NO123572B - - Google Patents
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- NO123572B NO123572B NO2189/69A NO218969A NO123572B NO 123572 B NO123572 B NO 123572B NO 2189/69 A NO2189/69 A NO 2189/69A NO 218969 A NO218969 A NO 218969A NO 123572 B NO123572 B NO 123572B
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- Norway
- Prior art keywords
- carbon atoms
- compounds
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- acid
- halogen
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- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- -1 derivatives of α-diethylamino-2,6-dimethylphenylacetate Chemical group 0.000 claims description 16
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000006278 bromobenzyl group Chemical group 0.000 claims description 3
- 125000004803 chlorobenzyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- KGFYHTZWPPHNLQ-AWEZNQCLSA-N rivaroxaban Chemical compound S1C(Cl)=CC=C1C(=O)NC[C@@H]1OC(=O)N(C=2C=CC(=CC=2)N2C(COCC2)=O)C1 KGFYHTZWPPHNLQ-AWEZNQCLSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- 235000019441 ethanol Nutrition 0.000 description 20
- 239000000243 solution Substances 0.000 description 13
- 235000019658 bitter taste Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 150000003841 chloride salts Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IOSXSVZRTUWBHC-LBTVDEKVSA-N Quassin Chemical compound CC([C@@H]1CC(=O)O[C@@H]([C@]21C)C1)=C(OC)C(=O)[C@@H]2[C@]2(C)[C@@H]1[C@H](C)C=C(OC)C2=O IOSXSVZRTUWBHC-LBTVDEKVSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000003398 denaturant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IOSXSVZRTUWBHC-UHFFFAOYSA-N quassin Natural products C1C(C23C)OC(=O)CC3C(C)=C(OC)C(=O)C2C2(C)C1C(C)C=C(OC)C2=O IOSXSVZRTUWBHC-UHFFFAOYSA-N 0.000 description 4
- 235000019640 taste Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000004925 denaturation Methods 0.000 description 3
- 230000036425 denaturation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical class OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011975 tartaric acid Chemical class 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OQWSVCXXAYKEFF-UHFFFAOYSA-N Brucin Natural products COc1cc2N3C4C5C(CC3=O)OC=CC6CN7CCC4(C7CC56)c2cc1OC OQWSVCXXAYKEFF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- SOGXBRHOWDEKQB-UHFFFAOYSA-N benzyl 2-chloroacetate Chemical class ClCC(=O)OCC1=CC=CC=C1 SOGXBRHOWDEKQB-UHFFFAOYSA-N 0.000 description 1
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical class CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RRKTZKIUPZVBMF-IBTVXLQLSA-N brucine Chemical compound O([C@@H]1[C@H]([C@H]2C3)[C@@H]4N(C(C1)=O)C=1C=C(C(=CC=11)OC)OC)CC=C2CN2[C@@H]3[C@]41CC2 RRKTZKIUPZVBMF-IBTVXLQLSA-N 0.000 description 1
- RRKTZKIUPZVBMF-UHFFFAOYSA-N brucine Natural products C1=2C=C(OC)C(OC)=CC=2N(C(C2)=O)C3C(C4C5)C2OCC=C4CN2C5C31CC2 RRKTZKIUPZVBMF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XIKIUQUXDNHBFR-UHFFFAOYSA-N monobenzyl phthalate Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 XIKIUQUXDNHBFR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VODRWDBLLGYRJT-UHFFFAOYSA-N propan-2-yl 2-chloroacetate Chemical compound CC(C)OC(=O)CCl VODRWDBLLGYRJT-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12F—RECOVERY OF BY-PRODUCTS OF FERMENTED SOLUTIONS; DENATURED ALCOHOL; PREPARATION THEREOF
- C12F5/00—Preparation of denatured alcohol
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- General Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biochemistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Nutrition Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Kvaternaere derivater av a-dialkylaminoeddiksyreestere for anvendelse som bitterstoffer. Quaternary derivatives of α-dialkylaminoacetic acid esters for use as bitter substances.
Foreliggende oppfinnelse angår kvaternære derivater av ot-dialkylaminoeddiksyreestere for anvendelse som bitterstof f er, spesielt som denatureringsmidler for etylalkohol eller blandinger inneholdende etylalkohol. The present invention relates to quaternary derivatives of o-dialkylaminoacetic acid esters for use as bitter substances, in particular as denaturants for ethyl alcohol or mixtures containing ethyl alcohol.
