US6072094A
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US
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Efficient synthesis of cyclopropylacetylene
Assignee: Merck and Co Inc
•
Filing: 1998-07-28
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Granted: 2000-06-06
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Expires: 2018-07-28
Abstract
Abstract An efficient and facile process for the preparation of cyclopropylacetylene from thioanisole and cyclopropyl substituted ketones or aldehydes is disclosed.
Inventors
- 👤 Sandor Karady
- 👤 Benjamin Marcune
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 10:44
CPC Classifications
C; C07; C07C; C07C13/00; C07C13/02; C07C13/04; C07C2601/00; C07C2601/02
Claims Analysis
Total Claims: 9
Claim 1
Independent Claim
118 words
A process for the preparation of cyclopropyl acetylene (CPA), represented by formula I: ##STR13## which comprises reacting a compound represented by formula II: ##STR14## wherein X is H, halo, CF 3 , or C 1-6 alkyl; in the presence of a base and a silylating agent, to a compound represented by formula III: ##STR15## wherein each R is independently a C 1-6 alkyl and X is described above; reacting a compound of formula III with a compound of formula IV: ##STR16## in the presence of a base to yield a vinyl thioether, represented by formula V and VI: ##STR17## reacting a compound of formula V and VI in the presence of potassium diaminopropane (KAPA) to yield cyclopropyl acetylene.
Claim 2
Dependent Claim
118 words
A process for the preparation of cyclopropyl acetylene (CPA), represented by formula I: ##STR13## which comprises reacting a compound represented by formula II: ##STR14## wherein X is H, halo, CF 3 , or C 1-6 alkyl; in the presence of a base and a silylating agent, to a compound represented by formula III: ##STR15## wherein each R is independently a C 1-6 alkyl and X is described above; reacting a compound of formula III with a compound of formula IV: ##STR16## in the presence of a base to yield a vinyl thioether, represented by formula V and VI: ##STR17## reacting a compound of formula V and VI in the presence of potassium diaminopropane (KAPA) to yield cyclopropyl acetylene.
Claim 3
Dependent Claim
40 words
The process of claim 1 wherein the base employed is phenyl lithium, Butyl lithium (BuLi) or potassium methyl and the compound of formula II is reacted with the base at a temperature of about -100° C. to about -60° C.
Claim 4
Dependent Claim
22 words
The process according to claim 2 wherein the temperature is about -95° C. to about -70° C. and the base is BuLi.
Claim 5
Dependent Claim
15 words
The process of claim 1 wherein the silylating agent employed are trialkylsilylchlorides, triakylsilyliodides and triflates.
Claim 6
Dependent Claim
20 words
The process of claim 4 wherein the silylating agents are trimethylsilylchloride, triethylsilylchloride, t-butyldimethylsilyl chloride, t-butyldiphenylsilylchloride, trimethylsilyltriflate, t-butyldimethylsilyltriflate, triethylsilyltriflate, and triethylsilyliodide.
Claim 7
Dependent Claim
11 words
The process of claim 5 wherein the silylating agent is trimethylsilylchloride.
Claim 8
Dependent Claim
114 words
A process for the preparation of cyclopropyl acetylene (CPA), represented by formula I: ##STR18## which comprises reacting a compound of formula II: ##STR19## wherein X is H, halo, CF 3 , or C 1-6 alkyl; in the presence of BuLi and TMSCl, to a compound represented by formula III: ##STR20## wherein each R is independently a C 1 alkyl and X is described above; reacting a compound of formula III with a cyclopropyl carboxaldehyde, represented by formula IV: ##STR21## in the presence of BuLi to yield vinyl thioethers, represented by formula V and VI: ##STR22## reacting a compound of formula V and VI in the presence of potassium diaminopropane (KAPA) to yield cyclopropyl acetylene.
Claim 9
Dependent Claim
114 words
A process for the preparation of cyclopropyl acetylene (CPA), represented by formula I: ##STR18## which comprises reacting a compound of formula II: ##STR19## wherein X is H, halo, CF 3 , or C 1-6 alkyl; in the presence of BuLi and TMSCl, to a compound represented by formula III: ##STR20## wherein each R is independently a C 1 alkyl and X is described above; reacting a compound of formula III with a cyclopropyl carboxaldehyde, represented by formula IV: ##STR21## in the presence of BuLi to yield vinyl thioethers, represented by formula V and VI: ##STR22## reacting a compound of formula V and VI in the presence of potassium diaminopropane (KAPA) to yield cyclopropyl acetylene.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 2003-06-06 | 2003-12-06 | 2004-06-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2007-06-06 | 2007-12-06 | 2008-06-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2011-06-06 | 2011-12-06 | 2012-06-06 | $7700.00 | Window Closed / Lapsed |