DE1228271B - Process for the preparation of thiacyclohexane-1,1-dioxides which are disubstituted in the 4-position - Google Patents
Process for the preparation of thiacyclohexane-1,1-dioxides which are disubstituted in the 4-positionInfo
- Publication number
- DE1228271B DE1228271B DEF37129A DEF0037129A DE1228271B DE 1228271 B DE1228271 B DE 1228271B DE F37129 A DEF37129 A DE F37129A DE F0037129 A DEF0037129 A DE F0037129A DE 1228271 B DE1228271 B DE 1228271B
- Authority
- DE
- Germany
- Prior art keywords
- thiacyclohexane
- dioxides
- condensation
- divinyl sulfone
- disubstituted
- 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 9
- 238000002360 preparation method Methods 0.000 title claims description 3
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 15
- -1 methylene compound Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 3
- 230000005494 condensation Effects 0.000 claims 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LXKNAUOWEJWGTE-UHFFFAOYSA-N 2-(3-methoxyphenyl)acetonitrile Chemical compound COC1=CC=CC(CC#N)=C1 LXKNAUOWEJWGTE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- PXNJGLAVKOXITN-UHFFFAOYSA-N 2-(4-nitrophenyl)acetonitrile Chemical compound [O-][N+](=O)C1=CC=C(CC#N)C=C1 PXNJGLAVKOXITN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- MRDUURPIPLIGQX-UHFFFAOYSA-N 2-(2-chlorophenyl)acetonitrile Chemical compound ClC1=CC=CC=C1CC#N MRDUURPIPLIGQX-UHFFFAOYSA-N 0.000 description 1
- DWJKILXTMUGXOU-UHFFFAOYSA-N 2-(2-methoxyphenyl)acetonitrile Chemical compound COC1=CC=CC=C1CC#N DWJKILXTMUGXOU-UHFFFAOYSA-N 0.000 description 1
- YPRFCQAWSNWRLM-UHFFFAOYSA-N 2-(2-nitrophenyl)acetonitrile Chemical compound [O-][N+](=O)C1=CC=CC=C1CC#N YPRFCQAWSNWRLM-UHFFFAOYSA-N 0.000 description 1
- GTIKLPYCSAMPNG-UHFFFAOYSA-N 2-(3-chlorophenyl)acetonitrile Chemical compound ClC1=CC=CC(CC#N)=C1 GTIKLPYCSAMPNG-UHFFFAOYSA-N 0.000 description 1
- WOJADIOTNFDWNQ-UHFFFAOYSA-N 2-(3-methylphenyl)acetonitrile Chemical compound CC1=CC=CC(CC#N)=C1 WOJADIOTNFDWNQ-UHFFFAOYSA-N 0.000 description 1
- PACGLQCRGWFBJH-UHFFFAOYSA-N 2-(4-methoxyphenyl)acetonitrile Chemical compound COC1=CC=C(CC#N)C=C1 PACGLQCRGWFBJH-UHFFFAOYSA-N 0.000 description 1
- RNHKXHKUKJXLAU-UHFFFAOYSA-N 2-(4-methylphenyl)acetonitrile Chemical compound CC1=CC=C(CC#N)C=C1 RNHKXHKUKJXLAU-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
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- HSAINENSYQIMMD-UHFFFAOYSA-N 4-(4-nitrophenyl)-1,1-dioxothiane-4-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCS(=O)(=O)CC1 HSAINENSYQIMMD-UHFFFAOYSA-N 0.000 description 1
- IVYMIRMKXZAHRV-UHFFFAOYSA-N 4-chlorophenylacetonitrile Chemical compound ClC1=CC=C(CC#N)C=C1 IVYMIRMKXZAHRV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- DJACTCNGCHPGOI-UHFFFAOYSA-N butyl 2-cyanoacetate Chemical compound CCCCOC(=O)CC#N DJACTCNGCHPGOI-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- NLFIMXLLXGTDME-UHFFFAOYSA-N propyl 2-cyanoacetate Chemical compound CCCOC(=O)CC#N NLFIMXLLXGTDME-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BUGOPWGPQGYYGR-UHFFFAOYSA-N thiane 1,1-dioxide Chemical compound O=S1(=O)CCCCC1 BUGOPWGPQGYYGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. CL:Int. CL:
C07dC07d
Deutsche Kl.: 12 q - 26 German class: 12 q - 26
Nummer: 1228 271Number: 1228 271
Aktenzeichen: F37129IVb/12qFile number: F37129IVb / 12q
