US2509171A - Primary alcohols from thiocarboxylic acids and esters - Google Patents

Primary alcohols from thiocarboxylic acids and esters Download PDF

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US2509171A
US2509171A US724918A US72491847A US2509171A US 2509171 A US2509171 A US 2509171A US 724918 A US724918 A US 724918A US 72491847 A US72491847 A US 72491847A US 2509171 A US2509171 A US 2509171A
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esters
acid
acids
raney nickel
primary alcohols
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Ruzicka Leopold
Prelog Vladimir
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BASF Schweiz AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
    • C07J31/006—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring not covered by C07J31/003
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C07J9/005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane containing a carboxylic function directly attached or attached by a chain containing only carbon atoms to the cyclopenta[a]hydrophenanthrene skeleton

Definitions

  • acids containing the group on V p and as thiocarboxylic acid esters are meant compounds containing the residue
  • a reductive desulphurization takes place with the formation of a primary alcohol.
  • the process is quite generally applicable to aliphatic, alicyclic, aromatic or heterocyclic thiocarboxylic acids containing more than two carbon atoms and esters thereof.
  • the starting materials may also contain substituents,
  • the thiocarboxylic acid group or ester group may be bound to a primary, secondary or tertiary carbon atom.
  • the esters such as the methyl or benzyl esters, have the advantage that they are more stable.
  • the aforesaid starting materials can be obtained easily and in good yield, by the action of the corresponding acid chloride on potassium hydrosulilde or on a mercaptan in the presence of a tertiary amine such as pyridine, triamylamine and the like.
  • catalysts such as are obtained by the decomposition of the socalled Raney alloys with solutions of caustic alkalies. Especially suitable is Raney nickel. Alternatively, there may be used other suitable pretreated metals charged with hydrogen, for example, Raney iron or Raney copper.
  • reaction conditions may vary within widelimits.
  • the reaction may be conducted with Raney nickel in the presence or absence of solvents such, for example, as ether, aliphatic alcohols or dioxane, a solvent being advantageously "cation i1'l9l4lNo. 724,91 ⁇ . ll Switaerland February 6,
  • reaction generally occurs at room temperature with the evolution of heat. In certain cases however, it is of advantage to heat the reaction mixture in order to accelerate the reaction.
  • the invention also includes the manufacture of a primary alcohol by starting from a carboxylic acid with the intermediate production of the corresponding thiocompounda
  • palmitic acid can be converted into cetyl alcohol, benzoic acid into benzyl alcohol, pentaaeetyl-gluconic acid into pentaacetylsorbitol, lid-acetoxy-etio-allocholanic acid into 33- acetoxy-etio-allocholanyl-methanol, and acetyloleanolic acid into monoacetylerythrodiol.
  • a special advantage of this process is that it can be carried out in a neutral medium under mild conditions, so that sensitive or easily reducible res- 2 idues present in the molecule remain unchanged.
  • pyridine carboxylic acids can be reduced to the corresponding hydroxymethylpyridines. It is also possible to obtain aminoalcohols from amino-carboxylic acids. When acylamino-carboxylic acids are used there are obtained amino-alcohols in which the amino-group is free or acylated depending on the nature of the acyl residue. Thus, for example, a carbobenzoxy-group is split of! during the reduction, whereas this does not occur in the case of a benzoyl group. It has also been found that optically active amino-alcohols can be obtained by the proces of the invention from optically active aminocarboxylic acids.
  • the hitherto known general processes for converting carboxylic acids into primary alcohols for example, the reduction of the esters with sodium and absolute alcohol or the catalytic hydrogenation of the esters under raised pressure and at high temperature, have the disadvantage that they are not applicable in the case of carboxylic acids which are sensitive to alkalies or are not stable at high temperatures.
  • the reduction of pyridine carbonlic acids by these known processes leads to piperidine derivatives.
  • the reduction of amino-carboxylic acids to amino-alcohols does not in general proceed smoothly. In particular it has not been possible hitherto to bring about the reduction of optically active aminocarboXYlic acids to amino-alcohols without extensive racemisation.
  • the products of the invention can be used for various purposes depending on their properties or serve as intermediate products.
