DE1670150A1 - Process for the production of propylene urea aldehydes - Google Patents

Description

BADISCHE ANILINE- & SODA-I ¹ ABRIK AG 1670 150

Our reference: O, Z. 24 480 Sm / Gn Ludwigshafen am Ehein, September 14, 1966

V experience for the production of propylene urea aldehydes

It has been found that propylene urea aldehydes of the general formula

N-CH ₉ -G-GHO _T

wherein the radicals Rp, Rz, R ₄ , Rc and Rg are hydrogen atoms, identical or different alkyl radicals, R ~ and R _{Q are} alkyl radicals and X is an oxygen or sulfur atom, the radical IL is alkyl or the radical ■ □

-CH ₂ -C-GHO, ^R 8

in which R ₇ and Rg have the meaning given, means, in very good yields and in a simple manner, if 449/66 propylene ureas of the general formula are obtained

-2-

009844/1885

~ 2 »O.Z. 24 480

Τ? -1\

XIg -I

II ■ OR,

6 ^R 5

wherein Rg, R *, R *, Bc, Rg and X have the meaning given above and R "denotes hydrogen or an alkyl group, with Formaldehyde and a CH-acidic aldehyde of the general formula

HC - CHO III, ^R 8

wherein R ^ and Rg have the aforementioned meaning, in the presence of an acid, optionally in the presence of a solution and / or; Is reacted Verdünnungssiittuls at a temperature between O and 120 ⁰ C to give each NH group of the urea output approximately stö'chiometrische amount of formaldehyde and the approximately stoichiometric amount used of the CH-acidic aldehyde. The process is preferably carried out in the temperature range between 40 and 100.degree.

In the preferred starting materials, the radicals R ₂ , R ^, R _t 4 and R, - are hydrogen atoms, identical or different alkyl radicals with 1 to 7 carbon atoms, Rg is a hydrogen atom or an alkyl radical with preferably 1 to 10 carbon atoms, R ^ and Rg are alkyl radicals with preferably 1 to 4 carbon atoms u'.a X is an oxygen or sulfur atom, the remainder Rg is hydrogen or an alkyl group with 1 to 17 carbon atoms. _ ^ _

009844/1885.

-.3 - 0.Z. 24 480

The process can be used for the reaction of, for example, 4-hydroxy-5,5-dimethyl-propylene-urea with formaldehyde and isobutyraldehyde represented by the following reaction equation *

HN NH +2 CH ₉ O + 2 CH-CHO -

Il / H

CH ₀ CH-OH CH, '

OHC-C-CH ₂ -N N-CH ₂ -C-CHO + 2

CH ₃ CH ₂ CH ^ CH ₃

/ ^G \ ^0H

CH ₃ CH ₃

The starting materials / can be very easily, for example by reacting a urea with formaldehyde and a CH-aeiden aldehyde in a molar ratio of about 1: 1: 1 or by reacting a urea with a CH-acidic aldehyde in a molar ratio of about 1: 2 in the presence a strong acid in the temperature range between 30 and 100 ⁰ C, produce.

As cyclic ureas II of the 4-hydroxypropylene (thio) urea type e.g. N ~ methyl-5,5-dimethyl-4-hydroxypropyleneurea, 4-hydroxy ~ 5,5-dimethyl-propyleneurea, 4-hydroxy-5,5-dimethyl-6-isopropyl-propyleneurea, 4-hydroxy-5-ethyl-5-butyl-6-isoheptyl-propyleneurea as well as the corresponding 4-hydroxypropylenethioureas. as

-4- 009844/1885

- 4 - O.Z. 24 480

4-Alkoxy-propylene ~ (thio) - ~ ureas can, for example 4-methoxy-5,5-dimethyl-propyleneurea, 4-läethoxy-5,5-dimethyl-6-isopropyl-propyleneurea, 4-butoxy-5,5-dimethyl-6-isopropylpropylene urea and the corresponding 4-alkoxypropylenethioureas can be used.

The formaldehyde can be used as an aqueous solution or in the form of trioxane or formaldehyde acetals. Among the CH-acidic Aldehydes are in particular isobutyraldehyde and 2-methylpentanal and 2-ethylhexanal are suitable.

Acids can be used in particular under the reaction conditions use non-oxidizing strong acids, e.g. hydrogen chloride, hydrogen bromide, concentrated hydrochloric acid, sulfuric acid, Oxalic acid or benzenesulfonic acid “You use them expediently in amounts of 5 to 40 wt. ^, based on to be reacted Urea.