Anmeldetag: 22. Juni 1962Filing date: June 22, 1962
Auslegetag: 10. November 1966Opening day: November 10, 1966
Es ist bekannt, 1,5-Dihalogenpentan mit Alkalisujfid zu Thiacyclohexan zu cyclisieren und dieses z. B. mit Wasserstoffperoxyd zu Thiacyclohexan-1,1-dioxid zu oxydieren. Ein anderer Weg in die Thiacyclohexan-Reihe beruht auf der Cyclisierung von ^,(e'-Dicarbäthoxy-diäthylsulfid zu Thiacyclohexanon-3-carbonsäureester, nachfolgender Verseifung und Decarboxylierung zum Thiacyclohexanon-4, Oxydation zum Thiacyclohexan-4-on-l,l-dioxid und Reduktion zum Thiacyclohexan-l.l-dioxid. Beide Wege sind für die Herstellung von 4,4-disubstituierten Thiacyclohexan-l.l-dioxiden wenig geeignet. Im ersten Fall müßten die Substituenten in dem 1,5-Dihalogenpentan bereits in 3-Stellung vorhanden sein, im zweiten Fall sind sie in der Thiacyclohexan^-on-l.l-dioxid-Stufe nachträglich einzuführen. Ferner ist bekannt, daß primäre Amine mit Divinylsulfon unter Ringschluß N-substituierte Thiazan-S-dioxide zu bilden vermögen.It is known to use 1,5-dihalopentane with Alkalisujfid to cyclize to thiacyclohexane and this z. B. with hydrogen peroxide to thiacyclohexane-1,1-dioxide to oxidize. Another route into the thiacyclohexane series is based on cyclization from ^, (e'-dicarbethoxy diethyl sulfide to thiacyclohexanone-3-carboxylic acid ester, Subsequent saponification and decarboxylation to thiacyclohexanone-4, oxidation to thiacyclohexan-4-one-l, l-dioxide and reduction to thiacyclohexane-l, l-dioxide. Both ways are not very suitable for the production of 4,4-disubstituted thiacyclohexane-1.l-dioxides. In the first In the case, the substituents in the 1,5-dihalopentane should already be present in the 3-position, im in the second case they are in the thiacyclohexan ^ -one-l-dioxide stage to be introduced subsequently. It is also known that primary amines with divinyl sulfone under Able to form ring closure N-substituted thiazane-S-dioxides.
Es wurde nun gefunden, daß man unmittelbar zu in 4-Stellung substituierten Thiacyclohexan-l.l-dioxiden gelangt, wenn man Divinylsulfon mit einer Methylenverbindung der allgemeinen FormelIt has now been found that thiacyclohexane-1.l-dioxides which are substituted in the 4-position can be obtained directly if you get divinyl sulfone with a methylene compound of the general formula
Ri-CH2-R2,Ri-CH 2 -R 2 ,
in der R1 den NC- oder O2N-ReSt und R2 einen
C1-C4-AIkYl-, NC-, R'OOC-, (R' = C1-C4-AIkVl-)
oder einen gegebenenfalls durch ein Chloratom, eine Methyl-, Nitro- oder Methoxygruppe substituierten
Phenylrest bedeutet, in einem nicht wäßrigen Lösungsmittel in Gegenwart von 0,1 bis 20 Molprozent einer
Base als Kondensationsmittel, bezogen auf molare Verfahren zur Herstellung von in 4-Stellung
disubstituierten Thiacyclohexan-l,l-dioxidenin which R 1 is the NC or O 2 N ReSt and R 2 is a C 1 -C 4 -AlkYl-, NC-, R'OOC-, (R '= C 1 -C 4 -AlkVl-) or optionally one is phenyl substituted by a chlorine atom, a methyl, nitro or methoxy group, in a non-aqueous solvent in the presence of 0.1 to 20 mol percent of a base as a condensing agent, based on molar processes for the preparation of in the 4-position
disubstituted thiacyclohexane-l, l-dioxides
Anmelder:Applicant:
Farbwerke Hoechst AktiengesellschaftFarbwerke Hoechst Aktiengesellschaft
vormals Meister Lucius & Brüning, Frankfurt/M.formerly Master Lucius & Brüning, Frankfurt / M.
