NO149427B - PROCEDURE FOR THE PREPARATION OF PHENYL - SUBSTANCE NAFTYL URETANES - Google Patents
PROCEDURE FOR THE PREPARATION OF PHENYL - SUBSTANCE NAFTYL URETANES Download PDFInfo
- Publication number
- NO149427B NO149427B NO752229A NO752229A NO149427B NO 149427 B NO149427 B NO 149427B NO 752229 A NO752229 A NO 752229A NO 752229 A NO752229 A NO 752229A NO 149427 B NO149427 B NO 149427B
- Authority
- NO
- Norway
- Prior art keywords
- phenyl
- urethanes
- alkyl
- naphthyl
- uretanes
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 title 1
- 239000000126 substance Substances 0.000 title 1
- -1 naphthyl urethanes Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003673 urethanes Chemical class 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 150000004780 naphthols Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 101100109871 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) aro-8 gene Proteins 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SUDHEDJJFGYYPL-UHFFFAOYSA-N ethyl n,n-dimethylcarbamate Chemical compound CCOC(=O)N(C)C SUDHEDJJFGYYPL-UHFFFAOYSA-N 0.000 description 2
- HZAXLDYESPYWTL-UHFFFAOYSA-N ethyl n-methyl-n-naphthalen-1-ylcarbamate Chemical compound C1=CC=C2C(N(C)C(=O)OCC)=CC=CC2=C1 HZAXLDYESPYWTL-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av fenyl- henholdsvis naftyl-uretaner med den generelle formel The present invention relates to a method for the production of phenyl or naphthyl urethanes with the general formula
hvor Ar betyr fenyl eller naftyl som eventuelt er substituert med alkyl eller alkoksy, og R og R' som er like eller forskjel-lige, betyr alkyl eller hydrogen, ved omsetning over en omestring av fenoler henholdsvis naftoler med uretaner, hvor den derved dannede hydroksylforbindelse som skal drives av koker lavere enn fenolen henholdsvis naftolen ArOH, i flytende fase i nærvær av katalysatorer ved temperaturer fra 100 til 300°C, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at man går ut fra et uretan med den generelle formel where Ar means phenyl or naphthyl which is optionally substituted with alkyl or alkoxy, and R and R' which are the same or different, means alkyl or hydrogen, by reaction over a transesterification of phenols or naphthols with urethanes, where the resulting hydroxyl compound which must be operated by boiling lower than the phenol or the naphthol ArOH, in the liquid phase in the presence of catalysts at temperatures from 100 to 300°C, and the peculiarity of the method according to the invention is that one starts from a urethane with the general formula
hvori Alk står for en alkylgruppe og R og R' har den ovennevnte betydning og at det som katalysator anvendes en Lewis-syre, foretrukket aluminiumtriklorid eller titantetraisopropylat. in which Alk stands for an alkyl group and R and R' have the above meaning and that a Lewis acid, preferably aluminum trichloride or titanium tetraisopropylate, is used as catalyst.
Det er kjent at disse forbindelser kan fremstilles fra de res-pektive fenol- og alkyl-isocyanater eller fra aryl-klor formia-ter og aminer ved anvendelse av en komplisert teknologi som medfører betraktelige farer på grunn av giftigheten av de an-vendte reagenser. It is known that these compounds can be prepared from the respective phenol and alkyl isocyanates or from aryl chloroformates and amines using a complicated technology which entails considerable dangers due to the toxicity of the reagents used.
Det er også kjent at disse uretaner kan fremstilles over en omestring av fenoler henholdsvis naftoler med uretaner, hvor den dannede hydroksylforbindelse som skal drives av eller av-destilleres, koker lavere enn den fenol henholdsvis naftol som skal innføres, idet man for dette hensiktsmessig arbeider ved temperaturer fra 100 til 300°C i flytende fase, hensiktsmessig i nævær av katalysatorer. Ved oppfinnelsen oppnås i forhold til tidligere metoder praktisk talt fullstendig selektivitet til det ønskede sluttprodukt. It is also known that these urethanes can be produced via a transesterification of phenols or naphthols with urethanes, where the hydroxyl compound formed, which is to be driven off or distilled off, boils lower than the phenol or naphthol that is to be introduced, as for this it is appropriate to work at temperatures from 100 to 300°C in the liquid phase, suitably in the presence of catalysts. With the invention, compared to previous methods, practically complete selectivity to the desired end product is achieved.
Disse produkter har en bred industriell anvendelse som in-sektisider hvorav noen er spesielt interessante på grunn av at de har en liten giftighet for andre dyr. These products have a wide industrial application as insecticides, some of which are particularly interesting due to their low toxicity to other animals.
