NO147024B - PROCEDURE FOR THE PREPARATION OF STERICALLY HIDDEN BIS OR POLYPHENOLS. - Google Patents
PROCEDURE FOR THE PREPARATION OF STERICALLY HIDDEN BIS OR POLYPHENOLS. Download PDFInfo
- Publication number
- NO147024B NO147024B NO772056A NO772056A NO147024B NO 147024 B NO147024 B NO 147024B NO 772056 A NO772056 A NO 772056A NO 772056 A NO772056 A NO 772056A NO 147024 B NO147024 B NO 147024B
- Authority
- NO
- Norway
- Prior art keywords
- tert
- butyl
- bis
- mol
- methylphenol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 49
- 235000013824 polyphenols Nutrition 0.000 title claims description 12
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 10
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000000047 product Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 33
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 17
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 8
- -1 acetal compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 4
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229920005565 cyclic polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000020335 dealkylation Effects 0.000 description 2
- 238000006900 dealkylation reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical class OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- XRXSBCHCLGSTHW-UHFFFAOYSA-N 2,4,5-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(C(C)(C)C)C=C1O XRXSBCHCLGSTHW-UHFFFAOYSA-N 0.000 description 1
- SBVHSWJZXOYLFE-UHFFFAOYSA-N 2,4,6-tris(2-methylpropyl)-1,3,5-trioxane Chemical compound CC(C)CC1OC(CC(C)C)OC(CC(C)C)O1 SBVHSWJZXOYLFE-UHFFFAOYSA-N 0.000 description 1
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- LKALLEFLBKHPTQ-UHFFFAOYSA-N 2,6-bis[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=CC(C)=CC=1CC1=CC(C)=CC(C(C)(C)C)=C1O LKALLEFLBKHPTQ-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- FCIMDZFOYJBMLV-UHFFFAOYSA-N 2-[(2-hydroxy-3,5-dimethylphenyl)methyl]-4,6-dimethylphenol Chemical compound CC1=CC(C)=C(O)C(CC=2C(=C(C)C=C(C)C=2)O)=C1 FCIMDZFOYJBMLV-UHFFFAOYSA-N 0.000 description 1
- WJWAGRXETZKFAH-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(2-phenylpropan-2-yl)phenyl]methyl]-4-methyl-6-(2-phenylpropan-2-yl)phenol Chemical compound OC=1C(C(C)(C)C=2C=CC=CC=2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C(C)(C)C1=CC=CC=C1 WJWAGRXETZKFAH-UHFFFAOYSA-N 0.000 description 1
- PGOFYKDJABUOQA-UHFFFAOYSA-N 2-benzyl-4-methyl-6-(2-methylpentan-2-yl)phenol Chemical compound CCCC(C)(C)C1=CC(C)=CC(CC=2C=CC=CC=2)=C1O PGOFYKDJABUOQA-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- TWWSMHPNERSWRN-UHFFFAOYSA-N acetaldehyde diisopropyl acetal Natural products CC(C)OC(C)OC(C)C TWWSMHPNERSWRN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/115—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using acetals
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Description
Foreliggende oppfinnelse vedrører fremgangsmåte til fremstilling av sterisk hindrede bis- eller polyfenoler som er egnet som effektive ikke-fargende og ikke-toksiske sta-biliseringsmidler med lav flyktighet for gummimaterialer, vulkanisater, plaster og andre organiske produkter. The present invention relates to a process for the production of sterically hindered bis- or polyphenols which are suitable as effective non-staining and non-toxic stabilizers with low volatility for rubber materials, vulcanizates, plasters and other organic products.
Stabiliseringsmidlene kan f.eks. være den velkjente forbindelse 2,2' -metylen-bis- (4-metyl-6-tert.-butylf enol) The stabilizers can e.g. be the well-known compound 2,2'-methylene-bis-(4-methyl-6-tert.-butylphenol)
("Antioxidant 2246, KAO-5") og lignende. ("Antioxidant 2246, KAO-5") and the like.
Det er kjent forskjellige metoder for fremstilling Different methods of production are known
av sterisk hindrede bisfenoler eller polyfenoler, for tiden anvendes f.eks. en fremgangsmåte til fremstilling av 2,2'-metylen-bis-(4-metyl-6-tert.-butylfenol) hvor det ønskede produkt oppnås ved alkylering av 4-metylfenol med isobutylen i nærvær av en katalysator, fulgt av separering og kondensasjon av den resulterende 2-tert.-butyl-4-metylfenol med formaldehyd. of sterically hindered bisphenols or polyphenols, currently used e.g. a process for the preparation of 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) where the desired product is obtained by alkylation of 4-methylphenol with isobutylene in the presence of a catalyst, followed by separation and condensation of the resulting 2-tert-butyl-4-methylphenol with formaldehyde.
Kondensasjonen utføres i nærvær av sure katalysatorer slik som svovelsyre. Prosessen utføres i en vandig emulsjon inneholdende et overflateaktivt middel og et organisk ppp-løsningsmiddel ved en temperatur i området 75-90°C. (Kfr. SU-PS 245 127 og US-PS 2 675 366). The condensation is carried out in the presence of acid catalysts such as sulfuric acid. The process is carried out in an aqueous emulsion containing a surfactant and an organic ppp solvent at a temperature in the range 75-90°C. (Cf. SU-PS 245 127 and US-PS 2 675 366).
Denne tidligere kjente teknikk er komplisert og der-for uegnet. This previously known technique is complicated and therefore unsuitable.
Fremgangsmåten ifølge den kjente teknikk utføres i The method according to the known technique is carried out in
to trinn og en stor mengde avløpsvann dannes (ca. 30. m 3- pr. tonn av produktet) som er forurenset med overflateaktive midler og organiske oppløsningsmidler. Dessuten anvendes som utgangsprodukt i prosessen p-kresol som er vanskelig å oppnå. two stages and a large amount of waste water is formed (approx. 30. m 3- per ton of the product) which is contaminated with surfactants and organic solvents. In addition, p-cresol is used as a starting product in the process, which is difficult to obtain.
På grunn av at p-kresol er et kritisk produkt, har man utviklet en annen metode for fremstilling av 2,2'-metylen-bis-(4-metyl-6-tert.-butylfenol) fra 2,6-di-tert-butyl-4-metylfenol basert på fremstilling av sistnevnte forbindelse utfra lett tilgjengelig og billig fenol. Prosessen er basert på dealkylering av 2,6-di-tert.-butyl-4-metylfenol fulgt av separering og kondensasjon av den resulterende 2-tert.-butyl-4-metylfenol med formaldehyd (SU-PS 403 663). Because p-cresol is a critical product, another method has been developed for the production of 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) from 2,6-di-tert -butyl-4-methylphenol based on the production of the latter compound from readily available and cheap phenol. The process is based on dealkylation of 2,6-di-tert-butyl-4-methylphenol followed by separation and condensation of the resulting 2-tert-butyl-4-methylphenol with formaldehyde (SU-PS 403 663).
