US2429411A - I-alkoxy-z - Google Patents
I-alkoxy-z Download PDFInfo
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- US2429411A US2429411A US2429411DA US2429411A US 2429411 A US2429411 A US 2429411A US 2429411D A US2429411D A US 2429411DA US 2429411 A US2429411 A US 2429411A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000001117 sulphuric acid Chemical class 0.000 description 24
- 235000011149 sulphuric acid Nutrition 0.000 description 24
- 239000002253 acid Substances 0.000 description 20
- 230000002378 acidificating Effects 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 12
- 125000004432 carbon atoms Chemical group C* 0.000 description 12
- MEIRRNXMZYDVDW-UHFFFAOYSA-N hexa-2,4-dien-1-ol Chemical compound CC=CC=CCO MEIRRNXMZYDVDW-UHFFFAOYSA-N 0.000 description 12
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006317 isomerization reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- -1 2-ethylhexen-2-al-1 Chemical compound 0.000 description 8
- NFDFQCUYFHCNBW-SCGPFSFSSA-N Dienestrol Chemical compound C=1C=C(O)C=CC=1\C(=C/C)\C(=C\C)\C1=CC=C(O)C=C1 NFDFQCUYFHCNBW-SCGPFSFSSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 150000002170 ethers Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000001476 alcoholic Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-Chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N 1-Butyne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- PADRFIOPYGPSDW-UHFFFAOYSA-N 5-methylhexa-2,4-dien-1-ol Chemical compound CC(C)=CC=CCO PADRFIOPYGPSDW-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N Crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 2
- MTZWHHIREPJPTG-UHFFFAOYSA-N Phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 2
- ACWQBUSCFPJUPN-HYXAFXHYSA-N Tiglic aldehyde Chemical compound C\C=C(\C)C=O ACWQBUSCFPJUPN-HYXAFXHYSA-N 0.000 description 2
- WFYPICNXBKQZGB-UHFFFAOYSA-N Vinylacetylene Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ICMWSAALRSINTC-UHFFFAOYSA-N penta-1,4-dien-3-ol Chemical compound C=CC(O)C=C ICMWSAALRSINTC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229960001367 tartaric acid Drugs 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
- C07C43/16—Vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Definitions
- Example 5 A mixture of 11.7 parts of divinylcarbinol and 100 parts of aqueous sulphuric acid (containing per 100 parts by volume 1 part of sulphuric acid is agitated at 20 C. during 24 hours in an atmosphere of nitrogen. The product is then isolated by ethereal extraction as is described in Example 1 and is fractionally distilled. There is obtained a fraction after two distillations B. P. 95-97 C./100 mms., u 1.4902. This substance is pentadiene-2:4-ol-1. When reacted with anaphthylisocyanate it gives an a-naphthylurethane M. P. 97.5 C. and with maleic anhydride it gives an addition product M. P. HIE-176 C. When allowed to stand in air pentadiene-2z4-ol-1 changes slowly yielding a transparent polymeric substance.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Oct. 21, 1947 I-ALKOXY-2,4-PENTADIENES AND SUBSTI- TUTED DERIVATIVES THEREOF Ewart Ray Herbert Jones, London, and John Talbot McCombie, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application December 19, 1944, Se-
' rial No. 568,940. In Great Britain February 10,
4 Claims. (on. 260 614) 31 v This invention relates to a process for the manufacture of new unsaturated compounds and more particularly it relates to the manufacture of onn'=ca -ca=(on -cn='ca a to give dienols of the formula CRR' (OH) CR =CR -CH=CR R in both of which formulae R, R, R R R and R have the significance given above, by a process which comprises subjecting the first mentioned dienols to the action of an acidic substance oi the kind hereinafter described.
