HK1153194A - Method for producing bicyclic guanidines by use of a cyclic urea - Google Patents
Method for producing bicyclic guanidines by use of a cyclic urea Download PDFInfo
- Publication number
- HK1153194A HK1153194A HK11107320.3A HK11107320A HK1153194A HK 1153194 A HK1153194 A HK 1153194A HK 11107320 A HK11107320 A HK 11107320A HK 1153194 A HK1153194 A HK 1153194A
- Authority
- HK
- Hong Kong
- Prior art keywords
- carbonate
- ether
- amine
- aminoalkyl
- temperature
- Prior art date
Links
Description
Background
Technical Field
The present invention relates to a method for preparing bicyclic guanidines.
Background
The well-known bicyclic guanidines, such as 1, 5, 7-triazabicyclo [5.5.0] dec-5-ene (TBD), are chemically active and, therefore, can be used to catalyze a variety of chemical reactions. An important consideration in the industrial development of bicyclic guanidines as catalysts (for any reaction) is that bicyclic guanidines are relatively inexpensive to purchase or easy to prepare. However, the disclosed methods of synthesizing bicyclic guanidines are often complex, often involve the use of multi-step synthetic processes, and/or require the use of prohibitively expensive starting materials that can be hazardous in many respects.
For example, some methods use carbon disulfide (CS) in the preparation of bicyclic guanidines2). However, there are regulatory and handling problems associated with the use of carbon disulfide. For example, air transport of carbon disulfide is generally prohibited. In addition, contact of air with carbon disulfide should be avoided because of the combination of high volatility, wide flammability range, and low ignition temperature to produce a flammable mixture.
Therefore, there is a need for a method of preparing bicyclic guanidines in relatively high yields while not using hazardous raw materials, such as carbon disulfide, as an ingredient for preparing the bicyclic guanidines.
Disclosure of Invention
The present invention relates to a method for preparing bicyclic guanidines, comprising heating the cyclic urea to a temperature > 200 ℃ to form the bicyclic guanidine.
The present invention also relates to a method of preparing a bicyclic guanidine, comprising providing a cyclic urea; and heating the cyclic urea in the presence of a non-hydrocarbon solvent to a temperature > 200 ℃ to form the bicyclic guanidine.
Detailed Description
As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages are to be read as if prefaced by the word "about", even if the term does not expressly appear. Plural encompasses singular and vice versa. For example, although reference is made herein (including the claims) to "an" (aminoalkyl) amine, "a" carbonate, combinations (i.e., multiple) of (aminoalkyl) amines and/or carbonates may be used.
As used herein, "plurality" means two or more.
As used herein, "include" and similar terms mean "includes without limitation".
When referring to any numerical range of values, such ranges are understood to include each and every number and/or fraction between the stated range minimum and maximum.
The present invention relates to a method for preparing bicyclic guanidines. In particular, the present invention relates to a method for preparing bicyclic guanidines, which method comprises heating a cyclic urea to a temperature > 200 ℃. It has been surprisingly found that the preparation of bicyclic guanidine via the methods disclosed herein can provide yields of ≧ 85%, such as from 90% to 95% of the bicyclic guanidine reaction product. Another advantage of the disclosed method is that the method does not require the use of carbon disulfide or other hazardous materials to prepare the bicyclic guanidine. Thus, any regulatory and/or environmental issues associated with the use of carbon disulfide are avoided.
As noted above, the disclosed methods include heating cyclic ureas to temperatures > 200 deg.C, such as 218 deg.C-240 deg.C, to form bicyclic guanidine reaction products. In certain embodiments, this heating step is performed in a substantially non-hydrocarbon solvent such as an ethereal solvent or an alcoholic solvent, or a combination thereof. Suitable ethereal solvents that can be used in the present invention include, without limitation, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether formaldehyde, or combinations thereof. Suitable alcohols that may be used in the present invention include, without limitation, ether functional alcohols, butyl carbitol, ethoxylated bisphenol a polyols, or combinations thereof. In certain embodiments, the ether functional alcohol comprises a glycol ether. Suitable glycol ethers that may be used in the present invention include, without limitation, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol butyl ether, or combinations thereof. It is understood that by conducting the reaction at a pressure such as up to 2500psig, low molecular weight, low boiling ethers, and/or alcohols may be used.
