β-Propiolactone. V. Reaction with Alcohols

Gresham, T. L.; Jansen, J. E.; Shaver, F. W.; Gregory, J. T.; Beears, W. L.

doi:10.1021/ja01183a034

Cited by 58 publications

(20 citation statements)

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“…31 Dibenzyl [(3R)-3,4-Bis(1-ethoxyethyl)-1,1-difluoro-2-oxobutyl]phosphonate (3c): This compound (yield 50%) was synthesised from 3b. 31 Methyl 3-(Tetrahydro-2H-pyranyloxy)propanoate (5a): 3,4-Dihydro-2H-pyran (9.6 mL, 105 mmol) and pyridinium p-toluenesulfonate (1.75 g, 7 mmol) were added to a solution of methyl 3-hydroxypropanoate [39] (7.75 g, 47.5 mmol) in anhydrous CH 2 Cl 2 (40 mL).…”

Section: Dibenzyl [(3r)-11-difluoro-2-oxo-34-bis(tetrahydro-2h-2-pymentioning

confidence: 99%

A Convenient Synthesis of Dibenzyl α,α-Difluoromethyl-β-ketophosphonates

2002

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Section: Dibenzyl [(3r)-11-difluoro-2-oxo-34-bis(tetrahydro-2h-2-pymentioning

confidence: 99%

A Convenient Synthesis of Dibenzyl α,α-Difluoromethyl-β-ketophosphonates

2002

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“…An analytical sample from hexane: mp 55-56 "C; NMR (CDClJ 0.88 (t, 3, CH3), 1.27 (s, 20, COCH2CH20), 10.80 ppm (br s, 1, C02H). (a) 3-(Dodecy1oxy)propionic Acid.…”

Section: Kondo Et Almentioning

confidence: 99%

Studies on biologically active nucleosides and nucleotides. 5. Synthesis and antitumor activity of some 2,2'-anhydro-1-(3',5'-di-O-acyl-.beta.-D-arabinofuranosyl)cytosine salts and 2,2'-anhydro-1-(3'-O-acyl-.beta.-D-arabinofuranosyl)cytosine 5'-phosphates

Kondo¹,

Nagura²,

Arai³

et al. 1979

J. Med. Chem.

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A series of 3',5'-diesters of a 2,2'-anhydro-1-(beta-D-arabinofuranosyl)cytosine salt bearing functional substituents on the ester side chains (4--16) have been synthesized. The synthesis of these diesters involved the reaction between cytidine and the corresponding acid anhydride or acid chloride in the presence of boron trifluoride etherate. Similar reaction of bis(cytidine 5'-)suberate (21) with pivaloyl chloride gave bis[2,2'-anhydro-1-(3'-O-pivaloyl-beta-D-arabinofuranosyl)cytosine 5'-]suberate dihydrochloride (22). The reaction could also be extended to a one-step synthesis of 3'-esters of 2,2'-anhydro-1-(beta-D-arabinofuranosyl)cytosine 5'-phosphate (24) from 5'-cytidylic acid. These compounds have been examined for antitumor activity against L1210 leukemia in BDF1 mice. The diesters with a long-chain carboxylic acid (4c, 7c, 12, and 24d) showed high activity when administered intraperitoneally. The compound 24d exhibited moderate activity when administered orally.

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“…The thermal degradation of poly(oxycarbonylethy1ene) was assumed to proceed via the typical ester pyrolysis reaction consisting of steps 1 and 2 according t o Eqs. (1) and (2). If the labile cr-hydrogen atoms with respect t o the carbonyl group in the p-propiolactone unit are substituted by methyl groups, the homopolymer of the di-substituted product is expected to be essentially more stable : Dry pivalolactone, a,a-dimethyl-P-propiolactone (VII), was cationically polymerized by addition of 0,l mol-yo of SnC14 as described from YAMASHITA~~).…”

Section: (Polypivalolactone) ( V I I I )mentioning

confidence: 99%

The thermal degradation of poly(oxycarbonylethylene) (poly‐β‐propiolactone)

et al. 1973

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The thermal degradation of poly(oxycarbonylethy1ene) (poly-P-propiolactone) has been investigated within a temperature range of 180-220°C and under various pressures. The degradation begins with a considerable decrease in molecular weight, followed by an accelerating formation of acrylic acid. The reaction involves the following steps: 1) Random chain scission of polymer chains by typical ester pyrolysis with the formation of fragments one of which containing a carboxylic group the other one a CC-double bond at the chain end (Eq. (1)). 2) Formation of the volatile acrylic acid by scissions at the chain end, the amount of acrylic acid or the weight-loss increasing with the number of fragmentations (Eq. (2)). 3) Autocatalysed acidic cleavage of the polyester fragments into an @-unsaturated esterand an acid as shown with low molecular model compounds (Eq. (8)). Substitution of the labile a-hydrogen atoms in poly(oxycarbonylethy1ene) by methyl groupssuch as in poly(oxycarbony1-1,l-dimethylethylene) -reduces the rate of degradation drastically. This observation together with the results obtained in the pyrolysis of the low-molecular model compounds, ethyl P-acetoxypropionate and P-acetoxypropionic acid, support the postulated mechanism. ZUSAMMENFASSUNG:Der thermische Abbau von Poly(oxycarbonylathy1en) (Poly-P-propiolacton) wurde bei 180-220°C und verschiedenem Druck untersucht. Zunachst erfolgt eine starke Verminderung der Molekulargewichte, danach bis zur vollstandigen Zersetzung eine beschleunigte Bildung von Acrylsaure. Die Reaktion verlauft iiber folgende Schritte : 1) Statistische Kettenspaltung durch Esterpyrolyse unter Bildung von Bruchstiicken mit ungesattigtem oder mit carboxylischem Kettenende (Gl. (1)). 2) Saurekatalysierter Abbau unter gleichzeitiger Abspaltung von Acrylsaure vom Kettenende her, wobei die Menge an Acrylsaure und damit der Gewichtsverlust mit der Anzahl der Fragmentierungen zunimmt (Gl. (2)). 3) Autokatalytische, saure Spaltung der Polyester-Bruchstiicke in einen a,P-ungesittigten Ester und eine Sauue, wie an niedermolekularen Modellverbindungen gezeigt werden konnte (Gl. (8)).Substitution der labilen a-Wasserstoffatome im Poly(oxycarbonylithy1en) durch Methylgruppenwie im Poly(oxycarbony1-1,l-dimethylathylen)setzt die Abbaugeschwindigkeit drastisch herab. Diese Beobachtung sowie die Resultate der Pyrolyse der Modellverbindungen, P-Acetoxypropionsaureiithylester und P-Acetoxypropionsaure, unterstiitzen den vorgeschlagenen Mechanismus.

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β-Propiolactone. V. Reaction with Alcohols

Cited by 58 publications

References 0 publications

A Convenient Synthesis of Dibenzyl α,α-Difluoromethyl-β-ketophosphonates

A Convenient Synthesis of Dibenzyl α,α-Difluoromethyl-β-ketophosphonates

Studies on biologically active nucleosides and nucleotides. 5. Synthesis and antitumor activity of some 2,2'-anhydro-1-(3',5'-di-O-acyl-.beta.-D-arabinofuranosyl)cytosine salts and 2,2'-anhydro-1-(3'-O-acyl-.beta.-D-arabinofuranosyl)cytosine 5'-phosphates

The thermal degradation of poly(oxycarbonylethylene) (poly‐β‐propiolactone)

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