Author: claimsbot

1. A method for cooling an article using a cryocooler, comprising the steps of:
setting a stationary point on a cold end of a cryocooler, and
mounting an article onto said stationary point to be cooled.
2. The cooling method as defined in claim 1, wherein said cold end is formed in circular shape, and said stationary point is set on an area substantially near and along a diameter of said cold end.
3. The cooling method as defined in claim 2, wherein said stationary point is set on an almost center of said cold end.
4. The cooling method as defined in claim 1, wherein two pairs of cooling cylinders are connected with said cold end so that a diagonal line connecting one pair of cooling cylinders is orthogonal to another diagonal line connecting the other pair of cooling cylinders, and a high pressure gas is supplied to the one pair of cooling cylinders and a low pressure gas is supplied to the other pair of cooling cylinders so that said stationary point is set on said cold end.
5. The cooling method as defined in claim 4, further comprising the steps of shifting a supply cycle of said high pressure gas from another supply cycle of said low pressure gas by a phase shift of 180 degrees and making said cold end of rigid material, wherein said cold end is not vibrated and said stationary point is set over said cold end.
6. A cryocooler comprising:
two pairs of cooling cylinders, and
a cold end with which said two pairs of cooling cylinders are connected so that a diagonal line connecting one pair of cooling cylinders is orthogonal to another diagonal line connecting the other pair of cooling cylinders,
wherein a high pressure gas is supplied to the one pair of cooling cylinders and a low pressure gas is supplied to the other pair of cooling cylinders so that a stationary point is set on said cold end.
7. The cryocooler as defined in claim 6, wherein said cold end is formed in circular shape and said stationary point is set on an area substantially near and along a diameter of said cold end.
8. The cryocooler as defined in claim 7, wherein said stationary point is set on an almost center of said cold end.
9. The cryocooler as defined in claim 8, wherein said cold end is made of rigid material, and a supply cycle of said high pressure gas is shifted from another supply cycle of said low pressure gas by a phase shift of 180 degrees so that said stationary point is set over said cold end.

The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.

1. An apparatus for visually detecting wear to an insert bowl, bushing, or spider, comprising:
a bowl having a central bore defined by an inner surface, said inner surface including an upper tapered section for engaging slips supporting a work string and a lower section;
a wear indicator means formed in the inner surface of said bowl, said wear indicator means providing a visual indicator of wear to the inner surface of said bowl.
2. The apparatus according to claim 1, wherein said wear indicator means comprises a groove.
3. The apparatus according to claim 2, wherein said groove is a substantially horizontal groove.
4. The apparatus according to claim 3, wherein said substantially horizontal groove extends around a circumference of the inner surface of said bowl.
5. An apparatus for visually detecting wear to an insert bowl, bushing, or spider, comprising:
a bowl having a central bore defined by an inner surface, said inner surface including an upper tapered section for engaging slips supporting a work string and a lower section;
a wear indicator means formed in the lower section of the inner surface of said bowl, said wear indicator means providing a visual indicator of wear to the inner surface of said bowl.
6. The apparatus according to claim 5, wherein said wear indicator means comprises a groove.
7. The apparatus according to claim 6, wherein said groove is a substantially horizontal groove.
8. The apparatus according to claim 7, wherein said substantially horizontal groove extends around a circumference of the inner surface of said bowl.
9. An apparatus for visually detecting wear to an insert bowl, bushing, or spider, comprising:
a bowl having a central bore defined by an inner surface, said inner surface including an upper tapered section for engaging slips supporting a work string and a lower section;
a groove formed in the inner surface of said bowl, said groove having an initial non-wear depth of at least \xbc inch, said groove providing a visual indicator of wear to the inner surface of said bowl.
10. The apparatus according to claim 9, wherein said groove is formed in the lower section of the inner surface of said bowl.
11. The apparatus according to claim 10, wherein said groove is a substantially horizontal groove.
12. The apparatus according to claim 11, wherein said substantially horizontal groove extends around a circumference of the inner surface of said bowl.
