DE164294C - - Google Patents
Info
- Publication number
- DE164294C DE164294C DENDAT164294D DE164294DA DE164294C DE 164294 C DE164294 C DE 164294C DE NDAT164294 D DENDAT164294 D DE NDAT164294D DE 164294D A DE164294D A DE 164294DA DE 164294 C DE164294 C DE 164294C
- Authority
- DE
- Germany
- Prior art keywords
- alcohol
- acid ester
- ethyl
- alcohols
- ester
- 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
- 150000002148 esters Chemical class 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 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 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 150000003138 primary alcohols Chemical class 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 description 20
- -1 aromatic alcohols Chemical class 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000001656 butanoic acid esters Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 3
- 150000002969 pentanoic acid esters Chemical class 0.000 description 3
- 229910001023 sodium amalgam Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 2
- BYEVBITUADOIGY-UHFFFAOYSA-N ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC BYEVBITUADOIGY-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WJTCHBVEUFDSIK-NWDGAFQWSA-N (2r,5s)-1-benzyl-2,5-dimethylpiperazine Chemical compound C[C@@H]1CN[C@@H](C)CN1CC1=CC=CC=C1 WJTCHBVEUFDSIK-NWDGAFQWSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- WJZIPMQUKSTHLV-UHFFFAOYSA-N 2-ethyldecanoic acid Chemical compound CCCCCCCCC(CC)C(O)=O WJZIPMQUKSTHLV-UHFFFAOYSA-N 0.000 description 1
- STZGBQSXOHEXRA-UHFFFAOYSA-N 2-ethyltetradecanoic acid Chemical compound CCCCCCCCCCCCC(CC)C(O)=O STZGBQSXOHEXRA-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- HGINADPHJQTSKN-UHFFFAOYSA-N Monoethyl malonic acid Chemical compound CCOC(=O)CC(O)=O HGINADPHJQTSKN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-N PYRUVIC-ACID Natural products CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- TYFQFVWCELRYAO-UHFFFAOYSA-N Suberic acid Natural products OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- ALSTYHKOOCGGFT-UHFFFAOYSA-N cis-oleyl alcohol Natural products CCCCCCCCC=CCCCCCCCCO ALSTYHKOOCGGFT-UHFFFAOYSA-N 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- ZHYZQXUYZJNEHD-VQHVLOKHSA-N geranic acid Chemical compound CC(C)=CCC\C(C)=C\C(O)=O ZHYZQXUYZJNEHD-VQHVLOKHSA-N 0.000 description 1
- 229930008392 geranic acid Natural products 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- ZWRUINPWMLAQRD-UHFFFAOYSA-N n-Nonyl alcohol Natural products CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N n-hexyl alcohol Natural products CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- VSMOENVRRABVKN-UHFFFAOYSA-N oct-1-en-3-ol Chemical compound CCCCCC(O)C=C VSMOENVRRABVKN-UHFFFAOYSA-N 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- YYZUSRORWSJGET-UHFFFAOYSA-N octanoic acid ethyl ester Natural products CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZHYZQXUYZJNEHD-UHFFFAOYSA-N trans-geranic acid Natural products CC(C)=CCCC(C)=CC(O)=O ZHYZQXUYZJNEHD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Die bisher gebräuchlichen Methoden zur Darstellung primärer Alkohole sind für die Technik in vielen Fällen wenig verwendbar, da einerseits die Ausbeuten bei diesen Verfahren meist ungenügend, andererseits die Ausgangsmaterialien zu kostspielig sind.The methods used to date for the preparation of primary alcohols are for the In many cases, the technology is of little use because, on the one hand, the yields in these processes mostly insufficient, on the other hand the starting materials are too expensive.
Es wurde nun gefunden, daß man durch Anwendung eines stark wirkenden Reduktionsmittels , wie Natrium in Gegenwart vonIt has now been found that by using a strong reducing agent , like sodium in the presence of
ίο wasserfreien Alkoholen, in technisch befriedigender Weise aus den Estern von Mono- oder Dicarbonsäuren die entsprechenden ein- oder mehrwertigen primären Alkohole gewinnen kann, und zwar gerade aus solchen Säuren, bei welchen die Reduzierbarkeit nicht durch die Gegenwart von anderen negativen Gruppen begünstigt wird.ίο anhydrous alcohols, in technically satisfactory Wise win the corresponding mono- or polyhydric primary alcohols from the esters of mono- or dicarboxylic acids can, and precisely from those acids in which the reducibility is not possible is favored by the presence of other negative groups.
