Novel compounds, compositions and processes

A process for preparing a compound having the formula ##STR135## wherein R.sub.1 through R.sub.4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX and --(CH.sub.2).sub.n OX with the proviso that R.sub.1 and R.sub.2 are not OH and when one of R.sub.3 or R.sub.4 is OH, the other cannot be OX,

• wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower alkynyl,
• n is an integer of from one to four,
• R.sub.5 -R.sub.15 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl with the proviso that one of R.sub.7 and R.sub.8 is always hydrogen and one of R.sub.11 and R.sub.12 is always hydrogen,
• A is oxygen or sulfur,
• B' and B.sub.1 ' are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, --O--lower alkenyl, thiol, thio lower alkyl and thio lower alkenyl,
• which comprises
• Step (1) Reaction of a compound having the formula ##STR136## with a compound having the formula ##STR137## to prepare a compound having the formula ##STR138## wherein R.sub.1 " through R.sub.4 " may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX" and --(CH.sub.2)--OX",
• wherein X" is selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, acyl and aralkyl,
• R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of acyl, aralkoxycarbonyl, aryloxy carbonyl, halogenated alkoxy carbonyl and alkyloxycarbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' is always a blocking group and one of R.sub.11 ' and R.sub.12 ' is always a blocking group and
• R.sub.15 " is lower alkyl, lower alkenyl, lower alkynyl, acyl or aralkyl,
• Step (2) Deoximation of compound IV of step 1 to prepare a compound having the formula ##STR139## Step (3) Deprotection of Compound V of Step 2 to a compound of formula I.

A process for preparing a compound having the formula ##STR145## wherein R.sub.1 through R.sub.4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX and --(CH.sub.2).sub.n --OX, with the proviso that R.sub.1 and R.sub.2 are not OH and when one of R.sub.3 or R.sub.4 is OH, the other cannot be OX,

• wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower alkynyl,
• n is an integer of from one to four,
• R.sub.5 -R.sub.15 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl, with the proviso that one of R.sub.7 and R.sub.8 is always hydrogen and one of R.sub.11 and R.sub.12 is always hydrogen,
• A is selected from the group consisting of oxygen and sulfur,
• B' and B.sub.1 ' are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, -O-lower alkenyl, thiol, thio lower alkyl and thio lower alkenyl,
• which comprises deblocking the amine groups on the actinamine moiety of compounds having the formula ##STR146## wherein R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of acyl, aralkoxy carbonyl, aryloxy carbonyl, halogenated alkoxycarbonyl and alkyloxycarbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' is always a blocking group and one of R.sub.11 ' and R.sub.12 ' is always a blocking group.

Anomers and asteric mixtures of a compound having the formula ##STR149## wherein R.sub.1 ' through R.sub.4 ' may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX' and --(CH.sub.2).sub.n --OX' with the proviso that R.sub.1 and R.sub.2 are not OH and when one of R.sub.3 or R.sub.4 is OH, the other cannot be OX',

• wherein X' is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, acyl and aralkyl,
• n is an integer of from one to four,
• R.sub.5 -R.sub.6, R.sub.9 -R.sub.10, R.sub.13 and R.sub.14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl,
• R.sub.15 ' is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, acyl and aralkyl,
• A is oxygen or sulfur,
• R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of aralkoxy carbonyl, aryloxy carbonyl, halogenated alkoxycarbonyl and alkyloxy carbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' and one of R.sub.11 ' and R.sub.12 ' is always a blocking group,
• B and B.sub.1 are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, -O-lower alkenyl, thiol, thio lower alkyl and thio lower alkenyl with the proviso that when the compound is selected from the group consisting of compounds having the formula ##STR150## B.sub.1 cannot be hydroxy;
• and when the compound has the formula ##STR151## B and B.sub.1 cannot be selected from the group consisting of hydrogen and hydroxy, and when the compound has the formula ##STR152## B and B.sub.1 cannot both be hydroxy.

