DD236312A1 - PROCESS FOR PREPARING SULFIDIC MORPHOLINIUM CHLORIDE - Google Patents
PROCESS FOR PREPARING SULFIDIC MORPHOLINIUM CHLORIDE Download PDFInfo
- Publication number
- DD236312A1 DD236312A1 DD27525185A DD27525185A DD236312A1 DD 236312 A1 DD236312 A1 DD 236312A1 DD 27525185 A DD27525185 A DD 27525185A DD 27525185 A DD27525185 A DD 27525185A DD 236312 A1 DD236312 A1 DD 236312A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- compounds
- sulfidic
- preparation
- general formula
- morpholinium
- Prior art date
Links
- JXYZHMPRERWTPM-UHFFFAOYSA-N hydron;morpholine;chloride Chemical compound Cl.C1COCCN1 JXYZHMPRERWTPM-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000126 substance Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 150000003573 thiols Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229940125782 compound 2 Drugs 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 5
- 150000001767 cationic compounds Chemical class 0.000 claims abstract 2
- 230000002349 favourable effect Effects 0.000 claims abstract 2
- -1 4-substituted morpholines Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- HUTXVUPGARJNHM-UHFFFAOYSA-N 1-(2-chloroethoxy)ethanol Chemical compound CC(O)OCCCl HUTXVUPGARJNHM-UHFFFAOYSA-N 0.000 claims 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 150000001348 alkyl chlorides Chemical class 0.000 claims 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical class CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000003947 ethylamines Chemical class 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 150000002780 morpholines Chemical class 0.000 claims 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical class C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 1
- NUSMTFFYLONGGV-UHFFFAOYSA-N 2-[2-[dodecyl-[2-(2-hydroxyethoxy)ethyl]amino]ethoxy]ethanol Chemical compound CCCCCCCCCCCCN(CCOCCO)CCOCCO NUSMTFFYLONGGV-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-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
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- SEXOVMIIVBKGGM-UHFFFAOYSA-N naphthalene-1-thiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1 SEXOVMIIVBKGGM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- OADNVNPVQYWJMK-UHFFFAOYSA-N undecane;hydrochloride Chemical compound Cl.CCCCCCCCCCC OADNVNPVQYWJMK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung sulfidischer Morpholiniumverbindungen, die als biologisch aktive Verbindungen, als Reagenzien in der Filmindustrie und als kationenaktive Verbindungen Anwendung finden koennen. Ziel der Erfindung ist die oekonomisch vorteilhafte Darstellung sulfidischer Morpholiniumchloride. Der Erfindung liegt die Aufgabe zugrunde, ein oekonomisch guenstiges Verfahren zur Herstellung dieser Verbindungen zu entwickeln. Die Aufgabe wird erfindungsgemaess dadurch geloest, dass Morpholiniumchloride der allgemeinen Formel 3 hergestellt werden, indem ethoxylierte Amine der allgemeinen Formel 1 mit Thionylchlorid zu a,v-Dichlorverbindungen der allgemeinen Formel 2 und diese mit Thiolen in Gegenwart von chlorwasserstoffbindenden Stoffen bei Temperaturen von 65 bis 150C und Reaktionszeiten von 4-8 Stunden umgesetzt werden, wobei die Thiole und die chlorwasserstoffbindenden Stoffe im Gemisch oder synchron in einem geeigneten Loesungsmittel zu den Loesungen der a,v-Dichlorverbindungen im Molverhaeltnis Thiol:Base:Verbindung 2 von vorzugsweise 1:2:1 zugegeben werden.The invention relates to a process for preparing sulfidic morpholinium compounds which can be used as biologically active compounds, as reagents in the film industry and as cationic compounds. The aim of the invention is the economically advantageous presentation of sulfidic morpholinium chlorides. The invention has for its object to develop a oeconomically favorable process for the preparation of these compounds. The object is achieved by the invention that Morpholiniumchloride the general formula 3 are prepared by ethoxylated amines of general formula 1 with thionyl chloride to a, v-dichloro compounds of general formula 2 and thiols in the presence of hydrogen chloride-binding substances at temperatures of 65 to 150C and Reaction times of 4-8 hours, wherein the thiols and the hydrogen chloride-binding substances in admixture or synchronously in a suitable solvent to the solutions of a, v-dichloro compounds in the molar ratio thiol: base: compound 2 of preferably 1: 2: 1 added become.
