US3676494A - Carboxylic acid amides - Google Patents

Carboxylic acid amides Download PDF

Info

Publication number
US3676494A
US3676494A US882302A US3676494DA US3676494A US 3676494 A US3676494 A US 3676494A US 882302 A US882302 A US 882302A US 3676494D A US3676494D A US 3676494DA US 3676494 A US3676494 A US 3676494A
Authority
US
United States
Prior art keywords
denotes
formula
carbon atoms
integer
alkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US882302A
Other languages
English (en)
Inventor
Hans Rudolf Biland
Max Duennenberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba AG filed Critical Ciba AG
Application granted granted Critical
Publication of US3676494A publication Critical patent/US3676494A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/28—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen, oxygen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom

Definitions

  • the invention concerns new carboxylic acid amides of the formula wherein M denotes a divalent bridge member of the series S, -S--A-S and S-CH CH (OCH CH S, A denotes an alkylene residue containing one to 18 carbon atoms, p denotes an integer from one to three, R denotes an alkyl group and R denotes alkyl or hydrogen.
  • R1 The subject of the invention is the new carboxylic acid H0 OA Ha1 amides of formula R2 R1 R1 HO -NH-C OA- M AC OHN ()H L l wherein M denotes a divalent bridge member of the series with about one mol of a mercaptan of formula 8-, SAS- and SCl-l CH -(O-CH CH S, A denotes an alkylene residue containing 1 to 18 carbon (6) r j atoms, p denotes an integer from one to three, R, denotes an T alkyl group with one to eight carbon atoms and R denotes hydrogen or an alkyl group with one to eight ca b atoms in the form of its alkali salt, with R,, R A and M having the Here the total number of carbon atoms for all A members abovememioned Significance and Hal representing a halogen normally does not amount to
  • M denotes a divalent bridge member S, S (8) I 1 (Cl-l S or SCl-l Cl-I --OCH CH -S-, q T T denotes an integer from one to six, n denotes an integer from I one to 12, R, denotes an alkyl group with one to eight carbon m the form of f j i R2 n and moms R2 denotes hydrogen or an alkyl group with one to 40 mg the abovementloned significance and Hal representing a eight carbon atoms and R denotes hydrogen or an alkyl halogen atom group containing one to four carbon atoms.
  • M denotes a divalent bridge member -S or S (CH )
  • S q denotes an integer from 1 to 6
  • n denotes an in a solvent which is inert towards the reagents (for example 5 5 alcohols or hydrocarbons).
  • R denotes an alkyl group with one to
  • the alkali salts of the dithiols can be manufactured in the eight carbon atoms and R denotes hydrogen or an alkyl group presence of a solvent by using the alkali metal, or through the with one to eight carbon atoms (with the alkyl group for R, use of the stoichiometric amount of an alkali alcoholate.
  • the and R in particular containing one to four carbon atoms), and compounds of formula (5) required as starting substances are furthermore compounds of formula obtained by the reaction, which is in itself known, of acid haa Ra 1-10 NH-o0-cmmm m 0Emu-004m OH wherein M, denotes a divalent bridge member S- or S lides, preferably acid chlorides, of formula (Cl-l S, q denotes an integer from one to six, m denotes an integer from one to four, and R denotes a branched alkyl Hal-A-CO-l-lal 10 group containing one to four carbon atoms.
  • the compounds defined above can be manufactured analogously to procedures which are in themselves known.
  • the compounds according to formula l) and analogously, those of the subordinate formulas can appropriately be obtained by reacting about two mols of a compound of formula R2 wherein A, Hal, R and R have the abovementioned significance. This reaction is carried out in the presence of a solvent which is inert towards the reagents, with the corresponding hydrogen halide acid being split off.
  • the resulting hydrogen halide acid can be removed from the reaction mixture by sucking-off, or be bonded by adding a hydrogen halide acceptor, (for example a tertiary amine).
  • acrylic and methacrylic acid derivatives for example acrylic acid alkyl esters, acrylamides and acrylonitrile; polyamides, for example from e-caprolactam or from adipic acid and a diamine; polyesters such as polyterephthalic acid glycol ester; natural and synthetic rubbers; lubricating oils; petrol; vegetashows the following data:
  • the compounds defined above are of preferred importance as stabilizers against oxidative influences in the case of HO NH O O CH2C1 polymerization products of a-olefines, that is to say in the case 2 5 5 of homopolymers and copolymers of a-olefines such as 7 preferably ethylene or propylene, and also in the case of substrates which predominantly contain homopolymersv or copolymers of a-olefines.
  • antioxidants small amounts of compounds of formula l that is to say about 0.01 to two percent relative to the amount of the substrate to be protected, in general suffice.
  • the antioxidants can for example be incorporated into the materials to be protected directly, that is to say by themselves, or together with other additives such as plasticizers, pigments, light protection agents or optical brighteners, and/or with the aid of solvents.
  • the antioxidative effect of the compounds of formula (1) also manifests itself in the light exposure test, in that these compounds are able to prevent or greatly to reduce oxidative processes induced by the action of light, for example the yellowing of polyethylene.
  • EXAMPLE 1 1.6 g of crystalline 61 percent strength sodium sulphide are dissolved in 100 ml of methanol. 7.425 g of the compound of formula used as the starting material is manufactured as follows: 23.5 g
  • the compounds of formula are obtained from the dried methylene chloride extracts.
  • M denotes a divalent bridge member of the series
  • SAS- and S-CH -CH (OCH -CH ),,S-, A denotes an alkylene containing one to 18 carbon atoms
  • p denotes an integer from one to three
  • R denotes an alkyl group with one to eight carbon atoms
  • R denotes Peroxide number milliequivalents of peroxidic oxygen)/kg 3 5 hydrogen or an alkyl group with one to eight carbon atoms.
  • a carboxylic acid amide according to claim 1 which corresponds to the formula Peroxide number Olive oil, without additive, freshly distilled 0 Olive oil, without additive, oxidized for 20 minutes 334 Olive oil with 0.2 of the compound l3 (partially dissolved) (Example I I28 Olive oil with 0.2 of the compound 26 (Example 2) 78 an integer from one to six, n denotes an integer from one to 12, R, denotes an alkyl group with one to eight carbon atoms, R denotes hydrogen or an alkyl group with l to eight carbon atoms and R denotes hydrogen or an alkyl group containing one to four carbon atoms; R and R cannot simultaneously be different from hydrogen.
  • a carboxylic acid amide according to claim 1 which corresponds to the formula 3 Olive oil with 0.2 of 2,6di-tert.butylwherein M, denotes a divalent bridge member -S(CH 4-methylphenol l22 S, q denotes an integer from one to six, n denotes an integer Olive oil with 0.2 of methylene-bis-(3- methyl-4-hydroxy-S-terLbUtylbenZene 137 from one to 12, R, denotes an alkyl group with one to eight carbon atoms and R denotes hydrogen or an alkyl group with to eight carbon atoms.
  • M denotes a divalent bridge member -S(CH 4-methylphenol l22 S
  • q denotes an integer from one to six
  • n denotes an integer Olive oil with 0.2 of methylene-bis-(3- methyl-4-hydroxy-S-terLbUtylbenZene 137 from one to 12
  • R denotes an al
  • a carboxylic acid amide according to claim 1 which cor- A mixture of 100 g of polyethylene powder (Microthene responds to the formula H0- NIICOC "Hz” Mi C l'iH2n "C OHN -OH I I L J l l R: R2 R1 R2 722, USl) and 0.2 g of one of the compounds mentioned in Table 6 is aged at 85 C for l6 hours in a circulating air oven.
  • melt index is determined according to ASTM from one to four and R denotes a branched alkyl group con- Specification D-l238-62-T.
  • the melt index equals the amount of polyethylene, in grams, which has flowed in 10 minutes through a standard die, and represents a measure of taining up to four carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US882302A 1968-12-13 1969-12-04 Carboxylic acid amides Expired - Lifetime US3676494A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1866468A CH506323A (de) 1968-12-13 1968-12-13 Verwendung von neuen Carbonsäureamiden als Antioxydantien für organische Materialien