Die Umwandlung der Carboxylgruppe (COOH) in die Carbinolgruppe (CH2 OH) hat man bisher durch Reduktion der Säurechloride oder Anhydride mittels Natriumamalgams oder des Zinkkupferpaars (Würtz, Friedel) zu erreichen gesucht, ebenso auch durch Reduktion von Laktonen mit Natriumamalgam (Kiliani, Fischer). Alle diese Methoden haben aber für die Technik keine Bedeutung, da die Ausbeuten schlecht und die entstehenden Alkohole durch Nebenprodukte verunreinigt sind.The conversion of the carboxyl group (COOH) into the carbinol group (CH 2 OH) has so far been achieved by reducing the acid chlorides or anhydrides using sodium amalgams or the zinc-copper pair (Würtz, Friedel), and also by reducing lactones with sodium amalgam (Kiliani, Fischer ). However, none of these methods are of any significance for technology, since the yields are poor and the alcohols formed are contaminated by by-products.
Das Neue der vorliegenden Erfindung besteht in dem Nachweise, daß selbst solche Säuren, deren Reaktionsfähigkeit nicht durch die Anwesenheit von Hydroxyl- oder Carbonylgruppen erhöht ist, durch die Einwirkung von Natrium und wasserfreien Alkoholen aufThe novelty of the present invention consists in the evidence that even such Acids whose reactivity is not due to the presence of hydroxyl or carbonyl groups is increased by the action of sodium and anhydrous alcohols
die Ester direkt zu den entsprechenden primären Alkoholen reduziert werden.the esters are reduced directly to the corresponding primary alcohols.
Zwar hat schon E. Fischer (Ber. d. D. ehem. Ges., 23, 1890, S. 932) angegeben, daß sich die Ester der Oxysäuren, ebenso wie Laktone, durch Natriumamalgam reduzieren lassen. Er hat aber nur eine Reduktion bis zu den Aldehyden (Zuckerarten) bewirkt, welche als Nebenprodukt »kleine Mengen des durch weitere Reduktion des Zuckers entstandenen Alkohols« enthielten (S. 932). Auf diese Arbeit Fischer's bezieht sich.offenbar auch die entsprechende Bemerkung von Se el ig (Organische Reaktionen und Reagentien, 1892, S. 276). Eine technische Methode zur allgemeinen Darstellung primärer Alkohole war damit nicht gegeben. Letztere gelingt bei den bisher bekannten. Bedingungen nicht mit Natriumamalgam, sondern erfordert eine wesentlich stärkere Einwirkung von Reduktionsmitteln. It is true that E. Fischer (Ber. D. D. former Ges., 23, 1890, p. 932) stated that the esters of oxyacids, as well as lactones, are reduced by sodium amalgam permit. But it only caused a reduction down to the aldehydes (types of sugar), which as a by-product »small amounts of the resulting from further reduction of the sugar Alcohol ”(p. 932). Fischer obviously refers to this work also the corresponding remark by Se elig (Organic Reactions and Reagents, 1892, P. 276). A technical method for the general representation of primary alcohols was so not given. The latter succeeds with the previously known. Conditions not with Sodium amalgam, but requires a much stronger exposure to reducing agents.
Daß die Ester von Säuren, welche, wie die , > Cyclohexenoncarbonsäure in ParaStellung zum Carboxyl eine Carbonylgruppe enthalten, bei der Behandlung mit Natrium und Alkohol neben der Oxysäure auch das entsprechende Oxycyclohexancarbinol liefern, ist bereits Gegenstand des Patents 148207. Dieser einzelne Fall läßt aber keineswegs. voraussehen, daß auch Säuren, welche derartige aktivierende Gruppen, wie es eine in ParaStellung befindliche Carbonylgruppe ist, nicht enthalten, als Ausgangsmaterialien für die technische Darstellung bisher schwer zugänglicher primärer Alkohole verwendbar sind. Denn esThat the esters of acids, which, like the,> Cyclohexenoncarbonsäure in ParaPosition to the Carboxyl contain a carbonyl group when treated with sodium and alcohol supplying the corresponding oxycyclohexanecarbinol in addition to the oxyacid is already available Subject of the patent 148207. This individual case by no means leaves. foresee that also acids which have such activating groups as there is one in the para position located carbonyl group is not included as starting materials for the technical Representation of previously difficult to access primary alcohols can be used. For it
ist allgemein bekannt, wie sehr derartige Reaktionen durch die Anwesenheit stark negativer Gruppen im Molekül beeinflußt und daß sie häufig überhaupt erst dadurch ermöglicht werden.it is well known how very negative such reactions are due to the presence Groups in the molecule and that it is often only made possible by this will.
