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41. 发明专利

FR1283510A 未知
公开(公告)号：FR1283510A
公开(公告)日：1962-02-02
申请号：FR854936
申请日：1961-03-08
申请人： BASF AG
发明人： BERDING CHRISTOPH , BECKMANN WILHELM , CROISSANT KARL , SCHWETER WALTER , REIS HERMANN , KUTEPOW NIKOLAUS VON
IPC分类号： B01J19/00 , C07C2/48

42. 发明专利

GB868324A Improvements in the isomerization of saturated aliphatic carboxylic acids 未知
公开(公告)号：GB868324A
公开(公告)日：1961-05-17
申请号：GB2614159
申请日：1959-07-30
申请人： BASF AG
发明人： ILLING GERHARD , KUTEPOW NIKOLAUS VON
IPC分类号： C07C51/353
摘要： Saturated aliphatic mono- and di-carboxylic acids having at least 4 carbon atoms are isomerised by heating them with carbon dioxide at temperatures between 150 DEG and 300 DEG C., preferably under a pressure between 20 and 700 atmospheres, in the presence of (a) a metal carbonyl and (b) chlorine, bromine, iodine and/or one or more compounds of one or more of these halogens, and preferably (c) a compound of bismuth, antimony, titanium, boron, tin or iron as an activator and (d) water. Suitable metal carbonyls are those of the 6th, 7th or 8th Group of the Periodic System, e.g. palladium, vanadium, chromium, iron, cobalt and nickel. The carbonyls may be introduced as such or formed in situ from a hydroxide, oxide, carbonate, acetate, chloride, bromide or iodide. Suitable halogen compounds are the compounds of the halogens with each other, alkyl and aryl halides, halogen hydracids and their salts. The activators may be the oxides, chlorides, bromides or iodides of the specified elements. Suitable activators are bismuth oxide, antimony oxide, bismuth iodide, antimony bromide, hexachlorostannic (IV) acid, trichloro-tri-iodo-antimonic (III) acid, hexachlorotitanic (IV) acid, trichlorotriiodoferric (III) acid and the partial hydrolysis products of said halogen acids. The activator may be supported on activated carbon, pumice or silica gel. If the activator is a compound containing chlorine, bromine or iodine it is not necessary to employ additional halogen or halogen compound. In Examples, (1) adipic acid is isomerized yielding 2-methylglutaric acid and small amounts of 2,3-dimethylsuccinic acid, 2-methylbutyric acid and valeric acid; (2) suberic acid yields a -methylpumelic acid; (3) sebacic acid yields 2-methylazelaic acid; (4) n-valeric acid yields 2-methylbutyric acid; (5) 2-methylbutyric acid yields n-valeric acid. The isomers are esterified with methanol and the mixture separated by distillation; (6) adipic acid is isomerized and the products are esterified with methanol in the presence of lead oxide and sulphuric acid to yield 2-methyl butyric acid methyl ester, methyl n-valerate, 2-methyl glutaric acid ester and dimethyl adipate and the products are separated by distillation.

43. 发明专利

FR1232721A 未知
公开(公告)号：FR1232721A
公开(公告)日：1960-10-11
申请号：FR802303
申请日：1959-08-07
申请人： BASF AG
发明人： MOELL HANS , KUTEPOW NIKOLAUS VON
IPC分类号： C07C23/14

44. 发明专利

FR1231981A 未知
公开(公告)号：FR1231981A
公开(公告)日：1960-10-04
申请号：FR801194
申请日：1959-07-27
申请人： BASF AG
发明人： ILLING GERHARD , KUTEPOW NIKOLAUS VON
IPC分类号： C07C51/353