Als Erfinder benannt:Named as inventor:
Dr. Otto Scherer, Bad Soden (Taunus);Dr. Otto Scherer, Bad Soden (Taunus);
Dr. Friedhelm Kluge, Frankfurt/M.-Höchst - -Dr. Friedhelm Kluge, Frankfurt / M.-Höchst - -
Mengen der Reaktionsteilnehmer, reagieren läßt, obwohl bisher noch nicht bekanntgeworden ist, daß Vmylsulfonverbindungen als Akzeptoren bei Micheal-Additionen reagieren. So sind z. B. in der ausführlichen Zusammenfassung in »Organic Reactions«, Bd. X, Kapitel 3, Reaktionen des Divinylsulfons mit CH-aciden Verbindungen nicht erwähnt. Darüber hinaus war das Gelingen der erfindungsgemäßen Umsetzung auch deshalb nicht zu erwarten, weil aus Journal of the Chemical Society, 1947, S. 1514, bekannt war, daß sich Divinylsulfon mit aliphatischen Nitroverbindungen, die eine CH2-Gruppe in Nachbarschaft zur NO2-Gruppe enthalten, nicht zu Thiacyclohexan-l,l-dioxiden umsetzen lassen.Quantities of the reactants, although it has not yet become known that Vmylsulfonverbindungen react as acceptors in Micheal additions. So are z. B. in the detailed summary in "Organic Reactions", Vol. X, Chapter 3, reactions of divinyl sulfone with CH-acidic compounds are not mentioned. In addition, the success of the implementation according to the invention was also not to be expected because it was known from Journal of the Chemical Society, 1947, p. 1514 that divinyl sulfone with aliphatic nitro compounds that have a CH 2 group in the vicinity of NO 2 - Group included, do not allow to convert to thiacyclohexane-l, l-dioxides.
Der Reaktionsverlauf sei am Beispiel der Umsetzung von Divinylsulfon mit Malonsäuredinitril im nachstehenden Schema veranschaulicht:The course of the reaction is given below using the example of the reaction of divinyl sulfone with malononitrile Scheme illustrates:
CH = CH2 CH = CH 2
O8SO 8 S
H2CH 2 C
CH = CH2 CH = CH 2
CN 'CN '
O2SO 2 S
CNCN
Als Umsetzungspartner für Divinylsulfon kommen neben Malonsäuredinitril Cyanessigsäureester, z. B. solche, die sich von niedrigmolekularen aliphatischen Alkoholen oder Benzylalkohol ableiten, Benzylcyanide, die gegebenenfalls z. B. durch ein Chloratom, eine Methyl-, Methoxy- oder Nitrogruppe substituiert sind, und Nitroalkane wie Nitromethan, Nitroäthan oder Nitropropan in Betracht. Im einzelnen seien beispielsweise noch folgende Ausgangsstoffe erwähnt: Cyanessigsäuremethylester, Cyanessigsäureäthylester, Cyanessigsäurepropylester, Cyanessigsäurebutylester, Benzylcyanid, o- und p-Nitrobenzylcyanid, o-, m- und p-Chlorbenzylcyanid, 0-, m- und p-Methylbenzylcyanid, o-, m- und p-Methoxybenzylcyanid genannt. Als basische Katalysatoren eignen sich Alkalialkoholate, wie Kaliummethylat, Natriumäthylat, Kalium-tert.-butylat, Alkaliamide, z. B. Natrium- und Kaliumamid, tertiäre organische Basen, wie Triäthylamin, Methylpiperidin, Methylmorpholin und Endoäthylenpiperazin, quartäre Stickstoffbasen, ζ. B. Tetraalkyl- und Trialkal-aryl-ammoniumhydroxide. Die Katalysatormenge liegt im allgemeinen zwischen 0,1 und 20 Molprozent, vorzugsweise zwischen 1 und 10 Molprozent.As a reaction partner for divinyl sulfone come in addition to malononitrile cyanoacetic acid esters, z. B. those derived from low molecular weight aliphatic alcohols or benzyl alcohol, benzyl cyanides, the possibly z. B. substituted by a chlorine atom, a methyl, methoxy or nitro group are, and nitroalkanes such as nitromethane, nitroethane or nitropropane into consideration. In detail are For example, the following starting materials are mentioned: methyl cyanoacetate, ethyl cyanoacetate, Propyl cyanoacetate, butyl cyanoacetate, benzyl cyanide, o- and p-nitrobenzyl cyanide, o-, m- and p-chlorobenzyl cyanide, 0-, m- and p-methylbenzyl cyanide, called o-, m- and p-methoxybenzyl cyanide. Alkali alcoholates are suitable as basic catalysts, such as potassium methylate, sodium ethylate, potassium tert-butoxide, alkali amides, e.g. B. Sodium and potassium amide, tertiary organic bases such as triethylamine, methylpiperidine, methylmorpholine and endoethylene piperazine, quaternary nitrogen bases, ζ. B. tetraalkyl and trialkal aryl ammonium hydroxides. The amount of catalyst is generally between 0.1 and 20 mol percent, preferably between 1 and 10 mole percent.