Die Reduktion der Ester zu den entsprechenden primären Alkoholen ist sowohl bei den aliphatischen und hydroaromatischen als auch bei den meisten aromatischen AlkoholenThe reduction of the esters to the corresponding primary alcohols is at both the aliphatic and hydroaromatic as well as most aromatic alcohols
ίο gelungen. Eine alleinige Ausnahme machen nach den bisherigen Erfahrungen die Benzoesäure und einige substituierte Benzoesäuren. Bei den ungesättigten Säuren wird die in tt-ß-Stellung zum Carboxyl befindliche Äthylenbindung in der Regel aufgelöst, während an anderer Stelle stehende Doppelbindungen meist unverändert bleiben.ίο succeeded. Make a sole exception According to previous experience, benzoic acid and some substituted benzoic acids. In the case of unsaturated acids, the ethylene bond in the tt-ß position to the carboxyl becomes usually dissolved, while double bonds standing elsewhere mostly remain unchanged.
Endlich sind für die Darstellung primärer Alkohole auch die um zwei Kohlenstoffatome reicheren Acetessigesterderivate zu verwenden. In diesen Fällen findet nachgewiesenermaßen die Säurespaltung vor der Reduktionswirkung statt. Die in statu nascendi zur Reduktion gelangenden Ester liefern ganz besonders gute Ausbeuten an Alkoholen.Finally, there are also those around two carbon atoms for the representation of primary alcohols to use richer acetoacetic ester derivatives. In these cases it has been proven the acid cleavage takes place before the reducing effect. The in statu nascendi for reduction obtained esters give particularly good yields of alcohols.
Als Reduktionsmittel benutzt man metallisches Natrium bei
freien Alkoholen.Metallic sodium is used as a reducing agent
free alcohols.
Gegenwartpresence
von wasser-of water
In ein mit Rückflußkühler und Tropftrichter versehenes Gefäß bringt man eine 6 Atomen entsprechende Menge metallisches Natrium in großen Stücken und läßt darauf durch den Tropf trichter nach und nach eine Mischung von einem Molekül der zu reduzierenden Ester mit dem drei- bis vierfachen Gewicht absoluten Alkohols fließen. Die Schnelligkeit des Zufließenlassens wird so geregelt, daß stets eine gleichmäßige lebhafte Reaktion unterhalten wird. Nachdem sämtlicher Ester eingetragen, wird die Reaktion durch Erhitzen beendet und der eventuell bleibende Rest von Natrium durch weitere Zugabe von Alkohol gelöst. Nach Zusatz von etwas Wasser wird der Äthylalkohol abdestilliert. Aus dem Rückstande isoliert man das Reduktionsprodukt durch Wasserdampfdestillation, durch Ausschütteln mit einem Lösungsmittel, z. B. Äther, oder auf sonst geeignete Weise. Aus der alkalischen Lauge kann man endlich einen Teil der Säure, welcher der Reaktion entgangen ist, wiedergewinnen. One is placed in a vessel equipped with a reflux condenser and a dropping funnel Amount of metallic sodium corresponding to 6 atoms in large pieces and leave on it through the dropping funnel gradually add a mixture of one molecule of the substance to be reduced Esters with three to four times the weight of absolute alcohol flow. the The speed of the inflow is regulated in such a way that it is always a steady, lively one Reaction is entertained. After all the esters have been added, the reaction begins terminated by heating and the remaining remainder of sodium by further Adding dissolved alcohol. After adding a little water, the ethyl alcohol is distilled off. The reduction product is isolated from the residue by steam distillation, by shaking with a solvent, e.g. B. ether, or in some other suitable way. From the alkaline lye one can finally recover part of the acid which has escaped the reaction.
Der in dem vorstehenden Beispiel genannte absolute Äthylalkohol kann auch durch andere wasserfreie Alkohole, wie Methylalkohol, Butylalkohol, Amylalkohol usw., ersetzt werden.The absolute ethyl alcohol mentioned in the above example can also be replaced by others anhydrous alcohols such as methyl alcohol, butyl alcohol, amyl alcohol, etc., can be replaced.
