GB2153826A - Unsaturated carboxylic acid - Google Patents
Unsaturated carboxylic acid Download PDFInfo
- Publication number
- GB2153826A GB2153826A GB08502998A GB8502998A GB2153826A GB 2153826 A GB2153826 A GB 2153826A GB 08502998 A GB08502998 A GB 08502998A GB 8502998 A GB8502998 A GB 8502998A GB 2153826 A GB2153826 A GB 2153826A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- methyl
- ester
- grms
- nonenoic
- 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.)
- Withdrawn
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- OCALSPDXYQHUHA-FNORWQNLSA-N 8-Methyl-6-nonenoic acid Chemical compound CC(C)\C=C\CCCCC(O)=O OCALSPDXYQHUHA-FNORWQNLSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 5
- 238000007239 Wittig reaction Methods 0.000 claims abstract description 5
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- -1 6-bromohexanoic acid ester Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- DXBULVYHTICWKT-UHFFFAOYSA-N ethyl 6-bromohexanoate Chemical compound CCOC(=O)CCCCCBr DXBULVYHTICWKT-UHFFFAOYSA-N 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 150000004714 phosphonium salts Chemical class 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- IXHFFNCBURGATB-UHFFFAOYSA-N ethyl 8-methylnon-6-enoate Chemical compound CCOC(=O)CCCCC=CC(C)C IXHFFNCBURGATB-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- XWWKSLXUVZVGSP-UHFFFAOYSA-N 6-chlorohexanoic acid Chemical compound OC(=O)CCCCCCl XWWKSLXUVZVGSP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000786363 Rhampholeon spectrum Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000002400 hexanoic acid esters Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing 8-methyl-6-nonenoic acid (useful as an intermediate) comprises (1) reacting caprolactone with hydrogen bromide and a lower aliphatic alcohol (preferably ethanol); (2) reacting the 6-bromohexanoic ester so formed with triphenylphosphine in a solvent; (3) reacting the triphenylphosphonium salt formed with isobutyraldehyde in accordance with the Wittig reaction; and (4) converting the 8-methyl-6-nonenoic ester formed to the free acid. Steps (3) and (4) can, if desired, be obtained.
Description
SPECIFICATION
Unsaturated carboxylic acid
This invention relates to the preparation of the unsaturated carboxylic acid, 8-methyl-6-nonenoic acid, which is useful as an intermediate in the synthesis of further valuable compounds.
According to the invention, there is provided a process for the preparation of 8-methyl6-nonenoic acid, comprising the steps of (1) reacting caprolactone with hydrogen bromide and a lower aliphatic alcohol to produce the corresponding 6-bromohexanoic acid ester;
(2) converting the 6-bromohexanoic acid ester so formed to the corresponding triphenylphosphonium salt by reaction with triphenylphosphine in a suitable solvent;
(3) reacting the triphenylphosphonium salt so formed with isobutyraldehyde in accordance with the Wittig reaction to form the corresponding ester of 8-methyl-6-nonenoic acid; and
(4) converting the ester to free 8-methyl-6-nonenoic acid.
Using ethanol in step (1), the reactions involved in the invention can be represented as follows
IBr EtOH ~ OEt Sten 1 t ) B m Caproictone Ethyl 6-bromohexanoate Mf 114 }191 223 Step'2 2 ? Phm Nw 485.3 SteD sCSO bozo Ethyl 8-methyl-6-nonenoate M.W. 198 Step 4 NaOH gl & ethyl-6-nonenoic acrid N.W, 170 If desired, steps (3) and (4) can be combined, the ester being converted to the acid in situ without intermediate isolation of the ester.
While in step (1), any lower aliphatic alcohol having 1 to 3 carbon atoms can be used, ethanol is preferred.
When ethanol is used, the ethyl ester can be directly produced in adequate yield, without the necessity for isolating the free acid first formed.
In step (2), dimethylformamide (DMF) or dioxane is generally used as solvent. However, t-butyl-methyl ether can be used with some advantage, since the salt is deposited as an oily layer from the reaction liquor, although the rate of reaction is slower.
The product obtained by the process of the invention in step (3) has chromatographic mobility and infra-red spectral properties consistent with its being ethyl 8-methyl-6-nonenoate.
It appears to be an essential feature of the process of the invention to use a bromine derivative of the hexanoic acid ester in step (2), since the Wittig reaction between the triphenylphosphonium salt derived from 6-chlorohexanoic acid and isobutyraldehyde under conditions similar to step (3) failed. The
Homer-Wittig reaction between the phosphonate derived from 6-chlorohexanoic acid ester and isobutyraldehyde also failed to produce any identifiable product.
The invention is illustrated by the following examples :
Example 1
Step (1)
Caprolactone monomer was converted into ethyl 6-bromohexanoate by the method described by Vogel (4th Edition, p. 531 ) with minor modifications. A sample of the crude oil product was distilled at b.p.
