PROCEDURE FOR the PRODUCTION OF NEW ONES 5-SUBSTTUIERTEN OXAZOLIDIN-2,4-DIONEN AND YOUR SALTS

The invention refers to a procedure for the production of new derivatives of the Oxazolidin--2,4-dions, which are useful as hypoglykämische means. Despite the early discovery of insulin and the following wide-spread use with the treatment of diabetes and the later discovery and use of sulphonyl-urine-rigid (e.g. chlorine prop. amide, Tolbutamid, Acetohexamid, Tolazamid) and Biguaniden (e.g. Phenformin) as oral hypoglykämische means remains the treatment by diabetes less than satisfyingly. The use of insulin, which is necessary required daily repeated with strong diabetes, where available synthetic hypoglykämische means are not effective, usually self injection. The determination of the suitable insulin dosage requires frequent Zuckerbestimmungen in the urine or in the blood. The processing of a surplus insulin dose causes Hypoglykämie with effects, which hand from mild Anomalitäten of blood glucose up to coma or even to death. Where effective, a synthetic hypoglykämisches means is preferred opposite insulin, since it is to be given more comfortably and less is inclined to release heavy hypeglykämische reactions. But the clinically available hypoglykämischen means are burdening unfortunately with other toxic features, which limit their use. In any case, where one of these means fails in individual cases, another can be successful. Anyhow exists obviously a constant need at hypoglykämischen means, which are less toxic or successful, where others fail. Beside the hypoglykämischen means specified above by a multiplicity of further connections was reported that they possess this kind of activity, like a recent overview of blank (Burger's Medicinal Chemistry, 4th edition, part of II, John Wiley and Sons, N.Y., S.I057-i080) shows. Available the according to invention Oxazolidin-2,4-dione is new connections; this despite the fact that the Oxazolidin-2,4-dione admits far away as connecting class is (as comprehensive overview see Clark Lewis, chem. rer. 58, P. 69-99). To well-known connections to this class 5-Phenyloxazolidin-2,4-dion, occasionally descriptive as intermediate stage for certain B-lactam-Antibiott'ka (US-PS Nr.2, belongs 721.197), as anti-depressive means (US-PS Nr.3, 699.229) and as cramp-solving means (Brink and Freeman, J. Neuro. Chem. 19 (7), S. 1783-i788); a row of 5-Phenyloxazolidin-2,4-dionen, at the Phenylring substitutes, e.g. 5 (4-Methoxyphenyl) - oxazolidin-2,4-dion (King and Clark Lewis, J. chem. one lake., P. 3077-3079 [! 961]), 5 (4-Chlorphenyl) - oxazolidin-2,4-dion (Najer et al., bulletin seconds. Chim. France, P. 1226-1230), 5 (4-Methylphenyl) - oxazolidin-2,4-dion (Reibsomer et al., J.Am. Chem. seconds. 61, P. 3491 - -3493) and 5 (4-Aminophenyl) - oxazolidin-2,4-dion (BE-PS Nr.i08026), 5 (2-Pyrryl) - oxazolidin-2,4-dion (Ciamacian and silver, Gazz. chim. ital. i6, 357, Ber. 19, 1708-1714). The latter connection, for which no Brauchharkeit admits is, shows only relatively weak hypoglykämische activity (S. later, table I). Oxazolidin-2,4-dion and substituted Oxazolidin-2,4-dione (in particular the 5-Methyl-und 5,5-Dimethyl-Derivate) were described as sour remainders, for the formation of acid addition salts with the hypoglykämischen basic Biguaniden are suitable (US-PS Nr.2, 961.377). In the context of the available investigations it was stated that neither Oxazolidin-2,4-dion themselves nor 5,5-Dimethyloxazolidin-2,4-dion possess the hypoglykämische activity available of the according to invention connections. In recent time a group of Spirooxazolidin-2,4-dion became - derivatives it described which are Aldosereduktase inhibitors, whereby they are useful with the treatment of certain complications of diabetes (US-PS Nr.4, 200.642}. A procedure for the synthesis of 3-Aryloxazolidin-2,4-dionen (whereby the group of aryls of 6 to! 2 C-atoms, unsubstituiert or substitutes with one or more halogen atoms, methyl or Methoxy) is article of the US-PS Nr.4, 220,787 exhibits. The usefulness of these connections is not given. Article invention is thus procedures for production of new racemischen or optical active connections general formula 1 R (I), where R (i) W 2) ù (ii) whereby W chlorine or fluorine and n 1 or 2 is, (iii) or X or whereby Y sulfur or oxygen, X hydrogen, halogen, methyl, Phenyl, Benzoyl or (c1 - C3) - Alkoxy, X hydrogen or methyl and X2 hydrogen or halogen mean, is, and of them pharmaceutical acceptable kationischen salts, which is characterized by that one phosgene with a connection of the general formula H R (II), NH where g 1 the above Meaning has and RZ (c1 _3 - alkyl) is, to a connection of the general formula (Ill) in an inert solvent converts and with or without isolation hydrolyzed, and, if gewü sch t, (A) eßne received connection of the formula O (Ia) in presence of a free radical catalyst to an intermediate connection of the formula W Br o bromiert and to a connection W (IC) transfers these of the formula (Ib), RST (B) (C) nisches salt. If R the meaning x, 4J % y or where W the above meaning has, a received racemische connection of the formula (I) into their optically active Enantiomeren dehydrobromiert, and/or a received connection of the formula (I) into a pharmaceutical acceptable separates katioX has 5 4-%, where Y sulfur or oxygen, X hydrogen, fluorine, chlorine, bromine, iodine, methyl, Phenyl, Benzoyl or (C! - CS) - Alkoxy, X hydrogen or methyl and X2 hydrogen, fluorine, chlorine, bromine or iodine to mean is, if X is hydrogen, covers the first formula the 5 (2-Furyl) -, 5 (3 - - Furyl) -, 5 (2-Thienyl) - and 6 (3-Thienyl) - derivatives of the Oxazolidin-2,4-dions, whereby the substituent X can sit at each free carbon position of the Furan/Thiophen Mnges, i.e. X X where and ¥ the above meaning have X and Ox is used as abbreviation for the Oxazolidin-2,4-dionring sitting in 5-Stellung, whereby, if both remainders of X and X have another meaning than hydrogen, which can sit second substituent at any free position in each of these six variants, whereby the second formula is to cover such connections, with those the Oxazolidin in 2, 3oder 7-Stellung of the Benzo furan/Benzo thiophen ring system be substituted can, i.e. Ox Ox the expression “pharmaceutical acceptable kationische salts” is to define such salts, like the alkali metal salts (e.g. Natrium-und of potassium salts), alkaline earth metal salts {e.g. Calcium-und of Magnesiumsalze) of aluminum salts, ammonium salts and salts with organic amines, like Benzathin (N, N' Dibenzyläthylendiamin), Cholin, Diäthanolamin, ethylen diamine, Meglumin (N-Methylglucamin), Benethamin (N-Benzylphenäthylamin), Diäthylamin, Piperazin, Tromethamin (2-Amino-2-hydroxymethyl-l, 3propandiol), Procain etc.. Available the according to invention connections possess hypoglykämische activity, which is again-reflected in its clinical usefulness for the lowering of the blood glucose value of hypoglykämischen humans and mammals on normal values. They have the special advantage to lower blood glucose values on a normal range without the danger of causing from Hypoglykämie to. Available the according to invention connections were tested on hypoglykämische (anti- hyperglykämische) activity with rats, to which the so-called glucose compatibility test heran2S is drawn, as in the following in detail described. Under the connections of the formula (I) are due to their excellent hypoglykämischen activity to most preferential connections the following: - (1-Methy1-2 - pyrrolyl) - oxazolidin -2,4-dion; 5 (1-Äthyl-2-pyrrollyl) - oxazclidin-2,4-dion; 5 (1-Phenyl-2-pyrrolyl) - oxazolidin-2,4-dion; 5 (2-Methoxy-3-pyridyl) - oxazolidin-2 4-dion; 5 (2-Äthoxy-3-pyridyl) - oxazolidin-2,4-dicn; I0 5 (5-Chlor-2-methoxy-3-pyridyl) - oxazolidin-2,4-dion; 5 - (5 - chlorine -2 - äthoxy-3-pyridyl) - oxazolid in -2,4-d ion; 5 (8-Chinolyl) - oxazolidin-2,4-dion; 5 (7-Methoxy-8-chinolyl) - oxazolidin-2,4-dion; 5 (6-Chlor-8-chinolyl) - oxazolidin-2,4-dion; 5 (6 - Fluor-8 - chinolyl) - oxazolidin -2,4-dion; 5 (2-Benzthiazolyl) - oxazolidin-2,4-dion; 5 (2-Thiazolyl) - oxazolidin-2,4-dion; - (6 - chlorine -8 - chrome anyl) - ox azoli D in -2,4-d ion 5 (6-Fluor-8-chromanyl] - oxazolidin-2,4-dion; - (5 - chlorine -2.3 - dihydro -7 - benzofuranyl) - oxazolidin -2,4-dion; 5 (3-Methyl-5-isoxazolyl) - oxazolidin-2,4-dion; 5 (3-Thienyl) - oxazolid [n-2,4-dion; 5 (4-Brom-3-thienyl) - oxazolidin -2,4-dion; 5 (4-Äthoxy-3-thienyl) - oxazolidin~2,4-dion; 5 (4-Äthoxy-2-methyl-3-thienyl) - oxazolidin-2,4-dion; 5 - (4-Methoxy-2 - methy1-3 - th ienyl) - oxazol idin -2.4 ~d ion; 5 (3-Methyl-2-thienyl) - oxazolidin-2,4-dion; 5 (3-Methoxy-2-thienyl) - oxazolidin-2,4-dion; 5 (3 - Furyl) - oxazolidin -2,4~dion; 5~ (2-Furyl) - oxazolidin-2,4-dion; 5 (3-Brom-2-furyl) - oxazolidin -2,4-dion; 5 (5 - Chlor-2 - furyl) - cxazolidin-2,4-dion; 5 (7-Benzo thienyl) - oxazolidin-2,4-dion and - (5-Chlor-7 - benzo fur any!) - oxazolidin-2,4-dion. Nr.$76974 with the procedure according to invention vird the Cnrboximidat (IL) with phosgene in an inert solvent, as tetrahydrofurane tert, in presence of 2 to 2.3 equivalents one. Amine (e.g. tri ethyl amine, N-Methylmorpholin) converted. A further equivalent tert. Amine one uses, if the Carboximidat is transferred into the acid addition salt (e.g. the Hydroehlorid). The temperature for the reaction is uncritical, but lower temperatures (e.g. - i0 to I0°C) are preferential, in particular during the first reaction stages, if the intermediate connection 4-Alkoxyoxazol-2-on (III) to be isolated is. The isolation of this intermediate connection effected via simply evaporation of the reaction mixture to dry ones. During the further conversion at higher temperatures (e.g. 20 to 150°C) or with aqueous processing the intermediate connection (IIl] is converted into the desired Oxazolidin-2,4~dion. If in the final product a primary or secondary amine function is gewüscht, this functional group is introduced over a Oxazolidin-2,4-dion with one (e.g. by katalytisehe hydrogenation or acid/metal) selectively to the primary or secondary amine reducible group. For example a N-Benzylindol can be used as preliminary stage for a Indolderivat. The Carboximidat (II) comfortably of the appropriate aldehyde one makes as follows; OSi (CH3) 3 I R/CN/(12) O R 0 R2 ARRANGE (11) CH (13) (IL). The aldehyde (11) is converted after standard functions (e.g. over the Bisulfit adduct, which is converted with cyanide in a two-phase, aqueous-organic solvent system) into there Cyanhydrin (13). On the other hand the aldehyde becomes by shifting with Trimethylsilylcarbonitril in presence of a catalytic portion of an Lewis acid, e.g. zinc iodide, into S Trimethylsilylcyanhydrin (! 