In certain embodiments, the cyclic urea is formed by the reaction of an (aminoalkyl) amine with a carbonate.
As used herein, the term "(aminoalkyl) amine" refers generally to a compound having the general formula H2N(CR3R4)nNH(CR5R6)mNH2Wherein n and m are independently an integer having a value of 2 to 6 and wherein R3，R4，R5And R6Independently hydrogen or a substituted or unsubstituted alkyl or aryl group. In addition, each is alone- -CR3R4- - - - - - - - -CR5R6The composition of the units may also differ from one another. For example, in certain embodiments the R3The radical may comprise- -CH2- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -5The radical may comprise- -CH2CH2CH2- -. In particular, suitable (aminoalkyl) amines are those wherein R is3，R4，R5And R6Independently is hydrogen or C1-C3Those of alkyl groups. Suitable (aminoalkyl) amines within the general formula disclosed in this paragraph and which may be used in the present invention include, without limitation, bis (2-aminoethyl) amine, bis (3-aminopropyl) amine, or a combination thereof.
Suitable carbonates that may be used in the present invention include, without limitation, alkyl and alkylene carbonates such as propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, or combinations thereof.
It should be noted that in certain embodiments, the reaction mixture used to form the cyclic urea may include a non-hydrocarbon solvent such as those disclosed in the preceding paragraph, or may include a hydrocarbon solvent such as xylene. Alternatively, in certain embodiments, the reaction mixture used to form the cyclic urea is substantially solvent-free. As used herein, "substantially solvent-free" means that a minor or incidental amount of organic solvent, such as 5 wt.% or 3 wt.% or 1 wt.% or less, based on all ingredients used in the reaction mixture, may be present.
In certain embodiments, a catalyst, such as an acid or base catalyst, may be added to the reaction mixture of the (aminoalkyl) amine and the carbonate. Any catalyst known in the art may be used. For example, suitable catalysts include, without limitation, inorganic acids, organic acids, lewis acids, dimethylaminopyridine, imidazole, and TBD.
In certain embodiments, the process begins by charging a reaction vessel with an (aminoalkyl) amine and a solvent. It should be noted that the solvent is either a hydrocarbon solvent such as xylene or a non-hydrocarbon solvent such as dipropylene glycol monobutyl ether. It should also be noted that in certain embodiments no solvent is added with the (aminoalkyl) amine.
The total amount of carbonate that can be added to the reaction vessel depends on the total amount of (aminoalkyl) amine used for the reaction and can therefore be any value, and the carbonate addition rate depends on the total amount of carbonate to be added to the reaction vessel. For example, in certain embodiments, the carbonate is added dropwise to the reaction vessel at a rate of 3 grams (g)/minute to 5 grams/minute for a total weight of from 120 grams to 130 grams, such as 124 grams.
The reaction vessel is then heated to a temperature and for a period of time sufficient to form the cyclic urea reaction product. In certain embodiments, the reaction vessel is heated to a temperature ranging from ≧ 80 deg.C, such as from 80 deg.C to 100 deg.C, for a time period ranging from 1 hour to 2 hours. After this initial heating step, a non-hydrocarbon solvent, such as those described above, is added to the reaction vessel. The reaction vessel is then heated to ≧ 130 ℃ for a period of 1 hour to 2 hours, thereby forming the cyclic urea reaction product.
In certain embodiments, after the formation of the cyclic urea reaction product, the reaction vessel is heated to a temperature and for a period of time sufficient to form the bicyclic guanidine reaction product. In certain embodiments, after formation of the cyclic urea, the reaction vessel is heated to a temperature > 200 ℃, such as from 218 ℃, and then heated to reflux for a period of time from 30 hours to 50 hours, such as 40 hours, thereby forming the bicyclic guanidine reaction product. If a hydrocarbon solvent is used in the step of forming the cyclic urea, care should be taken to distill the hydrocarbon solvent from the reaction vessel prior to the step disclosed in this paragraph. Thus, one skilled in the art will recognize that the reaction discussed in this paragraph is carried out in a substantially non-hydrocarbon solvent.
After the bicyclic guanidine is formed, it can be isolated by removing the non-hydrocarbon solvent from the reaction vessel. The isolated bicyclic guanidine, which is in a solid state, can then be added to any composition in which a bicyclic guanidine can be used. It should also be noted that the bicyclic guanidine can also be isolated via precipitation and/or crystallization. Thus, in certain embodiments, a solvent, such as heptane, hexane, or a combination thereof, is added, wherein the bicyclic guanidine is insoluble, thereby precipitating the bicyclic guanidine.