Auch die Isolierung des gebildeten Alkohols kann auf verschiedene Weise ausgeführt werden, welche den jeweiligen Eigenschaften des Produktes angepaßt ist.The alcohol formed can also be isolated in various ways which is adapted to the respective properties of the product.
Die erhaltenen Alkohole sind der verschiedensten technischen Anwendung fähig, sei es für sich, z. B. als Riechstoffe, sei es als Ausgangsmaterialien für die Darstellung ihrer Ester, der entsprechenden Aldehyde, Halogenderivate usw.The alcohols obtained are capable of a wide variety of technical applications, be it for yourself, z. B. as fragrances, be it as starting materials for the representation their esters, the corresponding aldehydes, halogen derivatives, etc.
Um die allgemeine Anwendbarkeit des beschriebenen Verfahrens darzutun, seien im folgenden eine Auswahl der nach ihm zu erhaltenden Alkohole namhaft gemacht, ohne daß diese Aufzählung auch nur im entferntesten vollständig sein kann.In order to demonstrate the general applicability of the method described, in following a selection of the alcohols to be obtained after him named, without that this list can only be remotely complete.
Aliphatische Alkohole.Aliphatic alcohols.
Normal - ButylalkoholNormal - butyl alcohol
CH3 CH2 CH2 CH2OHCH 3 CH 2 CH 2 CH 2 OH
(aus n-Buttersäureäthylester), Sp. ii6°, Phenylurethan, Fp. 570.(from n-butyric acid ethyl ester), Sp. ii6 °, phenyl urethane, m.p. 57 0 .
Normal - Amylalkohol
CH3- CH2 - CH2- CH2- CH2- OH Normal - amyl alcohol
CH 3 - CH 2 - CH 2 - CH 2 - CH 2 - OH
(aus η -Valeriansäureäthylester oder aus n-propylacetessigsaurem Äthyl).(from ethyl valerate or from n-propylacetoacetic acid Ethyl).
Normal - HexylalkoholNormal - hexyl alcohol
CH3(CH2J^CH2OH
(aus Capronsäureäthylester), Sp. 1560.
Isohexylalkohol (Methyl-2-pentanol-i)
CH3-CH2-CH2- CH(CH3)- CH2OH CH 3 (CH 2 J ^ CH 2 OH
(from ethyl caproate), col. 156 0 .
Isohexyl alcohol (methyl-2-pentanol-i)
CH 3 -CH 2 -CH 2 - CH (CH 3) - CH 2 OH
(aus Methyl-η - propylacetessigester), Sp. 146 bis 148 °.(from methyl-η-propyl acetic acid ester), col. 146 up to 148 °.
Isohexylalkohol (Methyl-4-pentanol-1)Isohexyl alcohol (methyl-4-pentanol-1)
(C HJ2 C H(C H2)2 -CH2OH
(aus Isobutylacetessigester), Sp. 160 bis 165 °. Normal - Octylalkohol (C HJ 2 CH (CH 2 ) 2 -CH 2 OH
(from isobutyl acetic acid ester), Sp. 160 to 165 °. Normal - octyl alcohol
CH3-(CH2J6-CH2- OHCH 3 - (CH 2 J 6 -CH 2 - OH
(aus Caprylsäureäthylester), Sp. 17 mm 96 °; Essigester Sp. 15 mm 98°.(from ethyl caprylate), Sp. 17 mm 96 °; Essigester Sp. 15 mm 98 °.
Normal - NonylalkoholNormal - nonyl alcohol
CH3-(CH2J7-CH2OHCH 3 - (CH 2 J 7 -CH 2 OH
(aus Pelargonsäureäthylester), Sp. 209 bis 2io° (unkorr.); Essigester, Sp. 8 mm no0; Buttersäureester, Sp. 14 mm 134 bis 1370; Valeriansäureester, Sp. 12 mm 142 bis 1460.(from ethyl pelargonate), Sp. 209 to 2io ° (uncorrupted); Ethyl acetate, col. 8 mm no 0 ; Butyric acid ester, Sp. 14 mm 134 to 137 0 ; Valeric acid ester, Sp. 12 mm 142 to 146 0 .
Normal - DecylalkoholNormal - decyl alcohol
CH3-(CH2J8- CH2-OH
(aus Caprinsäureäthylester), Sp. 12 mm 1200.
