公开(公告)号：CA739995A

公开(公告)日：1966-08-02

申请号：CA739995D

Applicant: BASF AG

Inventor： POMMER HORST ,  STILZ WALTER

公开(公告)号：GB1024483A

公开(公告)日：1966-03-30

申请号：GB1361463

申请日：1963-04-05

Applicant: BASF AG

Inventor： WITTIG GEORG ,  STILZ WALTER ,  POMMER HORST

IPC: C07C45/00 ,  C07C45/51 ,  C07C47/20

Abstract: a ,b -Unsaturated aldehydes or ketones are made by a process which comprises reacting an adldehyde or ketone with a Schiff's base in the presence of or after previous addition of a hydroxide, an amide or alcoholate of an alkali or alkaline earth metal, or an alkali or alkaline earth organo metallic compound, and preferably in the absence of water, the reaction product being first dehydrated and then hydrolysed in a known manner, preferably without first being isolated, or vice versa, or simultaneously, said Schiff's base being obtained from the condensation of an aldehyde or ketone having at least one methyl or methylene group adjacent to the carbonyl group, with a primary amine. The preferred aldehyde or ketone used as starting material has at least one double bond in conjugation with carbonyl group, or further the Schiff's base contains in its aldehyde or ketone grouping a double bond in conjugation to the CN group. Both the aldehydes or Schiff's bases may contain two carbonyl or two C = N groups in the molecule. Particularly suitable Schiff's bases are formed by acetaldehyde, propionaldehyde, crotonaldehyde, beta-methylcrotonaldehyde and acetone as one reactant, and cyclohexylamine as the other reactant. Suitable organometallic compounds are, for example, methyl lithium, phenyl lithium, phenyl sodium, alkali metal acetylides and Grignard compounds. Of the numerous other condensing agents listed typical are lithium amide, sodamide, and lithium piperidide. Suitable solvents for the reaction include ethers, hydrocarbons, both aliphatic and aromatic, liquid ammonia, dimethylformamide, N-methylpyrrolidone and dimethylsulphoxide. A long list of named aldehydes and ketones which may be used as starting materials include formaldehyde, acetaldehyde, acetone, methoxyacetone, citral, vitamin A aldehyde, beta-ionine, glyoxal, maleindialdehyde. In Example 1 cinnamaldehyde is prepared by condensing ethylidinecyclohexylamine with benzaldehyde using lithium di-isopropyl amide in ether, and hydrolysing the intermediate with sulphuric acid. Example 2 described the condensation of benzophenone with ethylidenecyclohexylamine using methyl lithium, the isolation of N - (3,3 - diphenyl - 3 - hydroxypropylidene) - cyclohexylamine and its subsequent conversion to beta-phenylcinnamaldehyde. Other intermediates prepared in this example include N-(3,3-diphenyl - 3 - hydroxy - 2 include N-(3,3-diphenyl - 3 - hydroxy -2 - methylpropylidine) - cyclohexylamine from benzophenone and propylidene cyclohexylamine, N - (5,5 - diphenyl - 5 - hydroxypentene-(2) - ylidene - (1) - cyclohexylamine from benzophenone and crotylidenecyclohexalamine, N -(3 - phenyl - 3 - hydroxypropylidene) - cyclohexylamine from benzaldehyde and ethylidenecyclohexylamine, N - [5 - (21,61,61 - trimethylcyclohexene - (11) - yl - (11) - 3 - methyl - 3 -hydroxypentene - (4) - ylidene - (1)] - cyclohexylamine from beta - ionone and ethylidenecyclohexylamine and N - (3 - phenyl - 3 - hydroxybutylidene - (1)) - cyclohexylamine from acetophenone and ethylidenecyclohexyl amine. The condensation of beta-ionone with ethylidenecyclohexylamine followed by hydrolysis and dehydration yields beta-ionylideneacetaldehyde, ethylidenecyclohexylamine condensed with cyclohexanone after hydrolysis and dehydration of the intermediate beta-[11-hydroxycyclohexyl - (11)] - ethylidene - cyclohexylamine gives cyclohexylideneacetaldehyde, and ethylidenecyclohexylamine condensed with acetophone and subsequently hydrolysed and dehydrated gives beta-phenylcrotonaldehyde. Named products include 6-methyl-octatrien - (3,5,7) - one(2), b -ionone, and cyclocitral.

