Ammonium Hydroxide → 6-Aminohexanoic Acid

HRID 842345Notes

Reaction equation

HRID 842345 reaction equation
[C:1]([CH2:3][CH2:4][CH2:5][CH2:6][C:7]([OH:9])=[O:8])#[N:2].[OH-].[NH4+]>CN1CCCC1=O>[C:1]([CH2:3][CH2:4][CH2:5][CH2:6][C:7]([OH:9])=[O:8])#[N:2].[NH2:2][CH2:1][CH2:3][CH2:4][CH2:5][CH2:6][C:7]([OH:9])=[O:8].[C:7]1(=[O:9])[NH:2][CH2:1][CH2:3][CH2:4][CH2:5][CH2:6]1

Participants

6

Reactant 2

HCID 14923Ammonium HydroxideHCID 199926Valeric acid, 5-cyano-2×

Product 3

HCID 5646-Aminohexanoic AcidHCID 7768CaprolactamHCID 199926Valeric acid, 5-cyano-

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
110 °C

Procedure

A 100 cc stainless steel (Parr reactor) stirred batch autoclave was used for the hydrogenation of 5-cyanovaleric acid (5CVA) in the presence of 5% Ru/TiO2 catalyst. 10.0 g of 5CVA mixture (92.8% 5CVA, 3.1 % 3CVA, and 3.4% 4-cyanovaleric acid (4CVA)), 1.0 g of 1-methyl-2-pyrrolidinone (NMP, internal standard), 40.0 g of ammonium hydroxide solution, and 1.0 g of 5% Ru/TiO2 were added in the reactor cup. The reactor was then assembled by securing the cup to the head, pressure tested with 100 psig (0.69 MPa) of nitrogen, and purged with nitrogen, followed by hydrogen. The reactor was then pressurized to 250 psig (1.8 MPa) with hydrogen and heated up to the reaction temperature (110° C.), under constant stirring. The pressure in the reactor was then brought up to the desired level (900 psig (6.3 MPa)) and maintained at that level throughout the entire duration of the run (4 hr). During the course of the reaction, samples (0.2 cc) were withdrawn periodically from the reactor through a sample port, connected to a dip leg inside the reactor, and analyzed by Hewlett-Packard 6890 gas chromatograph after derivatizing the sample with a mixture of bis-trimethylsilyl trifluoro acetamide (BSTFA) and trimethylchlorosilane. The conversion of 5CVA and selectivities and yields of 6-aminocaproic acid (6ACA) and caprolactam (CL) as a function of reaction time have been presented in Table 1.

Workup

  1. custompurged with nitrogen
  2. temperaturemaintained at that level throughout the entire duration of the run (4 hr)
  3. customDuring the course of the reaction, samples (0.2 cc)
  4. customwere withdrawn periodically from the reactor through a sample port
  5. additionwith a mixture of bis-trimethylsilyl trifluoro acetamide (BSTFA) and trimethylchlorosilane

Sources & evidence

ORD record
ord-935bd46f1b464dc6b519bf441f2f53ea
Source dataset
uspto-grants-2002_04
Patent number
US06372939B1

Reaction notes

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