Isodecylalkohol
C6H13CH-(CH3J-CH2-CH2-OH CH 3 - (CH 2 J 8 - CH 2 -OH
(from ethyl capric acid), Sp. 12 mm 120 0 . Isodecyl alcohol
C 6 H 13 CH- (CH 3 J-CH 2 -CH 2 -OH
(aus Hexylmethylakrylsäureäthylester mit 9 Atomen Natrium), Sp. 14 mm in bis Ii6°,(from ethyl hexylmethylakrylate with 9 atoms of sodium), Sp. 14 mm in up to Ii6 °,
Dimethyl-3 · 7-octanolDimethyl-3 x 7-octanol
(C HJ2 C H · C H2 · C H2 (C HJ 2 CH • CH 2 • CH 2
'CH. CHa·'CH. CH a
CH3 CH 3
OHOH
Sp. 14 bis ιό mm bei 115 bis 1200.Sp. 14 to ιό mm at 115 to 120 0 .
Der Alkohol wurde durch Reduktion des durch Kondensation und Wasserabspaltung aus Methyl - 6 - heptanon - 2 mit Jodessigester erhältlichen Äthylesters der Dimethyl -3-7-octensäure (Sp. 15 bis 17 mm 122 bis 1250) dargestellt.The alcohol was prepared by reducing the ethyl ester of dimethyl -3-7-octenoic acid (15 to 17 mm, 122 to 125 0 ) obtainable by condensation and elimination of water from methyl-6-heptanone-2 with iodoacetic ester.
Normal - Dodecylalkohol
CHf(CHJ10-CH2OH Normal - dodecyl alcohol
CHf (CHJ 10 -CH 2 OH
(aus Laurinsäureäthylester), Sp. 255 bis 2590; Essigsäureester, Sp. 10 mm 1400; Valerian säureester, Sp. 10 mm 1700.(from ethyl laurate), col. 255 to 259 0 ; Acetic acid ester, Sp. 10 mm 140 0 ; Valeric acid ester, Sp. 10 mm 170 0 .
Dimethyl-5 .9-decadien-(4.8)-ol (I)
C: CH-CH2- Dimethyl-5 .9-decadiene- (4.8) -ol (I)
C: CH-CH 2 -
C: CH- CH2- CH2- CH2(OH)C: CH- CH 2 - CH 2 - CH 2 (OH)
(Sp. 16 bis 18 mm 150 bis 1550) durch Reduktion des aus Citral und Malonsäuremonoäthylester erhältlichen Citrylidenessigesters gewonnen. (Sp. 16 to 18 mm 150 to 155 0 ) obtained by reducing the citrylidenessigester obtainable from citral and malonic acid monoethyl ester.
MyristinalkoholMyristic alcohol
(aus Myristinsäureäthylester), Fp. 38 °, Sp. 10 mm i6o°.(from ethyl myristic acid), melting point 38 °, bp 10 mm 160 °.
Penten-4-ol (I)Penten-4-ol (I)
CH2 : CH- CH2 · CH2 CH2 OH CH 2 : CH-CH 2 • CH 2 CH 2 OH
(aus Allylacetessigester, oder besser aus AUyI-essigsäureester), Sp. 142°.(from allylacetoacetic ester, or better from AUyI-acetic acid ester), Sp. 142 °.
Dimethyl-3, 7-octen-6-ol (I)Dimethyl-3, 7-octen-6-ol (I)
(CH3J2CiCHCHfCHfCH(CH3)-• CH2CH2- OH (CH 3 J 2 CiCHCHfCHfCH (CH 3 ) - • CH 2 CH 2 - OH
(Sp. 14 mm 115 bis 1170); Semicarbazon des Brenztraubensäureesters (Sp. 1120) aus 3-7-Dimethyl-6-octensäureester. (Sp. 14 mm 115 to 117 0 ); Semicarbazone of the pyruvic acid ester (Sp. 112 0 ) from 3-7-dimethyl-6-octenoic acid ester.
Um diesen Säureester zu gewinnen, hydrogeniert man Geraniumsäure. Das Kalisalz der so erhaltenen Rhodinolsäure, wird sodann mit Bromäthyl esterifiziert. Der Rhodinolsäureester (3 · 7 - Dimethyl - 6 - octensäureester) siedet bei 114 bis Ii6° unter 10 mm.Geranic acid is hydrogenated to obtain this acid ester. The potash salt the rhodinoleic acid thus obtained is then esterified with bromoethyl. The rhodinolic acid ester (3 · 7 - dimethyl - 6 - octenoic acid ester) boils at 114 to 16 ° below 10 mm.
