1. A print instruction device configured to instruct a print unit to print an image stored in an image storing unit storing a plurality of images, the print instruction device comprising:
a display unit configured to display information;
an operation unit configured to be operated by a user; and
a controller configured to:
judge whether each of the plurality of images stored in the image storing unit includes a person who is included in a past image which had been printed in the past;
set priority to each of the plurality of images which is judged to include the person included in the past image, based on at least one of:
a number of times of printing of the person included in the image;
the latest print date and time of the person included in the image;
a number of times of printing of the image;
the latest print date and time of the image; and
a frequency of printing of the image in a predetermined period of time;
control the display unit to display information regarding the image which is judged to include the person included in the past image in order of the priority and in a different form than information regarding the image which is judged not to include the person included in the past image;
receive a selection of an image for printing through the operation unit; and
instruct the print unit to print the selected image.
2. The print instruction device according to claim 1,
wherein the controller is further configured to generate and store print history information including information for identifying the selected image into a history storing unit when the controller instructs to print the selected image, and
wherein the controller judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the print history information.
3. The print instruction device according to claim 2,
wherein the print history information further includes information for identifying a person included in the selected image.
4. The print instruction device according to claim 1,
wherein the controller is further configured to receive a designation of a reference range from the user, the reference range being specified as a period of time defining a period starting from a certain time in the past to the present, andor being specified as a number of images printed lately, and
wherein the controller judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image within the reference range.
5. The print instruction device according to claim 1,
wherein the controller is further configured to perform facial recognition of the person included in each of the plurality of images, and
wherein the controller judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the facial recognition of the person.
6. A print instruction device configured to instruct a print unit to print an image stored in an image storing unit that stores a plurality of images, the print instruction device comprising:
a display unit configured to display information;
an operation unit configured to be operated by a user; and
a controller configured to:
judge whether each of the plurality of images stored in the image storing unit includes a person who is included in a past image which had been printed in the past;
set priority to each of the plurality of images which is judged to include the person included in the past image, based on at least one of:
a number of times of printing of the person included in the image;
the latest print date and time of the person included in the image;
a number of times of printing of the image;
the latest print date and time of the image; and
a frequency of printing of the image in a predetermined period of time;
control the display unit to display information regarding the image which is judged to include the person included in the past image in order of the priority while not to display information regarding the image which is judged not to include the person included in the past image;
receive a selection of an image for printing through the operation unit; and
instruct the print unit to print the selected image.
7. The print instruction device according to claim 6,
wherein the controller is further configured to generate and store print history information including information for identifying the selected image into a history storing unit when the controller instructs the print unit to print the selected image, and
wherein the controller judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the print history information.
8. The print instruction device according to claim 7,
wherein the print history information further including information for identifying a person included in the selected image.
9. The print instruction device according to claim 6,
wherein the controller is further configured to receive a designation of a reference range from the user, the reference range being specified as a period of time defining a period starting from a certain time in the past to the present, andor being specified as a number of images printed lately, and
wherein the controller judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image within the reference range.
10. The print instruction device according to claim 6,
wherein the controller is further configured to perform facial recognition of the person included in each of the plurality of images, and
wherein the controller judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the facial recognition of the person.
11. A print instruction system comprising a server and a terminal device connected to the server, configured to instruct a print unit to print an image stored in an image storing unit storing a plurality of images,
the server comprising a controller configured to:
judge whether each of the plurality of images stored in the image storing unit includes a person who is included in a past image which had been printed in the past; and
transmit a judgment result to the terminal device;
the terminal device comprising:
a display unit configured to display information;
an operation unit configured to be operated by a user; and
a controller configured to:
receive the judgment result from the server;
control the display unit to display information regarding the image which is judged to include the person included in the past image in a different form than information regarding the image which is judged not to include the person included in the past image based on the judgment result;
receive a selection of an image for printing through the operation unit; and
transmit a selection result to the server,
wherein the controller of the server is further configured to:
receive the selection result from the terminal device; and
instruct the print unit to print the selected image based on the selection result.
12. The print instruction system according to claim 11,
wherein the controller of the server is further configured to:
identify a user of the terminal device; and
generate and store print history information including information for identifying the selected image into a history storing unit for each user, when the controller instructs to print the selected image, and
wherein the controller of the server judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the print history information corresponding to the identified user.
