DE816544C - Process for the production of ª † -alkylthio- or -selenic fatty acids or their ª ‡ -amino-substituted derivatives - Google Patents
Process for the production of ª † -alkylthio- or -selenic fatty acids or their ª ‡ -amino-substituted derivativesInfo
- Publication number
- DE816544C DE816544C DEP4610A DEP0004610A DE816544C DE 816544 C DE816544 C DE 816544C DE P4610 A DEP4610 A DE P4610A DE P0004610 A DEP0004610 A DE P0004610A DE 816544 C DE816544 C DE 816544C
- Authority
- DE
- Germany
- Prior art keywords
- amino
- fatty acids
- alkylthio
- substituted derivatives
- selenic
- 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
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 7
- 229930195729 fatty acid Natural products 0.000 title claims description 7
- 239000000194 fatty acid Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 4
- 150000004665 fatty acids Chemical class 0.000 title claims 2
- 125000000457 gamma-lactone group Chemical group 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- QJPWUUJVYOJNMH-UHFFFAOYSA-N homoserine lactone Chemical compound NC1CCOC1=O QJPWUUJVYOJNMH-UHFFFAOYSA-N 0.000 description 6
- -1 selenium fatty acids Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930188620 butyrolactone Natural products 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- SWMDCXYSYSMCJM-UHFFFAOYSA-N 2-aminopentanethioic s-acid Chemical compound CCCC(N)C(S)=O SWMDCXYSYSMCJM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- YSAZOOWIZTZHGM-UHFFFAOYSA-N CCCC(N)C(O)=[Se] Chemical compound CCCC(N)C(O)=[Se] YSAZOOWIZTZHGM-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JQUQNGYUEFSZBS-UHFFFAOYSA-N [Na].CC Chemical compound [Na].CC JQUQNGYUEFSZBS-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OTIJNTWWDCIUNM-UHFFFAOYSA-N pentanethioic s-acid Chemical compound CCCCC(S)=O OTIJNTWWDCIUNM-UHFFFAOYSA-N 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- MJEJPPQFUJAISK-UHFFFAOYSA-M sodium methaneselenolate Chemical compound [Na+].[Se-]C MJEJPPQFUJAISK-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von y-Alkylthio- bzw. -selenfettsäuren bzw. deren a-aminosubstituierten Derivaten Bekanntlich lassen sich Laktone durch Einwirkung von Alkoholaten bzw. von Alkalicyaniden in Alkoxyfettsäuren bzw. Cyanfettsäuren verwandeln. Die Ausbeuten sind hierbei jedoch sehr unterschiedlich. Ferner ist schon beschrieben worden, daß aus Laktonen durch Einwirkung von Alkalisulfiden, -hydrosulfiden sowie -polysulfiden schwefelhaltige Dicarbonsäuren entstehen. So erhält man z. B. aus Butyrolakton durch Einwirkung von Na S H oder Na, S die Thiodibuttersäure.Process for the production of γ-alkylthio or selenium fatty acids or their α-amino-substituted derivatives is known to be lactones by action of alcoholates or of alkali metal cyanides in alkoxy fatty acids or cyano fatty acids transform. However, the yields here are very different. Furthermore is already has been described that from lactones by the action of alkali sulfides, hydrosulfides as well as polysulfides, sulfur-containing dicarboxylic acids are formed. So you get z. B. from butyrolactone through the action of Na S H or Na, S thiodibutyric acid.
Es wurde gefunden, daß man in guten Ausbeuten zu Alkylthio- bzw. -selenfettsäuren bzw. deren a-Aminoderivaten gelangt, wenn man auf y-Laktone bzw. deren d-Aminoderivate Alkali- oder Erdalkalimercaptide oder -selenide einwirken läßt. Man führt die Reaktion bei Temperaturen zwischen ioo und 200° durch und verwendet zweckmäßig ein indifferentes Verdünnungsmittel, z. B. Toluol oder Benzol. Die Reaktion geht im Verlauf von 2 Stunden vor sich, wobei sich zuerst das Alkylmercaptid an das Lakton unter Bildung eines isolierbaren Zwischenprodukts anlagert. Bei der Umsetzung des Butyrolaktons mit Natriummethylmercaptid entsteht ein Zwischenprodukt der folgenden wahrscheinlichen Formel: wobei R = CH, bedeutet. Diese Zwischenprodukte lagern sich beim Erhitzen auf Zoo bis 200° in die Natriumsalze der entsprechenden Alkylthiofettsäuren um nach Gleichung: Ganz analog ist die Umsetzung beim a-Amino-y-butyrolakton, die zum Natriumsalz der y-Methylthio-a-aminobuttersäure führt. Die Reaktion wird zweckmäßig in Abwesenheit primärer Alkohole durchgeführt, da die Ausbeuten sonst sehr schlecht sind.It has been found that alkylthio- or selenium fatty acids or their α-amino derivatives are obtained in good yields if γ-lactones or their α-amino derivatives are allowed to act on alkali metal or alkaline earth metal mercaptides or selenides. The reaction is carried out at temperatures between 100 and 200 ° and expediently uses an inert diluent such. B. toluene or benzene. The reaction proceeds over the course of 2 hours, the alkyl mercaptide first adding to the lactone to form an isolable intermediate. When the butyrolactone reacts with sodium methyl mercaptide, an intermediate product of the following likely formula is formed: where R = CH . When heated to a temperature of up to 200 °, these intermediate products are converted into the sodium salts of the corresponding alkylthio fatty acids according to the equation: The reaction with α-amino-γ-butyrolactone, which leads to the sodium salt of γ-methylthio-α-aminobutyric acid, is completely analogous. The reaction is expediently carried out in the absence of primary alcohols, since otherwise the yields are very poor.
