IE44189B1 - Method for synthesizing n-methyl ureas - Google Patents
Method for synthesizing n-methyl ureasInfo
- Publication number
- IE44189B1 IE44189B1 IE2665/76A IE266576A IE44189B1 IE 44189 B1 IE44189 B1 IE 44189B1 IE 2665/76 A IE2665/76 A IE 2665/76A IE 266576 A IE266576 A IE 266576A IE 44189 B1 IE44189 B1 IE 44189B1
- Authority
- IE
- Ireland
- Prior art keywords
- urea
- process according
- formaldehyde
- hydrogenation
- methyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 235000013877 carbamide Nutrition 0.000 title abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 9
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 125000002015 acyclic group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JOHLTMWXHJLNDE-UHFFFAOYSA-N methoxyurea Chemical compound CONC(N)=O JOHLTMWXHJLNDE-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
- C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for the preparation of N-methyl ureas is disclosed, the improvement consisting in that the reaction is a catalytic hydrogenation of a mixture of an urea and formaldehyde, carried out in a single-step run and in a definitely acidic environment, contrarily to the conventional art, under high temperatures and pressures. Temperatures of 50.degree.C150.degree.C and pressures of from 20 to 150 kgs./sq.cm. are the prefurred field of action.
Description
This invention relates to a process for producing N-methyl ureas.
A conventional technique for obtaining N-methylureas (as described in . United States Patent Sqecification No. 2,422,400) requires the following two steps:(a) the formation of an Ν-methoxy urea intermediate from a urea and formaldehyde in a basic environment and its separation from the reaction mixture, and (b) the hydrogenation, with a hydrogenation catalyst, of the N-methoxy urea intermediate after having adjusted the pH of the reaction medium to be within the range from 10.5 to 7.
According to the present invention, there is provided a process for producing an N-methyl urea, which comprises hydrogenating with hydrogen, in an acidic environment, a mixture of urea, which may be unsubstituted or substituted and acycylic or cyclic, and formaldehyde or a precursor of formaldehyde capable - of yielding formaldehyde under the hydrogenation conditions.
The present invention results in the addition of a methyl radical to at least one nitrogen atom of the urea. The urea starting material can be urea itself, i.e. NHg-CO-NHg, or a derivative thereof in which at least one, but not all, of the four hydrogen atoms has been replaced by a substituent, for example a methyl group.
With the process of the present invention, it is possible to obtain in a single 2. 418 0 step, and with good yields, the desired N-methyl urea.
Preferably the hydrogenation is effected in the presence of an active metallic hydrogenation catalyst.
As regards the general conditions of the hydrogenation, high working 5 pressures are preferably used; and the urea to be methylated and the formaldehyde are preferably used in stoichiometric amounts (i.e. one molecule of formaldehyde per methyl group which is to be introduced). If urea itself is used as the urea starting material, from one to four methyl groups can be introduced depending on the relative quantities of urea and formaldehyde employed, id always assuming that there is sufficient hydrogen present for the hydrogenation.
The reaction preferably takes place at a pH in the range from 3 to 5, preferably in the presence of a catalyst (generally from 1 to 10?£ by weight relative to the urea starting material), and under hydrogen pressure.
The absolute reaction pressure is preferably in the range from 20 kg/sq.cm. to 15 150 kg/sq.cm. and the temperature is preferably in the range from 50°C to 150°C.
Formaldehyde is conveniently employed either as a 37% aqueous solution or an amorphous paraformaldehyde in methanolic solution, or also as trioxane (i.e. metaformaldehyde).
The catalyst, when present, is conveniently a metal which has an hydrogenation 20 activity and is commonly used therefor (such as Ni, Pt or Pd), supported by an inert material.
The catalyst can be recycled a number of times without losing its initial activity.
The following Examples illustrate the present invention.
EXAMPLE 1 A 2-litre, high-pressure autoclave was charged with 210 grams (2.5 moles) of commercial ethylene-urea (also known as 2-imidazolidone), 150 grams (5 moles calculated as formaldehyde) of paraformaldehyde, 400 ml of methanol, 10 grams of 5% Pd on carbon, and sufficient H3PO4 to bring the pH to 3. 3. 418 9 Hydrogen was fed under an absolute pressure of 10 kg/sq.cm., and simultaneous stirring and heating were started. Absorption started at about 80°C and was rapidly continued up to a temperature in the range 130°C-140°C. The absolute pressure was kept at 30 kg./sq.cm.