Description
-2- 752 51-2- 752 51
Dabei stellen R' und R2 = Alkyl- (1-20 C-Atome), Cycloalkyl-, Aryl-, Aralkyl- oder Heteroarylreste dar.R 'and R 2 represent alkyl (1-20 C atoms), cycloalkyl, aryl, aralkyl or heteroaryl radicals.
Die Herstellung der Verbindungen 3 erfolgt in der Weise, daß die Mercaptoverbindungen R2SH und die chlorwasserstoffbindenden Stoffe im Gemisch oder synchron zu den α,ω-Dichlorverbindungen 2 zugegeben werden, wobei das Verhältnis Thiol:Base:Verbindung 2 vorzugsweise = 1:2:1 beträgt. Mit einem Überschuß an Base können die Verbindungen 2 zu 4-Organyl-4-[2-(2-chlorethoxy)ethyl]morpholinium-chloriden der allgemeinen Formel 4 bzw. mit einem Überschuß an Mercaptoverbindung zu α,ω-Diorganylthioverbindungen der allgemeinen Formel 5 reagieren.The preparation of the compounds 3 takes place in such a manner that the mercapto compounds R 2 SH and the hydrogen chloride-binding substances are added in a mixture or synchronously with the α, ω-dichloro compounds 2, the ratio thiol: base: compound 2 preferably = 1: 2: 1 amounts to. With an excess of base, the compounds 2 to 4-organyl-4- [2- (2-chloroethoxy) ethyl] morpholinium chlorides of the general formula 4 or with an excess of mercapto compound to α, ω-Diorganylthioverbindungen of the general formula. 5 react.
Für die Herstellung der Morpholiniumchloride 3 ist es nicht notwendig, die α,ω-Dichlorverbindungen 2 zu reinigen; sie können vorteilhafterweise als Rohprodukte eingesetzt werden.For the preparation of the morpholinium chlorides 3, it is not necessary to purify the α, ω-dichloro compounds 2; they can advantageously be used as crude products.
Als chlorwasserstoff bindende Stoffe werden geeignete billige Basen wie Natrium- oder Kaliumhydroxid, gegebenenfalls auch Alkalicarbonate verwendet. Die als Ausgangsstoffe verwendeten Amine sind vorzugsweise aliphatische Amine wie Methylamin, Butylamin oder Tetradecylamin, aber auch andere primäre Amine wie Benzylamin oder Anilin.Suitable hydrogen chloride-binding substances are suitable inexpensive bases such as sodium or potassium hydroxide, optionally also alkali metal carbonates. The amines used as starting materials are preferably aliphatic amines such as methylamine, butylamine or tetradecylamine, but also other primary amines such as benzylamine or aniline.
Als Verbindungen mit Mercaptogruppen können aliphatische Thiole, wie z. B. Methanthiol, Butan-1 -thiol, Hexan-1 -thiol oder Dodecan-1-thiol, aromatische Thiole, wie z. B. Thiophenol, Thiokresole oder 1 -Mercaptonaphthalen oder heterocyclische Thiole, wieAs compounds with mercapto groups aliphatic thiols, such as. Methanethiol, butane-1-thiol, hexane-1-thiol or dodecane-1-thiol, aromatic thiols, such as. As thiophenol, thiocresols or 1 -Mercaptonaphthalen or heterocyclic thiols, such as
z. B. 2-Mercaptothiazol, 2-Mercaptobenzthiazol, 2-Mercaptobenzimidazol oder ähnliche Verbindungen dienen.z. For example, 2-mercaptothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole or similar compounds.