Undekylen-io-ol (I)Undekylen-io-ol (I)
CiJ2 : CH(CH2J6 CH2OH
(aus Undekylensäureester).
OleinalkoholCiJ 2 : CH (CH 2 J 6 CH 2 OH
(from undekylenic acid ester).
Oleic alcohol
(aus Oleinsäureäthylester), Sp. 13 mm 207 °. Hydroaromatische Alkohole.
Hexahydrobenzylalkohol(from oleic acid ethyl ester), Sp. 13 mm 207 °. Hydroaromatic alcohols.
Hexahydrobenzyl alcohol
Hn C H2O HH n CH 2 OH
(aus Hexahydrobenzoesäureäthylester), Sp. Ii mm gegen 820; Phenylurethan Fp. etwa 82 °.(from ethyl hexahydrobenzoate), Sp. II mm against 82 0 ; Phenyl urethane m.p. about 82 °.
CampholenalkoholCampholing alcohol
C10H18OC 10 H 18 O
(aus Campholensäureäthylester), Sp. 211 bis 2130, d = I, 593. Essigsäureester Sp. 21 mm 135 bis 1360; Buttersäureester Sp. 257 bis 2590, Oxyd C10H18O Sp. 177 bis 1790.(from ethyl campholate), col. 211 to 213 0 , d = 1.593. Acetic acid ester, col. 21 mm 135 to 136 0 ; Butyric acid ester Sp. 257 to 259 0 , Oxide C 10 H 18 O Sp. 177 to 179 0 .
CampholalkoholCamphol alcohol
(aus Campholsäureäthylester), Fp. 6o°, Sp.(from ethyl campholate), m.p. 60 °, Sp.
Aromatische Alkohole.Aromatic alcohols.
PhenyläthylalkoholPhenylethyl alcohol
C6H5CH2CH2OH ■ S5 C 6 H 5 CH 2 CH 2 OH ■ S 5
(aus Phenylessigester), Sp. 214 bis 2160 (unkorr.) 12 mm 98 bis ι oo°; Ameisensäureester Sp. 12 mm 96 bis 97 °; Buttersäureester Sp. 12 mm 130 bis 1320; Valeriansäureester Sp. 10 mm 134 bis 1380.(from phenyl acetic ester), col. 214 to 216 0 (uncorrect.) 12 mm 98 to ι oo °; Formic acid ester Sp. 12 mm 96 to 97 °; Butyric acid ester Sp. 12 mm 130 to 132 0 ; Valeric acid ester Sp. 10 mm 134 to 138 0 .
PhenylpropylalkoholPhenylpropyl alcohol
C6H6(CHJ2-CH2OHC 6 H 6 (CHJ 2 -CH 2 OH
(aus Benzylacetessigester oder aus Zimtsäureester mit 8 Atomen Natrium), Sp. 12 mm 120°; Ameisensäureester Sp. 12 mm 1170; Buttersäureester Sp. 16 mm 151 bis 155°; \^aleriansäureester Sp. 18 mm 159 bis 161 °.(from benzyl acetic ester or from cinnamic acid ester with 8 atoms of sodium), Sp. 12 mm 120 °; Formic acid ester Sp. 12 mm 117 0 ; Butyric acid ester Sp. 16 mm 151 to 155 °; \ ^ aleric acid ester Sp. 18 mm 159 to 161 °.
ρ - Methoxyphenyläthylalkoholρ - methoxyphenyl ethyl alcohol
(CH3O)C6HfCH2-CH2-OH(CH 3 O) C 6 HfCH 2 -CH 2 -OH
(aus p-Methoxyphenylessigsäureester), Fp. gegen 22 bis 23 °, Sp. 364 bis 3660, 11 mm um 145°; Essigsäureester Sp. 11 mm 155 bis 1570... (p-Methoxyphenylessigsäureester), mp about 22 ° to 23 °, Sp 364-366 0, 11 mm by 145 °; Acetic acid ester Sp. 11 mm 155 to 157 0 .
Mehrwertige Alkohole.Polyhydric alcohols.
