CA2057109C - Process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols - Google Patents
Process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 33
- -1 2,2'-methylenebisbenzotriazolyl phenols Chemical class 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- JRRSZPBVIHXNBS-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)c1ccc(O)c(c1)-c1cccc2[nH]nnc12 JRRSZPBVIHXNBS-UHFFFAOYSA-N 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 4
- YHCGGLXPGFJNCO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=CC2=C1N=NN2 YHCGGLXPGFJNCO-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000009615 deamination Effects 0.000 description 3
- 238000006481 deamination reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- PSKABHKQRSJYCQ-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-6-[[3-(2H-benzotriazol-4-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)C=2C=3N=NNC=3C=CC=2)O)=C(O)C=1C1=CC=CC2=C1N=NN2 PSKABHKQRSJYCQ-UHFFFAOYSA-N 0.000 description 1
- BVNWQSXXRMNYKH-UHFFFAOYSA-N 4-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NN=N2 BVNWQSXXRMNYKH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000007966 viscous suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Compounds of formula wherein R1 and R2 are as defined in claim 1, are prepared by reacting a compound of formula with a compound of formula
Description
X05'7100 A-1845b/A
Process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols The present invention relates to a novel process for the preparation of 2,2'-methylenebisbenzotriazolyl phenols.
A process for the preparation of such compounds is disclosed in EP-A-180 993.
In this process, a benzotriazolyl phenol is reacted in a first step with an amine and forrnaldhyde in an organic solvent to give the corresponding Mannich base. In a second step, the isolated Mannich base is reacted with further benzotriazolyl phenol in another organic solvent to give the desired 2,2'-methylenebisbenzotriazolyl phenol.
It has now been found that symmetrical 2,2'-methylenebisbenzotriazolyl phenols are more simply and more rapidly obtainable than heretofore by carrying out the reaction of benzotriazolyl phenol, amine and formaldehyde in the absence of an organic solvent.
Accordingly, the invention relates to a process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols of formula OH OH
N
~1~ / 'N N / CH2 / N; ~ \
Rt \ N \ L \ ~ N~ / Rt wherein R1 is hydrogen, alkyl or alkoxy of 1 to 12 carbon atoms, phenyl, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety or halogen, and R2 is alkyl of 1 to 12 carbon atoms, alkyl of 1 to 12 carbon atoms which is substituted by C02H groups, phenyl, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety or cycloalkyl of 5 to 8 carbon atoms, which process comprises reacting a compound of formula ~0~7~0~
OH
~ N\
N
(2) w i R \ N
t \
wherein Rt and RZ have ttte given meanings, with a compound of formula ~3 (3) HH
~ Ra wherein R3 and R4 are each independently of the other alkyl of 1 to 4 carbon atoms, and with the compound of formula (4) CH20, or a polymer thereof, to give the corresponding Mannish base, and treating said Mannish base with a base, both reactions being carried out consecutively in the same reaction vessel without isolation of the intermediate.
The compounds of formula (1) are known, for example from EP-A-180 993 cited above.
The starting compounds of formula (2) are are also known and disclosed in US-A-4 g42 350 and EP-A-31 302, with processes for their preparation.
The 2,2'-methylenebisbenzotriazolyl phenols of formula (1) can be used as light stabilisers in organic polymers.
The substituent Rt in the compounds of formula (1) prepared by the process of this invention is, in addition to hydrogen, alkyl of 1 to 12 carbon atoms, typically methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl and dodecyl as well as corresponding branched isomers. Examples of suitable alkoxy radicals can be inferred from this recitation. Further, Rt is phenyl or phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety. Illustrative examples are phenylethyl and phenylpropyl, a-methylbenzyl, a,a-dimethylbenzyl and, preferably, benzyl. Rt may also be halogen, such as chloro or bromo. Preferably Rt is hydrogen, alkyl of 1 to 4 carbon atoms or chloro.
Suitable alkyl radicals RZ are the same as those cited for Rt. These alkyl radicals may be substituted by C02H groups to form groupings such as -CHZCH2CO2H. In addition to phenyl and phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety (examples as for Rt), R2 may also be cycloalkyl of 5 to 8 carbon atoms, typically cyclopentyl, ~~~~109 -cyclohexyl and cyclooctyl.
R3 and R4 in the compounds of formula (3) are each independently of the other alkyl of 1 to 4 carbon atoms, such as methyl, propyl and butyl, as well as corresponding branched isomers.
