Adipic Acid → Dibutyl Adipate

HRID 543335

Reaction equation

HRID 543335 reaction equation
[C:1]([OH:10])(=[O:9])[CH2:2][CH2:3][CH2:4][CH2:5][C:6]([OH:8])=[O:7].[CH2:11](O)[CH2:12][CH:13](O)[CH3:14].[CH2:17](O)[CH2:18][CH2:19][CH3:20]>[OH-].[OH-].[OH-].[OH-].[Ti+4].C1(C)C=CC=CC=1>[C:1]([O:10][CH2:17][CH2:18][CH2:19][CH3:20])(=[O:9])[CH2:2][CH2:3][CH2:4][CH2:5][C:6]([O:8][CH2:11][CH2:12][CH2:13][CH3:14])=[O:7]

Participants

6

Reactant 3

HCID 196Adipic AcidHCID 2631-Butanol2×HCID 78961,3-Butanediol

Product 1

HCID 7784Dibutyl AdipateYield 50.3%

Reagents, catalysts & solvents 2

HCID 88494Titanium hydroxideCatalystHCID 1140TolueneSolvent

Procedure

To a (2:1:2 mol) mixture of one mol (146 g) of adipic acid, 0.5 mol (45 g) of 1,3-butanediol and 1 mol (72 g) of n-butanol, were added 0.5 g of titanium tetrahydroxide and 60 ml of toluene, and dehydrating esterification was carried out. When acid value was decreased to 6 after 14 hours, 72 g (1 mol) of butanol was added and dehydrating esterification reaction was carried out until an acid value becomes 0.3. After a treatment for catalyst removal, distillation was carried out under reduced pressure to produce 65 g (about 25 mol%) of dibutyl adipate. Further 36 g (13 mol%) of ester-alcohol distillate fraction (160° C.-180° C./0.5 mmHg) was obtained. The yield of high boiling products was 128 g, 55% of the theoretical amount. Liquid chromatographic analysis results of these products showed that n=1 compound is less than the half and they are a mixture of total of 6 kinds of compounds including those with n=2 or greater. The bis-compound which distilled at 235° to 245° C./0.5 mmHg reduced pressure was 56 g which is only 24% of the calculated amount and the oligomer product was 72 g (produced in greater amount than bis-compound). By the addition of an excess amount of butanol, dehydrating esterification reaction is completed swiftly. However, ester interchange reaction occurred concurrently, and the terminals of the diol do not react and and an ester alcohol distillate fraction is formed. The diol is azeotropically distilled too. Although the composition of higher boiling products varies depending on reaction time, temperature, molar ratio, and the like, it was noted that the weight % of the bis compound never exceeded the half amount.

Workup

  1. customesterification reaction
  2. customAfter a treatment for catalyst removal, distillation

Sources & evidence

ORD record
ord-3bb5beaa3ed542c588749fb6d3069c0e
Source dataset
uspto-grants-1987_04
Patent number
US04661622

Linked notes

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