Intermediacy of aryl radicals and arylmetal compounds in reductive dehalogenation of halogenoarenes with lithium aluminium hydride

1983 ◽  
pp. 905 ◽  
Author(s):  
Athelstan L. J. Beckwith ◽  
Swee Hock Goh
Keyword(s):  
Reductive Dehalogenation ◽  
Lithium Aluminium Hydride ◽  
Aryl Radicals ◽  
Lithium Aluminium

Flavan derivatives. XII. Conversion of Flavan-3,4-cis-diols into trans-Diacetates, and a new route to 3,4-trans-Diacetoxy-2,3-cis-flavans

1965 ◽  
Vol 18 (1) ◽  
pp. 90
Author(s):  
JW Clark-Lewis ◽  
LR Williams
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Bromine Atom ◽  
Potassium Acetate ◽  
Reductive Dehalogenation ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Convenient Route ◽  
In Cis

Reaction of trans-trans-3-bromoflavan-4-ols with ethanolic potassium acetate is shown to lead to 2,3-cis-3,4-trans-4-ethoxy- and -4-acetoxy-flavan-3-ols, as well as to 2,3-cis-flavan-3,4-trans-diols. Flavan-3,4-cis-diols are converted into 3,4-trans-diacetates by acetylation with a mixture of acetic acid, acetic anhydride, and potassium acetate. cis-cis-Flavan-3,4-diols are thus converted into 3,4-trans-diacetoxy-2,3-cis-flavans, and 2,3-trans-flavan-3,4-cis-diols give trans-trans-diacetates. Epimerization of cis-cis-glycols to cis-trans-diacetates provides the most convenient route to 3,4-trans-3',4'-dimethoxy-6-methyl-2,3-cis-flavan, and to the corresponding 4'-methoxy analogue, and reduction with lithium aluminium hydride then gives the 2,3-cis-flavan-3,4-trans-diols. 3',4'-Dimethoxy-6-methyl-2,3-cis-flavan-3,4-trans-diol prepared in this way was converted into the corresponding carbonate, which is the first example of a 2,3-cis-3,4-trans-carbonate and completes the set of the four possible racemates in this series. The bromine atom is unreactive in cis-cis-3-bromo-3',4'- dimethoxy-6-methylflavan, but reductive dehalogenation with lithium aluminium hydride gave the ,β-flavan-4-ol (2,4-cis).

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.

3-(s-Hydrindacen-4-yl)propylamines and 4-(s-hydrindacen-4-yl)butylamines; Synthesis and pharmacological screening

1981 ◽  
Vol 46 (8) ◽  
pp. 1800-1807 ◽  
Author(s):  
Zdeněk Vejdělek ◽  
Marie Bartošová ◽  
Miroslav Protiva
Keyword(s):  
Malonic Acid ◽  
Local Anaesthetics ◽  
Lithium Aluminium Hydride ◽  
Spasmolytic Activity ◽  
Lithium Aluminium ◽  
Malonic Acid Derivatives ◽  
Pharmacological Screening ◽  
Hydroxyethyl Piperazine

4-Chloromethyl-s-hydrindacene (VIIa) was transformed via the malonic acid derivatives VIIIa and IXa to the acid Xb which afforded in four steps the homological acid Xc. Reactions of chlorides of both acids (XIbc ) with dimethylamine, 1-methylpiperazine and 1-(2-hydroxyethyl)piperazine led to the amides XIIbc-XIVbc which were reduced with lithium aluminium hydride to the title compounds IVcd-VIcd. The amines obtained show central neuroleptic effects only in subtoxic doses; they are also potent local anaesthetics and have significant spasmolytic activity of the neurotropic as well as musculotropic type.

Substituted N,N-Dimethyl-3-(phenylthio)- and -4-(phenylthio)benzylamines

1992 ◽  
Vol 57 (1) ◽  
pp. 194-203 ◽  
Author(s):  
Karel Šindelář ◽  
Vojtěch Kmoníček ◽  
Marta Hrubantová ◽  
Zdeněk Polívka
Keyword(s):  
Serotonin Receptors ◽  
Hydrobromic Acid ◽  
Antidepressant Activity ◽  
Benzoic Acids ◽  
Lithium Aluminium Hydride ◽  
Acid Chlorides ◽  
Activity Inhibition ◽  
Lithium Aluminium ◽  
The Brain

(Arylthio)benzoic acids IIa - IIe and VIb - VId were transformed via the acid chlorides to the N,N-dimethylamides which were reduced either with diborane "in situ" or with lithium aluminium hydride to N,N-dimethyl-(arylthio)benzylamines Ia - Ie and Vb - Vd. Leuckart reaction of the aldehydes IX and X with dimethylformamide and formic acid afforded directly the amines Va and Ve. Demethylation of the methoxy compounds Ia and Ve with hydrobromic acid resulted in the phenolic amines If and Vf. The most interesting N,N-dimethyl-4-(phenylthio)benzylamine (Va) hydrochloride showed affinity to cholinergic and 5-HT2 serotonin receptors in the rat brain and some properties considered indicative of antidepressant activity (inhibition of serotonin re-uptake in the brain and potentiation of yohimbine toxicity in mice).

Selective O-Methyloxime Formation From 6-Methoxy-2-[(1'-methyl-2',5'-dioxocyclopentyl)-methyl]-3,4-dihydronaphthalen-1(2H)-one

1994 ◽  
Vol 47 (4) ◽  
pp. 649 ◽  
Author(s):  
DJ Collins ◽  
GD Fallon ◽  
CE Skene
Keyword(s):  
Lithium Aluminium Hydride ◽  
X Ray ◽  
X Ray Crystallography ◽  
Lithium Aluminium ◽  
Major Isomer ◽  
Toluenesulfonic Acid ◽  
Ester Formation ◽  
Diastereomeric Mixture ◽  
A Minor

Reaction of 6-methoxy-2-[(1′-methyl-2′,5′-dioxocyclopentyl)methyl]-3,4-dihydronaphthalen-1(2H)-one (4a) with 1 or 2 moles of O- methylhydroxylamine hydrochloride in pyridine gave (1′SR,2RS)-6-methoxy-2-[(1′-methyl-2′,5′-dioxocyclopentyl)methyl]-3,4-dihydronaphthalen-1(2H)-one (E)-2′-O-methyloxime (5a), or the corresponding 2′,5′-bis(O-methyloxime ) (6), respectively. A minor product from the formation of the bis (O- methyloxime ) (6) was the (Z) isomer (5b) of the mono(O- methyloxime ) (5a); the structure and stereochemistry of (5a) and (5b) were established by X-ray crystallography. Reduction of the keto bis (O-methyloxime ) (6) with 0.25 mole of lithium aluminium hydride gave a diastereomeric mixture of the corresponding alcohols (7a), of which the major isomer was characterized by ester formation. The bis (O-methyloxime ) (6) could be hydrolysed to the parent triketone (4a), but it resisted deprotection with cetyltrimethylammonium permanganate. Reaction of the triketone (4a) with 1 mole of 4-anisidine in the presence of 4-toluenesulfonic acid resulted in retro Michael cleavage with formation of 3-(4′-methoxyphenyl)amino-2-methylcyclopent-2-en-1-one (1).

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