2) transferred. An inert solvent (e.g. dichloromethane, ether) is generally used, if the aldehyde is a solid, but if necessary only if the aldehyde is a liquid. The conversion temperature is uncritical, is however comfortable-proves low (e.g. 0 to 5°C) and the conversion can run hours or days at ambient temperature, depending upon necessity for complete conversion. If, hydrolyzed can the TrimethylI0 is wished more silyläther to the Cyanhydrin, comfortable-proves at low temperature (e.g. 10°C) in a two-phase, strongly acidified aqueous-organic solvent system. The Cyanhydrin (13) or the Trimethylsilyläther (12) becomes by a strongly sourly catalyzed Alkoholyse (under strictly water-free conditions) into the Carboximidat (II) converted. A comfortable method is those to loosen the nitrile simply in alcohol which was satisfied with hydrogen chloride, and the solution stand to leave, until the Carboximidatbildung is terminated. The temperature is uncritical, although lower temperatures (e.g. 0 to 25°C) generally to more optimal yields lead. The aldehydes necessary for the above syntheses are large, either in the trade or after literature methods, available. For example N-Alkylpyrrol-2-carbaldehyde by alkylating Pyrrol-2-carbaldehyd (Weygand, Organic Preparations, Interscience, New York, 1945, P. 403) under conditions received, which are indicated for the production of N-Alkylpyrrolen exemplarily particularly later, or by the Reimer Tieman Formylierung of N-Alkylpyrrol (see Weygand, loc. CIT); similarly 3-Formylindole received from Indolen (see Boyd and Robson, Biochem. J. 29, P. 55511935]), Shabica et al., J. to. Chem. seconds. 68, P. 1156); by rose mouth hydrogenation of the appropriate Säurechlorids (e.g. 3-Furaldehyd, Hayes, J. to. Chem. seconds. 71, 2581), from halogen methyl connections by the Sommelet reaction (e.g. 3-Thenaldehyd, Campaigne and LaSuer, J. to. Chem. seconds. 70, 1557), Formylierung (e.g. 2-Thenaldehyd, 3-Methyl-2-thenaldehyd, 5-Methyl-2-thenaldehyd; Watson and Michaels, J. to. Chem. seconds. 72, 1422, Organic Syntheses 31, 108, 3-Brom-2-thenaldehyd, Elliott et al., J. chem. seconds. (C), 2551), reduction of chlorine-methyl-substituted aldehydes (e.g. 5-Methyl -2-furaldehyd, Spence and game, J. chem. seconds., 338), oxidation of the appropriate alcohol (e.g. 2-Thenaldehyd, Emerson and Patrick, J. Org. Chem. one, 14, 790), reciprocal effect of Grignard reagents with Orthoameisensäureestern (e.g. 2-Thenaldehyd, Cagniant, bulletin seconds. chim. Franee 16, 849), Decarboxylierung of “- Ketosäuren (e.g.) 2-Thenaldehyd, Barger and Easson, J. chem. seconds., 2100), and Halogenierung (e.g. 2-Brom-3-thenaldehyd, Elliot et al., loc. CIT); furthermore a number of necessary aldehydes stands by hydrolysis of in accordance with. - Dihalogeniden, oxidation of primary alcohols, reciprocal effect from Grignard reagents with Orthoameisensäureestern and other well-known methods to the order. Further methods are in detail descriptive modes of production indicated in late. The pharmaceutical acceptable kationischen salts available of the according to invention connections, which form such salts, are manufactured easily by shifting of the acid forms with a suitable base, usually an equivalent, in a Cosolvens. Typical bases are sodium hydroxide, Natriummethylat, Natriumäthylat, sodium hydride, Kaliummethylat, magnesium hydroxide, calcium hydroxide, Benzathin, Cholin, Diäthanolamin, ethylen diamine, Meglumin, Benethamin, Diäthylamin, Piperazin and Tromethamin. Salts, which do not fail directly, are isolated by restricting to dry ones or by addition of a Nichtlösungsmittels. In some cases salts can be manufactured by mixing a solution of the acid with a solution of another salt of the cation (Natriumäthylhexanoat, magnesium oleate), using a solvent, in which the desired kationische salt fails, or be isolated otherwise by restricting and admitting a Nichtlösungsmittels. Acylierte of derivatives easily manufactured with use of standard conditions of the acylation, e.g. by shifting of the Oxazolidin-2,4-dion-Salzes (when or one comfortable-proves to such tert in situ by addition of an equivalent. Amine, like by tri ethyl amine or N-Methylmorpholin, of the Säurechlorids or Säureanhydrids) or by shifting of the Oxazolidin-2,4-dions with suitable organic isocyanate, if necessary in presence of a catalytic portion of one, suitable with an equivalent, tert. Amine base. In each case the conversion in an inert solvent, like toluol, is accomplished tetrahydrofurane or Methylenohlorid. S the temperature is uncritical and can lie in a large range (e.g. from 0 to 150°C). For the specialist it is clear that such an acylation is complicated by competitive or even selective Seitenketten (R) - acylation, if the Seitenkette contains a primary or secondary amine function. For the specialist it is clear that available the according to invention connections are asymmetrical and from there in two optically active enantiomeren forms can be present. The RA, case, hen connections form salts with organic amines as acids. These racemischen forms can be split up from there generally into the optically active forms according to the classical method of the education of diastereomerer salts with optically active amines, which are separable by selective crystallization; on the other hand can such connections, which have a basic amine function “by Salzbildung with an optically active acid, preferably a strong organic acid, like a sulfone acid, anfgespalten become. Generally it shows up that one of the enantiomeren forms exhibits a larger activity than the other one. The procedure according to invention can be supervised according to dünnschichtchromatographischen standard methods, to which commercial plates are used. Suitable Elutionsmittel is usual solvents, like chloroform, ethyl acetate or hexane, or suitable combinations hievon, which differentiate raw materials, products, by-products and in some cases intermediate connections. With these on the field of activity well-known methods are probably further improvements in methodology in the following in detail particularly represented examples possible for that, e.g. the selection of more optimal response times and temperatures as well as a selection assistance for opti2S paint procedures. Available the according to invention Oxazolidin-2,4-dione is for the clinical use as anti-diabetes means easily anzupassen.° the hypoglykämische activity necessary for this clinical use by the following filucose Verträglichkeitstest is defined. Healthy male Albinoratten is the experimental animals used for such purposes. One lets be hungry the test animals about 18 to 24 h. The rats are weighed, counted numbered/and divided in groups from 5 or 6, depending upon need. Each group of animals keeps then intraperitoneal a glucose dose (l g/kg) and oral either to water (controls) or connection (at a value usually within the range of 0! to 100 mg/kg). Blood glucose values (mg/100 valley) are measured in tail blood tests during one period of 3 h both with Kontrollals also at the treated groups. At equivalent blood glucose values for the hour of 0 in Kontrollund treated group the percentage of the lowering of blood glucose according to i/2, 1, 2 and 3 h computed as [blood glucose of control] - [blood lucose of of the treated animals] x 100 [blood glucose of control] clinical useful hypoglykämische means show with this test activity. The hypoglykämischen activities intended for available according to invention connections are arranged in the table I. This table notes the lowering of blood glucose in % after 1/2 and 1 h. A lowering of the blood glucose of 97o or over it shows statistically significant hypoglykämische activity with this test, such connections, which show significant activity only after 2 or 3 h, has such an activity shown in footnotes. Table I Hypoglykämi activity of Oxazolidin-2,4-dionen at the advice ten Glucoseverträglichkeit stest acre O acre 2-ThienyI 5-Benzoyl3-Brom5-Brom5-Chlor3-Methoxy5-Methoxy3-Methyl5-Methyl 5-Phenyl 3-Thienyl 4-Brom4-Methoxy4-Methoxy-2-methyl4-Äthoxy4-Äthoxy-2-methyl4-Propoxy2-Furyl 3-Brom5-BromDosis (mg/kg) 100,100,100,100,100 lowering of the Blutglucoselh 8 7 6 (A) of content in % RST 8 36 26 13 9 14 18 1 23 31 14 ll 16 19 7 ll 27 23 11 7 18! 0 11 11 19 2 11 19 17 16 7 17 12 I0 (B) 17 9 8 14 19 12 6 Nr.376974 table I {continuation) Hypoglykämi activity of Oxazolidin-2,4-dionen with the rat glucose compatibility test//NH acre IL O acre 5-Chlor3-Methoxy5-Methyl5-Phenyl3-Furyl 2 5-Dimethyl4-Jod3-Benz thienyl 7-Benz [bi thienyl 7-Benz furanyl 5--Chlorine 8-Chromanyl 6-Chlor6-Fluor 2,3-Dihydrobenzofuranyl 5-Chlor2-Pyrrolyl 1-Methyl1-Äthyl1 (1-Butyl) - 1-Phenyl 3-1ndolyl - bromine l-Methyl3-Pyridyl dose (mg/kg) i00 i0 I00 I00 i00 IO IO IO IOO lOO ioo IOO ioo ioo lOO lowering of the blood glucose content in % 1/2 h 1 h 21 27 6 17 14 33 (e) 19 (e) II -4 23 (e) 11 18 14 4 9 11 19 4 (C) 13 8 16 (f) 0 (f) 12 (D) zo (f) 11 9 23 (g) 8 17 16 13 32 i0 8 No. 376974 O table I (continuation) Hypoglykämi activity of Oxazolidin-2,4-dionen with the rat glucose compatibility test Nr.376974 O acre 2-Methoxy 2-Äthoxy2-Methoxy-5-chlor2-Äthoxy-5-chlor5-Chinolyl 6-Methoxy8-Chinolyl 6-Chlor6-Fluor 7-Methoxy2-Thiazolyl2-Benzthiazolyl5-1soxazolyl 3-MethylDosis (mg/kg) 18,100 lowering of the Blood glucose 1/2 h of content in LH 13 22 19 ii 8 17 24 (g) 7 (h) 16 16 - (i) I0 7 (j) (A) 11 after 2 h; (C) 10 after 3 h; (e) after 3/4 h; (g) after 3/4 h; (i) 12 after 3 h; (B) 9 after 2 h; (D) 16 after 2 h, 10 after 3 h; (f) after 1 1/2 h; (h) 9 after 2 h; (j) 24 after 2 h, 14 after 3 h. Available the according to invention Oxazolidin-2,4-dione is given humans and mammals either orally or parenterally clinically. The oral administration is preferred, since it is more comfortable and possible pain and provoking avoids by injection. Perhaps S however, under those the patient the drug not to swallow knows or the absorption after. oral administration, as by illness or other Anomalität, is substantial it is impaired that the active substance is parenterally given. With each administration way the dose portion amounts to about 0.10 until approximately 50 mg/kg Körpermasse/individual/day, preferably 0.20 until approximately 20 mg/kg Körpermasse/day, in a dose or subdivides given. The optimal dosage I0 however for everyone single individual who can be treated is determined by for the treatment the responsible person, whereby generally at the beginning of smaller and later rising doses are given, in order to determine the most suitable dosage. This varies with the particularly used ¥erblndung and with the individual who can be treated. The connections can be used in pharmaceutical preparations, be contained the connection or of them pharmaceutical acceptable acid salt in combination with a pharmaceutical acceptable carrier or diluent. Suitable ones pharmaceutical acceptable carriers are inert firm of fillers or solvents and sterile aqueous or organic solutions. The active connection is present in such pharmaceutical means in portions, which are sufficient, the desired dose portion within the range descriptive above to result in. Thus the connections with a suitable know determine or liquid carrier or solvent I0 to caps, tablets, powders, syrups, solutions, suspensions cd.dgl, to be combined for oral administration. The pharmaceutical center] know, if desired, additional components, like taste materials, u.dgl, contain sweet means, Exzipientien. For parenteral administration the connections with sterile aqueous or organic media to injectable solutions or suspensions can be combined. For example solutions in Sesamoder peanut oil, aqueous propylene glycol can be used u.dgl, just as aqueous solutions of more