13. An apparatus for visually detecting wear to an insert bowl, bushing, or spider, comprising:
a bowl having a central bore defined by an inner surface, said inner surface including an upper tapered section for engaging slips supporting a work string and a lower section;
a first substantially horizontal groove formed in the inner surface of said bowl;
a second substantially horizontal groove formed in the inner surface of said bowl;
said first and second substantially horizontal grooves providing a visual indicator of wear to the inner surface of said bowl.
14. The apparatus according to claim 13, wherein said first substantially horizontal groove has an initial non-wear depth less than an initial non-wear depth of said second substantially horizontal groove.
15. The apparatus according to claim 13, wherein said first substantially horizontal groove is formed in the upper tapered section of the inner surface of said bowl and said second substantially horizontal groove is formed in the lower section of the inner surface of said bowl.
16. The apparatus according to claim 13, wherein said first and second substantially horizontal grooves are each formed in the lower section of the inner surface of said bowl.
17. A method of visually detecting wear to an insert bowl, bushing, or spider, comprising the steps of:
a) providing a bowl having a central bore defined by an inner surface, said inner surface including an upper tapered section for engaging slips supporting a work string, a lower section, and a wear indicator means, said wear indicator means being formed in the inner surface of said bowl and providing a visual indicator of wear to the inner surface of said bowl; and
b) visually inspecting said wear indicator means for existence of wear to the inner surface of said bowl.
18. The method according to claim 17, wherein an inability to visually detect at least a portion of said wear indicator means signifies wear to the inner surface of said bowl that indicates that replacement of said bowl is necessary.
19. The method according to claim 17, wherein said wear indicator means is formed in the lower section of the inner surface of said bowl.
20. The method according to claim 17, wherein said wear indicator means comprises a groove.
21. The method according to claim 20, wherein said groove is a substantially horizontal groove.
22. The method according to claim 21, wherein said substantially horizontal groove extends around a circumference of the inner surface of said bowl.
23. The method according to claim 20, wherein said groove is machined in the inner surface of said bowl.
24. The method according to claim 23, wherein said groove is machined to an initial non-wear depth of at least \xbc inch.
25. A method of visually detecting wear to an insert bowl, bushing, or spider, comprising the steps of:
a) providing a bowl having a central bore defined by an inner surface, said inner surface including an upper tapered section for engaging slips supporting a work string, a lower section, a first substantially horizontal groove, and a second substantially horizontal groove, said first and second horizontal grooves each being formed in the inner surface of said bowl and providing a visual indicator of wear to the inner surface of said bowl; and
b) visually inspecting said first and second substantially horizontal grooves for existence of wear to the inner surface of said bowl.
26. The method according to claim 25, wherein said first substantially horizontal groove has an initial non-wear depth less than an initial non-wear depth of said second substantially horizontal groove.
27. The method according to claim 26, wherein an inability to visually detect at least a portion of said first substantially horizontal groove signifies wear to the inner surface of said bowl that does not indicate that replacement of said bowl is necessary and an inability to detect at least a portion of said second substantially horizontal groove signifies wear to the inner surface of said bowl that indicates that replacement of said bowl is necessary.
28. The method according to claim 25, wherein said first substantially horizontal groove is formed in the upper tapered section of the inner surface of said bowl and said second substantially horizontal groove is formed in the lower section of the inner surface of said bowl.
29. The method according to claim 25, wherein said first and second substantially horizontal grooves are each formed in the lower section of the inner surface of said bowl.

What is claimed is:

1. A method of making a compound of the formula (V-1):
19
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may be optionally substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl-(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, QF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4;
wherein the method comprises:
a) hydrolyzing a compound of the formula (VIg-1)
20
with an aqueous solution in the presence of a base,
d) protecting the amine group of the compound so formed, and
e) cyclizing the compound so formed with heat and an acid catalyst.
2. The method of claim 1, further comprising formation of the compound of the formula (VIg-1) by reacting a compound of the formula (VIf-1)
21
with hydroxylamine hydrochloride and an acid catalyst.
3. The method of claim 2, further comprising formation of the compound of the formula (VIf-1) by heating a compound of the formula (VIe-1)
22
wherein R7 is (C1-C6)alkyl or phenyl wherein the phenyl group may be optionally substituted with one, two, or three (C1-C6)alkyl, hydroxy, or halogen groups.