45. 发明专利

GB803778A Production of n-(hydrocarbon substituted) aminocarboxylic acids, their esters or salts 未知
公开(公告)号：GB803778A
公开(公告)日：1958-10-29
申请号：GB3571656
申请日：1956-11-22
申请人： BASF AG
发明人： REPPE WALTER , KUTEPOW NIKOLAUS VON , HOHENSCHUTZ HEINZ
摘要： The invention comprises reacting an aminocarboxylic acid, its esters with a monohydric aliphatic, cycloaliphatic or araliphatic alcohol, or its salts with alkali or alkaline earth metals such compounds containing at least one hydrogen attached to nitrogen, with CO, an olefinic hydrocarbon and water at room temperature or above and increased pressure, in the presence of iron or cobalt carbonyl or carbonyl hydride or an ammonium or amine salt, especially tertiary ring-combined amine salts, of such carbonyl hydrides, to produce N-(hydrocarbon substituted) aminocarboxylic acids, esters or salts, the molar ratio of CO to olefine being 2:1 to 5:1, preferably 3:1. The preferred temperatures and pressures are 80-160 DEG C. and 5-500 atmospheres, more preferably 10-200 atmospheres, and the preferred catalyst is iron pentacarbonyl. Suitable amino carboxylic acids include aliphatic monobasic acids with 2 to 6 C atoms, such as glycocoll, a -alanine, serine, valine and leucine; aliphatic dibasic acids such as glutamic and aspartic acids; acids containing two amino groups, such as ornithine and lysine; heterocyclic acids such as proline and hydroxyproline; aromatic acids, such as aminobenzoic, N - methylaminobenzoic, N - ethylaminobenzoic and aminonaphthoic acids. Suitable olefinic hydrocarbons include open chain monounsaturated olefines such as ethylene, propylene, n-butylene, iso-butylene, octylene, dodecylene, octadecylene; cyclic olefines such as cyclohexene and cyclo-octene; araliphatic olefines such as styrene; and diolefines such as butadiene, isoprene, dimethylbutadiene, hexanediene-(2,5) and piperylene. The addition of solvents, such as alcohols, hydrocarbons, esters, lactams and carboxylic acid amides is advantageous; in particular when reacting aminocarboxylic acid esters, it is advantageous to use the alcohol which constitutes the alcoholic component of the esters. The reaction is preferably carried out at alkaline pH, but may be carried out at neutral or slightly acid pH; in this last case the use of formic acid is preferred. The process may be continuous or discontinuous. Examples describe the reaction of a -alanine with ethylene, leucine with ethylene, d,l-proline with ethylene, p-aminobenzoic acid ethyl ester with propylene, anthranilic acid with ethylene and 3-amino-2-naphthoic acid with ethylene. The products are N-substituted by a group containing one carbon atom more than the olefine.

46. 发明专利

GB1125158A Carbonylation of olefinically or acetylenically unsaturated compounds 未知
公开(公告)号：GB1125158A
公开(公告)日：1968-08-28
申请号：GB5357465
申请日：1965-12-17
申请人： BASF AG
发明人： KUTEPOW NIKOLAUS VON , BITTLER KNUT , NEUBAUER DIETER , REIS HERMANN
IPC分类号： C07C51/14 , C07C51/58
摘要： 1,125,158. Carbonylation of unsaturated compounds. BADISCHE ANILIN- & SODAFABRIK A.G. 17 Dec., 1965 [19 Dec., 1964], No. 53574/65. Heading C2C. In a process for preparing carboxylic acids, esters or halides by reacting olefinically unsaturated compounds with carbon monoxide and water, or alcohol, or phenol, or a halogen halide, or by reacting acetylenically unsaturated compounds with carbon monoxide and a hydrogen halide, at elevated temperature and superatmospheric pressure in the presence of a palladium catalyst, the catalyst reused may be a solution obtained from the residue of the distillation and/or extraction of the acid constituents by alkaline reacting substances, of the reaction mixture, to which is added an organic phosphine. Phosphines mentioned are triarylphosphines and tricycloalkylphosphines. Examples describe the preparation of cyclododecadiene-(5,9) - carboxylic - (1) - carboxylic acid and the methyl and ethyl esters thereof and propionyl chloride in which the palladium catalyst is reused with the addition of organic phosphine.

