DE1067023B - Ver drive for the production of N carboxylic acid esters of cyclic dicarboximides - Google Patents
Ver drive for the production of N carboxylic acid esters of cyclic dicarboximidesInfo
- Publication number
- DE1067023B DE1067023B DENDAT1067023D DE1067023DA DE1067023B DE 1067023 B DE1067023 B DE 1067023B DE NDAT1067023 D DENDAT1067023 D DE NDAT1067023D DE 1067023D A DE1067023D A DE 1067023DA DE 1067023 B DE1067023 B DE 1067023B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- parts
- weight
- cyclic
- dicarboximides
- 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
- -1 cyclic dicarboximides Chemical class 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 title 1
- 238000000034 method Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000007792 addition Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N Succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims 1
- 229960002317 succinimide Drugs 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 16
- HIZCIEIDIFGZSS-UHFFFAOYSA-N Thiocarbonic acid Chemical compound SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- XKJCHHZQLQNZHY-UHFFFAOYSA-N Phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 206010061217 Infestation Diseases 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000008056 dicarboxyimides Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SPAMRUYRVYMHPV-UHFFFAOYSA-N 3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical compound C1=CCCC2C(=O)NC(=O)C21 SPAMRUYRVYMHPV-UHFFFAOYSA-N 0.000 description 2
- PNKFGNFOJYTIJU-UHFFFAOYSA-N CCOC(=S)N1C(=O)C2=CC=CC=C2C1=O Chemical compound CCOC(=S)N1C(=O)C2=CC=CC=C2C1=O PNKFGNFOJYTIJU-UHFFFAOYSA-N 0.000 description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N Furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N Glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003562 thiocarbonic acid ester halides Chemical class 0.000 description 2
- RCKMWOKWVGPNJF-UHFFFAOYSA-N Carbamazine Chemical compound CCN(CC)C(=O)N1CCN(C)CC1 RCKMWOKWVGPNJF-UHFFFAOYSA-N 0.000 description 1
- 230000036536 Cave Effects 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- ZHQLTKAVLJKSKR-UHFFFAOYSA-N Homophthalic acid Chemical compound OC(=O)CC1=CC=CC=C1C(O)=O ZHQLTKAVLJKSKR-UHFFFAOYSA-N 0.000 description 1
- 241000227653 Lycopersicon Species 0.000 description 1
- 241000222291 Passalora fulva Species 0.000 description 1
- 241000936613 Peronospora farinosa Species 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N Quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 241000282941 Rangifer tarandus Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N Thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical class OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion media Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QMUWBIHMKNGMJK-UHFFFAOYSA-N methanediolate Chemical class [O-]C[O-] QMUWBIHMKNGMJK-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atoms Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
Description
DEUTSCHESGERMAN
Es ist bekannt, daß man cyclische Dicarbonsäureimide mit Carbonsäurechloriden zu am Stickstoffatom substituierten Derivaten dieser Imide umsetzen kann (Heller und Jacobsohn, Berichte der Deutschen Chemischen Gesellschaft, Bd. 54 [ 1921], S. 1112; Titherley, Hicks, Journal of the Chemical Society, Bd. 89 [1906], S. 709). Die dabei erhaltenen Verbindungen, z. B. das N-Carbäthoxyphthalimid, besitzen jedoch im allgemeinen keine bemerkenswerten biologischen Eigenschaften.It is known that cyclic dicarboximides can be formed with carboxylic acid chlorides on the nitrogen atom can convert substituted derivatives of these imides (Heller and Jacobsohn, reports of the Germans Chemischen Gesellschaft, Vol. 54 [1921], p. 1112; Titherley, Hicks, Journal of the Chemical Society, Vol. 89 [1906], p. 709). The compounds obtained, for. B. the N-Carbäthoxyphthalimid have however, generally no remarkable biological properties.