Alternatively, the unseparated bicyclic guanidine can also be mixed with any composition, such as a coating composition, in which the bicyclic guanidine can be used. Thus, in certain embodiments, the unseparated bicyclic guanidine is cooled to room temperature and a diluent, such as a high boiling point diluent, is added to the reaction vessel prior to removing the non-hydrocarbon solvent from the reaction vessel. Suitable diluents that can be used in this step include, without limitation, ethoxylated bisphenol a, diethylene glycol diethyl ether formaldehyde, or combinations thereof. After removing the non-hydrocarbon solvent from the reaction vessel, the bicyclic guanidine and diluent mixture may be mixed with a coating composition such as an electrodepositable coating composition known in the art. For example, in certain embodiments, bicyclic guanidines produced by the methods disclosed herein may be incorporated into an electrodepositable coating composition disclosed in U.S. patent application No. 11/835,600, which is incorporated herein by reference in its entirety.
The methods disclosed herein generally produce 1 mole of water per 1 mole of bicyclic guanidine. Thus, in certain embodiments, water may be removed from the bicyclic guanidine reaction product using techniques known in the art.
While specific embodiments of the invention have been disclosed in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular disclosed embodiments are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.
Examples
Example 1:
a100 ml flask equipped with a reflux condenser and a distiller was purged with nitrogen and charged with 3, 3' -diaminodipropylamine (10g, 80mmol), dimethyl carbonate (6.9g, 80mmol) and a catalytic amount of 1, 5, 7-triazabicyclo [4.4.0 ]]Dec-5-ene (0.53g, 3.8 mmol). The mixture was heated to 130 ℃ and methanol was distilled off. The reaction was cooled when no more distillate was observed. By passing13C NMR confirmed the resulting bright orange oil as N- (3-aminopropyl) -N, N' -trimethyleneurea.
Example 2:
a100 mL flask equipped with a steam condenser operating at about 100 deg.C was purged with nitrogen and charged with N- (3-aminopropyl) -N, N' -trimethyleneurea (5.6g, 40mmol) and triglyme (36 g). The mixture was heated to 230 ℃ and held for 56 hours. By quantification of13C NMR confirmed conversion of the starting urea to 1, 5, 7-triazabicyclo [ 4.4.0%]The conversion of dec-5-ene was 94%.
Example 3:
a 500 ml flask was equipped with a steam column, distillation head, water cooled condenser, and collection flask. The reaction vessel was purged with nitrogen and charged with diethylene glycol dibutyl ether (100.0g), followed by 3, 3' -diaminodipropylamine (40.0g, 0.310mol) and 4- (N, N-dimethylamino) pyridine (4.00g, 0.033 mol). To the stirred solution, propylene carbonate (32.0g, 0.313mol) was added and the reaction was allowed to exotherm. After the exotherm, the reaction was heated to 218 ℃ and held for 4 hours, then the temperature was raised to 230 ℃ and held for 48 hours. The yield was determined by HPLC to be 55.7%.
Example 4:
a 500 ml flask was equipped with a steam column, a dean-stark trap filled with xylene, a water cooled condenser, and a collection flask. The reaction vessel was purged with nitrogen and charged with diethylene glycol dibutyl ether (100.0g), followed by 3, 3' -diaminodipropylamine (20.0g, 0.153 mol). To the stirred solution, propylene carbonate (16.00g, 0.157mol) was added and the reaction was allowed to exotherm. After the exotherm, the reaction was heated to 218 ℃ for 4 hours (h) and then the temperature was raised to 230 ℃ and held for 48 hours. The yield was 78.2% by HPLC.