Under these conditions, no further hydrogen absorption was experienced after two hours.
The contents of the autoclave were discharged, and the catalyst was filtered off; it was washed a number of times with water and methanol and was suitable for reuse.
The filtered solution was neutralized with sodium hydroxide, the methanol was distilled off, and N, N1-dimethyl-2-imidazolone was obtained, both the selectivity and the yield being greater than 952.
EXAMPLE 2 A 2-litre high-pressure autoclave was charged with 215 grams (2.4 moles) of Ν, N1-dimethylurea, 150 grams of paraformaldehyde (5 moles calculated as formaldehyde), 400 ml of methanol, 10 grams of 52 Pd on carbon, and sufficient H3PO4 to bring the pH to 3.
Hydrogen was initially fed under an absolute pressure of 30 kg/sq.cm., and both stirring and heating were started.
At a temperature of 100°C and at an absolute pressure of 80 kg/sq.cm., the hydrogen absorption was quick and was completed within about one hour of reaction. Ν,Ν,Ν1,Ν1-tetramethyl urea was obtained with both a yield and a selectivity over 902.
Claims (11)
1. CLAIMS:1. A process for producing an N-methyl urea, which comprises hydrogenating with hydrogen, in an acidic environment, a mixture of a urea, which may be unsubstituted or substituted and acyclic or cyclic, and formaldehyde or a precursor of formaldehyde capable cf yielding formaldehyde under the 5 hydrogenation conditions.
2. A process according to claim 1, wherein the hydrogenation takes place in the presence of a hydrogenation catalyst.
3. A process according to claim 2, wherein the catalyst is present in an amount of from 1 to 10% by weight of the urea starting material. 10
4. A process according to claim 2 or 3, wherein the catalyst comprises at least one of nickel, palladium and platinum.
5. A process according to any preceding claim wherein the hydrogenation reaction is carried out at a temperature in the range from 50°C to 150°C.
6. A process according to any preceding claim, wherein the hydrogenation 15 is carried out at an absolute pressure in the range from 20 to 150 kg/sq.cm.
7. A process according to any preceding claim, wherein the hydrogenation is effected at a pH in the range from 3 to 5.
8. A process according to any preceding claim, wherein the formaldehyde is used in the form of the precursor paraformaldehyde. 20
9. · A process according to any preceding claim, wherein for each methyl radical to be introduced into the urea molecule, there is employed approximately one molecule of formaldehyde per molecule of urea.
10. A process for producing an N-methyl urea, substantially as described in the foregoing Examples. 25
11. A urea in which at least one methyl group has been introduced onto a 5. 441- 89 nitrogen atom, by a process according to any preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT29962/75A IT1051036B (en) | 1975-12-03 | 1975-12-03 | PROCEDURE FOR THE SYNTHESIS OF N METHYL UREE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE44189L IE44189L (en) | 1977-06-03 |
| IE44189B1 true IE44189B1 (en) | 1981-09-09 |
Family
ID=11228764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE2665/76A IE44189B1 (en) | 1975-12-03 | 1976-12-03 | Method for synthesizing n-methyl ureas |
Country Status (31)
| Country | Link |
|---|---|
| JP (1) | JPS5271419A (en) |
| AR (1) | AR220673A1 (en) |
| AT (1) | AT350582B (en) |