Es wurde nun gefunden, daß man sehr gutjjjngjzid^ wirksame Verbindungen erhält, wenn man cycuscne Dicarbonsäureimide mit Thiokohlensäure-O-esterhalogeniden zu N-Thiocarbonsäure-Ö-estern cyclischer Dicarbonsäureimide umsetzt. "It has now been found that very gutjjjngjzid ^ active compounds are obtained when cycuscn e Dicarb onsäureimide cave with Thioko acid tert.-O-este rhalogeniden to N-thiocarboxylic acid esters Ö-cyclic Dicarbonsä UreI mi de converts. "
~Fm"da.s erfihdungsgemäße Verfahren geeignete Di- \ /carbonsäureimide sind z. B. die Imide aliphatischer )ζ Dicarbonsäuren, wie der _Malei|i^_Bernstein- oder -/—\ Glutarsäure, oder solcher aliphatischer Dicarbonsäu-( ren, deren aliphatische Kette durch Heteroatome, wie «o ein Sauerstoff-, Stickstoff- oder Schwefelatom, unterbrochen ist, z. B. der Diglykolsäure oder Thiodiglykolsäure, ferner die Imide aromatischer oder heterocyclisclier o-Dicarbonsäuren, wie der Phthal-, Hexahydrophthal-, der verschiedenen Tetrahydrophthal-, Endomethylen-tetrahydrophthal-, Homophthal- oder Naphthalsäure, der Pyridin-2,3-dicarbonsäure, der Thiophen-2,3-dicarbonsäure sowie deren Substitutionsprodukte. ~ Fm "da.s erfihdungsgemäße method suitable di- \ / carboxylic acid imides are, for example, the imides of aliphatic) ζ dicarboxylic acids such as the _Malei |. I ^ _Bernstein- or - ren \ glutaric acid, or such aliphatic dicarboxylic (whose - / aliphatic chain is interrupted by heteroatoms, such as an oxygen, nitrogen or sulfur atom, for example diglycolic acid or thiodiglycolic acid, and also the imides of aromatic or heterocyclic dicarboxylic acids, such as phthalic, hexahydrophthalic and various tetrahydrophthalic acids -, endomethylene-tetrahydrophthalic, homophthalic or naphthalic acid, pyridine-2,3-dicarboxylic acid, thiophene-2,3-dicarboxylic acid and their substitution products.
Als Thiokohlensäure-Oesterhalogentde geeignet sind vor allem die Chloride der Monothiokohlensäure-O-alkyl-, -aralkyl-, cycloalkyl- oder -arylester sowie solche Esterchloride, die sich von heterocyclischen Alkoholen, z. B. Furfurylalkohol, ableiten. Diese Thiokohlensäure-O-esterhalogenide können gegebenenfalls noch durch gegen Säure indifferente Substituenten, wie Halogenatome, Nitro1 öder Alkoxygruppen, substituiert sein. Sie können weiterhin auch ungesättigte Reste enthalten.Particularly suitable as thiocarbonic acid ester halides are the chlorides of monothiocarbonic acid-O-alkyl, aralkyl, cycloalkyl or aryl esters and those ester chlorides which are derived from heterocyclic alcohols, e.g. B. furfuryl alcohol derived. This thiocarbonic acid-O-ester-halides may optionally by indifferent to acid substituents such as halogen atoms, nitro 1 barren alkoxy groups, be substituted. They can also contain unsaturated residues.
Die Herstellung der als Ausgangsmaterial dienenden Thiokohlensäure-O-esterhalogenide kann nach an sich bekanntem Verfahren erfolgen, z. B. durch Einwirkung von Thiophosgen auf aliphatische, araliphatische, cycloaliphatische oder heterocyclische Alkohole bzw. aromatische oder heterocyclische Hydroxyverbindungen, oder aber sie können gemäß Patent 1 018054 durch chlorierende Spaltung von Dixanthogenen erhalten werden.The preparation of the thiocarbonic acid O-ester halides used as starting material can be carried out according to an known method take place, for. B. by the action of thiophosgene on aliphatic, araliphatic, cycloaliphatic or heterocyclic alcohols or aromatic or heterocyclic hydroxy compounds, or they can, according to Patent 1,018,054, by chlorinating cleavage of dixanthogens can be obtained.
