Tricyclic compounds

Details Tricyclic compounds Tricyclic compounds

1999-04-05

2001-07-31

Kumar, Shailendra (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Sulfonate esters

C548S473000, C548S474000, C549S213000, C549S383000, C549S433000, C558S047000, C558S048000, C558S051000, C564S172000, C564S270000, C564S336000, C564S337000, C564S338000

Reexamination Certificate

active

06268520

ABSTRACT:

OBJECTS OF THE INVENTION
It is an object of the invention to provide the novel compounds of formula I and a process of preparing the same.
It is another object othe invention to provide a novel process for the preparation of the compounds of formula II.
These and other objects and advantages of the invention will become obvious from the following detailed description.
THE INVENTION
The novel tricyclic compounds of the invention have the formula
wherein a) R
1
and R
2
are alkyl of 1 to 6 carbon atoms and R
3
is hydrogen or A—SO
2
— or b) R
2
and R
3
are hydrogen and R
1
is A—SO
2
— or c) R
1
, R
2
and R
3
are all hydrogen or all alkyl of 1 to 6 carbon atoms or d) R
1
is A—SO
2
— or hydrogen and R
2
and R
3
together with the oxygens to which they are attached form —O—X—O—, X is selected from the group consisting of —B(OR
4
)—, —C(O)— and —CR
5
R
6
—, R
4
is hydrogen or alkyl of 1 to 6 carbon atoms, R
5
and R
6
are individually selected from the group consisting of hydrogen, alkyl of 1 to 6 carbon atoms and phenyl optionally substituted with 1 to 3 members of the group consisting of —OH and alkyl and alkoxy of 1 to 6 carbon atoms or R
5
and R
6
together with the carbon atoms to which they are attached form a carbocyclic of 5 to 6 carbon atoms or e) R
3
is A—SO
2
— and R
1
and R
2
together with the oxygens to wich they are attached form —O—X—O— or f) R
1
is hydrogen and R
2
and R
3
are both alkyl of 1 to 6 carbon atoms or together with the oxygens to which they are attached form —O—X—O— and A is selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl optionally substituted with 1 to 3 alkyls of 1 to 6 carbon atoms and naphthyl optionally substituted with 1 to 5 alkyls of 1 to 6 carbon atoms.
Examples of alkyl of 1 to 6 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, tert.-butyl, isobutyl, pentyl and hexyl. If R
1
, R
2
, R
3
, R
5
and R
6
are alkyl, they may be the same or different. Examples of alkoxy of 1 to 6 carbon atoms are methoxy, ethoxy, isopropoxy, butoxy, etc.
Among the preferred compounds of formula I are those wherein R
1
, R
2
and R
3
are all hydrogen or all alkyl, preferably methyl, those wherein R
1
is A—SO
2
—, preferably tosyl and R
2
and R
3
are both hydrogen or both alkyl, preferably methyl, and those wherein R
1
is hydrogen and R
2
and R
3
are both methyl.
The process for the preparation of a compound of formula I comprises i) reacting a compound of the formula
wherein R′
1
, R′
2
and R′
3
respectively have the meaning as R
1
, R
2
and R
3
as defined, with the exception of hydrogen and for R′
3
—A—SO
2
—, with a halogenation agent to obtain the corresponding acyl halide, ii) reacting the latter with a reagent of the formula
wherein Ra and Rb individually are alkyl of 1 to 6 carbon atoms, or Ra and Rb together with the nitrogen atom to which they are attached form a heterocycle of 5 or 6 members optionally containing another heteroatom selected from O and N to obtain a compound of the formula
iii) reacting the latter with a halogenation agent to obtain a compound of the formula
wherein Hal
1
is halogen, iv) reacting the latter with a Lewis acid to obtain a compound of the formula:
corresponding to the compounds of formula I (a) as defined above in which R
3
is A—SO
2
—, to the compounds of formula I (c) as defined above in which all three of R
1
, R
2
and R
3
are alkyl and to the compounds of formula I (e), as defined above, optionally reacting the compound of formula (e), (v)—either if R′
1
is A—SO
2
— and R′
2
and R′
3
do not together represent —X—, with a hydrolysis agent to obtain a compound of formula
in which R″
2
and R″
3
both are alkyl corresponding to the compounds of formula I (a) as defined above in which R
3
is hydrogen, optionally reacting the latter with an alkylation agent to obtain a compound of the formula
