GB1570591A - Process for preparing n-methylolated amides and ethers thereof - Google Patents

Process for preparing n-methylolated amides and ethers thereof Download PDF

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GB1570591A
GB1570591A GB4729476A GB4729476A GB1570591A GB 1570591 A GB1570591 A GB 1570591A GB 4729476 A GB4729476 A GB 4729476A GB 4729476 A GB4729476 A GB 4729476A GB 1570591 A GB1570591 A GB 1570591A
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Novartis AG
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Priority claimed from CH1479875A external-priority patent/CH602501A5/xx
Priority claimed from CH1263676A external-priority patent/CH605671A5/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/22—Cellulose or wood; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Description

(54) PROCESS FOR PREPARING N-METHYLOLATED AMIDES AND ETHERS THEREOF (71) We, CIBA-GEIGY AG, a body corporate organised according to the laws of Switzerland, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to the production of optionally etherified basic methylol compounds and their salts.
The present invention provides a process for the production of optionally etherified basic methylol compounds corresponding to the general formula:
wherein R1, R2 and R3 independently of one another denote hydrogen, lower alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula:
or R, and R2, together with the nitrogen atom which links them, denote a 5membered or 6-membered heterocyclic radical, preferably pyrrolidino, piperidino, morpholino or piperazino, or R2 and R3, together with the grouping
which links them, may also denote a divalent 5-membered or 6-membered heterocyclic radical, especially an imidazolidino or piperazino ring, Q and Q, independently of one another denote alkylene with up to 8 carbon atoms and, preferably, Q denotes C2-C3-alkylene and denotes C,--C,-alkylene, Y denotes hydrogen, lower alkyl or -CH2-O-X and X denotes hydrogen or C1-C4-alkyl and at most two of R1,R2 and R3 can be the group of the formula (2), and their salts.
In the process the corresponding amides of the formula:
and there salts, wherein R1, R2, R3, Q and Q1 have the indicated meaning and Y' denotes hydrogen or lower alkyl, are methylolated with formaldehyde or a compound which supplies formaldehyde, appropriately at temperatures of 0 to 1000C and preferably at 200 to 600C and, optionally, the resulting methylol compounds are etherified with a C1-C4- alkanol, preferably in the presence of an acid, such as, for example, hydrochloric acid or phosphoric acid. Suitable formaldehyde donors are, above all, trioxane, paraformaldehyde or hexamethylenetetramine. If necessary, the methylolation is carried out in the presence of a basic catalyst, such as sodium hydroxide, sodium methylate or MgO.
The amides of the formula (8) can be obtained by reacting a corresponding diamino compound with an amide of a 1,2unsaturated aliphatic carboxylic acid or with a halogeno-acetamide, such as, for example, acrylamide or chloracetamide.
The quaternary salts can be manufactured in the customary manner by reacting the basic amides with suitable quaternising agents. Examples of suitable quaternising agents are alkyl halides, dialkylsulphates or alkyl p-methylbenzene-sulphonates. The addition salts can be obtained by adding an inorganic or organic acid to the free amines.
Examples which may be mentioned of amides which serve as starting materials of the formula (8) are: N,N'- dimethyl N,N' - fi - dipropionamido ethylenediamine, N,N' - diethyl- N,N' ,B- dipropionamido - ethylenediamine, N,N - dimethyl - N',N' - p dipropionamido - ethylenediamine, N,N diethyl - N',N' - A - di - propionamido ethylenediamine, N,N' - diacetamido piperazine, N,N' - di - ,B - propionamido piperazine, N,N' - di - fi - propionamido imidazolidine, N - - propionamido piperazine, N,N - dimethyl - N',N' - dipropionamido - propylenediamine, N,N diethyl - N',N' - , - dipropionamido propylenediamine and N - ss propionamido - N,N' - diethyl ethylenediamine.
The salts preferably correspond to the general formula:
wherein V, denotes hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (2), or R1, R2 and V1, together with the nitrogen atom which links them, denote a pyridine ring which is optionally substituted by lower alkyl and Ane denotes the anion of an organic or inorganic acid and R1,R2,R3, Q, Q1, Y and X have the indicated meaning.
Compounds of the formula (1) or (3) which contain only one or two groupings of the formula (2) are particularly valuable. In the case of the compounds of the formula (1), R1 and R2 are preferably both lower alkyl, or R2 and R3, together with the grouping