Als Lösungsmittel können Alkohole, Acetonitril, Nitromethan, Dimethylformamid, Dimethylsulfoxid und weitere bei nucleophilen Substitutionen übliche Solventien oder Gemische verwendet werden.Alcohols, acetonitrile, nitromethane, dimethylformamide, dimethyl sulfoxide and other solvents or mixtures customary in nucleophilic substitution can be used as the solvent.
Die Reaktion wird bei Temperaturen von 65-150°C, vorzugsweise bei Temperaturen von 80-1200C, durchgeführt; die Reaktionszeiten stellen sich dann auf 4-8 Stunden ein. Zur Verhinderung einer Oxidation der Thiole wird zweckmäßigerweise während der Reaktion Inertgas, vorzugsweise Stickstoff, durchgeleitet. Diß resultierenden Verbindungen 3 sind kristalline Verbindungen oder hochviskose Öle, zum Teil stark hygroskopisch und werden auf den üblichen Wegen (Kristallisation, Säulenchromatographie) rein erhalten.The reaction is carried out at temperatures of 65-150 ° C, preferably at temperatures of 80-120 0 C; the reaction times are then 4-8 hours. In order to prevent oxidation of the thiols, inert gas, preferably nitrogen, is expediently passed through during the reaction. The resulting compounds 3 are crystalline compounds or highly viscous oils, some strongly hygroscopic and are obtained in the usual ways (crystallization, column chromatography) pure.
Die Erfindung soll anhand von 8 Beispielen näher erläutert werden:The invention will be explained in more detail with reference to 8 examples:
Zu 17,6 g e-Butyl-S^-dioxa-o-aza-undecan-IJI-diol in 20 cm3 Chloroform werden 19 g Thionylchlorid bei 10-15 0C unter Rühren und Kühlen zugetropft. Man läßt das Gemisch über Nacht stehen und-entfernt das Lösungsmittel im Vakuum. Der Rückstand erstarrt im Kühlschrank. Er wird mit absolutem Ether gewaschen und aus absolutem Aceton umkristallisiert. Die Substanz ist hygroskopisch; der Schmelzpunkt beträgt 81-820C; die Ausbeute liegt bei 80% d. ThTo 17.6 g of e-butyl-S ^ dioxa-o-aza-undecane-IJI-diol in 20 cm 3 of chloroform 19 g of thionyl chloride are added dropwise at 10-15 0 C with stirring and cooling. The mixture is allowed to stand overnight and the solvent is removed in vacuo. The residue solidifies in the refrigerator. It is washed with absolute ether and recrystallized from absolute acetone. The substance is hygroscopic; the melting point is 81-82 0 C; the yield is 80% d. th
C12H26CI3NO2 (MM: 322,7); ber./gef.: C 44,66/44,34, H 8,12/7,69, N 4,34/4,55C 12 H 26 Cl 3 NO 2 (MM: 322.7); calculated: C 44.66 / 44.34, H 8.12 / 7.69, N 4.34 / 4.55
Die Darstellung erfolgt aus 6-Dodecyl-3,9-dioxa-6-aza-undecan-1,11 -diol wie bei Beispiel 1. Die Substanz fällt als Öl an, das zur Reinigung in absolutem Ether gelöst und mit Petrolether gefällt wird. Die Ausbeute an analysenreiner Substanz beträgt 40% d. Th. C20H42CI3NO2 (MM: 434,9); ber./gef.: C 55,23/55,20, H 9,73/9,66, N 3,22/3,21The preparation is carried out from 6-dodecyl-3,9-dioxa-6-aza-undecane-1,11-diol as in Example 1. The substance is obtained as an oil, which is dissolved in absolute ether for purification and precipitated with petroleum ether. The yield of reagent-free substance is 40% d. Th. C 20 H 42 Cl 3 NO 2 (MM: 434.9); c./gef .: C 55.23 / 55.20, H 9.73 / 9.66, N 3.22 / 3.21
