DK158303B - METHOD OF PREPARING ALPHA-CYAN-3-PHENOXYBENZYL ALCOHOL - Google Patents
METHOD OF PREPARING ALPHA-CYAN-3-PHENOXYBENZYL ALCOHOL Download PDFInfo
- Publication number
- DK158303B DK158303B DK378877A DK378877A DK158303B DK 158303 B DK158303 B DK 158303B DK 378877 A DK378877 A DK 378877A DK 378877 A DK378877 A DK 378877A DK 158303 B DK158303 B DK 158303B
- Authority
- DK
- Denmark
- Prior art keywords
- process according
- dimethylformamide
- phenoxybenzaldehyde
- reaction
- anhydrous
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/53—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
DK 158303BDK 158303B
- i -- i -
Opfindelsen angår en særlig fremgangsmåde til fremstilling af alpha-cyan-3-phenoxybenzylalkohol ved at omsætte bisulfitkombinationen af m-phenoxy-benzaldehyd med formlenThe invention relates to a particular process for the preparation of alpha-cyano-3-phenoxybenzyl alcohol by reacting the bisulfite combination of m-phenoxy-benzaldehyde of the formula
1 O—Q1 O-Q
jj^O-SO^Ta 10 med en forbindelse, som tilvejebringer CN -ioner, og denne fremgangsmåde er ejendommelig ved det i krav l's kendetegnende del anførte.10 with a compound providing CN ions, and this process is characterized by the characterizing part of claim 1.
Fremstilling af alpha-cyan-3-phenoxybenzylalkohol ud fra 15 bisulfitkombinationen af m-phenoxybenzaldehyd og alkalicyanid i vandig opløsning er kendt fra Houben-Weyl: "Methoden der Organischen Chemie", bind VIII/III, s. 274-277.Preparation of alpha-cyan-3-phenoxybenzyl alcohol from the bisulfite combination of m-phenoxybenzaldehyde and alkali cyanide in aqueous solution is known from Houben-Weyl: "Methoden der Organischen Chemie", Vol. VIII / III, pp. 274-277.
Ved fremgangsmåden ifølge opfindelsen anvendes enten vand 20 og et opløsningsmiddel eller et opløsningsmiddel eller en blanding af opløsningsmidler udvalgt fra gruppen af aproti-ske dipolære opløsningsmidler, hvorved i forhold til den kendte teknik reaktionsudbyttet og -hastigheden forøges, samtidig med at dannelse af uønskede biprodukter undgås.In the process of the invention, either water 20 and a solvent or solvent or mixture of solvents selected from the group of aprotic dipolar solvents are used, thereby increasing reaction yield and rate, while avoiding the formation of undesirable by-products. .
2525
Blandt de benyttede forbindelser til frembringelse af CN -ioner skal især nævnes cyanhydrogensyre,ammoniumcyanid, alkalimetalcyanider og jordalkalimetalcyanider.Among the compounds used to produce CN ions are in particular cyanogenic acid, ammonium cyanide, alkali metal cyanides and alkaline earth metal cyanides.
30 En fordelagtig udførelsesform for cyaneringen består i at benytte et alkalimetalcyanid.An advantageous embodiment of the cyanation consists in using an alkali metal cyanide.
Cyaneringen af bisulfitkombinationen kan udføres i vandigt miljø.The cyanation of the bisulfite combination can be carried out in an aqueous environment.
Den blanding af opløsningsmidler, hvori cyaneringen af bi- 35The mixture of solvents in which the cyanation of bi-
DK 158303 BDK 158303 B
- 2 - sulfitkombinationen af m-phenoxybenzaldehyd foretages, udgøres da især dels af vand, dels af et aprotisk dipolært opløsningsmiddel såsom dimethylformamid, dimethoxyethan, dimethylsulfoxid eller acetonitril.The sulphite combination of m-phenoxybenzaldehyde is made, in particular, is partly water, and partly an aprotic dipolar solvent such as dimethylformamide, dimethoxyethane, dimethylsulfoxide or acetonitrile.
55
Ifølge en fordelagtig arbejdsmåde udføres cyaneringen i en blanding af vand og dimethylformamid.According to an advantageous method, the cyanation is carried out in a mixture of water and dimethylformamide.
