EP3030547A1 - Verfahren zur herstellung von trisaziridinomethan - Google Patents
Verfahren zur herstellung von trisaziridinomethanInfo
- Publication number
- EP3030547A1 EP3030547A1 EP14744827.8A EP14744827A EP3030547A1 EP 3030547 A1 EP3030547 A1 EP 3030547A1 EP 14744827 A EP14744827 A EP 14744827A EP 3030547 A1 EP3030547 A1 EP 3030547A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aziridine
- chloroform
- reaction vessel
- total amount
- solvent
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 98
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 239000002585 base Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- PFBUKDPBVNJDEW-UHFFFAOYSA-N dichlorocarbene Chemical class Cl[C]Cl PFBUKDPBVNJDEW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic ethers Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
- C07D203/12—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Definitions
- the invention relates to a process for the preparation of trisaziridinomethane (I)
- Trisaziridinomethane is a compound that, due to its reactivity, is useful, for example, as a crosslinker in chemical compositions, as described in WO 03/089476.
- TAM The preparation of TAM by reacting aziridine with chloroform in the presence of a base is disclosed by W. Funke, Liebigs Ann. Chem. (1969) 725, 15.
- the base used is sodium methoxide or powdered NaOH.
- azirdine is used in a stoichiometric excess of 6 mol of aziridine per 1 mol of chloroform. Furthermore, the entire amount of aziridine is presented.
- a dichlorocarbene initially forms from the chloroform, which is highly reactive and reacts with azirdine to form the TAM. The total amount of aziridine is therefore submitted so that there is always enough aziridine to trap the dichlorocarbene as quickly as possible.
- TAM was also prepared in 1970 by Kostyanovskii and coworkers (Russ. Chem. Bull. (1970) 1815, translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No 8, pp 1918-1919, August 1970) from the sodium salt of aziridine.
- the sodium salt of aziridine is explosive.
- the yield is only 22%.
- Aziridine is a very reactive and therefore safety-critical compound. For a synthesis on an industrial scale special requirements are therefore made. The synthesis should exclude potential safety risks, while the synthesis should be as simple and inexpensive as possible. TAM is to be obtained by the synthesis in the highest possible yield and selectivity.
- the object of the present invention was therefore a process for the preparation of TAM, which is suitable for carrying out on an industrial scale and meets the above requirements as much as possible. Accordingly, the method defined above was found.
- the molar ratio of aziridine to chloroform is a maximum of 3: 1, which means that no more azerdine is used than corresponds to the stoichiometric ratios according to the above reaction equation.
- Azirdine may in particular also in smaller amounts than the stoichiometric amounts, z. B. be used in molar amounts of 2.9 or 2.8 to 1 mol of chloroform.
- the molar ratio of aziridine to chloroform is 2: 1 to 3: 1; more preferably, the molar ratio is 2.25: 1 to 2.75: 1.
- the reaction vessel contains a maximum of 50% of the total amount of aziridine before chloroform is added to the reaction vessel; that is, 0 to 50% of the aziridine in the reaction are submitted and then started with the addition of chloroform to the reaction vessel.
- the reaction vessel in which the above reaction is carried out contains 0 to 40%, more preferably 0 to 30, and most preferably 0 to 10% of the total amount of the aziridine before starting to add chloroform.
- more than 50% of the total amount of aziridine is added first as soon as with the Addition of chloroform was started (hereinafter also referred to as "subsequently added total amount of azerdine").
- the total amount of chloroform and the total amount of azerdine added subsequently are Forms more than 60, 70 or more than 90% of the total amount of the azerdine) continuously supplied to the reaction vessel over a longer period.
- the addition of the subsequently added total amount of azirdine can begin at the same time as the addition of chloroform. It can also be started first with the addition of chloroform and the addition of the subsequently supplied total amount of azirdine be started thereafter.
- the total amount of chloroform and the subsequently supplied total amount of azirdine are added so that the temperature in the reaction vessel does not rise above 50 ° C.
- the total amount of chloroform and the subsequent total amount of azirdine added over a similar period of time is kept constant during the addition. This ratio then corresponds to the molar ratio of the total amount of chloroform to the subsequently supplied total amount of azerdine.
- the total amount of chloroform and the subsequently added total amount of azirdine are continuously added over a similar period of time so that the temperature in the reaction vessel does not rise above 50 ° C., in particular not above 48 ° C.
