US2468725A - Preparation of long-chain esters of beta-thiodipropionic acid - Google Patents
Preparation of long-chain esters of beta-thiodipropionic acid Download PDFInfo
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- US2468725A US2468725A US740268A US74026847A US2468725A US 2468725 A US2468725 A US 2468725A US 740268 A US740268 A US 740268A US 74026847 A US74026847 A US 74026847A US 2468725 A US2468725 A US 2468725A
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- Prior art keywords
- beta
- preparation
- acid
- esters
- alcohol
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- Expired - Lifetime
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- 150000002148 esters Chemical class 0.000 title description 14
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003490 Thiodipropionic acid Substances 0.000 title description 4
- -1 organic acid esters Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 9
- 230000009965 odorless effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009967 tasteless effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/32—Organic compounds, e.g. vitamins containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B5/00—Preserving by using additives, e.g. anti-oxidants
- C11B5/0071—Preserving by using additives, e.g. anti-oxidants containing halogens, sulfur or phosphorus
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/045—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps containing substances which prevent the deterioration of soaps, e.g. light or heat stabilisers or antioxidants
Definitions
- This invention relates to a process for the preparation of the higher molecular weight alcohol esters of thiodicarboxylic acids and more particularly to the preparation of such esters of thiodipropionic acid. 4
- the 3-substituted mercaptoaliphatic organic acid esters and more particularly the mercaptopropionic acid esters have been found to be especially effective anti-rancidity agents for use in oils, fats, waxes and the like, as is described in the D. K. OLeary and in the Gribbins et al. Patents 2,397,960 and 2,397,976 of April 9, 1946. These esters have likewise been found suitable for use in soap for preventing rancidity as is described in the Gribbins Patent 2,416,052 of February 18, 1947. These uses demand esters of high quality that are not only colorless, for off-color is highly undesirable in soaps, food products and the like, but also odorless, for foreign odors are not tolerated in foods or in the better grades of soap and soap products.
- An object of the present invention is to provide a process for the preparation of esters of 3- substituted mercaptolaliphatic organic, acid esters which are substantially colorless and odorless.
- a further object is to provide a process for preparing the higher aliphatic alcohol esters of these 3-substituted mercaptopropionic acids and more particularly such esters of 3-substituted mercaptopropionic acid by the alcoholysis of the lower alkyl esters of 3-substituted merpaptopropionic acid, more particularly the methyl ester with higher aliphatic alcohols.
- the invention is directed to the preparation of substantially colorless and odorless higher aliphatic alcohol esters of a beta-thioether of an ester of propionic acid having the formula:
- ROOCCHzCHzS-X group and more particularly, thosecontaining from 10 to 24 carbon atoms and in which X is:
- a hydrocarbon group such as e. g.: the alkyl groups: methyl, ethyl, propyl, butyl, lauryl, and the aryl groups: phenyl, naphthyl, benzyl; and such groups as cyclohexyl; v
- An oxygenated-hydrocarbon group such as e. g.: the alcohol groups: hydroxymethyl, hydroxyethyl, and hydroxybutyl; the ether-groups;
- a sulfur-hydrocarbon group such as e. g.: mercaptoethyl, mercaptopropyl, mercaptobutyl, mercaptoisobutyl, mercaptohexyl and ethiaethyl.
- a sulfurand oxygenated-hydrocarbon group such as e. g.: carboxyethiaethyl,
- the product is then cooled rapidly to 40 to 50 C. and a suflicient amount of water and caustic soda or alkali dissolved in water added to neutralize the acid catalyst used. l Neutralization is carried out as accurately as possible in order not to contaminate the product.
- a catalyst and neutralizer being selected such that a. precipitate is obtained, such for example, as sulfuric acid and barium hydroxide or phosphoric acid and sodium hydroxide
- the filtered ester is subjected to a deodorizing treatment by passing it countercurrent to the flow of steam at a temperature between. and 225 C. and under a vacuum of less than about 40 millimeters, preferably below 20 millimeters.
- the above product was. further- 7 subjecting it to acountercurrent steam scrubbing proximately 190 C. (although temperatures be- 1'iormed,?.t I temperature .2.