Die Herstellung der N-Dicarbonsäureimid-thiocarbonsäure-O-ester kann entweder durch Einwirkung der Thiokohlensäure-O-esterhalogenide auf die Salze der Imide, vorzugsweise der Alkali- oder Erdalkalisalze, in indifferenten Lösungs- oder Dispersionsmitteln erfolgen oder aber durch Umsetzung der freienThe production of N-dicarboximide-thiocarboxylic acid-O-esters can either be caused by the action of the thiocarbonic acid O-ester halides on the salts the imides, preferably the alkali or alkaline earth salts, in inert solvents or dispersants be done or by implementing the free
C-. ■C-. ■ ■ ■'-■- ■ ■ '- ■ -
Verfahren zur Herstellung von N-CarbonsäureesternProcess for the preparation of N-carboxylic acid esters
cyclischer Dicarbonsäureimidecyclic dicarboximides
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk
Dr. Klaus Sasse, Köln-Stammheim, Dr. Richard Wegler, Leverkusen, und Dr. Ferdinand Grewe, Köln-Stammheim, sind als Erfinder genannt worden : Dr. Klaus Sasse, Cologne-Stammheim, Dr. Richard Wegler, Leverkusen, and Dr. Ferdinand Grewe, Cologne-Stammheim, have been named as the inventor :
Dicarbonsäureimide mit den Thiokohlensäure-Ö-esterhalogeniden in Gegenwart säurebindender Stoffe, wie tertiärer Amine, Alkali- oder Erdalkalicarbonite oder Erdalkalihydroxyde. Die Reaktion kann dann Jn organischen Lösungsmitteln oder auch in Wasser als Lör sungs- bzw. Dispersionsmittel ausgeführt werden, wobei die Dicarbonsäureimide im letzteren Fall zweckmäßigerweise durch basische Stoffe, wie Alkalihydroxyde oder -carbonate, in Lösung gebracht werden und dann mit den Thiokohlensäure-O-esterchloriden, die gegebenenfalls in einem wassermischbaren organischen Lösungsmittel gelöst wurden, umgesetzt werden. Erforderlichenfalls kann man auch; einen Emulgator zusetzen. Diese Reaktionen gehen in der Regel bereits bei gewöhnlicher Temperatur vor sich, teilweise unter erheblicher Wärmetönung, so daß gekühlt werden muß. Führt man das Verfahren mit den in einem organischen Lösungsmittel suspendierten Dicarbonsäureimidsalzen durch, so muß man im allgemeinen erhöhte Temperaturen anwenden.Dicarboximides with the thiocarbonic acid ester halides in the presence of acid-binding substances, such as tertiary amines, alkali or alkaline earth carbonites or alkaline earth metal hydroxides. The reaction can then be carried out in organic solvents or also in water as a solvent or dispersion medium, the dicarboximides in the latter case advantageously being brought into solution by means of basic substances such as alkali hydroxides or carbonates and then mixed with the thiocarbonic acid-O- ester chlorides, which may have been dissolved in a water-miscible organic solvent, are reacted. If necessary, you can also ; add an emulsifier. As a rule, these reactions already take place at ordinary temperature, sometimes with considerable heat release, so that cooling is necessary. If the process is carried out with the dicarboximide salts suspended in an organic solvent, it is generally necessary to use elevated temperatures.
Die Isolierung der nach dem erfiridungsgemäßen Verfahren erhaltenen N-Dicarbonsäüreimid-thiocarbonsäureester erfolgt in üblicher Weise entweder durch Aufarbeitung der erhaltenen Lösungen oder deii in den entsprechenden Lösungsmitteln erhaltenen schwerlöslichen Fällungen. |The isolation of the according to the invention Process obtained N-dicarboxylic acid imide thiocarboxylic acid ester takes place in the usual way either by working up the solutions obtained or deii in the sparingly soluble precipitates obtained from corresponding solvents. |
Die verfahrensgemäß erhaltenen N-Dicarboiisäureimid-thiocarbonsäureester besitzen ausgezeichnete ftThe N-dicarboiimide-thiocarboxylic acid esters obtained according to the process own excellent ft
909 638/367909 638/367
gizide Wirksamkeit ohne pflanzenschädigende EigensPRafien. Gicidal effectiveness without any plant-damaging properties.
29,4 Gewichtsteile Phthalimid werden in 250 Gewichtsteilen Dioxan unter Zusatz von 28 Gewichtsteilen Hexahydrodimethylanilin gelöst. Unter Rühren und Kühlung mit Eiswasser werden langsam 27,5 Gewichtsteile Thiokohlensäure-O-äthylesterchlorid zugetropft. Anschließend wird Vs Stunde bei Raumtemperatur und dann Vs Stunde bei 35 bis 40° C nachgerührt. Die abgekühlte Reaktionsmischung wird in 1 1 Wasser eingegossen, und die daraufhin abgeschiedenen Kristalle des N-Thiocarbäthoxyphthalimids29.4 parts by weight of phthalimide are dissolved in 250 parts by weight of dioxane with the addition of 28 parts by weight Hexahydrodimethylaniline dissolved. While stirring and cooling with ice water, 27.5 parts by weight are slowly increased Thiocarbonic acid O-ethyl ester chloride was added dropwise. The mixture is then stirred for an hour at room temperature and then for an hour at 35 to 40 ° C. The cooled reaction mixture is poured into 1 l of water, and the then deposited Crystals of N-thiocarbethoxyphthalimide
werden aus Alkohol umkristallisiert. Ausbeute 78°/o der Theorie; F. 106 bis 108° C.are recrystallized from alcohol. Yield 78% the theory; F. 106 to 108 ° C.
Tomatenpflanzen, die mit 0,05°/o N-Thiocarbäthoxyphthalimid enthaltenden Spritz- oder Stäubemitteln behandelt und nachträglich mit Cladosporium fulvum infiziert wurden, blieben vollständig befallsfrei. Der gleiche Effekt zeigte sich bei Reben, die mit Peronospora infiziert wurden.Tomato plants with 0.05% N-thiocarbethoxyphthalimide containing spray or dust and subsequently treated with Cladosporium fulvum were infected remained completely free of infestation. The same effect was seen in vines with downy mildew were infected.
30,2 Gewichtsteile Tetrahydrophthalimid werden in 250 Gewichtsteilen Dioxan unter Zusatz von 28 Gewichtsteilen Hexahydrodimethylanilin gelöst. Unter Rühren und Kühlung mit Eiswasser werden langsam 27,5 Gewichtsteile Thiokohlensäure-O-äthylesterchlorid zugetropft. Anschließend wird V» Stunde bei Raumtemperatur und dann 1U Stunde bei 35 bis 40° C nachgerührt. Die abgekühlte Reaktionsmischung wird in 11 Wasser eingegossen, und die daraufhin abgeschiedenen Kristalle des N-Thiocarbäthoxy-zlMetrahydrophthalimids 30.2 parts by weight of tetrahydrophthalimide are dissolved in 250 parts by weight of dioxane with the addition of 28 parts by weight of hexahydrodimethylaniline. While stirring and cooling with ice water, 27.5 parts by weight of thiocarbonic acid O-ethyl ester chloride are slowly added dropwise. The mixture is then stirred at room temperature for 1/2 hour and then at 35 to 40 ° C. for 1 hour. The cooled reaction mixture is poured into 1 liter of water, and the crystals of N-thiocarbethoxy-zl-metrahydrophthalimide which have then separated out are poured
der Theorie) N-Thiocarbäthoxyhexahydrophthalimid Otheory) N-Thiocarbäthoxyhexahydrophthalimid O
werden aus Alkohol umkristallisiert. Ausbeute 68"Vo der Theorie; F. 84 bis 85° C.are recrystallized from alcohol. Yield 68 "Vo of theory; mp 84 to 85 ° C.
30,6 g Hexahydrophthalsäureimid werden in 250 ml Benzol suspendiert und mit 28 g Hexahydrodimethylanilin versetzt. 27,4 g Thiokohlensäure-O-äthylesterchlorid werden tropfenweise bei Raumtemperatur zugegeben. Anschließend wird 1 Stunde bei Raumtemperatur und 1 Stunde bei 40 bis 50° C nachgerührt. Die abgesaugte Lösung wird mit Wasser gewaschen und das Benzol abdestilliert. Ausbeute 30,2 g (62,7 Vo30.6 g of hexahydrophthalic acid imide are suspended in 250 ml of benzene and mixed with 28 g of hexahydrodimethylaniline offset. 27.4 g of thiocarbonic acid O-ethyl ester chloride are added dropwise at room temperature. Then 1 hour at room temperature and stirred at 40 to 50 ° C for 1 hour. The extracted solution is washed with water and the benzene is distilled off. Yield 30.2 g (62.7 vol
N-C-OC2H8 NC-OC 2 H 8
OO
in Form eines hellgelben Öles.in the form of a light yellow oil.
14,7 g Phthalimid werden in 150 ml Dioxan gelöst und mit 14 g Hexahydrodimethylanilin versetzt. 18,5 g Thiokohlensäure-O- (2-äthoxyäthy 1) -esterchlorid werden tropfenweise bei Raumtemperatur zugegeben. Anschließend wird 1 Stunde bei 35 bis 40° C nachge-14.7 g of phthalimide are dissolved in 150 ml of dioxane, and 14 g of hexahydrodimethylaniline are added. 18.5 g Thiocarbonic acid O- (2-ethoxyethy 1) ester chloride added dropwise at room temperature. This is followed by 1 hour at 35 to 40 ° C.
ao rührt. Die nitrierte Mischung wird in Wasser gegossen. Das anfangs ölige Produkt kristallisiert und wird aus Alkohol umkristallisiert. Ausbeute 18 g (64,5 Vo der Theorie) N-[Thiocarbo-(2-äthoxy)]-phthalimid. ao stirs. The nitrated mixture is poured into water. The initially oily product crystallizes and is recrystallized from alcohol. Yield 18g (64.5 Vo of theory) N- [thiocarbo- (2-ethoxy)] phthalimide.
/Vc\/ V c \
N-C-O-C4H4-OC2H5 NCOC 4 H 4 -OC 2 H 5
" Il s"Il s
F. 87 bis 88° C.F. 87 to 88 ° C.
15,1 g (0,1 Mol d4-Tetrahydrophthalimid werden in 150 ml Benzol suspendiert und mit 8,7 g Pyridin versetzt. 12,1 g Thiokohlensäure-O-methylesterchlorid werden tropfenweise bei Raumtemperatur zugegeben. Anschließend wird 1 Stunde bei Raumtemperatur und 1 Stunde bei 40 bis 50° C nachgerührt. Die abgesaugte Lösung wird mit Wasser gewaschen und das Benzol abdestilliert. Ausbeute 14,8 g (66,2 °/o der Theorie) N-Thiocarbomethoxy-/d4-tetrahydrophthalimid15.1 g (0.1 mol of d 4 -tetrahydrophthalimide are suspended in 150 ml of benzene, and 8.7 g of pyridine are added. 12.1 g of thiocarbonic acid O-methyl ester chloride are added dropwise at room temperature. This is followed by 1 hour at room temperature and The mixture is subsequently stirred for 1 hour at 40 ° to 50 ° C. The solution which has been filtered off is washed with water and the benzene is distilled off, yielding 14.8 g (66.2 % of theory) of N-thiocarbomethoxy- / d 4 -tetrahydrophthalimide
N-C-OCH8 NC-OCH 8
in Form eines hellgelben Öles.in the form of a light yellow oil.
16,3 g (0,1 Mol) Endomethylen-tetrahydrophthalimid werden in 150 ml Benzol suspendiert und mit 14 g Hexahydrodimethylanilin versetzt. 12,1 g Thiokohlensäure-O-methylesterchlorid werden tropfenweise bei Raumtemperatur zugegeben. Anschließend wird 1 Stunde bei Raumtemperatur und 1 Stunde bei 40 bis 50° C nachgerührt. Die abgesaugte Lösung wird mit Wasser gewaschen und das Benzol abdestilliert.16.3 g (0.1 mol) of endomethylene tetrahydrophthalimide are suspended in 150 ml of benzene and mixed with 14 g of hexahydrodimethylaniline are added. 12.1 g of thiocarbonic acid O-methyl ester chloride are added dropwise at room temperature. Then 1 hour at room temperature and 1 hour at 40 Stirred up to 50 ° C. The suctioned off solution is washed with water and the benzene is distilled off.
