JPS5929688A - Preparation of acetylenecarbamide derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a stabilizer for synthetic resins, rubber, petroleum products, fats and oils, etc. industrially advantageously, by reacting a specific t-butylphenol with formaldehyde and an acetylenecarbamide simultaneously. CONSTITUTION:A t-butyphenol(e.g., 2,6-di-t-butylphenol, etc.) shown by the formula I (R is H, or 1-4C alkyl) is reacted with formaldehyde and acetylenecarbamide in a ratio preferably (4-6):(4-6):1 in a solvent such as usually methanol, n-hexane, etc. in the presence of a catalyst in an amount to give 4-6 times the molar quantity of acetylenecarbamide simultaneously under heating, to give the desired compound shown by the formula II (A is group shown by the formula III). EFFECT:Obtained in high yield and purified easily.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula (I) (1) representing a hydrogen atom or an alkyl group having a carbon number of . ) 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 (1) is a new compound previously discovered by the present inventors, and is a compound that can be used in various polymers such as synthetic resins, natural rubber, and synthetic rubber. It is very useful as a stabilizer for various organic substances such as lubricating oils, petroleum products such as fuel oil, oils and fats, and greases (Special Application Sho S Otsu-/Otsu 7g No. 3). A method for reacting 3-t-butyl-j-alkyl (or hydro)-hydroxybenzyl alcohol with 7-cetylene carbamide is disclosed.

The present inventors conducted further studies in order to industrially advantageously produce such a new and very useful acetylene carbamide derivative represented by the general formula (I), and found that t-
It was discovered that by reacting the kings of butylphenols, formaldehyde and acetylene carbamide, the target compound can be obtained in high yield, and industrially excellent results such as easy purification can be obtained, and the present invention has been achieved. It's arrived.

That is, the present invention provides t represented by the general formula (n) nh" (wherein R has the same meaning as above)
The present invention provides a method for producing an acetylene carbamide derivative represented by the general formula (1), which comprises simultaneously reacting butylphenol, formaldehyde, and acetylene carbamide.

In this reaction, the t-butylphenols represented by general formula (II) include 2-t-butylphenol, -
monomethyl-6-t-butylphenol, coethyl-6-t-butylphenol 1.2-n-propyl-6
-t-butylphenol, 2-1so-propyl-
t-butiflephenol, J-n-butyl-t-t-butylphenol 2, O-di-t-butiflephenol,
, 2-1s.

-butyl-t-butylphenol etc. are exemplified,
Further, formaldehyde is usually used in the form of an aqueous solution, a methanol solution, or formaldehyde.

The reaction molar ratio of acetylene carbamide, t-butylphenol and formaldehyde is usually /:3. j
-g: 3.3;-, preferably 9-A.

This reaction is usually carried out in the presence of a solvent, and alcohols such as methanol, ethanol, n-propyl (3) alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and lIec-butyl alcohol are used as the solvent. Examples include methanol and ethanol. In addition, in such an alcohol solvent, aliphatic hydrocarbons such as n-hexane and n-hebutane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, and tetrachloride. It is also possible to use a mixture of other organic solvents such as halogenated hydrocarbons such as carbon, aprotic polar solvents such as dimethylformamide, and dimethylsulfoxide.

The use of catalysts is effective in these reactions, and examples of catalysts include lithium hydroxide, alkali hydroxides such as sodium hydroxide, and potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and potassium hydroxide. Basic catalysts such as metal alkoxides such as t-butoxide are used. The amount of catalyst used is
Usually θ. /(1 to 2 times the mole range, preferably 17 to 6 times).

The reaction temperature varies depending on the solvent used, but is approximately λθ°C.
to 30° C1, preferably da θ~/. At 5θ°C,
It is usually carried out at the reflux temperature of the solvent system used.