  • Example 1 mixture is freed from the catalyst by filtration
  • Example 2 2 parts of thiobenzoic acid (Beilstein, 4th ed.. vol. 9. System No. 419) are added to a suspension of 18 parts of Raney nickel in 100 parts of aqueous ethanol of about 95 per cent. strength. The mixture is stirred for a few hours. It is then filteredand the resulting benzyl alcohol melting at 204 C. is recovered from the filtrate. Its phenylurethane melts at -76 C.
  • Example 3 5 parts of Raney nickel are added in portions to 1 part of thiopalmitic acid S-methyl ester [A. W. Ralston, E. W. Sedistorted and S. T. Bauer, Journalof Organic Chemistry, vol. 4, page 502 (1939)] in 100 parts of boiling aqueous ethanol of about per cent. strength. After working up.-
  • Benzyl alcohol is also obtained by carrying out the reaction in aqueous ethanol of about 70 per cent. strength.
  • Example 5 A solution of 1 part of thionicotinic acid 8- methyl ester (B. P.1-x 124 0.: obtained from nicotinic acid chloride and methyl mercaptan) in parts of ethanol is boiled in a reflux apparatus for a short time with 5 parts of Raney nickel. The whole is then filtered, thoroughly washed several times with aqueous ethanol, and fl-hydroxymethyl-pyridine is isolated from the filtrate by forming the picrate, which melts at 162-163 C.
  • Example 6 3p-acetoxy-etio-allothiocholanic acid S-methyl ester (melting at 158l59 0.; obtained from 33- acetoxy-etio-allocholanic acid chloride and methyl mercaptan in presence of pyridine) is treated with Raney nickel in a. manner analogous to that described in the foregoing examples.
  • Pentacetyl-sorbitol is obtained in an analogous a0 manner from pentacetyl-thiogluconic acid S- methyl ester (melting at 92-93 (3.; obtained from pentacetyl-gluconic acid chloride and methyl mercaptan in presence of pyridine). By subsequent acetylation with acetic anhydrlde there is obtained hexacetyl-sorbitol melting at 100 C.
  • Example 8 5 parts of acetyl-thioleanolic acid S-metbyl ester (melting at 167-168 C.; obtained from acetyl-oleanolic acid chloride and methyl mercaptan in presence of triamylamine) are treated with 60 parts of Raney nickel m 200 parts of ethanol to yield erythrodiol monoacetate melting at 2385-2239" C. By subsequent acetylation there is obtained from the latter product the known erythrodiol diacetate lneckmann, Helvetica Chimica Acta, vol. 19, page 247 (1936) l.
  • Example 9 By treating tetradecane-l l-carboxylic acid 5 methyl ester-l-thiocarboxylic acid S-methyl ester (melting at 52-53 0.; obtained fromthapsic acid methyl ester acid chloride and methyl mercaptan in pyridine) in ethereal solution in an analogous manner, there is obtained by reductive desulphurisation 15-hydroxy-pentadecane-1-carboxylic acid methyl ester melting at 54-55 C.
  • Example 10 24 parts of benzoylamino-thioacetic acid S- methyl ester (melting at 1l9.5-12l.5 C. obtained from benzoylaminoacetyl chloride and methyl mercaptan in pyridine) are treated in 400 parts of ethanol with 250 parts of Raney nickel for a Example 11
  • an ethereal solution of N- carbobenzoxy-d-thioalanine S-methyl ester (melting at 49-50 C.; obtained by the reaction of the chloride obtained from carbobenzoxy-d-(-)-alanine with methyl mercaptan in pyridine) is treated with Raney nickel.
  • the process of preparing primary alcohols which comprises treating a member selected from what is the group consisting of thiocarboxylic acids hav- 6o ing more than 2 carbon atoms and esters thereof with Raney nickel.
  • proceot primary alcohols which-comprises treating a member selected from the group consisting of aminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel.
  • the process of preparing primary alcohols which comprises treating a member selected from the group consisting of optically active acylaminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel.
  • the process of preparing primary alcohols which comprises treating a member selected from the group consisting of aminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel in a neutral solvent, and recovering the primary alcohol thus produced.
  • the process of preparing primary alcohols which comprises treating a member selected from the group consisting of acylaminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
  • the process of preparing primary alcohols which comprises treating a member selected from the group consisting of pyridinethiocarboxylic acids and esters thereof with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
  • the process of preparing primary alcohols which comprises treating a member selected from the group consisting of free and esterified thiocarboxylic acids containing an esterified carboxyl group with Raney nickel.
  • the process of preparing primary alcohols which comprises treating a member selected from the group consisting of free and esterified thiocarboxylic acids containing an esterified carboxyl group with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.

