Corticosteroid 17α-monoesters from 17α,21-cyclic orthoesters

Gardi, R.; Vitali, R.; Ercoli, A

doi:10.1016/s0040-4039(00)71749-7

Cited by 23 publications

(5 citation statements)

References 4 publications

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“…Analogous rearrangements of corticosteroid 17a-monoesters to the corresponding 21-monoesters has been postulated by Ringold, Rosenkranz & Sondheimer (1956), and reported by Gardi, Vitali & Ercoli (1961) for other steroids. 6/3-Hydroxylation has been reported to occur in mammalian liver (Axelrod & Miller, 1954;Mueller & Rumney, 1957), in adrenals (Haines, 1952;Meyer, Hayano, Lindberg, Gut & Rodgers, 1955), in the corpus luteum (Hayano, Lindberg, Wiener, Rosenkrantz & Dorfman, 1954) and in the placenta (Berliner & Salhanick, 1956).…”

Section: Discussionsupporting

confidence: 75%

ISOLATION AND IDENTIFICATION OF 6β, 17α, 21-Trihydroxy-6α-Methyl-Δ4-Pregnene-3,20-Dione (21-Acetate) FROM THE URINE OF HUMAN SUBJECTS TREATED WITH 6α-Methyl-17α-Acetoxyprogesterone

Castegnaro¹,

Sala²

1962

Journal of Endocrinology

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A new tetrazolium reducing compound, present as a conjugate which could be hydrolysed by \g=b\-glucuronidase, has been isolated from the urine of normal men and women and oophorectomized-adrenalectomized women, all of whom had received 100 mg./day 6\g=a\-methyl-17\g=a\-acetoxyprogesterone (MAP) either subcutaneously or orally. Detailed studies of its characteristics, including degradation reactions, ultraviolet and infrared spectra, combined with studies on known steroids, suggest that the new compound is 6\g=b\,17\g=a\,21-trihydroxy-6\g=a\-methyl-\g=D\4-pregnene-3,20-dione (21-acetate).It is suggested that MAP in vivo undergoes hydroxylation at C-21 in the absence of ovarian and adrenal tissue which up to the present have been considered essential for this metabolic process.

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Section: Discussionsupporting

confidence: 75%

ISOLATION AND IDENTIFICATION OF 6β, 17α, 21-Trihydroxy-6α-Methyl-Δ4-Pregnene-3,20-Dione (21-Acetate) FROM THE URINE OF HUMAN SUBJECTS TREATED WITH 6α-Methyl-17α-Acetoxyprogesterone

Castegnaro¹,

Sala²

1962

Journal of Endocrinology

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“…This gave 9.0 mg (52%) of 3a as a white solid; LIV max (CH,OH) 233 nm (a 53.4) (15); ir (KBr) 3 470, 3 230, 1 740-1 715, 1670, 1 620, 1 610, 1 280, 1 105-1 060, 890, 710 cm-l; nmr (DMSO-d,) 8 This material was prepared i n an identical manner as described for 4a except that the trimethylorthobenzoate was used without purification. The product of this reaction, as an oily residue, was dissolved in ethyl acetate and distributed equally on the appropriate number of 20 x 20 cm plates for preparative tlc.…”

Section: Betamethasone-i 243h 17-benzoate (3a)mentioning

confidence: 99%

Synthesis and purification of betamethasone‐1,2,4−³H and betamethasone‐1,2,4−³H 17‐benzoate

Merrill¹,

Vernice²

1971

J. Labelled Cpd. Radiopharm.

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“…Cyclic ortho esters derived from 17a,21-dihydroxy steroids hydrolyze under mild conditions to give mostly 17a-acyloxy-21-hydroxy derivatives from cyclic orthoacetates, orthopropionates, orthobutyrates, orthovalerates, and orthohexanoates (120, 122, 124, 124a, 254) and mixed 17a-and 21-formates from the cyclic orthoformates (97,98,120). Hydrolysis of 17a,21-cyclic ortho esters provides the only route to 17-acyloxy-21-hydroxy steroid derivatives (105a).…”

Section: A Synthetic and Other Applications Of Ortho Ester Hydrolysesmentioning

confidence: 99%

“…16,17-Alkoxyalkylenedioxy steroid derivatives (3) are readily hydrolyzed under acidic conditions (35,84,90,91,95,263); however, the ortho ester function is stable under conditions which cause acid hydrolysis of a 3-enol ether function (90). 17,21-Cyclic ortho ester derivatives of steroids (4) hydrolyze rapidly in aqueous methanolic hydrochloric acid (120)(121)(122) or aqueous solutions of carboxylic acids (97,98,124,254).…”

Section: Effect Of Structure On Reactivity In Ortho Ester Hydrolysismentioning

confidence: 99%

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

1970

Carboxylic Ortho Acid Derivatives - Preparation and Synthetic Applications

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In this chapter are considered reactions of trialkyl orthocarboxylates and tetraalkyl orthocarbonates which result in the formation of new carbonoxygen or carbon-halogen bonds. In most of these reactions the ortho ester (or an alkoxycarbonium ion derived from it) functions as an alkylating agent.Many of these reactions are useful synthetic tools. These include formation and hydrolysis of cyclic ortho ester derivatives of diols and triols (which serve to protect the hydroxyl groups of the polyols, and provide means for their mild monoacylation), alkylation of phenols, enols and acids (to form ethers and esters), and conversion of carbonyl compounds to acetals and ketals. Other reactions, such as the alkylation of halogens by ortho esters, are of only limited synthetic utility, while still others, such as the acidcatalyzed hydrolyses of ortho esters, are of interest primarily because of the light they shed on the mechanisms of reactions of ortho esters with nucleophilic reagents.

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Corticosteroid 17α-monoesters from 17α,21-cyclic orthoesters

Cited by 23 publications

References 4 publications

ISOLATION AND IDENTIFICATION OF 6β, 17α, 21-Trihydroxy-6α-Methyl-Δ4-Pregnene-3,20-Dione (21-Acetate) FROM THE URINE OF HUMAN SUBJECTS TREATED WITH 6α-Methyl-17α-Acetoxyprogesterone

ISOLATION AND IDENTIFICATION OF 6β, 17α, 21-Trihydroxy-6α-Methyl-Δ4-Pregnene-3,20-Dione (21-Acetate) FROM THE URINE OF HUMAN SUBJECTS TREATED WITH 6α-Methyl-17α-Acetoxyprogesterone

Synthesis and purification of betamethasone‐1,2,4−³H and betamethasone‐1,2,4−³H 17‐benzoate

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

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Corticosteroid 17α-monoesters from 17α,21-cyclic orthoesters

Cited by 23 publications

References 4 publications

ISOLATION AND IDENTIFICATION OF 6β, 17α, 21-Trihydroxy-6α-Methyl-Δ4-Pregnene-3,20-Dione (21-Acetate) FROM THE URINE OF HUMAN SUBJECTS TREATED WITH 6α-Methyl-17α-Acetoxyprogesterone

ISOLATION AND IDENTIFICATION OF 6β, 17α, 21-Trihydroxy-6α-Methyl-Δ4-Pregnene-3,20-Dione (21-Acetate) FROM THE URINE OF HUMAN SUBJECTS TREATED WITH 6α-Methyl-17α-Acetoxyprogesterone

Synthesis and purification of betamethasone‐1,2,4−3H and betamethasone‐1,2,4−3H 17‐benzoate

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

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Synthesis and purification of betamethasone‐1,2,4−³H and betamethasone‐1,2,4−³H 17‐benzoate