Phosphonium salts. II. The reaction of bis-phosphonium salts with metal hydrides

1969 ◽  
Vol 22 (7) ◽  
pp. 1399 ◽  
Author(s):  
JJ Brophy ◽  
MJ Gallagher
Keyword(s):  
Alkaline Hydrolysis ◽  
Metal Hydrides ◽  
Sodium Hydride ◽  
Lithium Aluminium Hydride ◽  
Phosphonium Salts ◽  
Lithium Aluminium

Ethane-1,2-bis-phosphonium salts are cleaved by sodium hydride to phos- phines in 55-80% yields with loss of the two-carbon bridge. The reaction is independent of the substituents at the phosphorus atoms. The same reaction is observed with an ethene-1,2-bis-salt and with but- 2-ene-1,4-bis(triphenylphosphonium) dibromide. It is suggested that a phosphorane is formed which subsequently fragments in a manner analogous to alkaline hydrolysis. ��� Lithium aluminium .hydride behaves similarly but loss of the bridge is competitive with loss of benzyl groups, and yields are generally better (> 70%).

(6,11-Dihydrodibenzo[b,e]thiepin-11-yl)methylamine, (4-methoxy-6,11-dihydrodibenzo[b,e]thiepin-11-yl)-methylamine and derivatives; Synthesis and pharmacological screening

1982 ◽  
Vol 47 (3) ◽  
pp. 984-993 ◽  
Author(s):  
Vladimír Valenta ◽  
Jan Metyš ◽  
Miroslav Protiva
Keyword(s):  
Formic Acid ◽  
Alkaline Hydrolysis ◽  
Antiinflammatory Activity ◽  
Primary Amines ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Methyl Derivatives ◽  
Curtius Reaction ◽  
Pharmacological Screening

Using the Curtius reaction, the acids VIa and VIv were transformed to the carbamates IVa and IVb which afforded by alkaline hydrolysis the primary amines Ia and Ib. The N-methyl derivatives IIab were obtained by reduction of the carbamates IVa with lithium aluminium hydride. The N,N-dimethyl derivatives IIIab resulted by methylation of the primary amines Iab with formaldehyde and formic acid. The synthesis of the acid VIb was carried out from phthalide and 2-methoxythiophenol in seven steps. The amines Iab-IIIab showed clear thymoleptic properties in the test of reserpine ptosis in mice and by inhibition of the perphenazine catalepsy in rats. The acid VIb has antiinflammatory activity.

Preparation of Phosphonomethyl Ethers Derived from 2-Phenylethanol and Its Amino Derivatives

1995 ◽  
Vol 60 (4) ◽  
pp. 659-669
Author(s):  
Marcela Krečmerová ◽  
Antonín Holý
Keyword(s):  
Antiviral Activity ◽  
Cell Cultures ◽  
Sodium Hydride ◽  
Amino Group ◽  
Lithium Aluminium Hydride ◽  
Adenine Ring ◽  
Lithium Aluminium ◽  
Amino Derivatives ◽  
Acyclic Nucleoside

A series of compounds derived from the acyclic nucleoside antiviral 9-(2-phosphonomethoxyethyl)adenine (PMEA), in which the adenine ring is replaced by phenyl, 4-aminophenyl, 3-aminophenyl or 3,5-diaminophenyl group, has been prepared starting from the corresponding phenethyl alcohols. 2-(3-Aminophenyl)ethanol was prepared from 3-nitrobenzoyl chloride using the Arndt-Eistert reaction. The primarily formed diazoketone Ia was converted into ethyl 3-nitrophenylacetate (IIa) which on catalytic hydrogenation afforded ethyl 3-aminophenylacetate (IIIa). Compound IIIa was reduced with lithium aluminium hydride to give 2-(3-aminophenyl)ethanol (IVa). 2-(3,5-Diaminophenyl)ethanol (IVb) was prepared analogously from 3,5-dinitrobenzoyl chloride. After protection of the amino group with dimethylaminomethylene group, the alcohol IVa was converted to diisopropyl 2-(3-aminophenyl)ethoxymethylphosphonate (XII) by reaction with sodium hydride and diisopropyl p-toluenesulfonyloxymethanephosphonate, followed by deprotection of the amino group by treatment with ammonia. Reaction of diisopropyl ester XII with bromotrimethylsilane gave free 2-(3-aminophenyl)ethoxymethylphosphonic acid (XVII). The same procedure, applied to the corresponding aminophenethyl alcohols, afforded: 2-(4-aminophenyl)ethoxymethylphosphonic acid (XVI) and 2-(3,5-diamino phenyl)ethoxymethylphosphonic acid (XVIII). The synthesized compounds were tested in vitro on cell cultures for the cytostatic and antiviral activity (HSV-1, HSV-2, VSV, VZV, CMV). No antiviral activity has been found for any of the compounds.

scholarly journals Reduction of Chalcones by Complex Metal Hydrides. III. Chalcone and Chain-deuterated Chalcones with Lithium Aluminium Hydride-Aluminium Chloride.

