DE1768080A1 - New halobenzocycloalkylnitriles and processes for their preparation - Google Patents
New halobenzocycloalkylnitriles and processes for their preparationInfo
- Publication number
- DE1768080A1 DE1768080A1 DE19681768080 DE1768080A DE1768080A1 DE 1768080 A1 DE1768080 A1 DE 1768080A1 DE 19681768080 DE19681768080 DE 19681768080 DE 1768080 A DE1768080 A DE 1768080A DE 1768080 A1 DE1768080 A1 DE 1768080A1
- Authority
- DE
- Germany
- Prior art keywords
- cyano
- isopropyl
- chloro
- halobenzocycloalkylnitriles
- phenyl
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 2
- -1 1-Cyano-1-isopropyl-4-bromo-5,6-dimethoxyindane Chemical compound 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 9
- 150000001241 acetals Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 241000251730 Chondrichthyes Species 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LILXDMFJXYAKMK-UHFFFAOYSA-N 2-bromo-1,1-diethoxyethane Chemical compound CCOC(CBr)OCC LILXDMFJXYAKMK-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- NDZXMOIVBGRFLC-UHFFFAOYSA-N 2-chloro-1,1-diethoxypropane Chemical compound CCOC(C(C)Cl)OCC NDZXMOIVBGRFLC-UHFFFAOYSA-N 0.000 description 1
- IBJJQTFDUHYOGM-UHFFFAOYSA-N 4-bromo-6,7-dimethoxy-1-propan-2-yl-3,4-dihydro-2H-naphthalene-1-carbonitrile Chemical compound C(#N)C1(CCC(C2=CC(=C(C=C12)OC)OC)Br)C(C)C IBJJQTFDUHYOGM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000007962 benzene acetonitriles Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B1/00—Sieving, screening, sifting, or sorting solid materials using networks, gratings, grids, or the like
- B07B1/42—Drive mechanisms, regulating or controlling devices, or balancing devices, specially adapted for screens
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Ä G Ä G
CHEMISCHE FABRIKENCHEMICAL FACTORY
Patent- u. Lizenz-Abteilung Ludwigshafen/Rhein,Patent and license department Ludwigshafen / Rhein,
Dr.W./2954 den 29. Februar 1968Dr.W./2954 on February 29, 1968
Neue- Halogenbenzocycloalkylnitrile und Verfahren zu derenNew halobenzocycloalkylnitriles and processes for their
HerstellungManufacturing
Es ist bekannt Halogenbenzocycloalkylverbindungen entweder durch Substitutionsreaktionen an entsprechend substituierten Benzocycloalkylverbindungen oder durch Halogenwasserstoff-Addition an Benzocycloalkeny!verbindungen darzustellen. So erhält man beispielsweise durch Chlorwasserstoffanlagerung an Inden das 1-Chlorindan oder an 1,2-Dihydronaphthalin das 1-Chlor-1,2,3,4-tetrahydronaphthalin. Diese Verbindungen sind auch aus den entsprechenden Hydroxylverbindungen erhältlich /M. Protiva et al. Chem. Listy 47, 213 (1953) ref. nach Chem. Abstr. 4_9, 199 (1955); R. Weisgerber Ber.dtsch.ehem.Ges. 44, 1436 (191127· In allen Pällen wird das Halogenatom jedoch in bereits bestehende Ringsysteme eingeführt.It is known halobenzocycloalkyl compounds either by substitution reactions on appropriately substituted ones Benzocycloalkyl compounds or by hydrogen halide addition to represent on benzocycloalkenyl compounds. So obtained, for example, by the addition of hydrogen chloride 1-chloroindane on indene or that on 1,2-dihydronaphthalene 1-chloro-1,2,3,4-tetrahydronaphthalene. These connections are also available from the corresponding hydroxyl compounds / M. Protiva et al. Chem. Listy 47, 213 (1953) ref. according to Chem. Abstr. 4-9, 199 (1955); R. Weisgerber Ber.dtsch.ehem.Ges. 44, 1436 (191127, however, in all cases the halogen atom is used in existing ring systems introduced.