Forbindelser med ekstremt bitter smak overfor mennesker, dyr, insekter og fugler er meget anvendbare for å gjøre materialer og stoffer udrikkbare eller uspisbare. En spesielt viktig anvendelse for slike stoffer er denaturering av etylalkohol, eller denaturering av preparater inneholdende etylalkohol, som ikke er blitt gjort udrikke-lige på andre måter. Det eksisterer således i mange land bestemmelser om at. etylalkohol som selges til industrielt bruk eller til det offentlige publikum, skal tilsettes ett eller flere denatureringsmidler. Visse av disse denatureringsmidler har den funksjon at den behandlede alkohol skal gjøres udrikkbar, slik at den ikke drikkes. En meget viktig klasse denatureringsmidler omfatter forbindelser med intenst bitter smak, f.eks. quassin eller brucin. Foreliggende oppfinnelse angår slike bitterstoffer. Compounds with an extremely bitter taste to humans, animals, insects and birds are very useful for making materials and substances undrinkable or inedible. A particularly important application for such substances is the denaturation of ethyl alcohol, or the denaturation of preparations containing ethyl alcohol, which have not been made undrinkable in other ways. There are thus provisions in many countries that. ethyl alcohol sold for industrial use or to the public must have one or more denaturants added. Certain of these denaturants have the function of rendering the treated alcohol undrinkable, so that it cannot be drunk. A very important class of denaturants includes compounds with an intensely bitter taste, e.g. quassin or brucin. The present invention relates to such bitter substances.
Ifølge foreliggende oppfinnelse er det tilveiebragt forbindelser for anvendelse som bitterstoffer, og disse er kjenneteg-net ved at de er kvaternære forbindelser av a-dialkylaminoeddiksyreestere og har formelen: hvor R er en alkylgruppe med 1-4 karbonatomer, en cykloalkylgruppe med 4-8 karbonatomer, en aralkylgruppe med 7-11 karbonatomer, fenyl eller en substituert fenylgruppe med formelen: According to the present invention, compounds are provided for use as bitter substances, and these are characterized by the fact that they are quaternary compounds of α-dialkylaminoacetic acid esters and have the formula: where R is an alkyl group with 1-4 carbon atoms, a cycloalkyl group with 4-8 carbon atoms , an aralkyl group with 7-11 carbon atoms, phenyl or a substituted phenyl group of the formula:
hvor R^" er et acyklisk hydrokarbonresiduum med 1-4 karbonatomer eller et halogenatom, og R11, R111, RIV og RV er halogen- eller hydro-genatomer; eller R"'" og er acykliske hydrokarbonresiduer med 1-4 karbonatomer og R"'"'*", R1"1"1 og R^V er et halogen- eller hydrogenatom; ;eller R1 og RV og ,en av gruppene R"<1>"<1>, R111, RIV er acykliske hydrokarbonresiduer med 1-4 karbonatomer mens resten av gruppene R II, R111 og RIV hver er et halogen- eller hydrogenatom; og R^ er alkyl-radikaler med 1-4 karbonatomer, Ri. er en benzyl-, klorbenzyl- eller ;(-) . ;brombenzylgruppe, A er et anion, og n er et tall som tilsvarer an-ionets valens. ;Typen og størrelsen på de acykliske hydrokarbonsubsti-tuenter R<1> og RV er begrenset av. det krav et de ikke skal påvirke ev-nen til R-j^-gruppen til å danne gruppen R.^000, slik det er vist i den generelle formel I. Det er således kjent at meget voluminøse substi-... IV ;tuenter i stillingene ved R og R kan hindre dannelsen av estergrup-pen R-^OOC-, fra forbindelser av typen R-^OH, hvor R^ representerer en ;substituert fenylgruppe. Når de ér acykliske hydrokarbonresiduer} inneholder således R<1> til RV fra 1 til 4 karbonatomer; Når de er halogenåtomer5 er det foretrukket at de er klor- eller bromatomer. ;De R-^-grupper som er substituerte ■ fenylgrupper med sub-stituenter, slik det er beskrevet ovenfor, i 2-, 6- eller 2-, 4-, 6-stillingene, har vist seg å være spesielt verdifulle for det foreliggende formål. ;Dét er antatt at forbindelsenes bitterhet frembringes av kationet. Anionet representert ved An^ ^ i den