En av hovedulempene med denne metode ligger også i dannelsen av en stor mengde surt avløpsvann inneholdende overflateaktive midler og organiske oppløsningsmidler. Rensing av slikt avløpsvann i kommersiell målestokk er temmelig komplisert og økonomisk ineffektivt. One of the main disadvantages of this method also lies in the formation of a large amount of acidic waste water containing surfactants and organic solvents. Purification of such waste water on a commercial scale is rather complicated and economically inefficient.
Det er også kjent en fremgangsmåte til fremstilling av 2,2 *-metylen-bis-(4-metyl-6-tert.-butylfenol) som har visse fordeler i forhold til de ovenfor omtalte metoder, fordi den gjør det mulig å eliminere dannelsen av avløps-vann. Ifølge denne fremgangsmåte oppnås det ønskede produkt fra 2,6-di-tert.-butyl-4-metylfenol i to trinn, nemlig: dealkylering av 2,6-di-tert.-butyl-4-metylfenol fulgt av separering og kondensasjon av den resulterende 2-tert.-butyl-4-metylfenol med et acetal i nærvær av en sur katalysator ved en temperatur i området 30-140°C (BE-PS 836 745 og DD-PS 121 777). ;Denne tidligere kjente prosess samt de tidligere beskrevne, omfatter to trinn og krever separering, i ren form, av 2-tert.-butyl-4-metylfenol som har en sterk og ubehagelig lukt, høy toksisitet og høy flyktighet. Dessuten kreves en komplisert prosessteknikk for utførelse av de ovenfor omtalte metoder. ;Ved hjelp av de beskrevne tidligere kjente metoder, er det dessuten bare mulig å fremstille bisfenoler. For fremstilling av polyfenoler, er det bare kjent kompliserte fler-trinns metoder. Polyfenoler fremstilles f.eks. ifølge US-PS ;3 297 575 ved omsetning av para-alkylfenoler med frie orto-stillinger med klormetylderivater av 2,6-dialkylfenoler ifølge nedenstående skjema: ;Formålet med foreliggende oppfinnelse er å eliminere de ovenfor nevnte ulemper med de tidligere kjente metoder. ;Foreliggende oppfinnelse er rettet mot tilveiebring-else, gjennom riktig valg av reaktanter og betingelser for deres reaksjon, av en enkel, ett-trinnsmetode for fremstilling av sterisk hindrede bis- og polyfenoler, hvilken fremgangsmåte gir et høyt utbytte av det ønskede produkt. ;Ifølge foreliggende oppfinnelse er det således til-veiebragt en fremgangsmåte til fremstilling av sterisk hindrede bis- eller polyfenoler med formelen: ;, ■. I ;hvor R' er hydrogen eller C1~C4 alkyl, R" og R"' er like eller forskjellige og representerer: ;hvor R er en tertiær -Cg'- alkylgruppe; • R^ og R2 er like ^ eller forskjellige .og representerer C,-C0 alkyl, C,-C„ lo 6 8 cykloalkyl eller C7~Cg aralkyl, og denne fremgangsmåte er kjennetegnet ved at sterisk hindrede 2,4 ,6-trialkylfenoler med formelen: hvor R, R.j og R^ har den ovenfor angitte betydning, omsettes med acetaler med den generelle formel: hvor R^ er -C,.-alkyl og R<1> har den ovenfor angitte betydning, eller med aldehyder med den generelle formel: ;hvor R' har den ovenfor angitte betydning, eller med deres cykliske eller lineære oligomere i surt medium ved en temperatur i området 60-200°C i nærvær av en sur katalysator. ;Som sure katalysatorer foretrekkes bruk av Brønstedt-syrer slik som svovelsyre, ortho-fosforsyre, polyfosforsyre, perklorsyre, toluensulfonsyre, naftalensulfonsyre og kation-vekslere i H+<->form eller Lewis-syrer slik som zinkklorid, aluminiumklorid, ferriklorid og bortrifluorid. Disse katalysatorer lar seg lett skille fra det ønskede produkt og man oppnår et høyt utbytte derav, dvs. minst 78,7% av de omsatte utgangs-2,4,6-trialkylfenoler, hovedsakelig minst 95% av det teoretiske utbytte. ;Visse acetaler omfatter avfallsprodukter fra andre synteser, spesielt er metylal et avfallsprodukt fra syntesen av isoprengummi. Mest foretrukket blant acetalforbindelsene, er metylal, etylal, dipentylformal, men man kan også bruke andre acetalforbindelser slik som dimetylacetal, dietyl-acetal og diisopropylacetal. ;Som aldehyder foretrekkes bruk av acetaldehyd, propionsyrealdehyd, smørsyrealdehyd, isosmørsyrealdehyd, valerianesyrealdehyd, isovalerianesyrealdehyd, fordi disse er lett tilgjengelige og lette å håndtere. Det er også mulig å bruke formaldehyd og andre aldehyder. ;Som donorer av -C,.-aldehyder i et surt medium kan man anvende cykliske polymerer av aldehyder slik som trioksan, paraldehyd, 2,4,6-tri-isobutyl-1,3,5-trioksan, fordi disse produkter er mer stabile ved lagring og lettere å håndtere enn monomere aldehyder. ;Blant cykliske polymerer er trioksan mest foretrukket fordi de mest verdifulle antioksydasjonsmidler er de hindrede bis- eller polyfenoler som har metylenbindinger mellom aromatiske ringer. ;Som donorer for -C,.-aldehyder i et surt medium kan man også anvende lineære polymerer av aldehyder siden disse polymerer, slik som cykliske polymerer av aldehyder, er mer stabile ved lagring. Paraformaldehyd er det mest foretrukne lineære polymeraldehyd fordi det, lik trioksan, sikrer in-korporering av metylenbindinger mellom aromatiske ringer og sørger således for dannelsen av de mest verdifulle metylen-bisfenoler eller metylenpolyfenoler. ;Foreliggende fremgangsmåte utføres på følgende måte: I en fire-halset reaktor forsynt med rører, termometer, kjøler og oppvarmingsbad, innføres en sterisk hindret 2,4,6-trialkylfenol slik som 2,6-di-tert.-butyl-4-metylfenol, en sur katalysator slik som svovelsyre eller en kation-veksler i H+<->form, eller zinkklorid, og blandingen oppvarmes til en bestemt temperatur under omrøring. Under opprettholdelse av denne temperatur og ved fortsatt omrøring i 0,5-2 timer, tilføres til reaktoren en acetalforbindelse slik som metylal eller et aldehyd slik som acetaldehyd, eller en donor for C.j -Cj--aldehyd i et surt medium, slik som paraf ormaldehyd. ;Prosesstemperaturen holdes i området 60-200°C. Ved fullendelse av prosessen fraskilles katalysatoren og det ønskede produkt isoleres på konvensjonell måte slik som f. eks. ved krystallisering. ;Utbyttet av det ønskede produkt er så høyt som 78,7-99,1% av det teoretiske utbytte, beregnet for den omsatte sterisk hindrede 2,4,6-trialkylfenol, hovedsakelig over 95%; for det mest effektive stabiliseringsmiddel, dvs. 2,2<1->metylen-bis-(4-metyl-6-tert.