1,2-Benzocycloalkylnitrile sind beispielsweise darstellbar du 'ch intramolekulare Cyclisierungsreaktion geeigneter1,2-Benzocycloalkylnitriles can be prepared, for example the intramolecular cyclization reaction is more suitable
_ 2 — 109844/1681 _ 2 - 109844/1681
KNOLL AGKNOLL AG
c-Chlorphenylalkylnitrile in Gegenwart τοη Kaliumamid β.P. Bunett u. J.A. Skorcz J.Org.Chem. 2J, 3836 (196227. Diese liber ein Arin verlaufende Ringschlufireaktion ist jedoch nicht für die Darstellung halogensubstituierter Ver bindungen geeignet.c-Chlorophenylalkylnitrile in the presence of τοη potassium amide β. P. Bunett and JA Skorcz J.Org.Chem. 2J, 3836 (196227. This ring closure reaction proceeding over an aryne is not suitable for the preparation of halogen-substituted compounds.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung neuer Halogenbenzocycloalkylnitrile der allgemeinen formelThe invention relates to a method for production new halobenzocycloalkylnitriles of the general formula
CH (CH2)-C - R1 CH (CH 2 ) -C - R 1
XJXJ
' CH,0 '^S CH _ CH Hai'CH, 0 ' ^ S CH _ CH shark
worin R.. ein Wasserstoff atom, einen niedermolekularen, geraden oder verzweigten Alkylrest, die Phenyl- oder Benzylgruppe, Hai ein Chlor- oder Bromatom und η und m die Zahlenpaare 0,0 oder 0,1 oder 1,0 bedeuten.where R .. is a hydrogen atom, a low molecular weight, straight line or branched alkyl radical, the phenyl or benzyl group, Hai a chlorine or bromine atom and η and m the number pairs 0,0 or Mean 0.1 or 1.0.
Das Verfahren betrifft die intramolekulare Ringachlufireaktion von Aldehyden bzw. deren Acetalen und ist dadurch gekennzeichnet, daß man einen Aldehyd der allgemeinen FormelThe method relates to the intramolecular Ringachlufireaction of aldehydes or their acetals and is characterized in that an aldehyde of the general formula
CH5O v CNCH 5 O v CN
109844/1681109844/1681
bzw. dessen Acetale mit gasförmigem Halogenwasserstoff oder mit Säurehalogeniden bei niederer Temperatur und in Gegenwart eines inerten Lösungsmittels umsetzt.or its acetals with gaseous hydrogen halide or with acid halides at low temperature and in the presence an inert solvent.
Die erfindungsgemäße intramolekulare Ringschlußreaktion von Aldehyden zu Halogenbenzocycloalkylnitrilen ist neuartig und wurde bis jetzt noch nicht in der Literatur beschrieben.The inventive intramolecular ring closure reaction of aldehydes to halobenzocycloalkylnitriles is novel and has not yet been described in the literature.
Der Mechanismus dieser Reaktion ist vermutlich vergleichbar mit dem einer einfachen Chlormethylierung /vgl. R.C. Fuson und CH. McKeever Org. React. ±, 63 (1942^7, wobei elektrophile Substitution stattfindet. Es war überraschend und keineswegs vorauszusehen, daß eine intramolekulare und keine intermolekulare Reaktion eintrat.The mechanism of this reaction is presumably comparable to that of a simple chloromethylation / cf. RC Fuson and CH. McKeever Org.React. ±, 63 (1942 ^ 7, with electrophilic substitution taking place. It was surprising and by no means to be foreseen that an intramolecular and no intermolecular reaction occurred.