water-solubly pharmaceutical acceptable acid addition salts of the connections. In such a way manufactured injectable solutions can be given then intravenously, intraperitoneal, subkutan or intramuskulär, whereby the intramuskuläre administration is preferential with humans. The following examples are to describe the invention more near, without this is to be limited however to it. Example I: 2 (6-Chlor-8-chromanyl) - 2-trimethylsiloxyäthannitril 7 g (0.086 mol) 6-Chlorchroman~8-carbaldehyd in 70 ml dichloromethane were cooled on 0 to 5°C. 100 mg zinc iodide were added and course-dripped then 4.26 g (0.043 mol) to Trimethylsilylcarbsnitril. The reaction mixture was agitated at ambient temperature 64 h, washed then nachein2S other with 3 portions of satisfied Natriumbiearbonatlösung and once with salt solution, over water-free magnesium sulfate dried, filtered and to the title product than oil restricted (9.5 g, IR (CH2 CI2) 2857, 1479, 1216, 1190, 1060 cm '). Example 2: ethyl l (6-chlor-8-chromanyl) - l-hydroxymethancarbeximidathydrochlorid to 250 m [(0 to 5°C) of cold satisfied äthanolischer hydrochloric acid was dripped 9.29 g of the product by example 1 in I5 ml ethanol, whereby the temperature under 10°C was held. [} as mixture was agitated 35 min with 0 to 5°C and restricted then to an oil. Crystallize from ethanol/ether resulted in 5.7 g title product, (Fp. 125 to 127°C (Zers.), m/e 271/269). Example 3 “5 (6-Gh! or-B-chromanyl) - oxazol idin -2,4-dien 5.4 g (18.6 mMol) of the product of example 2 were suspended in 250 ml tetrahydrofurane, added in an ice/a Wasser-Bad cooled and to 6.01 g (0.06 mol) tri ethyl amine. The cold mixture was durchperlt with phosgene 30 min, 1 h at ambient temperature and poured then on 1 1 pieces of ice was agitated. The deterrent reaction mixture was extracted with three portions dichloromethane. The united excerpts were washed with salt solution, dried over water-free magnesium sulfate and restricted to solids. The arrears were recrystallized from toluol, whereby 3.28 g became to receive cleaned title product. (Fp° 170 to 172°C, m/e 269/267). Analysis for CI2 HI0 0#NCh C computes: 53.84% 3.77% 5.23% found: 53,73 3.83% 5.48% example 4:2 - (6~Fluor-8-chromanyl) -2-trimethylsiloxyäthannitril after the function of the example 1 were converted 3.2 g (0.0178 mol) 6-Fluorchroman-8-carbaldehyd into the title product as oil (4.51 g, m/e 279, IR (CHC12) 1498, 1205, 1066 cm-*). Example 5: ethyl l (6-fluor-8-chromanyl) - l-hydroxymethancarboximidathydrochlorid with a response time of 1 h with 0 to 5°C the function of the example 2 was used, around 4,4 g of the product of example 4 to the title product (4.1 g, Fp.: 124 to 126°C (Zers.), to convert m/e 253). Example 6:5 - (6-Fluor-8-chromanyl) - oxazolidin-2,4-dion after the function of the example 3 3.9 g (0.0134 mol) of the product were converted from example into raw title product. Raw solids were taken up to 1 n caustic soda solution and extracted with two portions of ether. The product was precipitated by addition that aqueous to basisehen layer slowly to surplus 3 n hydrochloric acid. Recrystallize from toluol resulted in lo 2.73 g cleaned title product (Fp.: 174 to 176°C, m/e 251). Analysis for c1 tHI0 04 NF: C IS computes: 57.37% 4.01 5.58% found. 57.74% 3.91% 5.40% example 7:2 - (5-Chlor-2,3-dihydro-7-benzo furanyl) - 2-trimethylsiloxyäthannitril 900 mg (4.9 mMol) 5-Chlor-2,3-dihydrobenzo b furan-7-carbaldehyd in 25 ml Äbter were solved. 20 mg zinc iodide and then 970 mg (9.8 mMol) Trimethylsilylcarbonitril were added and the mixture 16 h at ambient temperature was agitated, diluted then with 50 ml ethers, washed with three portions of satisfied Natriumbiearbonatlösung and once with salt solution, dried, filtered over water-free magnesium sulfate and restricted to the title product, an oil, (1.4 g, m/e 283/281, IR (CH2 C12) 1479, 1457, 1435, 1180, 866, 848 cm-l). Example 8: Äthyl-1 - (5-chlor-2,3-dihydro-7-benzo furanyl) -1-hydroxymethancarboximidathydrochlorid after the function of the example 2 were converted 1.37 g of the connection from example 7 into the title product. At the beginning of insulating solids 2mal with ether were aufgesehlämmt again, whereby 1.28 g became to receive cleaned product (Fp.: 149 to 152°C (Zers.) m/e 257/255, IR (KBr) 3162, 2875, 1650, 1524, 1458 em). Example 9 " 5 (5-Chlor-2,3-dihydro-7-benzo furanyl) - oxazolidin-2,4-dion after the function of the example 3 were converted 1.1 g of the connection of example 8 into title product recrystallized from toluol (630 mg, Fp.: 197 to 199°C, m/e 255/253, IR (KBr) 3084, 1833, 1810, 1746 cm). Example 10:2 - (3-Methyl-5-isoxazolyl) - 2-trimethylsilyläthannitril after the function of the example 1 3.4 g (0.032 mol) were converted 3-blethylisoxazol-5-earbaldehyd into the title product, when oil isolates (6.5 g, no aldehyde Protoa in accordance with NMR). Example 11: ethyl l hydroxy l (3-methyl-5-isoxazolyl) - methancarboximidathydrochlorid 6.5 g of the product of example 10 were solved in 50 ml cold, satisfied äthanolischer hydrochloric acid and for 16 h with 5°C were held. 3.3 g title product were won by filtering (Fp.: 119 to 121°C). Example 12:5 - (3-Methyl-5-isoxazolyl) - oxazolidin-2,4-dion after the function of the example 3 2.2 g of the product were converted from example 11 into the title product. After dern deterring on pieces of ice the product in ethers was extracted, the united excerpts was getroeknet and to an oil (1.4 g) restricted. Further extracting 4s with methyl acetate and evaporation resulted in additional oil (0.4 g). The oils were combined and distributed between 25 ml 1 n caustic soda solution and 25 ml ethers. The aqueous-basic phase was separated, with konz. Hydrochloric acid acidified and with 25 ml ethyl acetate extracts. Ethyl acetate - excerpt was restricted with water rewashed, to dry ones, the arrears with ether rubbed (146 mg, Fp.: 173 to 175°C). The product verriebene with ether became the Troekne eingeSO confines and with fresh ether rubbed (238 mg, Fp.: 175 to 177°C). Example 13:2 - (3-Furyl) - 2-trimethylsiloxyäthannitril to a mixture of 1,92 g (20 mMol) 3-Furaldehyd and about 100 mg zinc iodide into 25 ml ethers were dripped 4.74 g (48 mMol) Trimethylsilylcarbonitril. The mixture was agitated about 16 h at ambient temperature. The reaction mixture was dried, filtered successively washed with satisfied Natriumbicarbonatlösung, water and salt solution, over water-free sodium sulfate and restricted in the vacuum to 2 (3-Furyl) - 2-trimethylsiloxyäthannitril (2.2 g, PNMR/CDCI3/ö: 0,2 (s, 9H), 5.4 (s, IH), 6.4 (m, IH), 7.3 (m, IH), 7.5 (m, IH). Example 14: ethyl l hydroxy l (3-furyl) - methancarboximidathydrochlorid 1.0 g 2 (3-Furyl-2-trimethylsiloxyäthannitril in 10 ml satisfied äthanolischer hydrochloric acid with 0 to 5°C one solved. The resulting solution was held 16 h with for instance 6°C. The reaction mixture was restricted on for instance the half volume and diluted with ether. Filtering and washing with ether resulted in 746 mg Äthyl~1-hydroxy-l (3-furyl) - methancarboximidathydrochlorid (Fp.: i18 bls I15°C, m/e 169). Example IS: 5 (3-Furyl) - oxazolidin-2,4-dion 1.5 g (7.6 mMol) ethyl l hydroxy l (8-furyl) - methancarhoximidathydrochlorid with ml tetrahydrofurane and 2.21 g (21.9 mMol) tri ethyl amine were brought together and cooled on 10°C. Phosgene was led 20 min long by the cooled reaction mixture. After further 30 min agitating the mixture was led 10 min long nitrogen by the mixture. The reaction mixture was poured slowly in 100 g broken ice. The product was extracted in two portions of ether and isolated raw product as oil by restricting. The oil was taken up to 5 ml 1 n caustic soda solution and extracted with Ähter. The aqueous-basic phase was acidified and extracted with fresh ether. The product was isolated as resin-like solid (600 mg) by evaporation of the latter ether excerpt. Rub with chloroform supplied cleaned 5 (3 - - Furyl) - oxazolidin-2,4-dion (109 mg, Fp.: 86 167 m/e to 88°C). Addition from hexane to in 2S the chloroform refugee product supplied a second product portion (66 mg, Fp.: 86 to 88°C, m/e 167). Analysis for CTHsO#N: Computed: 50.31% 3.01% 8.38% found: 49,97 3.13 8.37 example 16:2 - (6-Chlor-2-furyl) - 2-trimethylsiloxyäthannitril 2.7 g (21 mMol) 5-Chlor-2-furaldehyd was solved into 30 ml ethers. 6,3 ml (50 mMol) Trimethylsilylcarbonitril and about 60 ml zinc iodide were admitted and the mixture 1 1/2 h at ambient temperature was agitated, on which Dünnschichtchromatographie (hexane/ethyl acetate (8: 1) complete 3s conversion indicated. Restrict to dry ones resulted in 5.5 g 2 (5-Chlor-2-furyl) - 2-trimethylsiloxyäthannitril as oil (PNMR/CDCI3/ö: 0,3 (s, 9H), 5.4 (s, IH), 6.1 (D, IH), 6.5 (D, IH). Example lq: ethyl l (5-chlor-2-furyl) - l-hydroxymethancarboximidathydrochlorid 2.3 g 2 (6-Chlor-2-furyl) - 2-trimethylsiloxyäthannitril were solved in 25 ml satisfied äthanolischer hydrochloric acid with 0°C. The solution was held 2 1/2 h with 5°C and restricted then to an oil. Rub with 20 ml ethers supplied with to 1.2 g crystalline ethyl l (5-chlor-2-furyl) - l-hydrexymethancarboximidathydrochlorid (Fp.: 112 to i14°C, m/e 203). Example 18:5 - (6-Chlor-2-furyl) - oxazolidin-2,4-dion 1.2 g (5 mMol) ethyl l (5-chlor-2-furyl) - l-hydroxymethancarboximidathydrochlorid in ml tetrahydrofurane were suspended and cooled in an ice bath. After addition of 2,1 ml (15 filMol) tri ethyl amine was introduced phosgene 20 min into the reaction mixture, whereby the temperature was held with to 20°C. The mixture was rinsed with nitrogen and poured slowly in 100 ml broken ice. The deterrent reaction mixture was rewashed with 100 ml ethers extracted s0 and the ether with salt solution and restricted to an oil. The oil was taken up to 15 ml fresh ether, which extracts solution clarified and with 10 ml 1 n caustic soda solution. The basic excerpt became with konz. Hydrochloric acid acidified and product in ethyl acetate extracts. After rewashing with water the ethyl acetate layer was restricted to an oil (550 mg). A part of this oil (500 mg) became at approximately 50 ml silicagel with ttexan/ethyl acetate, 5: 1/5% acetic acid as Elutionsmittel chromatographiert. The column was dünnschichtchromatographisch supervised (same solvent). , Produkthaltige parliamentary groups eluierte late were combined, to dry ones restricted and with hexane rubbed, which t77 mg 5 (5-Chlor-2-furyl) - oxazolidin-2,4-dion resulted in [Fp.: 112 to 114°C, m/e 201, Rf 0.25 (5: 1 hexane/ethyl acetate with 5% acetic acid}]. Analysis for CTH4 04 NCI: Computed: 41.71% 2.00% 6.95% found: 41.80% 2.21% 6.77% example 19 2 (5-Brom-2-furyl) - 2-trimethylsi! oxyäthannitril 1.1 g (6 mMol) 5-Brom-2-furaldehyd were solved into 50 ml ethers. A katalytiseher portion (about 50 mg) zinc iodide was added and course-dripped then 746 mg (1.2 equivalents) to Trimethylsilylcarbonitril. The reaction mixture became by IR (to disappear the typical Carbonyl - absorption) and PNMR (disappear the typical aldehyde proton peak) supervises. After min at ambient temperature the reaction mixture was finally washed with satisfied Natriumbicarbonatlösung, 2mal with water and with salt solution, dried and restricted over water-free sodium sulfate, whereby 1.2 g became to receive 2 (5-Brom-2-furyl) - 2-trimethylsiloxyäthannitril as oil [PNMR/CDC13/“: 0,3 (s, 9H), 5.6 (s, 1H), 6.4 (D, 1H), 6.6 (D, 1H)]. Example 20: ethyl l (5-brom-2-furyl) - l-hydroxymethancarboximidathydrochlorid after the function of the example 14, exceptionally that the reaction mixture before the addition from ether was not restricted, did not become 1.2 g 2 (5-Brcm-2-furyl) - 2-trimethylsiloxyäthannitril in 480 mg ethyl l (5-brom-2-furyl) - l-hydroxymethancarboximidathydrochlorid converted (Fp.: 120 to 122°C, m/e 247, 249). A less more purely second portion (235 mg, Fp.: 104 to 106°C) one won by evaporation of the mother liquor and rubbing of the Rüekstandes with Ähter. Example 21:5 - (5b-Rome -2-furyl) - oxazolidin -2,4-dien 982 mg (3.4 mMol) ethyl l (5-brom-2-furyl) - l-hydroxymethancarboximidathydrochlorid became in 126 mg 5 (5-Brom-2-fury!)