I en særlig arbejdsform for iværksættelse af fremgangsmåden 10 ifølge opfindelsen udføres cyaneringen i vandigt miljø i nærværelse af et sdrt middel.In a particular mode of operation of the process 10 of the invention, the cyanation is carried out in aqueous environment in the presence of a special agent.
Dette sure middel kan være en stærk syre såsom svovlsyre eller saltsyre, men man benytter fortrinsvis en 15 carboxylsyre med ringe surhed.This acidic agent can be a strong acid such as sulfuric acid or hydrochloric acid, but preferably a low carboxylic acid is used.
Således består en foretrukken arbejdsform til udførelse af cyaneringen i vandigt miljø af bisulfitkombinationen i at arbejde i nærværelse af eddikesyre.Thus, a preferred mode of operation for performing the cyanation in aqueous environment consists of the bisulfite combination in working in the presence of acetic acid.
2020
Iføgle en foretrukket udførelsesform for fremgangsmåden ifølge opfindelsen indfører man til bevirkning af cyaneringen en suspension af bisulfitkombinationen af m-phenoxybenzaldehyd i en vandig opløsning af natriumcya-25 nid.According to a preferred embodiment of the process according to the invention, a suspension of the bisulfite combination of m-phenoxybenzaldehyde in an aqueous solution of sodium cyanide is introduced to effect the cyanation.
Ifølge en anden foretrukket arbejdsmåde for fremgangsmåden ifølge opfindelsen indfører man til bevirkning af cyaneringen en vandig opløsning af natriumcyanid i en 30 suspension af bisulfitkombinationen af m-phenoxybenzaldehyd i dimethylformamid, hvorefter man tilsætter eddikesyre.According to another preferred method of the process of the invention, to effect the cyanation, an aqueous solution of sodium cyanide is introduced into a suspension of the bisulfite combination of m-phenoxybenzaldehyde in dimethylformamide and then acetic acid is added.
Cyaneringen af bisulfitkombinationen af m-phenoxybenzaldehyd kan ligeledes udføres efter en meget original arbejds -35 måde, idet man arbejder i vandfrit miljø.The cyanation of the bisulfite combination of m-phenoxybenzaldehyde can also be carried out in a very original -35 way, working in anhydrous environment.
Cyaneringsmidlet er da fortrinsvis et vandfrit alkalimetal- - 3 -The cyanating agent is then preferably an anhydrous alkali metal -
DK 158303BDK 158303B
cyanid.cyanide.
Opløsningsmidlet eller blandingen af opløsningsmidler, der benyttes til udførelse af cyaneringen, vælges især blandt 5 vandfrie aprotiske dipolære opløsningsmidler såsom dime-thylformamid, dimethoxyethan, dimethylsulfoxid og acetoni-tril.In particular, the solvent or mixture of solvents used to perform the cyanation is selected from anhydrous aprotic dipolar solvents such as dimethylformamide, dimethoxyethane, dimethylsulfoxide and acetonitrile.
Det benyttede opløsningsmiddel til udførelse af denne cya 10 nering er fortrinsvis vandfrit dimethylformamid.The solvent used to carry out this cation is preferably anhydrous dimethylformamide.
Cyaneringen i vandfrit miljø udføres fortrinsvis uden tilsætning af et surt middel. Et vandfrit svagt surt middel såsom eddikesyre kan imidlertid benyttes.The cyanation in anhydrous environment is preferably carried out without the addition of an acidic agent. However, an anhydrous weakly acidic agent such as acetic acid may be used.
1515
En fordelagtig arbejdsmåde ved cyaneringsfremgangsmåden i vandfrit miljø består i at indføre et vandfrit alkalimetal-cyanid i en vandfri suspension af bisulfitkombinationen af m-phenoxy-benzaldehyd i dimethylformamid.An advantageous method of the cyanation process in anhydrous environment is to introduce an anhydrous alkali metal cyanide into an anhydrous suspension of the bisulfite combination of m-phenoxy-benzaldehyde in dimethylformamide.
