Hydrochloric Acid → 2,2-Bis(4-nitrobenzyl)-1,3-propandiol

HRID 537653Notes

Reaction equation

HRID 537653 reaction equation
[N+:1]([C:4]1[CH:29]=[CH:28][C:7]([CH2:8][C:9]([CH2:18][C:19]2[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=2)([C:14](OC)=[O:15])[C:10](OC)=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].[OH-].[Li+].Cl.B>C(OCC)(=O)C.O.O1CCCC1.CCOCC>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:8][C:9]([CH2:18][C:19]2[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=2)([CH2:10][OH:11])[CH2:14][OH:15])=[CH:28][CH:29]=1)([O-:3])=[O:2]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 3939Lithium HydroxideHCID 6331Borane2×HCID 59217458Dimethyl bis(4-nitrobenzyl)malonate2×

Product 1

HCID 229286162,2-Bis(4-nitrobenzyl)-1,3-propandiolYield 100%

Reagents, catalysts & solvents 4

HCID 962WaterSolvent3×HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Procedure

About 2 mole of 1-bromomethyl)-4-nitrobenze and about 1 mole of dimethyl malonate were mixed with excess methyl ethyl ketone (MEK) which was mixed with potassium carbonate at a temperature of about 50° C. for about 3 hours. After adding excess water at temperature of about 25° C., the above materials were precipitated to obtain about 1 mole of dimethyl 2,2-bis(4-nitrobenzyl)malonate. About 1 mole of dimethyl 2,2-bis(4-nitrobenzyl)malonate was mixed with water and tetrahydrofurane (THF) which was mixed with lithium hydroxide, and dimethyl 2,2-bis(4-nitrobenzyl)malonate at a temperature of about 25° C. for about 22 hours. After adding about 1 N of hydrochloric acid at a temperature of about 25° C., excess water and ether were added to extract about 1 mole of 2,2-bis(4-nitrobenzyl)maloic acid. THF and borane were added to about 1 mole of 2,2-bis(4-nitrobenzyl)maloic acid and THF, borane at a temperature of about 25° C. for about 20 hours. After adding excess water and ethyl acetate, about 1 mole of 2,2-bis(4-nitrobenzyl)propane-1,3-diol was obtained. Formaldehyde was added to about 1 mole of 2,2-bis(4-nitrobenzyl)propane-1,3-diol, and 2,2-bis(4-nitrobenzyl)propane-1,3-diol at a temperature of about 80° C. for about 30 minutes. Hydrogen bromide was added to, and 2,2-bis(4-nitrobenzyl)propane-1,3-diol, formaldehyde, and hydrogen bromide were reacted at a temperature of about 25° C. for about 3 hours to obtain about 1 mole of 2,2-bis((bromomethoxy)methyl)-1,3-bis(4-nitrophenyl)propane. After adding triphenylphosphine and carbon dichloride to 2,2-bis((bromomethoxy)methyl)-1,3-bis(4-nitrophenyl)propane at a temperature of about 23° C. for about 2 hours, about 1 mole of 4-formylphenyl 4-(4,4,4-trifluorobutoxy)benzoate was mixed with excess sodium hydride and THF at a temperature of about 23° C. for about 18 hours. Then, zinc chloride and carbon dichloride are added at a temperature of about 40° C. for about 16 hours to obtain about 1 mole of the compound represented by Chemical Formula 6.

Workup

  1. additionwere added

Sources & evidence

ORD record
ord-9f6101331aa14595bc42a02a2fd94e21
Source dataset
uspto-grants-2014_10
Patent number
US08865273B2

Reaction notes

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