| AU (1) | AU508607B2 (en) |
| BE (1) | BE849073A (en) |
| BG (1) | BG32846A3 (en) |
| BR (1) | BR7608197A (en) |
| CA (1) | CA1074333A (en) |
| CS (1) | CS193070B2 (en) |
| DD (1) | DD127478A5 (en) |
| DE (1) | DE2654928C3 (en) |
| DK (1) | DK536076A (en) |
| EG (1) | EG12262A (en) |
| ES (1) | ES454228A1 (en) |
| FR (1) | FR2333781A1 (en) |
| GB (1) | GB1517820A (en) |
| HU (1) | HU179578B (en) |
| IE (1) | IE44189B1 (en) |
| IN (1) | IN144718B (en) |
| IT (1) | IT1051036B (en) |
| LU (1) | LU76306A1 (en) |
| MX (1) | MX4021E (en) |
| NL (1) | NL167418C (en) |
| NO (1) | NO147274C (en) |
| PH (1) | PH13011A (en) |
| PL (1) | PL109171B1 (en) |
| PT (1) | PT65922B (en) |
| SE (1) | SE7613630L (en) |
| TR (1) | TR18980A (en) |
| YU (1) | YU292276A (en) |
| ZA (1) | ZA767109B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3581541D1 (en) * | 1985-09-10 | 1991-02-28 | Kawaken Fine Chemicals Co | METHOD FOR PRODUCING CYCLIC UREA DERIVATIVES. |
| US4617400A (en) * | 1985-09-11 | 1986-10-14 | Kawaken Fine Chemicals Co., Ltd. | Process for preparing cyclic urea derivatives |
| DE3800083A1 (en) * | 1988-01-05 | 1989-07-13 | Basf Ag | METHOD FOR PRODUCING CYCLIC N, N'-DIMETHYL UREA |
| DE4425696A1 (en) * | 1994-07-20 | 1996-01-25 | Basf Ag | Process for the preparation of 1,3-disubstituted imidazolidinones |
| DE19743760A1 (en) * | 1997-10-02 | 1999-04-08 | Basf Ag | Process for the preparation of cyclic urea derivatives |
-
1975
- 1975-12-03 IT IT29962/75A patent/IT1051036B/en active
-
1976
- 1976-11-26 DK DK536076A patent/DK536076A/en not_active Application Discontinuation
- 1976-11-29 ZA ZA767109A patent/ZA767109B/en unknown
- 1976-11-29 EG EG76748A patent/EG12262A/en active
- 1976-11-30 TR TR18980A patent/TR18980A/en unknown
- 1976-12-01 AU AU20145/76A patent/AU508607B2/en not_active Expired
- 1976-12-01 YU YU02922/76A patent/YU292276A/en unknown
- 1976-12-01 NO NO764100A patent/NO147274C/en unknown
- 1976-12-01 LU LU76306A patent/LU76306A1/xx unknown
- 1976-12-01 IN IN2141/CAL/76A patent/IN144718B/en unknown
- 1976-12-01 GB GB50196/76A patent/GB1517820A/en not_active Expired
- 1976-12-02 FR FR7636337A patent/FR2333781A1/en active Granted
- 1976-12-02 CA CA267,040A patent/CA1074333A/en not_active Expired
- 1976-12-02 AT AT894276A patent/AT350582B/en active
- 1976-12-02 HU HU76SA2998A patent/HU179578B/en unknown
- 1976-12-02 DD DD196085A patent/DD127478A5/xx unknown
- 1976-12-02 PH PH19190A patent/PH13011A/en unknown
- 1976-12-02 PT PT65922A patent/PT65922B/en unknown
- 1976-12-02 BR BR7608197A patent/BR7608197A/en unknown
- 1976-12-03 AR AR265719A patent/AR220673A1/en active
- 1976-12-03 NL NL7613527.A patent/NL167418C/en not_active IP Right Cessation
- 1976-12-03 MX MX765185U patent/MX4021E/en unknown
- 1976-12-03 PL PL1976194144A patent/PL109171B1/en unknown
- 1976-12-03 IE IE2665/76A patent/IE44189B1/en unknown
- 1976-12-03 CS CS767876A patent/CS193070B2/en unknown
- 1976-12-03 SE SE7613630A patent/SE7613630L/en not_active Application Discontinuation
- 1976-12-03 BG BG034826A patent/BG32846A3/en unknown
- 1976-12-03 BE BE172980A patent/BE849073A/en not_active IP Right Cessation
- 1976-12-03 DE DE2654928A patent/DE2654928C3/en not_active Expired
- 1976-12-03 ES ES454228A patent/ES454228A1/en not_active Expired
- 1976-12-03 JP JP51144818A patent/JPS5271419A/en active Pending
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