DE943648C - Process for the preparation of ylides of phosphorus - Google Patents
Process for the preparation of ylides of phosphorusInfo
- Publication number
- DE943648C DE943648C DEB33051A DEB0033051A DE943648C DE 943648 C DE943648 C DE 943648C DE B33051 A DEB33051 A DE B33051A DE B0033051 A DEB0033051 A DE B0033051A DE 943648 C DE943648 C DE 943648C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- ylides
- groups
- phosphorus
- solution
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 5
- 239000011574 phosphorus Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000004714 phosphonium salts Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005521 carbonamide group Chemical group 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- -1 carbon ester Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- APISVOVOJVZIBA-UHFFFAOYSA-N 2-(triphenyl-$l^{5}-phosphanylidene)acetonitrile Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=CC#N)C1=CC=CC=C1 APISVOVOJVZIBA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- ARPLQAMUUDIHIT-UHFFFAOYSA-M cyanomethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC#N)C1=CC=CC=C1 ARPLQAMUUDIHIT-UHFFFAOYSA-M 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IIHPVYJPDKJYOU-UHFFFAOYSA-N triphenylcarbethoxymethylenephosphorane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=CC(=O)OCC)C1=CC=CC=C1 IIHPVYJPDKJYOU-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5352—Phosphoranes containing the structure P=C-
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Verfahren zur Herstellung von Yliden des Phosphors Es ist bekannt, daB man durch Umsetzern. von metallorganischen Verbindungen, wie Phenyllithium, mit quartären Phosphoniumsalzen der allgemeinen Formel (I) sogenannte Ylide (II) erhält (vgl. G. W i t t i g und Mitarbeiter; Liebigs Ann. d. Chemie 580 [1g53], S. 48), z. B. In diesen Formeln bedeuten die Zeichen R gleiche oder verschiedene Aryl- oder Alkylgruppen, die auch indifferente Substituenten tragen und isolierte oder konjugierte Doppel- und bzw. oder Dreifach-Bindungen enthalten können, R' und R" Wasserstoff oder gleiche oder verschiedener Alkyl- oder Arylgruppen der bei R besprochenen Art und X ein Halogenatom. Man hat zur Darstellung von Yliden des Phosphors früher auch schon ein noch umständlicheres und gefährlicheres Verfahren benutzt, das in der Umsetzung von quartären Phosphoniumsalzen mit geschmolzenem Kalium besteht (vgl. die Dissertationen von Lüscher [Zürich 1g22] und -von I s 1 e r [Zürich 192q.] sowie die Arbeit von C o f f -m am und M ar vel, J. Am. Chem. Soc. 5 z [igz9], S. 3497). Ein neuerer Vorschlag geht dahin, als Halogenwasserstoff entfernende Mittel Alkalimetallamide zu verwenden.Process for the preparation of ylides of phosphorus It is known that converters. obtained from organometallic compounds such as phenyllithium with quaternary phosphonium salts of the general formula (I) so-called ylides (II) (cf. G. W ittig and coworkers; Liebigs Ann. d. Chemie 580 [1g53], p. 48), e.g. B. In these formulas, the symbols R denote identical or different aryl or alkyl groups which also carry indifferent substituents and can contain isolated or conjugated double and / or triple bonds, R 'and R "denote hydrogen or identical or different alkyl or aryl groups of the type discussed for R. and X a halogen atom. For the preparation of ylides of phosphorus, an even more cumbersome and dangerous process has been used in the past, which consists in the conversion of quaternary phosphonium salts with molten potassium (cf. the dissertations by Lüscher [Zurich 1g22 ] and -von I s 1 er [Zurich 192q.] as well as the work of C off -m am and M ar vel, J. Am. Chem. Soc. 5 z [igz9], p. 3497) to the use of alkali metal amides as hydrogen halide removing agents.
Es wurde nun gefunden, daß man Ylide des Phosphors bzw. ihre Lösungen in besonders vorteilhafter Weise ungefährlich erhält, wenn man die obengenannten Phosph oniumsalze mit Alkali- oder Erdalkalialkoholaten umsetzt. Zweckmäßig arbeitet man in Gegenwart von wasserfreien Lösungs- oder Vordünnungsmitteln, wie Benzol, Äther, Tetrahydrofuran oder Alkoholen, und unter Ausschluß von Luft, da die Ylide im allgemeinen sehr empfindlich gegen molekularen Sauerstoff und gegen Wasser sind. Die Ylide bilden sich im allgemeinen bereits bei gewöhnlicher Temperatur rasch; zuweilen ist Erwärmen förderlich.It has now been found that ylides of phosphorus or their solutions in a particularly advantageous manner non-hazardous if one receives the above Reacts phosphonium salts with alkali or alkaline earth alcoholates. Appropriate works one in the presence of anhydrous solvents or pre-diluents, such as benzene, Ether, tetrahydrofuran or alcohols, and with the exclusion of air, as the ylides are generally very sensitive to molecular oxygen and to water. The ylids generally form rapidly even at ordinary temperature; sometimes warming is beneficial.
