Triethoxy(phenyl)silane

Hydrolysis

Link to relevant study record(s)

Reference

Reference 1

Endpoint:

hydrolysis

Type of information:

experimental study

Adequacy of study:

supporting study

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

other: The study is well documented and meets generally accepted scientific prinicipels, but was not conducted to an Guideline and GLP.

Qualifier:

equivalent or similar to guideline

Guideline:

OECD Guideline 111 (Hydrolysis as a Function of pH)

Principles of method if other than guideline:

Screening method based on H-NMR. OECD mentioned but not specified as guideline followed

GLP compliance:

no

Transformation products:

not specified

pH:

4

DT50:

38 min

Type:

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

pH:

7

DT50:

> 10 h

Type:

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

pH:

9

DT50:

> 4 h

Type:

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

The half lives determined with the method used here, are not very accurate for the very short half lives and generally tend rather to higher values than to be too short. These limitations were considered acceptable, because the main goal of the study was to find out whether the 4 hours half life threshold of the WGK classification can be met or not.

Reference 2

Endpoint:

hydrolysis

Type of information:

(Q)SAR

Adequacy of study:

key study

Study period:

2013

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

results derived from a valid (Q)SAR model and falling into its applicability domain, with adequate and reliable documentation / justification

Justification for type of information:

Please refer to attached justification documents

Principles of method if other than guideline:

The result was obtained using an appropriate QSAR method (see attached QPRF for details).

Transformation products:

not specified

pH:

7

DT50:

1.5 h

Remarks on result:

other: 20-25 °C

pH:

4

DT50:

0.4 h

Remarks on result:

other: 20-25°C

pH:

5

DT50:

0.3 h

Remarks on result:

other: 20-25°C

pH:

9

DT50:

0.1 h

Remarks on result:

other: 20-25°C

Conclusions:

A hydrolysis half-life of approximately 1.5 hours was obtained for the substance using an appropriate calculation method. The result is considered to be reliable.

Reference 3

Endpoint:

hydrolysis

Type of information:

experimental study

Adequacy of study:

supporting study

Study period:

2017-01-12 to TBD

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

test procedure in accordance with generally accepted scientific standards and described in sufficient detail

Justification for type of information:

Please refer to the attached justification for grouping of substances provided in IUCLID Section 13.

Reason / purpose for cross-reference:

read-across source

Preliminary study:

The preliminary study was not required because methyltrimethoxysilane is known to be unstable in water.

Transformation products:

yes

No.:

#1

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

The decrease in concentration with time of methyltrimethoxysilane and the increase of concentration with time of methanol with time were followed (see Figure 1 and Figure 2). The anticipated reaction scheme is presented in the attachments section.

% Recovery:

>= 87.5 - <= 104

pH:

3

Temp.:

37 °C

Duration:

1 h

Remarks on result:

other: A molar recovery based on the quantity of methyltrimethoxysilane and molar equivalents of its hydrolysis product methanol (3 moles of methanol were assumed per mole of methyltrimethoxysilane) was between 87.5 and 104% at each time point

Key result

pH:

3

Temp.:

37 °C

Hydrolysis rate constant:

0.021 min-1

DT50:

33.3 min

Type:

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

Description of key information

Half-life for hydrolysis: approximately 1.5 hours at pH 7 and 20-25°C

Additional information

Please note: there is a study according to OECD 111 ongoing for the registered substance. The dossier will be updated with the new information once the final study report is available.

A hydrolysis half-life of approximately 1.5 h at 20-25 °C was obtained for the substance using an appropriate calculation method (PFA, 2011). The result is considered to be reliable and has been assigned as key study.

A QSAR that was developed by Peter Fisk Associates (2012c) predicts half-lives at 20-25 °C of 0.3 h at pH 4, 0.4 h at pH 5 and 0.1 h at pH 9. As the hydrolysis reaction may be acid or base catalysed, the rate of reaction is expected to be slowest at pH 7 and increase as the pH is raised or decreased.

For an acid-base catalysed reaction in buffered solution, the measured rate constant is a linear combination of terms describing contributions from the uncatalyzed reaction as well as catalysis by hydronium, hydroxide, and general acids or bases.

k_obs= k₀+ k_H3O+[H₃O⁺] + k_OH-[OH^-] + k_a[acid] + k_b[base]

At extremes of pH and under standard hydrolysis test conditions, it is reasonable to suggest that the rate of hydrolysis is dominated by either the hydronium or hydroxide catalysed mechanism. This is supported by studies for various organosilicon compounds in which calculation of kH3O+ and kOH- from the experimental results at pH 4 and 9, respectively, resulted in reasonable estimates of the half-life at pH 7.

Therefore, at low pH:

k_obs≈k_H3O+[H₃O⁺]

At pH 4 [H₃O⁺]=10^-4mol dm^-3and at pH2 [H₃O⁺]=10^-2mol dm^-3; therefore, k_obsat pH 2 should be approximately 100 times greater than k_obs at pH 4.

The half-life of a substance at pH 2 is calculated based on:

t_1/2(pH 2) = t_1/2(pH 4) / 100

The calculated half-life of triethoxy(phenyl) silane at pH 2 is therefore 0.002 h (0.12 seconds). However, it is likely that factors such as diffusion become rate-determining when the half-life is less than 5-10 seconds. As a worst-case it can therefore be considered that the half-life for triethoxy(phenyl) silane at pH 2 and 20-25 °C is approximately 5 seconds. Reaction rate increases with temperature therefore hydrolysis will be faster at physiologically relevant temperatures compared to standard laboratory conditions. Under ideal conditions, hydrolysis rate can be recalculated according to the equation:

DT₅₀(XºC) = DT₅₀(T) x e^(0.08.(T-X))

Where T = temperature for which data are available and X = target temperature.

For triethoxy(phenyl) silane the hydrolysis half-life at 37.5ºC and pH2 (relevant for conditions in the stomach following oral exposure), it is not appropriate to apply any further correction for temperature to the limit value and the hydrolysis half-life is therefore approximately 5 seconds.

Additional information about this endpoint could be gathered through a reliable study according to a screening method based on1H-NMR (2006). The substance has a half-life of 38 minutes at pH of 4, a half-life of >10 h at pH 7 and 25 °C and about 4 h at pH of 9. The half-lives as determined with the method used in this study are not very accurate for very short half-lives and generally tend to be applicable to longer half-life values rather than to shorter half-life values. These limitations were considered acceptable, because the main goal of the study was to find out whether the 4 hours half-life threshold of the WGK classification can be met or not.

Using the result from the calculation method together with the screening method based on1H -NMR, it can be concluded that the substance will hydrolyse rapidly. The initial hydrolysis products are phenylsilanetriol and ethanol.

 

In another supporting study (CRL, 2017), the hydrolysis of methyltrimethoxysilane dosed in corn oil was investigated under conditions designed to mimic the rat stomach. The half-life for disappearance of methyltrimethoxysilane applied in corn oil to gastric simulation buffer was 33 mins at pH 3 and 37°C. The data suggest that hydrolysis occurs rapidly once methyltrimethoxysilane is in contact with the aqueous layer and the rate determining step is the transfer of the methyltrimethoxysilane from the corn oil to the water. Methanol content increased proportionally to the decrease in methyltrimethoxysilane and combined recoveries of methanol and methyltrimethoxysilane ranged from 87.5 to 104%. The study was conducted according to an appropriate test protocol and is considered reliable.