13. The print instruction system according to claim 11,
wherein the controller of the server is further configured to:
identify a directory which stores the plurality of images in the image storing unit; and
generate and store print history information including information for identifying the selected image into a history storing unit for each directory, when the controller instructs to print the selected image, and
wherein the controller of the server judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the print history information corresponding to the identified directory.
14. A print instruction system comprising a server and a terminal device connected to the server, configured to instruct a print unit to print an image stored in an image storing unit storing a plurality of images,
the server comprising a controller configured to:
judge whether each of the plurality of images stored in the image storing unit includes a person who is included in a past image which had been printed in the past; and
set priority to each of the plurality of images which is judged to include the person included in the past image, based on at least one of:
a number of times of printing of the person included in the image;
the latest print date and time of the person included in the image;
a number of times of printing of the image;
the latest print date and time of the image; and
a frequency of printing of the image in a predetermined period of time and
transmit a judgment result and a priority setting result to the terminal device;
the terminal device comprising:
a display unit configured to display information;
an operation unit configured to be operated by a user; and
a controller configured to:
receive the judgment result and the priority setting result from the server;
control the display unit to display information regarding the image which is judged to include the person included in the past image in order of the priority while not to display information regarding the image which is judged not to include the person included in the past image based on the judgment result;
receive a selection of an image for printing through the operation unit; and
transmit a selection result to the server,
wherein the controller of the server is further configured to:
receive the selection result from the terminal device; and
instruct the print unit to print the selected image based on the selection result.
15. The print instruction system according to claim 14,
wherein the controller of the server is further configured to:
identify a user of the terminal device; and
generate and store print history information including information for identifying the selected image into a history storing unit for each user, when the controller instructs to print the selected image, and
wherein the controller of the server judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the print history information corresponding to the identified user.
16. The print instruction system according to claim 14,
wherein the controller of the server is further configured to:
identify a directory which stores the plurality of images in the image storing unit; and
generate and store print history information including information for identifying the selected image into a history storing unit for each directory, when the controller instructs to print the selected image, and
wherein the controller of the server judges whether each of the plurality of images stored in the image storing unit includes the person included in the past image based on the print history information corresponding to the identified directory.
17. A non-transitory computer readable medium having computer readable instructions stored thereon, the instructions, when executed by a computer, causing the computer to instruct a print unit to print an image stored in an image storing unit storing a plurality of images, configured to:
judge whether each of the plurality of images stored in the image storing unit includes a person who is included in a past image which had been printed in the past;
set priority to each of the plurality of images which is judged to include the person included in the past image, based on at least one of:
a number of times of printing of the person included in the image;
the latest print date and time of the person included in the image;
a number of times of printing of the image;
the latest print date and time of the image; and
a frequency of printing of the image in a predetermined period of time;
display information regarding the image which is judged to include the person included in the past image in order of the priority and in a different form than information regarding the image which is judged not to include the person included in the past image;
receive a user selection of an image for printing; and
instruct the print unit to print the selected image.
18. A non-transitory computer readable medium having computer readable instructions stored thereon, the instructions, when executed by a computer, causing the computer to instruct a print unit to print an image stored in an image storing unit storing a plurality of images, configured to:
judge whether each of the plurality of images stored in the image storing unit includes a person who is included in a past image which had been printed in the past;
set priority to each of the plurality of images which is judged to include the person included in the past image, based on at least one of:
a number of times of printing of the person included in the image;
the latest print date and time of the person included in the image;
a number of times of printing of the image;
the latest print date and time of the image; and
a frequency of printing of the image in a predetermined period of time;
display information regarding the image which is judged to include the person included in the past image in order of the priority without displaying information regarding the image which is judged not to include the person included in the past image;
receive a user selection of an image for printing; and
instruct the print unit to print the selected image.