公开(公告)号：CA726774A

公开(公告)日：1966-01-25

申请号：CA726774D

Applicant: BASF AG

Inventor： WITTIG GEORG ,  POMMER HORST ,  STILZ WALTER

公开(公告)号：FR1391323A

公开(公告)日：1965-03-05

申请号：FR969197

申请日：1964-03-31

Applicant: BASF AG

Inventor： WITTIG GEORG ,  STILZ WALTER ,  POMMER HORST

IPC: C07C45/51 ,  C07C47/20 ,  C07C49/20

公开(公告)号：GB960472A

公开(公告)日：1964-06-10

申请号：GB3765561

申请日：1961-10-20

Applicant: BASF AG

Inventor： STILZ WALTER ,  POMMER HORST ,  SCHMIDT FRANZ ,  BICZYSKO HANS ,  FESSMANN HEINZ

IPC: C08K5/04

Abstract: A mixture stabilized against heat and light comprises 99.99 to 95% by weight of a linear polyamide, polyurethane or polyurea and 0.01 to 5% by weight of a bis-styryl benzene or a stilbene, each of which bears 1 to 5-OR radicals attached directly to the benzene nuclei, R being hydrogen, an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, an aralkyl group with 7 to 10 carbon atoms or -(CH2)n-owhere n is an integer from 1 to 4 and the oxygen atoms are attached in the o-position. Many polymers and stabilizers are specified. In the examples: (1), (2), (3), (7), (9) and (13) hexamethylene diammonium adipate and e -caprolactam are co-polymerized in the presence of:-(1) and (3) 3:4-methylene-dioxy-41-carbomethoxystilbene; (3) 3-methoxy-4-hydroxy-41-carbomethoxystilbene; (7) (a) 1:4-bis-(31:41-methylene dioxystyryl) benzene; (b) 1:3-bis(31:41-methylene dioxystyryl) benzene; (c) 1:4-bis(4-a -tetrahydrofuranyloxystyryl) benzene; (d) 1:4-bis(4-hydroxystyryl) benzene; (9) 1:4-bis(31:41\h -methylene dioxystyryl) benzene and (13) 1:2-bis-(3:41-methylene-dioxystyryl) benzene. In the remaining examples: (4)3:4-methylene dioxy-31-carbomethoxystilbene is mixed with polycaprylic lactam; (5) 3:4-methylene dioxy-31-carbomethoxystilbene is mixed with polyhexamethylene adipamide; (6) 3:4-methylene dioxy-31-carbomethoxystilbene is mixed with polyo -aminoundecanoic acid; (8) 1:4-bis(31:41-methylene dioxy-b -cyano-styryl) benzene is mixed with poly-e -caprolactam; (10) 1:4-bis-(31:41 -methylene-dioxystyryl) benzene is mixed with polycapryllic lactam; (11) 1:4-bis-(31:41-methylene dioxystyryl) benzene is mixed with polyhexamethylene adipamide and (12) 1:4-bis-(31:41-methylene dioxystyryl) benzene is mixed with polyo -aminoundecanoic acid.

公开(公告)号：CA676352A

公开(公告)日：1963-12-17

申请号：CA676352D

Applicant: BASF AG

Inventor： FESSMANN HEINZ ,  BICZYSKO HANS ,  POMMER HORST ,  STILZ WALTER

公开(公告)号：CA675377A

公开(公告)日：1963-12-03

申请号：CA675377D

Applicant: BASF AG

Inventor： NIESWANDT WERNER ,  STAHL HELMUT ,  STILZ WALTER ,  POMMER HORST

公开(公告)号：FR1328799A

公开(公告)日：1963-05-31

申请号：FR903941

申请日：1962-07-13

Applicant: BASF AG

Inventor： STILZ WALTER ,  POMMER HORST ,  BICZYSKO HANS ,  FESSMANN HEINZ

IPC: C08K5/29

公开(公告)号：GB924762A

公开(公告)日：1963-05-01

申请号：GB1691560

申请日：1960-05-13

Applicant: BASF AG

Inventor： STILZ WALTER ,  POMMER HORST ,  GEHM ROBERT ,  SCHMIDT OSWALD ,  MERTENS HEINRICH ,  HEHL MANFRED ,  GRUNWALD WOLFGANG