- oxazolidin-2,4-dion converted Fp.: 126 to 129°C, m/e 245, 247, Rf 0.2 (5: 1 ttexan/ethyl acetate with 5% acetic acid), u.zw. to the function of the example BeispieI 22:2 - (3-Brom-2 [uryl) - 2-trimethylsiloxyäthannitril after the function of the example 13 1.75 g (10 mMol) 3-Brom-2-furaldehyd were converted into 50 ml ethers with 8,8 ml (70 mMol) Trimethylsilylcarbonitril in presence of approximately 100 mg zinc iodide. After 16 h reaction duration was decanted the supernatant ether phase by solids and restricted to dry ones, whereby 3 g 2 (3-Brom-2-furyl) - 2-trimethylsiloxyäthannitril err 0.7 (3: 1 hexane/ethyl acetate was received)]. Example 23: ethyl l (3-brom-2-furyl) - l-hydroxymethancarboximidathydrochlorid 6.8 g 2 (3-Brom-2-furyl) - 2-trimethoxysilyläthannitril were solved in 70 ml satisfied äthanolischer hydrochloric acid with O°C and for 2 h with for instance 5°C were held. Restrict to dry ones and rubbing with acetone resulted in 4.4 g ethyl l (3-brom-2-furyl) - l-hydroxymethancarboximidathydrochlorid [Fp.: 117 to I19°C (Zers.)]. Example 24:5 - (3-Brom-2-furyl) - oxazolidin-2,4-dion after the functions of the example 18, excluded that phosgene was introduced into the reaction mixture with 0 to 10°C, 4.4 g Äthy became! - l (3-brom-2-furyl) - l-hydroxymethancarboximidathydrochlorid into cleaned 5 (3-Brom-2-furyl) - oxazolidin-2,4-dion converted [847 mg, Fp.: 128 to 130°C, Rf 0.20 (5: 1 hexane/ethyl acetate with 5% acetic acid)]. Analysis for C7H404 NBr: C H N computes: 34.16% 1.63% 5.69% found: 34.30% 1.88% 5.67% example 25:2 - (2-Fury!)- 2-trimethylsiloxyäthaunitri! 24 g (0.25 mol) 2-Furaldehyd were gekühIt on 0 to 5°C, 500 mg zinc iodide were added and the mixture was agitated. 30 ml Trimethylsilylcarbonitri! were course-dripped. The mixture could warm up to ambient temperature and to about 64 h at ambient temperature was agitated. The Reaktionsgemiseh was treated, filtered with dichloromethane diluted, 2mal with satisfied Natriumbiearbonatlösung extracted, over water-free magnesium sulfate dried, with activated charcoal and to 36 g (74%) 2 (2-Furyl) - 2-trimethylsiloxyäthannitri! , a Ö! , restricted [PNMR/CDCI3/ö: 0,2 (s, 9H), 5.6 (s, IH), 6.4 (m, IH), 6.6 (m, 1H), 7.4 (D, IH)]. Example 26: ethyl l (2-furyl) - l-hydroxymethancarboximidat after the function of the example 14 became 15 g 2 (2-Furyl) - 2-trimethylsiloxyäthannitril with satisfied äthanolischer hydrochloric acid converted, with the exception that a response time was used by approximately 2 h. The raw product was isolated by restricting the Reaktionsgemisehes to an oil. The oil was distributed in 400 ml chloroform and satisfied Natriumbicarbonatlösung. The chloroform was dried 2mal washed with fresh satisfied Natriumbicarbonatlösung and once with salt solution, over water-free magnesium sulfate, filtered and to ethyl l - (2-furyl) - l-hydroxymethancarboximidat, an oil, restricted [10.6 g, 81%, PNMR/CDCI3/: 1,3 (t, 3H), 4.1 (q, 2H), 5.1 (s, IH), 4.8-5.2 (m, IH), 6.3 (m, 2H), 7.3 (D, IH)]. Example 27:5 - (2-Furyl) - oxazolidin-2,4-dion 10.5 g (6.2 mMol) ethyl l (2-furyl) - l-hydroxymethancarboximidat in 125 ml agitated tetrahydrofurane were solved and on 0 to 5°C cooled. 12,5g (0.124 mol) tri ethyl amine were added and the cold solution with phosgene 35 min was then flowed through, warmed up to ambient temperature and agitated further 16 h. The reaction mixture was poured slowly in 1 1 ice and water. The product was extracted in three portions ethyl acetate. The excerpts were combined and extracted product in four portions of I n caustic soda solution. The united aqueous excerpts were acidified with 6 n hydrochloric acid and extracted product in four portions of chloroform. The united chloroform excerpts were treated, filtered over water-free magnesium sulfate getroeknet, with activated charcoal and restricted to a raw product, an oil, (2.1 g). Säulenchromatographie at 100 g silicagel with 2: Cleaned 5 (2 - - Furyl) - oxazolidin-2,4-dion from restricting the parliamentary groups 86 to 48,281 mg (Fp resulted in 1 chloroform/ethyl acetate as Elutionsmittel in 10 valley parliamentary groups, dünnschiehtehromatographisch supervised. : 99 to I02°C, m/e 167). Recrystallize from toluol resulted in 235 mg more strongly cleaned product (Fp.: 101 to I03°0). Analysis for C7 H5 OaN: C H N computes: 50.31% 3.02% 8.38% found: 50.41% 3.25% 8.28% example 28:2 - (5-Phenyl-2-thienyl) - 2-trimethylsiloxyäthannitril 0.9 g 5-Phenyl-2-thenaldehyd into 35 ml ethers with 1 ml Trimethylsilylcarboniträl in presence of approximately 50 mg zinc iodide were converted. After I h agitating at ambient temperature indicated the Dünnschichtehromatographie complete conversion. Restrict up to dry ones resulted in 1.66 g 2 (5 - - Pheny1-2-thienyl) -2-trimethylsiloxy ethane nitrile, [Rf 0.5 (5: I hexane/ethyl acetate with 5% acetic acid)]. Example 29: Äthy1-l-hydroxy-1 (5-phenyl-2-thienyl) - methancarboximidathydrochlorid 1.6 g 2 (5-Phenyl-2-thienyl) - 2-trimethylsiloxyäthannitril were solved in 30 ml cold, satisfied äthanolischer hydrochloric acid and for about 17 h with 0 to 5°C were held. The reaction mixture was restricted to dry ones and with ethyl acetate rubbed, whereby 0.9 g ethyl l hydroxy l (5-phenyl) - 2 - - thienyl) - methancarboximidathydrochlorid was received [PNMR/DMSO/5: i, I (3H), 4.0 (2H), 5.2 (IH), 6.5 (IH)]. Example 30:5 - (5-Phenyl-2-thienyl) - oxazolidin-2,4-dion 790 mg (2.6 mMol) ethyl l hydroxy l (5-phenyl-2-thienyl) - methancarboximidathydrochlorid and 1.4 ml (I0 mMol) tri ethyl amine was converted with phosgene and isolated product, whereby the Elutionsmittel with the chromatography ethyl acetate/hexane, 2: 1, was, whereby 172 mg became to receive 5 (5-Phenyl -2-thienyl) - oxazolidin-2,4-dion (Fp.: 233 to 235°C). Analysis for C13 H9 03 LV: C H N computes: 60.23% 3.50% 5.40% found; 59.94% 3.65% 5.38% example 31:2 - (2-Thienyl) - 2-trimethylsiloxyäthannitril after the function of the example 25 56.1 g (46.8 valley, 0.5 mol) were converted 2-Thenaldehyd 16 h with 60 ml Trimethylsilylcarbonitril in presence of approximately 0.5 g zinc iodide, whereby 92 g became to receive 2 (2-Thienyl) - 2-trimethylsiloxyäthannitril as oil (m/e 211, PNMR/CDCI3 /5: 0,2 (s, 9H), 5.8 (s, IH), 6.9-7.6 (m, 3H). Example 32: ethyl l hydroxy l (2-thienyl) - methancarboximidat g 2 (2-Thienyl) - 2-trimethylsiloxyäthannitril became in 450 ml abs. Ethanol solved. The solution was cooled on 0 to 6°C and 40 min with hydrogen chloride flushes. The mixture was held 16 h with for instance 5°C and restricted to dry ones. The arrears were distributed with four 200 valley portions of ethers rubbed and then between 400 ml dichloromethane and satisfied Natriumbiearbonatlösung. The organic phase “was treated 2mal washed with satisfied Natriumbicarbonatlösung, with activated charcoal, filtered and restricted, whereby 10 g Äthyl-l-hydroxy-1 - (2-thienyl) - as oil were kept methanearboximidat, when standing solidified (PNMR/CDC13/ö: 1,2 (t, 3H), 4.1 (q, 2H), 6.2 (s, 1H), 5.9 (s, 1H), 6.8-7.3 (m, 3H), 7.3-8.1 (s, IH). Example 33:5 - (2-Thienyl) - oxazolidin-2,4-dion g (5.4 mMol) ethyl l hydroxy l (2-thienyl) - methancarboximidat and 15.1 ml (10.8 mMol) tri ethyl amine in 100 ml tetrahydrofurane were solved. The solution was cooled on 0 to 5°C and introduced 45 min “phosgene. With 0 to 5°C further 5 h one agitated. The reaction mixture was poured slowly over 1500 ml Eisstüeke. The product was extracted in 1,1 1 ethyl acetate in three portions. The united Äthylaeetatextrakte became then 2mal with satisfied Natriumbicarbonatlösung and 1mal with 1: 1 satisfied Natriumcabonatlösung/water extracts. The united Biearbonatund carbonate washing solutions was acidified with 6 n hydrochloric acid on pH 1 to 2 and extracted product into several portions of ether. The united ether excerpts were treated washed with salt solution, over water-free magnesium sulfate dried, with activated charcoal, filtered 0 and restricted to 3.0 g product. Recrystallize from toluol supplied 1.8 g 5 (2-Thienyl) - - oxazolidin-2,4-dion (Fp.: 138 to 140°C, m/e 183). Analysis for C? H5 NO3 S: C H N 5 computes: 45.89% 2.75% 7.65% found: 46.99% 2.87% 7.62% example 34:2 - (3-Methyl-2-thienyl) - 2-trimethylsiloxyäthannitril after the function of the example 25 31.6 g (0.25 mol) were converted 3-Methyl-2-thenaldehyd with 30 ml Trimethylsilylcarbonitril 16 h in presence of 500 ml zinc iodide. The Reaktionsgemiseh was diluted with 200 ml dichloromethane and continued to isolate also, which resulted in 52 g (93%) 2 (3-Methyl-2-thienyl) -2-trimethylsiloxyäthannitril [PNMR/CDCI3/“: 0,2 (s, 9H), 2.3 (s, 3H), 5.7 (s, 1H), 6.8 (D, IH), 7.25 (D, 1H)]. Example 35: ethyl l hydroxy l (3-methyl-2-thienyl) - methancarboximidat 13 g 2 (3-Methyl-2-thienyl) - 2-trimethylsiloxyäthannitril were dripped to 100 ml cold ethanol, which was satisfied with hydrogen chloride, whereby the temperature was held with 0 to 4°C. After 1 h with 0 to 4°C the reaction mixture was restricted to the Trockns. The arrears were distributed 3mal with 100 valley portions of ether rubbed and then between 300 ml dichloromethane and satisfied Natriumbicarbonatlösung. The separated dichloromethane layer was fat dried, filtered washed with two further portions of satisfied Natriumbicarbonatlösung, over water-free Magnesiumsu and to 8.0 g (69%) ethyl l hydroxy l (3-methyl-2-thienyl) - methancarboximidat restricted (Fp.: 73 to 76°C, m/e 199). Example 36:5 - (3-Methyl-2-thienyl) - oxazolidin-2,4-dion 6.0 g (0.03 mol) ethyl l hydroxy l (3-methyl-2-thienyl) - methancarboximidat were solved in 75 ml tetrahydrofurane and cooled on 0 to 5°C. 6.07 g (8.37 valley, 0.06 mol) tri ethyl amine were added, the solution with phosgene 35 min and poured slowly in 1 1 ice/water was durehspült. The product was extracted in three portions ethyl acetate. The ethyl acetate excerpts were combined and the product in four portions satisfied Bicarbonatlösung was extracted. The united aqueous excerpts were acidified with 6 n hydrochloric acid and the product in three portions blow Äthylaeetats re-extracted. United fresh organic excerpt over wasserfrsiem Magnssiumsulfat were dried, filtered and to 2.4 g (4! %) Product, an oil, restricted, when scratching crystallized. Recrystallize from toluol resulted in 1.84 g (31% entirely) cleaned 5 - (3-Methyl-2-thisnyl) ~oxazolidin-2,4-dion (Fp.: 119 to 121°C, m/e 197). Analysis for C8 H7 03 LV: N computes: 48.72% 3.58 7.10 found: 48.65% 3.58% 7.01% a second product portion (0.63 g) by extracting the ursprüchlichen ethyl acetate excerpts with three portions of 1 n caustic soda solution and following further isolation, like above, was received. Example 37:2 - (5-Methyl-2-thienyl) - 2-trimethylsiloxyäthannitril g (0.2 mol) 5-Methyl-2-thenaldehyd, 266 mg zinc iodide and 100 ml ethers were brought together and agitated at ambient temperature. 