Oppfinnelsen er basert på den erkjennelse at disse forbindelser kan fremstilles ved å omsette de nevnte aromatiske hydrok-syforbindelser og de nevnte alkyluretaner i nærvær av passende katalysatorer. The invention is based on the recognition that these compounds can be prepared by reacting the aforementioned aromatic hydroxy compounds and the aforementioned alkyl urethanes in the presence of suitable catalysts.
Reaksjonen gjennomføres i væskefase med eller uten løsnings-middel ved temperaturer mellom 100 og 300°C og spesielt mellom 150 og 250°C. Molforholdet mellom fenol henholdsvis naftol og uretan varieres mellom 10:1 og 1:10. Forbindelser kjent som Lewis-syrer, som for eksempel Al X^, Ti X^, Fe X^ og Sn X^, (hvor X er halogen, alkoksy, aryloksy) er effektive som katalysatorer. Det gis noen eksempler for å illustrere den ovennevnte reaksjon. The reaction is carried out in the liquid phase with or without solvent at temperatures between 100 and 300°C and especially between 150 and 250°C. The molar ratio between phenol and naphthol and urethane is varied between 10:1 and 1:10. Compounds known as Lewis acids, such as Al X 2 , Ti X 2 , Fe X 2 , and Sn X 2 , (where X is halogen, alkoxy, aryloxy) are effective as catalysts. Some examples are given to illustrate the above reaction.
EKSEMPEL 1 EXAMPLE 1
Ved 160°C og 100 mm Hg omsettes 14 gram a-naftol og 9 gram dimetyluretan i nærvær av 0,7 gram vannfritt Al Cl^. Reaksjonen ble fortsatt i 6 timer, den metanol som ble dannet under reaksjonen ble fjernet. Det ble oppnådd en 28% omdannelse av naftol, med praktisk talt full selektivitet til naftyl-metyluretan. At 160°C and 100 mm Hg, 14 grams of a-naphthol and 9 grams of dimethylurethane are reacted in the presence of 0.7 grams of anhydrous AlCl^. The reaction was continued for 6 hours, the methanol formed during the reaction was removed. A 28% conversion of naphthol was achieved, with practically full selectivity to naphthyl-methylurethane.
EKSEMPEL 2 EXAMPLE 2
Ved 170°C og 100 mm Hg ble 14 gram a-naftol og 18 gram dimetyluretan omsatt i nærvær av 1,5 gram titantetraisopropylat i løpet av 5 timer ved en omdannelse på 32% av naftol, med total selektivitet til metylnaftyluretan. At 170°C and 100 mm Hg, 14 grams of a-naphthol and 18 grams of dimethylurethane were reacted in the presence of 1.5 grams of titanium tetraisopropylate during 5 hours at a conversion of 32% of naphthol, with total selectivity to methylnaphthylurethane.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24394/74A IT1015378B (en) | 1974-06-25 | 1974-06-25 | PROCESS FOR THE PREPARATION OF AROMATIC URETHANS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO752229L NO752229L (en) | 1975-12-30 |
| NO149427B true NO149427B (en) | 1984-01-09 |
| NO149427C NO149427C (en) | 1984-04-18 |
Family
ID=11213371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO752229A NO149427C (en) | 1974-06-25 | 1975-06-23 | PROCEDURE FOR THE PREPARATION OF PHENYL-SUBSTANCE NAFTYL URETANES. |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS5647180B2 (en) |
| AR (1) | AR209308A1 (en) |
| AT (1) | AT339916B (en) |
| BE (1) | BE830366A (en) |
| BR (1) | BR7503974A (en) |
| CA (1) | CA1049032A (en) |
| CH (1) | CH605694A5 (en) |
| DD (1) | DD118619A5 (en) |
| DE (1) | DE2528367C3 (en) |
| DK (1) | DK285975A (en) |
| ES (1) | ES439058A1 (en) |
| FR (1) | FR2276294A1 (en) |
| GB (1) | GB1497837A (en) |
| IE (1) | IE41081B1 (en) |
| IN (1) | IN140485B (en) |
| IT (1) | IT1015378B (en) |
