JPS59164780A - Manufacture of 2-tertiary butyl-5-hydroxypyrimidine by hydrolyzing 2-tertiary butyl-5-bromo/ chloropyrimidine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] "The Pyrimidine" Interscience (1962) 2
03-2.04 states that the conversion of the active halide to a hydroxy group is somewhat unusual and not always easy. ``The Pyrimidine Interscience (1970), p. 148, ``Direct hydrolysis of chloropyrimidines to hydroxypyrimidines has been avoided for many years, but such a prohibition seems obsolete today.'' [Acids or alkalis can be used, although alkalis are more common.] However, with sodium methoxide, 2-t-dityl-5-
Attempts to hydrolyze promobilimine gave significant amounts of the by-product 2-t-butyl 2-rimidine.

It has been discovered that the hydrolysis of 2-t-butyl-5-halopyrimidines can be carried out in high yields and in high purity in the presence of a catalyst consisting of 2-t-butyl-5-disulfide, elemental sulfur or mixtures thereof. It was done.

The reaction is 100-300C1 preferably 150-22
It can advantageously be carried out at atmospheric pressure within Pa, rr, at a temperature of 0C and most preferably from 160 to 180C and in the presence of 0.5 to 20 mol of catalyst. A preferred catalyst is elemental sulfur, which is preferably 2,5
It is used in an amount of ˜75 mol%. Sodium methoxide°
is preferably used, however other alkali metal methoxides such as potassium methoxide can be used.

The hydrolysis is advantageously and preferably carried out in a methyl alcohol solvent.

The invention is explained in more detail in the Examples below. Therein, 2-, t-butyl-5-bromopyrimidine was hydrolyzed in excess methanol in the presence of sodium methoxide in a Parr Boni. The following product was obtained.

A: 2-t-butyl-pyrimidine B: 2-t-butyl-5-methoxypyrimidine C:
2-t-butyl-5-hydroxypyrimidine manipulation
Catalyst: F Near Temperature Product 1 None
0150 23 11 772 None
0150 37 11 583
2-Picoline-N-oxide 10152 12
12 694 2-Picoline-N-oxide 20152 12 1 765 Jean-Me04 Satano? Do 5160 12 1
916 G-n-Zuri 4 Bond ν Otsu 9 Do 10160
7 1 1057S0
5163 4 12 8888'
5165 5 1 9498
' 2.5153 7
15 801OS' 7.
5 156 4 - 100118'
5 155 8 4
．． 93128' 2.5155
7 2 9313 8'
1,5 160 10.14 - 10
1.4114 8' 0.5 1
60 12.06 - 97.5515°S'
2.5170 4-1
00* Hydrolysis of 2-tert-butyl-5-chloropyrimidine Direct chlorination of 2-1-butylpyrimidine with elemental chlorine in the presence of acetic acid or propionic acid at a temperature of 40° to 90C and preferably in the presence of a buffer. By becoming 2
It has been discovered that -t-butyl-5-chloropyrimidine can be produced in high yield and purity.

The 5-tert-butyl-5-chloropyrimidine advantageously has an exceptional insecticidal action.
2υmidin(5)yl]-(thiono)-(IF-ol)-phosphonic acid ester or ester aminer
An intermediate for the manufacture, which is described in US Pat. No. 4.127.
It is described in No. 652.

The chlorination of 2-tert-butylpyrimidine is preferably carried out in the absence of a catalyst and at a temperature of 55-65C. Preferably the solution of 2-t-butylpyrimidine contains 1.5 to 3.0 moles of pyrimidine per 11 solvent, although higher or lower concentrations can be used. In more dilute solvents, more energy is required to separate the desired product and chlorination of the solvent itself is more likely. In more concentrated solutions, the higher viscosity results in a homogeneous mixture. That is, it is difficult to retain the solution.

Suitable buffers include, for example, sodium acetate, potassium acetate,
Contains sodium pro2ionate and potassium propionate. Desirably, the buffer is soluble in the solution.

Sodium acetate is preferred.

A preferred solvent is acetic acid.

The chlorination reactions are illustrated in the examples below, all parts are by weight unless otherwise indicated.

1 0.022 25 0.026 60
4.5972 0.367 250 0.44
60 6.0753 0.734 500
0.88 6 (16,08640,7345000
,88606,09750,7345000,8860
6,07360,1680,12603,583 71,475001,766013,07981,47
Similar results are obtained using propionic acid as a solvent and/or using buffers such as potassium acetate, propion rRf thorium and potassium propionate.

Patent applicant: The Dow Chemical Company
given name)

Claims (1)

Claims: 1. Hydrolysis of 2-tert-butyl-5-halopyrimidine in the presence of an alkali metal methoxide and in the presence of a catalyst consisting of an N-oxide, disulfide, elemental sulfur, or a mixture thereof. A method for producing 2-1-butyl-5-hydroxypyrimidine consisting of: 2. The method of claim 1, wherein the halopyrimidine is 2-t-butyl-5-bromopyrimidine. 3. A method according to claim 2, wherein the reaction is carried out at 150-220c. 4. The method of claim 2, wherein the catalyst is: picoline-N-oxyr, di-n-butyl disulfide or elemental sulfur. 5. The method of claim 1, wherein the halopyrimidine is 2-t-butyl-5-chloropyrimidine. Item 6: 2-t-butyl-5-chloropyrimidine is 40 to 9
6. A process according to claim 5, prepared by chlorinating 2-t-bromopyrimidine with elemental chlorine in an acetic or propionic acid solution at a temperature of 0C in the absence of a catalyst. Claim 7: The reaction temperature is between 55 and 65 U.Claim 6:
The method described in section. Claim 8: The reaction is carried out for 3 to 15 hoursClaim 7:
The method described in section. 9. The method of claim 6, wherein the solvent is buffered with sodium acetate. 10. The method of claim 9, wherein the solvent is acetic acid.