CA1235139A - Process for preparing aminoalkylureas - Google Patents
Process for preparing aminoalkylureasInfo
- Publication number
- CA1235139A CA1235139A CA000451121A CA451121A CA1235139A CA 1235139 A CA1235139 A CA 1235139A CA 000451121 A CA000451121 A CA 000451121A CA 451121 A CA451121 A CA 451121A CA 1235139 A CA1235139 A CA 1235139A
- Authority
- CA
- Canada
- Prior art keywords
- general formula
- group selected
- solvent
- urea
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Invention An efficient process for selectively preparing monosubstituted urea-alkylenediamine addition compounds from urea and alkylenediamines in solvents having the formula R1OH where R1 is hydrogen or alkyd having from 1 to about 4 carbon atoms.
Description
US
sack round of the Invention The preparation of aminoalkylureas from urea and alkylenediamines generally involves extensive multi-step procedures or the use of hazardous reagents such as cynic acid and its salts. Quite often these conventional pro-Sirius involve either removal of hydrochloric acid or nitric acid from the reaction products after the reaction is completed, or careful handling of reactants prior to or during the reaction; and thus do not lend themselves to efficient large scale production of aminoalkylureas. It is further known from U.S. Patent No. 2,145,242 that dialkyl ureas can be prepared by heating urea with polyethylene-dominoes at elevated temperatures in solvents having no-natively high boiling points such as phenol, chrysalis, and hydroxydiphenyl. Not only are disubstituted alkylamines produced in these solvents at elevated temperatures, due in part to the rapid decomposition of urea, but the procedure is not useful in accordance with the present invention since the higher temperatures required to remove these solvents will promote decomposition of the mono-substituted amino-alkylureas.
Heretofore, a convenient economical process has not existed for the selective preparation of aminoalkylureas by the condensation of urea and alkylenediamines. Aminoalkyl-ureas made in accordance with the present invention are useful, inter alias as intermediates in the preparation of ~-adrenergic blocking agents such as disclosed in commonly assigned, cop ending Canadian application 415,282, filed November 10, 1982.
1 m hut So Summary of the Invention In one aspect the invention provides a process for selectively preparing a compound of general formula:
H N-A-NH-C(O)-NH (I) wherein A is a straight or branched chained aliphatic hydra-carbon having from 2 to about 10 carbon atoms; said process comprising: (a) reacting a Damon of general formula:
H2N-A-NH2 (II) wherein A is as defined above, with urea in a solvent of general formula:
RlOH (III) wherein Al is H or Of alkali, at a condensing temperature to produce the desired compound of general formula (I); and (b) removing the solvent.
In a further aspect the invention provides a process for selectively preparing a compound of general formula:
H2N-CI-(CH2)n-NH-C(O)-NH2 (IV) wherein n is an integer of from one to about 10, and R2 and R3, independently, are H, Cl_4alkyl, C3_7cycloalkyl, phenol or phenol substituted with a halogen, -OH, -ON, -N02, acetamido, lower-alkyl, lower-alkenyl, lower-alkynyl, lower-alkoxy or lower-hydroxyalkyl; said process comprising:
repeating steps (a) and (b) as described above but subset-lo/ -I -2-I
tuning a Damon of gent fat formula
sack round of the Invention The preparation of aminoalkylureas from urea and alkylenediamines generally involves extensive multi-step procedures or the use of hazardous reagents such as cynic acid and its salts. Quite often these conventional pro-Sirius involve either removal of hydrochloric acid or nitric acid from the reaction products after the reaction is completed, or careful handling of reactants prior to or during the reaction; and thus do not lend themselves to efficient large scale production of aminoalkylureas. It is further known from U.S. Patent No. 2,145,242 that dialkyl ureas can be prepared by heating urea with polyethylene-dominoes at elevated temperatures in solvents having no-natively high boiling points such as phenol, chrysalis, and hydroxydiphenyl. Not only are disubstituted alkylamines produced in these solvents at elevated temperatures, due in part to the rapid decomposition of urea, but the procedure is not useful in accordance with the present invention since the higher temperatures required to remove these solvents will promote decomposition of the mono-substituted amino-alkylureas.
