DE3306196A1 - Process for the preparation of imidazolylbenzaldehydes - Google Patents

Process for the preparation of imidazolylbenzaldehydes

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Publication number
DE3306196A1
DE3306196A1 DE19833306196 DE3306196A DE3306196A1 DE 3306196 A1 DE3306196 A1 DE 3306196A1 DE 19833306196 DE19833306196 DE 19833306196 DE 3306196 A DE3306196 A DE 3306196A DE 3306196 A1 DE3306196 A1 DE 3306196A1
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formula
fluorobenzaldehyde
imidazolylbenzaldehydes
imidazolyl
preparation
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DE19833306196
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DE3306196C2 (en
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Jürgen Dipl.-Chem. Dr. 5024 Pulheim Biedermann
Gerd Dipl.-Chem. Dr. 5000 Köln Hilboll
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A Natterman und Cie GmbH
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A Natterman und Cie GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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 ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • 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
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to novel processes for the preparation of imidazolylbenzaldehydes of the general formula I <IMAGE> from imidazoles by reaction with 4-fluorobenzaldehyde.

Description

Beschreibungdescription

Die vorliegende Erfindung betrifft neue Verfahren zur Herstellung von Imidazolyl-benzaldehyden der Formel I worin R1 Wasserstoff oder einen C1-C4-Niederalkylrest bedeutet.The present invention relates to new processes for the preparation of imidazolylbenzaldehydes of the formula I. in which R1 is hydrogen or a C1-C4 lower alkyl radical.

Imidazolylbenzaldehyde der Formel I sind wertvolle Zwischenprodukte, unter anderem zur Herstellung pharmakologisch wirksamer Substanzen.Imidazolylbenzaldehydes of the formula I are valuable intermediates, among other things for the production of pharmacologically active substances.

L.M.Sitkina und A.M.Simonov D(him. Geterotsikl. Soedin.L.M.Sitkina and A.M.Simonov D (him. Geterotsikl. Soedin.

Akad. Nauk Latv. SSR 1966 (1), 143-5; C.A. 65 (1966), 13686e7 beschreiben die Herstellung von 4(1-Imidazolyl)-benzaldehyd (R1=H) nach dem Ullmann-Verfahren durch 30-stündiges Erhitzen von Imidazol und 4-Brombenzaldehyd mit Kaliumcarbonat und katalytischen Mengen Kupfer(1)-bromid in Nitrobenzol auf 2000C bei einer Ausbeute von 30%.Akad. Nauk Latv. SSR 1966 (1), 143-5; C.A. 65 (1966), 13686e7 the production of 4 (1-imidazolyl) -benzaldehyde (R1 = H) by the Ullmann process by heating imidazole and 4-bromobenzaldehyde with potassium carbonate for 30 hours and catalytic amounts of copper (1) bromide in nitrobenzene at 2000C in one yield of 30%.

Dieses Verfahren wird auch in der DE-OS 29 23 815, Beispiel 1, Methode H, benutzt, wobei eine auf Brombenzaldehyd bezogene Ausbeute von 40% angegeben wird. Die von J.B.Polya (J.Chem.Soc.C, 1970, 85-91) für die Herstellung von 4-(1-Imidazolyl)-acetophenon aus Imidazol und 4-Bromacetophenon erfolgreich benutzte Variante (48-stündiges Erhitzen der beiden Komponenten in Pyridin mit Kaliumcarbonat und katalytischen Mengen Kupfer(2)-oxid, Ausbeute 82%) liefert bei der Übertragung auf Imidazol und 4-Brombenzaldehyd nur eine unbefriedigende Ausbeute von ca. 10 %.This process is also described in DE-OS 29 23 815, Example 1, Method H, is used, a yield based on bromobenzaldehyde of 40% being given. That by J.B.Polya (J.Chem.Soc.C, 1970, 85-91) for the preparation of 4- (1-imidazolyl) acetophenone Successfully used variant made from imidazole and 4-bromoacetophenone (48-hour heating the two components in pyridine with potassium carbonate and catalytic amounts of copper (2) oxide, Yield 82%) yields when transferred to imidazole and 4-bromobenzaldehyde only an unsatisfactory yield of approx. 10%.

Ferner ist literaturbekannt (M.R.Grimmett, Advances in Heterocyclic Chemistry, Vol. 27, 318 ff, Academic Press Inc.It is also known from the literature (M.R. Grimmett, Advances in Heterocyclic Chemistry, Vol. 27, 318 ff, Academic Press Inc.

