Synthetic transformations of dimethyl perfluoro-4-methyl-2-pentenedioate

1982 ◽  
Vol 47 (12) ◽  
pp. 3418-3423 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Sodium Borohydride ◽  
Title Compound ◽  
Sodium Methoxide ◽  
Fluorine Atom ◽  
Synthetic Transformations

Reaction of the title compound I with methanolic sodium methoxide proceeded with decarboxylation and substitution of the vinylic fluorine atom, the resulting product being methyl 2,4,5,5,5-pentafluoro-3-methoxy-2-pentenoate (II). Compound I reacted with chlorine to give dimethyl 2,3-dichloro-2,3,4-trifluoro-4-trifluoromethylpentanedioate (III) which was selectively hydrolyzed to potassium 1-methyl 2,3-dichloro-2,3,4-trifluoro-4-trifluoromethylpentanedioate (IV). This ester salt was transformed in two steps into methyl 2,3-dichloro-4-fluoroformylhexafluoropentanoate (VIII). Pyrolysis of IV afforded methyl 2-chlorohexafluoro-3-pentanoate (V). Reduction of the diester III with sodium borohydride led to 3-chloro-2,3,4-trifluoro-2-hydroxymethyl-4-trifluoromethyloxolane (IX) and 2,3-dichloro-2,3,4-trifluoro-4-trifluoromethyl-1,5-pentane diol (X).

The synthesis of D-angolosamine

1977 ◽  
Vol 55 (6) ◽  
pp. 1100-1103 ◽  
Author(s):  
Hans H. Baer ◽  
Fawzy F. Z. Georges
Keyword(s):  
Sodium Borohydride ◽  
Catalytic Hydrogenation ◽  
Title Compound ◽  
Amino Glycoside ◽  
Starting Point ◽  
Simplified Procedure

The synthesis of 2,3,6-trideoxy-3-dimethylamino-D-arabino-hexose hydrochloride (10) (D-angolosamine, a constituent of the antibiotic, angolamycin) is described. First, a simplified procedure for the preparation of methyl 6-deoxy-α-D-glucopyranoside from methyl α-D-glucopyranoside is recorded. The deoxy derivative served as the starting point for sequential preparation of methyl 3,6-dideoxy-3-nitro-α-D-glucopyranoside (1), its 2,4-diacetate (2), its 4-monoacetate (3), its 2-O-mesyl-4-acetate (4), its 2-mesylate (5), and methyl 2,3,6-trideoxy-3-nitro-α-D-erythro-hex-2-enopyranoside (6) essentially according to procedures previously established (in part, in the L-series). Treatment of 5 or 6 with sodium borohydride produced methyl 2,3,6-trideoxy-3-nitro-α-D-arabino-hexopyranoside (7). Catalytic hydrogenation of 7 gave the corresponding 3-amino glycoside hydrochloride (8) which was hydrolyzed to furnish 3-amino-2,3,6-trideoxy-D-arabino-hexose hydrochloride (9) (D-acosamine, the enantiomer of a component of the antibiotic, actinoidin). N,N-Dimethylation of 8 followed by hydrolysis afforded the crystalline title compound (10).

Aril Azines. II. Hydrogenation of p-Tolil Monoazine

1975 ◽  
Vol 53 (5) ◽  
pp. 748-752 ◽  
Author(s):  
Peter Yates ◽  
E. M. Levi
Keyword(s):  
Hydrogen Atom ◽  
Carbon Atom ◽  
Sodium Borohydride ◽  
Sodium Methoxide ◽  
Major Product ◽  
Lead Tetraacetate ◽  
Ring Closure ◽  
Carbonyl Carbon Atom ◽  
Carbonyl Carbon ◽  
Independent Synthesis

