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molecular formula C31H49O2P B580627 tBuBrettPhos CAS No. 1160861-53-9

tBuBrettPhos

Cat. No. B580627
M. Wt: 484.705
InChI Key: REWLCYPYZCHYSS-UHFFFAOYSA-N
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Patent
US09434698B2

Procedure details

A 600-mL, stainless steel, Parr® reactor was equipped with an overhead stirrer, thermocouple and a heating mantle. Tris(dibenzylideneacetone)dipalladium(0) (0.164 g, 0.179 mmol), di-tert-butyl(2′,4′,6′-triisopropyl-3,6-dimethoxybiphenyl-2-yl)phosphine (0.208 g, 0.429 mmol) and milled potassium phosphate tribasic (8.36 g, 39.4 mmol) were charged to the 600-mL reactor. The reactor was purged with argon for not less than 90 minutes. 2-Methyltetrahydrofuran (100 mL) was purged with argon for not less than 30 minutes and was transferred to the 600-mL reactor using a cannula under argon atmosphere. The reactor was tightly sealed, the contents were heated to 80° C. and stirred at this temperature for 30 minutes. A 500-mL round bottom flask equipped with a magnetic stir bar was charged with 6-(3-tert-butyl-5-(2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)-2-methoxyphenyl)naphthalen-2-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (25 g, 35.8 mmol), methanesulfonamide (4.09 g, 42.9 mmol) and ethyl acetate (200 mL), purged with argon for not less than 30 minutes with stirring and heated to 60° C. A clear solution was observed. This solution was transferred to the 600-mL reactor using a cannula under argon atmosphere. The reactor was tightly sealed, the contents were heated to 90° C. and stirred at this temperature for 14 hours. The reaction mixture was cooled to 35° C., solids were collected by filtration, washed with ethyl acetate (300 mL) and dried under high vacuum for 2-4 hours. The solids were then transferred to a 1-L, three-neck, round-bottom flask equipped with an overhead stirrer and a thermocouple. N-Acetyl-L-cysteine (0.58 g, 3.5 mmol), dimethylformamide (DMF) (100 mL) and glacial acetic acid (0.85 g) were charged to the 1-L flask; the contents were heated to 60° C. and mixed for 1 hour. The mixture was filtered through approximately 2-inch pad of diatomaceous earth and washed with DMF (50 mL). The dark-brown/black-colored solid collected on diatomaceous earth was discarded and the light yellow/clear filtrate was charged to a separate 1-L, three-neck, round-bottom flask equipped with an overhead stirrer, a thermocouple and a syringe pump. The DMF solution was mixed and methanol (300 mL) was added over 8 hours, while maintaining the internal temperature at 25±5° C. The white solid was collected by filtration washed with methanol (150 mL) and dried in a vacuum oven at 50° C. for not less than 8 hours. The title compound was isolated as a white solid (15.8 g, 89% yield).
[Compound]
Name
stainless steel
Quantity
0 (± 1) mol
Type
reactant
Reaction Step One
Name
6-(3-tert-butyl-5-(2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)-2-methoxyphenyl)naphthalen-2-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate
Quantity
25 g
Type
reactant
Reaction Step Two
Quantity
4.09 g
Type
reactant
Reaction Step Two
Quantity
200 mL
Type
solvent
Reaction Step Two
Quantity
0.58 g
Type
reactant
Reaction Step Three
Quantity
0.85 g
Type
solvent
Reaction Step Three
Quantity
100 mL
Type
solvent
Reaction Step Three
Quantity
0.208 g
Type
reactant
Reaction Step Four
Name
potassium phosphate tribasic
Quantity
8.36 g
Type
reactant
Reaction Step Four
Quantity
0.164 g
Type
catalyst
Reaction Step Four
Name
Yield
89%

Identifiers

REACTION_CXSMILES
C(P(C(C)(C)C)C1C(OC)=CC=C(OC)C=1C1C(C(C)C)=CC(C(C)C)=CC=1C(C)C)(C)(C)C.[O-]P([O-])([O-])=O.[K+].[K+].[K+].FC(F)(S(O[C:59]1[CH:68]=[CH:67][C:66]2[C:61](=[CH:62][CH:63]=[C:64]([C:69]3[CH:74]=[C:73]([N:75]4[CH:80]=[CH:79][C:78](=[O:81])[NH:77][C:76]4=[O:82])[CH:72]=[C:71]([C:83]([CH3:86])([CH3:85])[CH3:84])[C:70]=3[O:87][CH3:88])[CH:65]=2)[CH:60]=1)(=O)=O)C(F)(F)C(F)(F)C(F)(F)F.[CH3:90][S:91]([NH2:94])(=[O:93])=[O:92].C(N[C@H](C(O)=O)CS)(=O)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(O)(=O)C.CN(C)C=O.C(OCC)(=O)C>[C:83]([C:71]1[C:70]([O:87][CH3:88])=[C:69]([C:64]2[CH:65]=[C:66]3[C:61](=[CH:62][CH:63]=2)[CH:60]=[C:59]([NH:94][S:91]([CH3:90])(=[O:93])=[O:92])[CH:68]=[CH:67]3)[CH:74]=[C:73]([N:75]2[CH:80]=[CH:79][C:78](=[O:81])[NH:77][C:76]2=[O:82])[CH:72]=1)([CH3:85])([CH3:84])[CH3:86] |f:1.2.3.4,8.9.10.11.12|