New York and London, 1980), daß 2-Methylimidazole an der Methylgruppe sehr reaktiv sind und - vor allem unter basischen Bedingungen - leicht Kondensationsreaktionen mit Carbonylverbindungen eingehen.New York and London, 1980) that 2-methylimidazoles on the methyl group are very reactive and - especially under basic conditions - easy condensation reactions enter into with carbonyl compounds.

Überraschend wurde nun gefunden, daß die Herstellung von Imidazolylbenzaldehyden der Formel I nach 2 Verfahren möglich ist, die den bisher bekannten deutlich überlegen sind bzw. 2-Alkylimidazolylbenzaldehyde der Formel I mit R1= Alkyl erstmals in vertretbarem Aufwand zugänglich machen.It has now surprisingly been found that the production of imidazolylbenzaldehydes of the formula I is possible by 2 processes which are clearly superior to those previously known are or 2-alkylimidazolylbenzaldehydes of the formula I with R1 = alkyl for the first time in acceptable Make effort accessible.

Im ersten Verfahren werden Imidazolverbindungen der Formel II worin R1 die in Formel I angegebene Bedeutung hat, mit einem Fluorbenzaldehyd der Formel III in einem geeigneten aprotischen Lösungsmittel, wie z.B.In the first process, imidazole compounds of the formula II wherein R1 has the meaning given in formula I, with a fluorobenzaldehyde of the formula III in a suitable aprotic solvent, such as

Dimethylsulfoxid, Dimethylformamid, Sulfolan, in Gegenwart einer Hilfsbase, wie z.B. Kaliumcarbonat, Natriumcarbonat, Magnesiumoxid, Calciumcarbonat, bei Temperaturen zwischen 60° und 1400C, vorzugsweise bei 100" - 1200C, ggfs. in Schutzgasatmosphäre wie Stickstoff, Argon, Kohlendioxid, während 2-8 Stunden umgesetzt.Dimethyl sulfoxide, dimethylformamide, sulfolane, in the presence of an auxiliary base, such as potassium carbonate, sodium carbonate, magnesium oxide, calcium carbonate, at temperatures between 60 ° and 1400C, preferably at 100 "- 1200C, if necessary in a protective gas atmosphere such as nitrogen, argon, carbon dioxide, reacted for 2-8 hours.

Aus molaren Mengen Imidazol, 4-Fluorbenzaldehyd und Kaliumcarbonat erhält man so 4-(1-Imidazolyl)-benzaldehyd (Formel I, R1=H) in Ausbeuten von 75-85 %, sowie 4-(2-Methyl-1-imidazolyl)-benzaldehyd in Ausbeuten von 40-50%.From molar amounts of imidazole, 4-fluorobenzaldehyde and potassium carbonate 4- (1-imidazolyl) benzaldehyde (formula I, R1 = H) is obtained in yields of 75-85 %, and 4- (2-methyl-1-imidazolyl) -benzaldehyde in yields of 40-50%.

Im zweiten Verfahren werden Trimethylsilylimkiazole der Formel IV worin R1 die in Formel I angegebene Bedeutung hat, mit einem Fluorbenzaldehyd der Formel III bei Temperaturen von 100ob 1800C, vorzugsweise bei 1400-1800C, gegebenenfalls in einem Autoklaven, umgesetzt.In the second process, trimethylsilylimkiazoles of the formula IV in which R1 has the meaning given in formula I, reacted with a fluorobenzaldehyde of the formula III at temperatures of 100 to 1800C, preferably at 1400-1800C, optionally in an autoclave.

Aus molaren Mengen 2-Methyl-1-trimethylsilylimidazol (Formel IV, R1 = CH3) und 4-Fluorbenzaldehyd erhält man nach diesem Verfahren durch 3-6-stündiges Erhitzen bei einer Atmosphäre auf 1400-180"C 4-(2Methyl-1-imidazolyl)-benzaldehyd (Formel I, R1=CH3) in Ausbeuten von 45-55%.From molar amounts of 2-methyl-1-trimethylsilylimidazole (formula IV, R1 = CH3) and 4-fluorobenzaldehyde are obtained by this process after 3-6 hours Heat in an atmosphere of 1400-180 "C 4- (2-methyl-1-imidazolyl) benzaldehyde (Formula I, R1 = CH3) in yields of 45-55%.

Die neuen Verfahren sind in mehrfacher Hinsicht vorteilhaft.The new methods are advantageous in several ways.