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Description

Patented May 23, 1950 PRIMARY ALcouoLs mom moccanoxruc acms AND ns'raas Leopold Buaicka and Vladimir Prclog, Zurich,
Switaerland,
aslignentoGibaIimltedBaale,
Switzerland, a Swiss ii:-
No Drawing. App
herein to denote acids containing the group on V p and as thiocarboxylic acid esters are meant compounds containing the residue In the process of the invention a reductive desulphurization takes place with the formation of a primary alcohol. The process is quite generally applicable to aliphatic, alicyclic, aromatic or heterocyclic thiocarboxylic acids containing more than two carbon atoms and esters thereof. 'The starting materials may also contain substituents,
for example, hydrocarbon radicals or substituted or unsubstituted hydroxyl, carboxyl or amino groups. The thiocarboxylic acid group or ester group may be bound to a primary, secondary or tertiary carbon atom. As compared with the free thiocarboxylic acids, the esters, such as the methyl or benzyl esters, have the advantage that they are more stable. The aforesaid starting materials can be obtained easily and in good yield, by the action of the corresponding acid chloride on potassium hydrosulilde or on a mercaptan in the presence of a tertiary amine such as pyridine, triamylamine and the like.
As finely divided metals ch ged with hydrogen there are used, for example, catalysts such as are obtained by the decomposition of the socalled Raney alloys with solutions of caustic alkalies. Especially suitable is Raney nickel. Alternatively, there may be used other suitable pretreated metals charged with hydrogen, for example, Raney iron or Raney copper.
The reaction conditions may vary within widelimits. Thus, the reaction may be conducted with Raney nickel in the presence or absence of solvents such, for example, as ether, aliphatic alcohols or dioxane, a solvent being advantageously "cation i1'l9l4lNo. 724,91}. ll Switaerland February 6,
January 28, 1947, Se-
2 used which contains no water or only small quantities thereof. The reaction generally occurs at room temperature with the evolution of heat. In certain cases however, it is of advantage to heat the reaction mixture in order to accelerate the reaction.
The invention also includes the manufacture of a primary alcohol by starting from a carboxylic acid with the intermediate production of the corresponding thiocompounda In this manner, for example, palmitic acid can be converted into cetyl alcohol, benzoic acid into benzyl alcohol, pentaaeetyl-gluconic acid into pentaacetylsorbitol, lid-acetoxy-etio-allocholanic acid into 33- acetoxy-etio-allocholanyl-methanol, and acetyloleanolic acid into monoacetylerythrodiol. A special advantage of this process is that it can be carried out in a neutral medium under mild conditions, so that sensitive or easily reducible res- 2 idues present in the molecule remain unchanged.
Thus, for example, pyridine carboxylic acids can be reduced to the corresponding hydroxymethylpyridines. It is also possible to obtain aminoalcohols from amino-carboxylic acids. When acylamino-carboxylic acids are used there are obtained amino-alcohols in which the amino-group is free or acylated depending on the nature of the acyl residue. Thus, for example, a carbobenzoxy-group is split of! during the reduction, whereas this does not occur in the case of a benzoyl group. It has also been found that optically active amino-alcohols can be obtained by the proces of the invention from optically active aminocarboxylic acids.
On the other hand, the hitherto known general processes for converting carboxylic acids into primary alcohols, for example, the reduction of the esters with sodium and absolute alcohol or the catalytic hydrogenation of the esters under raised pressure and at high temperature, have the disadvantage that they are not applicable in the case of carboxylic acids which are sensitive to alkalies or are not stable at high temperatures. Thus, for example, the reduction of pyridine carbonlic acids by these known processes leads to piperidine derivatives. Furthermore, the reduction of amino-carboxylic acids to amino-alcohols does not in general proceed smoothly. In particular it has not been possible hitherto to bring about the reduction of optically active aminocarboXYlic acids to amino-alcohols without extensive racemisation.
It is also possible by means of the present proces in the case of polyearboxylic acids to convert only certain of the carboxyl groups into the cor-,
responding residues containing sulphur, and in this manner to produce hydroxy-carboxylic acids from polycarboxylic acids.
The action of Raney nickel on compounds containing sulphur has been investigated by J. Bougault, E. Cattelain and P. Chabrier [Comptes Rendus dc lAcademie des Sciences, vol. 208, page 657 (1939); Bulletin de la Socit Chimique de France vol. 6, page 34 (1939) and vol. 7, page 781 (1940)]; and also by R. Monzingo, D. E. Wolf, S. A. Harris and K. Folkers [Journal of the American Chemical Society, vol. 65, page 1013 1943)] Furthermore, the reductive desulphurization by means of Raney nickel has been described by the following authors: V. du Vigneaud and co-workers [Journal of Biological Chemistry, vol. 146, page 475 (1942) l; T. Reichstein and coworkers (Experientia, vol. 1, page 386 (19.45)]: N. K. Richtmeyer, C. J. Carr and C. 8. Hudson [Journal of the American Chemical Society, vol. 65, page 1477 (1943)]; E. Schwenk and co-workers Journal of Organic Chemistry, vol. 9, page 1 (1944)]; H. Hauptmann [British Chemical Abstracts, 1945, vol. II. D8' e'245]; and M. L. Wolfrom and J. V. Karabinos [Journal of American Chemical Society, vol. 65, page 909 (1944)].
Among these authors only Bougault and coworkers (100. cit.) treated a thiocarboxylic acid, namely, thioacetic acid with Raney nickel. They observed the formation of acetic acid in aqueous medium and acetaldehyde in absolute alcoholic medium.
From the foregoing literature references it could not be foreseen that that the reductive desulphurization in the case of thiocarboxylic acids and esters thereof would lead to the production of primary alcohols. It is surprising that pri- 7 mary alcohols could be obtained in this manner.
The products of the invention can be used for various purposes depending on their properties or serve as intermediate products.
The invention is described in greater detail in the following examples which are presented by way of illustration and not of limitation. In the examples, the quantities given are parts by weight.
Example 1 mixture is freed from the catalyst by filtration,
thoroughly washed, and evaporated to dryness. The residue is dissolved in petroleum etherbenzene (1:1), and adsorbed over aluminium oxide, and elutriated with benzene-ether and ether methanol (1:1), whereby pure cetyl alcohol is obtained which melts at 46-47.5 C. after recrystallisation from acetone.
