Mannich Bases Prepared from Steroids

deStevens, George; Halamandaris, Angela

doi:10.1021/jo01064a075

Cited by 10 publications

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“…The application of the Mannich reaction to steroids up until 1959 had been limited to a report by Julian on the preparation of 16-dimethylamino dehydroisoandrosterone. With my highly capable associate Angelina Halamandaris, we began to explore the synthesis of 2-substituted Mannich bases of 17-p-hydroxy-5a-androstane-3-one [29]. The Mannich bases so formed were devoid of hormonal activity.…”

Section: Steroidsmentioning

confidence: 99%

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Heterocyclic diversity: The road to biological activity

deStevens

1995

Progress in Drug Research / Fortschritte Der Arzneimittelforschung / Progrès Des Recherches Pharmaceutiques

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Section: Steroidsmentioning

confidence: 99%

“…The Mannich bases so formed were devoid of hormonal activity. However, it was of theoretical interest to study their brominations under kinetically controlled conditions [30]. Due to unfavorable 1,3-diaxial interaction, it was anticipated that the boat form would prevail (Figure 23).…”

Section: Steroidsmentioning

confidence: 99%

Heterocyclic diversity: The road to biological activity

deStevens

1995

Progress in Drug Research / Fortschritte Der Arzneimittelforschung / Progrès Des Recherches Pharmaceutiques

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“…The two isomers were characterized a s their picrates. Lithium aluininium hydride reduction of vinylogous ainides may lead t o loss of the carbonyl oxygen ( 5 , 6) or t o the production of aminoalcohols or aminoltetones (7)(8)(9).…”

Section: -(2-mentioning

confidence: 99%

SYNTHESIS OF 8-AZA-D-HOMO-18-NORESTRONE METHYL ETHER

Nelson¹,

Tamura²

1965

Can. J. Chem.

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Alkylation of the potassium salt of 1,4-dihydro-2,6-dimethoxybenzene with 2-(2-bromoethy1)piperidine yielded the bis-en01 ether I, which, on acid hydrolysis, afforded the crystalline vinylogous a~n i d e 11. Lithium aluminium hydride reduction of I1 gave two isomers of 1,2,3,4,4a,5.6,6a,8,9,10,10a-dodecahydro-7H-be1o[c]quioii-7-oie (111). A similar series of reactions starting with 1-(2-chloroethyl)-6-methoxy-l,2,3,4-tetrahydroisoquinoli1~e hydrochloride (V) gave two isoniers of 2,3,4, &, 6,7,11b,12,13,13a-decahydro-l)-mcthoxy-1H-di-In an earlier report (1) we described some nitrogen-containing tricyclic analogues of 18-nor-D-homoestrone having anti-inflammatory activity. This pharmacological finding prompted us to prepare some of the corresponding tetracyclic analogues. The preparation of two isomers of 2,3,4,4a,6,7,11b,12,13,13a-decahydro-9-1nethoxy-1H-dibenzo[a,f]-quinolizin-1-one (8-aza-D-homo-18-norestrone inethyl ether) (IX) is the subject of this paper.A number of years ago we (2) prepared 1-(2-hydroxyethyl)-6-methoxy-l,2,3,4-tetrahydroisoquinoline (IV) in anticipation of utilizing it a s a n intermediate in the preparation of IX. At the outset of the present work we utilized the more readily available 2-(2-11ydroxyethyl)piperidine (3) as a model of IV in our effort to elaborate two additional rings corresponding to the C and D rings of a steroid.2-(2-Hydroxyethy1)piperidine was converted t o 2-(2-broinoethy1)piperidine hydrobromide in 83% yield using hot 48% hydrobroinic acid. Conversion of 2-(2-hydroxyethy1)piperidine hydrobromide t o the corresponding 2-bromoethyl derivative was also effected using phosphorus tribromide (29y0 yield) or thionyl bromide (69y0 yield).Alkylation of the potassium salt of 1,4-dihydro-2,G-diinethoxybenzene (4) with 2-(2-bromoethy1)piperidine in liquid ammonia proceeded smoothly, giving 2-[2-(1,4-dihydro-2,5-dimethoxyphenyl)ethyl]piperidine (I). Hydrolysis of the bis-en01 ether was accompanied by cyclization of the intermediate dilietone, yielding the tricyclic vin\-logous amide 11 in 71y0 yield. Treatment of I1 with lithium aluminium hydride resulted in a net reduction of the carbon-carbon double bond, thereby giving a crystalline isomer (isomer A) of 111 in 44y0 yield and a liquid believed to represent a second isomer (isomer B) of I11 in 36(& yield. The two isomers were characterized a s their picrates. Lithium aluininium hydride reduction of vinylogous ainides may lead t o loss of the carbonyl oxygen ( 5 , 6) or t o the production of aminoalcohols or aminoltetones (7-9).The conversion of I1 to 111 can be pictured as a 1,4-reduction or a 1,2-reduction followed by hydrolysis of the ellanline to a 3-hydroxycyclohexenone, elimination of water, and finally a AIichael addition of the nitrogen t o the intermediate 2-substituted cyclohexenone. On the basis of a closely related example (9), the l,4-reduction rnechanisnl is t o be preferred.

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“…The ultraviolet spectrum of compound No. 4 with its unsubstituted amino group is different, showing maxima at 245 and 352 µ. Compound No.…”

Section: ™Xmentioning

confidence: 99%

“…Consecutive recrystallizations from methanol-benzene, benzene-ether, and from methanol three times afforded 0.52 g. of yellow crystals described as compound No. 4 of Table II.…”

Section: ™Xmentioning

confidence: 99%

Preparation of Some Steroidal Enamines¹

Clinton¹,

Manson²,

Stonner³

et al. 1962

J. Org. Chem.

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6 a,7 a-Oxido-ßß, 16a-dimethylpregnan-5 a-ol-3,20-dione (XIV). (a) By oxidation of 6,16a-dimethyl-Ar,-pregnene-33,-5a-diol-20-one (XIa). A solution of compound XIa (0.6 g., m.p. 176-17" +]d +50°) in acetone (60 cc.) was oxidized over a perio -5 min. by titration with 8 N chromic acid in 8 V sulfuric acid8 at 0 to 5°. Addition of water and extraction with ethyl acetate gave a semicrystalline residue. This material was chromatographed on neutral alumina (30 g.) whereby elution with benzene afforded a compound (350 mg.) with m.p. 235-245°. An analytical sample of the oxido ketone XlV was obtained by crystallization from acetone-ether: needles with m.p. 252-253°, [a]o +40.4°, vma, 3650, 1720, 1700 cm.-1. It showed no selective high ultraviolet absorption.

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Mannich Bases Prepared from Steroids

Cited by 10 publications

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Heterocyclic diversity: The road to biological activity

Heterocyclic diversity: The road to biological activity

SYNTHESIS OF 8-AZA-D-HOMO-18-NORESTRONE METHYL ETHER

Preparation of Some Steroidal Enamines¹

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Mannich Bases Prepared from Steroids

Cited by 10 publications

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Heterocyclic diversity: The road to biological activity

Heterocyclic diversity: The road to biological activity

SYNTHESIS OF 8-AZA-D-HOMO-18-NORESTRONE METHYL ETHER

Preparation of Some Steroidal Enamines1

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Preparation of Some Steroidal Enamines¹