Zur Ausführung des erfindungsgemäßen Verfahrens geht man in der Weise vor, daß man einen Aldehyd der allgemeinen Formel II, bzw. dessen Acetale in einem indifferenten Lösungsmittel löst. Als indifferente Lösungsmittel kann man beispielsweise Kohlenwasserstoffe wie Hexan, Benzol, Toluol oder Xylol oder Chlorkohlenwasserstoffe wie Methylenchlorid, Chloroform oder Tetrachlorkohlenstoffe einsetzen.To carry out the process according to the invention, one proceeds in such a way that an aldehyde of the general formula II, or its acetals dissolve in an inert solvent. Hydrocarbons, for example, can be used as inert solvents such as hexane, benzene, toluene or xylene or chlorinated hydrocarbons such as methylene chloride, chloroform or carbon tetrachloride insert.
109844/1681109844/1681
Ο LΟ L
CHEMISCHE FABRIKENCHEMICAL FACTORY
In die Aldehyd-Lösung bzw. in die Aldehydacetal-Lösung wird entweder Chlorwasserstoff oder Bromwasserstoff oder ein gasförmiges Säurehalogenid eingeleitet oder ein flüssiges Säurehalogenid zugetropft. Als Säurehalogenide werden Thionylchlorid, Phosphoroxychlorid, Phosphoroxybromid, Phosgen oder Phosphor(V)-chlorid verwendet. Um die Bildung von Nebenprodukten zu vermeiden, wird die Ringschlußreaktion bei Temperaturen von 0 - 30 0C durchgeführt, dabei richtet sich die Reaktionszeit nach der Reaktionsfähigkeit der eingesetzten Aldehyde. Im allgemeinen ist die Reaktion spätestens nach 2-3 Stunden beendet.Either hydrogen chloride or hydrogen bromide or a gaseous acid halide is passed into the aldehyde solution or into the aldehyde acetal solution, or a liquid acid halide is added dropwise. Thionyl chloride, phosphorus oxychloride, phosphorus oxybromide, phosgene or phosphorus (V) chloride are used as acid halides. In order to avoid the formation of by-products, the ring closure reaction at temperatures of 0 is - carried out 30 0 C, while the reaction time depends on the reactivity of the aldehydes used. In general, the reaction has ended after 2-3 hours at the latest.
Die Aufarbeitung erfolgt entweder in der Weise, daß das ausgefallene Reaktionsprodukt abfiltriert wird oder daß man das Lösungsmittel im Vakuum teilweise oder ganz entfernt und den erhaltenen Rückstand entweder durch Kristallisation oder durch Destillation reinigt. Man erhält die Halogenbenzocycloalkylnitrile im allgemeinen in Ausbeuten von 75 - 90 ^. Sie stellen wertvolle Zwischenprodukte für die Synthese coronarwirksamer Arzneimittel dar.Working up is carried out either in such a way that the precipitated reaction product is filtered off or that one the solvent partially or completely removed in vacuo and the residue obtained either by crystallization or purifies by distillation. The halobenzocycloalkylnitriles are obtained generally in yields of 75 - 90 ^. They provide valuable intermediates for the synthesis of coronary effects Medicinal products.
109844/1681109844/1681
K M O L L A. G.K M O L L A. G.
CHEMISCHE FABRIKENCHEMICAL FACTORY
Aldehyde der allgemeinen Formel II, bzw. deren Acetale sind erhältlich durch Alkylierung substituierter Benzylcyanide mit u-Halogenalkylaldehyddiacetalen. Die Freisetzung der Aldehyde aus den Acetalen kann in bekannter Weise durch Behandlung mit verdünnter Säure· erfolgen. Im allgemeinen verwendet man jedoch bei der Ringschlußreaktion direkt die Acetale, wobei man im allgemeinen niedermolekulare Alkylacetale einsetzt.Aldehydes of the general formula II or their acetals obtainable by alkylation of substituted benzyl cyanides with u-haloalkylaldehyde diacetals. The release of the Aldehydes from the acetals can be effected in a known manner by treatment with dilute acid. Generally used However, the acetals are used directly in the ring closure reaction, generally low molecular weight alkyl acetals begins.