1969 ◽  
Vol 23 ◽  
pp. 2409-2413 ◽  
Author(s):  
Tapio Hase ◽  
Boris Holm ◽  
Johannes Thomsen ◽  
Károly Kovács ◽  
Alf A. Lindberg ◽  
...  
Keyword(s):  
Metal Hydrides ◽  
Aluminium Chloride ◽  
Lithium Aluminium Hydride ◽  
Complex Metal ◽  
Lithium Aluminium

scholarly journals Reduction of Chalcones by Complex Metal Hydrides. II. 4- and 4'-Methoxychalcone with Lithium Aluminium Hydride-Aluminium Chloride.

1969 ◽  
Vol 23 ◽  
pp. 2403-2408 ◽  
Author(s):  
Tapio Hase ◽  
Olav Smidsrød ◽  
Arne Haug ◽  
Terence Painter ◽  
J. Rydberg ◽  
...  
Keyword(s):  
Metal Hydrides ◽  
Aluminium Chloride ◽  
Lithium Aluminium Hydride ◽  
Complex Metal ◽  
Lithium Aluminium

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

1968 ◽  
Vol 46 (21) ◽  
pp. 3391-3397
Author(s):  
T. A. Dobson ◽  
M. A. Davis ◽  
A. M. Hartung
Keyword(s):  
Sodium Hydride ◽  
Ammonium Hydroxide ◽  
Grignard Reagents ◽  
Lithium Aluminium Hydride ◽  
Tertiary Alcohols ◽  
Lithium Aluminium

Treatment of the syn-epoxyamide 3 with either ammonium hydroxide or sodium hydride gives 10,11-dihydro-anti-11-hydroxy-10,5-(iminomethano)-5H-dibenzo[a,d]cyclohepten-13-one (1a). This compound is readily converted to the syn-epimer 1c by oxidation to 1b and subsequent hydrogenation. The ketone 1b reacts with Grignard reagents to give the tertiary alcohols 1k,l which undergo hydrogenolysis to give the 11-substituted lactams 1q,r. Reduction of the lactams with lithium aluminium hydride gives the corresponding amines.

Convenient Synthesis of (Z)-7- and (E)-9-dodecene-1-yl Acetate, Components of Some Lepidoptera Insect Sex Pheromone

2017 ◽  
Vol 68 (1) ◽  
pp. 180-185
Author(s):  
Adriana Maria Andreica ◽  
Lucia Gansca ◽  
Irina Ciotlaus ◽  
Ioan Oprean
Keyword(s):  
Sex Pheromone ◽  
Coupling Reaction ◽  
Coupling Scheme ◽  
Lithium Aluminium Hydride ◽  
Terminal Alkyne ◽  
Mercury Derivative ◽  
Lithium Aluminium ◽  
Convenient Synthesis ◽  
Practical Synthesis ◽  
Insect Sex

Were developed new and practical synthesis of (Z)-7-dodecene-1-yl acetate and (E)-9-dodecene-1-yl acetate. The routes involve, as the key step, the use of the mercury derivative of the terminal-alkyne w-functionalised as intermediate. The synthesis of (Z)-7-dodecene-1-yl acetate was based on a C6+C2=C8 and C8+C4=C12 coupling scheme, starting from 1,6-hexane-diol. The first coupling reaction took place between 1-tert-butoxy-6-bromo-hexane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-oct-7-yne, which is transformed in di[tert-butoxy-oct-7-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromobutane obtaining 1-tert-butoxy-dodec-7-yne. After acetylation and reduction with lithium aluminium hydride of 7-dodecyne-1-yl acetate gave (Z)-7-dodecene-1-yl acetate with 96 % purity. The synthesis of (E)-9-dodecene-1-yl acetate was based on a C8+C2=C10 and C10+C2=C12 coupling scheme, starting from 1,8-octane-diol. The first coupling reaction took place between 1-tert-butoxy-8-bromo-octane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-dec-9-yne, which is transformed in di[tert-butoxy-dec-9-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromoethane obtaining 1-tert-butoxy-dodec-9-yne. After reduction with lithium aluminium hydride of 1-tert-butoxy-(E)-9-dodecene and acetylation was obtained (E)-9-dodecene-1-yl acetate with 97 % purity.

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