-butylfenol) er utbyttet så høyt som 97,8-99,1%. Ved foreliggende fremgangsmåte oppnås også forbindelser av høy kvalitet. Smeltepunktet for 2,2'-metylen-bis-(4-metyl-6-tert.-butylfenol) fremstilt ifølge oppfinnelsen, er således 131-131,5°C (ifølge litteraturen er produktets smeltepunkt 131-132°C). ;Foreliggende fremgangsmåte representerer flere fordeler overfor tidligere kjente metoder. De valgte reaktanter og betingelsene ved deres reaksjon gir de ønskede bisfenoler eller polyfenoler fra sterisk hindrede 2,4,6-trialkylfenoler i et enkelt trinn, og av denne grunn er prosessteknikken vesentlig forenklet og arbeidsbetingelsene er vesentlig for-bedret fordi det i prosessen ikke utvikles noe 4-metyl-2-tert.-butylfenol som har høy toksisitet, sterk og ubehagelig lukt samt høy flyktighet. De produkter som oppnås ved prosessen krever ingen ytterligere krystallisasjon. Bisfenoler eller polyfenoler kan oppnås fra monofenoler ved hjelp av foreliggende fremgangsmåte ved hensiktsmessig valg av reaksjonsbetingelser. De uomsatte utgangsproduktene resirkuleres tilbake til prosessen. De tertiære olefiner som oppnås ved reaksjonen, anvendes ved fremstilling av de sterisk hindrede 2,4,6-trialkylfenol-utgangsmaterialer. Fremgangsmåten eliminerer fullstendig dannelse av forurenset avløpsvann og forurenset atmosfære. ;Følgende eksempler illustrerer oppfinnelsen. ;Eksemp_el_1_ ;I en reaktor forsynt med en rører, termometer og et oppvarmingsbad anbringes 220 g (1 g mol) 2,6-di-tert.-butyl-4-metylfenol, 2,2 g konsentrert svovelsyre og blandingen oppvarmes til 120°C. Under opprettholdelse av temperaturen ved.120°C, tilføres 94 g (1,24 g mol) metylal i reaktoren i løpet av 1,5 timer. Ved fullendelse av reaksjonen fraskilles katalysatoren, flyktige produkter destilleres under vakuum for oppnåelse av 143,0 g 2,2'-metylen-bis-(4-metyl-6-tert.-butylfenol) som tilsvarer 97,8% av det teoretiske utbytte beregnet for omsatt 2,6-di-tert.-butyl-4-metylfenol (omdannelsesgrad for sistnevnte forbindelse er 86,0%). ;Etter en enkel omkrystallisering har produktet smeltepunkt på 131-131,5°C (litteraturen angir et smeltepunkt på 131-132°C). ;Det uomsatte 2,6-di-tert.-butyl-4-metylfenol og metylal resirkuleres tilbake til prosessen. ;Eksemp_el_2 ;Til en reaktor i likhet med den som er beskrevet i eksempel 1, tilføres 220 g (1 g mol) 2,6-di-tert.-butyl-4-metylfenol, 2,2 g konsentrert svovelsyre ved en temperatur på 120°C. 76 g (1,0 'g mol) metylal tilføres til reaktoren i løpet av 1 time. Reaksjonsmassen behandles på samme måte som angitt i eksempel 1 for dannelse av 112,9 g 2,2'-metylen-bis-(4-metyl-6-tert.-butylfenol) som utgjør 99,1% av det teoretiske utbytte, beregnet for omsatt 2,6-di-tert.-butyl-4-metylfenol (omdannelsesgrad for denne forbindelse er 67,0%). Uomsatt metylal og 2,6-di-tert.-butyl-4-metylfenol resirkuleres tilbake til prosessen. ;Eksemp_el_3 ;I reaktoren som beskrevet i eksempel 1, anbringes 220 g (1,0 g mol) 2,6-di-tert.-butyl-4-metylfenol, 2,2 g svovelsyre og 44 g (1 g mol) acetaldehyd tilføres til reaktoren i løpet av 1 time ved 125°C. Ved fullendelse av reaksjonen, behandles reaksjonsmassen som omtalt i eksempel 1 for oppnåelse av 124,6 g 1,1 -(5-metyl-3-tert.-butyl-2-hydroksyfeny1)etan hvilket tilsvarer 96,4% av det teoretiske utbytte, beregnet for omsatt 2,6-di-tert.-butyl-4-metylfenol (omdannelsesgrad 73%). ;Etter en enkel omkrystallisering har det resulterende produkt et smeltepunkt på 104-104,5°C (i litteraturen angis et smeltepunkt på 104,5°C). ;Uomsatt 2,6-di-tert.-butyl-4-metylfenol og acetaldehyd resirkuleres tilbake til prosessen. ;Eksemp_el_4 ;I reaktoren som beskrevet i eksempel 1, anbringes 212 g (0,5 g mol) 4 , 4'.-metylen-bis-(2 , 6-di-tert.-butylfenol) , 8,4 g zinkklorid og 10 g (0,111 g mol) trioksan tilsettes til blandingen i løpet av 30 minutter ved en temperatur på 200°C. Ved fullendelse av reaksjonen, fraskilles katalysatoren og flyktige produkter avdestilleres under vakuum og dette gir 193,7 g 2,2'-metylen-bis-/4-(3,5-di-tert.-butyl-4- hydroksybenzyl)-6-tert.-butylfenol/ i form av en harpiks med molekylvekt 736 (den teoretiske molekylvekt for konden-sasjonsproduktet er 748). ;Eksemp_el_5 ;I reaktoren som beskrevet i eksempel 1, anbringes ;170 g (0,5 g mol) 2,2'-metylen-bis-(4-metyl-6-tert.-butyl-fenol), 34 g av en kationutvekslerharpiks i H+<->form (sulfonert kopolymer av styren og divinylbenzen) og ved en temperatur på 160°C tilsettes 8,2 g (0,26 g mol) paraformaldehyd (beregnet for 95%-produktet) i løpet av 1 time. Ved fullendelse av reaksjonen, fraskilles katalysatoren og flyktige produkter avdestilleres under vakuum for oppnåelse av 141,9 ;g av en harpiks inneholdende 46,1 vekt-% av kondensasjons-produktet , dvs. 2,2'-metylen-bis-/4-metyl-6-(3-tert.-butyl-5- metyl-2-hydroksybenzyl)fenol/ og 53,9 vekt-% av utgangs-produktet. Den således oppnådde harpiks kan anvendes som et antioksydasjonsmiddel. ;Eksemp_el_6 ;I reaktoren som beskrevet i eksempel 1, anbringes ;282 g (1 g mol) 2,4,6-tri-tert.-butylfenol, 9 g konsentrert svovelsyre og 110 g (1,19 g mol) dipentylformal innføres i reaktoren i løpet av 2 timer ved 60°C. Ved fullendelse av reaksjonen, separeres katalysatoren og flyktige produkter avdestilleres under vakuum for oppnåelse av 120,7 g av det ønskede produkt, dvs. 2,2<1->metylen-bis-(4,6-di-tert.-butyl-fenol) hvilket tilsvarer 98,2% av det teoretiske utbytte, beregnet for omsatt 2,4,6-tri-tert.-butylfenol (omdannelsesgrad, for denne forbindelse er 53%) . ;Etter en enkel omkrystallisering av det resulterende prpdukt, oppnås et smeltepunkt på 141-142°C. ;Uomsatt 2,4,5-tri-tert.-butylfenol og dipentylformal ;resirkuleres tilbake til prosessen. ;Eksemgel_7 ;I reaktoren som beskrevet i eksempel 1, anbringes 155 g (0,5 g mol) 2 ,6-di-tert.-butyl-4-ct-metylbenzylf enol, 3,2 g paratoluensulfonsyre og 21,9 g (0,255 g mol) iso-valerianealdehyd tilsettes ved 150°C i løpet av 1,5 timer. Ved fullendelse av reaksjonen, fraskilles katalysatoren, ;og flyktige produkter avdestilleres under vakuum for oppnåelse av 120,9 g 1,1 -(6-tert.