- the above period may, for. B. 0.1 to 10 hours, in particular 1 to 5 hours. It depends naturally on the size of the reaction vessel, the amount of solvent used, the apparative embodiments, in particular the manner of cooling and measures for mixing (agitator).
- the reaction is carried out in the presence of a solvent.
- the solvent can be initially charged in the reaction vessel or fed during the reaction. In a preferred embodiment, the solvent is initially charged in the reaction vessel.
- a solvent which has a higher boiling point than aziridine.
- a solvent which has a higher boiling point than aziridine.
- Particular preference is given to using a solvent whose boiling point is at least 30 ° C. higher than the boiling point of ariridine.
- the above boiling points are the boiling points at normal pressure.
- the solvent may also be a mixture of different solvents.
- the solvent may be any aliphatic or aromatic solvent.
- aliphatic or aromatic hydrocarbons or ethers in particular aliphatic ethers, such as 1,4-dioxane, tert-amyl methyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane (monoglyme) or bis (2-methoxyethyl) ether (diglyme).
- aromatic hydrocarbons eg. As toluene, xylenes, ethylbenzene or mixtures thereof.
- the solvent can be in large quantities, for. B. in amounts of up to 500 parts by volume per 100 parts by volume of the total volume of the starting materials aziridine and chloroform is used.
- large amounts of solvents offer no advantage here. Preference is therefore given to using 30 to 100 parts by volume of solvent, particularly preferably 55 to 75 parts by volume of solvent per 100 parts by volume of the starting materials aziridine and chloroform.
- the solvent is preferably substantially free of water and, in a preferred embodiment, contains water at most in amounts of less than 5 parts by weight, in particular less than 1 part by weight, more preferably less than 0.1 part by weight, per 100 parts by weight of solvent , In a particularly preferred embodiment, the solvent contains no water.
- the reaction is preferably carried out in the presence of a base.
- For the base e can be z.
- the base is sodium or potassium hydroxide.
- the base in particular sodium or potassium hydroxide, is fed to the reaction vessel in the form of a powder.
- the base is preferably initially charged in the reaction vessel together with the solvent and optionally the above subset aziridine.
- the reaction is preferably continued until the desired conversion of chloroform or aziridine is achieved. In particular, the reaction is continued until more than 90%, more preferably more than 95% and most preferably more than 99% of the chloroform, in particular the total amount of chloroform are consumed.
- the temperature of the reaction mixture is preferably maintained at 20 to 50 ° C, in particular at 30 to 45 ° C.
- the product solution may contain solids, in particular salts. These are z. B. unreacted base, such as KOH or NaOH powder, or other salts of the cation of the base used, which may arise under the reaction conditions, for. As alkali chlorides or alkali metal formates. These solids can be separated by filtration from the product solution. It has proved to be advantageous to carry out such a filtration after the removal of the aziridine (see above). Upon filtration of an aziridine-containing product solution, aziridine may adhere to the separated solids (filter cake) and make disposal of the filter cake difficult.
- the product solution is filtered after separation of the unreacted aziridine to remove solids.
- TAM is very well suited for carrying out on an industrial scale. It can be carried out simply, effectively and inexpensively and is safety-friendly. TAM is obtained by the process in high yield and selectivity. This high yield of TAM is achieved with little use of starting materials. In particular, aziridine is used only in maximum stoichiometric amounts.
- anhydrous toluene 75 ml
- technical KOH powder technical, 85 wt.%, 2.1 mol , 139 g
- One-third of the total amount of anhydrous aziridine (26.7 ml, 0.52 mol) was added all at once with stirring.
- the chloroform (41.9 ml, 0.5 mol) and the remaining aziridine (53.5 ml, 1.04 mol) were metered in parallel, the temperature being monitored. The temperature did not rise above 48 ° C during the addition.
- the ratio with which chloroform and aziridine were added was approximately constant throughout the period of addition.
- the reaction was continued at 40 ° C until the chloroform is largely implemented (about 12 hours).
- the pressure was lowered and unreacted aziridine and a portion of the toluene distilled overhead.
- the precipitated solid (consisting mainly of KCl, potassium formate and unreacted KOH) was separated by filtration and discarded.
- the conversion of the chloroform is> 99% and the aziridine conversion is about 79%.
- Example 2 was carried out analogously to Example 1, but the amount of aziridine initially charged was halved (13.3 ml, 0.26 mol) , All other quantities remained constant. The chloroform conversion is> 99% and the aziridine conversion is about 77%. After removal of unreacted aziridine, an approximately 35% wt. Solution of TAM in toluene containing less than 2 wt% free aziridine was obtained. The yield of TAM dissolved in toluene, based on chloroform, was 60%.
