GB795131A - Improvements in or relating to the preparation of primary alcohols - Google Patents
Improvements in or relating to the preparation of primary alcoholsInfo
- Publication number
- GB795131A GB795131A GB5446/55A GB544655A GB795131A GB 795131 A GB795131 A GB 795131A GB 5446/55 A GB5446/55 A GB 5446/55A GB 544655 A GB544655 A GB 544655A GB 795131 A GB795131 A GB 795131A
- Authority
- GB
- United Kingdom
- Prior art keywords
- threo
- reduced
- ethyl ester
- nitrophenyl
- borohydride
- 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
- 150000003138 primary alcohols Chemical class 0.000 title abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 6
- -1 alkaline earth metal salt Chemical class 0.000 abstract 6
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract 5
- 239000012279 sodium borohydride Substances 0.000 abstract 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 4
- 229910052791 calcium Inorganic materials 0.000 abstract 4
- 239000011575 calcium Substances 0.000 abstract 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract 3
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 3
- PHWSCBWNPZDYRI-UHFFFAOYSA-N ethyl 4-nitrobenzoate Chemical compound CCOC(=O)C1=CC=C([N+]([O-])=O)C=C1 PHWSCBWNPZDYRI-UHFFFAOYSA-N 0.000 abstract 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 abstract 2
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 2
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 abstract 2
- 229910001638 barium iodide Inorganic materials 0.000 abstract 2
- 229940075444 barium iodide Drugs 0.000 abstract 2
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 2
- 239000001110 calcium chloride Substances 0.000 abstract 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012458 free base Substances 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract 2
- 229910001643 strontium iodide Inorganic materials 0.000 abstract 2
- WLZQSOUQRZKSBM-QMMMGPOBSA-N (2s)-3-hydroxy-2-(4-nitroanilino)propanoic acid Chemical class OC[C@@H](C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1 WLZQSOUQRZKSBM-QMMMGPOBSA-N 0.000 abstract 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 abstract 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 abstract 1
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical compound CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 abstract 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 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 150000001371 alpha-amino acids Chemical class 0.000 abstract 1
- 235000008206 alpha-amino acids Nutrition 0.000 abstract 1
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 229910052788 barium Inorganic materials 0.000 abstract 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 1
- 235000019445 benzyl alcohol Nutrition 0.000 abstract 1
- 229910001640 calcium iodide Inorganic materials 0.000 abstract 1
- 229940046413 calcium iodide Drugs 0.000 abstract 1
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- QKBCBEQAZDXTNT-LLVKDONJSA-N ethyl (2S)-2-amino-3-hydroxy-2-(4-nitrophenyl)propanoate Chemical compound C(C)OC([C@@](N)(CO)C1=CC=C(C=C1)[N+](=O)[O-])=O QKBCBEQAZDXTNT-LLVKDONJSA-N 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910052712 strontium Inorganic materials 0.000 abstract 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 abstract 1
Classifications
-
- 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
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
Primary alcohols are prepared by the reduction of carboxylic acids or their functional derivatives, for example esters, halides and anhydrides, with an alkaline earth metal borohydride. The reduction is preferably carried out in an hydroxy-free medium, e.g. ether or tetrahydrofuran, at temperatures in the range - 10 DEG to + 80 DEG C., but hydroxylic solvents such as ethanol may be used at - 10 DEG to - 50 DEG C. Instead of using alkaline earth metal borohydrides, the reduction may be effected with a mixture of an alkaline earth metal salt and a complex metal borohydride, the metal component of which is not an alkaline earth metal, e.g. an alkaline earth iodide or bromide with sodium or potassium borohydride. The reduction is highly selective leaving nitro groups and double bonds unaffected. This method of reduction may be applied to all types of carboxylic acid esters, e.g. aliphatic, aromatic and aryl aliphatic esters and particularly for alpha-aminoacids and their functional derivatives. Thus, both the threo and erithro-modifications of p-nitrophenyl serine esters, or N-acyl derivatives thereof are reduced to 1-(p-nitrophenyl)-2 - amino - 1 : 3 dihydroxypropane and its N-acyl derivatives, respectively. In examples: (1) and (2) p-nitrobenzoic acid ethyl ester is reduced to p-nitrobenzylalcohol with calcium iodide and sodium borohydride in tetrahydrofuran or ether; (3) threo-p-nitrophenyl serine ethyl ester N-acetate is reduced to threo-1-(p-nitrophenyl) - 2 - acetamido - 1 : 3 - dihydroxypropane as in (1); (4) 2-(p-nitrophenyl)-serine ethyl ester is reduced with calcium chloride and sodium borohydride in ethanol, the product is converted to the benzal and the latter to threo-1 - (p - nitrophenyl) - 2 - amino - 1 : 3 - dihydroxypropan hydrochloride from which the free base is liberated; (5) D(-)-threo-2-(p-nitrophenyl)-serine is esterified with ethanol and reduced as in (4) to the D(-)-threo-aminodiol; (6) threo-p-nitrophenyl serine methyl ether ethyl ester is reduced as in (1) to threo-1-(p-nitrophenyl)-1-methoxy - 2 - amino - 3 - hydroxypropane; (7) p-nitrobenzoic acid ethyl ester is reduced with calcium borohydride to p-nitrobenzyl alcohol; (8) p-nitrobenzoic acid ethyl ester is reduced as in (4); (9) threo-beta-phenylserine ethyl ester is reduced as in (4) to threo-1-phenyl-2-amino - 1 : 3 - dihydroxypropane, the product is converted to the p-nitrobenzoylamino compound or benzalamino compound and thence to the free base; (10) ethyl benzoate is reduced to benzyl alcohol with calcium borohydride; (11) phenyl acetic acid ethyl ester is reduced as in (10) to beta-phenyl ethanol; (12) threo-beta-phenylserine ethyl ester is reduced with strontium iodide and sodium borohydride, the product is converted to the benzal compound of threo - 1 - phenyl - 2 - amino - 1 : 3 dihydroxypropane or separated by extraction; (13) Example (12) is repeated using barium iodide; (14) threo-p-nitro-beta-phenylserine ethyl ester reduced as in (12) to threo-p-nitrophenylserinol; (15) p-nitrobenzoyl chloride is reduced to p-nitrobenzoyl alcohol with calcium borohydride. Specifications 699,821 and 795,130 are referred to.ALSO:In the reduction of carboxylic acids to primary alcohols, calcium, strontium, or barium borohydrides are used, which may be in a hydroxyl-free medium, e.g. ether or tetrahydrofuran, or a hydroxylic solvent, e.g. ethanol. In Examples 4, 8, 9, calcium chloride dissolved in absolute ethanol is reacted with sodium borohydride which may also be dissolved in absolute ethanol. In Examples 12, 13, strontium or barium iodide dissolved in tetrahydrofuran is reacted with powdered sodium borohydride. Specifications 699,821, [Group IV (b)], and 795,130 are referred to.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU795131X | 1954-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB795131A true GB795131A (en) | 1958-05-14 |
Family
ID=10980350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB5446/55A Expired GB795131A (en) | 1954-02-23 | 1955-02-23 | Improvements in or relating to the preparation of primary alcohols |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB795131A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3935280A (en) * | 1975-01-10 | 1976-01-27 | Aldrich-Boranes, Inc. | Reduction of amino acids in the presence of boron trifluoride |
-
1955
- 1955-02-23 GB GB5446/55A patent/GB795131A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3935280A (en) * | 1975-01-10 | 1976-01-27 | Aldrich-Boranes, Inc. | Reduction of amino acids in the presence of boron trifluoride |
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