which links them, also form a piperazino radical. Y is preferably hydrogen and X is, in particular, hydrogen or methyl. In the case of the compounds of the formula (3), R1, R2 and V1 are preferably all lower alkyl, Q is ethylene or (1,2- or 1,3-) propylene and Q1 is C,C-alkylene.
In the definition of the radicals lower alkyl and lower alkoxy represent those groups or group constituents which contain 1 to 5, and especially 1 to 3, carbon atoms, such as, for example, methyl, ethyl, npropyl, isopropyl, n-butyl, sec.-butyl or amyl, or methoxy, ethoxy or isopropoxy.
In connection with all of the above substituents, halogen denotes, for example, fluorine, bromine or, prefeiably, chlorine.
Optionally etherified methylol compounds of the general formula
wherein R4 and R5 both denote lower alkyl and R6 denotes hydrogen, lower alkyl or the group of the formula -Q3-CO-NH-CH2-O-X1 (5) or R, and R6, together with the grouping
which links them, denote a piperazino ring and R4 denotes hydrogen or the group of the formula (5), Q2 denotes ethylene or 1,2- or 1,3-propylene, Q3 denotes C1-C3- alkylene and X1 denotes hydrogen or methyl, are of primary interest.
Amongst the quaternary ammonium compounds of the formula (3), the quaternary ammonium salts of the formula (6)
wherein R4, R5 and V2 each denote lower alkyl, R'6 denotes lower alkyl or the group of the formula (7) -Q3-CO-NH-CII2OH, Q2 denotes ethylene or 1,2- or 1,3propylene and Q3 denotes C1-C3-alkylene and AnO has the indicated meaning, are particularly preferred.
The compounds of the formula:
in which R?, R2, R3. Q. Q, and Y are as defined above except that, in the definition of Y, X denotes hydrogen are novel and form another aspect of the present invention.
The compounds of the formula (1) and their salts are valuable products for the treatment of dyed or undyed cellulose fibre materials. In particular, they can be employed as starting materials for the manufacture of cationically modified cellulose materials such as are described and claimed in Application No. 47308/76 Serial No. 1570790. These cationically modified cellulose materials serve as anion exchangers, especially for the treatment of industrial effluents.
In the Examples which follow, and which further illustrate the present invention percentages are percentages by weight and parts are parts by weight.
Example 1 115 g of N,N - dimethyl - N',N' dipropionamido - ethylene - diamine obtained by an addition reaction of 2 mols of acrylamide with 1 mol of N,Ndimethylethylenediamine are dissolved in 93 ml of water and allowed to react, at a temperature of 0--10"C, with 85 ml of a 35.1% strength solution of formaldehyde until the content of free formaldehyde is 0.7%. 293 g of a 50% strength aqueous solution of the dimethylol compound of the formula (CH2)2N-CH2-C112- N(CH2CH2- CONH-CH2OH)2 (11) are obtained.
Example 2 68.5 g of N,N' - di - ,B - propionamido piperazine (melting point: 236--2379C), obtained by an addition reaction of 2 mols of acrylamide with 1 mol of piperazine, are dissolved in 313 ml of water and methylolated for 5 hours at 50--600C with 51.3 g of a 35.1% strength solution of formaldehyde, with the addition of 0.1 g of sodium hydroxide. A clear solution which has a formaldehyde content of 0.09% forms.
The solution is then evaporated completely and the residue is recrystallised from a mixture of ethanol and methanol (1:1).
27 g of a methylol compound of the formula
which has a melting point of 151--153"C are obtained.
Example 3 50 g of N,N' - diacetamido - piperazine (melting point: 278-2820C with decomposition), obtained by reacting piperazine and chloracetamide, are dissolved in 315 ml of water and methylolated with 42.8 g of a 35.1% strength solution of formaldehyde, with the addition of 0.1 g of sodium hydroxide. A solution which contains the methylol compound of the formula
which has a formaldehyde content of 0.06 S is obtained.
Example 4 27.2 g of N,N- diethyl - N',N' dipropionamido - propylene - diamine, obtained by an addition reaction of 2 mols of acrylamide with 1 mol of N,N diethylpropylenediamine, are dissolved in 150 ml of ethanol and quaternised with 11 g of ethyl bromide for 5 hours at 6-700C.
The resulting solution is then evaporated at 50"C, after which 35.9 g of the partially quaternised ammonium compound are obtained in the form of a viscous oil. The ammonium compound is dissolved in 185 ml of water and methylolated for 5 hours at 5e600C with 16.4 g of a 36.5% strength solution of formaldehyde, with the addition of 0.05 g of sodium hydroxide, to give a methylol compound of the formula o (C2H5)3N-CH2CH2CH2 N(CH2CH2CONHCH2OH)2 Bre (14) which has a formaldehyde content of 0.04 x.