- the product obtained in accord with this process was substantially odorless and colorless and wholly acceptable for comestible
- the other higher aliphatic alcohol esters of the other 3-substituted dicarboxylic acids may similarly prepared to give products thatare both odorless and tasteless" by reacting these-alcohols withthe methylfesters of the acids and subsequently it necessary removing the final traces-of odor'by the countercurrent flow steam distiila- Y vtiorrprocess. v I.
- beta-thiodipropionlc acid the higher alcohol consisting of a mixture or higher alcohols, pre "dominately lauryl alcohol, obtained by the catalytic hydrogenation of fats and oils underelevatv ed temperaturesl a'nd pressures, which comprises tween and 300. (3..maybeiusedl wherein-a.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented May 3, 1949' OFFICE PREPARATION OF LONG-CHAIN ESTERS OF BETA-THIODIPROPIONIC ACID William F. Gresham and Myers F. Gribbins, Wu mington, Del., assignors to E. I. du Pont de Nemours & Company, poration of Delaware Wilmington, Del., a cor- No Drawing. Application April 8, 1947, I Serial No. 740,268
Claims. (01. 250-481) This invention relates to a process for the preparation of the higher molecular weight alcohol esters of thiodicarboxylic acids and more particularly to the preparation of such esters of thiodipropionic acid. 4
The 3-substituted mercaptoaliphatic organic acid esters and more particularly the mercaptopropionic acid esters have been found to be especially effective anti-rancidity agents for use in oils, fats, waxes and the like, as is described in the D. K. OLeary and in the Gribbins et al. Patents 2,397,960 and 2,397,976 of April 9, 1946. These esters have likewise been found suitable for use in soap for preventing rancidity as is described in the Gribbins Patent 2,416,052 of February 18, 1947. These uses demand esters of high quality that are not only colorless, for off-color is highly undesirable in soaps, food products and the like, but also odorless, for foreign odors are not tolerated in foods or in the better grades of soap and soap products.
An object of the present inventionis to provide a process for the preparation of esters of 3- substituted mercaptolaliphatic organic, acid esters which are substantially colorless and odorless. A further object is to provide a process for preparing the higher aliphatic alcohol esters of these 3-substituted mercaptopropionic acids and more particularly such esters of 3-substituted mercaptopropionic acid by the alcoholysis of the lower alkyl esters of 3-substituted merpaptopropionic acid, more particularly the methyl ester with higher aliphatic alcohols. Other objects and advantages of the invention will hereinafter appear.
The invention is directed to the preparation of substantially colorless and odorless higher aliphatic alcohol esters of a beta-thioether of an ester of propionic acid having the formula:
ROOCCHzCHzS-X group and more particularly, thosecontaining from 10 to 24 carbon atoms and in which X is:
' 1. A hydrocarbon group such as e. g.: the alkyl groups: methyl, ethyl, propyl, butyl, lauryl, and the aryl groups: phenyl, naphthyl, benzyl; and such groups as cyclohexyl; v
2. An oxygenated-hydrocarbon group such as e. g.: the alcohol groups: hydroxymethyl, hydroxyethyl, and hydroxybutyl; the ether-groups;
2 methoxymethyl, methoxyethyl, and ethoxyethyl; the acid groups and the R esters thereof: carbonymethyl, carboiwethyl, carbo'xypropyl and carboxybutyl; and the aldehyde groups such as aldehydroethyl;
3. A sulfur-hydrocarbon group such as e. g.: mercaptoethyl, mercaptopropyl, mercaptobutyl, mercaptoisobutyl, mercaptohexyl and ethiaethyl.
4. A sulfurand oxygenated-hydrocarbon group such as e. g.: carboxyethiaethyl,
-CH2CH2SCH2CH:COOH carboxyethiaethdithiaethyl,
-cH2cHsscH2cH2scH2cH=coon carboxythiaisobutyl,
-CH 2CH2CH(CH3) SCHzCHzCOOH and carboxyethiapropyl,
is maintained until substantially no more of the lower alcohol, which is formed by the interchange, distills over, the product is then cooled rapidly to 40 to 50 C. and a suflicient amount of water and caustic soda or alkali dissolved in water added to neutralize the acid catalyst used. l Neutralization is carried out as accurately as possible in order not to contaminate the product. After filtering off the precipitated catalyst (a catalyst and neutralizer being selected such that a. precipitate is obtained, such for example, as sulfuric acid and barium hydroxide or phosphoric acid and sodium hydroxide) the filtered ester is subjected to a deodorizing treatment by passing it countercurrent to the flow of steam at a temperature between. and 225 C. and under a vacuum of less than about 40 millimeters, preferably below 20 millimeters.