23.5 g (0.24 mol) Trimethylsilylcarbonitril were course-dripped and the reaction mixture further 2 h was agitated. It was dried, filtered washed with 100 mI ether diluted, with two 50 valley portions of 5% Natriumbicarbonatlösung, with two 25 valley portions of salt solution washed, over water-free magnesium sulfate and restricted to the Troekne, whereby 42 g became to receive 2 (5-Methyl-2-thienyl) - 2-trimethylsiloxyäthannitril [PNMR/CDCI3 /6: 0,2 (s, 9H), 2.2 (s, 3H), 5.6 (s, IH, 6.6-7.4 (m, 2H)]. Example 38: ethyl l hydroxy l (5-methyl-2-thienyl) - methanearboximidathydrochlorid under cooling on 0 to 5°C 550 was satisfied ml ethanol with hydrogen chloride. 42 g 2 (5 - - Methyl-2-thienyl) - 2-trimethylsiloxyäthannitril were solved in portions and the solution 2 i/2 h with 0°C was held. The reaction mixture was restricted to dry ones and the arrears with diethylether rubbed, whereby 33 g ethyl l hydroxy l (5-methyl-2-thienyl) became to receive - methanearboximidathydrochlorid [Fp.: 122 to 123°C, PNMR/DMSO/ö: 1,1-1,6 (3H), 2.5 (3H), 4.6 (2H), 5.9 (1H), 6.6-7.2 (2H)]. Example 39: SE (5-Methyl-2-thienyl)--oxazolidin-2,4-dion S0 10 g (0.042 mol) ethyl l hydroxy l (5-methyl-2-furyl) - methancarbvximidathydrochlorid with 14,1 g (0.042 mol) tri ethyl amine in 250 ml tetrahydrofurane were brought together and cooled on 0 to 5°C. Into the cold reaction mixture phosgene was introduced during 30 min, it was warmed up to ambient temperature and poured by portion onto approximately 275 ml pieces of ice. The product was extracted in two 200 ml-portions ethyl acetate. The Äthylaeetat excerpts were combined and extracted with two 150 ml-portions 1 n caustic soda solution. The united aqueous excerpts were acidified with hydrochloric acid and then with two 250 valley portions blow ethyl acetate extracted. The last united organic excerpts were dried, filtered and restricted over water-free magnesium sulfate, whereby 7.2 g became to receive 5 (5-Methyl-2-thienyl) - oxazolidin-2,4-dion. Recrystallize from chloroform/hexane resulted in 910 mg cleaned product (Fp. 108 to 109°C, m/e 197). Example 40:2 - (5-Chlor-2-thienyl) - 2-trimethylsiloxyäthannitril g (34 mMol) 5-Chlorothenaldehyd with 50 mg zinc iodide and 30 were brought together ml diethylether and cooled on 0°C. 4.04 g (40 mMol) Trimethylsilylcarbonitril were course-dripped and the Reaktionsgemiseh was warmed up to ambient temperature and 4 h were agitated. Further same portions of Trimethylsilylcarbonitril and zinc iodide were added and the reaction mixture further 16 h was agitated. The Reaktionsgemiseh was washed to an oil with ether diluted, with two 30 valley portions of 5% Natriumbiearbonatlösung and lmal with 30 ml salt solution, over water-free magnesium sulfate dried and restricted to 4.0 g 2 (5-Chlor-2-thienyl) - 2-trimethylsiloxyäthannitril, [PNMR/CDCI3/: 0,3 (s, 9H), 5.7 (s, IH), 7.0 (q, 2H)]. Example 41: ethyl l (5-chlor-2-thienyl) - la-hydroxymethancarboximidathydrochlorid 4 g 2 (5-Chlor-2-thienyl) - 2-trimethylsiloxyäthannitril became in 100 ml abs. Ethanol solved. The solution was cooled on 0 to 5°C and satisfied with hydrogen chloride. The reaction mixture was held 16 h with 0°C, to dry ones restricted and with ether rubbed, whereby 3 g became to receive firm ethyl l (5-chlor-2-thienyl) - l-hydroxymethanearboximidathydrochlorid [PNMR/DMSO/, S: 1,2 (3H), 4.2 (2H), 5.3 (1H), 6.6 (1H), 6.9 (1H), 7.4 (1H), 8.4 (1H)]. Example 42:5 - (5-Chlor-2-thienyl) - oxazolidin-2,4-dion 3, O g (12 mMol) ethyl l (5-ehlor-2-thienyl) - l-hydroxymethancarboximidathydroehlorid and 4.0 g (39 mMol) tri ethyl amine were brought together in 90 ml tetrahydrofurane and cooled on 0°C. Into the mash phosgene 30 min was introduced, it was warmed up to ambient temperature and 16 h was agitated. The Reaktionsgemiseh was poured slowly in 100 ml Eisstüeke and extracted product in two 100 ml-portions of Äthylaeetat. The united Äthylaeetat excerpts were getroeknet, filtered with two 50 ml-Portlonen water and a 50 valley portion of satisfied sodium chlorid solution rewashed, over water-free magnesium sulfate and restricted to 2.5 g of a semisolid material. Recrystallize from toluol supplied 0.6 g cleaned 5 (5-Chlor-2-thienyl) - - oxazolidin -2.4 - dion (Fp.: 126 to 130°C). Analysis for CTH4 03 NC1S: N computes: 38.64% 1.84% 6.44% found. 38.17% 2.07 6.91% example 43:2 - (4-Brom-3-thienyl) - 2-trimethylsiloxyäthannitril 5.5 g (29 mMol) 4-Brom-3-thenaldehyd in 75 ml dichloromethane was cooled on 0 to 5°C. mg Zinkjbdid were added and whereupon 3.47 g (35 mMol) Trimethylsilylearbonitril over 3 min were course-dripped. The mixture was dried, filtered warmed up to ambient temperature, 16 h agitated, 2mal washed with satisfied Natriumbicarbonatlösung and then with salt solution, over water-free magnesium sulfate 4s and restricted to 7.6 g (90%) 2 (4-Brom-3-thienyl) - 2-trimethylsiloxyäthannitril, an oil, (m/e 291/289). Example 44: ethyl l (4-brom-3-thienyl) - l-hydroxymethanearboximidat 7.5 g 2 (4-Brom-3-thienyl) - 2-trimethylsiloxyäthannitril in 200 ml ethanol, in an ice bath cooled, were long flowed through with chlorine which first off 45 min. After further 20 min with 0 to 5°C was restricted the reaction mixture to the Troekne and with ether rubbed, in order to result in the hydrochloride of the product in form of a hygroscopic solid. The salt was taken up to a mixture from dichloromethane and satisfied Natriumbicarbonatlösung. The separated ethylen chloride layer was washed 2mal with satisfied Natriumbicarbonatlösung and then with salt solution, dried over water-free magnesium sulfate, received filtered and restricted, whereby 6.1 g (89%) ethyl l (4-brom-3-thienyl) - l-hydroxymethancarboximidat, an oil, (m/e 265/263). Example 45:5 - (4-Brom-3-thienyl) - oxazolidin-2,4-dion 6.0 g (23 mMol) ethyl l (4-brom-3-thienyl) - and 5.15 g (51 mMol) tri ethyl amine l-hydroxymethancarboximidat in 250 ml tetrahydrofurane was combined, in an ice/a Wasser-Bad cooled and 35 min long with Ph0sgen flowed through. The reaction mixture was agitated warmed up to ambient temperature, 1 1/2 h, poured slowly over 1 1 pieces of ice and extracted the product in three portions dichloromethane. The united dichloromethane excerpts were restricted to an oil, by addition of a small portion of ethers and hexane crystallized and into approximately 40 ml ethers rubbed, whereby 3.4 g (56%) became to receive 5 (4-Brom-3-thienyl) - oxazolidin-3,4-dion (Fp.: 158 to 161°C). Recrystallize from 40 ml toluol supplied 2.51 g cleaned product (Fp.: 164 to 166°C, m/e 263/261). Example 46:2 - (3-Thienyl) - 2-trimethylsiloxyäthannitril g (0.089 Mel) 3-Thenaldehyd, 120 mg zinc iodide and 60 ml ethers were combined and agitated. 10.6 g (0.107 mol) Trimethylsilylcarbonitril during 10 min and the Reaktionsgemiscb was dried, filtered 16 h were course-dripped agitated, with 60 ml ethers diluted, with two 30 valley portions of 5% Natriumb£carbonatlösung washed, with 30 ml salt solution washed, over water-free magnesium sulfate and restricted to 14.3 g 2 (3-Thienyl) - 2-trimethylsiloxyäthannitril an oil, [PNMR/CDCI3/ö: 0,2 (9H), 5.6 (IH), 7.0-7.5 (3H)]. Example 47: ethyl l hydroxy l (3-thienyl) - with 0 to 5°C 14.3 g (2 (3-Thienyl) became methancarboximidat - 2-trimethylsiloxyäthannitril by portion solved in 500 ml ethanol, which had been satisfied before with hydrogen chloride with 0 to 5°C. The solution was held 16 h with 0°C and the product as hydrochloride by evaporation of the reaction mixture to dry ones and rubbing of the arrears with ether was isolated. The salt was taken up to 400 ml chloroform and 100 ml satisfied Natriumbicarbonatlösung. The separated Cbloroformschicht was gstrocknet, filtered washed with further 100 ml satisfied Natriumbicarbonatlösung, with salt solution, over magnesium sulfate and to 12.5 g ethyl l hydroxy l (3-thienyl) - - methancarboximidat restricted. [PNMR/CDCI3/ö: 1,0-1,3 (3H), 4.8-5.3 (2H), 5.0 (IH), 6.9-7.2 (3H), 7.3-8.0 (IH)]. Example 48:5 - (3-Thienyl) - oxazolidin-2,4-dion 12.5 g (0.067 mol) ethyl l hydroxy (3-thienyl) - methancarboximidat and 16.1 g (0.159 mol) tri ethyl amine in 600 ml tetrahydrofurane were combined and cooled on 0°C. Into the mixture 30 min phosgene was introduced, it was warmed up to ambient temperature and 16 h was left untouched. The mixture was poured slowly in 600 ml ice/water (foams of surplus phosgene) and 2mal with 600 valley portions ethyl acetate extracts. The united excerpts were washed with two 800 valley portions of 1 n caustic soda solution. The united basic excerpts were acidified with hydrochloric acid and the product in two blow 300 valley portions ethyl acetate re-extracted. The united fresh excerpts were dried, filtered over water-free magnesium sulfate and restricted to solids (8.0 g). Recrystallize from hot toluol resulted in 5.5 g cleaned B (3-Thienyl) - oxazolidin-2,4-dion (Fp.: 133 to 136°C). Second recrystallizing from ethyl acetate/hexane resulted in additional cleaning (first portion: 2.352 g, Fp.: 136 to 138°C, m/e 183, IR (KBr): 5,5, 5.8 m). Example 49: Natrium-5 (3-thienyl) - oxazolidin-2,4-dion 3.0 g (16.4 mMol) 5 (3-Thienyl) - oxazolidin-2,4-dion were solved in 60 ml ethyl acetate and treated with 300 mg activated charcoal. After 10 min agitating with 20°C was filtered the mixture with ethyl acetate as washing liquid. After approximately 30 min 0.3 was added ml to water. The mash was granulated 30 min at ambient temperature, cooled then on 5°C and granulated further 30 min. Filter resulted in 3.37 g (95%) Natrium-5 (3-thienyl) - oxazolidin-2,4-dion as mono hydrate (Fp.: 208 to 210°C). Analysis for CTH4 03 NSNa0 H2 0: C H N O S well H2 0 computes: 37.67% 2.71% 6.28% 28.67% 14.37% 10.30% 8.07% found: 37.35% 3.03% 6.24% 27.83% 14.33% 10.76% 8.30% example 50:2 - (3-Brem-2-thienyl) - 2-trimethylsiloxyäthannitril 6 g (31 mMol) 3-Brom-2-thenaldehyd and 50 mg zinc iodide were combined with 180 ml dichloromethane. 