Hydrogenation of p-tolil monoazine (1b) over palladium-on-charcoal gives as the major product 4,5-dihydro-5-(p-toluyl)-3,4,5-tri-(p-tolyl)-1H-pyrazol-4-ol (2b), which has previously been obtained by treatment of 1b with sodium methoxide. Several minor products are formed, which include p-tolualdehyde, p-toluic acid, and p-toluamide, p-tolunitrile, p-tolualazine, and 3,4,5-tri-(p-tolyl)-4H-pyrazo-4-ol (9). The structure of the last compound, which is also formed on reduction of 1b with sodium borohydride, was established by its independent synthesis from 1,2,3-tri-(p-tolyl)-1,3-propanedione by oxidation with lead tetraacetate followed by treatment with hydrazine. It is suggested that 2b arises via reduction of a C=N bond of 1b and aldol ring closure. The minor hydrogenation products are of interest in that their formation involves C—C hydrogenolysis; it is suggested that this is initiated by addition of a hydrogen atom to a carbonyl carbon atom of 1b.

Potential noncataleptic neuroleptic agents: Synthesis and pharmacology of 7-chloro-4-[4-(2-hydroxyethyl)piperazino]-4,5-dihydrothieno[2,3-b]-1-benzothiepin

1983 ◽  
Vol 48 (10) ◽  
pp. 2970-2976 ◽  
Author(s):  
Zdeněk Polívka ◽  
Martin Valchář ◽  
Miroslav Protiva
Keyword(s):  
Sodium Borohydride ◽  
Potassium Carbonate ◽  
Title Compound ◽  
Potassium Hydroxide ◽  
Dopamine Metabolism ◽  
High Dose ◽  
Chloro Derivative ◽  
Hydroxyethyl Piperazine ◽  
Central Depressant ◽  
Boiling Toluene

Heating of 2,5-dichloroacetophenone with 2-thiophenethiol, potassium carbonate and copper gave 5-chloro-2-(2-thienylthio)acetophenone (V) which was subjected to the Willgerodt reaction with sulphur and morpholine. The product was a mixture of the thiomorpholide VI and oxothiomorpholide VII. After a partial separation the predominanting product VI was hydrolyzed without characterization with ethanolic potassium hydroxide to give the acid VIII. Cyclization by treatment with phosphorus pentoxide in boiling toluene gave 7-chlorothieno[2,3-b]-1-benzothiepin-4(5H)-one (X) which was reduced with sodium borohydride to the alcohol XII. A reaction with hydrogen chloride in benzene led to the chloro derivative XIII whose substitution reaction with 1-(2-hydroxyethyl)piperazine afforded the title compound IV. The product has strong central depressant and discoordinating activity, a low cataleptic efficity but in a relatively high dose it does not influence the dopamine metabolism in the rat brain.

scholarly journals Isomerization of 1-exo-4,5,67,8,8-Heptachloro-2,3-endo-epoxy-3a,4,7,7a-methanoindane with Base

1971 ◽  
Vol 49 (21) ◽  
pp. 3569-3571 ◽  
Author(s):  
W. P. Cochrane ◽  
M. A. Forbes
Keyword(s):  
Reductive Dechlorination ◽  
Title Compound ◽  
Sodium Methoxide ◽  
Structure Elucidation ◽  
Secondary Alcohol ◽  
Major Product ◽  
Excess Sodium

Treatment of the title compound, 2, with excess sodium methoxide produced an unsaturated secondary alcohol, 3. Structure elucidation was achieved by MnO2 oxidation followed by CrCl2 reductive dechlorination to give as the major product 2-oxa-4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-4,7-methanoindane.

scholarly journals 2-Chloro-6-fluorophenyl 4-chlorobenzoate

IUCrData ◽  
2016 ◽  
Vol 1 (3) ◽  
Author(s):  
Yasser Hussein Issa Mohammed ◽  
S. Naveen ◽  
N. K. Lokanath ◽  
H. R. Manjunath ◽  
Mohammed Al-Ghorbani ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Title Compound ◽  
Fluorine Atom ◽  
Aromatic Rings ◽  
Compound C

In the title compound, C13H7Cl2FO2, the dihedral angle between the aromatic rings is 49.96 (12)° and the fluorine atom issynto the C=O group. In the crystal, the molecules are linked into [010] chains by C—H...O hydrogen bonds and weak C—H...Cl interactions link these chains into sheets parallel to the (101) plane.