Heretofore, a convenient economical process has not existed for the selective preparation of aminoalkylureas by the condensation of urea and alkylenediamines. Aminoalkyl-ureas made in accordance with the present invention are useful, inter alias as intermediates in the preparation of ~-adrenergic blocking agents such as disclosed in commonly assigned, cop ending Canadian application 415,282, filed November 10, 1982.
1 m hut So Summary of the Invention In one aspect the invention provides a process for selectively preparing a compound of general formula:
H N-A-NH-C(O)-NH (I) wherein A is a straight or branched chained aliphatic hydra-carbon having from 2 to about 10 carbon atoms; said process comprising: (a) reacting a Damon of general formula:
H2N-A-NH2 (II) wherein A is as defined above, with urea in a solvent of general formula:
RlOH (III) wherein Al is H or Of alkali, at a condensing temperature to produce the desired compound of general formula (I); and (b) removing the solvent.
In a further aspect the invention provides a process for selectively preparing a compound of general formula:
H2N-CI-(CH2)n-NH-C(O)-NH2 (IV) wherein n is an integer of from one to about 10, and R2 and R3, independently, are H, Cl_4alkyl, C3_7cycloalkyl, phenol or phenol substituted with a halogen, -OH, -ON, -N02, acetamido, lower-alkyl, lower-alkenyl, lower-alkynyl, lower-alkoxy or lower-hydroxyalkyl; said process comprising:
repeating steps (a) and (b) as described above but subset-lo/ -I -2-I
tuning a Damon of gent fat formula
2 lo (Shannon (V) wherein n, R2, and R3 are as defined above, for the Damon of general formula (II) in step (a).
Detailed Description of the Invention In accordance with the present invention, disclosed is a procedure for selectively preparing aminoalkylureas having the formula H2N-A-NH-C(O)-NH2 from alkylenediamines having the formula H2N-A-NH2 where A
is a branched or straight chained aliphatic hydrocarbon have in from 2 to about 10 carbon atoms, by condensation with urea or alkyd substituted urea in solvents having a relatively libeling point until the reaction is completed, after which time the solvent is removed by -pa-, lo/
I
evaporation. Quite unlike the conventionally used procedures for preparing aminoalkylureas, the procedure of the present invention does not require that hydrochloric acid or nitric acid be washed away from the reaction product when the reaction is complete; nor does it require the use of isocyanate salts or its derivatives.
Included in the process of the present invention are compounds having the formula if H2N-C- ( SHEA ) n-NHC-NH2 wherein R2 and R3 are independently hydrogen, lower alkyd having from 1 to about 4 carbon atoms, cycloalkyl having from 3 to about 7 carbon atoms; unsubstituted phenol or phenol substituted with lower alkyd of from 1 to about 4 carbon atoms, lower alkenyl of from 2 to about 4 carbon atoms, lower alkynyl of 3 or 4 carbon atoms, lower alkoxy of from I to about 4 carbon atoms, halogen such as chlorine or fluorine and the like, acetamido, nutria hydroxy, lower hydroxyalkyl of from 1 to about 4 carbon atoms, or cyan; and n is on integer from 1 to about 10. These compounds are prepared by heating dominoes having the formula H2N-C- ( SHEA ) n-NH2 ....
with urea or alkyd substituted urea in solvents having the formula RlOH
where R1 is hydrogen or alkyd having from 1 to about 4 carbon atoms.
Alkylenediamines, in accordance with one embodiment of the present invention, include those where the primary amino groups are separated by straight chained aliphatic hydrocarbon radicals having from 2 to about 10 carbon atoms and preferably having from 2 to about 6 I, So carbon atoms, such as ethylenediamine, propylenediamine, twitter-methylenediamine, pentamethylenediamine, and the like; branched chained aliphatic hydrocarbon radicals preferably having from to about 10 carbon atoms and preferably from 3 to 6 carbon atoms such as 1 methylethylenediamine, 2 methylethylenediamine, 1,1 dim ethylene-Damon, 1,2 dimethylenediamine, 1,1 diethylenediamine, and the like.
