Bicyclic heterocyclic derivatives, their preparation and therapeutic use
A compound and heteroaryl technology, applied in the fields of bicyclic heterocyclic derivatives, their preparation and therapeutic use, can solve the problems of limited cancer subgroups, lower rapalogue efficacy than expected, etc.
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[0293] The reaction scheme for the preparation of compounds of formula (XLI) via steps f) to k) is shown in Scheme 4 below (in an embodiment using compounds of formula (CII) in step k).
[0294]
[0295] Option 4 : Reaction scheme for the preparation of compounds of formula (XLI) starting from compounds of formula (XIII) via steps f) to k).
[0296] The method for preparing the above-mentioned compound of formula (XIII) carried out in the above-mentioned step c) or f) typically comprises the following steps:
[0297] a) make the following formula (XI) compound nucleophilic attack following formula (X) compound, obtain following formula (XII) compound,
[0298] Described formula (XI) is:
[0299]
[0300] where m, R 2 , R 3 and R 4 as defined above,
[0301] Described formula (X) is:
[0302]
[0303] LG 2 as defined above and LG 1 and LG 4 is independently a leaving group, such as a halogen atom such as a chlorine atom,
[0304] Described formula (XII) is: ...
Embodiment 1
[0477] 1-{4-[6-Ethyl-8,8-dimethyl-2-(8-oxa-3-azabicyclo[3.2.1]oct-3-yl)-5-oxo- Synthesis of 5,6,7,8-tetrahydro-9-oxa-1,3,6-triazabenzocyclohepten-4-yl]-2-fluorophenyl}-3-methylurea
[0478]
[0479] Step 1.1: (preparation of formula (X) compound)
[0480] 4,6-Dichloro-2-methylthiopyrimidine-5-carbonyl chloride
[0481]
[0482]10 g of 4,6-dichloro-2-methylthiopyrimidine-5-carboxylic acid (41.83 mmol) were placed in 61 ml of thionyl chloride (836.54 mmol) under stirring. After 18 hours at 80° C., the thionyl chloride was distilled off and the residue was taken up twice with 15 ml of toluene and concentrated, yielding 10.77 g of 4,6-dichloro-2-methylthiopyrimidine-5-carbonyl chloride.
[0483] Step 1.2: (which corresponds to step a))
[0484] 4,6-Dichloro-2-methylthiopyrimidine-5-carboxylic acid ethyl-(2-hydroxy-2-methylpropyl)amide
[0485]
[0486] 4.9 g of 1-(ethylamino)-2-methylpropan-2-ol (41.82 mmol) and 17.5 ml of triethylamine (125.46 mmol) were placed i...
Embodiment 2
[0521] 1-{4-[6-Ethyl-8,8-dimethyl-2-((S)-3-methylmorpholin-4-yl)-5-oxo-5,6,7,8 -Synthesis of tetrahydro-9-oxa-1,3,6-triazabenzocyclohepten-4-yl]-2-fluorophenyl}-3-methylurea
[0522]
[0523] Step 2.1: (which corresponds to step e))
[0524] {4-[6-Ethyl-8,8-dimethyl-2-((S)-3-methylmorpholin-4-yl)-5-oxo-5,6,7,8-tetra tert-Butyl Hydrogen-9-Oxa-1,3,6-Triazabenzocyclohepten-4-yl]-2-fluorophenyl}carbamate
[0525]
[0526] 2.5 g of [4-(6-ethyl-2-methanesulfonyl-8,8-dimethyl-5-oxo-5,6,7,8-tetrahydro-9-oxa-1,3 , 6-Triazabenzocyclohepten-4-yl)-2-fluorophenyl]carbamate (19.66 mmol) in 20 ml of dioxane was placed in 4 microwave tubes respectively. A quarter of (S)-3-methylmorpholine (98.32 mmol) was added to each tube separately. The tubes were heated in a Biotage microwave machine at 100°C for 2 hours. The reaction medium is filtered and rinsed with MeOH. The solid was washed successively with water, acetonitrile and pentane. 3.7 g of {4-[6-ethyl-8,8-dimethyl-2-((S)-3-meth...
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