4. The method of claim 3, further comprising formation of the compound of the formula (VIe-1) by reacting a compound of the formhula (VId-1)
23
with a compound of the formula R7SO2-halide in the presence of a base.
5. The method of claim 4, further comprising formation of the compound of the formula (VId-1) by reducing a compound of the formula (VI-1)
24
with a reducing agent.
6. A method of making a compound of the formula (V-1):
25
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl-(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4;
wherein the method comprises:
a) reducing a compound of the formula (VI-1)
26
with a reducing agent to form a compound of the formula (VId-1)
27
b) reacting the compound of the formula (VId-1) so formed with a compound of the formula R7SO2-halide in the presence of a base to form a compound of the formula (VIe-1)
28
wherein:
R7 is (C1-C6)alkyl or phenyl wherein the phenyl group may be optionally substituted with one, two, or three (C1-C6)alkyl, hydroxy, or halogen groups;
c) heating the compound of the formula (VIe-1) so formed to form a compound of the formula (VIf-1)
29
d) reacting the compound of the formula (VIf-1) so formed with an acid catalyst and hydroxylamine hydrochloride to form a compound of the formula (VIg-1)
30
e) hydrolyzing the compound of the formula (VIg-1) so formed with an aqueous solution in the presence of a base;
f) protecting the amine group of the compound so formed; and
g) cyclizing the compound so formed with heat and an acid catalyst.
7. A method of making a compound of the formula (V-1):
31
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl-(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)N H(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4;
wherein the method comprises heating a compound of the formula (VIb-1)
32
in the presence of an acid catalyst.
8. The method of claim 7, further comprising formation of the compound of the formula (VIb-1) by reacting a compound of the formula (VIa-1)
33
with a silylating agent and further reacting the compound so formed with a reducing agent.
9. The method of claim 8, further comprising formation of the compound of the formula (Via-1) by reacting a compound of the formula (VI-1)
34
with ozone.
10. The method of claim 8, further comprising formation of the compound of the formula (VIa-1) by reacting a compound of the formula (VI-1)
35
with hypochlorous acid.
11. The method of claim 8, further comprising formation of the compound of the formula (VIa-1) by reacting a compound of the formula (VI-1)
36
with hypochlorous acid and further reacting the compound so formed with hydrogen in the presence of a catalyst.
12. A method of making a compound of the formula (V-1):
37
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m-groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)N H, (C1-C6)alkyl(CO)N H, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4;
wherein the method comprises:

a) reacting a compound of the formula (VI-1)
38
with ozone or hypochlorous acid to form a compound of the formula (VIa-1)
39
b) reacting the compound of the formula (Via-1) so formed with a silylating agent and further reacting the compound so formed with a reducing agent to form a compound of the formula (VIb-1)
40
c) heating the compound (VIb-1) so formed in the presence of an acid catalyst.
13. The method of claim 12, further comprising reacting the compound formed in step a) with hydrogen in the presence of a catalyst.
14. A method of making a compound of the formula (VI-1):
41
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl20 (CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-N H(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylH NSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4;
wherein the method comprises reacting a compound of the formula (VII-1)
42
with a Grinard reagent formed in situ by addition of 2-(2-bromo-ethyl)-1,3dioxane to a mixture comprising magnesium, alkylmagnesium halide, and the compound of the formula (VII-1).
15. The method of claim 14, further comprising formation of the compound of the formula (VII-1) by coupling N,O-dimethylhydroxylamine hydrochloride and a compound of the formula (VIII-1)
43
16. The method of any of claims 1-15, wherein R2 is 3-fluoro-benzyl.
17. The method of any of claims 1-15, wherein P is carbobenzyloxy, t-butoxy carbonyl or 9-fluorenyl-methylenoxycarbonyl.
18. The method of any of claims 1-15, wherein P is t-butoxy carbonyl.
19. The method of claim 2 or 6, wherein the acid catalyst comprises ptoluenesulfonic acid, methanesulfonic acid, or sulfuric acid.
