CA1180326A - 1,4-dioxaspiro[4,5]decene compounds - Google Patents
1,4-dioxaspiro[4,5]decene compoundsInfo
- Publication number
- CA1180326A CA1180326A CA000407793A CA407793A CA1180326A CA 1180326 A CA1180326 A CA 1180326A CA 000407793 A CA000407793 A CA 000407793A CA 407793 A CA407793 A CA 407793A CA 1180326 A CA1180326 A CA 1180326A
- Authority
- CA
- Canada
- Prior art keywords
- halogen
- acylamino
- aromatization
- carried out
- substituted
- 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
Links
- KEMLLBHQBONAAX-UHFFFAOYSA-N 1,4-dioxaspiro[4.5]dec-2-ene Chemical class C1CCCCC21OC=CO2 KEMLLBHQBONAAX-UHFFFAOYSA-N 0.000 title 1
- 229910052736 halogen Inorganic materials 0.000 claims abstract 10
- 150000002367 halogens Chemical group 0.000 claims abstract 10
- 125000004442 acylamino group Chemical group 0.000 claims abstract 8
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract 7
- -1 3-substituted-2-hydroxypropyl aryl ether Chemical class 0.000 claims abstract 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 5
- 239000001257 hydrogen Substances 0.000 claims abstract 5
- 125000004423 acyloxy group Chemical group 0.000 claims abstract 4
- 125000001691 aryl alkyl amino group Chemical group 0.000 claims abstract 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 4
- 125000005237 alkyleneamino group Chemical group 0.000 claims abstract 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000002252 acyl group Chemical group 0.000 claims abstract 2
- 125000004450 alkenylene group Chemical group 0.000 claims abstract 2
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract 2
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 125000001589 carboacyl group Chemical group 0.000 claims abstract 2
- 150000002431 hydrogen Chemical group 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 229910052717 sulfur Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims 10
- 238000005899 aromatization reaction Methods 0.000 claims 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- 239000002841 Lewis acid Substances 0.000 claims 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 claims 2
- 150000007517 lewis acids Chemical class 0.000 claims 2
- 239000012429 reaction media Substances 0.000 claims 2
- 150000003335 secondary amines Chemical class 0.000 claims 2
- 150000003512 tertiary amines Chemical class 0.000 claims 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003377 acid catalyst Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical class CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
?4-DIOXASPIRO[4,5] DECENE COMPOUNDS
ABSTRACT OF THE DISCLOSURE
A process for preparing 3-substituted-2-hydroxypropyl aryl ether .beta.-blockers of the formula;
wherein Y is halogen, hydroxy, lower acyloxy, amino, lower alkylamino, lower aralkylamino, lower acylamino, di-lower alkylamino, lower alkyleneamino, N-lower alkyl-N-lower aralkylamino, di-lower acylamino, N-lower aklyl-N-lower acylamino or N-tri-lower alkylsilylamino; one of P and R combined together with Q shows lower alkylene or alkenylene optionally interrupted by O, N or S and optionally substituted by lower alkyl, lower araklyl, lower carboxylic acyl, carboxy, protected carboxy;
hydroxy, lower alkoxy, lower acyloxy, oxo; amino, lower alkylamino, lower acylamino, nitro, nitroso, lower alkylthio, lower sulfonic acyl or halogen; and remaining R and P is hydrogen or halogen which comprises aromatizing a 2-(substituted methyl) -1,4,dioxaspiro[4,5]-decene compound of the formula:
ABSTRACT OF THE DISCLOSURE
A process for preparing 3-substituted-2-hydroxypropyl aryl ether .beta.-blockers of the formula;
wherein Y is halogen, hydroxy, lower acyloxy, amino, lower alkylamino, lower aralkylamino, lower acylamino, di-lower alkylamino, lower alkyleneamino, N-lower alkyl-N-lower aralkylamino, di-lower acylamino, N-lower aklyl-N-lower acylamino or N-tri-lower alkylsilylamino; one of P and R combined together with Q shows lower alkylene or alkenylene optionally interrupted by O, N or S and optionally substituted by lower alkyl, lower araklyl, lower carboxylic acyl, carboxy, protected carboxy;
hydroxy, lower alkoxy, lower acyloxy, oxo; amino, lower alkylamino, lower acylamino, nitro, nitroso, lower alkylthio, lower sulfonic acyl or halogen; and remaining R and P is hydrogen or halogen which comprises aromatizing a 2-(substituted methyl) -1,4,dioxaspiro[4,5]-decene compound of the formula:
Claims (11)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing 2-hydroxy-3-substituted-propyl aryl ethers represented by the following formula:
wherein Y is halogen, hydroxy, lower acyloxy, amino, lower alkylamino, lower aralkylamino, lower acylamino, di-lower alkylamino, lower alkyleneamino, N-lower alkyl-N-lower aralkylamino, di-lower acylamino, N-lower alkyl-N-lower acylamino or N-tri-lower alkylsilylamino; one of P and R combined togther with Q shows lower alkylene or alkenylene optionally interrupted by O, N or S and optionally substituted by lower alkyl, lower aralkyl, lower carboxylic acyl, carboxy, protected carboxy, hydroxy, lower alkoxy, lower acyloxy, oxo; amino, lower alkylamino, lower acylamino, nitro, nitroso, lower alkylthio, lower sulfonic acyl or halogen; and remining R and P is hydrogen or halogen; which comprises aromatizing a 2-(substituted methyl)-1,4-dioxaspiro[4,5]-decene compound presented by the following formula:
wherein Y, P, Q, and R are as defined above, X is hydrogen or halogen and the dotted line represents, if X is hydrogen, two double bonds or if X is halogen represents a double dond, wherein the aromatization is carried out by the action of a base, adsorbing agent, metal salt or heating.