Die Ausbeuten gegenüber den bekannten Verfahren werden von 30 - 40 % auf 75 - 85 % gesteigert (für Formel I, R1=H).The yields compared to the known processes are from 30 to 40 % increased to 75 - 85% (for formula I, R1 = H).

Der teure 4-Brombenzaldehyd wird durch den bedeutend preisgünstigeren 4-Fluorbenzaldehyd ersetzt.The expensive 4-bromobenzaldehyde is significantly cheaper because of the cheaper one 4-fluorobenzaldehyde replaced.

Die hohen Energiekosten der bekannten Verfahren mit 18-48-stündigem Erhitzen auf 2000C werden deutlich verringert durch 2-8-stündiges Erhitzen auf 1000-120"C bei Verfahren 1. Das giftige Nitrobenzol wird durch das physiologisch wesentlich unbedenklichere Dimethylsulfoxid ersetzt (Verfahren 1).The high energy costs of the known methods with 18-48 hour Heating to 2000C is significantly reduced by heating to 1000-120 "C for 2-8 hours in process 1. The toxic nitrobenzene becomes physiologically essential through the replaces safer dimethyl sulfoxide (method 1).

Verfahren 2 ist ohne Lösungsmittel durchführbar.Method 2 can be carried out without a solvent.

2-Alkylimidazolylbenzaldehyde sind nach beiden Verfahren erstmals mit vertretbarem Aufwand herstellbar.2-Alkylimidazolylbenzaldehydes are the first to use both processes Can be produced with reasonable effort.

Die erfindungsgemäßen Verfahren werden durch die folgenden Beispiele erläutert. Die angegebenen Schmelzpunkte wurden mit einem Büchi 510 - Schmelzpunktbestimmungsapparat gemessen und sind in "C angegeben und ebenso wie die in C angegebenen Siedepunkte nicht korrigiert.The methods of the invention are illustrated by the following examples explained. The melting points given were obtained using a Büchi 510 melting point apparatus measured and are given in "C and just like the boiling points given in C." not corrected.

Die IR-Spektren wurden mit den Geräten Perkin-Elmer 257 bzw.The IR spectra were recorded with the Perkin-Elmer 257 or

Nicolet NIC 3600 und die Massenspektren mit dem Gerät Varian MAT-311-A (70eV) aufgenommen.Nicolet NIC 3600 and the mass spectra with the Varian MAT-311-A (70eV) included.

Beispiel 1 4-(1-Imidazolyl)-benzaldehyd nach Verfahren 1.Example 1 4- (1-imidazolyl) -benzaldehyde according to process 1.

Eine Mischung aus 13,6 g Imidazol, 24,8 g 4-Fluorbenzaldehyd, 30,4 g Kaliumcarbonat und 200 ml Dimethylsulfoxid wird 8 Stunden bei 1000-1100C in Stickstoffatmosphäre gerührt.A mixture of 13.6 g imidazole, 24.8 g 4-fluorobenzaldehyde, 30.4 g g potassium carbonate and 200 ml dimethyl sulfoxide is 8 hours at 1000-1100C in a nitrogen atmosphere touched.

Nach Abkühlen auf 50°C wird das Reaktionsgemisch in 500 ml Wasser eingerührt. Der dabei ausgefallene Feststoff wird abgesaugt, mit Wasser gewaschen und anschließend aus 90%-igem Ethanol umkristallisiert.After cooling to 50 ° C., the reaction mixture is dissolved in 500 ml of water stirred in. The solid which has precipitated out is filtered off with suction and washed with water and then recrystallized from 90% ethanol.

Ausbeute: 26,6 g (77% der Theorie) Schmp. 1500-1510C Beispiel 2 4-(2Methyl-1-imidazolyl)-benzaldehyd nach Verfahren 1.Yield: 26.6 g (77% of theory) melting point 1500-1510C Example 2 4- (2-methyl-1-imidazolyl) -benzaldehyde according to procedure 1.