20. The method of claim 5 or 6, wherein the reducing agent comprises aluminum triisopropoxide and isopropanol.
21. The method of claim 8 or 12, wherein the reducing agent comprises N-Selectride.
22. The method of claim 8 or 12, wherein the silylating agent comprises 1,1,1,3,3,3-hexamethyl-disilazane.
23. A compound of the formula (VIg-1):
44
wherein:
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-0(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4,
or the salts or esters thereof.
24. A compound of the formula (VIf-1):
45
wherein:
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH-2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl-(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)N H, (C1-C6)alkyl(CO)NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO) (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NS,O2(C1-C6)alkyl, (C1-C6)alkylHNSO2, (C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4,
or the salts or esters thereof.
25. A compound of the formula (Vie-1)
46
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl;
R7 is (C1-C6)alkyl or phenyl wherein the phenyl group may be optionally substituted with one, two, or three (C1-C6)alkyl, hydroxy, or halogen groups; and
m is 0, 1, 2, 3, or 4.
26. A compound of the formula (VId-1):
47
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1P6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4.
27. A compound of the formula (VIb-1):
48
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO); (C1-C6)alkyl-NH(CO), (C11-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)N H, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylHNSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4.
28. A compound of the formula (VIa-1)
49
wherein:
P is a protecting group;
R2 is phenyl-(CH2)m, naphthyl-(CH2)m, (C3-C10)cycloalkyl-(CH2)m, (C1-C6)alkyl or (C2-C9)heteroaryl-(CH2)m, wherein each of said phenyl, naphthyl, (C3-C10)cycloalkyl or (C2-C9)heteroaryl moieties of said phenyl-(CH2)m, naphthyl(CH2)m, (C3-C10)cycloalkyl-(CH2)m or (C2-C9)heteroaryl-(CH2)m groups may optionally be substituted with one, two, or three substituents independently selected from the group consisting of hydrogen, halogen, CN, (C1-C6)alkyl, hydroxy, hydroxy(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, HO(CO), (C1-C6)alkyl-O(CO), HO(CO)(C1-C6)alkyl, (C1-C6)alkyl-O(CO)(C1-C6)alkyl, (C1-C6)alkyl(CO)O, (C1-C6)alkyl-(CO)O(C1-C6)alkyl, H(OC), H(OC)(C1-C6)alkyl, (C1-C6)alkyl(OC), (C1-C6)alkyl(OC)(C1-C6)alkyl, NO2, amino, (C1-C6)alkylamino, (C1-C6)alkyl2amino, amino(C1-C6)alkyl, (C1-C6)alkylamino(C1-C6)alkyl, (C1-C6)alkyl2amino(C1-C6)alkyl, H2N(CO), (C1-C6)alkyl-NH(CO), (C1-C6)alkyl2N(CO), H2N(CO)(C1-C6)alkyl, (C1-C6)alkyl-HN(CO)(C1-C6)alkyl, (C1-C6)alkyl2N(CO)(C1-C6)alkyl, H(OC)NH, (C1-C6)alkyl(CO)NH, (C1-C6)alkyl(CO)-NH(C1-C6)alkyl, (C1-C6)alkyl(CO)-N(C1-C6)alkyl(C1-C6)alkyl, (C1-C6)alkyl-S, (C1-C6)alkyl-(SO), (C1-C6)alkyl-SO2, (C1-C6)alkyl-SO2NH, H2NSO2, H2NSO2(C1-C6)alkyl, (C1-C6)alkylH NSO2(C1-C6)alkyl, (C1-C6)alkyl2NSO2(C1-C6)alkyl, CF3SO3, (C1-C6)alkyl-SO3, phenyl, phenoxy, benzyloxy, (C3-C10)cycloalkyl, (C2-C9)heterocycloalkyl, and (C2-C9)heteroaryl; and
m is 0, 1, 2, 3, or 4.
29. A compound of the formula (VI-1):
50
wherein P is a protecting group and R2 is 3-fluoro-benzyl.
30. A compound of the formula (VII-2):
51
wherein P is a protecting group and R2 is 3-fluoro-benzyl.
31. The compound of any of claims 25-30, wherein P is carbobenzyloxy, t-butoxy carbonyl or 9-fluorenyl-methylenoxy carbonyl.
32. The compound of any of claims 25-30, wherein P is t-butoxy carbonyl.
33. The compound of any of claims 23-28, wherein R2 is 3-fluoro-benzyl.
34. The compound of any of claims 23-28, wherein P is carbobenzyloxy, t-butoxy carbonyl or 9-fluorenyl-methylenoxy carbonyl.
35. The compound of any of claims 23-28, wherein P is t-butoxy carbonyl.

The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.

1. A coupling device for optical fibres comprising:
a first sheet defining a first plurality of through-holes, each of said first plurality of through-holes having at least a portion, with a diameter configured to be approximately a diameter of an optical fibre,
a second sheet joined to said first sheet by a face thereof, and
a third sheet, joined to said first sheet, and defining a second plurality of through-holes, each of said second plurality of through-holes having at least a portion with a diameter configured to be approximately the diameter of said optical fibre, said second plurality of through-holes aligned relative to the first plurality of holes of said first sheet, so as to form a plurality of recesses within each of which one of a plurality of said optical fibres is disposed.
2. The coupling device according to claim 1, wherein said first and third sheets are joined by a respective face.
3. The coupling device according to claim 1 or 2, characterised in that said optical fibres are fixed in said recesses with the aid of an optical glue filling up the residual space around the optical fibres in said recesses.
4. The coupling device according to claim 1, further comprising a spacer, arranged integrally between the first and third sheets, so as to hold them apart and parallel to one another, said plurality of recesses then comprising an initial section and a terminal section set apart from each other by a height of said spacer.
5. The coupling device according to claim 4, wherein said spacer forms a closed volume with the first and third sheets.
6. The coupling device according to claim 4 wherein each of said plurality of optical fibres are fixed in said plurality of recesses with a dose of glue disposed in said initial section and in that said closed volume is filled with an optical gel having an index of refraction close to that of the core of the optical fibre.
7. The coupling device according to claim 4, wherein said spacer is formed by a cylinder portion equipped with an upper face and with a lower face, the upper and lower faces being parallel and tightly attached to the first sheet and to the third sheet respectively.
8. The coupling device according to claim 4, wherein each of said optical fibres are fixed in a respective one of said plurality of recesses with a dose of glue injected into said initial section so as to form, with said optical fibre, a tight-fitting stopper in the initial section and in that said closed volume is filled with an optical oil having an index of refraction close to that of the core of the optical fibre, and further comprising a gas bubble in the optical oil to absorb any thermal expansion of the optical oil.
9. The coupling device according to claim 1, wherein said plurality of holes are formed by photolithography processes and reactive ion etching.
10. The coupling device according to claim 1, wherein said first and third sheets comprise alignment structures produced concomitantly with said holes by photolithography processes and reactive ion etching.
11. The coupling device according to claim 10, wherein said first and third sheets are mounted in a frame equipped with reference surfaces for said alignment structures.
12. The coupling device according to claim 1, wherein at least a portion of said plurality of optical fibres disposed within said plurality of rececesses is bare.
13. The coupling device according to claim 1, wherein at least a portion of said plurality of optical fibres are covered by a tube to mechanically protect each of the plurality of optical fibres.
14. A method of forming a coupling device for optical fibres comprising:
forming a first sheet with a first plurality of through-holes, each of said first plurality of through-holes having at least a portion with a diameter configured to be approximately a diameter of an optical fibre;
forming a second sheet;
joining said second sheet to said first sheet by a face thereof;
forming a third sheet with a second plurality of through-holes, each of said second plurality of through-holes having at least a portion with a diameter configured to be approximately the diameter of said optical fibre;
aligning said second plurality of through-holes relative to the first plurality of holes of said first sheet, so as to form a plurality of recesses within each of which one of a plurality of said optical fibres can be disposed; and
joining said third sheet to said first sheet.
15. The method of claim 14, further comprising forming the first and second plurality of holes by photolithography processes and reactive ion etching.
16. The method of claim 14, further comprising forming alignment structures on said first and third sheets concomitantly with said first and second plurality of holes by the photolithography processes and reactive ion etching.