Beispiel 3: 4-Butyl-4-[2-(2-butylthio-ethoxy)ethyl] morpholinium-chloridExample 3: 4-Butyl-4- [2- (2-butylthio-ethoxy) ethyl] morpholinium chloride
Eine Lösung von 6,3 g Butan-1-thiol und 5,6 g Ätznatron in 30 cm3 Ethanol werden zu einer siedenden Lösung von 22,5 g e-ButvI-i^i-dichlor-S^-dioxa-ö-aza-undecan-hydrochlorid in 50 cm3 Ethanol unter Rühren und Stickstoffspülung langsam zugetropft. Man erhitzt anschließend 6 Stunden zum Sieden, trennt vom Kochsalz und destilliert das Lösungsmittel im Vakuum ab. Der Rückstand ist ölig und kristallisiert unter absolutem Ether langsam durch. Die Ausbeute beträgt 18 g, das sind 76%d. Th. C16H34CINO2S (MM: 340,0); ber./gef.: N 4,12/3,94, Cl 10,1/10,2A solution of 6.3 g of butane-1-thiol and 5.6 g of caustic soda in 30 cm 3 of ethanol are added to a boiling solution of 22.5 g of e-Butyl-i-i-dichloro-S, -dioxa-o- aza undecane hydrochloride in 50 cm 3 of ethanol with stirring and nitrogen purging slowly added dropwise. The mixture is then heated to boiling for 6 hours, separated from the sodium chloride and the solvent is distilled off in vacuo. The residue is oily and crystallizes slowly under absolute ether. The yield is 18 g, that is 76% d. Th. C 16 H 34 CINO 2 S (MM: 340.0); calc .: N, 4.12 / 3.94, Cl, 10.1 / 10.2
Dodecan-1 -thiol wird mit 6-Butyl-1,11 -dichlor-S^-dioxa-e-aza-undecanhydrochlorid wie bei Beispiel 3 umgesetzt. Nach Umkristallisation aus absolutem Aceton schmilzt die Substanz bei 73°C. Die Ausbeute beträgt 67% d. Th. C24H50CINO2S (MM: 452,2); ber./gef.: Cl 7,84/8,01Dodecan-1-thiol is reacted with 6-butyl-1,11-dichloro-S ^ -dioxa-e-aza-undecane hydrochloride as in Example 3. After recrystallization from absolute acetone, the substance melts at 73 ° C. The yield is 67% d. Th C 24 H 50 CINO 2 S (MM: 452.2);. calc .: 7.84 / 8.01
Beispiel 5: 4-Butyl-4-[2-[2-(benzthiazol-2-yl-thio)ethoxy]ethyl]morpholinium-chlorid 2-Mercaptobenzthiazol wird mit 6-Butyl-1,11 -dichlor-S^-dioxa-e-aza-undecan-hydrochlorid wie im Beispiel 3 umgesetzt. Die Reinigung erfolgt durch Umkristallisation aus Aceton und wenig Ethanol. Die reine Substanz schmilzt bei 156°C und die Ausbeute beträgt 86% d. ThExample 5: 4-Butyl-4- [2- [2- (benzthiazol-2-yl-thio) ethoxy] ethyl] morpholinium chloride 2-Mercaptobenzothiazole is treated with 6-butyl-1,11-dichloro-S-dioxa -e-aza-undecane hydrochloride as implemented in Example 3. The purification is carried out by recrystallization from acetone and a little ethanol. The pure substance melts at 156 ° C and the yield is 86% d. th
C19H29CIN2O2S2 (MM: 417,0); ber./gef.: C 54,72/54,75 H 7,01/7,01 N 6,72/6,74C 19 H 29 CIN 2 O 2 S 2 (MM: 417.0); C / V .: C 54.72 / 54.75 H 7.01 / 7.01 N 6.72 / 6.74