Dimethyl - (2 · 2)-butandiol (1*4) (aus αα-Dimethylbernsteinsäureester) Sp. 10 mm 1230.Dimethyl - (2 · 2) -butanediol (1 * 4) (from αα-dimethylsuccinic acid ester) Sp. 10 mm 123 0 .
Dimethyl-(2 · 2)-pentandiol (1 · 5) (aus α α-Dimethylglutarsäureester), Sp. 12 mm 1300.Dimethyl (2 · 2) pentanediol (1 · 5) (from α α-dimethylglutaric acid ester), Sp. 12 mm 130 0 .
Hexandiol (ι ·6) (aus Adipinsäureester), Fp. 40°, Sp. 12 mm 151 °.Hexanediol (ι · 6) (from adipic acid ester), melting point 40 °, melting point 12 mm 151 °.
Methyl-(2)-hexandiol (1 · 6) (aus ß-Methyladipinsäureester), Sp. 15 mm 160 bis 165 °.Methyl- (2) -hexanediol (1 x 6) (from ß-methyladipic acid ester), Sp. 15 mm 160 to 165 °.
Octandiol (1 · 8) (aus Korksäureester) Sp. 20 mm um 1720, Fp. etwa 63 °.Octanediol (1 × 8) (from suberic acid ester) Sp. 20 mm around 172 0 , m.p. about 63 °.
Dekandiol (1 · 10) (aus Sebacinsäureester), Fp. 71 bis 720, Sp. 11 mm um 179°.Decanediol (1 × 10 6) (from sebacic acid ester), m.p. 71 to 72 0 , sp. 11 mm at 179 °.
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE164294C true DE164294C (en) | 1900-01-01 |
Family
ID=429903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT164294D Expired DE164294C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE164294C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE765726C (en) * | 1939-06-29 | 1953-04-27 | Hydrierwerke A G Deutsche | Process for the production of higher molecular weight alcohols |
| DE934524C (en) * | 1946-06-28 | 1955-10-27 | Innovations Chimiques Sinnova | Process for the production of high molecular weight alcohols by reducing esters with sodium |
-
0
- DE DENDAT164294D patent/DE164294C/de not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE765726C (en) * | 1939-06-29 | 1953-04-27 | Hydrierwerke A G Deutsche | Process for the production of higher molecular weight alcohols |
| DE934524C (en) * | 1946-06-28 | 1955-10-27 | Innovations Chimiques Sinnova | Process for the production of high molecular weight alcohols by reducing esters with sodium |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2542937C3 (en) | Fragrance-releasing solid block | |
| DE164294C (en) | ||
| DE2656801C2 (en) | Process for the production of carrier ampholytes for the isoelectric focusing of high molecular weight amphoteric substances | |
| DE1056139B (en) | Process for the preparation of alpha-amino-beta-oxy-carboxylic acid anilides | |
| DE1168894B (en) | Process for the preparation of dienocarboxylic acids with non-conjugated double bonds or their esters | |
| DE1929550A1 (en) | Process for the preparation of cyclic esters of dicarboxylic acids | |
| DE718072C (en) | Process for the preparation of therapeutically valuable primary alcohols | |
| DE938668C (en) | Process for the production of aldehydes by the addition of CO and H onto olefinic carbon compounds | |
| DE2558657A1 (en) | BRANCHED CHAIN CARBONIC ACIDS AS FRAGRANCES | |
| DE133631C (en) | ||
| DE708349C (en) | Process for the preparation of acid amide-like condensation products | |
| DE650380C (en) | Process for the preparation of morpholine or 2,6-dimethylmorpholine | |
| DE3049802C1 (en) | Bicyclic alcohols, their production and use | |
| DE2559433C3 (en) | Cyclopentene derivatives | |
| DE960188C (en) | Process for the preparation of long-chain, unbranched aliphatic monocarboxylic acids or their methyl esters | |
| DE1096904B (en) | Process for the production of the 17-undecenoate of OEstradiol | |
| DE248255C (en) | ||
| AT226736B (en) | Process for the production of deoxy sugars | |
| DE705641C (en) | Process for the production of carboxylic acid anhydrides | |
| DE709435C (en) | ||
| DE202790C (en) | ||
| DE1496832C3 (en) | Acid galvanic nickel bath | |
| DE155287C (en) | ||
| DE1255660B (en) | Process for the preparation of acetal peroxides containing glycol ether groups | |
| DE245532C (en) |