57-60 C/lmmto give the pure product, g.c. analysis 98.1%, in a yield equivalent to 87.6%. The bulk of the crude product was not distilled but taken on to step (2) without further purification.
Step 62) The crude ester prepared in step (1) (87 grms, 0.39M) and triphenylphosphine (105 grms, 0.4M) were dissolved in DMF (500 mls) and the solution was boiled under refluxfor 8 hours; reaction then appeared to be complete. The solution was concentrated under vacuum at 509C. The oily residue was shaken three times with 200 ml portions of toluene to remove excess triphenylphosphine, and was then dissolved in dichloromethane (500 mix). The solution was washed with 20% brine, dried, and evaporated to dryness.
The viscous residue weighed 150 grms (0.31 M,79.5% yield) and was taken on to step (3) without further purification.
Step (3) The crude phosphonium salt was dissolved in dichloromethane (500 mls) and half of this solution was taken for the subsequent reaction (i.e. 75 grms, 0.155M).
The solution was boiled under a reverse-Dean-and-Stark trap for 0.5 hours to remove any residual water.
After recooling to 25 C anhydrous potassium carbonate (23.1 grms, 0.167M) and 18-Crown-6 (420 mgs) were added. The mixture was stirred for 0.5 hours, reheated to boiling, and, while continuing to boil under reflux, a solution isobutyraldehyde (10.8 grms, 0.15M) in dichloromethane (300 mls) was added dropwise during 6 hours. The mixture was refluxed for a further 0.5 hours and allowed to cool overnight.
G.C. and T.L.C. analysis indicated the presence of a product having the expected chromatographic mobility; however a significant amount of phosphonium salt starting material remained unreacted.
300 mis of the dichloromethane was distilled off until the pot temperature rose to 60 C. Dioxane (200 mls) and anhydrous potassium carbonate (23.1 grms) were added and the mixture was reheated to 65"C. A solution of isobutyraldehyde (10.3 grms) in dioxane (200 mls) was dropped in during 2 hours while maintaining a pot temperature of 65-70 C. The reaction was heated to reflux during 1.5 hours and boiled under reflux (pot temperature, 95"C) for a further one hour.
T.L.C. analysis indicated virtually complete absence of phosphonium salt.
After cooling, the reaction mixture was diluted with 20% brine (400 mls) and extracted three times with ethyl acetate (400 mls, 2 x 200 mix). The combined extracts were washed to neutrality with 20% brine, dried and evaporated to dryness. The residue was extracted with cyclohexane (3 x 200 mix), to separate the product from the co-produced triphenylphosphine oxide, and the extracts were reconcentrated to a small volume and allowed to stand overnight. After filtration from a further small amount of triphenylphosphine oxide, the productwes recovered by distillation.
Yield: 16.9 grms; b.p. 50-60"C/0.2-0.4 mm, 55% of theory; G.C. analysis: about 95% major impurity low boiler about 1.5%;
T.L.C. analysis shows trace impurities;
I.R. analysis was consistent with the expected structure.
Step (4) The ethyl ester produced in step (3) was treated with aqueous sodium hydroxide and the free acid
liberated from the salt formed by acidification, and recovered by extraction.
Example 2
The process was carried out as in Example 1, except that the steps (3) and (4) were combined, the ester formed being converted in situ into the free acid.
The reaction mixture at the end of step (3) was directly treated with aqueous sodium hydroxide. This
resulted in a reaction mixture which was much easier to work up since the product acid is, of course, soluble
in aqueous alkali. Organic impurities, e.g. triphenylphosphine oxide can be removed by filtration and washing, and the free acid recovered by extraction from the acidified aqueous layer and distillation. The overall yield of distilled free acid was 81%.
Example 3
The process was carried out as in Example 1, except that in step (2), t-butylmethyl ether was used as the solvent. Although about 2 days reaction time was required to achieve a reasonable conversion, and the
reaction is much slower than using DMF as solvent as in Example 1, but has the advantage that the
precipitated oily salt can be separated merely by decanting the liquor. An average yield of 90% was obtained over three runs by recycling the liquor.
Example 4
Step 1: Ethyl 6-bromohexanoate
Caprolactone (2087 grms) (18.28M) was brought into reaction with a mixture of 48% hydrobromic acid (9.6 t) and 96% sulphuric acid (2.32 J). The product was taken into carbon tetrachloride (5 { ) and the washed
and dried extract was mixed with ethanol (1.5 f ) and p-toluene sulphonic acid (200 grms) and reacted by the azeotropic distillation method.
After a standard work-up, the crude concentrate (3897 grms, g.c. 96%) was distilled in vacuum to give ethyl 6-bromohexanoate, 3503 grms. (86%), g.c. 98.3%.