| LU (1) | LU72758A1 (en) |
| MW (1) | MW3475A1 (en) |
| NL (1) | NL7507588A (en) |
| NO (1) | NO149427C (en) |
| RO (1) | RO68015B (en) |
| SE (1) | SE426588B (en) |
| TR (1) | TR18923A (en) |
| ZA (1) | ZA753462B (en) |
| ZM (1) | ZM7275A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4991353A (en) * | 1972-12-29 | 1974-08-31 | ||
| DE2628713C2 (en) * | 1976-06-25 | 1987-02-05 | Siemens AG, 1000 Berlin und 8000 München | Rotationally symmetric two-mirror antenna |
| JPS62260405A (en) * | 1986-05-06 | 1987-11-12 | Junichi Matsumoto | Electromagentic wave reflecting member |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5760331B2 (en) * | 1972-03-06 | 1982-12-18 | Nippon Shokubai Kagaku Kogyo Kk |
-
1974
- 1974-06-25 IT IT24394/74A patent/IT1015378B/en active
-
1975
- 1975-05-28 ZA ZA00753462A patent/ZA753462B/en unknown
- 1975-06-03 GB GB23984/75A patent/GB1497837A/en not_active Expired
- 1975-06-05 MW MW34/75A patent/MW3475A1/en unknown
- 1975-06-05 IE IE1273/75A patent/IE41081B1/en unknown
- 1975-06-07 IN IN1135/CAL/1975A patent/IN140485B/en unknown
- 1975-06-10 TR TR18923A patent/TR18923A/en unknown
- 1975-06-12 ZM ZM72/75A patent/ZM7275A1/en unknown
- 1975-06-17 LU LU72758A patent/LU72758A1/xx unknown
- 1975-06-18 BE BE157440A patent/BE830366A/en not_active IP Right Cessation
- 1975-06-18 CH CH794975A patent/CH605694A5/xx not_active IP Right Cessation
- 1975-06-23 CA CA75229897A patent/CA1049032A/en not_active Expired
- 1975-06-23 FR FR7519580A patent/FR2276294A1/en active Granted
- 1975-06-23 NO NO752229A patent/NO149427C/en unknown
- 1975-06-24 DD DD186856A patent/DD118619A5/xx unknown
- 1975-06-24 BR BR3974/75A patent/BR7503974A/en unknown
- 1975-06-24 JP JP7704575A patent/JPS5647180B2/ja not_active Expired
- 1975-06-24 DK DK285975A patent/DK285975A/en unknown
- 1975-06-24 AR AR259322A patent/AR209308A1/en active
- 1975-06-24 AT AT483375A patent/AT339916B/en not_active IP Right Cessation
- 1975-06-25 SE SE7507318A patent/SE426588B/en not_active IP Right Cessation
- 1975-06-25 ES ES75439058A patent/ES439058A1/en not_active Expired
- 1975-06-25 DE DE2528367A patent/DE2528367C3/en not_active Expired
- 1975-06-25 RO RO82649A patent/RO68015B/en unknown
- 1975-06-25 NL NL7507588A patent/NL7507588A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| TR18923A (en) | 1977-12-20 |
| RO68015A (en) | 1983-04-29 |
| CH605694A5 (en) | 1978-10-13 |
| DE2528367A1 (en) | 1976-01-08 |
| ZA753462B (en) | 1976-05-26 |
| AT339916B (en) | 1977-11-10 |
| DK285975A (en) | 1975-12-26 |
| LU72758A1 (en) | 1975-10-08 |
| IE41081B1 (en) | 1979-10-10 |
| IT1015378B (en) | 1977-05-10 |
| ATA483375A (en) | 1977-03-15 |
| DE2528367B2 (en) | 1977-10-20 |
| FR2276294B1 (en) | 1979-08-03 |
| NO752229L (en) | 1975-12-30 |
| JPS5119742A (en) | 1976-02-17 |
| AR209308A1 (en) | 1977-04-15 |
| MW3475A1 (en) | 1976-11-10 |
| AU8168075A (en) | 1976-12-02 |
| RO68015B (en) | 1983-04-30 |
| IN140485B (en) | 1976-11-20 |
| DD118619A5 (en) | 1976-03-12 |
| SE7507318L (en) | 1975-12-29 |
| CA1049032A (en) | 1979-02-20 |
| GB1497837A (en) | 1978-01-12 |
| FR2276294A1 (en) | 1976-01-23 |
| DE2528367C3 (en) | 1978-06-08 |
| NL7507588A (en) | 1975-12-30 |
| ZM7275A1 (en) | 1976-03-22 |
| NO149427C (en) | 1984-04-18 |
| ES439058A1 (en) | 1977-02-01 |
| SE426588B (en) | 1983-01-31 |
| IE41081L (en) | 1975-12-25 |
| BE830366A (en) | 1975-10-16 |
| BR7503974A (en) | 1977-01-25 |
| JPS5647180B2 (en) | 1981-11-07 |
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