The example which follows illustrates a preferred embodiment of the invention in which parts are by weight unless otherwise indicated.
Eq:ample.-Stoichiometric amounts of dimethyi thiodipropionate and a mixture of alcohols, prinabsolute'to facilitate cipally l'auryl alcohol obtained in water was added (1% acid based on the ester) sac 99.2... I
by the cartons-' and the-temperature raised as rapidly-as possible to 2009p mately two hours.
-150-l60 C. .(made evident by the evolution of where it was'main'tained ior' approxi- The reaction started at niethanol) andproceeded quite rapidly until about I about 7 5 wasred'uced to about .290;millinije1ters'of mercury pl'ete methanol removaL- when the reaction-{was}.completed ino more distiliate coming oif) the-product was cooled rapidly I to 4,0 to 50 C. and the proper amounts 0! water cormilete.v At this 'point'th 'pre s and sodium hydroxidedissolved inwater added to neutralize 'the phosphoric acid catalyst to NaaHPOe'IHzC). The product was then"cooled to room temperature and filtered.
The above product was. further- 7 subjecting it to acountercurrent steam scrubbing proximately 190 C. (although temperatures be- 1'iormed,?.t I temperature .2. The process of clalm'l in which the product is deodorized by subjecting it to countercurrent v scrubbingwith steam, the scrubbing operation being'conducted at a temperature between 150 C,- to .225": C. and at absolute.
A' process for thepreparation of a substantially odorless: and tasteless stearylalcohol ester g, p e ure below 100 mm. B!
Lot betaathiodipropionic-acid, which comprises hea ing ethy beta thiodipi'opionate with stem] alcohol-inthe presenceloi anxacid catalyst while withdrawingthe methanolas formed, the reaction being conducted at a temperature below process .t or the "preparation or a substana ,tially odorless and tasteless higher. alcohol ester deodorized by":
operation maintained at a. temperature of apliquid stream of the-ester was continuously passed into-the top of areaction vessel and continuously withdrawn from'the bottom, superheated steam passing through the vessel counter-current to the now of ester, the deodorization being conducted at apressure'below 100 mm. and preferably as in this example, between. and mm; Hg absolute pressure. The product obtained in accord with this process was substantially odorless and colorless and wholly acceptable for comestible The other higher aliphatic alcohol esters of the other 3-substituted dicarboxylic acids may similarly prepared to give products thatare both odorless and tasteless" by reacting these-alcohols withthe methylfesters of the acids and subsequently it necessary removing the final traces-of odor'by the countercurrent flow steam distiila- Y vtiorrprocess. v I.
"We claim:
' '1. Av process for the preparation of a substantially odorless and tasteless monohydric alcohol-,
.- of beta-thiodipropionlc acid, the higher alcohol consisting ofa mixture or higher alcohols, pre "dominately lauryl alcohol, obtained by the catalytic hydrogenation of fats and oils underelevatv ed temperaturesl a'nd pressures, which comprises tween and 300. (3..maybeiusedl wherein-a.
heating" methyl beta-thlodipropionate with the aforesaid-higher alcohol-in the presence of an acid catalyst while withdrawing the methanol as formed, the reaction being conducted at a temperature below 250C; '5.2.A- process tor thepreparation of a substan tially odorless and tasteless monohydric alcohol ester of .beta-thiodipropionic acid, the alcohol containing 10in 24 carbon atoms, which. comprises heating a'lower dialkyl ester of beta-thicdipropionic, acid with amonohydric alcohol containing 10 to 24 carbon atoms in the presence of an acid catalyst while withdrawing the lower boiling alcohol formed, the reaction being conducted at a temperature below 250C.
WILLIAMEGRESHAM.
MYERS F; GRIBBINS.
REFERENCES CITED The'following references are of record in the file of this patent:
. UNITED STATES PATENTS Number in thepresenoeoi -e d-Qata s hflewlthdrawing themethan'ol' conducted at a p Certificate of Correction Patent No. 2,468,725.
. May 3, 1949.
WILLIAM F. GRESHAM ET AL.
It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:
Column 2, lines 4 and 5, for the Word aldehydroethyl read aldehydoethyl; line 16, for carboxythiaisobutyl read carbozyethiaisobutyl;
and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 11th day of October, A. D. 1949.
THOMAS F. MURPHY,
Assistant Commissioner of Patents.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US740268A US2468725A (en) | 1947-04-08 | 1947-04-08 | Preparation of long-chain esters of beta-thiodipropionic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US740268A US2468725A (en) | 1947-04-08 | 1947-04-08 | Preparation of long-chain esters of beta-thiodipropionic acid |
Publications (1)
Publication Number | Publication Date |
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US2468725A true US2468725A (en) | 1949-05-03 |
Family
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Family Applications (1)
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US740268A Expired - Lifetime US2468725A (en) | 1947-04-08 | 1947-04-08 | Preparation of long-chain esters of beta-thiodipropionic acid |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2559521A (en) * | 1948-11-27 | 1951-07-03 | Standard Oil Dev Co | Synthetic lubricant |
US3282890A (en) * | 1962-07-25 | 1966-11-01 | Eastman Kodak Co | Poly-alpha-olefins containing a diester of 3, 3'-thiodipropionic acid and 3-hydroxy-2, 2, 4-trimethylpentyl isobutyrate and optionally a sterically hindered phenol as stabilizers |
US4362887A (en) * | 1981-04-10 | 1982-12-07 | The Goodyear Tire & Rubber Company | Synergistic antioxidant mixtures |
US4370434A (en) * | 1981-04-10 | 1983-01-25 | The Goodyear Tire & Rubber Company | Mercapto acid ester antioxidants for polymers |
US4874391A (en) * | 1986-07-29 | 1989-10-17 | Ciba-Geigy Corporation | Process for photochemical stabilization of polyamide fiber material and mixtures thereof with other fibers: water-soluble copper complex dye and light-stabilizer |
US4942254A (en) * | 1981-11-05 | 1990-07-17 | Union Oil Company Of California | Methods for acid catalyzed reactions |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2122716A (en) * | 1933-08-02 | 1938-07-05 | Du Pont | Hydroxy carboxylic acid esters of long chain alcohols |
US2298186A (en) * | 1939-10-25 | 1942-10-06 | Du Pont | Ester |
-
1947
- 1947-04-08 US US740268A patent/US2468725A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2122716A (en) * | 1933-08-02 | 1938-07-05 | Du Pont | Hydroxy carboxylic acid esters of long chain alcohols |
US2298186A (en) * | 1939-10-25 | 1942-10-06 | Du Pont | Ester |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2559521A (en) * | 1948-11-27 | 1951-07-03 | Standard Oil Dev Co | Synthetic lubricant |
US3282890A (en) * | 1962-07-25 | 1966-11-01 | Eastman Kodak Co | Poly-alpha-olefins containing a diester of 3, 3'-thiodipropionic acid and 3-hydroxy-2, 2, 4-trimethylpentyl isobutyrate and optionally a sterically hindered phenol as stabilizers |
US4362887A (en) * | 1981-04-10 | 1982-12-07 | The Goodyear Tire & Rubber Company | Synergistic antioxidant mixtures |
US4370434A (en) * | 1981-04-10 | 1983-01-25 | The Goodyear Tire & Rubber Company | Mercapto acid ester antioxidants for polymers |
US4942254A (en) * | 1981-11-05 | 1990-07-17 | Union Oil Company Of California | Methods for acid catalyzed reactions |
US4874391A (en) * | 1986-07-29 | 1989-10-17 | Ciba-Geigy Corporation | Process for photochemical stabilization of polyamide fiber material and mixtures thereof with other fibers: water-soluble copper complex dye and light-stabilizer |
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