Eine Mischung aus 186 g 4-Fluorbenzaldehyd, 123 g 2-Methylimidazoi, 228 g Kaliumcarbonat und 2 l Dimethylsulfoxid wird 6 Stunden in Stickstoffatmosphäre bei 1000C gerührt. Nach Abkühlen wird die Mischung in 4 1 Wasser eingerührt und durch Zugabe von Salzsäure auf pH 2 gebracht. Anschließend wird mit Chloroform extrahiert und die Wasserphase durch Zugabe von 20%iger Natronlauge auf pH 9 eingestellt. Die Wasserphase wird mit Chloroform extrahiert, die Chloroformphase über Natriumsulfat getrocknet und eingeengt. Der Rückstand wird durch Säulenchromatographie (Kieselgel/Chloroform) gereinigt. Aus dem Chloroformextrakt der sauren Wasserphase werden durch Destillation 74 g Fluorbenzaldehyd (40%) zurückgewonnen.A mixture of 186 g of 4-fluorobenzaldehyde, 123 g of 2-methylimidazoi, 228 g of potassium carbonate and 2 l of dimethyl sulfoxide are added for 6 hours in a nitrogen atmosphere stirred at 1000C. After cooling, the mixture is stirred into 4 l of water and brought to pH 2 by adding hydrochloric acid. It is then extracted with chloroform and the water phase is adjusted to pH 9 by adding 20% sodium hydroxide solution. the The water phase is extracted with chloroform, the chloroform phase over sodium sulfate dried and concentrated. The residue is purified by column chromatography (silica gel / chloroform) cleaned. The acidic water phase is made from the chloroform extract by distillation 74 g of fluorobenzaldehyde (40%) recovered.

Ausbeute: 114 g (41% der Theorie) Schmp. 1070-1086C IR (in KBr): 1695 cm MS zm/e7: 186 (M+, 100%), 157 (16%), 144 (20%) 130 (20%), 116 (14%) Beispiel 3 4-(2Methyl-1-imidazolyl)-benzaldehyd nach Verfahren 2.Yield: 114 g (41% of theory) melting point 1070-1086C IR (in KBr): 1695 cm MS zm / e7: 186 (M +, 100%), 157 (16%), 144 (20%) 130 (20%), 116 (14%) example 3 4- (2-methyl-1-imidazolyl) -benzaldehyde according to method 2.

Zu 77g 2-Methyl-l-trimethylsilylimidazol (hergestellt durch Erhitzen von molaren Mengen 2-Methylimidazol, Chlortrimethylsilan und Triethylamin in Toluol, Ausbeute 84 % der Theorie. Kp. 1270-1310C, 35 Torr) werden in 20 Minuten unter schwachem Einleiten von Stickstoff bei 4Ü0-6Ü0C 629 4-Fluorbenzaldehyd zugetropft. Anschließend wird 6 Stunden bei Rückflußtemperatur gerührt, dabei fällt die Temperatur von 1800 auf 13Ü0C. Nach Abkühlen auf 700C wird die Reaktionsmischung auf 300 g Eis gegeben. Nach Ansäuern mit 18%iger Salzsäure wird mit Chloroform extrahiert, die Wasserphase durch Zugabe von 20%iger Natronlauge neutralisiert, der ausgefallene Feststoff abgesaugt, mit Wasser gewaschen und aus verdünntem Alkohol umkristallisiert und anschließend getrocknet.To 77g of 2-methyl-1-trimethylsilylimidazole (prepared by heating of molar amounts of 2-methylimidazole, chlorotrimethylsilane and triethylamine in toluene, Yield 84% of theory. Bp. 1270-1310C, 35 Torr) are in 20 minutes under weak Introducing nitrogen at 4Ü0-6Ü0C 629 4-fluorobenzaldehyde was added dropwise. Afterward is stirred for 6 hours at reflux temperature, the temperature falls from 1800 to 13Ü0C. After cooling to 70 ° C., the reaction mixture is poured onto 300 g of ice. After acidification with 18% hydrochloric acid, the mixture is extracted with chloroform, the water phase neutralized by adding 20% sodium hydroxide solution, the precipitated solid is filtered off with suction, washed with water and recrystallized from dilute alcohol and then dried.

Ausbeute: 48 g (52% der Theorie) Schmp. 106-108"C Nach den in den Beispielen 1 - 3 beschriebenen Verfahren werden hergestellt: 4-(2-Ethyl-imidazolyl)-benzaldehyd, 4-(2-Propyl-imidazolyl )-benzaldehyd, 4-(2-Butyl-imidazolyl)-benzaldehyd.Yield: 48 g (52% of theory) melting point 106-108 "C According to the Examples 1 - 3 described processes are produced: 4- (2-ethyl-imidazolyl) -benzaldehyde, 4- (2-propyl-imidazolyl) -benzaldehyde, 4- (2-butyl-imidazolyl) -benzaldehyde.