-butyl-4-a-metylbenzylfenol)-isopentan som tilsvarer 95,8% av det teoretiske utbytte, beregnet for omsatt 2,6-di-tert.-butyl-4-a-metylbenzylfenol (omdannelsesgrad for denne forbindelse er 88%). ;Eksem<g>el_<8>;I reaktoren som beskrevet i eksempel 1, anbringes 330 g (1,5 g mol) 2,6-di-tert.-butyl-4-metylfenol, 6,5 g konsentrert svovelsyre og 152 g (2 g mol) metylal tilsettes ;i løpet av 2 timer ved 150°C. Ved fullendelse av reaksjonen, fraskilles katalysatoren, og flyktige produkter avdestilleres under vakuum for oppnåelse av 200,3 g av det ønskede produkt, dvs. 2,6-di-(5-metyl-3-tert.-butyl-2-hydroksybenzyl)-para-kresol hvilket utgjør 87,1% av det teoretiske utbytte beregnet på basis av omsatt 2,6-di-tert.-butyl-4-metylfenol (omdannelsesgrad for sistnevnte produkt er 100%). ;Omkrystallisering av det fremstilte produkt gir et smeltepunkt på 163-163,5°C. ;Eksemp_el_9 ;I reaktoren som beskrevet i eksempel 1, anbringes 220 g (1,0 g mol) 2,6-di-tert.-butyl-4-metylfenol, 11 g ortho-fosforsyre og 66 g (1,5 g mol) acetaldehyd tilsettes ved en temperatur på 150°C i løpet av 1 time. Ved fullendelse av reaksjonen, fraskilles katalysatoren og flyktige produkter avdestilleres under vakuum for oppnåelse av 210 g av en blanding av 1,1 -(5-metyl-3-tert.-butyl-2-hydroksy-fenyDetan og 2,6-di-(5-metyl-3-tert.-butyl-2-hydroksymetyl-benzyl)para-kresol. Den resulterende blanding kan anvendes uten separering, som antioksydasjonsmiddel. Omdannelsesgraden for 2,6-di-tert.-butyl-4-metylfenol er 99%. ;Eksemgel_2Q ;I reaktoren som beskrevet i eksempel 1, anbringes ;123 g (0,5 g mol) 2-tert.-butyl-6-cykloheksyl-4-metylfenol, 42 g konsentrert svovelsyre, og blandingen oppvarmes ved en temperatur på 120°C. Ved denne temperatur tilsettes 47 g (1,12 g mol) metylal til reaktoren i løpet av 1,5 .timer. Ved fullendelse av reaksjonen fraskilles katalysatoren og flyktige produkter avdestilleres under vakuum for oppnåelse av 163,1 g 2,2'-metylen-bis-(4-metyl-6-cykloheksylfenol), hvilket utgjør 99,1% av det teoretiske utbytte, beregnet på basis av omsatt 2-tert.-butyl-6-cykloheksyl-4-metylfenol (omdannelsesgrad for sistnevnte forbindelse er 84%). ;Omkrystallisering av det resulterende produkt gir ;et smeltepunkt på 117-117,5°C. ;Uomsatt 2-tert.-butyl-6-cykloheksyl-4-metylfenol og metylal resirkuleres tilbake til prosessen. ;Eksemp_el_1_1_ ;I reaktoren som beskrevet i eksempel 1, anbringes ;159 g (0,5 g mol) 2,6-di-tert.-buty1-4-tert.-oktylfenol, ;2 g konsentrert svovelsyre og 36 g (0,5 g mol) smørsyre-aldehyd tilsettes til reaktoren ved en temperatur på 125°C ;i løpet av 1 time. Ved fullendelse av reaksjonen, fraskilles katalysatoren, og flyktige produkter avdestilleres under vakuum for dannelse av 103,3 g av det ønskede produkt, dvs. 1,1-(3-tert.-buty1-5-tert.-oktyl-2-hydroksyfenyl)butan, hvilket tilsvarer 95,3% av det teoretiske utbytte, beregnet for omsatt 2,6-di-tert.-butyl-4-tert.-oktylfenol (omdannelsesgrad ■for sistnevnte forbindelse er 75,0%). ;Uomsatt 2,6-di-tert.-butyl-4-tert.-oktylfenol og smørsyrealdehyd resirkuleres tilbake til prosessen. ;Eksemgel_12 ;I reaktoren som beskrevet i eksempel 1, anbringes ;234 g (1 g mol) 2-tert.-oktyl-4,6-xylenol, 2,4 g konsentrert svovelsyre og 76 g (1 g mol) metylal tilsettes ved en temperatur på 100°C i løpet av 1 time. Reaksjonsmassen behandles som angitt i eksempel 11 for oppnåelse av 63,5 g av det ønskede produkt, dvs. 2,2'-metylen-bis-(4,6-dimetylfenol), hvilket utgjør 81,1% av det teoretiske utbytte beregnet for omsatt 2-tert.-oktyl-4,6-xylenol (omdannelsesgrad for sistnevnte forbindelse er 61,2%). ;Uomsatt 2-tert.-oktyl-4,6-xylenol og metylal resirkuleres tilbake til prosessen. ;Eksemp_el_1_3 ;I reaktoren som beskrevet i eksempel 1, anbringes 58,5 g (0,25 g mol) 2,6-di-tert.-butyl-4-etylfenol, 1 g konsentrert svovelsyre og 19 g (0,25 g mol) metylal tilsettes til reaktoren ved 130°C i løpet av 30 minutter. Reaksjonsmassen blir deretter behandlet og 26,2 g 2,2'-metylen-bis-(4-etyl-6-tert.-butylfenol) oppnås, og dette tilsvarer 98,9% av det teoretiske utbytte, beregnet for omsatt 2,6-di-tert.-butyl-4-etylfenol (omdannelsesgrad for sistnevnte forbindelse er 57,5%). ;Omkrystallisering av produktet gir et smeltepunkt på 124,5-125,0°C. ;Uomsatt 2,6-di-tert.-butyl-4-etylfenol og metylal resirkuleres tilbake til prosessen. ;Eksempel_1_4 ;I reaktoren som beskrevet i eksempel 1, anbringes 141,0 g (0,5 g mol) 2-tert.-butyl-4-metyl-6-cumylfenol, ;1,5 g konsentrert svovelsyre og 52 g (0,5 g mol) etylal tilsettes til blandingen ved 130°C i løpet av 1 time. Ved fullendelse av reaksjonen, fraskilles katalysatoren og uomsatt 2-tert.-butyl-4-metyl-6-cumylfenol og etylal avdestilleres under vakuum for oppnåelse av 62,5 g av det ;ønskede produkt, dvs. 2,2'-metylen-bis-(4-metyl-6-cumyl-fenol), hvilket tilsvarer 78,7% av det teoretiske utbytte på basis av omsatt 2-tert.-butyl-4-metyl-6-cumylfenol (omdannelsesgrad for sistnevnte forbindelse er 68,5%) . ;Uomsatte produkter resirkuleres tilbake til prosessen. ;Eksempel_1_5 ;I reaktoren som beskrevet i eksempel 1, anbringes 70 ,5 ..g , (0 ,25 g mol)' 2-tert'. -heksyl-4-metyl-6c-bénzylf enol, ;20 g av en kationutvekslerharpiks-. i.jH*-f orm ? (sulfonert kopolymer av styren og divinylbenzen) og 17,4 g (0,3 g mol) propionsyrealdehyd tilsettes til-'1 reaktoren ved 1 45°C i'løpet av\30 minutter. Ved fullendelse av reaksjonen, fraskilles katalysatoren og f,iyktige --produkter avdestilleres . under., j vakuum for oppnåelse av 31,4 g 1 ,1'-(5-metyl-'3-benzyl-2-hydroksyf enyl) propan, hvilket tilsvarer 91,1;% av det teoretiske utbytte beregnet for omsatt 2-tert.-heksyl-4-metyl-6 -benzyl f enol ;• (omdannelsesgrad -(for .sistnevnte of orbindelse v er--63,2%) . ■ ;■-.■ <, ■ . ;. ■• i ■ ; .jr; eo--3 ~ o y >:' S. •>•. :'v:0: v .Uomsatt z2-tert. -"he.ksyl-4:-metyl-6,-b.enzylfenO'l' !og i.-,■.■[ Li. propionsyrealdehyd resirkuleres, ti.l bake <;ti.l pros.e:ssren .t: ; A method for the production of 2,2*-methylene-bis-(4-methyl-6-tert.