2020
Bisulfitkombinationen af m-phenoxybenzaldehyd viser sig således at være en meget nyttig forbindelse til fremstillingen af alpha-cyan-3-phenoxybenzylalkohol.Thus, the bisulfite combination of m-phenoxybenzaldehyde proves to be a very useful compound for the preparation of alpha-cyan-3-phenoxybenzyl alcohol.
25 Denne bisulfitkombination kan fremstilles, idet man i et opløsningsmiddel eller blanding af opløsningsmidler omsætter et alkalimetalbisulfit med m-phenoxybenzaldehyd.This bisulfite combination can be prepared by reacting in an solvent or mixture of solvents an alkali metal bisulfite with m-phenoxybenzaldehyde.
Som blanding af opløsningsmidler kan man især benytte en 30 blanding af vand, isopropylether og methanol eller en blanding af vand og isopropanol.In particular, as a mixture of solvents, a mixture of water, isopropyl ether and methanol or a mixture of water and isopropanol can be used.
Bisulfitkombinationen af m-phenoxybenzaldehyd frembyder den fordel frem for det isolerede aldehyd at være mere stabil 35 og at være tilgængelig for rensning ved krystallisation af et organisk opløsningsmiddel såsom ethylacetat. Det således opnåede rensede produkt har en udmærket renhed, nemlig afThe bisulfite combination of m-phenoxybenzaldehyde offers the advantage over the isolated aldehyde to be more stable and to be available for purification by crystallization of an organic solvent such as ethyl acetate. The purified product thus obtained has an excellent purity, viz
DK 158303 BDK 158303 B
- 4 - størrelsesordenen 98%, og kan ved cyanering omdannes til alpha-cyan-3-phenoxybenzylalkohol med næsten kvantitativt udbytte.- 4 - on the order of 98%, and can be converted to alpha-cyan-3-phenoxybenzyl alcohol by cyanation with almost quantitative yield.
5 alpha-cyan-3-phenoxybenzylakohol er en meget nyttig forbindelse i industrien, thi den benyttes især til fremstilling af cyclopropancarboxylsyreestere med dihalogenvinyl-kæde med stor insekticid aktivitet.5 alpha-cyan-3-phenoxybenzyl alcohol is a very useful compound in the industry, as it is used especially for the production of cyclopropane carboxylic acid esters with dihalogen vinyl chain with high insecticidal activity.
10 Nedenstående eksempler illustrerer fremgangsmåden ifølge opfindelsen.The following examples illustrate the process of the invention.
Præparation af bisulfitkombinationen af m-phenoxybenzaldehyd 15 I 800 ml isopropylether opløser man 200 g m-phenoxybenzaldehyd, og man tilsætter opløsningen en opløsning af 200 g natriummetabisulfit i 800 ml vand og derefter 250 ml methanol, hvorefter man omrører i 3 timer og ved 20 frasugning isolerer den dannede udfældning, som man vasker med en blanding af methanol og vand (50:50) og derefter med isopropylether, hvorefter man tørrer udfældningen og får 295 g bisulfitkombination af m-phenoxybenzaldehyd (indhold af mobilt hydrogen 95,5%).Preparation of the bisulfite combination of m-phenoxybenzaldehyde In 800 ml of isopropyl ether, 200 g of m-phenoxybenzaldehyde are dissolved and the solution is added a solution of 200 g of sodium metabisulfite in 800 ml of water and then 250 ml of methanol, then stirred for 3 hours and at 20 suction. isolates the formed precipitate which is washed with a mixture of methanol and water (50:50) and then with isopropyl ether, then the precipitate is dried to give 295 g of bisulfite combination of m-phenoxybenzaldehyde (content of mobile hydrogen 95.5%).
2525
Denne forbindelse kan renses ved krystallisation af 4 rumfang ethylacetat (udbytte 97,6%). Indholdet af mobilt hydrogen i det rensede produkt er mindst 98%.This compound can be purified by crystallization of 4 volumes of ethyl acetate (yield 97.6%). The content of mobile hydrogen in the purified product is at least 98%.