In an alternate embodiment of the present invention, alkaline-dominoes also include aliphatic hydrocarbon radicals having from 2 to about 10 carbon atoms substituted at various positions along the chain with cycloalkyl having from 3 to about 7 carbon atoms; phenol; or phenol substituted with alkyd of from 1 to about carbon atoms, alkenyl of from 2 to about 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, alkoxy of from 1 to about 4 carbon atoms, hydroxyalkyl of from 1 to about 4 carbon atoms, halogen such as chlorine or fluorine and the like, acetamido, vitro, hydroxy, or cyan.
In accordance with the present invention, the reaction can be carried out with urea or lower alkyd substituted urea such as methyl urea, ethyl urea, and propeller. Preferably, the reaction employs unsubstituted urea.
In accordance with the present invention, the reactants are heated at a temperature sufficient to cause the condensation of urea and the primary Damon with consequent liberation of ammonia; and without destruction of reactants. Preferably, condensing temperatures from about 60 to about 120C may be used, and more preferably from about 60 to about 100C. Although it is not necessary to heat the solvent at its boiling point during the reaction, I have found that refluxing the urea with alkylenediamines in solvents having boiling points within this temperature range has advantageously produced monosubstituted dominoes and has afforded a convenient process in accordance with the present invention.
Solvents, in accordance with the present invention, include but are not limited to those having the formula ROY, wherein R1 is hydrogen i513~ `
or lower alkyd. Preferably, when R1 is not hydrogen, it is an alkyd having from 1 to about 4 carbon atoms. Thus, in addition to water as a solvent. lower alcohols useful in the process of the present invention include methanol, ethanol, n-propanol, isopropyl, buttonhole, isobutyl alcohol, and the like. I have found, in accordance with the process of the present invention, that both water and isopropyl alcohol provide excellent yields of aminoalkylureas. Not only do these solvents facilitate the monosubstitution of the dominoes in accordance with the present invention, but advantageously they are easily removed from the completed reaction vessel without the need to elevate temperatures, which would cause the decomposition of the aminoalkylurea products.
Solvents having relatively higher boiling points, even though they could be heated at lower temperatures during the reaction of urea with the dominoes, would require that the temperature be elevated at the completion of the reaction to expel the solvent from the reaction vessel and possibly cause decomposition of the aminoalkylureas.
In accordance with the present invention, the condensation of urea with the appropriate Damon is allowed to proceed until the evolution of ammonia ceases. The evolution of ammonia from the refluxing reaction is conveniently determined by measuring the pi of the effluent in the condensing column. Useful reaction times for completion of the reaction include, but are not limited, to times from about 10 to 24 hours. It is to be understood however, that the duration of the reaction will depend upon the solvent and temperature at which that solvent is heated.
In accordance with the present invention, I have found that various amounts of urea and alkylenediamine can be used without affecting the selective monosubstitution of the Damon. For example, both a 1:1 and a 2:1 molar ratio of urea to alkylenediamine have been employed and both ratios produce identical monosubstituted products.
Furthermore, urea at concentrations of from about 2.5 to about 6.2 moleslliter and dominoes at concentrations of from about So to about 5.7 molesl1iter have been employed and produce identical products having excellent yields.
The following examples illustrate specific embodiments of the present invention and are not intended to limit the scope thereof.
Example I
This example describes the synthesis of a compound of the formula SHEA o H2N~C-CH2NHCNH2 SHEA
A quantity of 88.16 grams of 1,2-diamino-2~methyl propane (1 mole) and 60.6 grams of urea (1 mole) were reflexed for 10 hours in 176 ml deionized water at 100C, evaporated to an oil, azeotroped with Dixon (to remove residual water) forming a dry white solid. The white solid was dissolved in 350 ml of warm ethyl acetate, cooled for 3 hours and crystallized under No filtered, and washed with 100 ml of ethyl-acetate, and dried under vacuum at 60C giving a product having a melting point of 88-90C (57X yield). The NOR and IT spectra were consistent with the assigned structure, and the chemical analysis was consistent with the empirical formula (C, H, N, 45.96, 9.94, 31.93).
Example II
This example describes the synthesis of a compound of the formula .