generelle formel I, kan velges frå en rekke forskjellige syrer uten at dette har noen vesentlig effekt på saltets bitterhet. Således kan A n^ ^ representere anionet fra en alifatisk monokarboksylsyre, fortrinnsvis inneholdende fra 1 til 8 karbonatomer, monoanionet eller dianionet av en dikarboksylsyre som maleinsyre, ravsyre, adipinsyre, glutarsyre, o-, m- eller p-ftalsyre, eller et anion avledet fra en trivalent syre, så som trimellitinsyre, trimesinsyre, eller pyromellitinsyre. Anionet kan også representere monovalente eller divalente ioner av uorganiske syrer, såsom klorid-, bromid-, bisulfatJ- eller sulfationer. Når det er passende, kan man anvende anioner med høyere valens, hvis dette er ønskelig. ;Man foretrekker å anvende anioner avledet fra organiske karboksylsyrer fremfor de som er avledet fra uorganiske syrer, ettersom førstnevnte type syrer vanligvis gir kvaternære salter som er mindre korrosive. Salter av benzosyre, oksalsyre, vinsyre og ftalsyre er eksempler på forbindelser som er spesielt tilfredsstillende i så henseende. ;Typiske eksempler på kvaternære forbindelser som har bitter smak er benzyl-, klorbenzyl-eller brombenzyl-kvaternære salter av følgende a-dialkylaminoeddiksyreestere: ;a-dietylaminoetylacetat, ;a-dietylaminoisopropylacetat, ;oi-dimetylamino-2,4,6-trimetylfenylacetat, a-dimétylamino-2,6-dimetylfenylacetat, ;.a-dietylamino-2,6-dimetylfenylacetat. ;Typiske eksempler på syrer som kan brukes for fremstilling av salter med liten korroderende effekt på metaller i kontakt med deres oppløsninger i vandig alkohol er følgende: ;Benzosyre, ;o-, m- eller p-klorbenzosyre, ;o-, m- eller p-toluinsyre, ;o-, m- eller p-ftalsyre, ;oksalsyre, ;vinsyre. ;To spesielt effektive forbindelser med den ovenfor an-gitte generelle formel I og som er nyttige for denaturering av etylalkohol, er hydrogenftalatsaltene av benzylkvaternære derivater av a-dietylamino-2,6-dimetylfenylacetat og a-dietylamino-2,4,6-trimetyl-fenylacetat. ;Begge disse forbindelser er flere ganger bitrere enn quassin eller bucin, og de er blant de mest bitre forbindelser man nå kjenner til. Når de er oppløst i etylalkohol eller etylalkohol/vann-blandinger, kan deres bitre smak lett påvises i konsentrasjoner så lave som 1 del per million. Det er vanligvis meget ønskelig å kunne' anvende meget små konsentrasjoner for å gi nevnte etylalkohol eller etylalkoholoppløsninger en markert bitter smak. ;Foreliggende forbindelser kan lett fremstilles ved fremgangsmåter som i seg selv er kjente. En spesiell fremgangsmåte for fremstilling av forbindelsene er beskrevet i det følgende eksempel. Eksempel I. Hydrogenftalatsalt av benzylkvaternære derivater av a- dietylamino- 2, 6- dimetylfenylacetat. ;2,6-xylenol ble omsatt med en ekvimolar mengde av kloracetylklorid i 10 timer ved 110° - 120°C i en kolbe utstyrt med en tilbakeløpskjøler. Produktet ble destillert ved 90°C/200 - 300 mm Hg inntil mesteparten av det uomsatte kloracetylklorid var blitt fjernet. Råproduktene av xylylkloracetatesteren (20 g) ble kokt under tilbake-løp i benzen med dietylamin (15 g) i 1.5 time. Reaksjonsblandingen ble avkjølt, hvoretter dietylaminhydrokloridet ble frafiltert. Ben-zenfiltratet ble ekstrahert med flere porsjoner 8 % saltsyre, og de samlede ekstrakter ble nøytralisert med 3 % kaliumhydroksydoppløsning i nærvær av is. Produktet ble ekstrahert med dietyleter, og oppløs-ningen ble vasket med 10 % saltoppløsning inntil den var nøytral. Eteren ble fjernet ved fordampning, og det resulterende produkt tør-ket i en vakuumbeholder. Analyse vist.e at stoffet var 95.5 % rent a-dietylamino-2,6-dimetylfenylacetat. Esteren ble behandlet med et svakt overskudd av benzylklorid ved 100°C i 20 timer. Det viskøse oljeaktige produkt ble ekstrahert tre ganger med eter, og man fikk utfelt et fast produkt ved tilsetning av en ti ganger større mengde etylacetat. Produktet var et hvitt pulver, som ble ytterligere renset ;ved fraksjonert utfelling, hvorved man fikk i alt vesentlig rent a-dietylamino-2,6-dietylfenylacetat i