The starting-out materials of the formula given above may be obtained, when R is hydrogen. by
the partial hydrogenation of unsaturated i 1' 1- carbinols of the formula wherein R, R, R R and B have the $1 given above. Thus vinylethinylcarbinol CH2=CH.CH(OH) CECE may be hydrogenated to give divinylcarbinol CH2=CH.CH(OH) .CH=CH2 and propenylethinylcarbinol CHJCH=CH.CH(OH) .CECH
may be hydrogenated to give propenylvinylcarbinol, CH3CH=CH.CH(OH).CH=CHz; similarly z-methylpropenylethinyl carbinol (or, as it may also be named, 5-methylhexen-4-in-1-ol-8), (CH3)2C=CH.CH(OH).CECH, gives rise to 2- methylpropenylvinylcarbinol (or, as it may also be named, 5-methy1hexadien-1:4-01-3) (H3) 2C=CH.CH(OH) .CH=CHe 4-ethylocten-4-in-1-ol-3 crncincmcH=cEt.cH(on).cEcH
.- canoe 2 gives 4-ethyloctadien-1 :4-01-3 CHaCH2CHaCH=CEt.CH(OH) .CH=CH2 8-methylnonadien-2:7-in-4-ol-6 5 CHaCH=CI-I.CH(OH).CEC.CMe=CHCHa gives 3-methylnonatrien-2:4:7-01-6 CH3CH=CH.CH(OH) .CH==CH.CMe=CH.CHs octadien-1:6-in-3-ol-5 CI-Ia.CI-I=CH.CH(OH).C C.CH=CHQ gives octatrien-1:3:6-ol-5 CH:.CH=CH.CH(OH) .CH=CH.CH=C 2-methyloctadien-1:6-ln-3-ol-5 CHa.CH=CH.CH (OH) .CEC.CMG=CH2 gives 2-methyloctatrien-1z3; 6-01-5 CH3..CH(OH) .CH=CH.CMe==Cm 2 7-dimethyloctadien-1 6-in-3:pl-5
CI-Is.CMe--CH.CH(OH) .CEC.CMe'=CHz gives 2 'Zdimethyloctatrien-l :3 6-01-5- CHs.CMe=CH.CI-I(OH) .CH=CH.CMe=CHi z-methyl-fi-ethyldecadien-l:6-in-3-ol-5 CHzCHeCHaCH==CEiLCH(OH) .C-=-C.C'Me=CHa gives ?-methyl-6-ethyl-decatrien-l :3 6-01-5 omongomo eontomon .CH=OH.OMe=0Hn G-ethyldecemfi-in-B-ol-h CHaCH2CH2CH=CEt.CI-I(OH) .CECCHzCHa gives 6-ethyldecadien-3 6-01-5 QHsCHzCH=CEt.CI-I(OH).CH=CHCI-Ia and 3z5-dimethylhexen-4-in-1-ol-3 CEfiCMe 'CHCMdOH) CECH gives 3 :5=dimethy1hexadien-1 :4-01-3 CHsCMe=CI-I.CMe (OH) CH=CHz All these and other products are suitable for use in theprocess of the invention. The unsaturated ethinylcarbinols, from which the above dienols used in the process of the invention are obtained by partial hydrogenation, may themselves be obtained by known methods, that is to say by confor example acrolein, crotonaldehyde, 2-ethylhexen-2-al-1, z-methylcrotonaldehyde, or mesityl oxide, with alkali metal acetylides derived from, for example acetylene, ethylacetylene, vinylacetylene or 1:2-dimethy1vinylacetylene, under suitdensation of an unsaturated aldehyde or ketone,v
described for example in Nos. 2,125,384, 2,106,180,
2,106,181, and 2,106,182.
ere R is an alkyl radical the starting ma-' terials may not. of course be made by partial hydrogenation of an unsaturated ethinylcarbinol. However they can frequently be made by reduction of the corresponding ketone. Thus the dienol 2:8-dimethylheptadien-2z5-ol-4 CHICMFCHLCH(OH) .CH=CMeCH.1
may be made by reduction of phorone.
The acidic substances used in bringing about the isomerisation process of the invention are mineral acids for example boric acid, phosphoric acid, nitric acid, hydrochloric acid, and sulphuric acid, acid salts for example potassium hydrogen able conditions, is United States Patents sulphate, and organic acids, for example formic acid. acetic acid and tartaric acid. Also esterfying derivatives of these mineral or organic acids may be used, for example their anhydrides, for example acetic anhydride.
The reaction, when using the acids themselves, may conveniently be carried out in aqueous medium. An aqueous solution of the acidic substance may be used, of, for example, 25-25% strength, weight per volume, but more dilute or even stronger solutions may be used. The proces of the invention may conveniently be carried out for example by enclosing the dienol which it is desired to isomerise in a suitable vessel together with a substantial proportion of an aqueous solution of the acidic substance, the vessel being shaken or the contents stirred at, for example, atmospheric temperature, for a period which may vary from 3 to 100 hours or more or less according to the speed at which the reaction takes place. A solvent, for example ethanol, may be present if desired and this may be added in amount sufilcient to afford a homogeneous solution, in which case agitation may be omitted. The speed of isomerisation varies according to the particular acidic substance being used and also according to the strength of the solution of the acidic substance being used when working" of course desirable to avoid the presence of moisture. An anhydrous inert solvent may be used or a solvent may be dispensed with. Under these conditions the isomerised dienol is isolated in the form of its ester. Thus when using acetic anhydride it is isolated in the form of the acetate. Also when working in aqueous medium there is a tendency for the isomerised dienolto be partly or wholly converted to an ester by the isomerising acidic substance. Particularly is this the case when using certain acidic substances, for example hydrochloric acid. Esterification is favoured by high temperature and by high concentration of the acidic substance. Thus when using hydrochloric acid, if it is desired to avoid formation of the ester it is advisable to work with a dilute aqueous hydrochloric acid and at room temperature but using a stronger acid a good yield of ester may be obtained. When using sulphuric acid on the other hand isomerisation is not accompanied by appreciable esterflcation unless very high concentrations of acid are used.
Alternatively again the isomerisation may be carried out by using as acidic substance, for example concentrated sulphuric acid, in solution in an alcoholic solvent, for example methanol. ethanol or ethylene chlorohydrin. Under these conditions it is found that isomerisation is frequently accompanied by etheriilcation of the isomerised dienol in which case the product is isolated in the form of the ether.
The products obtained according to the invention are useful as intermediates in the manufacture of polymeric materials.
The invention is illustrated but not limited by the following examples in which parts. except where otherwise stated, are by weight:
trample 1 210 parts of propenylvinylcarbinol (hexadien- 1:4-01-3) are added to 550 parts of aqueous sulphuric acid (containing per parts by volume 1 part of sulphuric acid) in a vessel in which the air is replaced by nitrogen. The vessel is then shaken during 2 hours at 15--20 C. The contents of the vessel are then thoroughly extracted with ether. The ethereal extract is washed with water and with an aqueous solution of sodium bicarbonate until free from acid. It is then dried and distilled. There is thus obtained a colourlessliquid of B. P. 67-88 C./26 mms. and n l.48l0.' This is butadlenylmethylcarbinol (hexadien-1z3-ol-5). With. a-naphthyl isocyanate it gives an e-naphthylurethane M. P. 86.5-87.5 0.
Example 2 30 parts of propenylvinylcarbinol are added slowly to a cold solution of 1 part of concentrated sulphuric acid in 81 parts of methanol. The mixture is allowed to stand at 20 C. during 4 days. 500 parts of water are then added and the mixture is extracted with ether. The ethereal extract is washed until free from acid, dried and distilled. There is thus obtained a colourless liquid of B. P. 61-82 02/100 mms. and n 1.4488. This is 5-methcxyhexadiene-lz3.
Example 3 50 parts of propenylvinylcarbinol and 55 parts of acetic anhydride are mixed together and heated in an atmosphere of nitrogen on a steam-bath during 2 hours. Water is then added and when the acetic anhydride is completely hydrolysed the mixture is extracted with ether. The ethereal extract is washed with water and with aqueous sodium bicarbonate until free from acid and is then distilled. There is obtained a colourless liquid of B. P. 63-86 C./20 mms., and n 1.4583. This is 5-acetoxyhexadiene-1:3.
trample 4 116 parts or propenylvinylcarbinol are added slowly to a cold solution of 4 parts of concentrated sulphuric acid dissolved in v316 parts of absolute ethanol. The mixture-is allowed tostand for 20 hours at room temperature. 1500 parts of water are then added and the mixture is extracted with ether. The ethereal extract is washed with water until free from acid, dried and distilled. There is thus obtained a colourless, mobile liquid of B. P. 62.0-62.5 C./77 mms. and n -1.4484. This is 5-ethoxyhexadien-1z3.
Example 5 Example 6 A mixture of 11.7 parts of divinylcarbinol and 100 parts of aqueous sulphuric acid (containing per 100 parts by volume 1 part of sulphuric acid is agitated at 20 C. during 24 hours in an atmosphere of nitrogen. The product is then isolated by ethereal extraction as is described in Example 1 and is fractionally distilled. There is obtained a fraction after two distillations B. P. 95-97 C./100 mms., u 1.4902. This substance is pentadiene-2:4-ol-1. When reacted with anaphthylisocyanate it gives an a-naphthylurethane M. P. 97.5 C. and with maleic anhydride it gives an addition product M. P. HIE-176 C. When allowed to stand in air pentadiene-2z4-ol-1 changes slowly yielding a transparent polymeric substance.
Example 7 A mixture of 10 parts of isopropenylvinylcarbino], 100 parts of aqueous sulphuric acid (containing per 100 parts by volume 2 parts of sulphuric acid) and a trace of hydroquinone is agitated at C. during 24 hours in an atmosphere of nitrogen. Common salt is then added to the mixture until no more will dissolve. The product is then isolated by extraction with ether as is described in Example 1. There is obtained 2- methylpentadien-2z4-ol-1 as a colourless liquid B. P. 97-99 C./50 mms., 72-74 C./15 mms., 15, 1.5001. It gives with a-naphthylisocyanate an u-naphthylurethane M. P. 59-60 C. and with maleic anhydride an addition product M. P. 181-182" C.
Example 8 A mixture of parts of propenylvinylcarbinol, 124 arts of ethylene chlorohydrin and 1 part of concentrated sulphuric acid is stored at atmospheric temperature during 2-5 days. The product is then isolated as described in Example 1 and there is obtained after fractional distillation, 2-,6-chloroethoiqrhexadien-3:5, B. P. 79.5 C./7.5 mms., 15 1.4910. 4
We claim:
1. Process of preparing unsaturated ethers of the general formula.
wherein R stands for an alkyl grow containing up to 6 carbon atoms, R R, R. are each selected from the group consisting of hydrogen and alkyl groups containing up to 6 carbon atoms, and R is selected from the group consisting of hydrogen, the vinyl, methylvinyl and dimethylvinyl groups, which process comprises subjecting a compound of the general formula in which R, R, R, R and B. have' the same meaning as above, to the action of a mineral acid dissolved in an alcoholic solvent.
2. Process of preparing unsaturated ethers of the general formula wherein It stands for an alkyl group containing up to 6 carbon atoms. and R R, and R are each selected from the group consisting of hydrogen and alkyl groups containing up to 6 carbon atoms, which process comprises subjecting a compound of the general formula 'in which R 1K. and B have the same meaning as above, to the action of concentrated sulfuric acid dissolved in an alcoholic solvent.
3. Unsaturated ethers of the general iormula Aikoxy-CRR -CR"=CR -CH=CHR* wherein R stands for an alkyl group containing up to 6 carbon atoms, R R and R are each selected from the group consisting of hydrogen and alkyl groups containing up to 6 carbon atoms, and R is selected from the group consisting of hydrogen, the vinyl, methylvinyl 'and dimethyivinyl groups.