-butylphenol) is also known, which has certain advantages compared to the methods mentioned above, because it makes it possible to eliminate the formation of waste water. According to this method, the desired product is obtained from 2,6-di-tert-butyl-4-methylphenol in two steps, namely: dealkylation of 2,6-di-tert-butyl-4-methylphenol followed by separation and condensation of the resulting 2-tert-butyl-4-methylphenol with an acetal in the presence of an acid catalyst at a temperature in the range 30-140°C (BE-PS 836 745 and DD-PS 121 777). ;This previously known process as well as those previously described, comprises two steps and requires the separation, in pure form, of 2-tert.-butyl-4-methylphenol which has a strong and unpleasant odor, high toxicity and high volatility. In addition, a complicated process technique is required for carrying out the above-mentioned methods. Furthermore, with the help of the described previously known methods, it is only possible to produce bisphenols. For the production of polyphenols, only complicated multi-step methods are known. Polyphenols are produced e.g. according to US-PS ;3 297 575 by reacting para-alkylphenols with free ortho-positions with chloromethyl derivatives of 2,6-dialkylphenols according to the scheme below: ;The purpose of the present invention is to eliminate the above-mentioned disadvantages of the previously known methods. The present invention is aimed at providing, through the correct choice of reactants and conditions for their reaction, a simple, one-step method for the production of sterically hindered bis- and polyphenols, which method gives a high yield of the desired product. According to the present invention, a method for the production of sterically hindered bis- or polyphenols with the formula has thus been provided: ;, . In ;where R' is hydrogen or C1~C4 alkyl, R" and R"' are the same or different and represent: ;where R is a tertiary -Cg'- alkyl group; R 1 and R 2 are the same or different and represent C 1 -C 0 alkyl, C 1 -C 6 8 cycloalkyl or C 7 -C 8 aralkyl, and this method is characterized by the fact that sterically hindered 2,4,6-trialkylphenols with the formula: where R, R.j and R.sub.j have the meaning stated above, are reacted with acetals of the general formula: where R.sub.1 is -C,.-alkyl and R<1> has the meaning stated above, or with aldehydes with the general formula formula: where R' has the above meaning, or with their cyclic or linear oligomers in acidic medium at a temperature in the range 60-200°C in the presence of an acidic catalyst. As acid catalysts, the use of Brønstedt acids such as sulfuric acid, ortho-phosphoric acid, polyphosphoric acid, perchloric acid, toluenesulfonic acid, naphthalenesulfonic acid and cation exchangers in H+<-> form or Lewis acids such as zinc chloride, aluminum chloride, ferric chloride and boron trifluoride is preferred. These catalysts can be easily separated from the desired product and a high yield is obtained, i.e. at least 78.7% of the converted starting 2,4,6-trialkylphenols, mainly at least 95% of the theoretical yield. Certain acetals comprise waste products from other syntheses, in particular methylal is a waste product from the synthesis of isoprene rubber. Most preferred among the acetal compounds are methylal, ethylal, dipentyl formal, but other acetal compounds such as dimethyl acetal, diethyl acetal and diisopropyl acetal can also be used. As aldehydes, the use of acetaldehyde, propionic aldehyde, butyric aldehyde, isobutyric aldehyde, valeric aldehyde, isovaleric aldehyde is preferred because these are readily available and easy to handle. It is also possible to use formaldehyde and other aldehydes. As donors of -C,.-aldehydes in an acidic medium, one can use cyclic polymers of aldehydes such as trioxane, paraldehyde, 2,4,6-tri-isobutyl-1,3,5-trioxane, because these products are more stable on storage and easier to handle than monomeric aldehydes. Among cyclic polymers, trioxane is most preferred because the most valuable antioxidants are the hindered bis- or polyphenols that have methylene bonds between aromatic rings. Linear polymers of aldehydes can also be used as donors for -C,.-aldehydes in an acidic medium since these polymers, such as cyclic polymers of aldehydes, are more stable during storage. Paraformaldehyde is the most preferred linear polymer aldehyde because, like trioxane, it ensures the incorporation of methylene bonds between aromatic rings and thus ensures the formation of the most valuable methylene bisphenols or methylene polyphenols. The present method is carried out in the following way: In a four-necked reactor equipped with stirrer, thermometer, cooler and heating bath, a sterically hindered 2,4,6-trialkylphenol such as 2,6-di-tert.-butyl-4- methylphenol, an acid catalyst such as sulfuric acid or a cation exchanger in H+<-> form, or zinc chloride, and the mixture is heated to a certain temperature with stirring. While maintaining this temperature and with continued stirring for 0.5-2 hours, an acetal compound such as methylal or an aldehyde such as acetaldehyde, or a donor for C.j -Cj--aldehyde in an acidic medium, such as paraffin ormaldehyde. ;The process temperature is kept in the range 60-200°C. Upon completion of the process, the catalyst is separated and the desired product is isolated in a conventional manner, such as e.g. by crystallization. ;The yield of the desired product is as high as 78.7-99.1% of the theoretical yield, calculated for the reacted sterically hindered 2,4,6-trialkylphenol, mainly above 95%; for the most effective stabilizer, i.e. 2,2<1->methylene-bis-(4-methyl-6-tert-butylphenol) the yield is as high as 97.8-99.1%. High quality compounds are also obtained by the present method. The melting point for 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) produced according to the invention is thus 131-131.5°C (according to the literature, the product's melting point is 131-132°C). The present method represents several advantages over previously known methods. The selected reactants and the conditions of their reaction give the desired bisphenols or polyphenols from sterically hindered 2,4,6-trialkylphenols in a single step, and for this reason the process technique is significantly simplified and the working conditions are significantly improved because in the process no some 4-methyl-2-tert.-butylphenol which has high toxicity, strong and unpleasant odor and high volatility. The products obtained by the process do not require any further crystallization. Bisphenols or polyphenols can be obtained from monophenols using the present method by appropriate choice of reaction conditions. The unconverted output products are recycled back into the process. The tertiary olefins obtained by the reaction are used in the production of the sterically hindered 2,4,6-trialkylphenol starting materials. The process completely eliminates the formation of polluted wastewater and polluted atmosphere. The following examples illustrate the invention. ;Example_el_1_ ;In a reactor equipped with a stirrer, thermometer and a heating bath, 220 g (1 g mol) of 2,6-di-tert-butyl-4-methylphenol, 2.2 g of concentrated sulfuric acid are placed and the mixture is heated to 120° C. While maintaining the temperature at 120°C, 94 g (1.24 g mol) of methylal are fed into the reactor over 1.5 hours. Upon completion of the reaction, the catalyst is separated, volatile products are distilled under vacuum to obtain 143.0 g of 2,2'-methylene-bis-(4-methyl-6-tert.-butylphenol) which corresponds to 97.8% of the theoretical yield calculated for converted 2,6-di-tert-butyl-4-methylphenol (degree of conversion for the latter compound is 86.0%). ;After a simple recrystallization, the product has a melting point of 131-131.5°C (the literature indicates a melting point of 131-132°C). The unreacted 2,6-di-tert-butyl-4-methylphenol and methylal are recycled back to the process. ;Example_el_2 ;To a reactor similar to that described in example 1, 220 g (1 g mol) of 2,6-di-tert-butyl-4-methylphenol, 2.2 g of concentrated sulfuric acid are added at a temperature of 120°C. 76 g (1.0 g mol) of methylal are added to the reactor over the course of 1 hour. The reaction mass is treated in the same way as stated in example 1 to form 112.9 g of 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) which constitutes 99.1% of the theoretical yield, calculated for converted 2,6-di-tert-butyl-4-methylphenol (degree of conversion for this compound is 67.0%). Unreacted methylal and 2,6-di-tert-butyl-4-methylphenol are recycled back to the process. ;Example_el_3 ;In the reactor as described in example 1, 220 g (1.0 g mol) of 2,6-di-tert-butyl-4-methylphenol, 2.2 g of sulfuric acid and 44 g (1 g mol) of acetaldehyde are placed is fed to the reactor during 1 hour at 125°C. Upon completion of the reaction, the reaction mass is treated as described in example 1 to obtain 124.6 g of 1,1-(5-methyl-3-tert-butyl-2-hydroxyphenyl)ethane which corresponds to 96.4% of the theoretical yield , calculated for converted 2,6-di-tert-butyl-4-methylphenol (degree of conversion 73%). ;After a simple recrystallization, the resulting product has a melting point of 104-104.5°C (a melting point of 104.5°C is stated in the literature). Unreacted 2,6-di-tert-butyl-4-methylphenol and acetaldehyde are recycled back to the process. ;Example_el_4 ;In the reactor as described in example 1, 212 g (0.5 g mol) of 4,4'.-methylene-bis-(2,6-di-tert.-butylphenol), 8.4 g of zinc chloride and 10 g (0.111 g mol) trioxane is added to the mixture over 30 minutes at a temperature of 200°C. On completion of the reaction, the catalyst is separated and volatile products are distilled off under vacuum and this yields 193.7 g of 2,2'-methylene-bis-[4-(3,5-di-tert-butyl-4-hydroxybenzyl)-6 -tert.-butylphenol/ in the form of a resin with a molecular weight of 736 (the theoretical molecular weight of the condensation product is 748). Example 5 In the reactor as described in example 1, 170 g (0.5 g mol) of 2,2'-methylene-bis-(4-methyl-6-tert-butyl-phenol), 34 g of a cation exchange resin in H+<-> form (sulfonated copolymer of styrene and divinylbenzene) and at a temperature of 160°C, 8.2 g (0.26 g mol) of paraformaldehyde (calculated for the 95% product) are added over the course of 1 hour. On completion of the reaction, the catalyst is separated and volatile products are distilled off under vacuum to obtain 141.9 g of a resin containing 46.1% by weight of the condensation product, i.e. 2,2'-methylene-bis-/4- methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenol/ and 53.9% by weight of the starting product. The resin thus obtained can be used as an antioxidant. ;Example_el_6 ;In the reactor as described in example 1, 282 g (1 g mol) of 2,4,6-tri-tert.-butylphenol, 9 g of concentrated sulfuric acid and 110 g (1.19 g mol) of dipentyl formal are introduced into the reactor during 2 hours at 60°C. On completion of the reaction, the catalyst is separated and volatile products are distilled off under vacuum to obtain 120.7 g of the desired product, i.e. 2,2<1->methylene-bis-(4,6-di-tert-butyl- phenol) which corresponds to 98.2% of the theoretical yield, calculated for converted 2,4,6-tri-tert-butylphenol (degree of conversion for this compound is 53%). After a simple recrystallization of the resulting product, a melting point of 141-142°C is obtained. Unreacted 2,4,5-tri-tert-butylphenol and dipentyl formal are recycled back to the process. ;Eksemgel_7 ;In the reactor as described in example 1, 155 g (0.5 g mol) of 2,6-di-tert.-butyl-4-ct-methylbenzylphenol, 3.2 g of paratoluenesulfonic acid and 21.9 g ( 0.255 g mol) of iso-valeric aldehyde is added at 150°C over the course of 1.5 hours. On completion of the reaction, the catalyst is separated, and volatile products are distilled off under vacuum to obtain 120.9 g of 1,1 -(6-tert.-butyl-4-a-methylbenzylphenol)-isopentane which corresponds to 95.8% of the theoretical yields, calculated for converted 2,6-di-tert.