Zur Durchführung des Verfahrens gemäß der Erfindung verfährt man zweckmäßig in der Weise, daß man die Reaktionskomponenten und den Katalysator in einem nicht wäßrigen Lösungsmittel auf-To carry out the method according to the invention, it is expedient to proceed in the manner that the reaction components and the catalyst are dissolved in a non-aqueous solvent
609 710/311609 710/311
einander einwirken läßt. Als Lösungsmittel werden vorzugsweise niedrigmolekuläre Alkohole',· auch Kohlenwasserstoffe, wie Benzol oder Dimethylformamid, verwendet. In manchen Fällen ist es besonders vorteilhaft, die Reaktion z. B. in der Weise ablaufen zu lassen, daß man eine stark verdünnte Lösung' des Katalysators vorlegt und Divinylsulfon und die CH-acide Verbindung getrennt oder gemeinsam, gegebenenfalls ebenfalls gelöst, unter Rühren langsam zutropfen läßt.- Man' kann aber auch so vorgehen, daß man zunächst die CH-acide Verbindung mittels Alkoholaten oder Amiden in die entsprechenden Alkaliverbindungen überführt und diese dann mit Divinylsulfon zur Umsetzung bringt. Im allgemeinen bietet die letztgenannte Arbeitsweise jedoch keine besonderen Vorteile.allows each other to act. The solvents used are preferably low-molecular alcohols, also hydrocarbons, such as benzene or dimethylformamide are used. In some cases it is particularly advantageous the reaction z. B. to run in such a way that a very dilute solution 'des Submitted catalyst and divinyl sulfone and the CH-acidic compound separately or together, if necessary also dissolved, slowly added dropwise with stirring - you can also proceed as follows, that you first convert the CH-acidic compound into the corresponding using alcoholates or amides Transferred alkali compounds and then brings them to reaction with divinyl sulfone. In general however, the last-mentioned mode of operation does not offer any particular advantages.
Die Reaktionstemperatur liegt zwischen —20 und +1000C, insbesondere zwischen +20 und +80°C. Die Reaktionstemperatur ist natürlich mitbestimmt durch die Eigenschaften der Reaktionsteilnehmer und des verwendeten Lösungsmittels. Sofern man unter Druck arbeitet, kann man in vielen FäUen.auch höhere Temperaturen anwenden.The reaction temperature is between -20 and +100 0 C, in particular between +20 and + 80 ° C. The reaction temperature is of course partly determined by the properties of the reactants and the solvent used. If one works under pressure, one can also use higher temperatures in many pits.
Die nach dem erfindungsgemäßen Verfahren zugänglichen Thiacyclohexan-l,l-dioxide sind Zwischenprodukte für Pharmazeutika und Pflanzenschutzmittel. The thiacyclohexane-l, l-dioxides obtainable by the process according to the invention are intermediate products for pharmaceuticals and pesticides.