Example 2 2 parts of thiobenzoic acid (Beilstein, 4th ed.. vol. 9. System No. 419) are added to a suspension of 18 parts of Raney nickel in 100 parts of aqueous ethanol of about 95 per cent. strength. The mixture is stirred for a few hours. It is then filteredand the resulting benzyl alcohol melting at 204 C. is recovered from the filtrate. Its phenylurethane melts at -76 C.
Example 3 5 parts of Raney nickel are added in portions to 1 part of thiopalmitic acid S-methyl ester [A. W. Ralston, E. W. Segebracht and S. T. Bauer, Journalof Organic Chemistry, vol. 4, page 502 (1939)] in 100 parts of boiling aqueous ethanol of about per cent. strength. After working up.-
1 part of thiobenzoic acid S-methyl ester lObermeyer, Berichte der deutschen chemischen Gesellschaft, vol. 20. page 2922 (1887)] is heated to boiling in parts of ethanol. 5 parts of Raney nickel are then added, and the whole is heated for a short time longer in a, reflux apparatus, filtered to remove the catalyst. and the benzyl alcohol is isolated from the filtrate.
Benzyl alcohol is also obtained by carrying out the reaction in aqueous ethanol of about 70 per cent. strength.
Example 5 A solution of 1 part of thionicotinic acid 8- methyl ester (B. P.1-x 124 0.: obtained from nicotinic acid chloride and methyl mercaptan) in parts of ethanol is boiled in a reflux apparatus for a short time with 5 parts of Raney nickel. The whole is then filtered, thoroughly washed several times with aqueous ethanol, and fl-hydroxymethyl-pyridine is isolated from the filtrate by forming the picrate, which melts at 162-163 C.
Example 6 3p-acetoxy-etio-allothiocholanic acid S-methyl ester (melting at 158l59 0.; obtained from 33- acetoxy-etio-allocholanic acid chloride and methyl mercaptan in presence of pyridine) is treated with Raney nickel in a. manner analogous to that described in the foregoing examples. The
resulting product is dissolved in benzene and chromatographed over aluminium oxide. There is obtained 3fl-acetoxy-etio-allocholanyl-methanol, which melts at 141-142" C.. in a yield of 93 per cent.
By starting from A -3fl-acetoxy-etio-thiocholenic acid S-methyl ester melting at 183-184" C. there is obtained in a similar manner A -3pm.cetoxy-etio-cholenyl- 17) -methanol, which forms needles melting at 157-158 C.
Example 7 Pentacetyl-sorbitol is obtained in an analogous a0 manner from pentacetyl-thiogluconic acid S- methyl ester (melting at 92-93 (3.; obtained from pentacetyl-gluconic acid chloride and methyl mercaptan in presence of pyridine). By subsequent acetylation with acetic anhydrlde there is obtained hexacetyl-sorbitol melting at 100 C.
Example 8 5 parts of acetyl-thioleanolic acid S-metbyl ester (melting at 167-168 C.; obtained from acetyl-oleanolic acid chloride and methyl mercaptan in presence of triamylamine) are treated with 60 parts of Raney nickel m 200 parts of ethanol to yield erythrodiol monoacetate melting at 2385-2239" C. By subsequent acetylation there is obtained from the latter product the known erythrodiol diacetate lzimmermann, Helvetica Chimica Acta, vol. 19, page 247 (1936) l.
Example 9 By treating tetradecane-l l-carboxylic acid 5 methyl ester-l-thiocarboxylic acid S-methyl ester (melting at 52-53 0.; obtained fromthapsic acid methyl ester acid chloride and methyl mercaptan in pyridine) in ethereal solution in an analogous manner, there is obtained by reductive desulphurisation 15-hydroxy-pentadecane-1-carboxylic acid methyl ester melting at 54-55 C.
Example 10 24 parts of benzoylamino-thioacetic acid S- methyl ester (melting at 1l9.5-12l.5 C. obtained from benzoylaminoacetyl chloride and methyl mercaptan in pyridine) are treated in 400 parts of ethanol with 250 parts of Raney nickel for a Example 11 In a manner analogous to that described in the preceding example an ethereal solution of N- carbobenzoxy-d-thioalanine S-methyl ester (melting at 49-50 C.; obtained by the reaction of the chloride obtained from carbobenzoxy-d-(-)-alanine with methyl mercaptan in pyridine) is treated with Raney nickel. After the reductive desulphurisation the product is freed from the catalyst by filtration, and washed with alcohol. The filtrate is then acidified with hydrochloric acid, and'the acid solution is evaporated to dryness. In this manner d-(-)-alaninol hydrochloride is obtained. By allowing the hydrochloride to stand overnight with para-bromobenzoyl chlo- I ride in pyridine the .0:N-di-para-bromobenzoyl derivative is formed. The latter is purified in benzene solution by chromatography over aluminium oxide, and recrystallisation from ben- Zeno-petroleum ether. The product melts at 155 C.
Having thus described the invention claimed is:
1. The process of preparing primary alcohols which comprises treating a member selected from what is the group consisting of thiocarboxylic acids hav- 6o ing more than 2 carbon atoms and esters thereof with Raney nickel.
2. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of thiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
8. The proceot primary alcohols which-comprises treating a member selected from the group consisting of aminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel.
4. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of acylaminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel.
5. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of optically active acylaminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel.
6. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of aminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel in a neutral solvent, and recovering the primary alcohol thus produced.
'7. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of acylaminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
8. The process of preparing primary alcohols which comprises treating a member selected from the group consistin of optically active acylaminothiocarboxylic acids having more than 2 carbon atoms and esters thereof with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
9. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of pyridinethiocarboxylic acids and esters thereof 'with Raney nickel.
10. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of pyridinethiocarboxylic acids and esters thereof with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
11. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of free and esterified thiocarboxylic acids containing an esterified carboxyl group with Raney nickel.
12. The process of preparing primary alcohols which comprises treating a member selected from the group consisting of free and esterified thiocarboxylic acids containing an esterified carboxyl group with Raney nickel in a neutral organic solvent, and recovering the primary alcohol thus produced.
LEOPOLD RUZICKA. VLADIMIR PRELOG.
REFERENCES CITED The following references are of record in the file of this patent:
Bougault et al., Comptes Rendus 208, 657