Ausbeute 16,3 g (68,5% der Theorie) N-Thiocarbo-Yield 16.3 g (68.5% of theory) N-thiocarbo-
methoxy-endomethylen-tetrahydrophthalimid
Omethoxy-endomethylene-tetrahydrophthalimide
O
N-C-OCH8 NC-OCH 8
als ein hellgelbes Öl.than a light yellow oil.
len Hexahydrodimethylanilin gelöst und bei Raumtemperatur unter Rühren tropfenweise mit 13,6 Gewichtsteilen Thiokohlensäure-O-äthylesterchlorid versetzt. Die Mischung wird 1 Stunde bei 35 bis 40° C nachgerührt, abgekühlt und in 300 Gewichtsteile Wasser eingegossen. Das abgeschiedene öl wird in Benzol aufgenommen, mit Wasser gewaschen und über Natriumsulfat getrocknet. Nach dem Abdestillieren des benzols hinterbleiben 11,6 Gewichtsteile (62 %> der ίο Theorie) N-Thiocarbäthoxy-succinimid der Formellen hexahydrodimethylaniline and dissolved at room temperature 13.6 parts by weight of thiocarbonic acid O-ethyl ester chloride are added dropwise with stirring. The mixture is stirred for 1 hour at 35 to 40 ° C., cooled and poured into 300 parts by weight of water poured. The separated oil is taken up in benzene, washed with water and over sodium sulfate dried. After the benzene has been distilled off, 11.6 parts by weight (62%> the ίο theory) N-thiocarbethoxy-succinimide of the formula
CH2-C,CH 2 -C,
14,7 Gewichtsteile Phthalimid werden in 150 Gewichtsteilen Aceton unter Zusatz von 14 Gewichtsteilen Hexahydrodimethylanilin gelöst und bei Raumtemperatur unter Rühren tropfenweise mit 18,5 Gewichtsteilen Thiokohlensäure-O- (2-äthoxyäthyl) -esterchlorid versetzt. Die Mischung wird 1 Stunde bei 35 bis 40° C ao nachgerührt, abgekühlt und in 500 Gewichtsteile Wasser eingegossen. Dabei scheidet sich ein anfangs öliges, bald kristallisierendes Produkt ab, das zur weiteren Reinigung aus Alkohol umkristallisiert werden kann. Ausbeute 19,2 Gewichtsteile (69% der Theorie) »$ N- [Thiocarbo- (2-äthoxy-äthoxy) ] -phthalimid; F. 87 bis 88° C.14.7 parts by weight of phthalimide are dissolved in 150 parts by weight of acetone with the addition of 14 parts by weight of hexahydrodimethylaniline and 18.5 parts by weight of thiocarbonic acid O- (2-ethoxyethyl) ester chloride are added dropwise at room temperature with stirring. The mixture is subsequently stirred at 35 to 40 ° C. for 1 hour, cooled and poured into 500 parts by weight of water. An initially oily, soon crystallizing product separates out, which can be recrystallized from alcohol for further purification. Yield 19.2 parts by weight (69% of theory) »$ N- [thiocarbo- (2-ethoxy-ethoxy)] phthalimide; F. 87 to 88 ° C.
Mit O,l°/oigen Spritz- oder Stäubemitteln behandelte und nachträglich mit Phytophtora infestans infizierte Tomatenpflanzen blieben praktisch befallsfrei (Befallsquotient 2 gegenüber 100 für Kontrolle.)Treated with 0.1% spray or dust and tomato plants subsequently infected with Phytophtora infestans remained practically free from infestation (infestation quotient 2 versus 100 for control.)
N-C-OC4H5 NC-OC 4 H 5
CH1-C IlCH 1 -C II
Il s 0Il s 0
in Form eines nicht destillierbaren Öls.in the form of a non-distillable oil.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1067023B true DE1067023B (en) | 1959-10-15 |
Family
ID=593001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1067023D Pending DE1067023B (en) | Ver drive for the production of N carboxylic acid esters of cyclic dicarboximides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1067023B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1141130B (en) * | 1959-08-28 | 1962-12-13 | Rohm & Haas | Combating fungi and bacteria on plants |
-
0
- DE DENDAT1067023D patent/DE1067023B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1141130B (en) * | 1959-08-28 | 1962-12-13 | Rohm & Haas | Combating fungi and bacteria on plants |
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