Die Verwendung von Alkali- und Erdalkalimetallalkoholaten zur Herstellung der Ylide hat, insbesondere bei gleichzeitiger Verwendung von Alkoholen als Verdünnungsmittel, den überraschenden Vorteil, da:ß die erhaltenen Ylidlösungen in ihrer Reaktionsfähigkeit verlangsamt und differenziert sind; sie reagieren z. B: mit Aldehyden rasch, mit Ketonen erheblich langsamer und mit Ester-, Carbonamid- oder Nitrilgruppen erst nach Tagen in merklichem Ausmaß. Es gelingt deshalb, nach dem vorliegenden Verfahren auch Ylide herzustellen, deren Gruppen R,. R' oder R" außer Oxy- oder Äthergruppen auch Keto'-, Ester-, Carbonamid-, Carboxyl- oder Nitrilgruppen enthalten.The use of alkali and alkaline earth metal alcoholates for production the ylids, especially when using alcohols as a diluent, the surprising advantage that: ß the ylide solutions obtained in their reactivity are slowed down and differentiated; they react z. B: with aldehydes quickly, with Ketones much more slowly and only with ester, carbonamide or nitrile groups after days to a noticeable extent. It is therefore possible according to the present method also produce ylides whose groups R ,. R 'or R "except for oxy or ether groups also contain keto, ester, carbonamide, carboxyl or nitrile groups.
Dia in den folgenden Beispielen genannten Teile sind Gewichtsteile.The parts mentioned in the following examples are parts by weight.
Beispiel i In eine 2o bis 30° wartneLösung von 11,5 Teilen Natrium in 15o Teilen absol. Äthanol trägt man unter Rühren rasch eine Lösung von Zoo Teilern, Benzyltriphenylphosphoniumchlorid in 15o Teilen absol. Äthanol ein: Das Gemisch trübt sich: sofort und wird orangerot; nach etwa io Minuten zeigt es den pH-Wert 7 bis 8, und es ist ein Teil des Ylids in Form roter khomben ausgefallen, die an der Luft rasch zu einem weißen Pulver verwittern.. _ Beispiele Zu einer Lösung von 26o Teilen Triphenylphosphin in 13oo Teilen Benzol gibt man 122 Teile Chloressigsäureäthylesters Man kocht das Gemisch 5 Stunden unter Rückfluß, worauf man das ausgefallene Carbäthoxytnethyltriphenylphosphoniumchlorid absaugt, iriit Benzol wäscht und trocknet. Die Ausbeute beträgt 34o Teile, der Schmelzpunkt liegt bei 14.2°: Eine Lösung von i94 Teilen dieses Phosphoniutnsalzes in 4oo Teilen absol. Äthantil wird rasch in eine Lösung von 11,5 Teilen Natrium in i50 Teilen absol. Äthanol bei 2o.° eingerührt. Man erhält in fast quantitativer Ausbeute eine Lösung von Carbäthoxymethylentriphenylphosphin der Formel H5 C200C-CH = P (Cs,H5)3.Example i In a 20 to 30 ° solution of 11.5 parts of sodium in 15o parts Ethanol one quickly carries a solution of zoo dividers while stirring, Benzyltriphenylphosphonium chloride in 15o parts absol. Ethanol on: The mixture becomes cloudy: immediately and becomes orange-red; after about 10 minutes it shows the pH value 7 to 8, and there is a part of the ylid in the form of red khomben that turned out to be at weather quickly to a white powder in the air .. _ Examples of a solution of 26o parts of triphenylphosphine in 1300 parts of benzene are added to 122 parts of ethyl chloroacetate The mixture is refluxed for 5 hours, whereupon the precipitated Carbäthoxytnethyltriphenylphosphoniumchlorid sucks off, washes and dries with benzene. The yield is 340 parts and the melting point is at 14.2 °: A solution of 194 parts of this phosphonium salt in 400 parts absolute Ethantil is rapidly converted into a solution of 11.5 parts of sodium in 150 parts absolute Stir in ethanol at 20 °. One receives one in almost quantitative yield Solution of carbethoxymethylene triphenylphosphine of the formula H5 C200C-CH = P (Cs, H5) 3.
Beispiel 3 Zu einer Lösung von z66 Teilen Triphenylphosphin in 'goo Teilen Benzol gibt man 75 Teile Chloracetonitril. Man erhitzt das Gemisch 8 Stunden unter Rückflug zum Sieden, worauf man das auskristallisierteCyanmethyltriphenylphosphoniumchlorid absaugt. Die Ausbeute beträgt 27o Teile, der Schmelzpunkt liegt bei 244.°.Example 3 To a solution of 66 parts of triphenylphosphine in 'goo 75 parts of chloroacetonitrile are added to parts of benzene. The mixture is heated for 8 hours returning to the boil, whereupon the crystallized cyanomethyltriphenylphosphonium chloride sucks. The yield is 270 parts and the melting point is 244 °.
Eine Lösung von 175 Teilen dieses Phosphoniumsalzes in 6oo Teilen absol. Äthanol wird rasch in eine Lösung von 11,5 Teilen Natrium in 13o Teilen absol. Äthanol bei etwa 2o° eingerührt. Nach etwa 30 Minuten Rühren, ist die Bildung des Ylids praktisch vollständig; es scheidet sich aus der Lösung zum Teil als farbloses Kristallpulver aus, das vielleicht ein Äthanol-Additionsprodukt darstellt. Die Suspension zeigt die für das Cyanmethylen-triphenylphosphirn der Formel N C-C H = P (C8 H5) 3 zu erwartenden Umsetzungm Beispiel 4 Zu einer Lösung von 266 Teilen Triphenylphosphin in goo Teilen Benzol gibt man 93 Teile Chloracetamid. Man erhitzt das Gemisch 8 Stunden unter Rückfluß zum Sieden und erhält 3oo Teile Carbamidomethyltriphenylphosphoniu@mchlorid vom Schmelzpunkt 176°.A solution of 175 parts of this phosphonium salt in 600 parts of absol. Ethanol is rapidly converted into a solution of 11.5 parts of sodium in 130 parts. Stir in ethanol at about 20 °. After about 30 minutes of stirring, the formation of the ylid is practically complete; it separates out of the solution partly as colorless crystal powder, which is perhaps an ethanol addition product. The suspension shows the reaction to be expected for the cyanomethylene triphenylphosphine of the formula N CC H = P (C8 H5) 3 in Example 4 93 parts of chloroacetamide are added to a solution of 266 parts of triphenylphosphine in 100 parts of benzene. The mixture is refluxed for 8 hours and 300 parts of carbamidomethyltriphenylphosphonium chloride with a melting point of 176 ° are obtained.
Eine 4o bis 5o° warme Lösung von i8o Teilen dieses Phosphoniumsalzes in 45o Teilen absol. Äthanol wird in eine Lösung von 11,5 Teilen Natrium in i2o Teilen absol. Äthanol eingerührt. Das Gemisch, aus dem sich sofort ein farbloses Kristallpulver ausscheidet, reagiert nach io Minuten neutral. Es enthält in praktisch quantitativer Ausbeute- das Carb@amidomethylentriphenylphosphin der Formel H2N-CO-CH = P (C6H5)3 bzw. sein Alkoholadditionsprodukt, was durch die Umsetzung mit 4o Teilen Crotonaldehyd erwiesen wird, wobei man in rascher Reaktion neben Triphenylphosphinoxyd 33 Teile Sorbinsäureamid voin Schmelzpunkt 167 bis 168° erhält.A 40 to 50 ° warm solution of 180 parts of this phosphonium salt in 45o parts absolute Ethanol is dissolved in a solution of 11.5 parts of sodium in i2o Share absolute Stir in ethanol. The mixture that immediately becomes colorless Crystal powder separates, reacts neutrally after 10 minutes. It contains in handy quantitative yield - the carb @ amidomethylene triphenylphosphine of the formula H2N-CO-CH = P (C6H5) 3 or its alcohol addition product, which is achieved by the reaction with 40 parts Crotonaldehyde is proven, with one in rapid reaction in addition to triphenylphosphine oxide 33 parts of sorbic acid amide of melting point 167 to 168 ° are obtained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB33051A DE943648C (en) | 1954-10-20 | 1954-10-20 | Process for the preparation of ylides of phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB33051A DE943648C (en) | 1954-10-20 | 1954-10-20 | Process for the preparation of ylides of phosphorus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE943648C true DE943648C (en) | 1956-05-24 |
Family
ID=6963914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB33051A Expired DE943648C (en) | 1954-10-20 | 1954-10-20 | Process for the preparation of ylides of phosphorus |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE943648C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1026745B (en) * | 1954-10-20 | 1958-03-27 | Basf Ag | Process for the production of vitamin A acid or its esters |
| DE1096349B (en) * | 1958-08-28 | 1961-01-05 | Hoffmann La Roche | Process for the preparation of polyenocarboxylic acid esters and their saponification products |
| DE1268096B (en) * | 1959-05-15 | 1968-05-16 | Basf Ag | Optical brighteners |
-
1954
- 1954-10-20 DE DEB33051A patent/DE943648C/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1026745B (en) * | 1954-10-20 | 1958-03-27 | Basf Ag | Process for the production of vitamin A acid or its esters |
| DE1096349B (en) * | 1958-08-28 | 1961-01-05 | Hoffmann La Roche | Process for the preparation of polyenocarboxylic acid esters and their saponification products |
| DE1268096B (en) * | 1959-05-15 | 1968-05-16 | Basf Ag | Optical brighteners |
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