SHEA
A quantity of 529 grams of 1,2-diamino-2-methyl propane (6 moles) and 397 grams of urea ~6.6 moles) were reflexed for 24 hours in 1058 ml t828 grams) of isopropanol for 24 hours at 82C, evaporated to an oil, dissolved in 1 liter of Dixon, evaporated to an oil at 75C, dissolved Sly in 1 liter of ethyl acetate, cooled and crystallized under No, washed with 1 liter of 10% isopropanol on ethyl acetate, and dried under vacuum at 65C giving a product having the same physical and chemical properties as the product of Example I (67.2% yield).
Example III
-This example describes the synthesis of a compound having the formula H2NCH2CH2NHCNH2 (HAYAKAWA
A quantity of 30 grams of ethylenediamine (0.5 mole) and 30 grams urea (0.5 mole) were reflexed for 24 hours in 200 ml of isopropanol at 82C, evaporated to an oil, dissolved in ethyl acetate, filtered, oxalic acid added, filtered, dissolved in ethyl acetate again, cooled and crystallized giving a white powder having a melting point of 148-150C
(58X yield). The NOR and IT spectra were consistent with the assigned structure, and the chemical analysis was consistent with the empirical formula (C, H, N, 31.12, 5.67, 21.68).
Example IV
This example describes the synthesis of a compound of the formula SHEA
A quantity of 8.8 grams of 1,2-diamino-2-methyl propane (0.1 mole) and 6.0 grams of urea (0.1 mole) were reflexed for 5 hours (neat) at 125C, dissolved in an ethanol-ethylacetate mixture, filtered, cooled to 0C, filtered, washed with ethyl acetate, and dried in an oven to give a so - -compound having a melting point of 175-177C. The NOR and IT spectra were consistent with the assigned structure.
Example V
This examples describes the synthesis of a compound of the formula O OH O
., , 3 ..
SHEA
A quantity of 8.8 grams of 1,2-diamino-2-methyl propane (0.1 mole) and .0 grams of urea (0.1 mole) were heated in an oil bath for 3 hours in 20 grams of phenol, cooled to room temperature, dissolved in 100 ml of ethyl acetate, decanted, dissolved in 50 ml ethyl acetate, decanted again, dissolved in a mixture of ethyl acetate and ethanol, filtered, cooled to 0C, filtered washed with ethyl acetate followed by ether, and dried in an oven to give a compound having a melting point of 175-177C (81.6X yield). The NOR and IT spectra were consistent with the assigned structure and the chemical analysis was consistent with the empirical formula (C, H, N, 41.30, 7.96, 32.31).
Example VI
Example Y was repeated in all essential details with the exception that 12.1 grams (0.2 moles) urea were used. The compound (82.7% yield) produced was identical to that of Example V.
The present invention has been described in detail and with specific reference to its preferred embodiments; however, it is to be understood by those skilled in the art that modifications can be made ; thereto without departing from the spirit and scope thereof.
.
Detailed Description of the Invention In accordance with the present invention, disclosed is a procedure for selectively preparing aminoalkylureas having the formula H2N-A-NH-C(O)-NH2 from alkylenediamines having the formula H2N-A-NH2 where A
is a branched or straight chained aliphatic hydrocarbon have in from 2 to about 10 carbon atoms, by condensation with urea or alkyd substituted urea in solvents having a relatively libeling point until the reaction is completed, after which time the solvent is removed by -pa-, lo/
I
evaporation. Quite unlike the conventionally used procedures for preparing aminoalkylureas, the procedure of the present invention does not require that hydrochloric acid or nitric acid be washed away from the reaction product when the reaction is complete; nor does it require the use of isocyanate salts or its derivatives.
Included in the process of the present invention are compounds having the formula if H2N-C- ( SHEA ) n-NHC-NH2 wherein R2 and R3 are independently hydrogen, lower alkyd having from 1 to about 4 carbon atoms, cycloalkyl having from 3 to about 7 carbon atoms; unsubstituted phenol or phenol substituted with lower alkyd of from 1 to about 4 carbon atoms, lower alkenyl of from 2 to about 4 carbon atoms, lower alkynyl of 3 or 4 carbon atoms, lower alkoxy of from I to about 4 carbon atoms, halogen such as chlorine or fluorine and the like, acetamido, nutria hydroxy, lower hydroxyalkyl of from 1 to about 4 carbon atoms, or cyan; and n is on integer from 1 to about 10. These compounds are prepared by heating dominoes having the formula H2N-C- ( SHEA ) n-NH2 ....
with urea or alkyd substituted urea in solvents having the formula RlOH
where R1 is hydrogen or alkyd having from 1 to about 4 carbon atoms.
Alkylenediamines, in accordance with one embodiment of the present invention, include those where the primary amino groups are separated by straight chained aliphatic hydrocarbon radicals having from 2 to about 10 carbon atoms and preferably having from 2 to about 6 I, So carbon atoms, such as ethylenediamine, propylenediamine, twitter-methylenediamine, pentamethylenediamine, and the like; branched chained aliphatic hydrocarbon radicals preferably having from to about 10 carbon atoms and preferably from 3 to 6 carbon atoms such as 1 methylethylenediamine, 2 methylethylenediamine, 1,1 dim ethylene-Damon, 1,2 dimethylenediamine, 1,1 diethylenediamine, and the like.
In an alternate embodiment of the present invention, alkaline-dominoes also include aliphatic hydrocarbon radicals having from 2 to about 10 carbon atoms substituted at various positions along the chain with cycloalkyl having from 3 to about 7 carbon atoms; phenol; or phenol substituted with alkyd of from 1 to about carbon atoms, alkenyl of from 2 to about 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, alkoxy of from 1 to about 4 carbon atoms, hydroxyalkyl of from 1 to about 4 carbon atoms, halogen such as chlorine or fluorine and the like, acetamido, vitro, hydroxy, or cyan.
In accordance with the present invention, the reaction can be carried out with urea or lower alkyd substituted urea such as methyl urea, ethyl urea, and propeller. Preferably, the reaction employs unsubstituted urea.
In accordance with the present invention, the reactants are heated at a temperature sufficient to cause the condensation of urea and the primary Damon with consequent liberation of ammonia; and without destruction of reactants. Preferably, condensing temperatures from about 60 to about 120C may be used, and more preferably from about 60 to about 100C. Although it is not necessary to heat the solvent at its boiling point during the reaction, I have found that refluxing the urea with alkylenediamines in solvents having boiling points within this temperature range has advantageously produced monosubstituted dominoes and has afforded a convenient process in accordance with the present invention.
Solvents, in accordance with the present invention, include but are not limited to those having the formula ROY, wherein R1 is hydrogen i513~ `
or lower alkyd. Preferably, when R1 is not hydrogen, it is an alkyd having from 1 to about 4 carbon atoms. Thus, in addition to water as a solvent. lower alcohols useful in the process of the present invention include methanol, ethanol, n-propanol, isopropyl, buttonhole, isobutyl alcohol, and the like. I have found, in accordance with the process of the present invention, that both water and isopropyl alcohol provide excellent yields of aminoalkylureas. Not only do these solvents facilitate the monosubstitution of the dominoes in accordance with the present invention, but advantageously they are easily removed from the completed reaction vessel without the need to elevate temperatures, which would cause the decomposition of the aminoalkylurea products.
Solvents having relatively higher boiling points, even though they could be heated at lower temperatures during the reaction of urea with the dominoes, would require that the temperature be elevated at the completion of the reaction to expel the solvent from the reaction vessel and possibly cause decomposition of the aminoalkylureas.
In accordance with the present invention, the condensation of urea with the appropriate Damon is allowed to proceed until the evolution of ammonia ceases. The evolution of ammonia from the refluxing reaction is conveniently determined by measuring the pi of the effluent in the condensing column. Useful reaction times for completion of the reaction include, but are not limited, to times from about 10 to 24 hours. It is to be understood however, that the duration of the reaction will depend upon the solvent and temperature at which that solvent is heated.
In accordance with the present invention, I have found that various amounts of urea and alkylenediamine can be used without affecting the selective monosubstitution of the Damon. For example, both a 1:1 and a 2:1 molar ratio of urea to alkylenediamine have been employed and both ratios produce identical monosubstituted products.
Furthermore, urea at concentrations of from about 2.5 to about 6.2 moleslliter and dominoes at concentrations of from about So to about 5.7 molesl1iter have been employed and produce identical products having excellent yields.
The following examples illustrate specific embodiments of the present invention and are not intended to limit the scope thereof.
Example I
This example describes the synthesis of a compound of the formula SHEA o H2N~C-CH2NHCNH2 SHEA
A quantity of 88.16 grams of 1,2-diamino-2~methyl propane (1 mole) and 60.6 grams of urea (1 mole) were reflexed for 10 hours in 176 ml deionized water at 100C, evaporated to an oil, azeotroped with Dixon (to remove residual water) forming a dry white solid. The white solid was dissolved in 350 ml of warm ethyl acetate, cooled for 3 hours and crystallized under No filtered, and washed with 100 ml of ethyl-acetate, and dried under vacuum at 60C giving a product having a melting point of 88-90C (57X yield). The NOR and IT spectra were consistent with the assigned structure, and the chemical analysis was consistent with the empirical formula (C, H, N, 45.96, 9.94, 31.93).
Example II
This example describes the synthesis of a compound of the formula .
SHEA
A quantity of 529 grams of 1,2-diamino-2-methyl propane (6 moles) and 397 grams of urea ~6.6 moles) were reflexed for 24 hours in 1058 ml t828 grams) of isopropanol for 24 hours at 82C, evaporated to an oil, dissolved in 1 liter of Dixon, evaporated to an oil at 75C, dissolved Sly in 1 liter of ethyl acetate, cooled and crystallized under No, washed with 1 liter of 10% isopropanol on ethyl acetate, and dried under vacuum at 65C giving a product having the same physical and chemical properties as the product of Example I (67.2% yield).
Example III
-This example describes the synthesis of a compound having the formula H2NCH2CH2NHCNH2 (HAYAKAWA
A quantity of 30 grams of ethylenediamine (0.5 mole) and 30 grams urea (0.5 mole) were reflexed for 24 hours in 200 ml of isopropanol at 82C, evaporated to an oil, dissolved in ethyl acetate, filtered, oxalic acid added, filtered, dissolved in ethyl acetate again, cooled and crystallized giving a white powder having a melting point of 148-150C
(58X yield). The NOR and IT spectra were consistent with the assigned structure, and the chemical analysis was consistent with the empirical formula (C, H, N, 31.12, 5.67, 21.68).
Example IV
This example describes the synthesis of a compound of the formula SHEA
A quantity of 8.8 grams of 1,2-diamino-2-methyl propane (0.1 mole) and 6.0 grams of urea (0.1 mole) were reflexed for 5 hours (neat) at 125C, dissolved in an ethanol-ethylacetate mixture, filtered, cooled to 0C, filtered, washed with ethyl acetate, and dried in an oven to give a so - -compound having a melting point of 175-177C. The NOR and IT spectra were consistent with the assigned structure.
Example V
This examples describes the synthesis of a compound of the formula O OH O
., , 3 ..
SHEA
A quantity of 8.8 grams of 1,2-diamino-2-methyl propane (0.1 mole) and .0 grams of urea (0.1 mole) were heated in an oil bath for 3 hours in 20 grams of phenol, cooled to room temperature, dissolved in 100 ml of ethyl acetate, decanted, dissolved in 50 ml ethyl acetate, decanted again, dissolved in a mixture of ethyl acetate and ethanol, filtered, cooled to 0C, filtered washed with ethyl acetate followed by ether, and dried in an oven to give a compound having a melting point of 175-177C (81.6X yield). The NOR and IT spectra were consistent with the assigned structure and the chemical analysis was consistent with the empirical formula (C, H, N, 41.30, 7.96, 32.31).
Example VI
Example Y was repeated in all essential details with the exception that 12.1 grams (0.2 moles) urea were used. The compound (82.7% yield) produced was identical to that of Example V.
The present invention has been described in detail and with specific reference to its preferred embodiments; however, it is to be understood by those skilled in the art that modifications can be made ; thereto without departing from the spirit and scope thereof.