1-0yano-1-isopropyl-3-brom-5>6-dimethoxyindan1-0yano-1-isopropyl-3-bromo-5> 6-dimethoxyindane
Während 2 Stunden leitet man bei 5 - 15 0C in eine Lösung von 167,5 g (0,5 Mol) 1-(3f ,4'-I>imethoxyphenyl)-1-isopropyl-3f3-diäthoxy-butyronitril /erhalten durch Alkylierung von 1—(3'»4'— Dimethoxyphenyl)-2-methyl-butyronitril mit Bromaeetaldehyd-diäthylacetal7 in 500 com trockenem Toluol trockenen Bromwasserstoff ein. Es werden etwa 100 g Bromwasserstoff aufgenommen. Anschließend rührt man 3 Stunden bei 20 0C, läßt die Reaktionsmischung 12 Stunden bei 5 0C stehen und destilliert bei einer Badtemperatur von 30 0C das lösungsmittel im Vakuum ab. Der Rückstand wird mit 250 ecm Esaigsäureäthvlester versetzt und gekühlt. Man erhält nach Abfiltrieren des Niederschlags und Um- . kristallisieren aus Essigsäureäthylester 75 g (46 $ der Theorie)For 2 hours is introduced at 5 - (f 3, 4'-I> imethoxyphenyl) 15 0 C in a solution of 167.5 g (0.5 mol) of 1- -1-isopropyl-3 f 3-diethoxy-butyronitrile / obtained by alkylation of 1- (3 "» 4 "- dimethoxyphenyl) -2-methyl-butyronitrile with bromoeetaldehyde diethylacetal7 in 500 com dry toluene dry hydrogen bromide. About 100 g of hydrogen bromide are taken up. The mixture is then stirred for 3 hours at 20 ° C., the reaction mixture is allowed to stand for 12 hours at 5 ° C. and the solvent is distilled off in vacuo at a bath temperature of 30 ° C. The residue is mixed with 250 ecm of ethyl acetate and cooled. After filtering off the precipitate and um-. crystallize from ethyl acetate 75 g (46 $ of theory)
109844/1681 - 6 -109844/1681 - 6 -
KNOLL AGKNOLL AG
i-Cyano-i-isopropyl^-brom^.e-dimethoxyindan. P 107 - 108 0C.i-cyano-i-isopropyl ^ -bromo ^ .e-dimethoxyindane. P 107 - 108 0 C.
In ähnlicher Weise werden folgende Verbindungen hergestellt:In a similar way, the following connections are made:
1-Cyano-4-brom-6,7-dimethoxytetralin (P 103 °C; Ausbeute:1-cyano-4-bromo-6,7-dimethoxytetralin (P 103 ° C; yield:
42 $> der Theorie) aus 1-(3' ,4'-Dimethoxyphenyl)-4,4-diäthoxyvaleronitril, 42 $> of theory) from 1- (3 ', 4'-dimethoxyphenyl) -4,4-diethoxyvaleronitrile,
1-Cyano-1-isopropyl-4-brom-6,7-dimethoxytetralin (P 126 127 0C unter Zersetzung; Ausbeute 85 Ί» der Theorie) aus 1-(3»}4'-Dimethoxyphenyl)-1-isopropyl-4,4-diäthoxy-vaxeronitril.1-cyano-1-isopropyl-4-bromo-6,7-dimethoxytetralin (P 126 127 0 C with decomposition; yield 85 Ί » of theory) from 1- (3» } 4'-dimethoxyphenyl) -1-isopropyl- 4,4-diethoxy-vaxeronitrile.