4.0 g (5.2 valley, 41 mMol) Trimethylsilylcarbonitril were course-dripped. The reaction mixture was getreeknet, filtered 24 h at ambient temperature agitated, with 50 ml Methylenehlorid diluted, with 60 ml 5% Natriumbiearbonatlösung and then washed with 50 ml salt solution, over water-free Magnesiurnsulfat and to 7.2 g 2 (3-Brom-2-thienyl) - 2~trimethylsiloxyäthannitril a g ee ngt (ÖI, m/e 291/289). Example 51: ethyl l (3-brom-2-thienyl) ~l-hydroxymethancarboximidathydrochlorid with 0°C 7.0 g (24 mMol) were satisfied 2 (3-Brom-2-thienyl) - 2-trimethylsiloxyäthannitril in 210 ml ethanol with hydrogen chloride; after 30 min agitating at the same temperature was restricted the Reaktionsgemiseh to dry ones. Rub the firm arrears with ether supplied 7.0 g Äthy1-1 (3-brom-2-thienyl) - l-hydroxymethancarboximidathydroehlorid (Fp.: 120 to 122°C). Example 52:5 - (3-Brom-2-thienyl) - oxazolidin-2,4-dion 6.8 g (23 mMol) ethyl l (2-brom-2-thienyl) - l-hydroxymethanearboximidathydrochlorid and 7.6 g (10.5 valley, 76 mMol) tri ethyl amine were zusammengebraeht in 250 ml tetrahydrofurane. The mixture was cooled on 0 to 5°C, rain phosgene was warmed up to 30 introduced, to ambient temperature, 16 h was agitated and slowly on 300 ml pieces of ice eaten. The abgesehreckte reaction mixture was extracted 2mal with 200 ml portions of chloroform. The united chloroform excerpts were dried, filtered washed with 60 ml salt solution, over water-free magnesium sulfate and restricted to an oil. Addition of hexane and ether supplied crystalline product. IJmkristallisieren from toluol would result in 2.25 g 5 (3-Brom-2-thienyl) - oxazolidin-2,4-dion (Fp.: 138 to 139°C). Analysis for CTH4 03 NSBr: C H N S computes: 32.09% 1.59% 5.34% 12.21% found: 32.41% 1.75% 5.49% 12.61% example 53:2 - (3-Benzo thienyl) -2-trimethylsiloxyäthannitril aS 1.8 g (11 mMol) Benzo thiophen-3-carbaldehyd (J. chem. Soc. C, P. 339-340) and about 100 mg Zinjodid were brought together into 35 ml ethers. 1.98 g (20 mMol) Trimethylsilylcarbonitril were course-dripped. After approximately 1 h the Reaktionsgemiseh was dried, filtered successively washed with satisfied Natriumbicarbonatlösung, water and salt solution, over water-free sodium sulfate and to 2.5 g 2 (3~Benzo thienyl) - 2-trimethylsiloxyäthannitril 0 [oil, Rf 0.7 (1: 2 Äthylaeetat/hexane)] restricted. Example 54: ethyl l (3-benzo thienyl) - l-hydroxymethanearboximidathydroehlorid under cooling in an ice/a Wasser-Bad became 2.3 g 2 (3-Benzo thienyl) - 2-trimethylsiloxyäthannitril solved in 10 ml satisfied äthanolischer hydrochloric acid and held 16 h with for instance 5°C. The reaction mixture was restricted to dry ones, with ether rubbed, whereby 2.2 g 1 (3-Benzo thienyl) - l-hydroxymethancarboximidathydrochlorid was received (Fp. 128 to 131°C, m/e 235). Example 55:5 - (3-Benzo b thienyl) oxazolidin-2,4-dion 2.36 g (8.7 mMol) ethyl l (3-benzo thienyl) - l-hydroxymethancarboximidathydrochlorid and 2.64 g (26 mMol) tri ethyl amine were brought together in 50 ml tetrahydrofurane and cooled on 10°C. Phosgene was led by the cooled Reaktionsgemiseh 30 min and rinsed then min with nitrogen. The reaction mixture was poured slowly in 100 ml ice and extracted 2mal with ether. The united ether excerpts were dried, filtered with water and then with salt solution rewashed, over water-free sodium sulfate and restricted to 1.7 g of a resin-like solid. This raw product was loosened in 1 n caustic soda solution, washed 2mal with ether and acidified with 6 n hydrochloric acid, whereby 950 mg cleaned 5 (3-Benzo thienyl) - - oxazolidin-2,4-dion were received (Fp.: 202 to 205°C, m/e} 238). Analysis for C11 HTO3 LV: Computed: 56.64% 3.02% 6.00% found: 56.74% 3.18% 5.69% example 56:2 - (7-Benzo thienyl) - 2-trimethylsiloxyäthannitril 1.3 g (8 mMol) Benzo thiophen-7-carbaldehyd (J. suppl. chem. ones 39, 2829) into 85 ml ethers were solved. 1,5 ml (12 mMoI) Trimethylsilylcarbonitril and about 60 ml zinc iodide were added and the mixture 1 h at ambient temperature was agitated, on which Dünnschichtchromatorgraphie indicated complete transformation. The reaction mixture was kept restricted to dry ones, whereby 2.2 g 2 (7-Benzo thienyl) - l-hydroxymethancarboximidathydrochlorid [oil, Rf 0.6 IL: 5 ethyl acetate/Hexan/5 acetic acid) example 57: Äthyl-1 (7-benzo thienyl) -1-hydroxymethancarboximidathydrochlorid after the function of the example 54 became 2.1 g 2 (7-Benzo thienyl) - 2-trimethylsiloxyäthannitril with 35 ml satisfied äthanolischer hydrochloric acid in 1,1 g ethyl l (7-benzo thienyl) - l - hydroxymethancarboximidathydrochlorid (Fp.: 120 to 122°C after recrystallizing from acetone) converted. Example 58:5 - (7-Benzo thienyl) - oxazolidin-2,4-dion after the function of the example 55 1.1 g (4 mMol) became ethyl l (7-benzo thienyl) - l - hydroxymethancarboximidathydrochlorid and 1.7 ml (12 mMol) tri ethyl amine with phosgene converted. The raw product, when oil isolates, was loosened into 25 ml ethers and extracted product in 50 ml 1 n caustic soda solution. This aqueous excerpt became with kenz. Hydrochloric acid acidified and product in fresh ether extracts, which was rewashed with water and restricted in the vacuum to 670 mg of firm arrears. This arrears were recrystallized, whereby 0.45 g 5 (7-Benzo - thienyl) - oxazolidin-2,4-dion (Fp.: 130 to 132°C) was received. Analysis for C11 H7 03 LV: C H N computes: 56.64% 3.02% 6.00% found: 56.42% 3.18% 91% example 59:3 - (4-Methoxy-3-thienyl) - 2-trimethylsiloxyäthannitril after the function of the example 13 2.6 g (18.3 mMol) were converted 4-Methoxy-3-thenaldehyd and 2.15 g (21.7 mMol) TrimethylsilyIcarbonitril into 250 ml ethers into presence of 50 ml zinc iodide into 3,9 g title product, an oil, (m/e 241). Example 60: methyl l hyäroxy l (4-methoxy-3-thienyl) - methancarboximidathydrochlorid 100 ml more satisfied methanolic hydrochloric acid was held in an ice bath with 0 to 5°C. 3.9 g of the TiteIproduktes of example 59 in 20 ml methanol were course-dripped and the mixture 1 h with 0 to 5°C was held. The reaction mixture was restricted to determination and the arrears with ether rubbed, whereby 2.76 g title product [Fp.: 94 to 99°C (Zers.)] was received. Recrystallize cleaned title product from methanol/ether resulted in 1.51 g [Fp.: 112 to 114°C (Zers.), m/e 201]. Example 61:5 - (4-Methoxy-3-thienyl) - oxazolidin-2,4-dion after the function of the example 15 1.3 g (5.5 mMol) of the product of example 60 and 1.7 g (17 mMo [) became tri ethyl amine converted in 50 ml tetrahydrofurane with phosgene 30 min with 0 to 5°C. The reaction mixture was agitated over night at ambient temperature. Slowly on 500 ml broken ice was extracted poured lp with three 50 valley portions of chloroform. The united organic layers were dried, filtered washed with salt solution, over water-free magnesium sulfate and restricted to dry ones. Recrystallizes from toluol resulted in 50] mg cleaned title product [Fp.: 120 to 122°C, eat (KBr) 1377, 1732, 1767, 1808 cm. I0 analysis for C8H70 LV: H computes: 45.06% 3.31% 6.57% found: 45,31 3.41% 6.85% example 62:3 - (4-Äthoxy-3-thienyl) - 2-trimethylsiloxyäthannitril after the function of the example 13 was converted 8.1 g (0.052 mol) 4-Äthoxy-3-thenaldehyd and 6.13 g (0.062 mol) Trimethylsilylcarbonitril into 300 ml ethers into presence of 50 mg zinc iodide into 18 g title product, a viscous oil; PNMB indicated the absence of the aldehyde - proton. Example 63: ethyl l hydroxy l (4-äthoxy-3-thienyl) - methancarboximidathydrochlorid using ethanol in place of methanol, otherwise however after the function of the example 60, 13 g of the product of example 62 in 9,23 g title connection [Fp became.: 126 to 128°C (Zers.)] converted. Example 64:5 - (4-Äthoxy-2-thienyl) - oxazolidin-2,4-dion with 1 h Einleiteh of phosgene with 0 to 5°C and a further response time of 1 h at ambient temperature 9.2 g of the product were converted from example 63 into the title product. For product isolation the reaction mixture was poured in 1,5 1 cut up ice and extracted with three 200 ml-portions of chloroform. The organic layers were combined and extracted with three 150 valley portions 1 n caustic soda solution. The basic excerpts were rewashed united with 200 ml fresh chloroform, acidified again with 3 n hydrochloric acid and extracted with three 200 ml-portions chloroform. The last three organic excerpts were dried, filtered combined, with salt solution washed, over magnesium sulfate, restricted to solids and the arrears from toluol crystallized, whereby 4.06 g became to receive title connection [Fp.: 144 to 146°C, m/e 227, IR (KBr) 1822, 1737, 1568 cm-*]. Analysis for CgHgO4 LV: C H N computes: 47,57 3.99% 6.17% found: 47.18% 4.04% 6.06% the chloroform rewashing liquid were re-extracted with three 150 ml-portions of more freshly 1 n caustic soda solution. These basic excerpts were combined, and additional product (980 mg, Fp.: 144 to 146°C) one won likewise. Example 6S: 2 - [4 (n-Propoxy) -3-thienyl] - 2-trimethylsiloxyäthannitrii after the function of the example 13 was converted 3.1 g (18 mMol) 4 (n-Propoxy) - 3-thenaldehyd and 2.28 g (2.9 valley, 23 mMol) Trimethylsilylcarbonitril into 250 ml ethers into presence of 50 mg zinc iodide into 4,6 g title product, an oil, 5 [m/e 269, IR (CH2 CI2) 2936, 1558 cm-l]. Example 66: ethyl l hydroxy l [4 (n-propoxy) - 3-thienyl] - methancarboximidathydrochlorid with a response time addition terminated of 20 min after was used the function of the example 63, around 4,5 g of the product of example 65 in 3,05 g title product [Fp.: to convert 127 to 129°C (Zers.)]. Example 67:5 - [4 (n-Propoxy) - 3-thienyl] - oxazolidin-2,4-dion after the function of the example 61 became 2.8 g (0.01 mol) of the product of example 66 in 1,63 g from Toluel recrystallized 5 [4 (n-Propoxy) - 3-thienyl] - oxazolidin-2,4-dion (Fp.: 134 to 136°C, m/e 241, IR (KBR) 1827, 1747, 1564 cm-*) converted. Example 68:2 - (4-Methoxy-2-methyl-3-thienyl) - 2-trimethylsiloxyäthannitril after the function of the example 13 5.2 g (33.3 mMol) were converted 4-Methoxy-2-m œ thyl-3-thenaldehyd and 3.96 g (40 mMol) Trimethylsilylcarbonitril into 350 ml ethers into presence of 50 mg zinc iodide into 7,3 g title product, in an isolated manner as viscous oil [m/e 255, IR (CH2 C12) 1575, 1204, 1075 cm. Example 69: Äthyl_l_hydroxy_l (4-methoxy-2-methyl-3-thienyl) - methancarboximidathydrochlorid the function of the example 63 was applied to 7,7 g product of example 68 for the production of 5,8 g of a mixture of the title connection and the appropriate Äthoxyäthers (it. PNMR about 40% methyl ether and 60% ethyl ethers, m/e 243 and/or 229). A part of this mixture 12.5 g) was taken up to 100 ml methanol and introduced on 0 to 5°C cooled and 1 h long hydrogen chloride gas. After 1 h further agitating with 0°C the reaction mixture was restricted to a viscous oil. Crystallize from ether resulted in 2.1 g title product [Fp.: 123 to 125°C (Zers.), m/e 229]. Example 70: Äthy - - (hydr XY) - 1 (4-äth xy-2-methy -3-thieny) - methanc rb ximidathydr CH rid a part that methyl/ethyl mixture ether of example 69 (2.5 g) to 100 ml ethanol was taken up and cooled on 0°C. Into the cold solution 1 h hydrogen chloride was introduced, 1 further h were agitated with 0°C and restricted to an oil. The oil by rubbing with ether one crystallized. Renewed mixing into a paste with in ethers supplied 2.07 g title product [Fp.: 105 to 107°C (Zers.), m/e 243]. 2s example V1: 5 (4--Methoxy-2-methy1-3-thienyl) - oxazolidin -2,4-dien with a response time of 3 1/2 h at ambient temperature, otherwise however after the function of the example 15, became 2.0 g (7.5 mr ol) of the product of example 69 in 0,52 g from toluol umkrista! lisiertes title product converted. [Fp.: 179 to 181°C, m/e 227, IR (KBr) 1820, 1750, 1727, 1583 cm-*]. Example 72:5 - (4-Äthoxy-2-methyl-3-thienyl) --oxazolidin-2,4-dien after the function of example 71 were converted 1.9 g of the product of the example 70 into 245 mg title product [Fp.: 136 to 138°C, m/e 241, IR (KBr} 1824, 1743 cm. Example 73:5 - (5-Chlor-7-benzo furany) - oxazoldin-2,4-dion I00 mg (0.39 mMol) title product of example 50 in 6 ml chloroform were suspended and 100 mg (0! 