Die Anwesenheit von sekundären Alkoholen, z. B. Cyclohexanol, gibt jedoch gute Ausbeuten und ist für manche Umsetzungen vorteilhaft. Die Verfahrensprodukte sollen zur Herstellung von Arzneimitteln verwendet werden.The presence of secondary alcohols, e.g. B. cyclohexanol there however, good yields and is advantageous for some reactions. The process products are intended to be used in the manufacture of pharmaceuticals.
Beispiel Z Z Mol reines, pulverisiertes Natriummethylmercaptid wird in Toluol suspendiert und bei 40' mit Z Mol Butyrolakton behandelt. Das entstandene Anlagerungsprodukt wird auf der Nutsche abgesaugt und 2 Stunden auf Zoo bis 150 ' im Ölbad erhitzt. Nach dem Erkalten wird die Schmelze in Wasser gelöst und angesäuert, wobei sich ein Öl abscheidet. Bei der Destillation geht die y-Methylthiobuttersäure bei Kp. 127 bis Z29° über. Ausbeute: 6o°/, der Theorie.Example Z Z becomes mol of pure, powdered sodium methyl mercaptide suspended in toluene and treated at 40 'with Z mol of butyrolactone. The resulting Addition product is sucked off on the suction filter and 2 hours on Zoo to 150 'heated in an oil bath. After cooling, the melt is dissolved in water and acidified, whereby an oil separates. The γ-methylthiobutyric acid goes in the distillation at bp. 127 to Z29 ° over. Yield: 60% of theory.
Beispiel 2 II kg a-Aminobutyrolakton läßt man in eine Suspension von 7,5 kg Natriummethylmercaptid in Toluol unter Rühren einlaufen, wobei die Temperatur von 30 auf 6o' steigt. Das Toluol wird abgedampft und der Rückstand 3 Stunden auf 145 bis 15o° erhitzt. Nun wird die Schmelze in Wasser gelöst und mit Eisessig angesäuert. Es fallen 7,5 kg a-Amino-y-methylthiobuttersäure in farblosen Kristallen aus. Ausbeute etwa 6o°/, der Theorie.Example 2 II kg of a-aminobutyrolactone are left in a suspension of 7.5 kg of sodium methyl mercaptide run in toluene with stirring, the temperature increases from 30 to 6o '. The toluene is evaporated and the residue for 3 hours Heated between 145 and 15o °. Now the melt is dissolved in water and acidified with glacial acetic acid. 7.5 kg of α-amino-γ-methylthiobutyric acid precipitate in colorless crystals. yield about 60 ° /, of theory.
Beispiel 3 In eine Suspension von 1/1o Mol Natriumäthyhnercaptid in 5o ccm Toluol läßt man bei 8o0 ZZ g a-Aminobutyrolakton einlaufen. Nun wird 2 Stunden auf Z5o° erwärmt. Nach dem Lösen in Wasser und Ansäuern erhält man etwa 49 a-Amino-y-äthylthiobuttersäure. Beispiel 4 In eine Suspension von '/1o Mol Natriummethylselenid in Zoo ccm Toluol läßt man bei 5o° ZZ g a-Aminobutyrolakton einfließen. Nach dem Verdampfen des Toluols erhitzt man den Rückstand 2 Stunden auf 15o'. Die Schmelze wird in Wasser gelöst und angesäuert. Man erhält 5 g a-Amino-y-methylselenobuttersäure vom F. 27o° (Zersetzung).Example 3 In a suspension of 1/10 mole of sodium ethane captide in 5o ccm of toluene is allowed to run in at 8o0 ZZ g of α-aminobutyrolactone. Now it will be 2 hours heated to Z50 °. After dissolving in water and acidifying, about 49 a-amino-y-ethylthiobutyric acid is obtained. Example 4 In a suspension of 1/10 mol of sodium methyl selenide in zoo cc of toluene allowed to flow in at 50 ° ZZ g of a-aminobutyrolactone. After the toluene has evaporated the residue is heated to 150 'for 2 hours. The melt is dissolved in water and acidified. 5 g of α-amino-γ-methylselenobutyric acid with a melting point of 270 ° (decomposition) are obtained.