2-Cyano-2-phenyl-4-chlor-617-dimethoxytetralin2-cyano-2-phenyl-4-chloro-6 1 7-dimethoxytetralin
In eine Lösung von 20 g (0,052 Mol) 1-Phenyl-1-(3·,4*-dimethoxybenzyl)-3,3-diäthoxy-butyronitril ^erhalten durch Alkylierung von 1-Phenyl-2-(3',4'-dimethoxyphenyl)-propionitril mit Bromacetaldehyd-diäthylacetal/ in 100 ecm trockenem Toluol leitet man bei 20 0C 15 Minuten lang Chlorwaeserstoffg8 3 ein. Beim Abkühlen der Reaktionsmischung kristallisiert das 2-Cyano-2-phenyl-4-chlor-6,7-dimethoxytetralin aus. "Umkristallisieren aus Essigsäureäthylester liefert 13»2 g (78 Ί» der Theorie) der reinen Verbindung; P 108 0C (unter Zersetzung).In a solution of 20 g (0.052 mol) of 1-phenyl-1- (3, 4 * -dimethoxybenzyl) -3,3-diethoxy-butyronitrile ^ obtained by alkylation of 1-phenyl-2- (3 ', 4' -dimethoxyphenyl) propionitrile with bromoacetaldehyde diethylacetal / in 100 cc of dry toluene passing a 15 minutes at 20 0 C 3 Chlorwaeserstoffg8. When the reaction mixture cools, the 2-cyano-2-phenyl-4-chloro-6,7-dimethoxytetralin crystallizes out. "Recrystallization from ethyl acetate provides 13" 2 g (78 Ί "of theory) of the pure compound; P 108 0 C (with decomposition).
— 7 — 109844/1681 - 7 - 109844/1681
N O L L A-.- G.N O L L A -.- G.
1-Cyano-1-isopropyl-4-chlor-6t7-dimethoxytetralin1-cyano-1-isopropyl-4-chloro-6 t 7-dimethoxytetralin
In eine Lösung von 17,5 g "!-("3·1 f 4'-Diniethoxyphenyl)-1-isopropyl-4,4-diäthoxy-valeronitril (0,05 Mol) ^erhalten durch Alkylierung von 1-(3' ,4'-3)imethoxyphenyl)-1-isopropylacetonitril mit 2-Chlorpropionaldehyd-diäthylacetal in 100 ecm trockenem Toluol leitet man bei 20 0C 30 Minuten lang trockenen Chlorwasserstoff ein. Anschließend wird das Lösungsmittel im Vakuum abdestilliert und der Rückstand aus Essigsäureäthylester umkristallisiert. Man erhält 10,05 g (74 # der Theorie) 1-Cyano-1-isopropyl-4-chlor-6,7-3imethoxytetralin; F 110 - 111 0C (unter Zersetzung).In a solution of 17.5 g of "! - (" 3 · 1 f 4'-diniethoxyphenyl) -1-isopropyl-4,4-diethoxy-valeronitrile (0.05 mol) ^ obtained by alkylating 1- (3 ' , 4'-3) imethoxyphenyl) -1-isopropylacetonitril with 2-chloropropionaldehyde diethylacetal in 100 cc of dry toluene passing a 30 minutes dry hydrogen chloride at 20 0 C. The solvent is then distilled off in vacuo and the residue is recrystallized from ethyl acetate. 10.05 g (74 # of theory) 1-cyano-1-isopropyl-4-chloro-6,7-3imethoxytetralin are obtained; F 110-111 0 C (with decomposition).
In ähnlicher Weise erhält man aus 1-(3*,4'-Dimethoxyphenyl)-1-benzyl-4,4-diäthoxy-valeronitril das 1-Cyano-1-benzyl-4-chlor-6,7-dimethoxytetralin; (Έ1 134 - 135 °C unter Zersetzung; Ausbeute: 77 1» der Theorie).In a similar way, 1-cyano-1-benzyl-4-chloro-6,7-dimethoxytetralin is obtained from 1- (3 *, 4'-dimethoxyphenyl) -1-benzyl-4,4-diethoxy-valeronitrile; (Έ 1134-135 ° C with decomposition; yield: 77 1 »of theory).
109844/1681109844/1681
KNOLL· AG.KNOLL AG.
CHEMISCHE FABRIKENCHEMICAL FACTORY
1-C.yanO"1-i3opropyl-4-chlor--6t7-dimethoxytetralin1-C.yanO "1-i3opropyl-4-chloro - 6 t 7-dimethoxytetralin
Zu einer Lösung von 30 g (0,087 Mol)i-(3f,4'-Dimethoxyphenyl)-1-isopropyl-4,4-diäthoxy-valeronitril in 200 ecm Benzol tropft man bei 200C 30 g (0,25 Mol) Thionylchlorid innerhalb von 10 Minuten zu. Anschließend läßt man zwei Tage bei Raumtemperatur stehen, engt unter Vakuum bei 300C ein und saugt den Kristallbrei ab. Nach Waschen mit Äther erhält man 10,4 g (40,8 $> der Theorie) 1-Cyano-1-ieopropyl-4-chlor-6,7-dimethoxytetralin. F 1120C.(, F 3 4'-dimethoxyphenyl) To a solution of 30 g (0.087 mol) i- -1-isopropyl-4,4-diethoxy-valeronitrile in 200 cc of benzene is added dropwise at 20 0 C. 30 g (0.25 mol ) Thionyl chloride within 10 minutes. The mixture is then left to stand for two days at room temperature, concentrated in vacuo at 30 ° C. and the crystal pulp is filtered off with suction. After washing with ether 10.4 g (40.8 $> of theory) of 1-cyano-1-ieopropyl-4-chloro-6,7-dimethoxy tetraline. F 112 0 C.
109844/1681109844/1681
Claims (8)
CH — CH0 / L 2 '
CH - CH 0
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681768080 DE1768080A1 (en) | 1968-03-29 | 1968-03-29 | New halobenzocycloalkylnitriles and processes for their preparation |
| NL6902657A NL6902657A (en) | 1968-03-29 | 1969-02-20 | |
| GB921669A GB1195358A (en) | 1968-03-29 | 1969-02-20 | New Halogenobenzocycloalkylnitriles and Process for their Preparation |
| AT173369A AT288365B (en) | 1968-03-29 | 1969-02-20 | Process for the preparation of new halobenzocycloalkyl nitriles |
| FR6904785A FR2004999A1 (en) | 1968-03-29 | 1969-02-25 | Halogenated benzo-cycloalkyl nitriles |
| BR20734469A BR6907344D0 (en) | 1968-03-29 | 1969-03-20 | PROCESS FOR THE PREPARATION OF HALOGENOBENZOCYCLE-ALKYLONITRILLES |
| BE730678D BE730678A (en) | 1968-03-29 | 1969-03-28 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681768080 DE1768080A1 (en) | 1968-03-29 | 1968-03-29 | New halobenzocycloalkylnitriles and processes for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1768080A1 true DE1768080A1 (en) | 1971-10-28 |
Family
ID=5699588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681768080 Pending DE1768080A1 (en) | 1968-03-29 | 1968-03-29 | New halobenzocycloalkylnitriles and processes for their preparation |
Country Status (7)
| Country | Link |
|---|---|
| AT (1) | AT288365B (en) |
| BE (1) | BE730678A (en) |
| BR (1) | BR6907344D0 (en) |
| DE (1) | DE1768080A1 (en) |
| FR (1) | FR2004999A1 (en) |
| GB (1) | GB1195358A (en) |
| NL (1) | NL6902657A (en) |
-
1968
- 1968-03-29 DE DE19681768080 patent/DE1768080A1/en active Pending
-
1969
- 1969-02-20 NL NL6902657A patent/NL6902657A/xx unknown
- 1969-02-20 GB GB921669A patent/GB1195358A/en not_active Expired
- 1969-02-20 AT AT173369A patent/AT288365B/en not_active IP Right Cessation
- 1969-02-25 FR FR6904785A patent/FR2004999A1/en not_active Withdrawn
- 1969-03-20 BR BR20734469A patent/BR6907344D0/en unknown
- 1969-03-28 BE BE730678D patent/BE730678A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR6907344D0 (en) | 1973-04-26 |
| BE730678A (en) | 1969-09-29 |
| FR2004999A1 (en) | 1969-12-05 |
| NL6902657A (en) | 1969-10-01 |
| AT288365B (en) | 1971-03-10 |
| GB1195358A (en) | 1970-06-17 |
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