.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for selectively preparing a compound of general formula:
H2N-A-NH-C(O)-NH2 (I) wherein A represents a group selected from a straight and branched chained aliphatic hydrocarbon having from 2 to about 10 carbon atoms; said process comprising:
(a) reacting a diamine of general formula:
H2N-A-NH2 (II) wherein A is as defined above, with urea in a solvent of general formula:
RlOH (III) wherein Rl represents a group selected from H
and Cl-4alkyl, at a condensing temperature to produce the desired compound of general formula (I); and (b) removing the solvent.
H2N-A-NH-C(O)-NH2 (I) wherein A represents a group selected from a straight and branched chained aliphatic hydrocarbon having from 2 to about 10 carbon atoms; said process comprising:
(a) reacting a diamine of general formula:
H2N-A-NH2 (II) wherein A is as defined above, with urea in a solvent of general formula:
RlOH (III) wherein Rl represents a group selected from H
and Cl-4alkyl, at a condensing temperature to produce the desired compound of general formula (I); and (b) removing the solvent.
2. The process of claim 1, wherein step (a), the reaction is effected under reflux, and for the solvent of general formula (III), Rl represents a group selected from H
and C2-4alkyl.
and C2-4alkyl.
3. The process of claim 2, wherein the solvent is selected from the group consisting of water and isopropanol.
4. The process of claim 1, 2 or 3, wherein step (a), for the diamine of general formula (II), A represents a group selected from a straight and branched chained ali-phatic hydrocarbon having from 2 to about 6 carbon atoms.
5. The process of claim 1, 2 or 3, wherein step (a), for the diamine of general formula (II), A is substituted with a group selected from phenyl and substituted-phenyl, wherein the phenyl substituent is selected from the group consisting of a halogen, -OH, -CN, -NO2, acetamido, lower-alkyl, lower-alkenyl, lower-alkynyl, lower-alkoxy and lower-hydroxyalkyl.
6. A process for selectively preparing a compound of general formula:
(IV) wherein n is an integer of from one to about 10, and R2 and R3, independently, represent a group selected from H, Cl-4alkyl, C3-7cycloalkyl, phenyl and phenyl substituted with a group selected from a halogen, -OH, -CN, -NO2, acetamido, lower-alkyl, lower-alkenyl, lower-alkynyl, lower-alkoxy and lower-hydroxyalkyl; said process comprising:
(a') reacting a diamine of general formula:
(V) wherein n, R2 and R3 are as defined above, with urea in a solvent of general formula (III) as defined in claim 1, at a condensing temperature to produce the desired compound of general formula (IV); and (b') removing the solvent.
(IV) wherein n is an integer of from one to about 10, and R2 and R3, independently, represent a group selected from H, Cl-4alkyl, C3-7cycloalkyl, phenyl and phenyl substituted with a group selected from a halogen, -OH, -CN, -NO2, acetamido, lower-alkyl, lower-alkenyl, lower-alkynyl, lower-alkoxy and lower-hydroxyalkyl; said process comprising:
(a') reacting a diamine of general formula:
(V) wherein n, R2 and R3 are as defined above, with urea in a solvent of general formula (III) as defined in claim 1, at a condensing temperature to produce the desired compound of general formula (IV); and (b') removing the solvent.
7. The process of claim 6, wherein step (a'), the reaction is effected under reflux, and for the solvent of general formula (III), Rl represents a group selected from II
and C2-4alkyl.
and C2-4alkyl.
8. The process of claim 7, wherein the solvent is selected from the group consisting of water and isopropanol.
9. The process of claim 6, 7 or 8, wherein step (a'), for the diamine of general formula (V), n is an integer of from one to about 5, and R2 and R3, independently, represent a group selected from H, -CH3 and -C2H5.
10. The process of claim 6, 7 or 8, wherein step (a'), for the diamine of general formula (V), n is 2 or 3, and R2 and R3, independently, represent a group selected from H and -CH3.