form av forbindelsens benzyl-kloridkvaternære salt. Dette salt ble underkastet smaksprøve av en gruppe på 17 personer. ;Kloridsaltet og natriumhydrogenftalatet i et svakt overskudd ble tilbakeløpskokt i 5 timer i etariol (74 OP). Reaksjonsblandingen ble filtrert varmt for å fjerne natriumklorid og overskuddet av natriumhydrogenftalat. Hydrogenftalatsaltet ble frafiltrert ved rom-temperatur og omkrystallisert fra etanol (71* OP). Dette salt ble også underkastet smaksprøver av en gruppe på 17 personer. where R^" is an acyclic hydrocarbon residue of 1-4 carbon atoms or a halogen atom, and R11, R111, RIV and RV are halogen or hydrogen atoms; or R"'" and are acyclic hydrocarbon residues of 1-4 carbon atoms and R" '"'*", R1"1"1 and R^V is a halogen or hydrogen atom; ;or R1 and RV and ,one of the groups R"<1>"<1>, R111, RIV are acyclic hydrocarbon residues with 1-4 carbon atoms while the rest of the groups R II, R111 and RIV are each a halogen or hydrogen atom; and R 1 are alkyl radicals with 1-4 carbon atoms, Ri. is a benzyl, chlorobenzyl or ;(-) . ;bromobenzyl group, A is an anion, and n is a number corresponding to the valence of the anion. ;The type and size of the acyclic hydrocarbon substituents R<1> and RV are limited by. the requirement that they should not affect the ability of the R-j^ group to form the group R.^000, as shown in the general formula I. It is thus known that very voluminous substituents in the positions at R and R can prevent the formation of the ester group R-^OOC-, from compounds of the type R-^OH, where R^ represents a substituted phenyl group. When they are acyclic hydrocarbon residues} thus R<1> to RV contain from 1 to 4 carbon atoms; When they are halogen atoms5, it is preferred that they are chlorine or bromine atoms. The R-^ groups which are substituted ■ phenyl groups with substituents, as described above, in the 2-, 6- or 2-, 4-, 6-positions have been found to be particularly valuable for the present purpose. It is believed that the bitterness of the compounds is produced by the cation. The anion represented by An^ ^ in the general formula I can be chosen from a number of different acids without this having any significant effect on the bitterness of the salt. Thus, A n^ ^ may represent the anion of an aliphatic monocarboxylic acid, preferably containing from 1 to 8 carbon atoms, the monoanion or the dianion of a dicarboxylic acid such as maleic acid, succinic acid, adipic acid, glutaric acid, o-, m- or p-phthalic acid, or an anion derived from a trivalent acid, such as trimellitic acid, trimesic acid, or pyromellitic acid. The anion can also represent monovalent or divalent ions of inorganic acids, such as chloride, bromide, bisulphate or sulphate ions. When appropriate, higher valence anions can be used if desired. ;One prefers to use anions derived from organic carboxylic acids rather than those derived from inorganic acids, as the former type of acids usually give quaternary salts which are less corrosive. Salts of benzoic acid, oxalic acid, tartaric acid and phthalic acid are examples of compounds which are particularly satisfactory in this respect. ;Typical examples of quaternary compounds which have a bitter taste are benzyl, chlorobenzyl or bromobenzyl quaternary salts of the following α-dialkylaminoacetic acid esters: ;α-diethylaminoethyl acetate, ;α-diethylaminoisopropylacetate, ;o-dimethylamino-2,4,6-trimethylphenylacetate, α-dimethylamino-2,6-dimethylphenylacetate, α-diethylamino-2,6-dimethylphenylacetate. ;Typical examples of acids that can be used for the production of salts with little corrosive effect on metals in contact with their solutions in aqueous alcohol are the following: ;Benzoic acid, ;o-, m- or p-chlorobenzoic acid, ;o-, m- or p-toluic acid, o-, m- or p-phthalic acid, oxalic acid, tartaric acid. Two particularly effective compounds of the above general formula I which are useful for the denaturation of ethyl alcohol are the hydrogen phthalate salts of benzyl quaternary derivatives of α-diethylamino-2,6-dimethylphenylacetate and α-diethylamino-2,4,6-trimethyl -phenylacetate. ;Both of these compounds are several times more bitter than quassin or bucine, and they are among the most bitter compounds now known. When dissolved in ethyl alcohol or ethyl alcohol/water mixtures, their bitter taste can be easily detected at concentrations as low as 1 part per million. It is usually very desirable to be able to use very small concentrations to give said ethyl alcohol or ethyl alcohol solutions a markedly bitter taste. The present compounds can be easily prepared by methods which are known per se. A special method for preparing the compounds is described in the following example. Example I. Hydrogen phthalate salt of benzyl quaternary derivatives of α-diethylamino-2,6-dimethylphenylacetate. ;2,6-xylenol was reacted with an equimolar amount of chloroacetyl chloride for 10 hours at 110°-120°C in a flask equipped with a reflux condenser. The product was distilled at 90°C/200-300 mm Hg until most of the unreacted chloroacetyl chloride had been removed. The crude products of the xylyl chloroacetate ester (20 g) were refluxed in benzene with diethylamine (15 g) for 1.5 hours. The reaction mixture was cooled, after which the diethylamine hydrochloride was filtered off. The benzene filtrate was extracted with several portions of 8% hydrochloric acid, and the combined extracts were neutralized with 3% potassium hydroxide solution in the presence of ice. The product was extracted with diethyl ether and the solution was washed with 10% saline until neutral. The ether was removed by evaporation and the resulting product dried in a vacuum vessel. Analysis showed that the substance was 95.5% pure α-diethylamino-2,6-dimethylphenylacetate. The ester was treated with a slight excess of benzyl chloride at 100°C for 20 hours. The viscous oily product was extracted three times with ether, and a solid product was precipitated by adding a tenfold larger amount of ethyl acetate. The product was a white powder, which was further purified by fractional precipitation, whereby essentially pure α-diethylamino-2,6-diethylphenylacetate was obtained in the form of the benzyl chloride quaternary salt of the compound. This salt was subjected to a taste test by a group of 17 people. The chloride salt and the sodium hydrogen phthalate in a slight excess were refluxed for 5 hours in etariol (74 OP). The reaction mixture was hot filtered to remove sodium chloride and excess sodium hydrogen phthalate. The hydrogen phthalate salt was filtered off at room temperature and recrystallized from ethanol (71* OP). This salt was also subjected to taste tests by a group of 17 people.
Smaksprøvene ble utført med oppløsninger som inneholdt en del alkohol per tre deler vann. Man fant at en.oppløsning av 4 deler per million av kloridet i fermenteringsalkoholen (74 OP) var bitrere enn en prøve av en tilsvarende alkohol inneholdende et bitterstoff i en mengde som tilfredsstiller U.K. Customs & Exercise Regula-tions. En tilsvarende prøve med en oppløsning av tre deler per million av hydrogenftalatsaltet viste at gruppen ikke kunne skille mellom prøveoppløsningen og prøven som tilfredsstilte nevnte Exercise Regu-lations, idet begge oppløsninger igjen ble prøvet som en oppløsning av en del alkohol per tre deler vann. The taste tests were carried out with solutions containing one part alcohol per three parts water. It was found that a solution of 4 parts per million of the chloride in the fermentation alcohol (74 OP) was more bitter than a sample of a corresponding alcohol containing a bittering substance in an amount satisfying the U.K. Customs & Exercise Regula-tions. A corresponding sample with a solution of three parts per million of the hydrogen phthalate salt showed that the group could not distinguish between the sample solution and the sample that satisfied the aforementioned Exercise Regulations, as both solutions were again tested as a solution of one part alcohol per three parts water.
