33719-95-8Relevant academic research and scientific papers
Transformation of natural chlorophyll-a into chlorophyll-c analogs possessing the 17-acrylate residue
Xu, Meiyun,Tamiaki, Hitoshi
, p. 1864 - 1866 (2014)
Chlorophyll(Chl)-a derivatives possessing C18HC17HCH2CH2 were transformed into Chl-c analogs possessing C18=C17CH= CH through dehydrogenation to C18=C17, dihydroxylation to C18(OH)C17(OH), and double dehydration. This is the first re
A novel and convenient conversion of chlorins to phytoporphyrins during the modification of chlorophyll derivatives
Ma, Lifu,Dolphin, David
, p. 7791 - 7794 (2007/10/02)
Chlorophyll derivatives 2a, 2b, 2c and 3 have been readily converted to their corresponding phytoporphyrins 5a, 5b, 5c in excellent yields using benzoyl chloride in DMF. This method affords a new and efficient route to prepare monovinyl porphyrins which can be used as intermediates for the further preparation of chlorophyll related petroporphyrins and regiochemically pure benzoporphyrin derivatives for use in photodynamic therapy.
Meso Substitution of Chlorophyll Derivatives: Direct Route for Transformation of Bacteriopheophorbides d into Bacteriopheophorbides c
Smith, Kevin M.,Goff, Dane A.,Simpson, Daniel J.
, p. 4946 - 4954 (2007/10/02)
In order to develop a procedure for direct methylation of methyl bacteriopheophorbides d (Bmph-d) to afford methyl bacteriopheophorbides c (Bmph-c), severalm reactions involving meso substitution of chlorophyll derivatives were investigated.Treatment of zinc(II) methyl mesopyropheophorbide a (7b) with bromine in chloroform accomplished oxidation, presumably via the ?-cation radical, to the corresponding porphyrin, phylloerythrin methyl ester (16); meso bromination (to give 17) resulted when metal-free methyl mesopyropheophorbide a (7) was treated with bromine in chloroform.Friedel-Crafts cyanation (cyanogen bromide/aluminum chloride ) of copper(II) methyl mesopyropheophorbide a (7a) gave 40-50percent yields of the meso-cyanochlorin 18 after demetalation, but attempts to transform the cyano group into methyl were unsuccessful.Oxidation reactions of 7 using thallium(III) trinitrate resulted in formation of the corresponding meso-nitrochlorins 20.Treatment of copper(II) methyl mesopyropheophorbide a (7a) with chloromethyl methyl sulfide and titanium tetrachloride afforded the meso-methylthiomethyl derivative 19a (74-77percent yields); use of the nickel(II) complex 7d likewise gave 80-84percent yields of 19b.With Raney nickel both 19a and 19b gave good yields of the required meso-methyl metallochlorins 3a and 3b, respectively, the former being readily demetalated with HCl gas in dichloromethane to give the meso-methylchlorin 3.Thus, the Bmph-d to Bmph-c transformation was accomplished by initially protecting the vinyl group in methyl pyropheophorbide a (9) as the corresponding 2-chloroethylgroup; the copper(II) complex 25a was then methylthiomethylated, treated with Raney nickel (to give 26a), and finally demetalated with HCl gas to give 27.Compound 27 has previously been converted into Bmph-c (4) by treatment with base (to give the 2-vinyl derivative) followed by hydration of the vinyl with HBr in acetic acid.
