JPH0352467B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, A is

[Formula] is shown. Here, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) The present invention relates to a method for producing an acetylene carbamide derivative shown in the following. The acetylene carbamide derivative represented by the above general formula () is a new compound previously discovered by the present inventors, and is used in various polymers such as synthetic resins, natural rubber, and synthetic rubber, as well as in lubricating oils, It is extremely useful as a stabilizer for various organic substances such as petroleum products such as fuel oil, oils and fats, and greases.
No. 56-167434) also discloses a method for producing the same, in which p-hydroxybenzyl alcohols and acetylene carbamide are reacted. The present inventors conducted further studies to industrially advantageously produce such a novel and extremely useful acetylene carbamide derivative represented by the general formula (), and as a result, they completed the present invention. . That is, the present invention provides general formula () (In the formula, R has the same meaning as above, R' represents an alkyl group having 1 to 4 carbon atoms) and acetylene carbamide are reacted. The present invention provides a method for producing an acetylene carbamide derivative represented by the formula (). In this reaction, the dialkyldithiocarbamate derivatives represented by the general formula () include 3-t-butyl-4-hydroxybenzyldimethyldithiocarbamate, 3-methyl-5-t-butyl-4-hydroxybenzyl dimethyldithiocarbamate, 3,5-di-t-butyl-4-hydroxybenzyl dimethyldithiocarbamate, 3-methyl-5-t-butyl-4-hydroxybenzyl diethyldithiocarbamate, 3,5-di-t-butyl-4-hydroxybenzyl Examples include dibutyl dithiocarbamate, 3-ethyl-5-t-butyl-4-hydroxybenzyl dipropyldithiocarbamate, and the reaction molar ratio of such dialkyldithiocarbamate derivative and acetylene carbamide is usually 3.5 to 5:1. Preferably 4-4.6:1
It is. This reaction is usually carried out in the presence of a solvent, and examples of the solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol. , methanol and ethanol are preferably used. In addition, the use of catalysts is effective in this reaction, and such catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium t-butoxide. A basic catalyst such as the like is used, and the amount used is usually 3.5 to 12 times, preferably 8 to 10 times by mole, relative to acetylene carbamide. The reaction temperature ranges from about 20°C to the reflux temperature of the reaction system, but it is usually carried out at the reflux temperature. To separate the target compound from the reaction mixture, for example, after the reaction is complete, the basic catalyst is neutralized with an acid, the product is extracted using a water-insoluble solvent such as toluene, and the organic solvent layer is separated. After washing with water, this can be concentrated, and if necessary, recrystallization can be performed from the concentrated solution. Thus, according to the method of the present invention, the desired product can be easily obtained in high yield. The present invention will be explained below with reference to Examples. Example 1 3,5-di-t-butyl-4-hydroxybenzyl dimethyldithiocarbamate was placed in a 300 ml four-necked flask equipped with a thermometer, stirrer, and condenser.
15.62g (0.046mol), acetylene carbamide 1.42
g (0.01 mol) and methanol 50ml,
After replacing the air in the container with nitrogen, 6.59 g (0.100 mol) of 85% by weight potassium hydroxide is added. Thereafter, the temperature was raised and the mixture was reacted under reflux for 3 hours. After the reaction is complete, neutralize with hydrochloric acid, add toluene for extraction, wash the toluene layer with water, concentrate, and add n-
By adding hexane and recrystallizing, N,N′,N″,N-tetrakis(3,
5-di-t-butyl-4-hydroxybenzyl)
9.85 g (yield 97%) of acetylene carbamide was obtained. (Melting point 244-246℃) Elemental analysis C ₆₄ H ₉₄ N ₄ O ₆ Calculated values in parentheses C: 75.45% (75.70%) H: 9.30% (9.33%) N: 5.50% (5.52%) FD-MS Molecule Ion peak: 1014 Example 2 Into the same flask as used in Example 1, 3-t-
Butyl-5-methyl-4-hydroxybenzyl
Diethyldithiocarbamate 14.97g (0.046mol), acetylene carbamide 1.42g (0.01mol)
After charging 50 ml of methanol and purging the air in the container with nitrogen, add 19.28 g (0.100 mol) of a 28% by weight sodium methoxide methanol solution.
Thereafter, the temperature was raised and the mixture was reacted under reflux for 10 hours. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain N,N',N'',N-tetrakis (3
-t-butyl-5-methyl-4-hydroxybenzyl)acetylenecarbamide 7.79g (yield 92%)
I got it. Melting point 225-227℃ Elemental analysis C ₅₂ H ₇₀ N ₄ O ₆ Calculated values in parentheses C: 73.83% (73.73%) H: 8.51% (8.33%) N: 6.60% (6.61%) FD-MS Molecular ion peak :846

Claims (1)

[Claims] 1. General formula (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R' represents an alkyl group having 1 to 4 carbon atoms.) Reacting the dialkyldithiocarbamate derivative represented by the formula with acetylene carbamide. A general formula characterized by (In the formula, A represents [Formula]. Here, R has the same meaning as above.) A method for producing an acetylene carbamide derivative represented by the following.