30 Eksempel 1Example 1
Fremstilling af alpha-cyan-3-phenoxybenzylalkohol (i vandigt miljø)Preparation of alpha-cyan-3-phenoxybenzyl alcohol (in aqueous environment)
Til 40 ml dimethylformamid sætter man under nitrogenatmos-35 fære i løbet af ca. 1 minut 20 g bisulfitkombination af m-phenoxybenzaldehyd, og man omrører den dannede suspension i 15 minutter ved 20°C, afkøler til 5°C og tilsætter i lø-To 40 ml of dimethylformamide is added under nitrogen atmosphere over approx. 1 g 20 g bisulfite combination of m-phenoxybenzaldehyde and stirring the resulting suspension for 15 minutes at 20 ° C, cool to 5 ° C and add in solution.
DK 158303 BDK 158303 B
- 5 - bet af 20 minutter uden at overskride 10°C en opløsning af 5,4 g kaliumcyanid i 20 ml vand, omrører i 2 timer ved 5°C, eliminerer ved filtrering udfældningen, tilsætter filtratet 100 ml vand og 100 ml ethylacetat, rører om, fraskiller ved 5 dekantering den vandige fase, ekstraherer den med 100 ml ethylacetat, forener de organiske faser, vasker dem med vand, tørrer dem, inddamper dem til tørhed under formindsket tryk, opløser resten i ether, vasker etheropløsningen med vand, tørrer den,inddamper den til tørhed og får 14,46g 10 alpha-cyan-m-phenoxybenzylalkohol-- 5 - 20 minutes without exceeding 10 ° C a solution of 5.4 g of potassium cyanide in 20 ml of water, stirring for 2 hours at 5 ° C, eliminating by filtration the precipitate, adding the filtrate 100 ml of water and 100 ml of ethyl acetate, stir, separate by decanting the aqueous phase, extracting it with 100 ml of ethyl acetate, combining the organic phases, washing them with water, drying them, evaporating them to dryness under reduced pressure, dissolving the residue in ether, washing the ether solution with water, drying it evaporates to dryness and gives 14.46g of 10 alpha-cyan-m-phenoxybenzyl alcohol.
Eksempel 2Example 2
Sammenligning med den kendte teknik 2A Fremstilling af alpha-cyan-3-phenoxybenzylalkohol 15 (i vandigt miljø uden opløsningsmidler) I 200 ml demineraliseret vand indfører man 100 g bisulfit-kombination af m-phenoxybenzaldehyd (styrke 94,8 g eller %), tilsætter ved 20°C en opløsning af 17 g natriumcyanid i 20 200 ml vand, omrører i 16 timer ved 20-25°C under nitrogen- atmosfære, ekstraherer med isopropylether, behandler på sædvanlig måde, inddamper til tørhed og får 70 g alpha-cy-an-3-phenoxybenzylalkohol (udbytte 93,9%).Comparison with the Prior Art 2A Preparation of alpha-cyan-3-phenoxybenzyl alcohol 15 (in aqueous environment without solvents) Into 200 ml of demineralized water 100 g of bisulfite combination of m-phenoxybenzaldehyde (strength 94.8 g or%) is added at 20 ° C a solution of 17 g of sodium cyanide in 20 200 ml of water, stir for 16 hours at 20-25 ° C under nitrogen atmosphere, extract with isopropyl ether, treat as usual, evaporate to dryness and obtain 70 g of alpha-cy -an-3-phenoxybenzyl alcohol (yield 93.9%).
25 Renheden af den opnåede forbindelse bestemmes ved acetyle-ring til 71,5 g eller %, dvs. at det korrigerede udbytte, hvor der tages hensyn til udgangs- og slutproduktets renhed, bliver 70,8%.The purity of the compound obtained is determined by acetylation to 71.5 g or%, i.e. that the corrected yield taking into account the purity of the starting and final product is 70.8%.
30 Ved tyndtlagschromatografi på silicagel med benzen, ethylacetat og eddikesyre (90:8:2) som elueringsmiddel afsløres diverse urenheder, bl.a. m-phenoxybenzaldehyd (7-10%) og forbindelsen 3530 By thin layer chromatography on silica gel with benzene, ethyl acetate and acetic acid (90: 8: 2) as eluant, various impurities are disclosed, e.g. m-phenoxybenzaldehyde (7-10%) and compound 35
DK 158303 BDK 158303 B
- 6 - r-v OH ,-* /V \—/ ii i \_/ /,—v i en mængde på omkring 4%.- 6 - r-v OH, - * / V \ - / ii i \ _ / /, - v in an amount of about 4%.