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. Process for preparing compounds of the formula (I)
in which
R1 and R2 are each independently a monovalent radical which in each case has 1 to 30 carbon atoms or
PR1R2 as a whole is a 5- to 9-membered heterocyclic radical which contains a total of 2 to 50 carbon atoms and optionally contains up to three further heteroatoms which are selected from the group of oxygen and nitrogen, and
A1 and A2 are each independently a substituted or unsubstituted ortho-arylene radical and
E is E1 or E2 where E1 is an unsubstituted, monosubstituted or disubstituted vicinal cis-alkenediyl radical and E2 is a vicinal alkanediyl radical in which the two yl carbon atoms each bear one or two hydrogen atoms,
comprising
in a step a), reacting compounds of the formula (II)
in which A1, A2 and E are each as defined above with compounds of the formula (III)
R1R2P-Hal\u2003\u2003(III)
in which R1 and R2 are each as defined above and
Hal1 is chlorine, bromine or iodine,
in the presence of acid or base,
to form compounds of the formula (IV)
in which A1, A2, E, R1 and R2 are each as defined above and
in a step b), reducing the compounds of the formula (IV) to compounds of the formula (I).
2. Process according to claim 1, characterized in that R1 and R2 are each independently C1\u2013C18-alkyl, C3\u2013C12-alkenyl, C1\u2013C18-perfluoroalkyl, C1\u2013C18-perfluoroalkoxy, C1\u2013C18-alkoxy, C5\u2013C24-aryl, C5\u2013C24-aryloxy, C5\u2013C25-arylalkyl, C5\u2013C25-arylalkoxy or NR4R5 where R4 and R5 are each independently C1\u2013C12-alkyl, C5\u2013C14-aryl or C6\u2013C15-arylalkyl, or NR4R5 as a whole is a 5- to 7-membered cyclic amino radical having a total of 4 to 12 carbon atoms, or
PR1R2 as a whole is a 5- to 7-membered heterocyclic radical of the formula (V)
in which
Het1 and Het2 are each independently absent, or are each oxygen or NR5 where R5 is C1\u2013C12-alkyl, C5\u2013C14-aryl or C6\u2013C15-arylalkyl and
K is an alkanediyl radical having 2 to 25 carbon atoms, a divalent arylalkyl radical having 5 to 15 carbon atoms, an arylene radical having a total of 5 to 14 carbon atoms or a 2,2\u2032-(1,1\u2032-bisarylene) radical having a total of 10 to 30 carbon atoms.
3. Process according to claim 1, characterized in that A1 and A2 are each independently an ortho-phenylene radical of the formula (VI)
in which
n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and
R6 is in each case independently selected from the group of fluorine, chlorine, bromine, iodine, nitro, free and protected formyl, C1\u2013C12-alkyl, C1\u2013C12-alkoxy, C1\u2013C12-haloalkoxy, C1\u2013C12-haloalkyl, C5\u2013C14-aryl, C6\u2013C15-arylalkyl or radicals of the formula (VII)
L-Q-T-W\u2003\u2003(VII)
in which, each independently,
L is absent or is C1\u2013C8-alkylene or C2\u2013C8-alkenylene and
Q is absent or is oxygen, sulphur or NR7
where
R7 is hydrogen, C1\u2013C8-alkyl, C6\u2013C15-arylalkyl or C5\u2013C14-aryl and
T is a carbonyl-group and
W is R8, OR8, NHR9 or N(R9)2,
where
R8 is C1\u2013C8-alkyl, C5\u2013C15-arylalkyl or C5\u2013C14-aryl and
R9 is in each case independently C1\u2013C8-alkyl, C5\u2013C14-arylalkyl or C4\u2013C15-aryl, or N(R9)2 together is a 5- or 6-membered cycloamino radical,
or a radical of the formulae (VIIIa\u2013g)
L-W\u2003\u2003(VIIIa)
L-SO2-W\u2003\u2003(VIIIb)
L-NR12SO2R12\u2003\u2003(VIIIc)
L-SO3Z\u2003\u2003(VIIId)
L-PO3Z2\u2003\u2003(VIIIe)
L-COZ\u2003\u2003(VIIIf)
L-CN\u2003\u2003(VIIIg)
in which L, Q, W and R8 are each as defined under the formula (VII) and Z is hydrogen or M1 where M1 is as defined under the definition of R7.
4. Process according to claim 1, characterized in that E is a radical of the formulae (IXa) or (IXb) where, in formula (IXa)
R10 and R11 are each independently hydrogen, cyano, fluorine, chlorine, bromine, iodine, C1\u2013C18-alkyl, C4\u2013C24-aryl, C5\u2013C25-arylalkyl, CO2M, CONH2, SO2N(R12)2, SO3M1, where R12 is in each case independently as defined above or is a radical of the formula (X),
T2-Het3-R13\u2003\u2003(X)
in which
T2 is absent or is carbonyl,
Het3 is oxygen or NR12 where R12 is hydrogen, C1\u2013C12-alkyl, C5\u2013C14-aryl or C6\u2013C15-arylalkyl and
R13 is C1\u2013C18-alkyl, C5\u2013C24-aryl or C5\u2013C25-arylalkyl,
and, in formula (IXb),
R14 and R15 are each independently hydrogen, C1\u2013C18-alkyl, C5\u2013C24-aryl or C5\u2013C25-arylalkyl.
5. Process according to at least one of claims 1 to 4, characterized in that
10-cyano-5-diphenylphosphinyl-5H-dibenzoa,dcycloheptene (CNtroppPh) 5-(2S,5S-2,5-dimethylphospholanyl)-5H-dibenzoa,dcycloheptene (S,S-tropphosMe)
5-(2R,5R-2,5-dimethylphospholanyl)-5H-dibenzoa,dcycloheptene (R,R-tropphosMe)
(10-methoxy-5H-dibenzoa,dcyclohepten-5-yl)diphenylphosphine (MeOtroppPh)
(10-methoxy-5H-dibenzoa,dcyclohepten-5-yl)dicyclohexylphosphine (MeOtroppCyc)
(5S)-10-(\u2212)-menthyloxy-5H-dibenzoa,dcyclohepten-5-yldiphenylphosphine, (S-menthyloxytroppPh) and (5R)-10-(\u2212)-menthyloxy-5H-dibenzoa,dcyclohepten-5-yl-diphenylphosphine (R-menthyloxytroppPh) are prepared.
6. Process according to claim 1, characterized in that acids are used for step a).
7. Process according to claim 1, characterized in that the acids used are those which, based on an aqueous reference scale and 25\xb0 C., have a pKa value of 5.5 or less.
8. Process according to claim 1, characterized in that step a) is carried out at a temperature of \u221220\xb0 C. to 100\xb0 C.
9. Process according to claim 1, characterized in that stereoisomer mixtures of compounds of the formula (IV), are separated before carrying out step b).
10. Process according to at least one of claims 1 to 9, characterized in that at least one of the R1, R2, A1, A2 and E radicals in the compounds of the formula (IV) is converted to another R1, R2, A1, A2 and E radical.
11. Process according to claim 1, characterized in that the reduction in step b) is carried out in the presence of hydrosilicon compounds.
12. Process according to claim 1, characterized in that the reduction in step b) is carried out at a temperature of 20\xb0 C. to 200\xb0 C.
13. Process according to claim 1, characterized in that the resulting compounds are reduced to the free phosphines in a further step.
14. Compounds of the formula (IVa)
in which A1, A2 and E are each as defined in claim 1.
15. 5-Dichlorooxyphosphoryl-5H-dibenzoa,dcycloheptene (troppoCl) and 5-dibromooxyphosphoryl-5H-dibenzoa,dcycloheptene (troppoBr).
16. Process for preparing compounds of the formula (IVa)
in which A1, A2 and E are each as defined in claim 1 and
Hal is in each case chlorine, bromine or iodine,
comprising reacting
compounds of the formula (II) as defined in claim 1 in the presence of acid or base with compounds of the formula (IIIa)
PHal3\u2003\u2003(IIIa)
in which
Hal is in each case independently chlorine, bromine or iodine.
17. Process according to claim 16, characterized in that the compounds of the formula (IVa) are also reacted with compounds of the formula (XII)
R12-M\u2003\u2003(XII)
in which R1 and R2 are each as defined in claim 1, and M, in the case that
R1 or R2 are to be bonded to the phosphorus atom via an oxygen atom, is hydrogen or 1n equivalent of a metal or of a metal fragment having the valency n, and, in the case that
R1 or R2 are to be bonded to the phosphorus atom via a nitrogen atom, is hydrogen, and, in the case that
R1 or R2 are to be bonded to the phosphorus atom via a carbon atom, is 1n equivalent of a metal or of a metal fragment having the valency n,
the same also applying in a similar manner to radicals in which R1R2 as a whole is a divalent radical.
18. Process according to claim 17, characterized in that the resulting compounds are reduced to the free phosphines in a further step.
19. A process for preparing ligand for metals or conducting catalytic processes comprising providing the compounds of claim 14.
20. The process of claim 19, characterized in that the catalytic processes are hydrogenations and hydrosilylations.