WHAT WE CLAIM IS: 1. A process for the manufacture of an optionally etherified basic methylol compound of the formula:
or a salt thereof, wherein R1, R2 and R3 independently of one another denote hydrogen, lower (as hereinbefore defined) alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula:
or Rl and R2, together with the nitrogen atom which links them, denote a 5membered or 6-membered heterocyclic radical, or R2 and R3, together with the grouping
which links them, may also denote a divalent 5-membered or 6-membered heterocyclic radical, Q and Ql independently of one another denote alkylene with up to 8 carbon atoms, Y denotes hydrogen, lower alkyl or -CH2-O-X and X denotes hydrogen or C1-C4-alkyl, such that at most two of Ra, R2 and R3 can be the group of the formula (2), which comprises methylolating an amide of the formula:
in which R1, R2, R3, Q and Q1 are as defined above and Y' denotes hydrogen or lower alkyl with formaldehyde or with a compound which supplies formaldehyde and, optionally, etherifying the methylol compound with a C1-C4-alkanol and, optionally, converting the resulting product into a salt, before or after the methylolation or etherification.
2. A process according to claim 1, wherein the methylolation is carried out at 0 to 1000C.
3. A process according to claim 1, wherein the methylolation is carried out in the presence of a basic catalyst.
4. A process according to any one of claims 1 to 3, wherein the resulting basic Nmethylolamide is quaternised with a quaternising agent.
5. A process according to claim I substantially as hereinbefore described.
6. A process according to claim 1 substantially as described in any one of Examples 1 to 4.
7. A methylol compound as defined in claim 1 whenever manufactured by a process as claimed in any one of claims 1 to 5.
8. A methylol compound as defined in claim 1 whenever manufactured by a process as claimed in claim 6.
9. A basic methylol compound of the formula:
or a salt thereof, wherein R" R2 and R3 independently of one another denote hydrogen, lower (as hereinbefore defined) alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula:
or R, and R2, together with the nitrogen atom which links them, denote a 5membered or 6-membered heterocyclic radical, or R2 and R3, together with the grouping
which links them, also denote a divalent 5membered or 6-membered heterocyclic radical, Q and Q, independently of one another denote alkylene with up to 8 carbon atoms, Y denotes hydrogen, lower alkyl or CH2-OH such that at most two of R,. R2 and R3 can be the group of the formula (2a).
10. A compound according to claim 9, wherein R, and R2 each denote lower alkyl.
11. A compound according to claim 9, wherein R, and R2, together with the nitrogen atom which links them, represent a pyrrolidino, piperidino, morpholino or piperazino radical.
12. A compound according to claim 9, wherein R2 and R3, together with the grouping
which links them, represent an imidazolidinyl or piperazino radical.
13 A compound according to any one of claims 9 to 12, wherein Q denotes C2-C3- alkylene and Q, denotes C1-C3-alkylene.
14. A compound according to claim 9, which is in the form of a salt of the formula:
in which V, denotes hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula:
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (22)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    or Rl and R2, together with the nitrogen atom which links them, denote a 5membered or 6-membered heterocyclic radical, or R2 and R3, together with the grouping
    which links them, may also denote a divalent 5-membered or 6-membered heterocyclic radical, Q and Ql independently of one another denote alkylene with up to 8 carbon atoms, Y denotes hydrogen, lower alkyl or -CH2-O-X and X denotes hydrogen or C1-C4-alkyl, such that at most two of Ra, R2 and R3 can be the group of the formula (2), which comprises methylolating an amide of the formula:
    in which R1, R2, R3, Q and Q1 are as defined above and Y' denotes hydrogen or lower alkyl with formaldehyde or with a compound which supplies formaldehyde and, optionally, etherifying the methylol compound with a C1-C4-alkanol and, optionally, converting the resulting product into a salt, before or after the methylolation or etherification.
  2. 2. A process according to claim 1, wherein the methylolation is carried out at 0 to 1000C.
  3. 3. A process according to claim 1, wherein the methylolation is carried out in the presence of a basic catalyst.
  4. 4. A process according to any one of claims 1 to 3, wherein the resulting basic Nmethylolamide is quaternised with a quaternising agent.
  5. 5. A process according to claim I substantially as hereinbefore described.