Butan-1 -thiol wird mit 6-Dodecyl-1,11 -dichlor-S^-dioxa-B-aza-undecanhydrochlorid (Rohprodukt) wie bei Beispiel 3 umgesetzt. Die Substanz ist eine zähe klebrige Masse und wird zur Reinigung in absolutem Ether gelöst und mit Petrolether gefällt. Die Ausbeute beträgt 40-50 % d. ThButane-1-thiol is reacted with 6-dodecyl-1,11-dichloro-S ^ -dioxa-B-aza-undecane hydrochloride (crude product) as in Example 3. The substance is a viscous sticky mass and is dissolved in absolute ether for purification and precipitated with petroleum ether. The yield is 40-50% d. th
C24H50CINO2S (MM: 452,2); ber./gef.: Cl 7,84/7,38C 24 H 50 CINO 2 S (MM: 452.2); calc .: 7.84 / 7.38
15 g ö-Butyl-S^-dioxa-e-aza-undecan-UI-diol in 30 cm3 Chloroform werden unter Kühlung bei 10-15°C mit 15,5 g Thionylchlorid versetzt. Man läßt über Nacht stehen, gießt in das gleiche Volumen Wasser ein und macht mit Natronlauge schwach alkalisch (ρμ8). Nach etwa 5 Minuten läßt sich dünnschichtchromatographisch bereits die Bildung der Morpholiniumverbindung nachweisen. Man läßt einige Stunden stehen, trennt die Chloroformschicht ab und schüttelt die wäßrige Phase nochmals mit Chloroform aus. Das Lösungsmittel wird abdestilliert und der Rückstand aus absolutem Aceton umkristallisiert. Aus der Mutterlauge läßt sich mit Ether weitere Substanz fällen. Die Ausbeute beträgt 80% d. Th., der Schmelzpunkt ist 1240C15 g of δ-butyl-S-dioxa-e-aza-undecane-UI-diol in 30 cm 3 of chloroform are added with cooling at 10-15 ° C with 15.5 g of thionyl chloride. It is allowed to stand overnight, poured into the same volume of water and makes with sodium hydroxide slightly alkaline (ρμ8). After about 5 minutes, the formation of the morpholinium compound can already be detected by thin-layer chromatography. The mixture is allowed to stand for a few hours, the chloroform layer is separated off and the aqueous phase is shaken out again with chloroform. The solvent is distilled off and the residue is recrystallized from absolute acetone. From the mother liquor can be precipitated with ether more substance. The yield is 80% d. Th., The melting point is 124 0 C.
C12H25CI2NO2 (MM: 286,2); ber./gef.: C 50,35/49,89 H 8,80/8,73 N 4,89/4,81C 12 H 25 Cl 2 NO 2 (MM: 286.2); c./f .: C 50.35 / 49.89 H 8.80 / 8.73 N 4.89 / 4.81
Eine Lösung von 45,2 g e-Butyl-UI-dichlor-S^-dioxa-e-aza-undecan-hydro-chlorid in 100 cm3 Ethanol wird zu einer siedendenA solution of 45.2 g of e-Butyl-UI-dichloro-S ^ -dioxa-e-aza-undecane-hydro-chloride is dissolved in 100 cm 3 of ethanol to a boiling
Lösung von 28 g Butan-1-thiol und 16,8 g Ätznatron in 80 cm3 Ethanol unter Rühren und Stickstoffspülung zugetropft. Man erhitzt 7 Stunden lang am Rückfluß, destilliert das Ethanol ab und fraktioniert im Vakuum. Kp = 183°C/6 Pa; nD 20= 1,4851Solution of 28 g of butane-1-thiol and 16.8 g of caustic soda in 80 cm 3 of ethanol was added dropwise with stirring and nitrogen purge. The mixture is heated for 7 hours at reflux, the ethanol is distilled off and fractionated in vacuo. K p = 183 ° C / 6 Pa; n D 20 = 1.4851
Die Ausbeute beträgt 32 g, das sind 58% d. Th.The yield is 32 g, which is 58% d. Th.