En forlænget reaktionstid gør ikke reaktionen mere fuldstændig, men begunstiger dannelsen af urenheder.An extended reaction time does not make the reaction more complete, but favors the formation of impurities.
5 2B Fremstilling af alpha-cyan-3-phenoxybenzylalkohol (i vandigt miljø med opløsningsmidler) I 7,4 liter dimethylformamid indfører man 3,700 kg bisul-10 fitkombination af m-phenoxybenzaldehyd (styrke 98%), tilsætter i løbet af ca. 10 minutter ved 5°C under omrøring en opløsning af 0,765 kg natriumcyanid i 3,8 liter vand, tilsætter i løbet af ca. 30 minutter ved 5°C 3,8 liter eddikesyre, omrører yderligere 30 minutter ved 10°C, hælder 15 reaktionsblandingen i en blanding af vand og ethylacetat, rører om, fraskiller ved dekantering den vandige fase, eks-traherer den atter to gange med ethylacetat, forener de organiske faser, vasker dem med vand, tørrer dem, tilsætter 0,34 kg aktivkul og 0,37 kg natriumsulfat, rører om, fil-20 trerer, inddamper til tørhed ved destillation under formindsket tryk og får 2,770 kg alpha-cyan-3-phenoxybenzyl-alkohol (indeholdende ca. 1% dimethylformamid).5 2B Preparation of alpha-cyano-3-phenoxybenzyl alcohol (in aqueous environment with solvents) In 7.4 liters of dimethylformamide 3,700 kg of bisul-10-fit combination of m-phenoxybenzaldehyde (strength 98%) is added over a period of approx. 10 minutes at 5 ° C with stirring a solution of 0.765 kg of sodium cyanide in 3.8 liters of water, add over approx. 30 minutes at 5 ° C 3.8 liters of acetic acid, stir another 30 minutes at 10 ° C, pour the reaction mixture into a mixture of water and ethyl acetate, stir, separate by decanting the aqueous phase, extract it twice again with ethyl acetate, combines the organic phases, washed them with water, dried them, added 0.34 kg of activated charcoal and 0.37 kg of sodium sulfate, stirred, filtered, evaporated to dryness under reduced pressure and obtained 2,770 kg of alpha. cyan-3-phenoxybenzyl alcohol (containing about 1% dimethylformamide).
Den opnåede forbindelse har følgende egenskaber: Nitrogen- 25 indhold 6,3 g pr. 100 g (teoretisk 6,20), bevægeligt hydrogen: 100%.The compound obtained has the following properties: Nitrogen content 6.3 g per 100 g (theoretical 6.20), moving hydrogen: 100%.
Til opbevaring tilsættes denne forbindelse 13,5 ml eddikesyre.For storage, this compound is added with 13.5 ml of acetic acid.
3030
DK 158303BDK 158303B
- 7 -- 7 -
Udbytte: omkring 90% af den rene forbindelse.Yield: about 90% of pure compound.
Konklusion: 5 Med vand som det eneste opløsningsmiddel (2A) fås et udbytte af den rene ønskede forbindelse på omkring 70%. Den opnåede forbindelse indeholder adskillige urenheder. Ved tilsætning af f.eks. dimethylformamid og eddikesyre (2B) forøges udbyttet af den rene ønskede forbindelse til om 10 kring 90%.Conclusion: With water as the only solvent (2A), a yield of the pure desired compound of about 70% is obtained. The compound obtained contains several impurities. By adding e.g. dimethylformamide and acetic acid (2B) increase the yield of the pure desired compound to about 10% by 90%.