Tilsvarende smaksprøver ble utført med alkoholiske opp-løsninger (3 deler vann til 1 del alkohol) med hydrogenftalatsaltet, idet man som standardoppløsning anvendte 23 deler per million quassin i en tilsvarende alkoholisk oppløsning. Man fant på denne måten at hydrogenftalatsaltet var ca. syv ganger bitrere enn den tilsvarende quassinmengde. Corresponding taste tests were carried out with alcoholic solutions (3 parts water to 1 part alcohol) with the hydrogen phthalate salt, using 23 parts per million quassin in a corresponding alcoholic solution as a standard solution. It was found in this way that the hydrogen phthalate salt was approx. seven times more bitter than the corresponding quantity of quassin.
Eksempel 2 Benzoatsalt av benzylkvaternært derivat av ct- dietylamino-2, 6- dimetylfenylacetat. ct-diet<y>lamino-2,6-dimet<y>lfen<y>lacetat i form av sitt ben-zylkloridsalt ble fremstilt som i eksempel 1, og dette ble tilbakeløp-kokt med natriumbenzoat i 5 timer i etanol (74 OP). Etter filtrering fikk man at produktet hadde en bitter smak som var uskillbar f.ra kloridet eller hydrogenftalatsaltene, noe som bekrefter at anionet ikke Example 2 Benzoate salt of benzyl quaternary derivative of ct-diethylamino-2, 6-dimethylphenylacetate. ct-diet<y>lamino-2,6-dimeth<y>lphen<y>lacetate in the form of its benzyl chloride salt was prepared as in Example 1, and this was refluxed with sodium benzoate for 5 hours in ethanol (74 OP). After filtration, it was found that the product had a bitter taste that was indistinguishable from the chloride or hydrogen phthalate salts, which confirms that the anion is not
er særlig viktig. is particularly important.
Eksempel 3 Kloridsalt av benzylkvaternære derivater av a- dietylaminoisopropylacetat. Example 3 Chloride salt of benzyl quaternary derivatives of α-diethylaminoisopropyl acetate.
Kloreddiksyre ble omsatt uten katalysator med et stort overskudd av isopropanol. Mesteparten av vann/isopropanolazeotropen ble fjernet fra den tilbakeløpskokende blanding ved hjelp av et uttak over en 10-platers kolonne. En fraksjon som kokte ved 149° - 151°C, besto i alt vesentlig av isopropylkloracetat, og denne fraksjon ble oppsamlet. Reaksjon med dietylamin var tilsvarende det som er beskrevet i eksempel 1, men man holdt antallet vandige vaskeoppløsninger på et minimum, på grunn av den større løselighet for t-aminet. Salt-dannelsen med benzylklorid var som beskrevet i eksempel 1. Chloroacetic acid was reacted without a catalyst with a large excess of isopropanol. Most of the water/isopropanol azeotrope was removed from the refluxing mixture by means of an outlet over a 10-plate column. A fraction boiling at 149°-151°C consisted essentially of isopropyl chloroacetate, and this fraction was collected. Reaction with diethylamine was similar to that described in example 1, but the number of aqueous washing solutions was kept to a minimum, due to the greater solubility of the t-amine. The salt formation with benzyl chloride was as described in example 1.
Eksempel 4 Example 4
Ved å anvende den fremgangsmåte som er beskrevet i eksempel 1, ble kvaternære kloridsalter basert på følgende fenoler også fremstilt, og man fant at alle var ekstremt bitre forbindelser. Using the procedure described in Example 1, quaternary chloride salts based on the following phenols were also prepared and all were found to be extremely bitter compounds.
kresol, cresol,
2-, 4-, 6-trimetylfenol, 2-, 4-, 6-trimethylphenol,
2,6-diklorfenol. 2,6-dichlorophenol.
Eksempel 5 Example 5
Metyl-, etyl- og benzylkloracetatestrene ble fremstilt ved fremgangsmåter som i seg selv er kjente og omdannet til de tilsvarende kvaternære kloridsalter ved å anvende den fremgangsmåte som er beskrevet i eksempel 3. Man fant at alle kloridsalter av benzylkvaternære derivater av a-dietylaminometyl-, etyl- eller benzylace-tater var bitre forbindelser. The methyl, ethyl and benzyl chloroacetate esters were prepared by methods known per se and converted to the corresponding quaternary chloride salts by using the method described in example 3. It was found that all chloride salts of benzyl quaternary derivatives of α-diethylaminomethyl-, ethyl or benzyl acetates were bitter compounds.