47. 发明专利

GB1123018A Production of unsaturated lactones having a five-membered ring 未知
公开(公告)号：GB1123018A
公开(公告)日：1968-08-07
申请号：GB5357365
申请日：1965-12-17
申请人： BASF AG
发明人： KUTEPOW NIKOLAUS VON , MEIER FRITZ , NEUBAUER DIETER
IPC分类号： C07C51/14 , C07C51/54 , C07D315/00
摘要： Unsaturated g -lactones are prepared by reacting olefins with CO at elevated temperature and superatmospheric pressure, in presence of either (a) 0.01-20 wt. per cent (based on olefin) Pd and 0.2-150 parts (based on wt. of Pd) HX (X = halogen) or (b) 0.01-20 wt. per cent (based on olefin) Pd-halide, and optionally HX; the amount of HX used in either alternative not exceeding 20 mole per cent of the olefin. Ethylene gives a mixture of products of formulae which may be hydrogenated to g -caprolactone. The use of propylene, mixed butylenes and butadiene is also exemplified; other starting materials mentioned are butene-1, 2-ethylhexene-1, allyl chloride, ethyl crotonate and acrylonitrile.

48. 发明专利

FR1476301A 未知
公开(公告)号：FR1476301A
公开(公告)日：1967-04-07
申请号：FR57979
申请日：1966-04-18
申请人： BASF AG
发明人： KUTEPOW NIKOLAUS VON , BITTLER KNUT , MEIER FRITZ , NEUBAUER DIETER
IPC分类号： C07C51/145

49. 发明专利

GB1043143A Production of open chain oligomers of 1,3-dienes 未知
公开(公告)号：GB1043143A
公开(公告)日：1966-09-21
申请号：GB2964563
申请日：1963-07-26
申请人： BASF AG
发明人： SEIBT HUBERTUS , KUTEPOW NIKOLAUS VON
IPC分类号： B01J31/16 , B01J31/18 , B01J31/24 , C07C2/40
摘要： Open chain dimers of 1,3-diolefins are obtained by dimerizing the diene in the presence of a catalyst containing zero valent nickel and a compound of trivalent phosphorus, arsenic or antimony and in the presence of at least an equimolar amount with reference to nickel of a non-aromatic organic hydroxyl compound, i.e. one wherein the hydroxyl is attached to an aliphatic or cycloaliphatic carbon atom. The catalysts are conventional and may also contain carbon monoxide, an olefin, an acetylene or an a ,b -olefinically unsaturated aldehyde or nitrile and may be formed in situ from a nickel compound, reducing agent and electron donor. Amounts of 0.001-1% by weight calculated as nickel based on diene are used. The hydroxyl compound may contain 1-15 carbons and is preferably saturated and may also contain alkoxy groups, e.g. methanol, ethanol, propanols, butanols, 2-ethylhexanol-1,crotyl alcohol,cyclohexyl carbinol, cyclohexanol, cyclo-octanol, benzyl alcohol, b -phenylethyl alcohol, lauryl alcohol, cinnamyl alcohol or methyl or butyl glycol. The alcohol is preferably used as solvent also being used in molar amounts of 2-5 times nickel; alternatively a hydrocarbon solvent is added. A phenolic or amine polymerization inhibitor may be added. Reaction is effected at 0-250 DEG C. and up to 20 atmospheres gauge. Catalysts containing phosphites yield from butadiene mainly octatriene-1,3,6, those containing phosphines octatriene-1,3,7, and those containing phosphorous acid triamides octatriene-2,4,6.ALSO:3 - (But - 2 - enyl) - 4,5 - diacid anhydridecyclohexene-1 is obtained by a Diels-Alder condensation of octatriene-1,3,6 with maleic anhydride. The di-n-butyl ester of the acid is produced on reacting the anhydride with n-butanol in the presence of hydrochloric acid. The ester is used as a plasticizer.

50. 发明专利

FR1460266A 未知
公开(公告)号：FR1460266A
公开(公告)日：1966-06-17
申请号：FR42575
申请日：1965-12-16
申请人： BASF AG
发明人： KUTEPOW NIKOLAUS VON , MEIER FRITZ , NEUBAUER DIETER
IPC分类号： C07C51/14 , C07C51/54 , C07D315/00

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