US3883558A - 4-N-batyroxymethyl-1,3-dioxolanes - Google Patents
4-N-batyroxymethyl-1,3-dioxolanes Download PDFInfo
- Publication number
- US3883558A US3883558A US270879A US27087972A US3883558A US 3883558 A US3883558 A US 3883558A US 270879 A US270879 A US 270879A US 27087972 A US27087972 A US 27087972A US 3883558 A US3883558 A US 3883558A
- Authority
- US
- United States
- Prior art keywords
- formula
- dioxolane
- derivatives
- methyl
- acid
- 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
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 18
- 150000004862 dioxolanes Chemical class 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000000796 flavoring agent Substances 0.000 abstract description 9
- 235000019634 flavors Nutrition 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000013350 formula milk Nutrition 0.000 description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019568 aromas Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- -1 nbutyl Chemical group 0.000 description 3
- 235000014594 pastries Nutrition 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000000075 primary alcohol group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BKWNHSJEUMUSFL-UHFFFAOYSA-N C(CCC)(=O)OCC1OCCO1 Chemical compound C(CCC)(=O)OCC1OCCO1 BKWNHSJEUMUSFL-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001656 butanoic acid esters Chemical class 0.000 description 1
- GENAAZKZRURPIA-UHFFFAOYSA-N butanoic acid;2-hydroxypropanoic acid Chemical compound CCCC(O)=O.CC(O)C(O)=O GENAAZKZRURPIA-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/205—Heterocyclic compounds
- A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
Definitions
- This invention relates to the fields of flavourants and substituted dioxolanes.
- the dioxolane flavourants provided by the present invention have the following general formula 2 3 ⁇ c R1 co CHg-EQH wherein R represents a straight-chain or branchedchain alkyl or alkenyl group containing 2-6 C-atoms, R represents a hydrogen atom or an alkyl group containing l3 C-atoms and R" represents a grouping of the formula in which R represents a hydrogen atom or a hydroxy group and R and R each independently represent a hydrogen atom or a straight-chain or branched-chain alkyl or alkenyl group containing up to 6 C-atoms.
- the dioxolane derivatives of formula 1 above are manufactured by either a. cyclising a diol of the general formula RCOOCH --CHOHCH OH with a carbonyl compound of the general formula R COR (III) b. esterifying the primary alcohol group of a compound of the general formula with an acid of the general formula or a functional derivative thereof; in which formulae R, R and R have the significance given earlier.
- R represents a straight-chain or branched-chain alkyl or alkenyl group containing 26 C-atoms. Examples of such groups are: ethyl, n-propyl, isopropyl, nbutyl, isobutyl, secbutyl, tertbutyl, n-pentyl and n-hexyl (including their structural isomers), and l'-propenyl, l'-methyl-l' propenyl and 2'-propenyl, R preferably represents the n-propyl group, in which case the derivatives of formula I are butyric acid esters.
- R represents a hydrogen atom or an alkyl group containing l-3 C-atoms, ie the methyl, ethyl, n-propyl or isopropyl group.
- R represents a hydrogen atom or the methyl group.
- R represents a grouping of formula (a) or (b).
- alkyl and alkenyl groups which may be present on said groupings as a substituent denoted by R and/or R are alkyl groups containing l-6 C-atoms such as those mentioned earlier in connection with R and R and alkenyl groups containing 2-6 C atoms such as vinyl, l'-and 2'-propenyl, l'-butenyl etc.
- the dioxolane derivatives of formula I provided by the present invention are distinguished. as has surprisingly been found by particular flavour properties, on the basis of which they can be used as flavourings in aroma compositions. Of particular interest is the but tery aroma of certain of the derivatives of formula I, particularly of the following three derivatives:
- the concentration of the dioxolane derivatives of formula I in aroma compositions such as butter or fruit aromas can lie between about 0.01 and parts per thousand, but it preferably lies in the range of 0.1 to 10 parts per thousand, In finished products aromatized with such aroma compositions such as pastry, fruit tarts etc correspondingly lower concentrations of the dioxolane derivatives of formula I (for example 01 to 10 parts per million) are present.
- an aldehyde or ketone of formula lll is acetalized or ketalised in a manner known per se with a diol of formula ll. namely an a-monoester of gly'cerine. with cyclisation to a dioxolane derivative of formula i.
- the acetalisation or ketalisation is advantageously carried out by heating the mixture of the components in the presence of a sol- ⁇ ent and expediently in the presence of an acidic catalyst with continuous removal of the water w hich forms. for example. by means of an entraining agent.
- solvents which are usually employed for this purpose such as. for example. aromatic and saturated aliphatic hydrocarbons teg. benzene. toluene or n-pentane l. Such solvents facilitate the continuous removal of the watertwhich forms during the cyclisation iby' azeotropic distillation.
- acidic catalysts there can be used the substances which are usually used for acetalisations or ketalisations; for example. mineral acids such as sulphuric acid. phosphoric acid and perchloric acid. strong organic acids such as trichloroacetic acid or p-toluenesul phonic acid and Lewis acids such as. for example. boron trifluoride etc.
- the primary alcohol group of a cycloacetal or cycloketal alcohol of formula l ⁇ ' is esterified to yield a dioxolane derivative of formula I with an acid offormula or with a functional derbative of such an acid teg. the anhydride or a halide such as the chloride).
- the esterification can be carried out according to methods known per se; for example. by acylation according to Schotten-Baumann in the presence of a base. or by reaction of an alcohol of formuia l ⁇ ' with an acid of formula or its anhydride in the presence of an acidic catalyst and expediently in the presence of a solvent and with continuous removal of the water which forms.
- acidic catalysts there can be used those mentioned earlier in connection with embodirnent (al of the process.
- 1.4-Diand 1.2.4-trisubstituted dioxolane derivatives such as those of formula I hereinbefore can theoreti' cally exist in a cis and a trans form (see. for example. J. Chem. Soc. 19 0. 263 J. It will be undertood that formula l is meant to include the cis and trans forms as well as mixtures of these two forms.
- the derivatives of formula I manufactured in accordance with the process provided by this invention are obtained mostly as cistrans isomer mixtures with about the same amounts of cis and trans forms.
- EXAMPLE 1 48.6 g of glycerin-a-monon-buty'rate. 14.4 g of nbutyraldehyde and 150 ml of hexane are boiled in the presence of 0.1 g of p-toluenesulphonic acid for 14 hours under a w ater-separator. The mixture obtained after expulsion of the theoretically expected amount of water is cooled and carefully washed neutral. After drying 0 ⁇ er potassium carbonate. the solvent is distilled off and the residue 141 g) fractionally distilled. The propyl-4 butyroxymethyl-dioxolane which is obtained in a yield of 8 boils at C 0.2 mmHg'. m?” [4315.
- EXANlPLE 3 200 g of acetylmethylcarbinol. 366 g of a-glycerin-nmonobuty'rate. 1300 ml of benzene and S g of p-toluenesulphonic acid are mixed in a 4'necked stirring flask provided with a water separator and boiled at reflux with stirring. After 5 hours. the amount of water expelled amounts to about 40 ml. corresponding to an approximately complete reaction. The mixture is cooled and poured into 500 ml of saturated aqueous sodium hydrogen carbonate solution. The benzene solution is separated off in a separating funnel and washed thoroughly with water. After drying for a short time.
- EXAMPLE 4 chloride are then added dropwise over a period of minutes and the resulting mixture is stirred for a period of 5 hours. the temperature being allowed to rise gradually to room temperature. The mixture is then washed and formula ofthis material (see Example I l ofTableJ, as well as those of other dioxolane derivatives encompassed by this invention, are given in the accompanying Table:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Seasonings (AREA)
- Fats And Perfumes (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1089371A CH557814A (de) | 1971-07-23 | 1971-07-23 | Verfahren zur herstellung von neuen geschmackstoffen. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3883558A true US3883558A (en) | 1975-05-13 |
Family
ID=4367935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US270879A Expired - Lifetime US3883558A (en) | 1971-07-23 | 1972-07-12 | 4-N-batyroxymethyl-1,3-dioxolanes |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3883558A (nl) |
| JP (2) | JPS5512908B1 (nl) |
| BE (1) | BE786556A (nl) |
| BR (1) | BR7204528D0 (nl) |
| CH (1) | CH557814A (nl) |
| ES (1) | ES405074A1 (nl) |
| FR (1) | FR2147091B1 (nl) |
| GB (1) | GB1352092A (nl) |
| IT (1) | IT1048945B (nl) |
| NL (1) | NL149805B (nl) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159347A (en) * | 1977-08-24 | 1979-06-26 | International Flavors & Fragrances Inc. | Flavoring with cyclic acetals of 2-methyl-2-pentenal |
| US4198393A (en) * | 1977-08-24 | 1980-04-15 | International Flavors & Fragrances Inc. | Cyclic acetals of 2-methyl-2-pentenal and food flavor uses thereof |
| US4315952A (en) * | 1980-12-04 | 1982-02-16 | International Flavors & Fragrances Inc. | Flavoring with dioxolanes |
| US4379754A (en) * | 1980-12-04 | 1983-04-12 | International Flavors & Fragrances Inc. | Aliphatic branched olefin dioxolanes, dithiolanes, and oxathiolanes and uses thereof in augmenting or enhancing the aroma and/or taste of consumable materials |
| US4381243A (en) * | 1980-12-04 | 1983-04-26 | International Flavors & Fragrances Inc. | Aliphatic branched olefin dioxolanes, dithiolanes, and oxathiolanes and uses thereof in augmenting or enhancing the aroma and/or taste of consumable materials |
| US4435315A (en) | 1980-02-08 | 1984-03-06 | Henkel Kommanditgesellschaft Auf Atkien | Use of alkyl-substituted 1,3-dioxolanes as perfuming agents |
| CN101494999A (zh) * | 2006-07-28 | 2009-07-29 | 吉万奥丹股份有限公司 | 有机化合物的使用方法 |
| US10227321B2 (en) * | 2014-12-26 | 2019-03-12 | Melchior Material And Life Science France | Soothing pro-pheromonal composition for mammals |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2453609B1 (fr) * | 1978-08-02 | 1988-04-01 | Polak Frutal Works | Procede pour la fixation d'aldehydes aromatisants en vue de leur application dans le domaine alimentaire |
| IL59407A (en) * | 1979-03-06 | 1983-12-30 | Sanofi Sa | Di-n-propylacetic acid diesters of glycerol,their preparation and pharmaceutical compositions containing them |
| JP5003180B2 (ja) * | 2007-01-30 | 2012-08-15 | 日油株式会社 | グリセリルモノ（メタ）アクリレートの製造法 |
| WO2016104154A1 (ja) | 2014-12-26 | 2016-06-30 | 東レ株式会社 | 部分分繊繊維束の製造方法および製造装置、部分分繊繊維束 |
| ES2858748T3 (es) | 2016-06-20 | 2021-09-30 | Toray Industries | Método de producción de haz de fibras parcialmente separado |
| WO2017221656A1 (ja) | 2016-06-21 | 2017-12-28 | 東レ株式会社 | 部分分繊繊維束とその製造方法、および部分分繊繊維束を用いた繊維強化樹脂成形材料とその製造方法 |
| CN109312503B (zh) | 2016-06-21 | 2021-04-23 | 东丽株式会社 | 部分分纤纤维束及其制造方法 |
| US11371171B2 (en) | 2016-06-22 | 2022-06-28 | Toray Industries, Inc. | Production method for separated fiber bundle, separated fiber bundle, fiber-reinforced resin molding material using separated fiber bundle, and production method for fiber-reinforced resin molding material using separated fiber bundle |
| WO2017221658A1 (ja) | 2016-06-22 | 2017-12-28 | 東レ株式会社 | 部分分繊繊維束の製造方法と部分分繊繊維束、および部分分繊繊維束を用いた繊維強化樹脂成形材料とその製造方法 |
| MX2019008528A (es) | 2017-02-02 | 2019-09-09 | Toray Industries | Haz de fibra parcialmente separadas y metodo para la fabricacion del mismo, haz de fibras cortadas usando el mismo, y material de formacion de resina reforzada con fibra. |
| CN111542655B (zh) | 2018-01-26 | 2022-09-23 | 东丽株式会社 | 增强纤维束 |
| US11377528B2 (en) | 2018-01-26 | 2022-07-05 | Toray Industries, Inc. | Reinforcing fiber mat, and fiber-reinforced resin forming material and method of producing same |
| CN111630218B (zh) | 2018-02-01 | 2022-08-02 | 东丽株式会社 | 部分分纤纤维束、中间基材、成型品及其制造方法 |
| EP3859064A4 (en) | 2018-09-28 | 2023-07-12 | Toray Industries, Inc. | PARTIALLY SPLIT FIBER BEAM AND METHOD FOR PRODUCING IT |
| CN112955496B (zh) | 2018-10-31 | 2023-10-20 | 东丽株式会社 | 纤维增强树脂材料及其制造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2680735A (en) * | 1952-07-09 | 1954-06-08 | Rohm & Haas | Resinous esters of acrylic acid and methacrylic acid |
| US3184441A (en) * | 1959-04-06 | 1965-05-18 | Du Pont | Air-drying esters of 1, 3-cyclic acetals |
| US3291860A (en) * | 1965-01-29 | 1966-12-13 | Archer Daniels Midland Co | Unsaturated esters of 1, 3-cyclic acetals as monomers for unsaturated polyester resins |
-
1971
- 1971-07-23 CH CH1089371A patent/CH557814A/xx not_active IP Right Cessation
-
1972
- 1972-06-09 NL NL727207891A patent/NL149805B/nl not_active IP Right Cessation
- 1972-06-16 IT IT25806/72A patent/IT1048945B/it active
- 1972-07-10 BR BR4528/72A patent/BR7204528D0/pt unknown
- 1972-07-12 US US270879A patent/US3883558A/en not_active Expired - Lifetime
- 1972-07-20 BE BE786556D patent/BE786556A/xx unknown
- 1972-07-20 JP JP7212872A patent/JPS5512908B1/ja active Pending
- 1972-07-21 FR FR7226326A patent/FR2147091B1/fr not_active Expired
- 1972-07-21 GB GB3422172A patent/GB1352092A/en not_active Expired
- 1972-07-22 ES ES405074A patent/ES405074A1/es not_active Expired
-
1975
- 1975-10-14 JP JP12372075A patent/JPS532946B2/ja not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2680735A (en) * | 1952-07-09 | 1954-06-08 | Rohm & Haas | Resinous esters of acrylic acid and methacrylic acid |
| US3184441A (en) * | 1959-04-06 | 1965-05-18 | Du Pont | Air-drying esters of 1, 3-cyclic acetals |
| US3291860A (en) * | 1965-01-29 | 1966-12-13 | Archer Daniels Midland Co | Unsaturated esters of 1, 3-cyclic acetals as monomers for unsaturated polyester resins |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159347A (en) * | 1977-08-24 | 1979-06-26 | International Flavors & Fragrances Inc. | Flavoring with cyclic acetals of 2-methyl-2-pentenal |
| US4198393A (en) * | 1977-08-24 | 1980-04-15 | International Flavors & Fragrances Inc. | Cyclic acetals of 2-methyl-2-pentenal and food flavor uses thereof |
| US4435315A (en) | 1980-02-08 | 1984-03-06 | Henkel Kommanditgesellschaft Auf Atkien | Use of alkyl-substituted 1,3-dioxolanes as perfuming agents |
| US4315952A (en) * | 1980-12-04 | 1982-02-16 | International Flavors & Fragrances Inc. | Flavoring with dioxolanes |
| US4379754A (en) * | 1980-12-04 | 1983-04-12 | International Flavors & Fragrances Inc. | Aliphatic branched olefin dioxolanes, dithiolanes, and oxathiolanes and uses thereof in augmenting or enhancing the aroma and/or taste of consumable materials |
| US4381243A (en) * | 1980-12-04 | 1983-04-26 | International Flavors & Fragrances Inc. | Aliphatic branched olefin dioxolanes, dithiolanes, and oxathiolanes and uses thereof in augmenting or enhancing the aroma and/or taste of consumable materials |
| CN101494999A (zh) * | 2006-07-28 | 2009-07-29 | 吉万奥丹股份有限公司 | 有机化合物的使用方法 |
| US20090311403A1 (en) * | 2006-07-28 | 2009-12-17 | Givaudan Sa | Method of Using Organic Compounds |
| US10227321B2 (en) * | 2014-12-26 | 2019-03-12 | Melchior Material And Life Science France | Soothing pro-pheromonal composition for mammals |
Also Published As
| Publication number | Publication date |
|---|---|
| CH557814A (de) | 1975-01-15 |
| IT1048945B (it) | 1980-12-20 |
| FR2147091A1 (nl) | 1973-03-09 |
| DE2233245A1 (de) | 1973-02-01 |
| FR2147091B1 (nl) | 1977-12-30 |
| JPS5163969A (nl) | 1976-06-02 |
| NL7207891A (nl) | 1973-01-25 |
| JPS532946B2 (nl) | 1978-02-01 |
| GB1352092A (en) | 1974-05-15 |
| BE786556A (fr) | 1973-01-22 |
| NL149805B (nl) | 1976-06-15 |
| BR7204528D0 (pt) | 1973-06-26 |
| JPS5512908B1 (nl) | 1980-04-04 |
| ES405074A1 (es) | 1975-07-16 |
| DE2233245B2 (de) | 1975-06-26 |
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