wherein Y is halogen, hydroxy, lower acyloxy, amino, lower alkylamino, lower aralkylamino, lower acylamino, di-lower alkylamino, lower alkyleneamino, N-lower alkyl-N-lower aralkylamino, di-lower acylamino, N-lower alkyl-N-lower acylamino or N-tri-lower alkylsilylamino; one of P and R combined togther with Q shows lower alkylene or alkenylene optionally interrupted by O, N or S and optionally substituted by lower alkyl, lower aralkyl, lower carboxylic acyl, carboxy, protected carboxy, hydroxy, lower alkoxy, lower acyloxy, oxo; amino, lower alkylamino, lower acylamino, nitro, nitroso, lower alkylthio, lower sulfonic acyl or halogen; and remining R and P is hydrogen or halogen; which comprises aromatizing a 2-(substituted methyl)-1,4-dioxaspiro[4,5]-decene compound presented by the following formula:
wherein Y, P, Q, and R are as defined above, X is hydrogen or halogen and the dotted line represents, if X is hydrogen, two double bonds or if X is halogen represents a double dond, wherein the aromatization is carried out by the action of a base, adsorbing agent, metal salt or heating.
2. A process of claim 1, wherein the aromatization is carried out by the reaction of a secondary amine.
3. A process of claim 1, wherein the secondary amine is morpholine or piperidine and the reaction is carried out at 80 degress C to 150 degrees C.
4. A process of claim 1, wherein the aromatization is carried out by the action of a Lewis acid.
5. A process of claim 4, wherein the Lewis acid is one selected from stannic chloride, boron trichloride and titanium tetrachloride.
6. A process of claim 4, wherein the aromatization is carried out in the presence of a tertiary amine.
7. A process of claim 6, wherein the tertiary amine is triethylamine, tributylamine, trioctylamine, quinuclidine or 1,4-diazabicylco[2,2,2]octane.
8. A process of claim 4, wherein Y is lower alkylamino or lower alkyleneamino.
9. A process of claim 1, wherein the aromatization is carried out by the action of a mineral acid or adsorbent.
10. A process of claim 1, wherein the starting 2-(substituted methyl)-1,4-dioxaspiro is prepared by treating a cyclohexenone compound of the following formula:
wherein P, Q, X, R and the dotted line are as defined in claim 1 or its reactive derivative with a 3-substituted-propyleneglycol compound of the following formula:
wherein Y is as defined in claim 1, or its reactive derivative in an inert solvent optionally in the presence of an acid catalyst for condensation at a temperature of range from -50 degrees C to 150 degrees C.
wherein P, Q, X, R and the dotted line are as defined in claim 1 or its reactive derivative with a 3-substituted-propyleneglycol compound of the following formula:
wherein Y is as defined in claim 1, or its reactive derivative in an inert solvent optionally in the presence of an acid catalyst for condensation at a temperature of range from -50 degrees C to 150 degrees C.
11. A process of claim 10, wherein said starting compound as prepared in a reaction medium is subjected in the same reaction medium to said subsequent aromatization step to prepare the final product.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000407793A CA1180326A (en) | 1979-03-07 | 1982-07-21 | 1,4-dioxaspiro[4,5]decene compounds |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27010/1979 | 1979-03-07 | ||
JP2701079A JPS55118432A (en) | 1979-03-07 | 1979-03-07 | 2-spipo-1,3-dioxolane compound and new synthesis of aromatic ether by its ring opening reaction |
JP1039980A JPS56108764A (en) | 1980-01-30 | 1980-01-30 | Novel synthesis of beta-blocker |
JP10399/1980 | 1980-01-30 | ||
CA000346987A CA1139760A (en) | 1979-03-07 | 1980-03-04 | 1,4-dioxaspiro¬4,5| decene compounds |
CA000407793A CA1180326A (en) | 1979-03-07 | 1982-07-21 | 1,4-dioxaspiro[4,5]decene compounds |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000346987A Division CA1139760A (en) | 1979-03-07 | 1980-03-04 | 1,4-dioxaspiro¬4,5| decene compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1180326A true CA1180326A (en) | 1985-01-02 |
Family
ID=27426222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000407793A Expired CA1180326A (en) | 1979-03-07 | 1982-07-21 | 1,4-dioxaspiro[4,5]decene compounds |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA1180326A (en) |
-
1982
- 1982-07-21 CA CA000407793A patent/CA1180326A/en not_active Expired
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |