium ions FcC(R) N + Me2.
TL;DR: In this article, a ring-hydroxylated, stable diazonium salt was derived from tetrafluoroanthranilic acid with nitrosylsulfuric acid in acetic acid.
Abstract: Diazotization of tetrafluoroanthranilic acid with nitrosylsulfuric acid in acetic acid gave a ring-hydroxylated, stable diazonium salt 4, which was isolated in high yield. Several reactions on this diazo compound were carried out. Replacement of the diazonium group with hydrogen, chlorine, or bromine was accomplished with the usual reagents. The reaction of diazo compound with diazomethane afforded a benzoxadiazine compound 13. Other related polyfluoroaromatic compounds were prepared.
TL;DR: In this paper, the following new compounds have been prepared: 2α-, 4α, 4β-, 6β, 6β- and 12α-hydroxy-5α-androstanes; the acetates of these alcohols and of the 1α-, 1β-, 2β-, 12β-, 15α- and 15β-hydroxynodes; 3α, and 3β-hexylhexyloxynodes (3β-and-hexynodes) 5α androst-1-ene; a series of esters and ethers
Abstract: The following new compounds have been prepared: 2α-, 4α-, 4β-, 6β- and12α-hydroxy-5α-androstanes; the acetates of these alcohols and of the 1α-, 1β-, 2β-, 6α-, 12β-, 15α- and 15β-hydroxy-5α-androstanes; 3α- and 3β-hydroxy-5α-androst-1-ene and 1β-hydroxy-5α-androst-2-ene; a series of esters and ethers derived from the 3-hydroxy-5α-androstanes. Some methoxy-5α-androstanes were obtained conveniently from the alcohols with diazomethane.
TL;DR: In this paper, the N -acetyl group of benzyl 2-acetamido-4,6- O -benzylidene-α-d -glucopyranoside with ethanolic potassium hydroxide gave the free crystalline amine.
TL;DR: In this paper, the authors describe the catalysts of cobalt molybdate catalysts for disproportionation of propene parallel activities for converting diazomethane into nitrogen and ethylene.
Abstract: Activities of cobalt molybdate catalysts for disproportionation of propene parallel activities for converting diazomethane into nitrogen and ethylene.
TL;DR: In this article, the synthesis of 5-nitro-2-furonitrile compounds from 3-N-acetyl (IIa) and N-morpholinomethyl compounds from acetic anhydride and when the Mannich reaction was utilized respectively.
Abstract: In a continuation of our previous papers concerning the syntheses with 5-nitro-2-furonitrile, 2-(5-nitro-2-furyl)vinyl-1,2,4-oxadiazoles and -1,2,3-triazoles were prepared from 3-(5-nitro-2-furyl)acrylonitrile (I). When I was treated with diazomethane in ether, 4-[2-(5-nitro-2-furyl)vinyl]-1,2,3-triazole (II) was obtained. II gave N-acetyl (IIa) and N-morpholinomethyl (IIb) compounds when treated with acetic anhydride and when the Mannich reaction was utilized respectively. 3-(5-Nitro-2-furyl)acrylamide oxime (III) was prepared by the usual method from I and hydroxylamine. The treatment of III with benzaldehyde and acid anhydrides or chlorides afforded 3-[2-(5-nitro-2-furyl)vinyl]-5-phenyl-4,5-dihydro-1,2,4-oxadiazoline (IV) and O-acyl-3-(5-nitro-2-furyl)acrylamide oximes (IIIa—IIIe) respectively. The O-acyl-amide oximes were found to cyclize to 3-[2-(5-nitro-2-furyl)vinyl]-5-alkyl-1,2,4-oxadiazole (V–VII) in their thermal analyses.
TL;DR: Urinary anthranilic acid was converted to methyl salicylate by treatment with nitrous acid and diazomethane, and was analysed by gas chromatography using an OV-17 column and it was found that a large amount of p-cresol was excreted in normal urine.
TL;DR: The corresponding 5-aroyl derivatives were obtained by reaction of aromatic carboxylic acid chlorides with 3-ethylrhodanine, and their chemical and physicochemical properties were studied as discussed by the authors.
Abstract: The corresponding 5-aroyl derivatives were obtained by reaction of aromatic carboxylic acid chlorides with 3-ethylrhodanine, and their chemical and physicochemical properties were studied. It is shown that they are completely enolized and stabilized by intramolecular hydrogen bonding; the side-chain carbonyl group undergoes enolization. Methylation with diazomethane gives O-ethers α-methoxyarylidene derivatives of 3-ethylrhodanine and S-ethers, which exist as dipolar ions.
TL;DR: Indoles may be obtained by treating o-acylanilines in ether-THF with diazomethane and MgI2(LiI) as discussed by the authors.
Abstract: Indoles may be obtained by treating o-acylanilines in ether–THF with diazomethane and MgI2(LiI) or with dibromomethane and Li–Hg.