GB600114A - Improvements in and relating to the synthesis of derivatives of stilbene and di-benzyl - Google Patents
Improvements in and relating to the synthesis of derivatives of stilbene and di-benzylInfo
- Publication number
- GB600114A GB600114A GB2602845A GB2602845A GB600114A GB 600114 A GB600114 A GB 600114A GB 2602845 A GB2602845 A GB 2602845A GB 2602845 A GB2602845 A GB 2602845A GB 600114 A GB600114 A GB 600114A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methyl
- produce
- dimethyl
- derivative
- followed
- 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
- PJANXHGTPQOBST-VAWYXSNFSA-N (E)-Stilbene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 title abstract 2
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 230000002194 synthesizing Effects 0.000 title 1
- 230000000875 corresponding Effects 0.000 abstract 10
- IEVIXDLZSRLUHW-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diol Chemical compound C=1C=CC=CC=1C(O)=C(O)C1=CC=CC=C1 IEVIXDLZSRLUHW-UHFFFAOYSA-N 0.000 abstract 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N Bibenzyl Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 abstract 3
- 239000007818 Grignard reagent Substances 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 150000004795 grignard reagents Chemical class 0.000 abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- NHVSJSFJPMWGKP-UHFFFAOYSA-N 1-(4-methoxy-2-methylphenyl)-2-(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1CC(=O)C1=CC=C(OC)C=C1C NHVSJSFJPMWGKP-UHFFFAOYSA-N 0.000 abstract 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- QIAFMBKCNZACKA-UHFFFAOYSA-N Hippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 abstract 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N Thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract 2
- 239000003610 charcoal Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000006900 dealkylation reaction Methods 0.000 abstract 2
- 230000017858 demethylation Effects 0.000 abstract 2
- 238000010520 demethylation reaction Methods 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 2
- VYKZQEAQZIYXFI-UHFFFAOYSA-N 2-(4-methoxy-2-methylphenyl)acetic acid Chemical compound COC1=CC=C(CC(O)=O)C(C)=C1 VYKZQEAQZIYXFI-UHFFFAOYSA-N 0.000 abstract 1
- CXJOONIFSVSFAD-UHFFFAOYSA-N 2-(4-methoxyphenyl)acetyl chloride Chemical compound COC1=CC=C(CC(Cl)=O)C=C1 CXJOONIFSVSFAD-UHFFFAOYSA-N 0.000 abstract 1
- SJHPCNCNNSSLPL-UHFFFAOYSA-N 4-(ethoxymethylene)-2-phenyloxazol-5-one Chemical compound O1C(=O)C(=COCC)N=C1C1=CC=CC=C1 SJHPCNCNNSSLPL-UHFFFAOYSA-N 0.000 abstract 1
- WICYVKGMEJSDAO-UHFFFAOYSA-N 4-methoxy-2-methylbenzaldehyde Chemical compound COC1=CC=C(C=O)C(C)=C1 WICYVKGMEJSDAO-UHFFFAOYSA-N 0.000 abstract 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N Anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 abstract 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N Ethyl iodide Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 abstract 1
- 238000003747 Grignard reaction Methods 0.000 abstract 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N Methyl iodide Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N Phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 abstract 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000003301 hydrolyzing Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 abstract 1
- XXTWNWQHEGVDMQ-UHFFFAOYSA-N methyl 2-(4-methoxy-2-methylphenyl)acetate Chemical compound COC(=O)CC1=CC=C(OC)C=C1C XXTWNWQHEGVDMQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract 1
- 239000001632 sodium acetate Substances 0.000 abstract 1
- 235000017281 sodium acetate Nutrition 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- 235000021286 stilbenes Nutrition 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- 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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
- C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
- C07C39/215—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring containing, e.g. diethylstilbestrol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
- C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Compounds of the general formula <FORM:0600114/IV(b)/1> in which R1, R2, R3, R4, R5 an R6 are each hydrogen or an alkyl group, and R1 or R3 or both R1 and R3 is or are an alkyl group or groups are obtained by carrying out a Grignard reaction upon the corresponding desoxybenzoin derivative to form the corresponding tertiary carbinol and if the dihydroxy compound is the desired product, followed by dealkylation. The corresponding dibenzyl derivatives are obtained by the hydrogenation of the dialkoxystilbene or dihydroxystilbene formed as above and if desired followed by dealkylation or by the direct reduction of the desoxybenzoin derivative. In examples: (1) 2-methyldesoxyanisoin is reduced with amalgamated zinc and concentrated hydrochloric acid to produce 2-methyl-4 : 41-dimethoxy-dibenzyl which is demethylated to produce 2-methyl-4 : 41-dihydroxydibenzyl; (2) ms : 2-dimethyldesoxyanisoin is treated as in example (1) to produce b - 2-dimethyl - 4 : 41 - dimethoxydibenzyl and b : 2-dimethyl - 4 : 41 - dihydroxydibenzyl; (3) 21-methyldesoxyanisoin is treated with a Grignard reagent and the product heated to produce b : 2 - dimethyl - 4 : 41 - dimethoxystilbene which is hydrogenated in the presence of palladized charcoal to the corresponding dibenzyl derivative; (4) b -ethyl-2-methyl-desoxyanisoin is converted by means of a Grignard reagent followed by dehydration of the product with phosphorous tribromide to b -ethyl-a : 2-dimethyl-4 : 41-dimethoxystilbene which is demethylated to the corresponding dihydroxystilbene. The corresponding dibenzyl compounds are obtained by hydrogenation; (5) ms : 2 : 21 - trimethyldesoxyanisoin is treated with a Grignard reagent and the product is dehydrated to produce a : b : 2 : 21-tetramethyl-4 : 41-dimethoxystilbene which on demethylation gives the corresponding dihydroxystilbene; (6) a : b : 2 : 21 - tetramethyl - 4 : 41 - dimethox - stilbene is hydrogenated in the presence of palladized charcoal to produce the corresponding dimethoxydibenzyl derivative which on demethylation gives the dihydroxydibenzyl derivative. 2-Methyl, 21-methyl and 2 : 21-dimethyldesoxy-anisoin are obtained by condensing the corresponding 4-methoxyphenylacetyl chloride with the corresponding anisole in the presence of aluminium chloride. ms : 2 - Dimethyl and b -ethyl-2-methyl-desoxy-anisoin are obtained by heating a solution of 2-methyldesoxyanisoin in ethanol with sodium ethoxide and methyl or ethyl iodide. 2-Phenyl-4-(21-methyl-41-methoxy-benzal)-5-oxazolone is obtained by heating together 2-methyl - 4 - methoxy - benzaldehyde, hippuric acid, sodium acetate and acetic anhydride. Methyl - 2 - methyl - 4 - methoxyphenylacetate is obtained from the oxazolone above by treatment with caustic soda followed by oxidation with hydrogen peroxide and esterification. 2 - Methyl - 4 - methoxyphenylacetic acid is obtained by hydrolysing the ester above. The acid chloride and amide are obtained on treatment with thionyl chloride and ammonia respectively.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB600114A true GB600114A (en) | 1948-03-31 |
Family
ID=1739746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2602845A Expired GB600114A (en) | 1945-10-05 | Improvements in and relating to the synthesis of derivatives of stilbene and di-benzyl |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB600114A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2165700A1 (en) * | 1970-12-31 | 1972-07-20 | Ibm | Nematic substances |
-
1945
- 1945-10-05 GB GB2602845A patent/GB600114A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2165700A1 (en) * | 1970-12-31 | 1972-07-20 | Ibm | Nematic substances |
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