Publications (1)

Publication Number Publication Date
US3676494A true US3676494A (en) 1972-07-11

Family

ID=4434515

Family Applications (1)

Application Number Title Priority Date Filing Date
US882302A Expired - Lifetime US3676494A (en) 1968-12-13 1969-12-04 Carboxylic acid amides

Country Status (9)

Country Link
US (1) US3676494A (enrdf_load_html_response)
JP (1) JPS4934911B1 (enrdf_load_html_response)
BE (1) BE743093A (enrdf_load_html_response)
CH (1) CH506323A (enrdf_load_html_response)
DE (1) DE1961177A1 (enrdf_load_html_response)
FR (1) FR2026064A1 (enrdf_load_html_response)
GB (1) GB1241617A (enrdf_load_html_response)
IL (1) IL33479A0 (enrdf_load_html_response)
NL (1) NL6918693A (enrdf_load_html_response)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038246A (en) * 1972-06-29 1977-07-26 Ciba-Geigy Corporation Butadiene rubbers stabilized with thiodialkanoamidophenols
US4083721A (en) * 1974-08-14 1978-04-11 Fuji Photo Film Co., Ltd. Photographic phenolic couplers with amido coupling-off groups
US4218327A (en) * 1976-04-05 1980-08-19 Shell Oil Company Stabilizing the viscosity of an aqueous solution of polysaccharide polymer
US4412024A (en) * 1981-09-14 1983-10-25 Sandoz Ltd. Concentrated solutions of aromatic oxamide stabilizers
US4485034A (en) * 1980-09-20 1984-11-27 Sandoz Ltd. Aromatic oxamides useful as stabilizers
US4634728A (en) * 1985-01-17 1987-01-06 Mallinckrodt, Inc. Polyol carboxyalkylthioalkanoamidophenol compounds and organic material stabilized therewith
US4734519A (en) * 1986-06-05 1988-03-29 Mallinckrodt, Inc. Pentaerythritol co-esters
US4925578A (en) * 1984-11-19 1990-05-15 Shell Oil Company Polymer-thickened aqueous solutions containing a mercaptobenzothiazole