  6. 6. A process according to claim 1 substantially as described in any one of Examples 1 to 4.
  7. 7. A methylol compound as defined in claim 1 whenever manufactured by a process as claimed in any one of claims 1 to 5.
  8. 8. A methylol compound as defined in claim 1 whenever manufactured by a process as claimed in claim 6.
  9. 9. A basic methylol compound of the formula:
    or a salt thereof, wherein R" R2 and R3 independently of one another denote hydrogen, lower (as hereinbefore defined) alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula:
    or R, and R2, together with the nitrogen atom which links them, denote a 5membered or 6-membered heterocyclic radical, or R2 and R3, together with the grouping
    which links them, also denote a divalent 5membered or 6-membered heterocyclic radical, Q and Q, independently of one another denote alkylene with up to 8 carbon atoms, Y denotes hydrogen, lower alkyl or CH2-OH such that at most two of R,. R2 and R3 can be the group of the formula (2a).
  10. 10. A compound according to claim 9, wherein R, and R2 each denote lower alkyl.
  11. 11. A compound according to claim 9, wherein R, and R2, together with the nitrogen atom which links them, represent a pyrrolidino, piperidino, morpholino or piperazino radical.
  12. 12. A compound according to claim 9, wherein R2 and R3, together with the grouping
    which links them, represent an imidazolidinyl or piperazino radical.
  13. 13 A compound according to any one of claims 9 to 12, wherein Q denotes C2-C3- alkylene and Q, denotes C1-C3-alkylene.
  14. 14. A compound according to claim 9, which is in the form of a salt of the formula:
    in which V, denotes hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula:
    or Rl, R2 and Vl, together with the nitrogen atom which links them, denote a pyridine ring which is optionally substituted by lower alkyl and AnO denotes the anion of an organic or inorganic acid and R1, R2, R3, Q, Ql and Y are as defined in claim 9.
  15. 15. A compound according to claim 14, wherein R1, R2 and V, all denote lower alkyl, Q denotes ethylene or 1,2- or 1,3propylene and Q, denotes C1-C3-alkylene.
  16. 16. A compound according to claim 9 or 14 which contains one or two groupings of the formula:
    in which Q, and Y have the meaning indicated in claim 9.
  17. 17. A compound according to claim 9 of the formula:
    in which R4 and R5 both denote lower alkyl and R6 denotes hydrogen, lower alkyl or the group of the formula: -Q3-CO-NH-CH2-OH (5a) or R5 and R6, together with the grouping
    which links them, denote a piperazino ring and R4 denotes hydrogen or the group of the formula (5a), Q2 denotes ethylene or 1,2or 1,3-propylene and Q3 denotes C1-C3- alkylene.
  18. 18. A compound according to claim 14 of the formula:
    in which R4, R5 and V2 each denote lower alkyl, R'6 denotes lower alkyl or the group of the formula (7) -Q3-CO-NH-CH2OH, Q2 denotes ethylene or 1,2- or 1,3propylene, Q3 denotes C1-C3-alkylene and Ann has the meaning indicated in claim 14.
  19. 19. A compound of the formula: (CH 3)2-N-CH2-CH2- N(CH2CH2- CONH-CH2OH)2.
  20. 20. A compound of the formula:
  21. 21. A compound of the formula:
  22. 22. A compound of the formula: n (C2H5)3N-CH2CH2CH2 N(CH2CH2CONHCH2OH)2 Byre.
GB4729476A 1975-11-14 1976-11-12 Process for preparing n-methylolated amides and ethers thereof Expired GB1570591A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1479875A CH602501A5 (en) 1975-11-14 1975-11-14
CH1263676A CH605671A5 (en) 1976-10-06 1976-10-06 Opt. etherified basic methylol cpds. and salts

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DE (1) DE2650966A1 (en)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4577013A (en) * 1983-12-22 1986-03-18 Ciba-Geigy Corporation Ionically modified cellulose material, its preparation and its use
US5010184A (en) * 1984-07-06 1991-04-23 Ciba-Geigy Corporation Ionically modified agarose

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3324235A1 (en) * 1983-07-01 1985-01-10 Schering AG, 1000 Berlin und 4709 Bergkamen NEW COMPLEX ILLUMINATORS, COMPLEX AND COMPLEX SALTS
JP4736168B2 (en) * 2000-09-11 2011-07-27 東洋製罐株式会社 Microwave heating container

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4577013A (en) * 1983-12-22 1986-03-18 Ciba-Geigy Corporation Ionically modified cellulose material, its preparation and its use
US5010184A (en) * 1984-07-06 1991-04-23 Ciba-Geigy Corporation Ionically modified agarose

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JPS5262223A (en) 1977-05-23
FR2331551A1 (en) 1977-06-10

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PS Patent sealed
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PCNP Patent ceased through non-payment of renewal fee