- Example 3 diglyme instead of toluene
- Example 3 was carried out analogously to Example 1, but instead of toluene, bis (2-methoxyethyl) ether (diglyme) was used as the solvent.
- the chloroform conversion is> 99% and the aziridine conversion is about 70%.
- Solution of TAM in diglyme containing less than 2% by weight of free aziridine was obtained.
- the yield of TAM dissolved in diglyme, based on chloroform, was 73%.
- Comparative Example 1 was carried out analogously to Example 1, but the amount of aziridine charged was minimized to 13.3 ml (0.26 mol), increasing the amount of aziridine dropped (80.3 ml, 1.56 mol). All other quantities remained constant. The chloroform conversion is> 99% and the aziridine conversion is about 70%. After removal of unreacted aziridine, an approximately 40% solution of TAM in toluene containing less than 2% free aziridine is obtained. The yield of TAM dissolved in toluene based on chloroform was 67%.
- Example 1 Compared to Example 1 it is shown that despite the use of a significant excess of aziridine, the yield of TAM remains the same. An excess of aziridine has no advantages in the TAM synthesis, it only increases the effort in the workup. During the reaction of the starting materials, large temperature increases occurred, which makes the entire implementation of the reaction more difficult on an industrial scale, in particular places great demands on the cooling and makes a significant reduction in the feed rates necessary.
- Example 4 was carried out analogously to Example 1, but the amount of toluene was increased to 100 ml. All other quantities remained constant. The chloroform conversion is> 99% and the aziridine conversion is about 73%. After removal of unreacted aziridine, an approximately 37% solution of TAM in toluene containing less than 2% free aziridine was obtained. The yield of TAM dissolved in toluene based on chloroform was 62%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14744827.8A EP3030547A1 (de) | 2013-08-06 | 2014-07-28 | Verfahren zur herstellung von trisaziridinomethan |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13179402 | 2013-08-06 | ||
EP14744827.8A EP3030547A1 (de) | 2013-08-06 | 2014-07-28 | Verfahren zur herstellung von trisaziridinomethan |
PCT/EP2014/066119 WO2015018676A1 (de) | 2013-08-06 | 2014-07-28 | Verfahren zur herstellung von trisaziridinomethan |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3030547A1 true EP3030547A1 (de) | 2016-06-15 |
Family
ID=48915924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14744827.8A Withdrawn EP3030547A1 (de) | 2013-08-06 | 2014-07-28 | Verfahren zur herstellung von trisaziridinomethan |
Country Status (6)
Country | Link |
---|---|
US (1) | US20160185762A1 (zh) |
EP (1) | EP3030547A1 (zh) |
JP (1) | JP2016527289A (zh) |
KR (1) | KR20160040204A (zh) |
CN (1) | CN105452218A (zh) |
WO (1) | WO2015018676A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2701867T3 (es) | 2014-10-14 | 2019-02-26 | Basf Se | Uso de hexadeca-8,15-dienal como producto químico aromático |
WO2016177814A1 (en) | 2015-05-04 | 2016-11-10 | Basf Se | Process for the preparation of melonal |
KR20180034496A (ko) | 2015-07-22 | 2018-04-04 | 바스프 에스이 | 푸란-2,5-디카르복실산을 제조하는 방법 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050222081A1 (en) * | 2002-04-17 | 2005-10-06 | Gianolio Diego A | Cross-linked hyaluronate compounds |
-
2014
- 2014-07-28 WO PCT/EP2014/066119 patent/WO2015018676A1/de active Application Filing
- 2014-07-28 KR KR1020167003319A patent/KR20160040204A/ko not_active Application Discontinuation
- 2014-07-28 JP JP2016532309A patent/JP2016527289A/ja active Pending
- 2014-07-28 EP EP14744827.8A patent/EP3030547A1/de not_active Withdrawn
- 2014-07-28 US US14/909,785 patent/US20160185762A1/en not_active Abandoned
- 2014-07-28 CN CN201480043711.5A patent/CN105452218A/zh active Pending
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2015018676A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN105452218A (zh) | 2016-03-30 |
JP2016527289A (ja) | 2016-09-08 |
US20160185762A1 (en) | 2016-06-30 |
KR20160040204A (ko) | 2016-04-12 |
WO2015018676A1 (de) | 2015-02-12 |
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