After the reaction is completed, the basic catalyst is neutralized with dioxylic acids if necessary, the solvent is distilled, and the product is extracted by adding a water-insoluble solvent such as toluene to the concentrate. After washing the organic layer with water, The crude product obtained by concentrating the layer or by distilling off the solvent after neutralizing the basic catalyst is isolated by a known method such as washing with water after separation from the furnace. Purification can be carried out by known means such as recrystallization or solvent washing.

Thus, according to the method of the present invention, an acetylene carbamide derivative represented by general formula (I) having a structure corresponding to the t-butylphenol used as a raw material can be easily obtained in high yield.

The present invention will be explained below with reference to Examples.

Example/X) Oml four-flask equipped with thermometer, stirrer and condenser 3.6-di-t-butylphenol //, 33;
y (θ, θS mole), acetylene carbamide/, +x
P (θ, θ1 mol), 6% by weight formaldehyde methanol solution 3.6.5y (θ, θS mol), methanol, 2. ! ml and n-hexane, 23 Tlt. After replacing the air in the container with nitrogen, g, szg°
3 and 9 y of potassium dihydroxide (θ, θj mol) were added, the temperature was raised, and the mixture was reacted under reflux for 1/θ hour. After the reaction is complete,
After acid precipitation with 3θml (θ, θmol) of 2N hydrochloric acid, extraction is performed by adding toluene/θθml, and the extracted toluene layer is washed with water. The toluene layer was concentrated under reduced pressure, and the concentrate was recrystallized by adding n-hexane J Oml to obtain white crystalline N,N',I,N''-tetrakis(3,5-di-t-butyluda-hydroxy). Benzyl) acetylene carbamide 9.73; p (yield 96%) was obtained. Melting point, 2
4tg ~: 2111°C Elemental analysis C64"94N4o6 Calculated value within 0 C7,
5', 30% (7,5,7θ%)H? , nigga (
9,33%) N j, l/! Achi (J-J-, 2chi) D-M
S Molecular ion beak: /θ/Da'H-NMR (C厖3.■) δ/, 37 7.2Hs δg, /θ RiHd J=/, jHzδ'1.5
7 'l Hd J = /, 5Hz δ g, 9 O 2Hs δj, / Gda Hs δ O, 97 gHs Example 2 In a reactor similar to Example/, 2-t-butyl-6-methylphenol was added. 2/P (6.05 mol), acetylene carbamide/, 11.2 y (0.01 mol), 3
7 layers te16 e) It? ! J9. θSy(0,
05 mol) and 80 liters of methanol. After replacing the air in the container with nitrogen, 97% water (7) sodium oxide θ6y (0.05 mol) was added, the temperature was raised, and the mixture was reacted under reflux for 7.5 hours. After the reaction was completed, acid precipitation was performed with 30 ml of 2N hydrochloric acid, followed by extraction by adding ethyl acetate/θθmt, and the extracted ethyl acetate layer was post-treated in the same manner as in Example to obtain white crystalline N, N', 1/,
, N″-tetrakis(3-t-butyl-j-methyl-der-hydroxybenzyl)acetylenecarbamide 7, g7
(yield 23%).

Melting point 2~〃7°C Elemental analysis Calculated value in C5□H7oN4060 C73,9
/ 俤 (73,77%) H, 3! % (0.2g) N Otsu, sg % (Otsu, Otsu. 2%) D-MS Molecular ion peak: g4'l.

'H-NMR (CD (u3, TMS) δ/
, 33 3 Hs δ, 2. /3 /koHa δ3.97 ZHd J=/jHz(g'
) δg, niθ guHa δda, ni/daHd J=/jHzδg,g
7. 2Ha δ6.6'l 4tHbr,i

Claims (1)

[Scope of Claims] t-Butylphenols represented by the general formula (wherein R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 2), formaldehyde, and acetylene carbamide are simultaneously reacted. The characteristic general formulas have the same meanings as above. ) A method for producing an acetyresocarbamide derivative.