It is appropriate to carry out the reaction in the presence of solution and / or Diluents such as water or dioxane to carry out. the Solvents and / or diluents can be used individually or as a mixture.

The substances are generally reacted in the theoretical molar ratio. Slight deviations from this molar ratio, e.g. up to 10 mol $, however, are possible.

-5-

009844/1885

- 5 - 0.7t. 24 480

The method according to the invention is one Condensation reaction caused by the addition of higher amounts of acid, possibly together with an increase in the reaction temperature, can be accelerated. In many cases it is possible to do this even at low temperatures in the presence of large amounts of acid to obtain the propylene (thio) urea aldehydes. on the other hand it is possible to carry out the reaction at a higher temperature in the presence of lower amounts of acid. The choice of The temperature depends on the respective reactants and can be reduced if the addition of acid is increased and vice versa.

The compounds that can be produced by this process are valuable Intermediate products, e.g. for the production of aminocarboxylic acids.

The parts given in the following examples are parts by weight.

Example 1

In a stirred apparatus with a reflux condenser, 50 parts of a 50 wt. Immediately after the addition of acid, the temperature rises to about 50 to 60 ^° C. After 6 etündigem stirring at 80 to 85 ⁰ C the reaction mixture to room temperature,

Q098U / 1886

6 - O.Z. 24 480

cooled and neutralized with dilute sodium hydroxide solution. The resulting 4-Siethoxy-5,5-dimethyl-propylene-urea-N, N 'dineopental is extracted exhaustively from the reaction mixture with chloroform. Drying the chloroform phase with sodium sulfate and evaporating off the chloroform gives 265 parts of crude product. The purification is carried durcn high vacuum distillation, the main fraction having as a viscous oil having a boiling range 175-188 ⁰ C at 0.5 torr and begins to crystallize after standing for several days. Analysis; C ₁₇ H ₅₀ O ₄ N ₂ (326)

Calculated: C 62.6 <fo H 9.2 # 0 19.6? SN 8.6 # Found: C 62.3 1 ° H 9.2 fo 0 19.4 1 ° N 8.3 #

Example 2 '- ■ · ■

A mixture of 186 parts of 4-hydroxy-5,5-dimethyl-6-isopropyl-propyleneurea, 200 parts of 30% formaldehyde solution and 144 parts of isobutyraldehyde is mixed with 50 parts of concentrated hydrochloric acid in a stirred apparatus with intensive reflux cooling and heated at reflux temperature for 5 hours . The reaction mixture is then cooled to room temperature and neutralized with sodium hydroxide solution. After extraction with chloroform, the chloroform solution is dried with sodium sulfate, filtered and the filtrate is evaporated under reduced pressure. 325 parts of 4-hydroxy-5,5-dimethyl-O-isopropyl-propylene urea-N, Έ '-dineopental are obtained For purification, the product can be recrystallized from a little chloroform.

009844/1885 ~

- 7 -. O.Z. 24

Analysis: C ₁₉ H ₃₄ O ₄ ST ₂ (354)

Calculated: C 64.5 % H 9.6 $ O 18.1 # IT 7-9 #

Found: C 64.0 % H 10.0 fo 0 17.8% S 7.8 <f <>

9844/1885

Claims (1)

- JB '- OoZ. 24 480 Claim Process for the production of propylene urea aldehydes the general formula R ₇ N-CH ₀ -C-CHO 2 ι ^ R R R ₄ ^R 5 in which the radicals Rp, IU, R «, Rc" and Rg are hydrogen atoms, identical or different alkyl radicals, R ₇ and Rg are alkyl radicals and X is an oxygen or sulfur atom, the radical R .. alkyl or the radical. = .. ". -CH ₉ -C-CHO wherein R ™ and Rg have the meaning given, characterized in that propylene ureas of the general formula where Rr ,, R. ,, R ₁ , R ^, S- and X have the aforementioned meaning and R _{Q is} hydrogen or an alkyl group, with formaldehyde and a CH-acidic aldehyde of the general formula HC-CHO III, in which Rj and Rg have the aforementioned meaning, in the presence of an acid, optionally in the presence of a solvent and / or diluent, at a temperature between 0 and "120 ° C., the approximately stoichiometric amount of formaldehyde being used for each NH group of the starting urea and the approximately stoichiometric amount of the CH-acidic aldehyde is used. BADISOHE ANILINE - '& SOEA-FABRIK AG 98A4 / 18.85 BAD ORIGINAL