Beispiel 5 In eine heiße Lösung von 8 g Natrium in Zoo ccm Cyclohexanol wird ein Cberschuß von Methyhnercaptan eingeleitet. Die so erhaltene Lösung von CH,SNa in Cyclohexanol wird mit 28 g a-Aminobutyrolakton versetzt und Z Stunde am Rückflußkühler erhitzt, wobei sich ein weißes Salz abscheidet. Nach dem Abkühlen wird in Wasser gelöst, mit Äther vom Cyclohexanol abgetrennt und angesäuert. Es scheiden sich 8 g a-Amino-y-methylthiobuttersäure ab.Example 5 In a hot solution of 8 g sodium in zoo cc cyclohexanol an excess of methylcaptan is introduced. The solution of CH, SNa in cyclohexanol is mixed with 28 g of a-aminobutyrolactone and Z hour on The reflux condenser is heated, a white salt separating out. After cooling down is dissolved in water, separated from the cyclohexanol with ether and acidified. It 8 g of α-amino-γ-methylthiobutyric acid separate.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4610A DE816544C (en) | 1948-10-02 | 1948-10-02 | Process for the production of ª † -alkylthio- or -selenic fatty acids or their ª ‡ -amino-substituted derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4610A DE816544C (en) | 1948-10-02 | 1948-10-02 | Process for the production of ª † -alkylthio- or -selenic fatty acids or their ª ‡ -amino-substituted derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE816544C true DE816544C (en) | 1951-10-11 |
Family
ID=7359559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP4610A Expired DE816544C (en) | 1948-10-02 | 1948-10-02 | Process for the production of ª † -alkylthio- or -selenic fatty acids or their ª ‡ -amino-substituted derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE816544C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0245231A1 (en) * | 1986-05-08 | 1987-11-11 | Monsanto Company | Process for the preparation of alkylthioalkanoate salts |
| US4883911A (en) * | 1986-05-08 | 1989-11-28 | Monsanto Company | Process for the preparation of alkylthioalkanoate salts |
| EP0498765A1 (en) * | 1991-02-04 | 1992-08-12 | Ciba-Geigy Ag | Process for the preparation of alkyl- and arylthiocarboxylic acids and esters thereof |
-
1948
- 1948-10-02 DE DEP4610A patent/DE816544C/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0245231A1 (en) * | 1986-05-08 | 1987-11-11 | Monsanto Company | Process for the preparation of alkylthioalkanoate salts |
| US4777289A (en) * | 1986-05-08 | 1988-10-11 | Monsanto Company | Process for the preparation of alkylthioalkanoate salts |
| US4883911A (en) * | 1986-05-08 | 1989-11-28 | Monsanto Company | Process for the preparation of alkylthioalkanoate salts |
| EP0498765A1 (en) * | 1991-02-04 | 1992-08-12 | Ciba-Geigy Ag | Process for the preparation of alkyl- and arylthiocarboxylic acids and esters thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE887506C (en) | Process for the production of organic compounds | |
| DE1543957B1 (en) | Process for the preparation of bis (hydroxydialkylbenzyl) sulfides | |
| DE816544C (en) | Process for the production of ª † -alkylthio- or -selenic fatty acids or their ª ‡ -amino-substituted derivatives | |
| DE2446256C3 (en) | Process for the preparation of hexahydrothieno [3,4-d] -imidazole-2,4-dione | |
| US2788355A (en) | 6, 8-dithioloctanoic acid, salts and esters thereof | |
| DE1211168B (en) | Process for the preparation of organoantimony compounds | |
| DE938846C (en) | Process for the preparation of new ring-substituted 4-aminouracils | |
| DE3201761C2 (en) | ||
| DE2345360A1 (en) | PROCESS FOR THE PRODUCTION OF TRANSCHRYSANTHEMUM MONOCARBONIC ACID AND ALKYLESTERS THEREOF | |
| US2033542A (en) | Mixed furyl-alkyl ketones | |
| DE853445C (en) | Process for the preparation of diisopropylxanthogen disulfide | |
| DE2363573B2 (en) | Process for the preparation of mercaptocarboxylic acid esters | |
| DEP0004610DA (en) | Process for the production of gamma-alkyl-thio- or -selenic fatty acids or their alpha-amino-substituted derivatives | |
| DE1518404C (en) | Process for the preparation of m-aminophenylalyl sulfides | |
| DE1300574B (en) | Process for the preparation of thiacycloalkanes | |
| DE894244C (en) | Process for the production of sulfur-containing organic compounds | |
| DE2436943C3 (en) | o-Hydroxy-omega- (methylsulfinyl) acetonaphthones and process for their preparation | |
| DE1140568B (en) | Process for the production of methyl isothiocyanate | |
| DE903931C (en) | Process for the production of nitriles of fatty aromatic hydrocarbons | |
| US2648677A (en) | Addition product of thianaphthene sulfone and malonic acid esters | |
| DE614396C (en) | Process for the preparation of thionaphthene derivatives | |
| AT233574B (en) | Process for the preparation of new sulfonamides of the pyrimidine series | |
| DE945448C (en) | Process for the preparation of new compounds with 2 to 5 linearly linked bicyclo- [2, 2, 1] -heptane rings | |
| DE1543957C (en) | Process for the preparation of bishydroxy dialkylbenzyl) sulfides precipitate from 1242617 | |
| DE1793406C3 (en) | Process for the preparation of sulfonium sulfitobetaines |