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2301705A1 (de) * 1973-01-13 1974-07-25 Agfa Gevaert Ag Photographisches material mit einemulgierten farbkupplern und verfahren zu ihrer herstellung
US4108830A (en) 1975-07-21 1978-08-22 The Goodyear Tire & Rubber Company Sulfur-containing phenolic antioxidants
CA1084062A (en) * 1975-07-21 1980-08-19 Richard H. Kline Sulfur containing bisphenol antioxidants
DE3567451D1 (en) * 1985-01-17 1989-02-16 Mallinckrodt Inc Dithiodialkanoamidophenol compounds and organic material stabilized therewith
JP7228302B1 (ja) * 2022-06-16 2023-02-24 竹本油脂株式会社 合成繊維用処理剤、合成繊維、及び合成繊維用処理剤の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Takahashi et al, Yakugaku Kenkyu, Vol. 36, 149 162; (1965). *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038246A (en) * 1972-06-29 1977-07-26 Ciba-Geigy Corporation Butadiene rubbers stabilized with thiodialkanoamidophenols
US4083721A (en) * 1974-08-14 1978-04-11 Fuji Photo Film Co., Ltd. Photographic phenolic couplers with amido coupling-off groups
US4218327A (en) * 1976-04-05 1980-08-19 Shell Oil Company Stabilizing the viscosity of an aqueous solution of polysaccharide polymer
US4485034A (en) * 1980-09-20 1984-11-27 Sandoz Ltd. Aromatic oxamides useful as stabilizers
US4412024A (en) * 1981-09-14 1983-10-25 Sandoz Ltd. Concentrated solutions of aromatic oxamide stabilizers
US4925578A (en) * 1984-11-19 1990-05-15 Shell Oil Company Polymer-thickened aqueous solutions containing a mercaptobenzothiazole
US4634728A (en) * 1985-01-17 1987-01-06 Mallinckrodt, Inc. Polyol carboxyalkylthioalkanoamidophenol compounds and organic material stabilized therewith
US4734519A (en) * 1986-06-05 1988-03-29 Mallinckrodt, Inc. Pentaerythritol co-esters

Also Published As

Publication number Publication date
GB1241617A (en) 1971-08-04
JPS4934911B1 (enrdf_load_html_response) 1974-09-18
IL33479A0 (en) 1970-02-19
CH506323A (de) 1971-04-30
FR2026064A1 (enrdf_load_html_response) 1970-09-11
NL6918693A (enrdf_load_html_response) 1970-06-16
DE1961177A1 (de) 1970-07-09
BE743093A (enrdf_load_html_response) 1970-06-12

Similar Documents

Publication Publication Date Title
US3676494A (en) Carboxylic acid amides
SU747422A3 (ru) Способ получени производных пролина
EP0197407B1 (de) Verfahren zur Herstellung von 1,2-Dithiolan-3-pentansäure (Thioctsäure)
Godt Jr et al. The Synthesis of organic trithiocarbonates1
US3927091A (en) Carboxylic acid amides
US3905968A (en) Preparation of 1,2-dichloro-3-amino propane derivatives
US3810929A (en) Polycarboxylic acid-bridged thio-methylenephenol antioxidants
Kato et al. Preparation and some reactions of bis (thioacyl) sulfides
DE2729986C2 (enrdf_load_html_response)
US3544566A (en) Process for producing areno-oxazinones
US3769284A (en) 2,4-disubstituted 3-amino-cyclohexenones
US4055599A (en) N-(Alkylhydrobenzyl)-alkylthio- and mercapto-acetamides
US3691186A (en) Certain substituted benzthiazole-n-oxides and their preparation
US2449440A (en) Aryl esters of tertiary carbamic acid
US3478095A (en) Preparation of phosphonamides
DE3639400C2 (enrdf_load_html_response)
US2775608A (en) Sulfonic acid esters of 2-dialkylamine ethanols
US2408094A (en) Process
US3068266A (en) 2-(substituted-benzyl)-1, 3-propanedisulfonates
US2668855A (en) Alkylene-bis(oxyalkylene-ammonium) compounds
US3708488A (en) Process for the preparation of n,n'-disulfide compounds
JPS63146855A (ja) ３‐第三ブチル‐　あるいは　３‐　第三ブチル‐５‐　アルキル‐４‐　ヒドロキシフエニル‐（アルカン）　カルボン酸とポリチオール類のオキシエチラートとのエステル、その製造方法および安定剤としてのその用途
US2957006A (en) New salts of basic ethers of diphenyl ethinyl carbinols and the production thereof
US2050190A (en) Vulcanization of rubber
EP0039905B1 (de) Verfahren zur Herstellung von 2-Chlorbenzothiazol