Step 2 : Phosphonium salt
A mixture of ethyl 6-bromohexanoate (1708 grms, 7.66M), triphenylphosphine (2009 grms, 7.66M) and dioxane (2.5 C) was boiled under gentle reflux for 48 hours until no starting material remained.
Steps 314: Cis-8-methyl-6-nonenoic acid
The solution from Step (3) was diluted, under nitrogen, with dioxane (4.4 e) and dichloromethane (2.3 t), potassium carbonate (1.59 Kg., 1 1.5M), isobutyraldehyde (830 grms, 11 .5M) and 18-crown-6 (10.5 grms, 0.5M%) were added and the mixture was boiled under gentle reflux for 48 hours, when utilisation of phosphonium salt was virtually complete. After cooling, 30% w/w aqueous sodium hydroxide (2043 grms, 1 5.32M) was added and the mixture was reheated to 50 to hydrolyse the product ester. When hydrolysis was complete, the mixture was recooled, diluted with water (4 e) and concentrated by distillation to remove most of the dioxane.The precipitated triphenylphosphine oxide was filtered off and washed well with 5% sodium hydroxide and water.
The combined alkaline mother liquors and washings were extracted twice with toluene (3 t, 2 P)to remove any remaining neutral impurities and the acidified with cooling at less than 20"C to pH 1-2 with concentrated hydrochloric acid.
The liberated product acid was extracted into ethyl acetate (three extracts) and the combined extracts were washed neutral with water, dried and concentrated.
The concentrate (1700 grms) was dissolved in cyclohexane (1500 grms) with warming. On cooling to ambient temperature a crystalline impurity deposited and was filtered off. The mother liquors were reconcentrated.
The residue was subjected to a careful fractional distillation to give cis-methyl-6-nonenoic acid, 872.5 grms, (67%), g.c. 99.3%, I.R. spectrum showing absence of trans-isomer.
The cis-isomer can be converted to the trans-isomer, if required, by known methods.
Claims (7)
1. A process for the preparation of 8-methyl-6-nonenoic acid, comprising the steps of :
(1) reacting caprolactonewith hydrogen bromide and a lower aliphatic alcohol to produce the corresponding 6-bromohexanoic acid ester;
(2) converting the 6-bromohexanoic acid ester so formed to the corresponding triphenylphosphonium salt by reaction with triphenylphosphine in a suitable solvent;
(3) reacting the triphenylphosphonium salt so formed with isobutyraldehyde in accordance with the Wittig reaction to form the corresponding ester of 8-methyl-6-nonenoic acid; and
(4) converting the ester to free 8-methyl-6-nonenoic acid.
2. A process as claimed in Claim 1, wherein the lower aliphatic alcohol used in step (1) is ethanol.
3. A process as claimed in Claim 1, or Claim 2, wherein steps (3) and (4) are combined, the ester being converted to the acid in situ without intermediate isolation.
4. A process as claimed in any one of Claims 1 to 3, wherein dimethylformamide or dioxane is used as the solvent in step (2).
5. A process as claimed in any one of Claims 1 to 3, wherein t-butyl-methyl ether is used as the solvent in step (2).
6. A process for the preparation of 8-methyl-6-nonenoic acid, substantially as herein before described with reference to any one of Examples 1 to 4.
7. 8-methyl-6-nonenoic acid prepared by a process as claimed in any one of Claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08502998A GB2153826A (en) | 1984-02-07 | 1985-02-06 | Unsaturated carboxylic acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848403150A GB8403150D0 (en) | 1984-02-07 | 1984-02-07 | Unsaturated carboxylic acid |
| GB08502998A GB2153826A (en) | 1984-02-07 | 1985-02-06 | Unsaturated carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8502998D0 GB8502998D0 (en) | 1985-03-06 |
| GB2153826A true GB2153826A (en) | 1985-08-29 |
Family
ID=26287293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08502998A Withdrawn GB2153826A (en) | 1984-02-07 | 1985-02-06 | Unsaturated carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2153826A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1231200A1 (en) * | 2001-02-07 | 2002-08-14 | Basf Aktiengesellschaft | Process for the production of cis-hexadec-6-enoic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1364727A (en) * | 1970-11-13 | 1974-08-29 | Roussel Uclaf | Preparation of unsaturated carboxylic acids and esters |
-
1985
- 1985-02-06 GB GB08502998A patent/GB2153826A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1364727A (en) * | 1970-11-13 | 1974-08-29 | Roussel Uclaf | Preparation of unsaturated carboxylic acids and esters |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1231200A1 (en) * | 2001-02-07 | 2002-08-14 | Basf Aktiengesellschaft | Process for the production of cis-hexadec-6-enoic acid |
| US6781004B2 (en) | 2001-02-07 | 2004-08-24 | Basf Aktiengesellschaft | Process for the preparation of cis-6-hexadecenoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8502998D0 (en) | 1985-03-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |