CA1067505A - Procede pour l'oxydation d'alcools allyliques primaires et d'alcools benziliques - Google Patents

Procede pour l'oxydation d'alcools allyliques primaires et d'alcools benziliques

Info

Publication number: CA1067505A
Authority: CA; Canada
Prior art keywords: alcohol; primary; oxidation; alcohols; oppenauer
Prior art date: 1975-05-30
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired

Application number

CA239,165A

Other languages

English (en)

Other versions

CA239165S (en

Inventor

William J. Ehmann

Walter E. Johnson (Jr.)

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

SCM Corp

Original Assignee

SCM Corp

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1975-05-30

Filing date

1975-11-07

Publication date

1979-12-04

1975-11-07 Application filed by SCM Corp filed Critical SCM Corp

1979-12-04 Application granted granted Critical

1979-12-04 Publication of CA1067505A publication Critical patent/CA1067505A/fr

Status Expired legal-status Critical Current

Links

238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
-1 benzylic alcohols Chemical class 0.000 title claims abstract description 22
230000003647 oxidation Effects 0.000 title claims abstract description 22
238000000034 method Methods 0.000 title claims abstract description 13
125000000746 allylic group Chemical group 0.000 title abstract description 3
HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 38
238000006243 chemical reaction Methods 0.000 claims abstract description 33
238000006036 Oppenauer oxidation reaction Methods 0.000 claims abstract description 20
229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
239000001257 hydrogen Substances 0.000 claims abstract description 16
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
150000003138 primary alcohols Chemical class 0.000 claims abstract description 13
150000004808 allyl alcohols Chemical group 0.000 claims abstract description 7
239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 25
150000001299 aldehydes Chemical class 0.000 claims description 20
239000003054 catalyst Substances 0.000 claims description 19
XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 14
NDTYTMIUWGWIMO-UHFFFAOYSA-N perillyl alcohol Chemical compound CC(=C)C1CCC(CO)=CC1 NDTYTMIUWGWIMO-UHFFFAOYSA-N 0.000 claims description 14
229930007631 (-)-perillyl alcohol Natural products 0.000 claims description 7
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
235000019445 benzyl alcohol Nutrition 0.000 claims description 7
235000005693 perillyl alcohol Nutrition 0.000 claims description 7
RXBQNMWIQKOSCS-UHFFFAOYSA-N (7,7-dimethyl-4-bicyclo[3.1.1]hept-3-enyl)methanol Chemical compound C1C2C(C)(C)C1CC=C2CO RXBQNMWIQKOSCS-UHFFFAOYSA-N 0.000 claims description 4
125000002015 acyclic group Chemical group 0.000 claims description 4
239000006227 byproduct Substances 0.000 claims description 4
239000007795 chemical reaction product Substances 0.000 claims description 4
239000000203 mixture Substances 0.000 claims description 3
BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 2
RXBQNMWIQKOSCS-RKDXNWHRSA-N Myrtenol Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2CO RXBQNMWIQKOSCS-RKDXNWHRSA-N 0.000 claims description 2
230000000875 corresponding effect Effects 0.000 claims 2
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
239000000370 acceptor Substances 0.000 description 14
229910052782 aluminium Inorganic materials 0.000 description 13
GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 12
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 7
150000001875 compounds Chemical class 0.000 description 7
239000000047 product Substances 0.000 description 7
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 5
238000005882 aldol condensation reaction Methods 0.000 description 5
229940043350 citral Drugs 0.000 description 5
WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 5
HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
RUMOYJJNUMEFDD-UHFFFAOYSA-N perillyl aldehyde Chemical compound CC(=C)C1CCC(C=O)=CC1 RUMOYJJNUMEFDD-UHFFFAOYSA-N 0.000 description 4
GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 3
239000005792 Geraniol Substances 0.000 description 3
150000001298 alcohols Chemical class 0.000 description 3
238000004458 analytical method Methods 0.000 description 3
230000003197 catalytic effect Effects 0.000 description 3
229940113087 geraniol Drugs 0.000 description 3
150000002576 ketones Chemical class 0.000 description 3
QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
238000007086 side reaction Methods 0.000 description 3
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 2
239000002253 acid Substances 0.000 description 2
238000010533 azeotropic distillation Methods 0.000 description 2
238000009833 condensation Methods 0.000 description 2
125000004122 cyclic group Chemical group 0.000 description 2
125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 2
238000011065 in-situ storage Methods 0.000 description 2
JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 description 2
239000000376 reactant Substances 0.000 description 2
239000011541 reaction mixture Substances 0.000 description 2
238000010992 reflux Methods 0.000 description 2
150000003333 secondary alcohols Chemical class 0.000 description 2
238000006467 substitution reaction Methods 0.000 description 2
MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 2
ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical compound COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 description 2
ARSUYSCIFANSEF-JXMROGBWSA-N (2e)-2,6-dimethylocta-2,7-dien-1-ol Chemical compound C=CC(C)CC\C=C(/C)CO ARSUYSCIFANSEF-JXMROGBWSA-N 0.000 description 1
UVXVZRHRFYHHES-UHFFFAOYSA-N 2,6-dimethylocta-2,7-dienal Chemical compound C=CC(C)CCC=C(C)C=O UVXVZRHRFYHHES-UHFFFAOYSA-N 0.000 description 1
SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
229930008411 3,7-dimethylocta-2,6-dien-1-ol Natural products 0.000 description 1
125000001931 aliphatic group Chemical group 0.000 description 1
230000000052 comparative effect Effects 0.000 description 1
238000006482 condensation reaction Methods 0.000 description 1
230000001419 dependent effect Effects 0.000 description 1
238000004821 distillation Methods 0.000 description 1
125000001183 hydrocarbyl group Chemical group 0.000 description 1
150000002431 hydrogen Chemical class 0.000 description 1
125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
238000002955 isolation Methods 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
238000012986 modification Methods 0.000 description 1
230000004048 modification Effects 0.000 description 1
239000007800 oxidant agent Substances 0.000 description 1
BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 1
239000002244 precipitate Substances 0.000 description 1
238000002360 preparation method Methods 0.000 description 1
238000003822 preparative gas chromatography Methods 0.000 description 1
OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
239000002904 solvent Substances 0.000 description 1
239000007858 starting material Substances 0.000 description 1
239000000758 substrate Substances 0.000 description 1
MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

