US3676510A - Polyene hydrocarbons and process for obtaining same - Google Patents
Polyene hydrocarbons and process for obtaining same Download PDFInfo
- Publication number
- US3676510A US3676510A US109007A US3676510DA US3676510A US 3676510 A US3676510 A US 3676510A US 109007 A US109007 A US 109007A US 3676510D A US3676510D A US 3676510DA US 3676510 A US3676510 A US 3676510A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbons
- reaction
- obtaining same
- followed
- polyene hydrocarbons
- 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 - Lifetime
Links
- -1 Polyene hydrocarbons Chemical class 0.000 title claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims abstract description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001530 fumaric acid Substances 0.000 claims abstract description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 3
- 239000011976 maleic acid Substances 0.000 claims abstract description 3
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 150000005840 aryl radicals Chemical class 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/39—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms
- C07C13/42—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms with a bicycloheptene ring structure
- C07C13/43—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms with a bicycloheptene ring structure substituted by unsaturated acyclic hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Definitions
- R R R R R and R may be hydrogen, alkyl or aryl radicals, and which may be prepared through a Diels- 5 References Ci d Alder reaction between a cyclopentadiene and (a) a dihalidealkenyl compound, followed by dehydrohalogenation with basic agents, or (b) esters of fumaric or maleic acid, followed UNITED STATES PATENTS by reaction with a Grignards reagent and then by dehydration of the alcohol, are disclosed.
- the present invention relates to triene hydrocarbons containing two conjugated double bonds and having the following general formula:
- R, R R R R R and R" have the aforesaid meanings, and X is a halogen as Cl, Br or I.
- the reactions according to the process of the present invention are carried out at a temperature comprised in the range from -l0 to 100 C and in the presence of a solvent which may be selected from esters as tetrahydrofurane, dioxane, ethyl ether, butyl ether and the like, or aromatic hydrocarbons as benzene, toluene, xylenes or mixtures of the cited solvents.
- Typical unrestrictive examples of triene compounds according to the present invention are the following ones:
- the resulting alcohol was purified by crystallizing it from pentane; it was dehydrated by dissolving into pyridine, and dropping 4 moles of SO Cl into the reaction solution, at 0 C. After about 60 minutes, the solution was returned to room temperature, then treated by a watery solution of CH COOH, extracted by ether, and the extract was washed by a solution of NaHCO A product was isolated by an isomerization employing tri dialkylamides of the phosphoric acid as catalysts (French Patv 1.529.455) and then by a distillation, which product had MW 174 and b.p. +80 C/l mmHg.
- the gas-chromatographic retention time (on 3 m EAS column on 5 percent of 60-80 mesh firebrick) was 4 minutes 2 seconds at l50 1 C.
- R R R R R and R are hydrogen. alkyl or aryl radicals.
- a process for preparing polyene hydrocar in claim 1 consisting in reacting a diene as with a. dihalide alkenyl as lions as claimed UNWEU STATES PATENT @FFEQE *CERTIWCATE @F IMEREQTWN Patent No. 3,676,510 Dated July 11 1972 Inventor) Sergio Arrighetti, et a].
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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1965870 | 1970-01-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3676510A true US3676510A (en) | 1972-07-11 |
Family
ID=11160138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US109007A Expired - Lifetime US3676510A (en) | 1970-01-22 | 1971-01-22 | Polyene hydrocarbons and process for obtaining same |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3676510A (fr) |
| AT (2) | AT305968B (fr) |
| BE (1) | BE761681A (fr) |
| CA (1) | CA976988A (fr) |
| CH (1) | CH536263A (fr) |
| DE (1) | DE2102948A1 (fr) |
| FR (1) | FR2075696A5 (fr) |
| GB (1) | GB1344845A (fr) |
| LU (1) | LU62465A1 (fr) |
| NL (1) | NL7100916A (fr) |
| ZA (1) | ZA71423B (fr) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3214483A (en) * | 1959-09-30 | 1965-10-26 | Du Pont | Products of the reaction of an allene with a cyclopentadiene |