Claims (3)

Patentansprüche 1. Verfahren zur Herstellung von Imidazolylbenzaldehyden der allgemeinen Formel I worin R1 Wasserstoff oder einen C1-C4-Niederalkylrest bedeutet, dadurch gekennzeichnet, daß die Umsetzung der Imidazolverbindung mit 4-Fluorbenzaldehyd durchgeführt wird.Claims 1. Process for the preparation of imidazolylbenzaldehydes of the general formula I. wherein R1 is hydrogen or a C1-C4 lower alkyl radical, characterized in that the reaction of the imidazole compound with 4-fluorobenzaldehyde is carried out. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man eine Imidazolverbindung der Formel II worin R1 die in Formel I angegebene Bedeutung hat, mit einem Fluorbenzaldehyd der Formel III in einem geeigneten aprotischen Lösungsmittel, wie z.B.2. The method according to claim 1, characterized in that an imidazole compound of the formula II wherein R1 has the meaning given in formula I, with a fluorobenzaldehyde of the formula III in a suitable aprotic solvent, such as Dimethylsulfoxid, Dimethylformamid, Sulfolan, in Gegenwart einer Hilfsbase, wie z.B. Kaliumcarbonat, Natriumcarbonat, Magnesiumoxid, Calciumcarbonat, bei Temperaturen zwischen 60° und 140"C, vorzugsweise bei 1000-1200C, umsetzt. Dimethyl sulfoxide, dimethylformamide, sulfolane, in the presence of a Auxiliary base, such as potassium carbonate, sodium carbonate, magnesium oxide, calcium carbonate, at temperatures between 60 ° and 140 "C, preferably at 1000-1200C. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Trimethylsilylimidazole der Formel IV worin R1 die in Formel I angegebene Bedeutung hat, mit einem Fluorbenzaldehyd der Formel III bei Temperaturen von 100"-180"C, vorzugsweise bei l4o0-l800Q, gegebenenfalls in einem Autoklaven umsetzt.3. The method according to claim 1, characterized in that trimethylsilylimidazoles of the formula IV in which R1 has the meaning given in formula I, is reacted with a fluorobenzaldehyde of the formula III at temperatures of 100-180 ° C., preferably at 140 ° -1800 ° C., optionally in an autoclave.
DE19833306196 1983-02-23 1983-02-23 Process for the preparation of imidazolylbenzaldehydes Granted DE3306196A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0234350A2 (en) * 1986-02-26 1987-09-02 A. Nattermann & Cie. GmbH Process for producing imidazolylthiophenaldehydes
CN104130192A (en) * 2014-07-30 2014-11-05 齐鲁工业大学 Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2923815A1 (en) * 1978-06-13 1980-01-10 Kissei Pharmaceutical NEW IMIDAZOLE DERIVATIVES AND CONTAINING PHARMACEUTICAL COMPOSITIONS
DE3212304A1 (en) * 1982-04-02 1983-10-06 Nattermann A & Cie IMIDAZOLYLPHENYL-TETRAHYDROPYRIDAZINE, METHOD FOR THE PRODUCTION THEREOF AND PHARMACEUTICAL PREPARATIONS CONTAINING THEM

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2923815A1 (en) * 1978-06-13 1980-01-10 Kissei Pharmaceutical NEW IMIDAZOLE DERIVATIVES AND CONTAINING PHARMACEUTICAL COMPOSITIONS
DE3212304A1 (en) * 1982-04-02 1983-10-06 Nattermann A & Cie IMIDAZOLYLPHENYL-TETRAHYDROPYRIDAZINE, METHOD FOR THE PRODUCTION THEREOF AND PHARMACEUTICAL PREPARATIONS CONTAINING THEM

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chem. Abstr. 65, 13686e, 1966, 2 *
HOUBEN-WEYL: Methoden der organischen Chemie, 4. Aufl., Bd. V/3, Stuttgart, Thieme-Verlag, 1962, S. 482-489 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0234350A2 (en) * 1986-02-26 1987-09-02 A. Nattermann & Cie. GmbH Process for producing imidazolylthiophenaldehydes
EP0234350A3 (en) * 1986-02-26 1989-07-05 A. Nattermann & Cie. GmbH Process for producing imidazolylthiophenaldehydes
CN104130192A (en) * 2014-07-30 2014-11-05 齐鲁工业大学 Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof
CN104130192B (en) * 2014-07-30 2017-05-24 齐鲁工业大学 Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof

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