Eksempel 3Example 3
Fremstilling af alpha-cyan-3-phenoxybenzylalkohol (i vandfrit miljø) 15 I 80 ml vandfrit dimethylformamid indfører man 20 g vandfri bisulfitkombination af m-phenoxybenzaldehyd og indfører under indifferent atmosfære ved 0°C 3,3 g vandfrit natriumcyanid, omrører i 45 minutter ved 0°C, foretager en udtagning 20 af reaktionsblandingen, på hvilken man ved chromatografisk analyse konstaterer, at omdannelsen af bisulfitkombinationen af m-phenoxybenzaldehydet til alpha-cyan-3-methoxyben-zylalkohol er total, hælder reaktionsblandingen i en blanding af vand, is, eddikesyre og isopropylether, rører 25 om, fraskiller ved dekantering den organiske fase, ekstra-herer med isopropylether, vasker de organiske ekstrakter med vand, tørrer, inddamper til tørhed og får 13,8 g alpha-cyan-3-phenoxybenzylalkohol.Preparation of alpha-cyan-3-phenoxybenzyl alcohol (in anhydrous environment) 15 In 80 ml of anhydrous dimethylformamide, 20 g of anhydrous bisulfite combination of m-phenoxybenzaldehyde are introduced and, under inert atmosphere at 0 ° C, 3.3 g of anhydrous sodium cyanide are stirred for 45 minutes. at 0 ° C, take out 20 of the reaction mixture, upon which it is found by chromatographic analysis that the conversion of the bisulfite combination of the m-phenoxybenzaldehyde to alpha-cyano-3-methoxybenzyl alcohol is complete, pour the reaction mixture into a mixture of water, ice , acetic acid and isopropyl ether, stir 25, separate by decanting the organic phase, extract with isopropyl ether, wash the organic extracts with water, dry, evaporate to dryness and obtain 13.8 g of alpha-cyan-3-phenoxybenzyl alcohol.
30 3530 35
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7625938 | 1976-08-27 | ||
| FR7625938A FR2362829A1 (en) | 1976-08-27 | 1976-08-27 | BISULFIC COMBINATION OF METAPHENOXY BENZALDEHYDE, METHOD OF PREPARATION AND APPLICATION TO THE PREPARATION OF A-CYANO 3-PHENOXY BENZYL ALCOHOL |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK378877A DK378877A (en) | 1978-02-28 |
| DK158303B true DK158303B (en) | 1990-04-30 |
| DK158303C DK158303C (en) | 1990-10-01 |
Family
ID=9177185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK378877A DK158303C (en) | 1976-08-27 | 1977-08-26 | PROCEDURE FOR PREPARING ALPHA-CYAN-3-PHENOXYBENZYL ALCOHOL |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5328142A (en) |
| BE (1) | BE858127A (en) |
| CA (1) | CA1088566A (en) |
| CH (1) | CH623808A5 (en) |
| DE (1) | DE2738643C2 (en) |
| DK (1) | DK158303C (en) |
| FR (1) | FR2362829A1 (en) |
| GB (1) | GB1567531A (en) |
| IE (1) | IE45374B1 (en) |
| IT (1) | IT1079949B (en) |
| NL (1) | NL7709435A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA7911B (en) * | 1978-01-31 | 1980-01-30 | Roussel Uclaf | Optically-active substituted benzyl alcohol and process for preparing it |
| FR2458542A1 (en) * | 1979-06-12 | 1981-01-02 | Roussel Uclaf | PROCESS FOR THE PREPARATION OF OPTICALLY ACTIVE ALCOHOL A-CYANES |
| DE2938112A1 (en) * | 1979-09-20 | 1981-04-16 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING (ALPHA) -CYANO-PHENOXY-BENZYL ESTERS |
| JPS5970481A (en) * | 1982-10-14 | 1984-04-20 | Toyota Central Res & Dev Lab Inc | Spot welding method |
| JPH0547946Y2 (en) * | 1987-02-20 | 1993-12-17 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS515450B1 (en) * | 1971-06-29 | 1976-02-20 |
-
1976
- 1976-08-27 FR FR7625938A patent/FR2362829A1/en active Granted
-
1977
- 1977-07-26 JP JP8891877A patent/JPS5328142A/en active Granted
- 1977-08-03 GB GB3259877A patent/GB1567531A/en not_active Expired