It is preferred to use those compounds of formula (2) wherein Rt is hydrogen, alkyl of 1 to 4 carbon atoms or halogen, preferably chloro, and R2 is alkyl of 1 to 12 carbon atoms, and, mare particularly, wherein Rt is hydrogen and R2 is alkyl of 6 to 12 carbon atoms. A
particularly preferred alkyl radical R2 is tent-octyl.
R3 and R4 in the compounds of formula (3) preferably have the same meaning and are preferably methyl or butyl.
In addition to formaldehyde, it is also possible to use as compound of formula (4) a polymer of formaldehyde, such as paraformaldehyde [(CH20)", n=12-30] or trioxane.
The process of this invention may be carried out, for example, by charging a benzotriazolyl phenol and formaldehyde to the reactor, conveniently under underpressure, typically 1 to 50 mbar, and converting this mixture into a melt. The dialkylamine is passed into this melt and the reaction mixture is then allowed to continue to react at somewhat higher temperature, typically from 120 to 150°C. The pressure in the reactor may rise during this phase to about 1700-1900 mbar. Normally the reaction can be discontinued even after 2 to 4 hours. The melt, which now contains the Mannich base and unreacted benzotriazolyl benzene, is allowed to cool and the water of reaction and excess amine are removed by applying a vacuum. The Mannich base is not isolated and is further reacted in the same reactor. For deamination, a base, for example an alkali metal alcoholate such as sodium methanolate or ethanolate, or an alkali metal hydroxide such as sodium or potassium hydroxide, is added to the reaction mixture, and the batch is heated to about 180 to 220°C under underpressure, typically 150 to 200 mbar. Normally the deamination is terminated after 2 to 4 hours. To neutralise the base, the melt is taken up in a higher boiling solvent such as xylene, and treated with a carboxylic acid, preferably formic or acetic acid. After clarification by filtration, the reaction product is worked up by conventional methods such as crystallisation, distillation or extraction. The melt crystallisation as working up or purification step can follow directly after the neutralisation with the carboxylic acid. In this case, the addition of the organic solvent is 2~~'~1~9 dispensed with. Unreacted benzotriazolyl phenol can be recovered from the higher boiling organic solvent by distillation, for example by means of a thin-film evaporator, whereby the yield, based on consumed benzotriazolyl phenol, usually rises by 4 to 10 %. The solvent can be recycled.
Characteristic of the inventive process is that it can be carried out as a one-pot process in the absence of an organic solvent.
In addition to an increase in yield of pure product, this process affords further significant advantages over the prior art process disclosed in EP-A-180 993. Compared with this prior art, the process of this invention shortens the total reaction time of 34 hours (24 hours for step 1, 10 hours for step 2) to 4 to 8 hours. This means that the inventive process leads to higher yields of product in only a sixth to an eighth of the time required solely for the first reaction step in EP-A-180 993, without loss of purity of the product. The space-time yield is improved in the practice of this invention by at least the factor 5.
In the practice of this invention, the isolation of the intermediate (Mannich base of OH
/ sN~N / CH2 N\
formula R1 \ ~N~ \ ~ R4 ), or even the purification of this intermediate, is also unnecessary.
In EP-A-180 993, different organic solvents are used for the first and second reaction steps. The problems associated therewith, i.e. the purification or disposal of the solvent, do not arise in the process of this invention.
These advantages make it clearly apparent that the process of this invention is a simple and very economic method of preparing 2,2'-methylenebisbenzotriazolyl phenols.
It is preferred to carry out the inventive process in the temperature range from 60 to 300°C, preferably from 130 to 220°C. The first step up to the preparation of the Mannich base is carried out at 60 to 150°C, preferably at 120 to 150°C, and the second step up to the formation of the final product is carried out at 180 to 300°C, preferably at 180 to 220°C. It is necessary to carry out the second step in the presence of a base, for example of 20~~~.09 an alkali metal aicoholate or alkali metal hydroxide. The molar ratios of the compounds of formulae (2), (3) and (4) is preferably 2:1:1 to 2:3:3, more particularly 2:2.5:1.5.
The process of this invention is especially suitable for the preparation of 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazolylphenol] by reacting the compound of formula (2), wherein Rt is hydrogen and R2 is tert-octyl, with a compound of formula (3), wherein R3 and R4 are simultaneously methyl or butyl, and formaldehyde, which compounds are used in the molar ratio of 2:2:1 to 2:2.2:1.1, and the reaction temperature is the the range from 130 to 220°C.
The invention is illustrated in more detail by the following Examples in which percentages are by weight.
Examyle 1: A 0.75 1 double-jacket flask, tested to 1.5 bar overpressure, and equipped with gas inlet tube, descending cooler with receiving flask and vacuum connecting tube with cooling trap to the vacuum pump, is charged with 323.2 g (1.0 mol) of 4-(1,1,3,3-tetra-methyl)butyl-6-benztriazol-2-ylphenol and 16.5 g (0.55 mol) of paraformaldehyde. After evacuating the flask to 20 mbar and closing it, the mixture is fused at a jacket temperature of 120°C, whereupon the pressure rises to about 270 mbar. Then 24.8 g (0.55 mol) of gaseous dimethylamine are introduced into the readily stimable melt at 100-105°C over 30 minutes. The final pressure rises to 900-1000 mbar. The reaction mixture is heated to 135°C and stirred at this temperature for 2 to 4 hours, the pressure rising to 1800 mbar.
After cooling to 90°C, the water of reaction, together with unreacted amine, is removed by applying a vacuum and heating to 130°C. The pressure is released with nitrogen and then 2.2 g (0.04 mol) of sodium methylate are added as catalyst to the reaction mass which, after applying a vacuum of 200 mbar, is heated rapidly to 200°C. From about 145-155°C, the splitting off of dimethylamine is observed. After stirring for 2 to 4 hours at 200°C and about 200 mbar, the deamination ceases and the reaction is complete. After dissolving the melt in 200 g of a xylene mixture, the alkaline catalyst is neutralised with 3.2 ml of formic acid (85 %), the solution is clarified by filtration at 130°C and the filtrate is washed with 75 g of a xylene mixture. Crystallisation is effected by cooling to about 0°C. The viscous suspension is filtered with suction, washed with 10(? g of a xylene mixture, and the product is dried in a vacuum drying oven at 120°C. Yield: 294 g of product in the form of a yellowish powder (89.3 % of theory, based on consumed benzotriazolyl phenol), m.p. 197.6°C, transmission (5 % in chloroform) at 450 nm: 96.4 %, at 500 nm: 97.7 %).
_6_ The washing liquor can be completely concentrated by evaporation and die residue distilled on a thin-film evaporator such that the unreacted benzotriazolyl phenol can be recovered in quantitative yield. In this way 4 to 10 % of unreacted benzotriazolylphenol can be recovered and used in the next batch. The yield, based on consumed benzotriazolyl-phenol, is thus 90-92 % of theory.
Example 2: A 0.75 1 sulfonation flask equipped with anchor stirrer, reflux condenser, nitrogen inlet and oil bath is charged with 323.2 g (1.0 mol) of 4-(1,1,3,3-tetramethyl)but-yl-6-benztriazol-2-yl phenol and 16.5 g (0.55 mol) of paraformaldehyde together with 142.2 g (1.1 mol) of dibutylamine. The suspension is heated to about 100°C and stirred for 6 hours at 100-102°C. Excess dibutylamine and the water of reaction are removed by distillation at 5 mbar and 120°C. Subsequent working up is effected as described in Example l, but under a pressure of 5 mbar and the reaction time is only 1 to 2 hours.
Yield: 277-290 g of product in the form of a yellowish powder (84-88 % of theory, based on benzotriazolyl phenol; m.p. 197°C, transmission 5 % in chloroform) at 450 nm: 97.0 %, at 500 nm: 98.8 %).
The mother liquor can be worked up as in Example 1. The yield then rises to 88-92 % of theory.
Example 3: The 0.75 i double jacket pressure reactor of Example 1 is charged with 323.2 g (1.0 mol) of 4-(1,1,3,3-tetramethyl)butyl-6-benzotriazol-2-yl phenol, 15.6 g (0.52 mol) of paraformaldehyde and 134.4 g (1.04 mol) of dibutylamine. The reactor is evacuated to 100 mbar and closed. The suspension is heated to 135°C and stirred for 1 hour at this temperature, the pressure rising to about 1.7 bar. The further steps are carried out in accordance with the general procedure described in Example l, except that the amount of catalyst is reduced to 0.01 mol, corresponding to 0.54 g or 1 mol %.
Yield: 277 io 290 g of product in the form of a yellowish powder (84 to 88 %
of theory, based on the benzotriazolyl phenol used, or 88 to 92 %, based on consumed benzotriazolyl phenol, m.p.: 197.5°C, transmission (5 % in chloroform) at 450 nm: 97.9 %, at 500 nm:
99.4 %).
Process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols The present invention relates to a novel process for the preparation of 2,2'-methylenebisbenzotriazolyl phenols.
A process for the preparation of such compounds is disclosed in EP-A-180 993.
In this process, a benzotriazolyl phenol is reacted in a first step with an amine and forrnaldhyde in an organic solvent to give the corresponding Mannich base. In a second step, the isolated Mannich base is reacted with further benzotriazolyl phenol in another organic solvent to give the desired 2,2'-methylenebisbenzotriazolyl phenol.
It has now been found that symmetrical 2,2'-methylenebisbenzotriazolyl phenols are more simply and more rapidly obtainable than heretofore by carrying out the reaction of benzotriazolyl phenol, amine and formaldehyde in the absence of an organic solvent.
Accordingly, the invention relates to a process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols of formula OH OH
N
~1~ / 'N N / CH2 / N; ~ \
Rt \ N \ L \ ~ N~ / Rt wherein R1 is hydrogen, alkyl or alkoxy of 1 to 12 carbon atoms, phenyl, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety or halogen, and R2 is alkyl of 1 to 12 carbon atoms, alkyl of 1 to 12 carbon atoms which is substituted by C02H groups, phenyl, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety or cycloalkyl of 5 to 8 carbon atoms, which process comprises reacting a compound of formula ~0~7~0~
OH
~ N\
N
(2) w i R \ N
t \
wherein Rt and RZ have ttte given meanings, with a compound of formula ~3 (3) HH
~ Ra wherein R3 and R4 are each independently of the other alkyl of 1 to 4 carbon atoms, and with the compound of formula (4) CH20, or a polymer thereof, to give the corresponding Mannish base, and treating said Mannish base with a base, both reactions being carried out consecutively in the same reaction vessel without isolation of the intermediate.
The compounds of formula (1) are known, for example from EP-A-180 993 cited above.
The starting compounds of formula (2) are are also known and disclosed in US-A-4 g42 350 and EP-A-31 302, with processes for their preparation.
The 2,2'-methylenebisbenzotriazolyl phenols of formula (1) can be used as light stabilisers in organic polymers.
The substituent Rt in the compounds of formula (1) prepared by the process of this invention is, in addition to hydrogen, alkyl of 1 to 12 carbon atoms, typically methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl and dodecyl as well as corresponding branched isomers. Examples of suitable alkoxy radicals can be inferred from this recitation. Further, Rt is phenyl or phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety. Illustrative examples are phenylethyl and phenylpropyl, a-methylbenzyl, a,a-dimethylbenzyl and, preferably, benzyl. Rt may also be halogen, such as chloro or bromo. Preferably Rt is hydrogen, alkyl of 1 to 4 carbon atoms or chloro.
Suitable alkyl radicals RZ are the same as those cited for Rt. These alkyl radicals may be substituted by C02H groups to form groupings such as -CHZCH2CO2H. In addition to phenyl and phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety (examples as for Rt), R2 may also be cycloalkyl of 5 to 8 carbon atoms, typically cyclopentyl, ~~~~109 -cyclohexyl and cyclooctyl.
R3 and R4 in the compounds of formula (3) are each independently of the other alkyl of 1 to 4 carbon atoms, such as methyl, propyl and butyl, as well as corresponding branched isomers.
It is preferred to use those compounds of formula (2) wherein Rt is hydrogen, alkyl of 1 to 4 carbon atoms or halogen, preferably chloro, and R2 is alkyl of 1 to 12 carbon atoms, and, mare particularly, wherein Rt is hydrogen and R2 is alkyl of 6 to 12 carbon atoms. A
particularly preferred alkyl radical R2 is tent-octyl.
R3 and R4 in the compounds of formula (3) preferably have the same meaning and are preferably methyl or butyl.
In addition to formaldehyde, it is also possible to use as compound of formula (4) a polymer of formaldehyde, such as paraformaldehyde [(CH20)", n=12-30] or trioxane.
