tert-butyl 3,5,5-trimethylperoxyhexanoate

Hydrolysis

Link to relevant study record(s)

Reference

Endpoint:

hydrolysis

Type of information:

experimental study

Adequacy of study:

key study

Study period:

2010-05-21 to 2010-08-04

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Qualifier:

according to guideline

Guideline:

OECD Guideline 111 (Hydrolysis as a Function of pH)

Version / remarks:

2004

Deviations:

no

Qualifier:

according to guideline

Guideline:

EU Method C.7 (Degradation: Abiotic Degradation: Hydrolysis as a Function of pH)

Version / remarks:

2008

Deviations:

no

GLP compliance:

yes (incl. QA statement)

Radiolabelling:

no

Analytical monitoring:

yes

Details on sampling:

The samples were measured by the previously validated reverse phase HPLC method using UV detection .

Buffers:

- pH 4: 3 mL 0.2 M Sodium hydroxide and 375 mL 0.2 M Potassium hydrogen phthalate were diluted to 1500 mL with ultra-pure water,
- pH 7: 221.7 mL 0.2 M Sodium hydroxide and 375 mL 0.2 M Potassium dihydrogen phosphate were diluted to 1500 mL with ultra-pure water,
- pH 9: 160.5 mL 0.2 M Sodium hydroxide and 375 mL 0.2 M Boric acid and Potassium chloride were diluted to 1500 mL with ultra-pure water.

Details on test conditions:

TEST SYSTEM
- Measures taken to avoid photolytic effects: The hydrolysis reaction was carried out using a dark thermostat to avoid photolytic effects.
- Measures to exclude oxygen: Nitrogen was bubbled into the water for five minutes before the preparation of the solutions in order to exclude oxygen.

TEST SOLUTION
Stock solution (~5 mg/mL): ~50 mg of the test item was dissolved in acetonitrile to a total volume of 10 mL. The test solutions were prepared by dilution of the “stock solutions for the hydrolysis test” with the corresponding buffer solutions, just before analysis and start of the storage. 1500 mL sterile solutions were prepared at pH 4, 7 and 9. Solutions were transferred into ~22 mL screw-cap glass tubes with PTFE septa. The solution was analysed at the start of the tests and then at appropriate time intervals: in order to get at least six other data points in the range of 10 to 90 % hydrolysis. The test solutions were prepared by five-hundred fold dilution of the “stock solutions for the hydrolysis test” with the corresponding buffer solutions.

Duration:

5 d

pH:

4

Initial conc. measured:

ca. 10 mg/L

Duration:

5 d

pH:

7

Initial conc. measured:

ca. 10 mg/L

Duration:

5 d

pH:

9

Initial conc. measured:

ca. 10 mg/L

Number of replicates:

2

Negative controls:

yes

Remarks:

control buffer

Statistical methods:

No statistical method performed.

Preliminary study:

Based on the results of the preliminary test the hydrolysis rate of TBPIN was found to be 54 % at pH 4 and 63 % at pH 7. Hydrolysis rate at pH 9 was approximately 100 % after 5 days at 50 degree C.

Transformation products:

no

Details on hydrolysis and appearance of transformation product(s):

The decomposition of the substance was monitored by HPLC-UV. The decomposition of the test substance TBPIN is well known and results in the formation of tert-butanol and 3,5,5-Trimethylhexanoic acid. The degradation product tert-butanol can not be detected under the given validated test method neither from the decomposition chromatogram nor by using the corresponding reference substance. It was not possible to detect the decomposition product 3,5,5-Trimethylhexanoic acid as the required compound could not be ordered from the suppliers.
The LCQ analyse of the decomposition solution did not provide any additional information on the degradation products.

% Recovery:

85

pH:

4

Temp.:

25 °C

Duration:

5 d

% Recovery:

94

pH:

7

Temp.:

25 °C

Duration:

5 d

% Recovery:

95

pH:

9

Temp.:

25 °C

Duration:

5 d

Key result

pH:

4

Temp.:

15 °C

Hydrolysis rate constant:

0.004 h-1

DT50:

186 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

4

Temp.:

37 °C

Hydrolysis rate constant:

0.005 h-1

DT50:

149 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

4

Temp.:

60 °C

Hydrolysis rate constant:

0.009 h-1

DT50:

75 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

7

Temp.:

15 °C

Hydrolysis rate constant:

0.01 h-1

DT50:

69 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

7

Temp.:

37 °C

Hydrolysis rate constant:

0.02 h-1

DT50:

34 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

7

Temp.:

60 °C

Hydrolysis rate constant:

0.027 h-1

DT50:

26 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

9

Temp.:

15 °C

Hydrolysis rate constant:

0.009 h-1

DT50:

78 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

9

Temp.:

37 °C

Hydrolysis rate constant:

0.028 h-1

DT50:

25 h

Type:

(pseudo-)first order (= half-life)

Key result

pH:

9

Temp.:

60 °C

Hydrolysis rate constant:

0.332 h-1

DT50:

2.1 h

Type:

(pseudo-)first order (= half-life)

Validity criteria fulfilled:

yes

Conclusions:

The calculated half lives of the hydrolysis reactions at pH 4, pH 7 and pH 9 are as follows:
t 1/2 at pH 4 and 15 degree C: 186 h, 37 degree C: 149 h, 60 degree C: 75 h;
t 1/2 at pH 7 and 15 degree C: 69 h, 37 degree C: 34 h, 60 degree C: 26 h;
t 1/2 at pH 9 and 15 degree C: 78 h, 37 degree C: 25 h, 60 degree C: 2.1 h.
Based on the results obtained, test substance tert-butyl 3,5,5-trimethylperoxyhexanoate is hydrolytically unstable at pH 4, pH 7 and pH 9 under the conditions investigated.

Executive summary:

The hydrolysis of tert-Butylperoxy-3,5,5-trimethylhexanoat in different pH buffer solutions was investigated according to OECD Guideline No. 111 and EU method C.7. The analysis of tert-Butylperoxy-3,5,5-trimethylhexanoat was carried out with a HPLC method using UV detection. Sterile aqueous buffer solutions of different pH values (pH 4, 7, 9) were prepared with tert-Butylperoxy-3,5,5-trimethylhexanoat stock solutions and buffer solutions. The hydrolysis of tert-Butylperoxy-3,5,5-trimethylhexanoat was examined at pH 4, 7 and 9 at three temperatures: 15 ± 0.5 degree C, 37 ± 0.5 degree C and 60 ± 0.5 degree C. Tert-Butylperoxy-3,5,5-trimethylhexanoat concentrations in the buffer solutions were: ca. 10 mg/L (ca. 0.046 mM). The calculated half-lives of the hydrolysis reactions at pH 4, pH 7 and pH 9 are given in the following table:

Buffer solution	Temperature, °C	t1/2, hours
pH 4	15	186
	25	161
	37	149
	60	75
pH 7	15	69
	25	51
	37	34
	60	26
pH 9	15	78
	25	40
	37	25
	60	2.1

Based on the results obtained, test substance tert-Butylperoxy-3,5,5-trimethylhexanoat is hydrolytically unstable at pH 4, pH 7 and pH 9 under the conditions investigated.

Description of key information

tert-butyl-3,5,5-trimethylperoxyhexanoate was tested for hydrolysis as a function of pH according to OECD 111 and EU method C.7. Based on the main study, tert-butyl-3,5,5-trimethylperoxyhexanoate is hydrolytically unstable at pH 4, pH 7 and pH 9.

Key value for chemical safety assessment

Half-life for hydrolysis:

213.2 h

at the temperature of:

12 °C

Additional information

tert-butyl-3,5,5-trimethylperoxyhexanoate was tested for hydrolysis as function of pH according to OECD 111 and EU method C.7.

In the supporting study, the hydrolysis rate of tert-butyl-3,5,5-trimethylperoxyhexanoate was found to be 54 % at pH 4 and 63 % at pH 7. Hydrolysis rate at pH 9 was approximately 100 % after 5 days at 50 °C. A half-time determination was however not possible, based on the data generated in this study.

In the key study, the hydrolysis of tert-butyl-3,5,5-trimethylperoxyhexanoate was examined at pH 4, 7 and 9 at three temperatures: 15 ± 0.5 °C, 37± 0.5 °C and 60± 0.5 °C. The calculated half lives of the hydrolysis reactions at pH 4, pH 7 and pH 9 are as follows:

t 1/2 at pH 4 and 15 °C: 186 h, 37 °C: 149 h, 60 °C: 75 h;

t 1/2 at pH 7 and 15 °C: 69 h, 37 °C: 34 h, 60 °C: 26 h;

t 1/2 at pH 9 and 15 °C: 78 h, 37 °C: 25 h, 60 °C: 2.1 h

tert-butyl-3,5,5-trimethylperoxyhexanoate is hydrolytically unstable at pH 4, pH 7 and pH 9.