A process for preparing a compound having the formula ##STR155## wherein R.sub.1 through R.sub.4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX and --(CH.sub.2).sub.n --OX, with the proviso that R.sub.1 and R.sub.2 are not OH and when one of R.sub.3 and R.sub.4 are OH, the other cannot be OX,

• wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl,
• n is an integer of from one to four,
• R.sub.5 -R.sub.15 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl,
• R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of aralkoxy carbonyl, aryloxy carbonyl, halogenated alkoxy carbonyl and alkyloxycarbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' is always a blocking group and one of R.sub.11 ' and R.sub.12 ' is always a blocking group,
• B' and B.sub.1 ' are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, -o-lower alkenyl, thiol, thio-lower alkyl and thio-lower alkenyl,
• A is oxygen or sulfur, which comprises removing protecting groups in R.sub.1 " through R.sub.4 " and R.sub.15 " positions in from a compound having the formula consisting of ##STR156## wherein R.sub.1 "-R.sub.4 " may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX" and --(CH.sub.2)OX",
• wherein X" is lower alkyl, lower alkenyl and lower alkynyl, acyl or aralkyl and R.sub.15 " is lower alkyl, lower alkenyl, lower alkynyl, acyl or aralkyl, with the proviso that at least one of R.sub.1 " through R.sub.4 " or R.sub.15 " includes an acyl or aralkyl.

A process for preparing a compound having the formula ##STR159## wherein R.sub.1 "-R.sub.4 " are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX" and --(CH.sub.2).sub.n OX";

• wherein X" is selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, acyl and aralkyl;
• n is an integer of from one to four;
• R.sub.15 " is acyl, aralkyl, lower alkyl, lower alkenyl, lower alkynyl;
• R.sub.5 -R.sub.6, R.sub.9 -R.sub.10, R.sub.13 -R.sub.14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl,
• R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of aralkoxy carbonyl, aryloxy carbonyl, halogenated alkoxy carbonyl and alkyloxycarbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' is always a blocking group and one of R.sub.11 ' and R.sub.12 ' is always a blocking group;
• B' and B.sub.1 ' are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, --o--lower alkenyl, thiol, thio lower alkyl, thio lower alkenyl;
• and
• A is oxygen or sulfur,
• which comprises deoximating a compound having the formula ##STR160## thereto.

Anomers and asteric mixtures of a compound having the formula ##STR163## wherein R.sub.1 " through R.sub.4 " may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX" and --(CH.sub.2).sub.n --OX",

• wherein X" is selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, acyl and aralkyl,
• n is an integer of from one to four,
• R.sub.5 -R.sub.6, R.sub.9 -R.sub.10, R.sub.13 and R.sub.14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl,
• R.sub.15 " is lower alkyl, lower alkenyl, lower alkynyl, acyl and aralkyl,
• A is oxygen or sulfur,
• R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of aralkoxy carbonyl, aryloxy carbonyl, halogenated alkoxy carbonyl and alkyloxy carbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' and one of R.sub.11 ' and R.sub.12 ' is always a blocking group,
• B and B.sub.1 are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, --O--lower alkenyl, thiol, thio lower alkyl and thio lower alkenyl with the proviso that when the compound is a compound having the formula ##STR164## wherein CBz is carbobenzyloxy then B.sub.1 cannot be hydrogen.

A process for preparing a compound having the formula ##STR166## which comprises coupling a compound having the formula ##STR167## with a compound having the formula ##STR168## wherein R.sub.1 "-R.sub.4 " may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower aminoalkyl, --OX" and --(CH.sub.2).sub.n OX";

• wherein X" is selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl acyl and aralkyl,
• n is an integer of from one to four;
• R.sub.5 -R.sub.6, R.sub.9 -R.sub.10, R.sub.13 -R.sub.14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl,
• R.sub.15 " is acyl, aralkyl, lower alkyl, lower alkenyl and lower alkynyl,
• R.sub.7 ', R.sub.8 ', R.sub.11 ' and R.sub.12 ' are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl and a blocking group selected from the group consisting of aralkoxycarbonyl, aryloxy carbonyl, halogenated alkoxy carbonyl and alkyloxycarbonyl with the proviso that one of R.sub.7 ' and R.sub.8 ' is always a blocking group and one of R.sub.11 ' and R.sub.12 ' is always a blocking group;
• B' and B.sub.1 " are selected from the group consisting of hydrogen, hydroxy, lower alkoxy, --O--lower alkenyl, thiol, thio lower alkyl and thio lower alkenyl;
• and
• A is oxygen or sulfur,
• with the proviso that where the prepared compound IV has the formula ##STR169## wherein CBz is carbobenzyloxy, then B.sub.1 " cannot be hydrogen.