Som bitterstoff kan a-dietylamino-2,6-dimetylfenylacetat og dets benzylhydrogenftalatkvaternære salt brukes i konsentrasjoner så lave som en del i 50 millioner, men den foretrukne mengde vil selvsagt variere med det produkt man ønsker å gi en bittersmak. As a bittering agent, α-diethylamino-2,6-dimethylphenylacetate and its benzyl hydrogen phthalate quaternary salt can be used in concentrations as low as one part in 50 million, but the preferred amount will of course vary with the product to which a bitter taste is desired.
På grunn av disse produkters sterkt varierende natur er det nesten umulig å fastslå en øvre grense, ettersom en bitter smak dels kan velges for sin behagelige effekt eller sin ubehagelige effekt. Nor-. malt vil det vanligvis ikke være nødvendig å bruke mengder utover 0.155. Det kan imidlertid være hensiktsmessig å fremstille konsentrerte opp-løsninger for derved senere å kunne lette fremstillingen av oppløs-ninger med meget lave konsentrasjoner. Due to the highly variable nature of these products, it is almost impossible to establish an upper limit, as a bitter taste can be chosen partly for its pleasant effect or its unpleasant effect. Nor-. malt, it will not usually be necessary to use amounts in excess of 0.155. However, it may be appropriate to prepare concentrated solutions in order to facilitate later the preparation of solutions with very low concentrations.
For denaturerende formål vil de anvendte mengder vanligvis være bestemt av de offentlige bestemmelser i hvert enkelt land. Normalt vil man med tilfredsstillende resultat kunne anvende mengder varierende fra 0.01 % til 1 del per million. Mens den nedre grense ofte er fastslått av slike regler, kan de øvre grenser være regulert av andre faktorer, såsom omkostninger eller det residuum som blir til-bake ved fordampning av alkoholen. Hvis f.eks. alkoholen anvendes i visse preparater, såsom eau de cologne, er det f.eks. uønsket at en total fordampning av preparatet fra huden skal etterlate et ubehage-lig residuum. Av denne grunn er det ofte ønskelig å begrense inn-holdet av ikke-flyktige stoffer i preparatet til mindre enn 100 ppm. For denaturing purposes, the amounts used will usually be determined by the public regulations in each individual country. Normally, quantities varying from 0.01% to 1 part per million can be used with satisfactory results. While the lower limit is often determined by such rules, the upper limits can be regulated by other factors, such as costs or the residue left behind when the alcohol evaporates. If e.g. the alcohol is used in certain preparations, such as eau de cologne, it is e.g. it is undesirable that a total evaporation of the preparation from the skin should leave an unpleasant residue. For this reason, it is often desirable to limit the content of non-volatile substances in the preparation to less than 100 ppm.
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GB25610/68A GB1200987A (en) | 1968-05-29 | 1968-05-29 | Quaternary compounds of dialkylamino acetic acid esters |
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NO123572B true NO123572B (en) | 1971-12-13 |
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BE (1) | BE733802A (en) |
DE (1) | DE1925841A1 (en) |
FR (1) | FR2009968A1 (en) |
GB (1) | GB1200987A (en) |
NL (1) | NL6908138A (en) |
NO (1) | NO123572B (en) |
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CH614347A5 (en) * | 1975-09-29 | 1979-11-30 | Hoffmann La Roche | |
DE3403880A1 (en) * | 1984-02-04 | 1985-08-08 | Hoechst Ag, 6230 Frankfurt | SALTS OF SS-ALKYLAMINOPROPIONIC ACID ESTERS CONTAINING FLUORALKYL GROUPS, METHOD FOR THEIR SYNTHESIS AND THE USE THEREOF FOR THE PREPARATION OF AQUEOUS POLYACRYLATE DISPERSIONS CONTAINING FLUORINE KYLL |
-
1968
- 1968-05-29 GB GB25610/68A patent/GB1200987A/en not_active Expired
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1969
- 1969-05-21 DE DE19691925841 patent/DE1925841A1/en active Pending
- 1969-05-28 FR FR6917309A patent/FR2009968A1/en not_active Withdrawn
- 1969-05-28 NL NL6908138A patent/NL6908138A/xx unknown
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DE1925841A1 (en) | 1970-05-14 |
BE733802A (en) | 1969-12-01 |
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