4. Unsaturated ethers of the general formula REFERENCES CITED The following references are of record the die of this patent:
UNITED STATES PATENTS Number Name Date 2,373,956 Hearne et a1. Apr. 1'1, 1945 2,207,070 Reppe et a]. July 9, 1940 2,344,085 Halbig et al. Mar. 14, 1944 OTHERREFIRENCES Delaby, Comptes Rendus de lAcedemie des Sciences, vol. 181 (1925). pp. 722-724. I
Prevost, Comptes Rendus de IAcedemie des Sciences, vol 184 (1927), p. 1562.
Young et al., Jour. Am. Chem. Soc.. vol. 61
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2429411A true US2429411A (en) | 1947-10-21 |
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|---|---|---|---|
| US2429411D Expired - Lifetime US2429411A (en) | I-alkoxy-z |
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| Country | Link |
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| US (1) | US2429411A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606930A (en) * | 1949-03-22 | 1952-08-12 | Glaxo Lab Ltd | 6-methylocta-3:5:7-trien-2-one |
| US2707196A (en) * | 1949-09-28 | 1955-04-26 | Woods Gilbert Forrest | Open chain analogs of benzene and methods of preparation |
| US2819317A (en) * | 1953-03-27 | 1958-01-07 | Ethyl Corp | Polyolefinic alcohols of increased conjugation from soybean and menhaden oils |
| US3429970A (en) * | 1961-02-02 | 1969-02-25 | Hoffmann La Roche | Method of hindering the metamorphosis and reproduction of arthropodes |
| US3452105A (en) * | 1963-10-25 | 1969-06-24 | Givaudan Corp | 3-hydroxy-7-isobutyl-1,6-octadiene |
| US4263463A (en) * | 1973-04-20 | 1981-04-21 | Sumitomo Chemical Company, Limited | Acetylenic secondary alcohols |
| US4391300A (en) * | 1980-09-02 | 1983-07-05 | Habegger International | Pipe patching clamp |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2207070A (en) * | 1937-03-24 | 1940-07-09 | Jasco Inc | Process of converting compounds of the acetylene series into compounds of the ethylene series |
| US2344085A (en) * | 1939-08-24 | 1944-03-14 | Halbig Paul | Process for the polymerization of alkoxy-butadienes |
| US2373956A (en) * | 1940-08-29 | 1945-04-17 | Shell Dev | Rearrangement of unsaturated aliphatic alcohols |
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- US US2429411D patent/US2429411A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2207070A (en) * | 1937-03-24 | 1940-07-09 | Jasco Inc | Process of converting compounds of the acetylene series into compounds of the ethylene series |
| US2344085A (en) * | 1939-08-24 | 1944-03-14 | Halbig Paul | Process for the polymerization of alkoxy-butadienes |
| US2373956A (en) * | 1940-08-29 | 1945-04-17 | Shell Dev | Rearrangement of unsaturated aliphatic alcohols |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606930A (en) * | 1949-03-22 | 1952-08-12 | Glaxo Lab Ltd | 6-methylocta-3:5:7-trien-2-one |
| US2707196A (en) * | 1949-09-28 | 1955-04-26 | Woods Gilbert Forrest | Open chain analogs of benzene and methods of preparation |
| US2819317A (en) * | 1953-03-27 | 1958-01-07 | Ethyl Corp | Polyolefinic alcohols of increased conjugation from soybean and menhaden oils |
| US3429970A (en) * | 1961-02-02 | 1969-02-25 | Hoffmann La Roche | Method of hindering the metamorphosis and reproduction of arthropodes |
| US3452105A (en) * | 1963-10-25 | 1969-06-24 | Givaudan Corp | 3-hydroxy-7-isobutyl-1,6-octadiene |
| US4263463A (en) * | 1973-04-20 | 1981-04-21 | Sumitomo Chemical Company, Limited | Acetylenic secondary alcohols |
| US4391300A (en) * | 1980-09-02 | 1983-07-05 | Habegger International | Pipe patching clamp |
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