Example 5:
a 5L flask was equipped with a water cooled condenser and the flask was purged with nitrogen. The flask was charged with xylene (300.0g) and 3, 3' -diaminodipropylamine (180.0g, 1.37 mol). An 11.6% (w/w) mixture of TBD in diethylene glycol diethyl ether formaldehyde was heated to 100 ℃ to dissolve the TBD and added to the heated reaction vessel. Propylene carbonate (142.5g, 1.40mol) was added to the stirred solution and the reaction was allowed to exotherm. After the exotherm subsided, the reaction was heated to 90 ℃ for 2 hours. The temperature was then raised to 130 ℃ and held for 3 hours. The reflux condenser was removed and replaced with a steam condenser, an ampere-Stark trap filled with xylene, and a water cooled condenser. The reaction was diluted with diethylene glycol diethyl ether formaldehyde and a 1: 1(w/w) mixture of ethoxylate bisphenol A (1875.00 g). The reaction was heated to 218 ℃ for 8 hours and then finally to 240 ℃ for 40 hours. The yield was 48% by HPLC.
Example 6:
a 1L flask was equipped with a water cooled condenser and the flask was purged with nitrogen. The flask was charged with 3, 3' -diaminodipropylamine (100.0g, 0.673mol) and 6.96g of a 15.4% (w/w) mixture of TBD in diethylene glycol diethyl ether formaldehyde, which was heated to 100 ℃ to dissolve the TBD. Dimethyl carbonate (70.0g, 0.777mol) was added to the stirred solution and the reaction was allowed to exotherm. After the exotherm subsided, the reaction was heated to 90 ℃ for 2 hours. The reflux condenser was replaced with a steam condenser, distillation apparatus, and collection flask, and then the reaction temperature was raised to 130 ℃. Methanol produced by the reaction was distilled off. Tetraethyl orthosilicate (180.0g, 0.864mol) was slowly added to the reaction over several hours via the addition funnel. After all the tetraethyl orthosilicate was added, the reaction temperature was raised to 180 ℃ and held for 8 hours. The temperature was then raised to 230 ℃ for 30 hours and the ethanol produced by the reaction was distilled off. The reaction yield was 35% by HPLC.
Example 7:
a500 ml flask was purged with nitrogen and charged with 3, 3' -diaminodipropylamine (24.0g, 0.183mol), xylene (40.0), and 1.80g of a 14.4% (w/w) mixture of TBD in diethylene glycol diethyl ether formaldehyde, which was heated to 100 ℃ to dissolve the TBD. Propylene carbonate (19.00g, 0.186mol) was added to the stirred solution and the reaction was allowed to exotherm. After the exotherm, the reaction was heated to 90 ℃ for 2 hours. The reaction was cooled to 70 ℃ and dipropylene glycol monobutyl ether (250.0g) was added to the reaction vessel. The reflux condenser was replaced with a steam condenser and a dean-stark trap filled with xylene. The temperature was then maintained at 218 ℃ for 6 hours. The temperature was then raised to 240 ℃ and held for 50 hours. The yield was 90% by HPLC.
Claims (28)
1. A method of preparing a bicyclic guanidine, the method comprising heating a cyclic urea to a temperature > 200 ℃ to form the bicyclic guanidine.
2. The method of claim 1, wherein the cyclic urea is the reaction product of an (aminoalkyl) amine and a carbonate.
3. The method of claim 1, wherein the temperature is from 218 ℃ to 250 ℃.
4. The process according to claim 1, wherein the temperature is 250 ℃ or more.
5. The method of claim 2, wherein the (aminoalkyl) amine comprises bis (3-aminopropyl) amine.
6. The method of claim 2, wherein the carbonate comprises propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, or a combination thereof.
7. The method of claim 2, wherein the method further comprises adding a catalyst to the reaction mixture of the (aminoalkyl) amine and the carbonate.
8. The method of claim 7, wherein the catalyst is an acid catalyst.
9. The method of claim 8, wherein the acid catalyst comprises a mineral acid, an organic acid, a lewis acid, or a combination thereof.
10. The process of claim 7, wherein the catalyst is a base catalyst.
11. The process of claim 11, wherein the base catalyst comprises dimethylaminopyridine, imidazole, TBD, or a combination thereof.
12. The method of claim 1, wherein the reaction occurs in a substantially non-hydrocarbon solvent.
13. The method of claim 12, wherein the substantially non-hydrocarbon solvent comprises an ethereal solvent.
14. The method of claim 13, wherein the ethereal solvent comprises triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether formaldehyde, tetraethylene glycol dimethyl ether, diphenyl ether, or combinations thereof.
15. The method of claim 12, wherein the substantially non-hydrocarbon solvent comprises an alcohol.
16. The method of claim 15, wherein the alcohol comprises an ether functional alcohol, butyl carbitol, ethoxylated bisphenol a, or combinations thereof.