Inputs

Step One
Name
stainless steel
Quantity
0 (± 1) mol
Type
reactant
Smiles
Step Two
Name
6-(3-tert-butyl-5-(2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)-2-methoxyphenyl)naphthalen-2-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate
Quantity
25 g
Type
reactant
Smiles
FC(C(C(C(F)(F)F)(F)F)(F)F)(S(=O)(=O)OC1=CC2=CC=C(C=C2C=C1)C1=C(C(=CC(=C1)N1C(NC(C=C1)=O)=O)C(C)(C)C)OC)F
Name
Quantity
4.09 g
Type
reactant
Smiles
CS(=O)(=O)N
Name
Quantity
200 mL
Type
solvent
Smiles
C(C)(=O)OCC
Step Three
Name
Quantity
0.58 g
Type
reactant
Smiles
C(C)(=O)N[C@@H](CS)C(=O)O
Name
Quantity
0.85 g
Type
solvent
Smiles
C(C)(=O)O
Name
Quantity
100 mL
Type
solvent
Smiles
CN(C=O)C
Step Four
Name
Quantity
0.208 g
Type
reactant
Smiles
C(C)(C)(C)P(C1=C(C(=CC=C1OC)OC)C1=C(C=C(C=C1C(C)C)C(C)C)C(C)C)C(C)(C)C
Name
potassium phosphate tribasic
Quantity
8.36 g
Type
reactant
Smiles
[O-]P(=O)([O-])[O-].[K+].[K+].[K+]
Name
Quantity
0.164 g
Type
catalyst
Smiles
C=1C=CC(=CC1)/C=C/C(=O)/C=C/C2=CC=CC=C2.C=1C=CC(=CC1)/C=C/C(=O)/C=C/C2=CC=CC=C2.C=1C=CC(=CC1)/C=C/C(=O)/C=C/C2=CC=CC=C2.[Pd].[Pd]

Conditions

Temperature
Control Type
UNSPECIFIED
Setpoint
80 °C
Stirring
Type
CUSTOM
Details
stirred at this temperature for 30 minutes
Rate
UNSPECIFIED
RPM
0
Other
Conditions are dynamic
1
Details
See reaction.notes.procedure_details.

Workups

ADDITION
Type
ADDITION
Details
were charged to the 600-mL reactor
CUSTOM
Type
CUSTOM
Details
The reactor was purged with argon for not less than 90 minutes
CUSTOM
Type
CUSTOM
Details
2-Methyltetrahydrofuran (100 mL) was purged with argon for not less than 30 minutes
CUSTOM
Type
CUSTOM
Details
The reactor was tightly sealed
CUSTOM
Type
CUSTOM
Details
A 500-mL round bottom flask equipped with a magnetic stir bar
CUSTOM
Type
CUSTOM
Details
purged with argon for not less than 30 minutes
STIRRING
Type
STIRRING
Details
with stirring
TEMPERATURE
Type
TEMPERATURE
Details
heated to 60° C
CUSTOM
Type
CUSTOM
Details
The reactor was tightly sealed
TEMPERATURE
Type
TEMPERATURE
Details
the contents were heated to 90° C.
STIRRING
Type
STIRRING
Details
stirred at this temperature for 14 hours
Duration
14 h
TEMPERATURE
Type
TEMPERATURE
Details
The reaction mixture was cooled to 35° C.
FILTRATION
Type
FILTRATION
Details
solids were collected by filtration
WASH
Type
WASH
Details
washed with ethyl acetate (300 mL)
CUSTOM
Type
CUSTOM
Details
dried under high vacuum for 2-4 hours
Duration
3 (± 1) h
CUSTOM
Type
CUSTOM
Details
equipped with an overhead stirrer
TEMPERATURE
Type
TEMPERATURE
Details
the contents were heated to 60° C.
ADDITION
Type
ADDITION
Details
mixed for 1 hour
Duration
1 h
FILTRATION
Type
FILTRATION
Details
The mixture was filtered through approximately 2-inch pad of diatomaceous earth
WASH
Type
WASH
Details
washed with DMF (50 mL)
CUSTOM
Type
CUSTOM
Details
The dark-brown/black-colored solid collected on diatomaceous earth
ADDITION
Type
ADDITION
Details
the light yellow/clear filtrate was charged to a separate 1-L, three-neck, round-bottom flask
CUSTOM
Type
CUSTOM
Details
equipped with an overhead stirrer
ADDITION
Type
ADDITION
Details
The DMF solution was mixed
ADDITION
Type
ADDITION
Details
methanol (300 mL) was added over 8 hours
Duration
8 h
TEMPERATURE
Type
TEMPERATURE
Details
while maintaining the internal temperature at 25±5° C
FILTRATION
Type
FILTRATION
Details
The white solid was collected by filtration
WASH
Type
WASH
Details
washed with methanol (150 mL)
CUSTOM
Type
CUSTOM
Details
dried in a vacuum oven at 50° C. for not less than 8 hours

Outcomes

Product
Details
Reaction Time
30 min
Name
Type
product
Smiles
C(C)(C)(C)C=1C(=C(C=C(C1)N1C(NC(C=C1)=O)=O)C=1C=C2C=CC(=CC2=CC1)NS(=O)(=O)C)OC
Name
Type
product
Smiles
Measurements
Type Value Analysis
AMOUNT: MASS 15.8 g
YIELD: PERCENTYIELD 89%

Source

Source
Open Reaction Database (ORD)
Description
The Open Reaction Database (ORD) is an open-access schema and infrastructure for structuring and sharing organic reaction data, including a centralized data repository. The ORD schema supports conventional and emerging technologies, from benchtop reactions to automated high-throughput experiments and flow chemistry. Our vision is that a consistent data representation and infrastructure to support data sharing will enable downstream applications that will greatly improve the state of the art with respect to computer-aided synthesis planning, reaction prediction, and other predictive chemistry tasks.
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