C20H43NO2S2 (MM: 393,7); ber./gef.: C 61,02/61,04 H 11,01/10,67 N 3,56/3,50C 20 H 43 NO 2 S 2 (MM: 393.7); C / C .: C 61.02 / 61.04 H 11.01 / 10.67 N 3.56 / 3.50
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27525185A DD236312A1 (en) | 1985-04-17 | 1985-04-17 | PROCESS FOR PREPARING SULFIDIC MORPHOLINIUM CHLORIDE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27525185A DD236312A1 (en) | 1985-04-17 | 1985-04-17 | PROCESS FOR PREPARING SULFIDIC MORPHOLINIUM CHLORIDE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD236312A1 true DD236312A1 (en) | 1986-06-04 |
Family
ID=5566933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD27525185A DD236312A1 (en) | 1985-04-17 | 1985-04-17 | PROCESS FOR PREPARING SULFIDIC MORPHOLINIUM CHLORIDE |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD236312A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10123210C1 (en) * | 2001-05-12 | 2002-10-02 | Clariant Gmbh | New ether carboxylic acids and salts derived from alkoxylated mercaptobenzothiazoles are used as corrosion inhibitors in metal working and petroleum and natural gas recovery and processing |
-
1985
- 1985-04-17 DD DD27525185A patent/DD236312A1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10123210C1 (en) * | 2001-05-12 | 2002-10-02 | Clariant Gmbh | New ether carboxylic acids and salts derived from alkoxylated mercaptobenzothiazoles are used as corrosion inhibitors in metal working and petroleum and natural gas recovery and processing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1235904B (en) | Process for the production of guanidine derivatives | |
| DE69104041T4 (en) | ORTHO-SUBSTITUTED BIPHENYLGUANID DERIVATIVES AND THESE ANTIDIABETIC OR HYPOGLYCAEMIC AGENTS. | |
| DD202538A5 (en) | METHOD FOR PRODUCING SUBSTITUTED UREA DERIVATIVES | |
| DE1159462B (en) | Process for the preparation of s-triazine derivatives | |
| CH633542A5 (en) | METHOD FOR PRODUCING UREA DERIVATIVES. | |
| DE1795328A1 (en) | 3-aminopyrrolidines and process for their preparation | |
| CH620682A5 (en) | Process for the preparation of novel 2,6-disubstituted 2-phenyliminoimidazolidines and their acid addition salts | |
| DD236312A1 (en) | PROCESS FOR PREPARING SULFIDIC MORPHOLINIUM CHLORIDE | |
| CH343388A (en) | Process for the preparation of new amides | |
| DE1670183A1 (en) | Tetrazole derivatives and processes for their preparation | |
| DE68912797T2 (en) | Process for the preparation of arylsulfonylalkylamides. | |
| DE1246722B (en) | Process for the production of urea derivatives | |
| DE2825194C2 (en) | ||
| DE2031826C3 (en) | Process for the N-acylation of inorganic or organic compounds containing amino groups | |
| EP0224849B1 (en) | 4-mercaptobenzonitriles and process for their preparation | |
| DE935127C (en) | Process for the preparation of N-aryl-N'-aminoalkylureas | |
| EP0427161B1 (en) | Picolylselenobenzamides of aminopyridines, anilines and picolylamines | |
| DE3223802C2 (en) | ||
| DE866647C (en) | Process for the production of secondary 1,3-alkenediamines | |
| DE3530061A1 (en) | METHOD FOR PRODUCING GUANIDINOTHIAZOLE DERIVATIVES | |
| EP0041170B1 (en) | 3-nitro-pivaloyl-acetanilides, processes for their preparation and their utilization | |
| AT379806B (en) | METHOD FOR PRODUCING A NEW THIADIAZOLE COMPOUND | |
| AT372940B (en) | METHOD FOR PRODUCING (D) - (-) - PHYDROXYPHENYLGLYCYL CHLORIDE HYDROCHLORIDE | |
| DD154817A5 (en) | METHOD OF ILLUSTRATING THE MOLECULAR COMPOUNDS OF BETA-DIAETHYLAMINOETHYLAMIDE OF P-CHLOROPHENOXYESETIC ACID WITH 4-N-BUTYL-3,5-DIKETO-1,2-DIPHENYLPYRAZOLIDINE | |
| AT235306B (en) | Process for the production of new carbamic acid derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENJ | Ceased due to non-payment of renewal fee |