11. The process of claim 6, 7 and 8, wherein step (a'), for the diamine of general formula (V), n is one, and R2 and R3, independently, represent a group selected from H and -CH3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49317883A | 1983-05-10 | 1983-05-10 | |
| US493,178 | 1990-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1235139A true CA1235139A (en) | 1988-04-12 |
Family
ID=23959211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451121A Expired CA1235139A (en) | 1983-05-10 | 1984-04-02 | Process for preparing aminoalkylureas |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS59210060A (en) |
| AU (1) | AU562839B2 (en) |
| CA (1) | CA1235139A (en) |
| NZ (1) | NZ208045A (en) |
| ZA (1) | ZA843320B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK175099B1 (en) * | 1987-06-25 | 2004-06-01 | Dow Agrosciences Llc | Process for the preparation of urea derivatives |
-
1984
- 1984-04-02 CA CA000451121A patent/CA1235139A/en not_active Expired
- 1984-05-03 AU AU27664/84A patent/AU562839B2/en not_active Ceased
- 1984-05-03 NZ NZ20804584A patent/NZ208045A/en unknown
- 1984-05-03 ZA ZA843320A patent/ZA843320B/en unknown
- 1984-05-09 JP JP9271584A patent/JPS59210060A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| AU562839B2 (en) | 1987-06-18 |
| NZ208045A (en) | 1987-08-31 |
| JPH0359897B2 (en) | 1991-09-12 |
| JPS59210060A (en) | 1984-11-28 |
| ZA843320B (en) | 1984-12-24 |
| AU2766484A (en) | 1984-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2137758C1 (en) | Method of preparing 1-(alkoxymethyl)pyrrole compounds | |
| KR950008489A (en) | Method for preparing 1,3,5-triazine | |
| CA1235139A (en) | Process for preparing aminoalkylureas | |
| WO1987004433A1 (en) | Preparation of 3-dimethylamino-7-methyl-1,2,4-benzotriazine-1-oxide and azapropazone | |
| Booth et al. | Synthesis of 9-hydroxyalkyl-substituted purines from the corresponding 4-(C-cyanoformimidoyl) imidazole-5-amines | |
| US5504207A (en) | Process and intermediate for the preparation of terazosin hydrochloride dihydrate | |
| CA1126758A (en) | 1,1,3,5-substituted biuret compound and a pharmaceutical composition containing the same | |
| US3701797A (en) | Process for preparing diaminomaleonitrile | |
| US3969466A (en) | Preparation of hydrazodicarbonamide | |
| US3954750A (en) | Preparation of hexahydro-1,3,5-trialkanoyl-s-triazines | |
| Sadek et al. | Activated nitriles in heterocyclic synthesis. Synthesis of several new pyrimidine and pyridazine derivatives | |
| US2714105A (en) | Benzoxazine diones and methods of preparing the same | |
| JPH06509557A (en) | How to carry out chemical reactions with formaldehyde | |
| Pazdera et al. | A new knowledge about the synthesis of 1-phenyl-3-(2-cyanophenyl) thiourea | |
| US1904229A (en) | Gesellschaft | |
| Bolis et al. | v-Triazolines. Part 8. 1-Aryl-4-alkyl-and-aryl-thiomethyl-5-amino-v-triazolines: synthesis and reactions with bases | |
| Ozeki et al. | A new sandmeyer iodination of 2-aminopurines in non-aqueous conditions: combination of alkali metal iodide and iodine as iodine sources | |
| CA1274828A (en) | Triazolo(1,5-c) pyrimidines as bronchodilating agents | |
| SU1705283A1 (en) | Method of 3-substituted 1-n-dialrylamino-2,2-(dicyano)methylene-4-cyanopyrrolidines synthesis | |
| KR20070012540A (en) | Drying method for the preparation of crystalline solid famciclovir | |
| US3122547A (en) | 2, 4, 7-triamino-6-pteridine carboxamides | |
| SU1698248A1 (en) | Method of preparing 9-h-9-chloro-1,10-anthracenedionon | |
| JPS62258368A (en) | Production of quinazolin-4-one | |
| RU2021273C1 (en) | Method of synthesis of 2,6-disubstituted 2,4,6,8-tetraazabicyclo[3,3,0]octane-3,7-diones | |
| JPH0665260A (en) | Production of sodium bistrimethylsilylamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |