US2647133A - Allyl derivatives of coumarin - Google Patents
Allyl derivatives of coumarin Download PDFInfo
- Publication number
- US2647133A US2647133A US292726A US29272652A US2647133A US 2647133 A US2647133 A US 2647133A US 292726 A US292726 A US 292726A US 29272652 A US29272652 A US 29272652A US 2647133 A US2647133 A US 2647133A
- Authority
- US
- United States
- Prior art keywords
- coumarin
- fibers
- products
- allyl
- allyl derivatives
- 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title description 5
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title description 3
- 229960000956 coumarin Drugs 0.000 title description 2
- 235000001671 coumarin Nutrition 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 description 11
- 239000000835 fiber Substances 0.000 description 8
- -1 ALLYL Chemical class 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 5
- 210000002268 wool Anatomy 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000009994 optical bleaching Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MESJRHHDBDCQTH-UHFFFAOYSA-N 3-(dimethylamino)phenol Chemical class CN(C)C1=CC=CC(O)=C1 MESJRHHDBDCQTH-UHFFFAOYSA-N 0.000 description 1
- FUXZRRZSHWQAAA-UHFFFAOYSA-N 5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C1=C(N)C=C2S(=O)(=O)C3=CC(N)=CC=C3C2=C1 FUXZRRZSHWQAAA-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical class OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical group CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
Definitions
- the present invention relates to a new class of compounds which are useful for the whitening of wool and silk and synthetic fibers, such as nylon and cellulose acetate.
- These fibers generally have a slight yellow cast and, as the material becomes older, the yellow hue develops further and is not removed by laundering or dry cleaning. This same yellowing is characteristic of cellulosic fibers, and numerous products have been recommended recently for the optical bleaching of such materials. These optical bleaching agents function by absorbing ultraviolet light and re-emitting it in the form of visual light of such a wave length or hue that it neutralizes the yellow cast and gives a pure white fabric.
- the products which have been used for cellulosic fibers have been largely derivatives of diaminostilbenedisulfonic acid and benzidine sulfone disulfonic acid.
- Such products are of little value for the whitening of wool, silk, and synthetic fibers, since they have little or no affinity for such fibers under neutral or weakly acidic conditions, such as prevail in application with detergents.
- One product which has been recommended for this purpose is 4- methyl 7 diethylaminocouma-rin. This compound has the desired effect when used in suflicient amounts, but tends to give the fiber a pink cast, which is not desirable. This is particularly true in the case of cellulose acetate.
- R, R and X are lower alkyl radicals and C3H5 is either a propen-l-yl or a propen- 2-yl (allyl) group.
- the products are characterized, in general, by a surprisingly increased fluorescence intensity and by the fact that they do not impart an undesirable pink hue to the fibers to which they are applied.
- the alkyl groups attached to the amino nitrogen atom may contain from one to 18 carbon atoms, but we have discovered that the higher It is an advantage of thepresent invention that these varied condensationsdo not requirespecial conditions but proceed smoothly. underthe infiuence of an acid catalyst, such" as: zinc chloride. This would have been quite impossible to predict, since it is generally believedtl'iatthe condensation proceeds through the enol form of' the beta-keto ester and since it is well known that the presence of an alpha substituent in a beta -keto ester inhibits this enolization.
- this product When applied to wool from an acid bath, this product shows about 40% greater fluorescence than the corresponding compound unsubstituted in the 3-position. It also has a strong whitening action on acetate, whereas 4-methyl-7-diethylaminocoumaringives acetatefiberan undesirable pink hue.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
Description
Patented July 28, 1 953 7 2,647,133 ALLYL DERIVATIVES F COUMARIN Robert Sidney Long, Bound Brook, N. J., and
Carleton Alfred Sears, Stamford, Conn., assignors to American Cyanamid' Company, New York, N. Y., a corporation of Maine No Drawing. Application June 10, 1952,
Serial No. 292,726
Claims.
The present invention relates to a new class of compounds which are useful for the whitening of wool and silk and synthetic fibers, such as nylon and cellulose acetate.
These fibers generally have a slight yellow cast and, as the material becomes older, the yellow hue develops further and is not removed by laundering or dry cleaning. This same yellowing is characteristic of cellulosic fibers, and numerous products have been recommended recently for the optical bleaching of such materials. These optical bleaching agents function by absorbing ultraviolet light and re-emitting it in the form of visual light of such a wave length or hue that it neutralizes the yellow cast and gives a pure white fabric. The products which have been used for cellulosic fibers have been largely derivatives of diaminostilbenedisulfonic acid and benzidine sulfone disulfonic acid.
Such products are of little value for the whitening of wool, silk, and synthetic fibers, since they have little or no affinity for such fibers under neutral or weakly acidic conditions, such as prevail in application with detergents. There has been, therefore, a great need for products of modified structure which will have the desired property of absorbing ultraviolet light and converting it to visual light of the proper wave length and, in addition, the property of having aflinity for the above-mentioned fibers under neutral or weakly acidic conditions. One product which has been recommended for this purpose is 4- methyl 7 diethylaminocouma-rin. This compound has the desired effect when used in suflicient amounts, but tends to give the fiber a pink cast, which is not desirable. This is particularly true in the case of cellulose acetate.
The products of this invention are represented by the general formula shown below:
CsHi R! in which R, R and X are lower alkyl radicals and C3H5 is either a propen-l-yl or a propen- 2-yl (allyl) group.
As indicated above, the products are characterized, in general, by a surprisingly increased fluorescence intensity and by the fact that they do not impart an undesirable pink hue to the fibers to which they are applied.
Compounds of this type may be prepared by the condensation of a metadialkylaminophenol with an alpha-substituted beta-keto ester. This preparation may be represented by the general.
equation shown below:
Thus, it is apparent that variation of X groups will lead to a variation of the substituents in the 4-position of the coumarin nucleus. For example, ethyl a-allyl-acetoacetate in which X is methyl will lead to a 3-propenyl-4-methylcoumarin. By varying X, the substituent in the 4-position can be changed. Thus, ethyl a-allylvaleroacetate will produce a 3-propeny1--butylcoumarin.
We are aware of the possibility that the double bond in the allyl group may shift under the reaction conditions to conjugate with the double bonds in the coumarin nucleus. Such a rearrangement is illustrated below for the-reaction product from ethyl a-allylacetoacetate and metadiethylaminophenol Since either of these products might be expected from the reaction and the actual product is in fact probably a mixture, both products fall within our invention. We have therefore referred to the substituent CsHs as a prcpenyl group, by which is meant either of propen-2-yl (allyl) group or the propen-l-yl group.
The alkyl groups attached to the amino nitrogen atom may contain from one to 18 carbon atoms, but we have discovered that the higher It is an advantage of thepresent invention that these varied condensationsdo not requirespecial conditions but proceed smoothly. underthe infiuence of an acid catalyst, such" as: zinc chloride. This would have been quite impossible to predict, since it is generally believedtl'iatthe condensation proceeds through the enol form of' the beta-keto ester and since it is well known that the presence of an alpha substituent in a beta -keto ester inhibits this enolization.
The very'striking. degree of fluorescence and the: desirable shade of: fluorescence exhibited-by these compounds when theyare applied to fibers such as wool, silk, nylon, and cellulose acetate does not admit of complete explanation in the present state ofthe art, since theories" of fluorescence are still somewhat incomplete. It was completely unpredictable that this particular combination of 3,4-disubstitution in the coumarin ring with adialkylamino group present in the benzene ring should prove so strikingly effective. It is particularly noteworthy that even close chemical relatives which differ only in that they do not contain the substituent in the 3-position are appreciably weaker in their fluorescence.
The-present invention is further illustrated by the following examples; Parts are by weight unlessotherwise specified.
Example (CiHDzN A mixture of 41.5 parts of m-diethylaminophenol,:.63.8 parts of ethylu-allylacetoacetate,
and 17 parts of anhydrouszincchloride was acetone and adding sulfuric acid The sulfate so obtained melts at 192-194 C.
When applied to wool from an acid bath, this product shows about 40% greater fluorescence than the corresponding compound unsubstituted in the 3-position. It also has a strong whitening action on acetate, whereas 4-methyl-7-diethylaminocoumaringives acetatefiberan undesirable pink hue.
Substitution of m-dimethylaminophenol for m-diethylaminophenol gives the expected 3-propenyl 4 methyl 7 dimethylaminocoumarin. This compound has a similar strong whitening action on wool, silk, and acetate fibers.
We claim:-
1. Compounds-having the formula:
in which-R, l-t and- X are lowr alkylra'dicals'.
2. A compound having the formula:
5. A compound having the formula:
R'OBERTISIID'NEYT LONG. CARLETONAIFRED SEARS.
No references" cited.
Claims (1)
1. COMPOUNDS HAVING THE FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US292726A US2647133A (en) | 1952-06-10 | 1952-06-10 | Allyl derivatives of coumarin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US292726A US2647133A (en) | 1952-06-10 | 1952-06-10 | Allyl derivatives of coumarin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2647133A true US2647133A (en) | 1953-07-28 |
Family
ID=23125930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US292726A Expired - Lifetime US2647133A (en) | 1952-06-10 | 1952-06-10 | Allyl derivatives of coumarin |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2647133A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3008969A (en) * | 1958-05-21 | 1961-11-14 | American Cyanamid Co | 4-substituted-7-carboalkoxyamino-coumarins |
| DE1186078B (en) * | 1961-08-12 | 1965-01-28 | Cassella Farbwerke Mainkur Ag | Process for the preparation of derivatives of 7-oxycoumarin |
| US3201421A (en) * | 1962-05-09 | 1965-08-17 | Dept Of Chemistry | Preparation of alkyl psoralens |
| DE1210883B (en) * | 1961-11-09 | 1966-02-17 | Cassella Farbwerke Mainkur Ag | Process for the preparation of derivatives of 7-oxycoumarin |
| US3891569A (en) * | 1974-02-11 | 1975-06-24 | Us Navy | Lasing dyes |
| US3927033A (en) * | 1974-11-25 | 1975-12-16 | Peter R Hammond | Lasing dye and method of preparation |
| EP4015512A1 (en) | 2020-12-16 | 2022-06-22 | AMO Ireland | Optically active devices |
-
1952
- 1952-06-10 US US292726A patent/US2647133A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3008969A (en) * | 1958-05-21 | 1961-11-14 | American Cyanamid Co | 4-substituted-7-carboalkoxyamino-coumarins |
| DE1186078B (en) * | 1961-08-12 | 1965-01-28 | Cassella Farbwerke Mainkur Ag | Process for the preparation of derivatives of 7-oxycoumarin |
| DE1210883B (en) * | 1961-11-09 | 1966-02-17 | Cassella Farbwerke Mainkur Ag | Process for the preparation of derivatives of 7-oxycoumarin |
| DE1246754B (en) * | 1961-11-09 | 1967-08-10 | Cassella Farbwerke Mainkur Ag | Process for the preparation of derivatives of 7-oxycoumarin |
| US3201421A (en) * | 1962-05-09 | 1965-08-17 | Dept Of Chemistry | Preparation of alkyl psoralens |
| US3891569A (en) * | 1974-02-11 | 1975-06-24 | Us Navy | Lasing dyes |
| US3927033A (en) * | 1974-11-25 | 1975-12-16 | Peter R Hammond | Lasing dye and method of preparation |
| EP4015512A1 (en) | 2020-12-16 | 2022-06-22 | AMO Ireland | Optically active devices |
| WO2022128832A1 (en) | 2020-12-16 | 2022-06-23 | Merck Patent Gmbh | Optically active devices |
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