| US3220988A (en) * | 1958-08-26 | 1965-11-30 | Hooker Chemical Corp | Polyhalogen containing bicyclic compounds and polymers thereof |
| US3347944A (en) * | 1965-10-01 | 1967-10-17 | Union Carbide Corp | Production of alkylidenebicycloheptenes |
-
1971
- 1971-01-18 BE BE761681A patent/BE761681A/fr unknown
- 1971-01-19 CA CA103,122A patent/CA976988A/en not_active Expired
- 1971-01-19 FR FR7101617A patent/FR2075696A5/fr not_active Expired
- 1971-01-21 LU LU62465D patent/LU62465A1/xx unknown
- 1971-01-22 AT AT54371A patent/AT305968B/de not_active IP Right Cessation
- 1971-01-22 ZA ZA710423A patent/ZA71423B/xx unknown
- 1971-01-22 US US109007A patent/US3676510A/en not_active Expired - Lifetime
- 1971-01-22 NL NL7100916A patent/NL7100916A/xx not_active Application Discontinuation
- 1971-01-22 AT AT620172A patent/AT314497B/de not_active IP Right Cessation
- 1971-01-22 CH CH103571A patent/CH536263A/fr not_active IP Right Cessation
- 1971-01-22 DE DE19712102948 patent/DE2102948A1/de active Pending
- 1971-04-19 GB GB2042071A patent/GB1344845A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3220988A (en) * | 1958-08-26 | 1965-11-30 | Hooker Chemical Corp | Polyhalogen containing bicyclic compounds and polymers thereof |
| US3214483A (en) * | 1959-09-30 | 1965-10-26 | Du Pont | Products of the reaction of an allene with a cyclopentadiene |
| US3347944A (en) * | 1965-10-01 | 1967-10-17 | Union Carbide Corp | Production of alkylidenebicycloheptenes |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2075696A5 (fr) | 1971-10-08 |
| DE2102948A1 (de) | 1971-07-29 |
| AT305968B (de) | 1973-03-26 |
| CA976988A (en) | 1975-10-28 |
| AT314497B (de) | 1974-04-10 |
| GB1344845A (en) | 1974-01-23 |
| CH536263A (fr) | 1973-04-30 |
| NL7100916A (fr) | 1971-07-26 |
| BE761681A (fr) | 1971-07-01 |
| LU62465A1 (fr) | 1971-09-02 |
| ZA71423B (en) | 1971-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ishiyama et al. | Palladium (0)-catalyzed thioboration of terminal alkynes with 9-(alkylthio)-9-borabicyclo [3.3. 1] nonane derivatives: stereoselective synthesis of vinyl sulfides via the thioboration-cross-coupling sequence | |
| Cremer et al. | Syntheses of substituted phosphetanes and related derivatives | |
| US3457318A (en) | Alkenyl adamantanes | |
| BR112016020155B1 (pt) | método para formação de um composto de almíscar macrocíclico, e heterodímero | |
| Pinke et al. | Nickel-promoted methylvinylcyclopropane rearrangements. Mechanistic relevance to the cis-1, 4-hexadiene to 2-methyl-1, 3-pentadiene isomerization | |
| EP4206182A1 (fr) | Composé ester | |
| Vedejs et al. | Synthesis of olefins from thionocarbonates by an alkylation-reduction sequence | |
| US3676510A (en) | Polyene hydrocarbons and process for obtaining same | |
| Burns et al. | Chemistry of singlet oxygen. XXIV. Low temperature photooxygenation of 1, 2-dihydronaphthalenes | |
| US3234264A (en) | 1-cyano and 1-carbamoyl-3-alkylbicyclo [1.1.0] butanes and processes for preparing the same | |
| US2953607A (en) | Process for the preparation of tertiary alkyl cyclopentadienes | |
| US3577473A (en) | Method for producing 5-isopropylidene-2-norbornene | |
| Katada et al. | Synthesis of adamantane derivatives. 73. Thermal cycloaddition reactions of thiocarbonyl compounds. 4. Synthesis of novel adamantane-2-spirothiaheterocycles via [4+ 2] cycloaddition reactions of adamantanethione with conjugated dienes | |
| Berger et al. | Reaction of vinylferrocenes with tetracyanoethylene | |
| Müller et al. | Generation and Trapping of Cyclopropenes from 2‐Alkoxy‐1, 1‐dichlorocyclopropanes | |
| Khalaf et al. | New Friedel-Crafts chemistry. XXIII. Mechanism of the aluminum chloride catalyzed rearrangement of tert-pentylbenzene to 2-methyl-3-phenylbutane | |
| US3441629A (en) | Isomerization of acyclic triene compounds | |
| Ando et al. | Reaction of silylene with allenes: Alkylidenesilacyclopropane and silatrimethylenemethane | |
| Strobach | Ynamines from 1, 1-difluoro-2-aryl and 2-alkylethylenes | |
| US3275700A (en) | Preparation of alkyladamantanes having an ethyl substituent | |
| US2798100A (en) | Diarylated ketoses | |
| Pews et al. | Hexabromocyclopentadiene V. The Diels-Alder reaction of hexabromocyclopentadiene | |
| Schipperijn et al. | A novel type of catalysis of the [2+ 2] cycloaddition of cyclopropenes | |
| US3036136A (en) | Cyclopentadiene derivatives | |
| US3676511A (en) | Polyene hydrocarbons containing two conjugated double bonds and process for obtaining same |