CA239,165A 1975-05-30 1975-11-07 Procede pour l'oxydation d'alcools allyliques primaires et d'alcools benziliques Expired CA1067505A (fr)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
US58211375A	1975-05-30	1975-05-30

Publications (1)

Publication Number	Publication Date
CA1067505A true CA1067505A (fr)	1979-12-04

Family

ID=24327903

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CA239,165A Expired CA1067505A (fr)	1975-05-30	1975-11-07	Procede pour l'oxydation d'alcools allyliques primaires et d'alcools benziliques

Country Status (2)

Country	Link
CA (1)	CA1067505A (fr)
GB (1)	GB1496378A (fr)

1975
- 1975-11-07 CA CA239,165A patent/CA1067505A/fr not_active Expired
- 1975-11-18 GB GB4751975A patent/GB1496378A/en not_active Expired

Also Published As

Publication number	Publication date
GB1496378A (en)	1977-12-30

Publication	Publication Date	Title
US4094914A (en)	1978-06-13	Process for the production of divalent alcohols
US2533172A (en)	1950-12-05	Hydrolysis of vinyl ethers
US4692547A (en)	1987-09-08	Process for the preparation of glyoxylic hemiacetal esters
US4298762A (en)	1981-11-03	Process for the oxidation of primary allylic and benzylic alcohols
CA1067505A (fr)	1979-12-04	Procede pour l'oxydation d'alcools allyliques primaires et d'alcools benziliques
US4055601A (en)	1977-10-25	Process for the oxidation of primary allylic alcohols
US4740639A (en)	1988-04-26	Process for preparation of 2,4-disubstituted-1,5-pentanediols
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US4663488A (en)	1987-05-05	Oppenauer oxidation of geraniol/nerol
US3225102A (en)	1965-12-21	Allenic aldehydes
US5874635A (en)	1999-02-23	Preparation of γ, δ-unsaturated ketones by the carroll reaction in cyclic carbonates or γ-lactones
US4618725A (en)	1986-10-21	Preparation of α-methyl-substituted ketones
Kuivila et al.	1951	Reactions of Aldehydes and Ketones with Alkyl Borates1
US3739032A (en)	1973-06-12	Process for the preparation of unsaturated ethers
US4990697A (en)	1991-02-05	Process for producing homoallyl alcohols
CA1059526A (fr)	1979-07-31	Procede pour l'oxydation d'alcools allyliques primaires
US2576901A (en)	1951-11-27	Preparation of delta-valero-lactones
US3819719A (en)	1974-06-25	Production of alkoxy phenolic compounds
JPS6365057B2 (fr)	1988-12-14
US2406652A (en)	1946-08-27	Ketols from isophorones and homologues thereof
US4301084A (en)	1981-11-17	Process for the preparation of carboxylic acid esters of β-formyl-crotyl alcohol by an allyl rearrangement
USRE29201E (en)	1977-05-03	Production of alkoxy phenolic compounds
US5792876A (en)	1998-08-11	Process for producing acetals
US3114772A (en)	1963-12-17	Preparation of allyl-substituted ketones
USRE29200E (en)	1977-05-03	Production of alkoxy phenolic compounds