The process of this invention may be carried out, for example, by charging a benzotriazolyl phenol and formaldehyde to the reactor, conveniently under underpressure, typically 1 to 50 mbar, and converting this mixture into a melt. The dialkylamine is passed into this melt and the reaction mixture is then allowed to continue to react at somewhat higher temperature, typically from 120 to 150°C. The pressure in the reactor may rise during this phase to about 1700-1900 mbar. Normally the reaction can be discontinued even after 2 to 4 hours. The melt, which now contains the Mannich base and unreacted benzotriazolyl benzene, is allowed to cool and the water of reaction and excess amine are removed by applying a vacuum. The Mannich base is not isolated and is further reacted in the same reactor. For deamination, a base, for example an alkali metal alcoholate such as sodium methanolate or ethanolate, or an alkali metal hydroxide such as sodium or potassium hydroxide, is added to the reaction mixture, and the batch is heated to about 180 to 220°C under underpressure, typically 150 to 200 mbar. Normally the deamination is terminated after 2 to 4 hours. To neutralise the base, the melt is taken up in a higher boiling solvent such as xylene, and treated with a carboxylic acid, preferably formic or acetic acid. After clarification by filtration, the reaction product is worked up by conventional methods such as crystallisation, distillation or extraction. The melt crystallisation as working up or purification step can follow directly after the neutralisation with the carboxylic acid. In this case, the addition of the organic solvent is 2~~'~1~9 dispensed with. Unreacted benzotriazolyl phenol can be recovered from the higher boiling organic solvent by distillation, for example by means of a thin-film evaporator, whereby the yield, based on consumed benzotriazolyl phenol, usually rises by 4 to 10 %. The solvent can be recycled.
Characteristic of the inventive process is that it can be carried out as a one-pot process in the absence of an organic solvent.
In addition to an increase in yield of pure product, this process affords further significant advantages over the prior art process disclosed in EP-A-180 993. Compared with this prior art, the process of this invention shortens the total reaction time of 34 hours (24 hours for step 1, 10 hours for step 2) to 4 to 8 hours. This means that the inventive process leads to higher yields of product in only a sixth to an eighth of the time required solely for the first reaction step in EP-A-180 993, without loss of purity of the product. The space-time yield is improved in the practice of this invention by at least the factor 5.
In the practice of this invention, the isolation of the intermediate (Mannich base of OH
/ sN~N / CH2 N\
formula R1 \ ~N~ \ ~ R4 ), or even the purification of this intermediate, is also unnecessary.
In EP-A-180 993, different organic solvents are used for the first and second reaction steps. The problems associated therewith, i.e. the purification or disposal of the solvent, do not arise in the process of this invention.
These advantages make it clearly apparent that the process of this invention is a simple and very economic method of preparing 2,2'-methylenebisbenzotriazolyl phenols.
It is preferred to carry out the inventive process in the temperature range from 60 to 300°C, preferably from 130 to 220°C. The first step up to the preparation of the Mannich base is carried out at 60 to 150°C, preferably at 120 to 150°C, and the second step up to the formation of the final product is carried out at 180 to 300°C, preferably at 180 to 220°C. It is necessary to carry out the second step in the presence of a base, for example of 20~~~.09 an alkali metal aicoholate or alkali metal hydroxide. The molar ratios of the compounds of formulae (2), (3) and (4) is preferably 2:1:1 to 2:3:3, more particularly 2:2.5:1.5.
The process of this invention is especially suitable for the preparation of 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazolylphenol] by reacting the compound of formula (2), wherein Rt is hydrogen and R2 is tert-octyl, with a compound of formula (3), wherein R3 and R4 are simultaneously methyl or butyl, and formaldehyde, which compounds are used in the molar ratio of 2:2:1 to 2:2.2:1.1, and the reaction temperature is the the range from 130 to 220°C.
The invention is illustrated in more detail by the following Examples in which percentages are by weight.
Examyle 1: A 0.75 1 double-jacket flask, tested to 1.5 bar overpressure, and equipped with gas inlet tube, descending cooler with receiving flask and vacuum connecting tube with cooling trap to the vacuum pump, is charged with 323.2 g (1.0 mol) of 4-(1,1,3,3-tetra-methyl)butyl-6-benztriazol-2-ylphenol and 16.5 g (0.55 mol) of paraformaldehyde. After evacuating the flask to 20 mbar and closing it, the mixture is fused at a jacket temperature of 120°C, whereupon the pressure rises to about 270 mbar. Then 24.8 g (0.55 mol) of gaseous dimethylamine are introduced into the readily stimable melt at 100-105°C over 30 minutes. The final pressure rises to 900-1000 mbar. The reaction mixture is heated to 135°C and stirred at this temperature for 2 to 4 hours, the pressure rising to 1800 mbar.
After cooling to 90°C, the water of reaction, together with unreacted amine, is removed by applying a vacuum and heating to 130°C. The pressure is released with nitrogen and then 2.2 g (0.04 mol) of sodium methylate are added as catalyst to the reaction mass which, after applying a vacuum of 200 mbar, is heated rapidly to 200°C. From about 145-155°C, the splitting off of dimethylamine is observed. After stirring for 2 to 4 hours at 200°C and about 200 mbar, the deamination ceases and the reaction is complete. After dissolving the melt in 200 g of a xylene mixture, the alkaline catalyst is neutralised with 3.2 ml of formic acid (85 %), the solution is clarified by filtration at 130°C and the filtrate is washed with 75 g of a xylene mixture. Crystallisation is effected by cooling to about 0°C. The viscous suspension is filtered with suction, washed with 10(? g of a xylene mixture, and the product is dried in a vacuum drying oven at 120°C. Yield: 294 g of product in the form of a yellowish powder (89.3 % of theory, based on consumed benzotriazolyl phenol), m.p. 197.6°C, transmission (5 % in chloroform) at 450 nm: 96.4 %, at 500 nm: 97.7 %).
_6_ The washing liquor can be completely concentrated by evaporation and die residue distilled on a thin-film evaporator such that the unreacted benzotriazolyl phenol can be recovered in quantitative yield. In this way 4 to 10 % of unreacted benzotriazolylphenol can be recovered and used in the next batch. The yield, based on consumed benzotriazolyl-phenol, is thus 90-92 % of theory.
Example 2: A 0.75 1 sulfonation flask equipped with anchor stirrer, reflux condenser, nitrogen inlet and oil bath is charged with 323.2 g (1.0 mol) of 4-(1,1,3,3-tetramethyl)but-yl-6-benztriazol-2-yl phenol and 16.5 g (0.55 mol) of paraformaldehyde together with 142.2 g (1.1 mol) of dibutylamine. The suspension is heated to about 100°C and stirred for 6 hours at 100-102°C. Excess dibutylamine and the water of reaction are removed by distillation at 5 mbar and 120°C. Subsequent working up is effected as described in Example l, but under a pressure of 5 mbar and the reaction time is only 1 to 2 hours.
Yield: 277-290 g of product in the form of a yellowish powder (84-88 % of theory, based on benzotriazolyl phenol; m.p. 197°C, transmission 5 % in chloroform) at 450 nm: 97.0 %, at 500 nm: 98.8 %).
The mother liquor can be worked up as in Example 1. The yield then rises to 88-92 % of theory.
Example 3: The 0.75 i double jacket pressure reactor of Example 1 is charged with 323.2 g (1.0 mol) of 4-(1,1,3,3-tetramethyl)butyl-6-benzotriazol-2-yl phenol, 15.6 g (0.52 mol) of paraformaldehyde and 134.4 g (1.04 mol) of dibutylamine. The reactor is evacuated to 100 mbar and closed. The suspension is heated to 135°C and stirred for 1 hour at this temperature, the pressure rising to about 1.7 bar. The further steps are carried out in accordance with the general procedure described in Example l, except that the amount of catalyst is reduced to 0.01 mol, corresponding to 0.54 g or 1 mol %.
Yield: 277 io 290 g of product in the form of a yellowish powder (84 to 88 %
of theory, based on the benzotriazolyl phenol used, or 88 to 92 %, based on consumed benzotriazolyl phenol, m.p.: 197.5°C, transmission (5 % in chloroform) at 450 nm: 97.9 %, at 500 nm:
99.4 %).
Claims (10)
1. A one-pot process in the absence of an organic solvent, for the preparation of a symmetrical 2,2'-methylene-bisbenzotriazolyl phenol of formula wherein R1 is hydrogen, alkyl or alkoxy of 1 to 12 carbon atoms, phenyl, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety or halogen, and R2 is alkyl of 1 to 12 carbon atoms, alkyl of 1 to 12 carbon atoms which is substituted by CO2H groups, phenyl, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety or cycloalkyl of 5 to 8 carbon atoms, which process comprises reacting a compound of formula wherein R1 and R2 are as defined above, with a compound of formula wherein R3 and R9 are each independently of the other alkyl of 1 to 4 carbon atoms, and with a compound of formula (4) CH2O, or a polymer thereof, to give the corresponding Mannich base, and treating said Mannich base with a base, both reactions being carried out consecutively in the same reaction vessel without isolation of the intermediate.
2. A process according to claim 1, wherein R1 is hydrogen, alkyl of 1 to 4 carbon atoms or halogen, and R2 is alkyl of 1 to 12 carbon atoms.
3. A process according to claim 2, wherein R1 is hydrogen and R2 is alkyl of 6 to 12 carbon atoms.
4. A process according to claim 3, wherein R2 is tert-octyl.
5. A process according to any one of claims 1 to 4, wherein R3 and R4 are methyl or butyl.
6. A process according to any one of claims 1 to 5, wherein the process is carried out in the temperature range from 60 to 300°C.
7. A process according to any one of claims 1 to 5, wherein the process is carried out in the temperature range from 130 to 220°C.
8. A process according to any one of claims 1 to 7, wherein the compounds of formulae (2), (3) and (4) are reacted in the molar ratio of 2:1:1 to 2:3:3.
9. A process according to any one of claims 1 to 7, wherein the compounds of formulae (2), (3) and (4) are reacted in the molar ratio of 2:2.5:1.5.
10. A process for the preparation of 2,2.'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazolylphenol] according to claim 1, by reacting the compound of formula (2), wherein R1 is hydrogen and R2 is 4-(1,1,3,3-tetramethylbutyl), with a compound of formula (3), wherein R3 and R4 is methyl or butyl, and formaldehyde, in the molar ratio of 2:2:1 to 2:2.2:1.1, and in the temperature range from 130 to 220°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3903/90-9 | 1990-12-11 | ||
| CH390390 | 1990-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2057109A1 CA2057109A1 (en) | 1992-06-12 |
| CA2057109C true CA2057109C (en) | 2002-05-21 |
Family
ID=4265987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2057109 Expired - Lifetime CA2057109C (en) | 1990-12-11 | 1991-12-09 | Process for the preparation of symmetrical 2,2'-methylenebisbenzotriazolyl phenols |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0490815B1 (en) |
| JP (1) | JP3223377B2 (en) |
| CA (1) | CA2057109C (en) |
| DE (1) | DE59103040D1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE194609T1 (en) | 1995-03-28 | 2000-07-15 | Hoffmann La Roche | AMINOMETHYLATION OF TOCOPHEROLS |
| JP4162274B2 (en) * | 1996-07-31 | 2008-10-08 | 城北化学工業株式会社 | Process for producing bis (2-hydroxyphenyl-3-benzotriazole) methanes |
| JP4155606B2 (en) * | 1996-12-12 | 2008-09-24 | 城北化学工業株式会社 | Benzotriazolyl-alkylene bisphenol compound, process for producing the same, and stabilized organic material containing the same |
| JP2963945B2 (en) | 1997-05-08 | 1999-10-18 | 大塚化学株式会社 | 2,2'-bis (6-benzotriazolylphenol) compound |
| JP5270134B2 (en) | 2007-11-12 | 2013-08-21 | 株式会社コーセー | Ultraviolet absorber water dispersion composition |
| JP5551391B2 (en) * | 2009-08-12 | 2014-07-16 | 大和化成株式会社 | Method for producing methylenebisbenzotriazolyl (hydroxyalkyl) phenol compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61115073A (en) * | 1984-11-09 | 1986-06-02 | Adeka Argus Chem Co Ltd | Production of 2, 2'-methylenebis(4-substituted-6 benzotriazolylphenzol |
-
1991
- 1991-12-03 DE DE59103040T patent/DE59103040D1/en not_active Expired - Lifetime
- 1991-12-03 EP EP19910810939 patent/EP0490815B1/en not_active Expired - Lifetime
- 1991-12-09 CA CA 2057109 patent/CA2057109C/en not_active Expired - Lifetime
- 1991-12-10 JP JP34992991A patent/JP3223377B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04290877A (en) | 1992-10-15 |
| JP3223377B2 (en) | 2001-10-29 |
| CA2057109A1 (en) | 1992-06-12 |
| DE59103040D1 (en) | 1994-10-27 |
| EP0490815A1 (en) | 1992-06-17 |
| EP0490815B1 (en) | 1994-09-21 |
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