GB650887A - A process for the preparation of unsaturated aldehydes - Google Patents
A process for the preparation of unsaturated aldehydesInfo
- Publication number
- GB650887A GB650887A GB33854/47A GB3385447A GB650887A GB 650887 A GB650887 A GB 650887A GB 33854/47 A GB33854/47 A GB 33854/47A GB 3385447 A GB3385447 A GB 3385447A GB 650887 A GB650887 A GB 650887A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydrolysed
- acetylene
- ethoxy
- reacted
- hydrogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001299 aldehydes Chemical class 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 3
- 150000002576 ketones Chemical class 0.000 abstract 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 abstract 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 abstract 2
- NCYCYZXNIZJOKI-OVSJKPMPSA-N Retinaldehyde Chemical compound O=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-OVSJKPMPSA-N 0.000 abstract 2
- WMYNMYVRWWCRPS-UHFFFAOYSA-N ethynoxyethane Chemical group CCOC#C WMYNMYVRWWCRPS-UHFFFAOYSA-N 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 235000020945 retinal Nutrition 0.000 abstract 2
- 239000011604 retinal Substances 0.000 abstract 2
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 abstract 2
- BCFCTTHZFYZOHT-UHFFFAOYSA-N 1-bromo-2-ethoxyethene Chemical group CCOC=CBr BCFCTTHZFYZOHT-UHFFFAOYSA-N 0.000 abstract 1
- CUCVSVQCMKSHRT-UHFFFAOYSA-N 1-bromo-2-ethoxyethyne Chemical group BrC#COCC CUCVSVQCMKSHRT-UHFFFAOYSA-N 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 239000012445 acidic reagent Substances 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 abstract 1
- HJCNOCJDGPFRNM-UHFFFAOYSA-N ethynoxybenzene Chemical group C#COC1=CC=CC=C1 HJCNOCJDGPFRNM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- 235000006408 oxalic acid Nutrition 0.000 abstract 1
- 229960002847 prasterone Drugs 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 150000002266 vitamin A derivatives Chemical class 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J13/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having a carbon-to-carbon double bond from or to position 17
- C07J13/007—Normal steroids containing carbon, hydrogen, halogen or oxygen having a carbon-to-carbon double bond from or to position 17 with double bond in position 17 (20)
-
- 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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Aldehydes of the formula R1R2C=CH-CHO are prepared from compounds of the formula R1R2C(OH)-CH=CH-OR3 by treatment with an acidic reagent resulting in intramolecular conversion; R1 is hydrogen or a hydrocarbon residue which may be substituted, R2 is a hydrocarbon residue which may be substituted and R1 and R2 may be connected by a ring system; R3 is an alkyl, aryl or aralkyl group. The starting materials may be obtained from ketones R1R2CO by (1) treatment with a metal derivative of a compound CH=C.OR3 to give R1R2C(OH)-C C-OR3 followed by reduction, or (2) treatment with a metal derivative of a compound CH2= CH-OR3. In examples, (1) phenoxy-acetylene is converted into its Grignard compound with ethyl magnesium bromide and reacted with the C18 ketone of the Vitamin A series. The resulting acetylenic carbinol is catalytically hydrogenated to the corresponding ethylenic carbinol and the latter hydrolysed to Vitamin A aldehyde with oxalic acid; (2) a Grignard compound is prepared from 1-ethoxy-2-bromethylene and magnesium and reacted with C18 ketone as in (1), the product being hydrolysed to Vitamin A aldehyde; (3) 1-ethoxy-2-brom-acetylene is converted into its Grignard compound with ethyl magnesium bromide and reacted with acetophenone. The product is hydrogenated and hydrolysed with hydrochloric acid to give b -methyl-cinnamic aldehyde; (4) ethoxy-acetylene is converted into its Grignard compound with ethyl magnesium bromide and reacted with b -ionone. The product is purified by chromatography and hydrogenated and hydrolysed as in (1) to give b -ionylidene-acetaldehyde; (5) the Grignard compound of ethoxy-acetylene is treated with dehydro-androsterone acetate and the product hydrogenated and hydrolysed with hydrochloric acid, yielding 3-acetoxy-pregnadiene-5 : 17-al-21.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL650887X | 1946-10-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB650887A true GB650887A (en) | 1951-03-07 |
Family
ID=19793610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB33854/47A Expired GB650887A (en) | 1946-10-30 | 1947-12-22 | A process for the preparation of unsaturated aldehydes |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE478169A (en) |
| DE (1) | DE824943C (en) |
| GB (1) | GB650887A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3031507A (en) * | 1957-10-31 | 1962-04-24 | Rhone Poulenc Sa | Gamma-cyclohexylcrotonaldehyde |
| DE1196177B (en) * | 1963-07-30 | 1965-07-08 | Basf Ag | Process for the preparation of 2-hydroxy-2,3-dihydrocitral |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1042576B (en) * | 1954-01-18 | 1958-11-06 | Hoffmann La Roche | Process for the preparation of ª,ª-unsaturated aldehydes |
-
0
- BE BE478169D patent/BE478169A/xx unknown
-
1947
- 1947-12-22 GB GB33854/47A patent/GB650887A/en not_active Expired
-
1948
- 1948-12-28 DE DEP27258A patent/DE824943C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3031507A (en) * | 1957-10-31 | 1962-04-24 | Rhone Poulenc Sa | Gamma-cyclohexylcrotonaldehyde |
| DE1196177B (en) * | 1963-07-30 | 1965-07-08 | Basf Ag | Process for the preparation of 2-hydroxy-2,3-dihydrocitral |
Also Published As
| Publication number | Publication date |
|---|---|
| DE824943C (en) | 1951-12-17 |
| BE478169A (en) |
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