corresponding to the compounds of formula I (c) as defined above, in which R
1
, R
2
and R
3
are alkyl, optionally subjecting the latter to a hydrolysis of all alkoxys to obtain a compound of the formula
corresponding to the compound of formula I (c) as defined above, in which R
1
, R
2
and R
3
are hydrogen, (viii) or subjecting a compound of formula (e) in which all three of R′
1
, R′
2
and R′
3
are alkyl, to a hydrolysis of all alkoxys to obtain the compound of formula (h) defined above, ix) optionally reacting the latter with a protection reagent of diols chosen from compounds of the formulae:
B(OR
4
)
3
, C(O)R
5
R
6
, C(O)Y
2
and CR
5
R
6
(Y)
2
,
wherein R
4
, R
5
and R
6
are as defined above and Y is halogen or Ar—O— in which Ar is phenyl optionally substituted by 1 to 3 substituents selected from the group consisting of alkyl, alkoxy, hydroxy, amino, alkylamino, dialkylamino and nitro; or with a reagent of the formula CH
2
(Y)
2
, Y being defined as above, in the presence of a reagent of the formula P(Hal)
5
, in which Hal is halogen, followed by a hydrolysis to obtain a compound of the formula
corresponding to the compounds of formula I (d) as defined above in which R
1
is hydrogen, which is treated with an agent of the formula A—SO
2
Y, in which A is defined as in claim
1
and Y is defined as above to obtain a compound of the formula
corresponding to the compounds of formula I (d) as defined above in which R
1
is A—SO
2
—, x) optionally reacting the latter with a deprotection reagent of the diol to obtain a compound of the formula
corresponding to the compounds of formula I as defined above in which R
2
and R
3
are hydrogen, optionally reacting the latter with an alkylation agent to obtain a compound of the formula
corresponding to the compounds of formula I (b) as defined above xii) optionally reacting a compound of formula (j) or (l) with a hydrolysis agent of A—SO
2
—O— to obtain a compound of the formula
or
respectively, corresponding to the compounds of formula I (f) as defined above.
Examples of the halogenation agent reacted with the compound of formula a are thionyl chloride, oxalyl chloride and other agents forming an acid halide. The reagent of formula b may be prepared from cyclopentanone and a secondary amine, for example diethylamine, piperidine, piperazine or, preferably, morpholine. The operation is carried out in the presence of a strong acid catalyst such as p-toluene sulfonic acid.
The action of the enamine of formula b on the acid halide is preferably carried out in the presence of a tertiary amine such as triethylamine or pyridine. The halogenation agent which is reacted with the compound of formula c can be, for example, thionyl chloride, phosgene, phosphorus oxychloride or, preferably, oxalyl chloride. The Lewis acid used for the cyclization of the compound of formula d is for example aluminium chloride, titanium tetrachloride, or preferably ferric chloride, or tin tetrachloride. The reaction, as with those which precede, can be carried out in a halogenated solvent such as methylene chloride, chloroform or dichloroethane.
The hydrolysis leading to the compound of formula f, i or l′ can be carried out by the action of sodium hydroxide, potassium hydroxide or sodium or potassium carbonate in the presence of an aqueous alkanol. The hydrolysis leading to the compound of formula h can be carried out with a dealkylation agent such as boron tribromide, aluminium chloride, hydrochloric acid, or also a mercaptan such as thiophenol.
The alkylation of the compounds of formulae f and k can be any standard agent known to a man skilled in the art for the alkylation of phenols. There can be mentioned for example an alkyl halide such as methyl or ethyl iodide, an alkyl sulfate such as methyl or ethyl sulfate, or diazomethane. If appropriate, the operation can be carried out in the presence of a base such as a hydroxide or an alkali metal carbonate in an organic solvent, for example a halogenated solvent, and if appropriate, in the presence of a phase transfer agent, for example a quaternary ammonium salt such as tetra-n-butyl ammonium bromide.
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