Route of synthesis for tertiary alkyl esters

Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfonate esters

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560 16, 564162, C07C30300, C07C30915

Patent

active

053877071

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

This invention relates to pro-drugs and is particularly concerned with novel intermediates for production of enzyme activatable pro-drugs.


DESCRIPTION OF THE RELATED ART

Over the years, many cytotoxic compounds have been discovered which are of potential use in cancer chemotherapy. Nitrogen mustards form one important family of such cytotoxic compounds. The clinical use of cytotoxic compounds in general and nitrogen mustards in particular has been limited because of the poor selectivity in the cytotoxic effect between tumour cells and normal cells.
One approach to overcome this problem has involved the development of so-called pro-drugs which are derivatives of the cytotoxic drug, often a relatively simple derivative, whose cytotoxic properties are considerably reduced compared to those of the Parent drug. Numerous proposals have been made for the administration of such pro-drugs to patients under regimes whereby the pro-drug is only converted to the cytotoxic drug in the region of the intended site of action.
One particularly promising approach involves the conversion of the nitrogen mustard into a reaction product with an amino acid or oligopeptide to for a pro-drug which can be converted to the parent nitrogen mustard at the site of intended action under the influence of an enzyme. This approach can be put into practice by the utilization of an antibody/enzyme conjugate in association with a pro-drug. The antibody/enzyme conjugate is one formed from an antibody to tumour associated antigen and an enzyme that will convert the pro-drug to the cytotoxic drug. In clinical practice, the antibody/enzyme conjugate is first administered to the patient and is allowed to localize in the region of the tumour to be treated. The pro-drug is then administered to the patient so that conversion of the pro-drug to the cytotoxic drug is also localized in the region of the tumour to be treated under the influence of the localized enzyme. Such a system is described in International Application PCT/GB88/00181, published as WO88/07378.
Specific pro-drugs that can be used in the above-mentioned International Application are those based upon benzoic acid nitrogen mustards. The cytotoxic benzoic acid nitrogen mustard is converted, in accordance with the procedures described in our above-mentioned International Application, into an amide by reaction with an alpha-amino acid, the preferred alpha-amino acid being glutamic acid. In this case, the glutamic acid is linked to the nitrogen mustard through an amide bond formed between the carboxy group of the benzoic acid nitrogen mustard and the alpha-amino group of the glutamic acid.
Other pro-drugs can be prepared based on benzoic acid nitrogen mustards where the carboxy group is converted into a derivative with an oligopeptide or other protecting group which is removed in vivo, under the influence of an enzyme localized in the region of the tumour to be treated.
Pro-drugs of the type described in the above-mentioned Application and other pro-drugs embodying the same principle are administered as pro-drugs where the carboxy groups present in the glutamic acid or analogous residue, for example aspartic acid, are in free carboxylic acid form. These pro-drugs are prepared by synthetic methods in which the carboxy group present in the glutamic acid or analogous reactant is protected.
One pro-drug of particular interest is the compound of the formula (I): ##STR2## wherein X represents a group ##STR3## and where P is a protecting group or hydrogen. The protecting group may be a straight or branched chained C.sub.1-6 alkyl, for example ethyl or tertiary butyl. The compound of the formula (I) can be prepared from a compound of formula (II): The above mentioned International Application describes the synthesis of compound (I) from compound (II) via an intermediate (III): ##STR4## by reaction of (III) with methanesulphonyl chloride in pyridine. However, this reaction results in three major products, since the hydrogens of the two terminal hydroxy groups may each be s

REFERENCES:
"Novel Prodrugs Which Are Activated to Cytotoxic Alkylating Agents by Carboxypeptidave G1" Springer et al., J. Med. (1990) 33(2):677-681.

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