Claims (1)

1. THE PROCESS OF PREPARING PRIMARY ALCOHOLS WHICH COMPRISES TREATING A MEMBER SELECTED FROM THE GROUP CONSISTING OF THIOCARBOXYLIC ACIDS HAVING MORE THAN 2 CARBON ATOMS AND ESTERS THEREOF WITH RANEY NICKEL.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2586533A (en) * 1948-04-01 1952-02-19 Ayerst Mckenna & Harrison Acylated thiol esters from etiobilienic acid esters
US3232950A (en) * 1962-01-31 1966-02-01 Schering Corp 5-(2'-picolyl)5-hydroxy-dibenzo[a,d]cyclohepta[1,4]diene and acid addition salts thereof
EP0004741A2 (en) * 1978-04-05 1979-10-17 Syntex (U.S.A.) Inc. Thio etianic acid derivatives, their preparation and pharmaceutical use

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* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2586533A (en) * 1948-04-01 1952-02-19 Ayerst Mckenna & Harrison Acylated thiol esters from etiobilienic acid esters
US3232950A (en) * 1962-01-31 1966-02-01 Schering Corp 5-(2'-picolyl)5-hydroxy-dibenzo[a,d]cyclohepta[1,4]diene and acid addition salts thereof
EP0004741A2 (en) * 1978-04-05 1979-10-17 Syntex (U.S.A.) Inc. Thio etianic acid derivatives, their preparation and pharmaceutical use
EP0004741A3 (en) * 1978-04-05 1979-11-14 Syntex (U.S.A.) Inc. Thio etianic acid derivatives, their preparation and pharmaceutical use

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