- 1977-08-25 IT IT5078577A patent/IT1079949B/en active
- 1977-08-26 CH CH1047077A patent/CH623808A5/en not_active IP Right Cessation
- 1977-08-26 DE DE19772738643 patent/DE2738643C2/en not_active Expired
- 1977-08-26 DK DK378877A patent/DK158303C/en not_active IP Right Cessation
- 1977-08-26 BE BE180440A patent/BE858127A/en not_active IP Right Cessation
- 1977-08-26 NL NL7709435A patent/NL7709435A/en not_active Application Discontinuation
- 1977-08-26 IE IE179077A patent/IE45374B1/en unknown
- 1977-08-26 CA CA285,527A patent/CA1088566A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH623808A5 (en) | 1981-06-30 |
| FR2362829B1 (en) | 1979-03-02 |
| BE858127A (en) | 1978-02-27 |
| JPS6213342B2 (en) | 1987-03-25 |
| CA1088566A (en) | 1980-10-28 |
| IE45374B1 (en) | 1982-08-11 |
| IE45374L (en) | 1978-02-27 |
| NL7709435A (en) | 1978-03-01 |
| FR2362829A1 (en) | 1978-03-24 |
| GB1567531A (en) | 1980-05-14 |
| IT1079949B (en) | 1985-05-13 |
| DK158303C (en) | 1990-10-01 |
| JPS5328142A (en) | 1978-03-16 |
| DE2738643C2 (en) | 1986-06-05 |
| DK378877A (en) | 1978-02-28 |
| DE2738643A1 (en) | 1978-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SU1200848A3 (en) | Method of producing esters from cis- or trans-cyclopropancarboxylic acids and racemic alpha-cyano-3-phenoxy-benzyl alcohol | |
| DE2827627A1 (en) | NEW COMPOUNDS WITH A CYCLOPROPAN RING, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN THE PRODUCTION OF CYCLOPROPANE DERIVATIVES WITH A DIHALOVINYL CHAIN | |
| DK158303B (en) | METHOD OF PREPARING ALPHA-CYAN-3-PHENOXYBENZYL ALCOHOL | |
| NO136714B (en) | ||
| DE1793679B2 (en) | S-d'-R-r-X-S'-Oxo-cyclopentyl) propionic acids and their allyl esters | |
| EP0252353B1 (en) | 4-benzyloxy-3-pyrrolin-2-one-1-yl-acetamide, preparation and use | |
| CH472404A (en) | Process for the production of new indole derivatives | |
| US3824262A (en) | Process for preparing ethylenic carboxylic acids | |
| DE1620286B1 (en) | Process for the preparation of pyrrole derivatives | |
| DE1958514A1 (en) | Process for the preparation of apovincaminic acid amides | |
| EP0029117B1 (en) | 10-bromosandwicine and 10-bromoisosandwicine, as well as their additions salts with pharmacolical acceptable acids process for their preparation and their use | |
| Poonia et al. | Coordinative role of alkali cations in organic synthesis. 3. Selective methylations of 5-hydroxy-2-hydroxymethyl-. gamma.-pyrone | |
| Ling et al. | CCI.—Crystalline glucose–ammonia and iso glucosamine | |
| DE2436332A1 (en) | SUBSTITUTED TETRAHYDROFURANS AND PROCESS FOR THEIR PRODUCTION | |
| GB1329848A (en) | Process for preparing dibenzofuran derivatives | |
| US4202835A (en) | Preparation of α-cyano-3-phenoxy-benzyl alcohol | |
| SU106378A1 (en) | The method of obtaining 4-amino-5-formylamino-uracil | |
| SU322049A1 (en) | WAY OF OBTAINING 17a-ACETATE 3-METHYL ETHER | |
| DE1768540C (en) | Process for the preparation of gona 1,3,5 (10) -triene 17 ones | |
| DE1123668B (en) | Process for the production of indoles halogenated and / or nitrated in the benzene nucleus | |
| US2648689A (en) | Preparation of p' (benzoylsulfamyl) phthalanilic acid | |
| KR860001817B1 (en) | Process for the preparation of ethyleneimine derivatives | |
| DE1125442B (en) | Process for the production of DL-threonine | |
| CH368504A (en) | Process for preparing a novel lactone containing bromine | |
| EP0023663A2 (en) | Method for the preparation of new heterocycles that contain oxygen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUP | Patent expired |