IPC: C11D1/00 ,  D06L3/12

Abstract: Substituted 1,4-bis-styryl benzenes of the general formula: in which X and X1 stand for carboxylic ester groups or N-alkyl carboxylic amide groups, are prepared by reacting terephthaladehyde with an ester of a carbalkoxy-benzylphosphonic acid or with an ester of a halogenmethylbenzoic acid, with the aid of a triarylphosphine and an alkali alcoholate, and if necessary converting the ester groups of the products into amide groups. These substituted 1,4-bis-styryl benzenes are optical brightening agents (Group IV(c)). In Example 1, the methyl ester of p-chlormethylbenzoic acid is stirred with triphenylphosphine in dimethylformamide at 80 DEG C. for 3 hours; and then terephthalaldehyde followed by sodium methylate are added. The product is 1,4-bis-(para-carbmethoxy-styryl)-benzene, and this is converted, by heating it with diethanolamine, into 1,4-bis-(para-carbodiethanolamidostyryl)-benzene Example 8 refers to 1,4-bis-(meta-carbdiethanolamido-styryl)-benzene. Example 9 describes the preparation of a mixture of 1,4-bis-(para-carbethoxy-styryl) - benzene, 1,4 - bis - (metacarbmethoxy-styryl)-benzene and 1-(para-carbmethoxy-styryl) - 4-(meta1-carbmethoxy-styryl)-benzene, by reacting terephthalaldehyde with a mixture of meta- and para-carbmethoxy-benzyl-phosphonic acid diethyl ester. The mixture of 1,4-bis-styryl-benzene diesters is then reacted with diethanolamine. Example 19 states that 1,4-bis-(meta-carb-N-cyclohexylisopropanol-amidostyryl)-benzene is obtained by reacting 1,4 - bis - (meta-carbmethoxy-styryl)-benzene with N-cyclohexyl-iso-propanolamine. It is stated that X and X1 in the general formula may stand for COO.C2H4OH, and similar groups. Compounds wherein the hydrogen atoms of the hydroxy groups in both the amides and the esters are substituted by glycol ether groups are obtained by the reaction of the amides or esters with ethylene oxide or propylene oxide. Specification 813,539 is referred to.ALSO:Substituted 1, 4-bis-styryl benzenes of the general formula in which X and X1 stand for carboxylic ester groups or N-alkyl carboxylic amide groups, act as brightening agents for textiles, paper and leather. The brightening agent is preferably used in aqueous medium in amounts of about 0,0015 to 0.05% with reference to the weight of the substrate to be brightened. In Example 1, previously bleached cotton fabric is treated, for 20 minutes, in a liquor, at 50 DEG to 60 DEG C., containing 0,003 to 0,01 grams per litre of the compound having the structure and 5 grams per litre of sodium sulphate decahydrate, the liquor to fabric ratio being 50:1. After rinsing and drying, the fabric has a dazzling whiteness of good fastness to light and washing. Examples 5, 6 and 7 relate to the use of the same compound for brightening polycaprolactam fabric, yellowish paper, and soiled clothing, respectively. Example 8 describes the use of 1, 4-bis-(metacarbdiethanolamidostyryl)-benzene for brightening cotton fabric. For the preparation of the brightening agents, (see Group IV(b)). Specification 813,539 is referred to.

公开(公告)号：FR1304494A

公开(公告)日：1962-09-21

申请号：FR877039

申请日：1961-10-25

Applicant: BASF AG

Inventor： STILZ WALTER ,  POMMER HORST ,  SCHMIDT FRANZ ,  BICZYSKO HANS ,  FESSMANN HEINZ

IPC: C08K5/04

Abstract: A mixture stabilized against heat and light comprises 99.99 to 95% by weight of a linear polyamide, polyurethane or polyurea and 0.01 to 5% by weight of a bis-styryl benzene or a stilbene, each of which bears 1 to 5-OR radicals attached directly to the benzene nuclei, R being hydrogen, an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, an aralkyl group with 7 to 10 carbon atoms or -(CH2)n-owhere n is an integer from 1 to 4 and the oxygen atoms are attached in the o-position. Many polymers and stabilizers are specified. In the examples: (1), (2), (3), (7), (9) and (13) hexamethylene diammonium adipate and e -caprolactam are co-polymerized in the presence of:-(1) and (3) 3:4-methylene-dioxy-41-carbomethoxystilbene; (3) 3-methoxy-4-hydroxy-41-carbomethoxystilbene; (7) (a) 1:4-bis-(31:41-methylene dioxystyryl) benzene; (b) 1:3-bis(31:41-methylene dioxystyryl) benzene; (c) 1:4-bis(4-a -tetrahydrofuranyloxystyryl) benzene; (d) 1:4-bis(4-hydroxystyryl) benzene; (9) 1:4-bis(31:41\h -methylene dioxystyryl) benzene and (13) 1:2-bis-(3:41-methylene-dioxystyryl) benzene. In the remaining examples: (4)3:4-methylene dioxy-31-carbomethoxystilbene is mixed with polycaprylic lactam; (5) 3:4-methylene dioxy-31-carbomethoxystilbene is mixed with polyhexamethylene adipamide; (6) 3:4-methylene dioxy-31-carbomethoxystilbene is mixed with polyo -aminoundecanoic acid; (8) 1:4-bis(31:41-methylene dioxy-b -cyano-styryl) benzene is mixed with poly-e -caprolactam; (10) 1:4-bis-(31:41 -methylene-dioxystyryl) benzene is mixed with polycapryllic lactam; (11) 1:4-bis-(31:41-methylene dioxystyryl) benzene is mixed with polyhexamethylene adipamide and (12) 1:4-bis-(31:41-methylene dioxystyryl) benzene is mixed with polyo -aminoundecanoic acid.