-butyl-4-a-methylbenzylphenol (degree of conversion for this compound is 88%). ;Exem<g>el_<8>;In the reactor as described in example 1, 330 g (1.5 g mol) of 2,6-di-tert-butyl-4-methylphenol, 6.5 g of concentrated sulfuric acid and 152 g (2 g mol) of methylal are added over 2 hours at 150°C. On completion of the reaction, the catalyst is separated, and volatile products are distilled off under vacuum to obtain 200.3 g of the desired product, i.e. 2,6-di-(5-methyl-3-tert-butyl-2-hydroxybenzyl) -para-cresol which constitutes 87.1% of the theoretical yield calculated on the basis of converted 2,6-di-tert-butyl-4-methylphenol (degree of conversion for the latter product is 100%). Recrystallization of the product produced gives a melting point of 163-163.5°C. ;Exemp_el_9 ;In the reactor as described in example 1, 220 g (1.0 g mol) of 2,6-di-tert-butyl-4-methylphenol, 11 g ortho-phosphoric acid and 66 g (1.5 g mol ) acetaldehyde is added at a temperature of 150°C during 1 hour. On completion of the reaction, the catalyst is separated and volatile products are distilled off under vacuum to obtain 210 g of a mixture of 1,1-(5-methyl-3-tert.-butyl-2-hydroxy-phenylDetane and 2,6-di- (5-methyl-3-tert-butyl-2-hydroxymethyl-benzyl)para-cresol. The resulting mixture can be used without separation as an antioxidant. The degree of conversion of 2,6-di-tert-butyl-4-methylphenol is 99%. ;Eksemgel_2Q ;In the reactor as described in example 1, 123 g (0.5 g mol) of 2-tert.-butyl-6-cyclohexyl-4-methylphenol, 42 g of concentrated sulfuric acid are placed, and the mixture is heated at a temperature of 120° C. At this temperature, 47 g (1.12 g mol) of methylal are added to the reactor during 1.5 hours. Upon completion of the reaction, the catalyst is separated and volatile products are distilled off under vacuum to obtain 163.1 g 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), which constitutes 99.1% of the theoretical yield, calculated on the basis of converted 2-tert.-butyl-6-cyclohexyl-4-methylpheno l (degree of conversion for the latter compound is 84%). Recrystallization of the resulting product gives a melting point of 117-117.5°C. Unreacted 2-tert.-butyl-6-cyclohexyl-4-methylphenol and methylal are recycled back to the process. ;Examp_el_1_1_ ;In the reactor as described in example 1, ;159 g (0.5 g mol) of 2,6-di-tert.-butyl1-4-tert.-octylphenol, ;2 g of concentrated sulfuric acid and 36 g (0 .5 g mol) of butyric aldehyde is added to the reactor at a temperature of 125°C over the course of 1 hour. On completion of the reaction, the catalyst is separated, and volatile products are distilled off under vacuum to form 103.3 g of the desired product, i.e. 1,1-(3-tert.-butyl1-5-tert.-octyl-2-hydroxyphenyl) )butane, which corresponds to 95.3% of the theoretical yield, calculated for converted 2,6-di-tert.-butyl-4-tert.-octylphenol (degree of conversion for the latter compound is 75.0%). ;Unreacted 2,6-di-tert.-butyl-4-tert.-octylphenol and butyric aldehyde are recycled back to the process. ;Eksemgel_12 ;In the reactor as described in example 1, 234 g (1 g mol) 2-tert.-octyl-4,6-xylenol, 2.4 g concentrated sulfuric acid and 76 g (1 g mol) methylal are added at a temperature of 100°C during 1 hour. The reaction mass is treated as indicated in example 11 to obtain 63.5 g of the desired product, i.e. 2,2'-methylene-bis-(4,6-dimethylphenol), which amounts to 81.1% of the theoretical yield calculated for converted 2-tert.-octyl-4,6-xylenol (degree of conversion for the latter compound is 61.2%). Unreacted 2-tert.-octyl-4,6-xylenol and methylal are recycled back to the process. ;Example_el_1_3 ;In the reactor as described in example 1, 58.5 g (0.25 g mol) of 2,6-di-tert-butyl-4-ethylphenol, 1 g of concentrated sulfuric acid and 19 g (0.25 g mol) methylal is added to the reactor at 130°C during 30 minutes. The reaction mass is then treated and 26.2 g of 2,2'-methylene-bis-(4-ethyl-6-tert.-butylphenol) is obtained, and this corresponds to 98.9% of the theoretical yield, calculated for converted 2.6 -di-tert.-butyl-4-ethylphenol (degree of conversion for the latter compound is 57.5%). Recrystallization of the product gives a melting point of 124.5-125.0°C. Unreacted 2,6-di-tert-butyl-4-ethylphenol and methylal are recycled back to the process. ;Example_1_4 ;In the reactor as described in example 1, 141.0 g (0.5 g mol) of 2-tert.-butyl-4-methyl-6-cumylphenol, ;1.5 g concentrated sulfuric acid and 52 g (0 .5 g mol) of ethyl alcohol is added to the mixture at 130°C over the course of 1 hour. On completion of the reaction, the catalyst is separated and unreacted 2-tert.-butyl-4-methyl-6-cumylphenol and ethyl alcohol are distilled off under vacuum to obtain 62.5 g of the desired product, i.e. 2,2'-methylene- bis-(4-methyl-6-cumyl-phenol), which corresponds to 78.7% of the theoretical yield on the basis of converted 2-tert.-butyl-4-methyl-6-cumylphenol (degree of conversion for the latter compound is 68, 5%). Unsold products are recycled back into the process. ;Example_1_5 ;In the reactor as described in example 1, 70.5 ..g , (0.25 g mol)' of 2-tert' are placed. -hexyl-4-methyl-6c-benzylph enol, ; 20 g of a cation exchange resin-. i.jH*-f worm ? (sulfonated copolymer of styrene and divinylbenzene) and 17.4 g (0.3 g mol) of propionic acid aldehyde are added to the reactor at 145°C over 30 minutes. On completion of the reaction, the catalyst is separated and volatile products are distilled off. under., j vacuum to obtain 31.4 g of 1,1'-(5-methyl-'3-benzyl-2-hydroxyphenyl)propane, which corresponds to 91.1% of the theoretical yield calculated for reacted 2- tert-hexyl-4-methyl-6-benzyl phenol; (degree of conversion -(for .the latter of orbindelse v is--63.2%) . ; -. <, . ;. i ; .jr; eo--3 ~ o y >:' S. > . :'v:0 : v . Unreacted z2-tert. -"hex.xyl-4:-methyl-6,-b.enzylphenO'l' ! and i.-, .[ Li. propionic acid aldehyde is recycled, ti.l bake <;ti.l pros.e:ssren .t: ;
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU762372253A SU732232A1 (en) | 1976-06-14 | 1976-06-14 | Method of preparing sterically-hindered bis- or polyphenols |