04 ml, 0.39 mMol) until (trimethylsilyl) - trifluoracetamid caused in a portion. After 1 min agitating 69 mg (0.39 mMol) were added N-Bromsuccinimid as well as a trace (only one crystal) to Benzoylperoxyd. The mixture was cooled 2 h at the return flow warmed up, on ambient temperature, filtered by unsolvable lugs and restricted to semisolid material under a nitrogen stream. The arrears were distributed between i n caustic soda solution and methyl acetate. The aqueous layer was washed separated, with fresh ethyl acetate, acidified with I n hydrochloric acid and extracted with three portions of chloroform. The chloroform excerpts were getroeknet, filtered combined, over water-free magnesium sulfate, restricted to an oil and 44 mg title product made of toluol crystallized (Fp.: 154 to 157°C, m/e 251/253). Mode of production i: 6-Hydroxychinolin-5-carbaldehyd g sodium hydroxide were solved in 35 ml water under cooling, ml chloroform were admitted to 5 g 6-Hydroxychinolin in 15 and the reaction mixture at the return flow (about 90°C) 12 h warmed up, whereby two further 15 ml-portions of chloroform were added, one after 2 h and the other one after 6 h. The reaction mixture was cooled and won raw product by filtering. The raw product was treated solved in 125 ml hot water, with activated charcoal, filtered, cooled hot and headed for and filtered with acetic acid, in order resulted in 2,5 g title product to (Fp.: 136 to 137°C, m/e 173, PNMR/CDCI3 the aldehyde proton shows at 10,5 ppm and aromatic protons with 7,2 to 9.4 ppm). Mode of production 2:6 - Methoxychinolin-5-carbaldehyd 1.7 g (9.8 mMol) of the product of the preceding mode of production in 85 ml acetone were brought together with 1,21 g (8.8 mMol) potassium carbonate. 0,83 ml (8.8 mMol) dimethyl sulfate was added and the mixture at ambient temperature 16 h was agitated. Further 0.34 ml (2.5 mMol) potassium carbonate and 0.23 ml (2.5 mMol) dimethyl sulfate was added and the mixture further 4 h at ambient temperature was agitated and then 3 h with 60°C. The reaction mixture was cooled on ambient temperature, filtered off salts and restricted the filtrate to dry ones. The arrears were washed 1mal with Wassen and 1mai taken up to ethyl acetate, successively with two portions 1 n ammonium hydroxide, with salt solution, over water-free magnesium sulfate; dried, filters and: - to Q, 78 G. title product restricted [Rf 0.35 (2: 1 ethyl acetate/chloroform), PNMR/CDCla/5 (ppm): 4,2 (s, 3H), 7.4-9.1 (m, 5H), RST, 3 (s, IH)]. Mode of production 8:7 - Hydroxychinolin-8-carbaldehyd after the function of mode of production 1 became 5 g 7-Hydroxychinolin in 3,3 g title product (Fp.: 127 to 130°C, m/e 173, PNMR/CDCI3 the aldehyde proton shows at 10,8 ppm, aromatic protons with 7 0 to 8.9 ppm) converted. Mode of production 4:7 - Methoxy-8-carbaldehyd after the function of mode of production 2 were converted 8.3 g (19 mMol) of the product of the previous mode of production into 2,1 g title product [PNMB/CDCI3 /5 (ppm): 4,1 (s, 3H), 7.5-9.0 (m, 5H), 11.2 (s, IH)]. Mode of production 5:6 - Chlorchroman g zinc sponge, 7.5 g mercury (II) chloride 125 ml water and 4 ml konz. Hydrochloric acid, 5 min was brought together vibrated and serves left and liquids from the received amalgamierten zinc was decanted. A mixture from 100 ml water and 126 ml konz. Hydrochloric acid and then the metal were added to 15 g 6-Chlor-4-chromanon and the mixture 1 1/2 h at the return flow was cooled cooked, on ambient temperature, by the zinc decanted and DEK-done with three portions ethers extracted. The united excerpts were dried, filtered over water-free magnesium sulfate and restricted to 14 g of an oil. The oil became at 400 g silicagel with hexane/ether 9:1, when Elutionsmittel under dünnschichtchromatographischer monitoring chromatographiert at 15 valley parliamentary groups. Pure product parliamentary groups were combined and restricted to 8.72 g title product, an oil, [PNMR (CDCI3/(ppm): 2,0 (m, 2H) 8 7 (t 2H), 4.1 (t, 2H), 6.9 (m, 3H), m/e 170/168, Rf 0.88 (2: 1 hexane/ether)]. Mode of production 6:6 - Chlorchroman-8-carbaldehyd 8.6 g (0.051 mol) product of the preceding mode of production in 75 ml dichloromethane were cooled in an ice/a Wasser-Bad. 19.34 g (11.2 valley, 0.101 mol) titanium tetrachloride were added and course-dripped then 6.2 g (0.054 mol) to 1,1-Dichlormethylmethyläther. The reaction mixture was agitated 30 min with 0°C and poured then slowly in 400 ml satisfied Natriumbicarbonatlösung. The aqueous phase was extracted with three fresh portions dichloromethane. The united organic layers were dried, filtered washed with salt solution, over water-free magnesium sulfate and restricted to 7.9 g Titelvsrbindung [Fp.: 83 to 86°C, PNMR/CDC13/(ppm): 2,0 (m, 2H), 2.8 (t, 2H), 4.2 (t, 2H), 7.1-7.5 (m, 2H), 10.2 (s, 1H), m/e 198/196]. Mode of production 7:6 - Fluorchroman after the functions of the mode of production 5 became 15 g 6-Fluor--4-chromanon in 5,7 g of chromatographiertes 6-Fluorchroman converted [oil, PNMR/CDC13/ö (ppm): 2,0 (m, 2H), 3.8 (t, 2H), 4.1 (t, 2H), 6.8 (m, 3H), Rf 0.68 - (2: 1 hexane/ether), m/e 152]. Mode of production 8:6 - Fluorchroman-8-carbaldehyd 59 after the functions of the mode of production 6 were converted 5.5 g (0.036 mol) product of the preceding mode of production into first Tietelprodukt isolated as viscous oil, which from hexane one crystallized (3.4 g, Fp.: 54 to 57°C, m/e 180). Mode of production 9:3 - Methyl-5-isoxazolcarboxamid g 3-Methyl-5-isoxazolcarbonsäure were agitated 10 h in 350 ml Thionylchlorid rüekflußgekocht, then at ambient temperature 16 h, clarified by filtering and restricted to an oil. The oil was restricted several times with hot hexane rubbed and the united hexane solutions, in order the Säurechlorid to receive (16.2 g to 21 g) as a solid. Under agitating so manufactured Säurechlorid (35 g) became by portion to 300 ml konz. Ammonium hydroxide at ambient temperature given. After i h granulating 24.2 g title product were won by filtering (Fp.: 180 to 182°C). Mode of production 10:3 - Methyl-5-isoxazolcarbonltril g product of the preceding mode of production were mixed thoroughly with 10 g Phosphorpentoxyd and brought on into an oil bath before-heated up on 140°C. The bath temperature was increased to 200°C and 2.9 g title product by distillation in the vacuum was won [IR (film): Nitrile gang with 2220 cm, no amide peak in the 1700 cm-X-range]. Mode of production ii: 3-Methyl-5-isoxazolcarbaldehyd 1.08 g (0.01 mol) product of the previous mode of production were solved into 25 ml ethers and cooled on -40°C. 12 ml (1-molar in hexane, 0.012 mol) Diisobutylaluminiumhydrid were admitted with -40°C during 15 min. The mixture was agitated with -30 to -35°C 10 min. Under stops of the temperature with -20°C 60 was added ml ethyl acetate. With -25°C 15 was course-dripped ml methanol and with -20°C 3 ml 6 n hydrochloric acid. The reaction mixture was warmed up to 5°C and the organic phase was washed with 25 ml water and restricted to an oil. The oil became at 50 ml silicagel with 1: 1 ether/hexane as Elutionsmittel chromatographiert. Product parliamentary groups were combined and restricted to 0.42 g title product (Fp.: 39 to 41°C). A small sample, by sublimating further cleaned, had a Fp.: from 43 to 45°C. Mode of production 12:5 - Chlorbenzo furan-2-carbonsäure 31.3 g (0.2 mol) 5-Chlorsalicylaldehyd were solved in 200 ml 2-Butanon. 82.9 g (0.6 mol) potassium carbonate and then 95.5 g (0.4 mol) Diäthyl-2-brommalonat were admitted and the mixture 5 h at the return flow was warmed up, cooled then, filtered off by salts and restricted to an oil. The OIL was distributed between 500 ml 10%iger sulfuric acid and 500 ml ethers. The aqueous layer was extracted with two 250 valley portions of fresh ether. The united organic layers were dried, filtered washed with salt solution, over water-free magnesium sulfate and restricted to a second oil. The second oil was loosened in 400 ml 10%iger äthanolischer caustic potash solution, 1 h at the return flow and restricted to solids was warmed up. The solids were filtered solved in 1 00 ml water, by insoluble substance-pure, acidified with 6 n hydrochloric acid and won precipitated solids by filtering. 19 g cleaned title product were received by renewed mixing into a paste with of the solids in 1 1 water (Fp.: 259 to 262°C, m/e 198/196}. Mode of production 13:5 - Chlorbenzo furan 7.8 g connection of the preceding mode of production were brought together with 700 mg copper powders and 50 ml Chinolin and the mixture 50 min at the return flow was warmed up, cooled then to ambient temperature and diluted with 500 ml ethers. Insoluble was filtered off and the filtrate was washed successively with five 200 valley portions of 2 n hydrochloric acid and 1mal with salt solution, dried over water-free magnesium sulfate and restricted to 6.2 g oil. The oil was chromatographiert by 200 g silicagel with ether as Elutionsmittel at 300 valley parliamentary groups. The parliamentary groups 1 and 2 were combined and restricted to 6.1 g title product, an oil. Mode of production 14:5 - Chlor-2,3-dihydrobenzo furan 12.2 g (5%) Pd/C in 400 ml acetic acid were before-hydrogenated with atmospheric pressure and 25°C. 6.1 g title product of the preceding mode of production in 100 ml acetic acid were added and the hydrogenation was continued, until somewhat more than 1 equivalent hydrogen was used up. The catalyst was filtered off over Diatomenerde. The filtrate was neutralized with satisfied potassium carbonate solution and extracted with four 200 valley portions of ether. The united excerpts were dried, filtered washed with salt solution, over water-free magnesium sulfate and restricted to an oil. The oil was chromatographiert at 400 g silicagel with Hexan/3% ether as Elutionsmittel under dünnschichtchromatographischer monitoring at 15 valley parliamentary groups. The pure product parliamentary groups 70 to 90 were combined and restricted to 2.15 g title connection [oil, Rf 0.32 (hexane), m/e 156/154]. Mode of production 15:5 - Chlor-2,3-dihydrobenzo furan -7-carbaldehyd after the function of the mode of production 6 were converted 2.1 g connection of the preceding mode of production into with isomers aldehyde polluted raw product. 0.93 g cleaned title product were received to simmering hexane, filtering and cooling of the filtrate by digesting the raw product in 50 ml [Fp.: 79 to 81°C, Rf 0.55 (chloroform), m/e 184/182]. Mode of production 16:3 - Furaldehyd 19.6 g (0.2 mol) 3-Furylmethanol dripped in 50 ml dichloromethane to a mash ven 64.5 g (0.3 mol) Pyridiniumchlorchromat in 450 ml dichloromethane. The exotherms reaction, which led to violent return flow, by occasional cooling with a Eishad one steered. After min had themselves resin-like determine separated. The reaction mixture was diluted with 600 ml ethers and the supernatant liquid by a combination was separated from decanting and filtering. The filtrate was led by synthetic Magnesiumsilikat (Florisil) in a short column, whereby ether served as Elutionsmittel. Caught parliamentary groups were combined and restricted to an oil. Distillation of the oil supplied 7.6 g 3-Furaldehyd (kp.: 68 to 72°C/5320-5985 Pa). Alternatively this aldehyde is made after the rose mouth reaction of 3-Furancarbonsäurechlorid (Hayes, J. to. Chem. seconds. 