3-Hydroxy-N,N-dimethyl-3-(2-thienyl)propanamine

2006 ◽  
Vol 62 (4) ◽  
pp. o1289-o1290 ◽  
Author(s):  
Min-Li Tao ◽  
Ai-Jun Li ◽  
Jian Wang ◽  
Jing Ma ◽  
Dong-Zhi Liu
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Sodium Borohydride ◽  
Title Compound ◽  
Compound C ◽  
Centrosymmetric Dimers

The title compound, C9H15NOS, was prepared by the reduction of 2-thienyl 2-(dimethylamino)ethyl ketone hydrochloride with sodium borohydride. In the crystal structure, O—H...N hydrogen bonds link pairs of molecules into centrosymmetric dimers.

C-Nucleosides and related compounds. VIII. Synthesis of 5-(4′β-hydroxymethyl-2′β,3′α-dihydroxycyclopent-1′β-yl)-6-azauracil

1976 ◽  
Vol 54 (18) ◽  
pp. 2925-2934 ◽  
Author(s):  
G. Just ◽  
R. Ouellet
Keyword(s):  
Double Bond ◽  
Title Compound ◽  
Sodium Methoxide ◽  
Alder Reaction ◽  
Oxidative Cleavage ◽  
Diels Alder ◽  
Keto Ester ◽  
Diels Alder Reaction ◽  
Related Compounds

Starting from the Diels–Alder reaction of trans-β-bromoacrylic acid with cyclopentadiene, a synthesis of the substituted bicycloheptene 8 is described. The stereochemistry of the substituents is clearly defined. Oxidative cleavage of the double bond in the compound 8c afforded an acid keto ester 10 that was treated with thiosemicarbazide. Treatment of the resulting thiosemicarbazone 11 with sodium methoxide gave a 3-thioxo-1,2,4-triazine-5-one compound that was converted into the title compound.

Reduction of aromatic nitrocompounds by sodium borohydride in methanol in the presence of sodium methoxide

Tetrahedron ◽  
1996 ◽  
Vol 52 (28) ◽  
pp. 9541-9552 ◽  
Author(s):  
Jerzy Suwiński ◽  
Pawel Wagner ◽  
Elizabeth M. Holt
Keyword(s):  
Sodium Borohydride ◽  
Sodium Methoxide ◽  
Aromatic Nitrocompounds

Preparation and some reactions of bis(2',3'-O-carbonyl-6-azauridine) 5',5''-carbonate

1988 ◽  
Vol 53 (7) ◽  
pp. 1568-1573 ◽  
Author(s):  
Pavel Drašar ◽  
Jiří Beránek
Keyword(s):  
Title Compound ◽  
Sodium Methoxide ◽  
Cyclic Carbonate

Reaction of 6-azauridine (I) with phosgene and hexamethylphosphoramide afforded the title compound II. Both its 2',3'-cyclic carbonate groups were selectively deblocked with methanolic sodium methoxide under preservation of the internucleoside carbonate bridge. The carbonate II was also converted into the 5',5''-carbonyloxybis(2,2'-anhydro) derivative III by heating with imidazole in N,N-dimethylformamide. Several analogues of II were prepared by reaction of 1,1'-carbonyldiimidazole with the corresponding nucleosides in N,N- dimethylformamide.

3-(4-Chlorophenyl)-6-methyl-1,6-dihydro-1,2,4,5-tetrazine

2006 ◽  
Vol 62 (7) ◽  
pp. o2875-o2876 ◽  
Author(s):  
Feng Xu ◽  
Wei-Xiao Hu ◽  
Wei Zhou ◽  
Chun-Nian Xia
Keyword(s):  
Sodium Borohydride ◽  
Title Compound ◽  
Boat Conformation ◽  
Compound C

The title compound, C9H9ClN4, was prepared from sodium borohydride and 3-(4-chlorophenyl)-6-methyl-1,2,4,5-tetrazine. The molecule can be considered to be homoaromatic. The tetrazine ring adopts an unsymmetrical boat conformation.

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