Zu einer Lösung von 0,2 g Natrium in 200 ecm Äthanol wird innerhalb von 30 Minuten unter Kühlung ein Gemisch aus 24 g Divinylsulfon und 23 g Cyanessigsäureäthylester bei 20 bis 30° C zugetropft. Der gebildete Niederschlag wird nach Zugabe von 0,4 ecm Eisessig abgesaugt. Durch Extrahieren mit Benzol erhält man 25 g 4-Cyan-4-carbäthoxy-thiacyclohexan-l,l-dioxid vom F. 96 0C.To a solution of 0.2 g of sodium in 200 ecm of ethanol, a mixture of 24 g of divinyl sulfone and 23 g of ethyl cyanoacetate is added dropwise at 20.degree. To 30.degree. C. over a period of 30 minutes with cooling. The precipitate formed is filtered off with suction after adding 0.4 ecm of glacial acetic acid. Extraction with benzene to obtain 25 g of 4-cyano-4-carbethoxy-thiacyclohexane-l, l-dioxide, melting at 96 0 C.
In der im Beispiel 1 beschriebenen Weise werden 24 g Divinylsulfon mit 13,2 g Malonsäuredinitril bei —10° C umgesetzt und aufgearbeitet. Man erhält 21 g 4-Cyan-4-carbrminoäthoxy-thiacyclohexan-l,l-dioxid vom F. 124° C. .In the manner described in Example 1, 24 g of divinyl sulfone with 13.2 g of malononitrile are added -10 ° C implemented and worked up. 21 g of 4-cyano-4-carbrminoethoxy-thiacyclohexane-1,1-dioxide are obtained from the mp 124 ° C.
In 3 1 Benzol werden 12 g einer 35%igen methanolischen Lösung von Trimethyl-benzyl-ammoniumhydroxyd gegeben. Dann wird innerhalb von 8 Stunden bei 70° C eine Lösung von 24 g Divinylsulfon und 13,2 g Malonsäuredinitril in 500 ecm Benzol unter Rühren zugetropft. Es wird 2 Stunden nachgerührt und über Nacht abgekühlt. Aus der Reaktionslösung kristallisieren über Nacht 26 g einer Substanz aus, aus der nach Umkristallisieren aus o-Dichlorbenzol 17 g Thiacyclohexan -1,1 - dioxid - 4,4 - dinitril vom F. 233 bis 235°C erhalten werden.In 3 1 of benzene is 12 g of a 35% strength methanolic solution of s given trimethyl-benzyl-ammonium hydroxide. A solution of 24 g of divinyl sulfone and 13.2 g of malononitrile in 500 ecm of benzene is then added dropwise with stirring at 70 ° C. over the course of 8 hours. The mixture is stirred for 2 hours and cooled overnight. 26 g of a substance crystallize out of the reaction solution overnight, from which, after recrystallization from o-dichlorobenzene, 17 g of thiacyclohexane-1,1-dioxide-4,4-dinitrile with a melting point of 233 to 235 ° C. are obtained.
In 51 Benzol werden 20 g einer 35 %igen methanolischen Lösung von Trimethyl-benzyl-ammoniumhydroxyd gegeben. Dann wird unter Rühren bei 60 bis 70° C innerhalb von 80 Stunden eine Lösung von 24 g Divinylsulfon und 24 g Benzylcyanid eingetropft. Nach dem Erkalten wird von 10 g Festsubstanz abgesaugt, die Benzollösung mit verdünnter Salzsäure ausgeschüttelt und eingedampft. Aus dem Rückstand erhält man durch Destillation unter 0,2 Torr eine bei 190 bis 205° C übergehende Fraktion von 15 g, die nach Umkristallisieren aus Methanol 5' 14 g 4-Phenyl-4-cyan-thiacyciohexan-l,i-dioxid vom F. 145 bis 147°C ergeben.In 51 g of benzene, 20 ig of a 35% methanolic solution of s given trimethyl-benzyl-ammonium hydroxide. A solution of 24 g of divinyl sulfone and 24 g of benzyl cyanide is then added dropwise with stirring at 60 to 70 ° C. over the course of 80 hours. After cooling, 10 g of solid substance are sucked off, the benzene solution is shaken out with dilute hydrochloric acid and evaporated. A fraction of 15 g which passes over at 190 to 205 ° C. and which, after recrystallization from methanol 5 '14 g of 4-phenyl-4-cyano-thiacyciohexane-l, i-dioxide, is obtained from the residue by distillation under 0.2 torr F. 145 to 147 ° C.
ίο In eine Lösung von 0,2 g Natrium in 100 ecm Äthanol werden 16 g p-Nitrobenzylcyanid gegeben. Dann werden in die tiefrotgefärbte Flüssigkeit innerhalb von 10 Minuten 12 g Divinylsulfon eingetropft, wobei die Temperatur von 20° C auf etwa 55° C ansteigt. Man erhitzt 2 Stunden unter Rückfluß, gibt 0,4 ecm Eisessig hinzu und erhält beim Abkühlen 23,5 g einer dunkelgefärbten, kristallinen Substanz, die man durch Umkristallisieren aus Äthanol unter Zusatz von Kohle reinigt. Das erhaltene 4-p-Nitrophenyl-4-cyan-thiacyclohexan-l,l-dioxid schmilzt bei 184° C.ίο In a solution of 0.2 g of sodium in 100 ecm Ethanol is added to 16 g of p-nitrobenzyl cyanide. Then, in the deep red colored liquid within 12 g of divinyl sulfone were added dropwise over a period of 10 minutes, the temperature rising from 20 ° C to about 55 ° C. The mixture is heated under reflux for 2 hours, 0.4 ecm of glacial acetic acid is added and obtained on cooling 23.5 g of a dark-colored, crystalline substance, which can be obtained by recrystallization from ethanol Addition of coal cleans. The 4-p-nitrophenyl-4-cyano-thiacyclohexane-1,1-dioxide obtained melts at 184 ° C.
Setzt man 30 g m-Methoxybenzylcyanid mit 24 g Divinylsulfon in der im Beispiel 4 beschriebenen Weise um, so erhält man 13 g 4-m-Methoxyphenyl-4-cyan-thiacyclohexan-l,l-dioxid vom F. 166° C.If 30 g of m-methoxybenzyl cyanide are used with 24 g Divinyl sulfone in the manner described in Example 4, 13 g of 4-m-methoxyphenyl-4-cyano-thiacyclohexane-1,1-dioxide are obtained with a temperature of 166 ° C.
Beispiel 7
30 Example 7
30th
In 41 Benzol werden 15 g einer 35 %igen methanolischen Lösung von Trimethyl-benzyl-ammoniumhydroxyd gegeben. Innerhalb von 20 Stunden werden 30 g Nitroäthan und 48 g Divinylsulfon, gelöst in 500 ecm Benzol, bei 75° C unter Rühren zugetropft. Man saugt nach dem Erkalten von etwas Festsubstanz ab, engt das Filtrat auf 0,51 ein und isoliert durch Zugabe von Cyclohexan 35 g kristallines 4-Methyl-4-nitrothiacyclohexan-l,l-dioxid vom F. 156 bis 158° C.In 41 g of benzene is 15 ig of a 35% methanolic solution of s given trimethyl-benzyl-ammonium hydroxide. 30 g of nitroethane and 48 g of divinyl sulfone, dissolved in 500 ecm of benzene, are added dropwise at 75 ° C. with stirring over the course of 20 hours. After cooling, some solid matter is filtered off with suction, the filtrate is concentrated to 0.51 and 35 g of crystalline 4-methyl-4-nitrothiacyclohexane-l, l-dioxide with a melting point of 156 to 158 ° C. is isolated by adding cyclohexane.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF37129A DE1228271B (en) | 1962-06-22 | 1962-06-22 | Process for the preparation of thiacyclohexane-1,1-dioxides which are disubstituted in the 4-position |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF37129A DE1228271B (en) | 1962-06-22 | 1962-06-22 | Process for the preparation of thiacyclohexane-1,1-dioxides which are disubstituted in the 4-position |
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| Publication Number | Publication Date |
|---|---|
| DE1228271B true DE1228271B (en) | 1966-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF37129A Pending DE1228271B (en) | 1962-06-22 | 1962-06-22 | Process for the preparation of thiacyclohexane-1,1-dioxides which are disubstituted in the 4-position |
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| Country | Link |
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| DE (1) | DE1228271B (en) |
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1962
- 1962-06-22 DE DEF37129A patent/DE1228271B/en active Pending
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| None * |
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