71, 2581). Mode of production 17:2 - (2-Fury!)- l, 3-dioxolan 42 ml (0.5 mol) 2-Furaldehyd, 50 ml (0.9 mol) ethylen glycol and about 200 mg p-Toluolsulfonsäure were brought together in 150 ml toluol and the mixture 6 h was return flow-cooked, whereby by-product water in a Dean strong case was collected. The mixture was cooled, diluted with 500 ml ethers and clarified by filtering. The filtrate was washed with 200 ml satisfied Natriumbicarbonatlösung and the organic phase by filtering was clarified again. This second filtrate was washed with 200 ml water and the organic layer to dry ones was restricted, whereby 45 g 2 (2-Furyl) - l, 3-dioxolan, an oil became to receive. Mode of production 18:2 - (5-Chlor-2-furyl) - l, 3-dioxolan 14 g (0.1 Mel) 2 (2-Furyl) - l, 3-diexolan were solved in 100 ml tetrahydrofurane and cooled the solution on -25 to -20°C. In this temperature range 45 ml (2,2-molar, 0.1 mol) Butyllithium in hexane were added during 10 min. The mixture could warm up during 25 min to 0°C and to -30°C was cooled. Under keeping a temperature range from -30 to -25°C 23.7 g (0.1 mol) were admitted hexadecimal chlorine ethane in 50 ml to tetrahydrofurane during min. The reaction mixture was warmed up to ambient temperature, 1 1/2 h was agitated, cooled again on 5°C and diluted slowly with 500 ml water. The product was extracted in ether (2 X.500 valley) and as oil (15.8 g) won by restricting to dry ones. The oil became at 200 ml silicagel with hexane/ethyl acetate, 8: 1, when Elutionsmittel under dünnschichtchromatographischer monitoring at silicagel with the same Elutionsmittel chromatographiert. The early predukthaltigen parliamentary groups were combined and restricted to 5 g cleaned 2 (5-Chlor-2-furyl) - -1,3-dioxolan as oil [Rf 0.6 (8: 1) hexane/ethyl acetate)]. Mode of production 19:5 - Chlor-2-furaldehyd 4.8 g 2 (5-Chlor-2-furyl) - l, 3-dioxolan were solved into 20 ml ethers. 10 ml 6 n hydrochloric acid was added and the two-phase mixture 1 h at ambient temperature was agitated. The ether phase was separated, washed with wet and restricted to 2.8 g 5-Chlor-2-furaldehyd, an oil. Mode of production 20:5 - Brom-2-furylcarboxamid g 5-Brom-2-furancarbonsäure were isolated 3 h with 60 ml Thionylchlorid at the return flow cooked s0 and the appropriate Säurechlorid as oil by restricting. The acid chloride reached 150 ml agitated konz. Ammeniumhydroxyd dripped. Filter supplied 17.0 g 5-Brom-2-furylcarboxamid (Fp.: 140 to 143°C), mode of production 21:5 - Brom-2-furylcarbonitril g 5-Brom-2-furylcarboxamid were zusammengebraeht with 50 ml Phosphoroxychlorid and for 24 h at the return flow were cooked. The mixture was poured on ice and the product in ethers was extracted, which resulted in 6.4 g 5-Brom-2-furylcarbonitril, in the case of restricting an oil. Mode of production 22:5 - Brom-2-furaldehyd 2.3 g (13 mMol) 5-Brom-2-furylearbonitril were solved into 50 ml ethers and cooled under nitrogen on 10°C. 1.9 g (13 mMol) Diisobutylaluminiumhydrid as 25 0 ige solution in toluol were course-dripped, whereby the temperature close -10°C was held. The reaction mixture could warm up to ambient temperature and to about 6 h was agitated. It was acidified on 0 to 5°C cooled, with 1 ml methanol diluted, with 8 n hydrochloric acid, washed with water and restricted to 1.2 g 5-Brom-2-furaldehyd (Fp “: 74 to 76°C). Mode of production 23:3 - Brom-2-furaldehyd 6.5 g (70 mMol) PhosphoroxychIorid were given to 5.4 g (70 mMol) dimethylformamide with 0 to 10°C. That up-all-ends mash with 10 ml Dichloräthylen was diluted. At a temperature close 10°C was shifted the mixture with 9,2 g (63 mMol) 3-Bromfuran. The Reaktionsgemiseh was warmed up 1 h to 58 to 60°C and rüekgekühlt then on 10°C. 15 g Natriumaeetattrihydrat, solved in 25 ml water, were admitted slowly under good agitating, whereby the temperature was held with 10 to 30°C. The mixture was warmed up again to 68 to 72°C 20 min, cooled to ambient temperature and diluted with 20 ml water. The product was extracted into 75 ml ethers and the ether with water and restricted to 0.9 g 3-Brom-2-furaldehyd, was rewashed an oil. [Rf 0.65 (3: 1 hexane/ethyl acetate)]. Mode of production 25:5 - Phenyl-2-thenaldehyd 1.6 g (0.01 mol) 1-Phenylthiophen (manufactured after J. to. Chem. Soc. 46, 2339 1924) was solved in 20 ml tetrahydrofurane and cooled with -40°C. 4,5 ml (2,2-molar) Butyllithium in hexane were added during 3 min, whereby the temperature was held with -40 to -30°C. The mixture was warmed up to 0°C and cooled then on -40°C. 1,2 ml (15 mMol) dimethylformamide was admitted, whereby the temperature was held with -40 to -39°C. The mixture was warmed up to ambient temperature and 1/2 h thereby was held, deterred again 0°C down-cooled, with 6 ml 6 n hydrochloric acid, diluted with 10 ml water and extracted with 20 ml ethers. Evaporate the ether excerpt to dry ones resulted in 1.9 g raw product. Recrystallize out about ml hexane supplied 0.9 g cleaned S-Phenyl-2-thenaldehyd (Fp.: 90 to 92°C). Mode of production 26:4 - Brom-3-thenaldehyd g (0.062 mol) 3,4-Dibromthiophen (J. Org. Chem. 36, 2690) into 20 ml ethers was cooled on -70°C and 34.8 ml (2,1-molar, 0.073 mol) Butyllithium in hexane during 5 min were course-dripped. After 5 min agitating with -70°C was transferred the solution by a PP hose (nylon) under Stiekstoffdruck into a solution by 6,8 g (0.093 mol) dimethylformamide into 35 ml ethers. The received mixture was dried, filtered 2 h at the return flow warmed up, on ambient temperature cooled, successively washed with two portions of 1 n Salusäure, 1mal with satisfied Natriumbiearbonatlösung and 1mal with salt solution, over water-free magnesium sulfate and restricted to an oil. The oil was distilled 2mal, whereby 5.7 g 4-Brom-8-thenaldehyd became to receive BS (kp.: 81 to 84°C/! 06.4 Pa, m/e 192/190). Mode of production 27: Methyl-4-methoxy-8-thenoat g Methyl-4-acetoxy-8-thenoat (US-PS Nr.3, 144.285) were solved in 20 ml methanol and given to 100 ml methanol, the 0.31 ml konz. Sulfuric acid contained. The mixture was cooked 4 days at the return flow, neutralized then with 0,6 g Natriumacetat and the solvent: evaporated. The arrears were taken up to 200 ml ethers. The ether solution was getroeknet, filtered successively washed with two 50 valley portions water, two 50 valley portions of 1 n caustic soda solution and two 50 valley portions of salt solution, over water-free Maguesiumsulfat and restricted to 4.85 g of an oil, which crystallized when standing (Fp.: 64 to 66°C). One regenerated after only one day, only a small yield of the desired product (2.2 g) became isolated. The two 1 n caustic soda solution excerpts were combined and acidified, which led to the precipitation of 5,13 g Methyl-4-hydroxy-3-thenoat. As this alcohol in 100 ml methanol, the 0.3 ml konz. Sulfuric acid contained, was solved and three days at the return flow cooked, supplied the above processing 2.10 g title product (Fp.: 64 to 66°C). Mode of production 28:1 - (4-Methoxy-3-thienyl) - methanol 3.9 g (23 mMol) Methyl-4-methoxy-3-thenoat (US-PS Nr.4, 144.235) were solved in 50 ml toluol and cooled in an acetone/a dry ice bath. 46 ml (1-molar in hexane, 46 mMol) DiisobutyllO aluminum hydride were course-dripped during 30 min. The mixture was agitated further 2 h at the bath temperature and could warm up then to ambient temperature. At a temperature under 30°C 14.7 g (18.6 valley, 0.46 mol) were slowly admitted to methanol. The mixture was then agitated 16 h at ambient temperature, on which a granular precipitation had formed. The mixture was filtered over Diatomeenerde, whereby with methanol one washed. Filtrate and washing liquids were combined and restricted to 2.8 g title product, an oil, (m/e 144). Mode of production 29” 4-Methoxy-3-thenaldehyd 6.4 g (29.7 mMol) Pyridiniumchlorchromat were solved in 100 ml dichloromethane and given in a portion to a solution from 2,8 g (19.8 mMol) of the product of the previous mode of production, likewise in 100 ml dichloromethane. The reaction mixture was agitated at ambient temperature 3 h, diluted with 200 ml ethers and decanted by the black precipitation. The precipitation was washed with two 100 valley portions of ether. DEK-done and the washing liquids were combined and filtered, washed successively with two portions of 1 n hydrochloric acid, a portion water, two portions of 1 n caustic soda solution and a portion of the salt solution, dried, filtered over water-free magnesium sulfate and restricted to 2.6 g title connection, an oil, [m/e 142, IR (CH2 C12) 1688, 1544 cm-*]. Mode of production 30: Äthyl-4-äthoxy-3-thenoat for instance after the function of the US-PS Nr.4, 144.235 were solved 20 g Methyl-4-acetoxy-3-thenoat in 240 ml ethanol and 0.62 ml konz. Sulfuric acid added. The reaction mixture was held for 79 h under weak return flow, neutralized then with 1,2 g Natriumacetat and restricted to an oil. The latter was distributed between 400 ml ethers and 50 ml water. The organic layer was separated and dried, filtered successively washed with 75 ml water, three 50 valley portions of 1 n caustic soda solution and two 75 valley portions of salt solution, over water-free magnesium sulfate and restricted to 14.9 g title product, an oil, (PNMR does not indicate only ethyl ester, Methylester). Mode of production 31:1 - (4-Äthoxy-3-thienyl) - methanol after mode of production 28 14 g of the product of the previous mode of production were converted into 9,15 g title product, an oil. 4Q mode of production 32:4 - Äthoxy-3-thenaldehyd after mode of production 29 were converted 9.15 g of the product of the previous Nerstelhngsweise into 8,18 g title product, isolated first as oil, which crystallized when cooling rapidly [Fp.: 42 to 45°C, m/e 156, IR (KBr) 3090, 2977, 1688 cm-l]. Mode of production 33: n-Propyl-4 (n-propoxy) - 3-thenoat after mode of production 30 became with a return flow time of 10 days 6 g Methyl-4-acetoxy -3-thenoat in 750 ml 1-Propanol, the 0.19 ml konz. Sulfuric acid contained, in 5,4 g title product, an oil, converted (m/e 228). Mode of production 34:1 - [4 (n-Propoxy) - 3-thienyl] - methanoI 5D after Herstllungsweise 28 were reduced 5.4 g of the product of the previous Nerstellungsweise to 3.44 g title connection, in an isolated manner as oil (m/e 172). Mode of production 35:4 - (n-Propoxy) - 3-thenaldehyd after mode of production 29 3.34 g of the product of of the preceding mode of production were converted into 3,19 g title connection [m/e 170, IR (CH2 C12) 1689, 1539 cm-*]. Mode of production 36: Äthy! - 4-methoxy-2-methyl-3-thenoat 7.8 g Äthyl-4-hydroxy-2-methyl-3-thenoat (chem. Ber. 48, 593) became with 600 ml methanol and 0.25 ml konz. Sulfuric acid brought together and 21 h at the return flow cooked. The reaction mixture was washed to an oil to an oil restricted, into 500 ml ethers taken up, with two 50 ml-portions of 1 n caustic soda solution and then lmal with salt solution, over water-free Maguesiumsulfat dried and restricted to 7.8 g title product, (m/e 200, PNMR/CDC13: Singlet: OCH3-Protonen with 8,9 ppm). The product is polluted with a small portion of the appropriate Methylesters.