17. The method of claim 16, wherein the ether functional alcohol comprises a glycol ether.
18. The method of claim 17, wherein the glycol ether comprises diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, or combinations thereof.
19. A method of preparing a bicyclic guanidine, the method comprising:
providing a cyclic urea; and
heating the cyclic urea in the presence of a non-hydrocarbon solvent to a temperature > 200 ℃ to form the bicyclic guanidine.
20. The method of claim 19, wherein the cyclic urea is the reaction product of an (aminoalkyl) amine and a carbonate.
21. The method of claim 20, wherein the (aminoalkyl) amine comprises bis (3-aminopropyl) amine.
22. The method of claim 20, wherein the carbonate comprises propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, or a combination thereof.
23. The method of claim 20, wherein the method further comprises adding a catalyst to the reaction mixture of the (aminoalkyl) amine and the carbonate.
24. The method of claim 19, further comprising adding a diluent to the bicyclic guanidine; and removing the non-hydrocarbon solvent.
25. The method of claim 19, wherein the temperature is 220 ℃ to 250 ℃.
26. The method of claim 19, wherein the temperature is 250 ℃.
27. The method according to claim 19, wherein the diluent comprises ethoxylated bisphenol a, diethylene glycol diethyl ether formaldehyde, or a combination thereof.
28. An electrodepositable coating composition comprising the bicyclic guanidine prepared according to claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/118,082 | 2008-05-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK1153194A true HK1153194A (en) | 2012-03-23 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8039618B2 (en) | Method for producing bicyclic guanidines by use of a cyclic urea | |
| US8334380B2 (en) | Method for producing bicyclic guanidines by use of a cyclic urea and a dehydrating agent | |
| CN101528674B (en) | Iminium salts and methods of preparing electron deficient olefins using such novel iminium salts | |
| JP6192653B2 (en) | Method for producing trioxane from an aqueous formaldehyde source | |
| KR20180128018A (en) | Acrylic acid, and a method for producing the same | |
| CN106470968A (en) | The method preparing 1,1 disubstituted vinyl monomers | |
| EP2280977B1 (en) | Method for producing bicyclic guanidines by use of a cyclic thiourea | |
| KR101764477B1 (en) | Method for producing polyalkylene glycol derivative having amino group at end, with narrow molecular weight distribution | |
| KR101684044B1 (en) | Methods for producing 1,5,7-triazabicyclo[4.4.0] dec-5-ene by reaction of a disubstituted carbodiimide and dipropylene triamine | |
| KR20200020441A (en) | process for preparing cyclic carbonate using hyper crosslinked polymers and hyper crosslinked polymers for selective formation of cyclic carbonates | |
| KR101938338B1 (en) | Method for recycling alkylene oxide in the process of polyalkylene carbonate production | |
| HK1153194A (en) | Method for producing bicyclic guanidines by use of a cyclic urea | |
| Wang et al. | Synthesis of a novel poly (ethylene glycol) grafted triethylamine functionalized dicationic ionic liquid and its application in one-pot synthesis of 2-amino-2-chromene derivatives in water | |
| CN110294768B (en) | Method for synthesizing pinoxaden through 2, 6-diethyl-4-methyl phenylmalonate | |
| JP2011506528A (en) | Process for producing (S) -2-amino-1-propanol (L-alaninol) from (S) -1-methoxy-2-propylamine | |
| JP7525112B2 (en) | Method for producing urea derivatives | |
| CN108064220B (en) | Recovery of acetic acid | |
| RU2320678C1 (en) | Method for preparing polyphenylethoxysiloxane | |
| HK1152706B (en) | Method for producing bicyclic guanidines by use of a cyclic thiourea | |
| HK1194370A (en) | Method for producing bicyclic guanidines by use of a cyclic thiourea | |
| CN120842077A (en) | An organic monomer containing a polymerizable ketal structure and its preparation method and application | |
| CN120157689A (en) | A type of bimetallic zinc catalyst, preparation method and application in depolymerization of polycaprolactone | |
| KR20160140707A (en) | Alkylene oxide polymer production method | |
| JP5907418B2 (en) | Method for producing hydroxyl-containing acetal compound | |
| JPS60223819A (en) | 2-methylene-1,3-dioxocane homopolymer |