Publications (3)
Publication Number | Publication Date |
---|---|
NO772056L NO772056L (en) | 1977-12-15 |
NO147024B true NO147024B (en) | 1982-10-11 |
NO147024C NO147024C (en) | 1983-01-26 |
Family
ID=20665542
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO772056A NO147024C (en) | 1976-06-14 | 1977-06-13 | PROCEDURE FOR THE PREPARATION OF STERICALLY HINED BIS OR POLYPHENOLS. |
Country Status (18)
Country | Link |
---|---|
JP (1) | JPS5315349A (en) |
AT (1) | AT352706B (en) |
BE (1) | BE855676A (en) |
BR (1) | BR7703857A (en) |
CA (1) | CA1109894A (en) |
CH (1) | CH633505A5 (en) |
DE (1) | DE2726762C3 (en) |
DK (1) | DK146908C (en) |
FI (1) | FI65421C (en) |
FR (1) | FR2354988A1 (en) |
GB (1) | GB1555728A (en) |
IE (1) | IE45388B1 (en) |
IT (1) | IT1114877B (en) |
NL (1) | NL172053C (en) |
NO (1) | NO147024C (en) |
PT (1) | PT66676B (en) |
SE (1) | SE442632B (en) |
SU (1) | SU732232A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4222884A (en) * | 1978-12-04 | 1980-09-16 | Ethyl Corporation | Antioxidant |
US4532059A (en) * | 1982-11-25 | 1985-07-30 | Ciba-Geigy Corporation | Benzylated phenols |
US6207866B1 (en) | 1997-07-11 | 2001-03-27 | Nippon Petrochemicals Company, Limited | Method for producing diarylmethane or its derivatives |
JP2000016952A (en) | 1998-07-01 | 2000-01-18 | Nippon Petrochem Co Ltd | Production of hydrocarbon |
JP4376367B2 (en) | 1999-09-20 | 2009-12-02 | 新日本石油株式会社 | Hydrocarbon solvent and pressure-sensitive copying material using the same |
CN105859771B (en) * | 2016-03-25 | 2018-09-14 | 维思普新材料(苏州)有限公司 | A kind of preparation method of aryl phosphine hydrochlorate nucleating agent |
-
1976
- 1976-06-14 SU SU762372253A patent/SU732232A1/en active
-
1977
- 1977-06-13 IT IT24626/77A patent/IT1114877B/en active
- 1977-06-13 NL NLAANVRAGE7706496,A patent/NL172053C/en not_active IP Right Cessation
- 1977-06-13 AT AT414877A patent/AT352706B/en not_active IP Right Cessation
- 1977-06-13 DK DK260377A patent/DK146908C/en not_active IP Right Cessation
- 1977-06-13 SE SE7706829A patent/SE442632B/en not_active IP Right Cessation
- 1977-06-13 NO NO772056A patent/NO147024C/en unknown
- 1977-06-13 CA CA280,418A patent/CA1109894A/en not_active Expired
- 1977-06-14 FR FR7718180A patent/FR2354988A1/en active Granted
- 1977-06-14 GB GB24793/77A patent/GB1555728A/en not_active Expired
- 1977-06-14 JP JP6949577A patent/JPS5315349A/en active Granted
- 1977-06-14 BR BR7703857A patent/BR7703857A/en unknown
- 1977-06-14 IE IE1216/77A patent/IE45388B1/en unknown
- 1977-06-14 FI FI771872A patent/FI65421C/en not_active IP Right Cessation
- 1977-06-14 BE BE178436A patent/BE855676A/en not_active IP Right Cessation
- 1977-06-14 CH CH731077A patent/CH633505A5/en not_active IP Right Cessation
- 1977-06-14 DE DE2726762A patent/DE2726762C3/en not_active Expired
- 1977-06-15 PT PT66676A patent/PT66676B/en unknown
Also Published As
Publication number | Publication date |
---|---|
PT66676A (en) | 1977-07-01 |
PT66676B (en) | 1978-11-15 |
AT352706B (en) | 1979-10-10 |
SE7706829L (en) | 1977-12-15 |
CA1109894A (en) | 1981-09-29 |
IE45388L (en) | 1977-12-14 |
IT1114877B (en) | 1986-01-27 |
FI65421B (en) | 1984-01-31 |
SE442632B (en) | 1986-01-20 |
SU732232A1 (en) | 1980-05-05 |
FI65421C (en) | 1984-05-10 |
FR2354988A1 (en) | 1978-01-13 |
GB1555728A (en) | 1979-11-14 |
BR7703857A (en) | 1978-04-25 |
JPS558500B2 (en) | 1980-03-04 |
DE2726762C3 (en) | 1981-10-15 |
JPS5315349A (en) | 1978-02-13 |
ATA414877A (en) | 1979-03-15 |
BE855676A (en) | 1977-12-14 |
NL172053B (en) | 1983-02-01 |
NL7706496A (en) | 1977-12-16 |
FR2354988B1 (en) | 1981-11-27 |
DK260377A (en) | 1977-12-15 |
IE45388B1 (en) | 1982-08-11 |
DE2726762B2 (en) | 1980-08-21 |
NO147024C (en) | 1983-01-26 |
CH633505A5 (en) | 1982-12-15 |
DE2726762A1 (en) | 1977-12-22 |
DK146908B (en) | 1984-02-06 |
FI771872A (en) | 1977-12-15 |
NL172053C (en) | 1983-07-01 |
NO772056L (en) | 1977-12-15 |
DK146908C (en) | 1984-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Holly et al. | Condensation products of aldehydes and ketones with o-aminobenzyl alcohol and o-hydroxybenzylamine | |
KR950003332B1 (en) | PREPARATION METHOD FOR Ñß-,ÑÔ-UNSATURATED KETONES | |
US4845249A (en) | 4-fluoro-3-bromo benzaldehyde acetals | |
NO147024B (en) | PROCEDURE FOR THE PREPARATION OF STERICALLY HIDDEN BIS OR POLYPHENOLS. | |
US3957824A (en) | 4-hydroxycoumarins | |
US4087468A (en) | Preparation of grignard reagents of halodienes and preparation of dienols | |
Murahashi et al. | Methylene-hydantoin and related compounds. I. On the reaction of pyruvic acid and urea: the synthesis of 5-methylene-hydantoin | |
US2638479A (en) | Method for the preparation of esters of beta-oxy aldehydes | |
US5019655A (en) | Method of preparing 4-dichlorophenyl-1-tetralones | |
US4319052A (en) | Method for preparing sterically hindered bis- or polyphenols | |
Kuivila et al. | Reactions of Aldehydes and Ketones with Alkyl Borates1 | |
US5395978A (en) | Process for selective preparation of hydroxybenzaldehydes | |
US4908481A (en) | Preparation of 1-(4-hydroxy-phenyl)-butan-3-one and novel intermediates | |
US2800513A (en) | Manufacture of trialkoxyalkanes | |
US4381416A (en) | Process for producing isoprene | |
US2108427A (en) | Preparation of alpha, beta unsaturated ketones | |
US4694111A (en) | Alkoxyalkylation of phenol | |
US4035505A (en) | 4-Hydroxycoumarin compounds useful as anticoagulant rodenticides | |
Kleinspehn et al. | Cyclizations leading to 2-acylpyrroles and 2-pyrrolecarboxylic esters | |
US4046816A (en) | Process for preparing resorcinol monoethers | |
US4021491A (en) | Manufacture of 2,6,6-trimethyl-cyclohex-2-en-1-one | |
US2768967A (en) | Process for manufacture of 2, 5 diketo-8-nonen-3-ol | |
US2543472A (en) | Nitro cyclic acetals | |
US3021375A (en) | Process for the preparation of 2, 4-bis-(chloromethyl)-toluene | |
Horning et al. | ALICYCLIC-AROMATIC ISOMERIZATIONS. 2, 5-DIMETHYL-3-ALKYLPHENOLS FROM 3-METHYL-5-ALKYL-2-CYCLOHEXEN-1-ONES THROUGH THE MANNICH REACTION |